THE SYNTHESES AND CDMPLEXATION OF SOME 1,5 CYCLDPOLYMETHYLENETETRAZ OLES AND BTTETRAZOLES Thesis: TEE the meme 0T Ph f" ' 7° - MECMMAM SEEEE UNWERSITT * ‘ ERANK MICHAEL D‘TTRI ' 1963 ‘ " 0-169 LIBRARY Michigan State University This is to certifg that the thesis entitled THE SYNTHESES AND COMPLEXATION OF SOME l , 5—CYCLOP OLYMETHYLENETETRAZOLES AND BITETRAZOLES presented by Frank Michael D'Itri has been accepted towards fulfillment of the requirements for Ph. D. degree in Chemistry Major professo Date August 6, 1968 '\ 511E SYNTHES 1, 5-CYCL n a h ‘ H ~ Nil-1 . N . ~. “\A'n-n: .u- . K . M -n . A “A 33‘ ""2“ \..m\‘“ “A. Tuls‘tl \“ . ‘~\ \‘ :"Q ~~~ A“ DC. ABSTRACT THE SYNTHESES AND COMPLEXATION OF SOME l , 5—CYCLOPOLYMETHYLENETETRAZOLES AND BITETRAZOLES by Frank Michael D'Itri The purpose of this investigation was to study the influence of substituent groups on the physicochemical and pharmacological properties of the respective l,5-cyclopolymethylenetetrazoles and bitetrazoles. A series of l,5—cyclopolymethylenetetrazoles were synthesized with the hydrocarbon chain containing 3,A,6, 7,8,9, and 11 methylene groups (hereafter abbreviated as CnMT where n indicates the number of methylene groups in the compound)‘. The donor properties of these tetrazoles were investigated by spectrophotometric and potentio— metric techniques. The spectrophotometric study consisted of the measurement of the cyclopolymethylenetetrazole—iodine charge-transfer complex formation constants for the reaction CnMT + 12 :fzchToI in the 5—350 interval» 2 The solvent was l,2—dichloroethane, and the data were Obtained with a Beckman model DU spectrophotometer equipped with Beckma‘n thermospacers to control the temperature of the sample compartment. 91.5.. L--.- Tie enthalpy and reitens were deters! n . * statility cons: Fun: - . 'l!‘ a F Oct ---..-v.. L3.‘S o - Frank Michael D'Itri- The enthalpy and entropy changes for the complexing reactions were determined from the temperature coefficient of the stability constant. The donor properties of cyclopolymethylenetetrazoles were rather weak, and the formation constant values at 25° ranged from 1.112 to 2.611 liter mole—l. There does not seem to be a simple correlation between the length of the hydrocarbon chain and the stability of the iodine complex. The potentiometric study consisted of the determination of the dissociation constants for the complexes formed between silver(I) nitrate and the water soluble 1,5— cyclopolymethylenetetrazoles (tri, tetra, penta, hexa, and heptamethylenetetrazole). The stoichiometry of the reaction is given by the following equation. H O + 2 + ___.___=_ M Ag(CnMT)2 Ag + 2Cn T W..— K . IL Data were obtained with a Beckman expanded scale pH meter and a two compartment cell equipped with a Corning NAS 11-18 sodium ion electrode, a Beckman silver billet electrode or a silver plated on platinum electrode immersed in the silver solutions connected by means of a ”salt- bridge" of 1.0 [I potassium nitrate solution to a saturated calomel reference electrode. The concentrations of free silver ion in solutions of the respective silver(I) nitrate-l, 5—cyclopolymethylenetetrazole complex was V “refined by comparin; tithe calibration c v) (I) H. (I; (II 1/; {u Frank Michael D'Itri determined by comparing the observed potential readings with the calibration curve. A constant ionic strength with 0.1 and 0.14 M potassium nitrate was employed. There— fore, the activity coefficients of the silver ion can be considered to remain constant in all the solutions stud— ied. These complexes of the general formula Ag(CnMT)2+ were all nearly equally stable. The pKf values at 25° ranged from —2.91 to —3.,l3 with the exception of the heptamethylenetetrazole—silver(I) complex which differed by about 0.3 pKf unit. Once again, no simple correlation appears to exist between the length of the hydrocarbon chain and the stability of the respective silver(I) complex. The crystalline complexes, bis(trimethylenetetrazole)- silver(l) and bis(tetramethylenetetrazole silver(l) nitrate analogous to bis(pentamethylenetetrazole)silver(I) nitrate (l) were prepared and characterized. l,l'-Diphenyl-5,5T-bitetrazole was prepared to study its coordination propertieso Attempts to prepare solid complexes with copper(II) perchlorate hexahydrate dehy- drated with 2,2-dimethoxypropane in various solvents (2,3) were unsuccessful, and all of the starting material was recovered unreacted. The complexing ability of l,l'-diphenyl—5,5t-bitetrazole in 1,2—dichloroethane and nitromethane was studied by the method of continuous variations with iodine and copper(I‘I) perchlorate E' 'zn‘qtrate respective} "itedthat, surpri: glass with the airy Lie ccurse cf ‘ sassy: cpciyteti . , , -\ . - " H ‘lnn-n . . “A‘ ' “,V-d;\l. -v. v .. . , f 4 _\ a . .. _ c- ‘I‘n-v—Au 9 “«U~v...v.». , I .. n '1‘“. . , _ - r ’- ' ’V ~-\au-u:‘: . r , _ _ _~ ~ . , . A a: , . .. .’~.~-Cr an“, ..-v- v“ at“ “u: S“QA..'.. 3"».-‘1 «5 ‘l ¥‘ .u ‘_ = h .. ~.w~.5‘ 4 .~~\,e - u :»~‘ \ 'V “H“ '1 \ ... '¢ . ~ ~ \ V14 ‘-‘ 2 q . \ “nu ~ \ “l Ix ._ ‘ Frank Michael DVItri tmxahydrate respectively. The spectrophotometric data hflicated that, surprisingly,the bitetrazole does not form cmmflexes with the above Lewis-acids. In the course of this investigation the following new 6,6-dihalocyclopolymethylenetetrazoles and bitetrazoles were synthesized. l. 6,6—Dichlorotetramethylenetetrazole 2. 6,6—Dibromotetramethylenetetrazole 3. 6,6—Dichloropentamethylenetetrazole A. 6,6—Dibromopentamethylenetetrazole 5. 6,6-Dichlorohexamethylenetetrazole 6. 5,5'=Diphenyl—l,l'—bitetrazole 7. l,A-Bis(5-phenyl-l-tetrazolyl)-n—butane The attempted preparations of bis(l—phenyl~5= tetrazolyl)methane5 1,2—bis(l—phenyl-S—tetrazolyl)ethane, lflfl—dimethyl and l,lVudi—tert-butyl—5,5Vmbitetrazole were unmwcessful. In each case the respective nmr, infrared, mm mass spectra of the isolated reaction product indicated ' thm:the expected compound was not obtained. The most plmmible explanation for the failure of these syntheses is Hm availability of alkyl hydrogen atoms which facilitate arearrangement of the imide chloride intermediate. REFERENCES l. A.I. Popov and R. D. Holm, J. Am. Chem. Soc.D EL» 3250 (1959). 2. F.M. DVItri and A.I. PopOV, Inorg» Chem... g. 1670 (19663 3. F.M. D'Itri and A.I. Popov, ibid., g. 597 (1967). FIT—E:- THE SYNTHESES AND COMPLEXATION OF SOME l,5-CYCLOPOLYMETHYLENETETRAZOLES AND BITETRAZOLES By Frank Michael D'Itri A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1968' PLEASE NOTE: Not original copy. Blurred and faint type on several pages. Filmed as received. UNIVERSITY MICROFILMS. The authl etion to Dr. A counsel, and e author's gradu Gratitud ACKNOWLEDGMENTS The author gratefully expresses his sincere appreci- ation to Dr. A. I. Popov for his friendship, guidance, counsel, and encouragement throughout the course of the author's graduate studies. Gratitude is also extended to the Department of Chemistry, Michigan State University, the Socony Mobil Oil Company, and the National Institutes of Health of the Department of Health, Education, and Welfare for financial aid. Thanks are extended to Professor William E. Stone, Department of Physiology, University of Wisconsin, Madison, Wisconsin, for the determination of the pharmacological properties of the various cyclopolymethylenetetrazoles. The author also wishes to express appreciation to W. J. McKinney for suggestions, information, and the 00mPUter program used in this study and to R. H. Erlich and R. G. Hamilton for their valuable technical assistance. ii ‘ .. :1 __ 1+..- INTRODUCTION HISTORICAL EXPERIMENTAL E In IL Genera Chemic Prepai methyl Prepa: methyl Prepal 6,6-1): TABLE OF CONTENTS INTRODUCTION . I I a o o I a t a e a n HISTORICAL . o I I o o o g a o o n o 0 EXPERIMENTAL PART 0 o u I u o o o a o e o I. General . . . . II. Chemicals . ‘. . . . . a o o a o 0 III. Preparation of Precursors to Cyclopoly— methylenetetrazole . . . . . . IV. Preparation of the Various Cyclopoly— methylenetetrazoles . . . . . c a V. Preparation of the Precursors to 6,6-Dihalocyclopolymethylenetetrazoles VI. Preparation of the Various 6,6-Dihalocyclopolymethylenetetrazoles . VII. Preparation of Precursors to 1,1'—Diphenyl—5,5'—bitetrazole . . . VIII. Preparation of Precursors to d,w-Bis(5—phenyl—l-tetrazolyl) . . . IX. Preparation of l,l-Diphenyl~5,5‘—bitetrazole X. Preparation of d,m—Bis(5—phenyl-l—tetrazolyl)—n7alkanes o XI. Preparation of the Precursor of a,m—Bis(l—phenyl-S—tetrazolyl)—g—alkanes XII. Attempted Preparation of d,w-Bis(l—phenyl—S-tetrazolyl)—n—alkanes XIII. Preparation of Precursor of l,l‘—Di-tert-butyl-5,5'-bitetrazole . iii Page 26 26 27 31 33 MO 53 55 57 59 60 62 r'y': XIV. Attenm 1,l'-E XV. Spectr XVI. Potent XVII. Prepar Metal propar XVIII. Prepai silver silver RESULTS AND DIE 1. The Me 1—! 1—! [—4 IV. \7 1—4 XIV. Attempted Preparation of 1’1'_Dimethyl— and 1,1‘-Di—tert-butyl-5,5'—bitetrazole . . . . 63 XV. SpectrOphotometric Studies . . . . . . . 6Ll XVI. Potentiometric Studies , . . . . . . . 87 XVII. Preparation and Characterization of Transition Metal Complexes with l,3—Bis(5—tetrazolyl)—n¢ prOpane and l,A—Bis(5—tetrazolyl)—nfbutane . . 101 XVIII. Preparation of Bis(trimethylenetetrazole)— silver(I) and Bis(tetramethylenetetrazole)— silver(I) Nitrate . . . . . . . . . . ll6 RESULTS AND DISCUSSION . . . . . . . . . . . 118 I. The Mechanism of the Intramolecular Rearrangement of -Azedoalkanenitriles in the Preparation of Tri- and Tetramethylene— tetrazole . . . . . . . . . . . . . 118 II. The Mechanism of the Schmidt Reaction in the Preparation of the 1,5—Cyclopolymethylene— tetrazoles . . . . . . . . . . . . l20 III. Evaluation of the Nuclear Magnetic Resonance, Infrared, and Mass Spectra of the Various 1,5—Cyclopolymethylenetetrazoles . . . . . 123 IV. Spectrophotometric Study of the Coordination Ability of the 1,5—Cyclopolymethylene— tetrazoles . . . . . . . . . . . . 126 V. Spectrophotometric Study of the Coordination Ability of the Various Bitetrazoles . . . . 128 VI. Potentiometric Study of the Coordination Ability of the 1,5—Cyclopolymethylene— tetrazoles . . . . . . . . . . . . 131 RECOMMENDATIONS FOR FUTURE STUDIES . . . . . . . 134 LITERATURE CITED . . . . . . . . . . . . . 137 APPENDICES . . . . . . . . . . . 1A5 iv LIST OF TABLES Table. ‘ Page I. Absorbances and Formation Constants for the _Trimethylenetetrazole—Iodine Complex in Purified 1,2—Dichloroethane . . . . . . . 70 II. Absorbances and Formation Constants for the Tetramethylenetetrazole-Iodine Complex in Purified 1,2-Dichloroethane . . . . . . . 72 III. Absorbances and Formation Constants for the Pentamethylenetetrazole—Iodine Complex in Purified 1,2—Dichloroethane . . . . . . . 7A IV. Absorbances and Foramtion Constants for the Hexamethylenetetrazole—Iodine Complex in Purified l,2—Dichloroethane . . . . . . . 76 V. Absorbances and Formation Constants for the HeptamethylenetetrazolegIodine Complex in Purified 1,2—dichloroethane . . . . . . . 78 VI. Absorbances and Formation Constants for the Undecamethylenetetrazole—Iodine Complex in Purified 1,2—Dichloroethane . . . . . . . 80 VII. Thermodynamic Constants for the Reaction CnMT + I2:::CnMT-I2 in l,2—Dichloroethane Solutions at 25° . . . . . . . . . . 82 VIII. Approximate Ion Apparent Selectivity of the Corning NAS 11-18 Sodium Ion Electrode at pH 7 a o o o o o o o a o o o o 88 IX. Silver Nitrate Working Calibration Curves for the Respective Silver Electrodes . . . . 97 X. Experimental Data from the Potentiometric Studies in 0.1 M Potassium Nitrate Solutions at 25° . . . . . . . . . . 102 XI. Experimental Data from the Potentiometric Studies in 0.A M Potassium Nitrate Solutions at 25° . . . . . . . . . . 103 .._- L— .J—L‘W Table XII. XIII. XIV. Elemel Complt propat butanE Calcui Spins Table Page XII. Elemental Analyses of Some Transition Metal Complexes with l, 3- Bis(5-tetrazolyl)-n- prOpane and l, A— Bis(5- tetrazolyl)-n- butane . . . . . . . . . . . . . . 107 XIII. Calculated Magnetic Moments and Unpaired Spins of Some Transition Metal Complexes with l, 3— Bis(5- tetrazolyl)-n-propane and l, A— Bis— (5— tetrazolyl)— n—butane . . . . . . . . 108 XIV. Electronic Absorption Spectra (cm—l) of the Transition Metal Complexes of l 3— Bis— (5— tetrazolyl)- -n—propane and 1, A Bis(5— tetrazolyl)— —n—butane . . . . . . . 113 XV. The Average pKf Values for the Reaction + _; + Ag + 2CnMTvAg(CnMT)2 A o a t o o o 132 vi LIST OF FIGURES Figure 6. 7. 8. The relations between log K and l/T for (l) trimethylenetetrazole (2) pgntamethylene— tetrazole (3) tetramethylenetetrazole (A) hexamethylenetetrazole, and (5) heptamethylenetetrazole . . . . .‘ . . Absorption spectra of tetramethylenetetrazole— iodine system in l,2-dichloroethane solutions, _ . , -A 012 - 8.89X10 M, CCLIMT (M) (l) 0.00 (2) 0.0A2 (3) 0.084 (A) 0.126 (5) 0.168 (6) 0.210 (7) 0.252 (8) 0.29A (9) 0.337 (10) o 379 (11> 0.1425 0 o o o o I a o o a a 0 Response of the Corning NAS 11—18 sodium ion electrode to silver ions relative to potassium ions . . . . . . . . a. Silver electroplating cell, b. silver potentiometric cell . . . . . . . . . Silver nitrate working calibration curves 0.1 M aqueous potassium nitrate solutions, A. Corning NAS 11—18 sodium ion electrode (left scale), B. silver plated on platinum electrode (right scale), C. Beckman silver billet electrode (right scale) . . . . Silver nitrate working calibration curves 0.A M aqueous potassium nitrate solutions, A. Corning NAS 11-18 sodium ion electrode (left scale), B. silver plated on platinum electrode (right scale, C. Beckman silver billet electrode (right scale) . . . . The potentiometric titration curves of A, l,3—bis(5—tetrazolyl)-n-prOpane and B, l,A— bis(5-tetrazolyl)—n—bu€ane with tetrabutyl— ammonium hydroxide—in methanol . . . . A continuous variations study at 680 mu of COpper(II) perchlorate hexahydrate with A, l,3-bis(5—tetrazolyl)—n—propane and B, l,A-bis(5—tetrazolyl)—§—butane . . . . . vii Page 86 90 . 105 . 111 Figure 10. ll. Molar ratio study of l x 10 3 M copper(II) perchlorate hexahydrate with A, l, A— bis(5- tetrazolyl)—n—butane and B, l ,3— bis(5- tetrazolyl)- -n—propane in purified ethanol at 670 mu . . . . . . . . . . . Reflectance spectra of the respective A. nickel(II), B. cobalt(II), and C. copper(II) perchlorate complexes with 1,3—bis(5—tetrazolyl)—M—butane Reflectance spectra of the respective A. nickel(II), B. cobalt(II), and C. copper(II) perchlorate complexes with l,A—bis(5—tetrazolyl)—M—butane viii Page 112 11A 115 Appendix I. LIST OF APPENDICES SpeCtra I o a a n o' a o. o u ' A o 1. Infrared spectrum of A—azidobutyro- nitrile (neat) . . . . . . . . 2. Nuclear magnetic resonance spectrum of A-azidobutyronitrile (neat) . . ., . 3. Infrared Spectrum of 5-azidovalero— nitrile (neat) . . . . . . . . A. Nuclear magnetic resonance spectrum of 5-azidovaleronitrile (neat) . . . 5. Infrared spectrum of trimethylene— tetrazole (KBr) . . . . . . . . . 6. Nuclear magnetic resonance spectrum of trimethylenetetrazole (CHCl3) . . . 7. Mass spectrum of trimethylenetetrazole 8. Infrared spectrum of tetramethylene— tetrazole (KBr) . . . . . . . . 9. Nuclear magnetic resonance spectrum of tetramethylenetetrazole (CHC13) . . 10. Mass spectrum of tetramethylene— tetrazole . . . . . . . ll. Infrared spectrum of pentamethylene— tetrazole (KBr) . . . . . . . 12. Nuclear magnetic resonance spectrum of pentamethylenetetrazole (CHCl3) . . 13. Mass spectrum of hexamethylene— tetrazole . . . . . . . 1“. Infrared Spectrum of hexamethylene- tetrazole (KBr) . . . . . . . . 15. Nuclear magnetic resonance spectrum of hexamethylenetetrazole (CClu) . Page . 1A6 . 147 , 148 . 149 ,. 150 . 151 . 152 . 153 . 15A . 155 156 . 157 158 159 160 161 2A. 25. 26. 27. 28, 30. 31, 32, Appendix 16. l7. 18. 19° 20. 21. 22. 23. 2A. 25. 26. 27. 28. 29. 30. 3l. 32. Mass spectrum of hexamethylenetetrazole Infrared spectrum of heptamethylene— tetrazole (KBr) . . . . . . . Nuclear magnetic resonance spectrum of heptamethylenetetrazole (CClu) . . . Mass spectrum of heptamethylene- tetrazole . . . . . . . . . . Infrared spectrum of octamethylene— tetrazole (KBr) . . . . . . . Nuclear magnetic resonance spectrum of octamethylenetetrazole (CHCl3) . . . Mass spectrum of octamethylene- tetrazole . . . . . . . . . . Infrared spectrum of nonamethylene- tetrazole (KBr) . . . . . . . . Nuclear magnetic resonance spectrum of nonamethylenetetrazole . . . . Infrared spectrum of undecamethylene— tetrazole (KBr) . . . . . . . Nuclear magnetic resonance spectrum of undecamethylenetetrazole (CHCl3) Infrared spectrum of 2,2—dichloro—6— azacyclohexanone (KBr) . . . . Infrared spectrum of 2,2—dichloro-7— azacycloheptanone (KBr) . . . . Infrared spectrum of 2,2—dichloro-8— azacyclooctanone (KBr) . . . . Infrared spectrum of 2,2—dichloro—l3— azacyclotridecanone (KBr) . . . . Infrared spectrum of 2,2—dibromo—6— azacyclohexanone (KBr) . . . . . Infrared spectrum of 2,2—dibromo—7— azacycloheptanone (KBr) . . . . . Page 162 163 16A 165 166 167 168 169 170 171 172 173 174 175 176 177 178 ; L. ._-_ur..‘.'.' Appendix Appendix 33‘ 3a. 35. 39. AC. Al. A2. Infrared spectrum of 2,2—dibromoe8- azacyclooctanone (KBr) o 0 Infrared spectrum of 6,6-dichloro- tetramethylenetetrazole (KBr) Nuclear magnetic resonance spectrum of 6,6-dichlorotetramethylenetetrazole (CHCl3) . . .7 . . o o 0 Infrared spectrum of 6,6—dibromotetra- methylenetetrazole (KBr) 0 Nuclear magnetic resonance spectrum of 6,6—dibromotetramethylenetetrazo1e (0H013) . . . . . Infrared spectrum of 6,6-dichloro— pentamethylenetetrazole (KBr) o 0 Nuclear magnetic resonance spectrum of 6,6-dichloropentamethylenetetrazole (0H013> . . . . Infrared spectrum of 6,6—dibromo- pentamethylenetetrazole (KBr) o o o a Nuclear magnetic resonance spectrum of 6,6—dibromopentamethylenetetrazole (CHC13) . . . . o o a 0 Infrared spectrum of 6,6—dichlorohexa— methylenetetrazole (KBr) 0 Nuclear magnetic resonance spectrum of 6,6-dichlorohexamethylenetetrazole (CH013) . . . . Infrared spectrum of N,N'-dipheny1— oxamide (KBr) . o o o 9 Infrared spectrum of N,N‘—diphenyl- oxalimidyl chloride (KBr) Infrared spectrum of N,N‘-diphenyl—5,5'— bitetrazole (KBr) . o u Infrared spectrum of 5,5'—dipheny1— l,1'—bitetrazole (KBr) xi 0 o o Page 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 Al I 56. 57. - Com] the Appendix 48. Infrared spectrum of l,4-bis(5- phenyl—l—tetrazolyl)-n—butane (KBr) . #9. Infrared spectrum of N,N'- diphenylmalonamide (KBr) . . . . . 50. Infrared spectrum of N,N'—dipheny1- succinamide (KBr) a . . . . . 51. Infrared spectrumcfl‘N,NF—di—tert— butyloxamide (KBr) . . . a o . . 52. Infrared spectrum of l,3-bis(5— tetrazolyl)-n—butane (KBr) . . . 53. Infrared spectrum of 1,4—bis(5- tetrazolyl)—n—butane (KBr) . . . . 5“. Infrared spectrum of the copper(II) perchlorate complex with l,4-bis(5- tetrazolyl)—n—butane (Nujol) . 55. Infrared spectrum of the COpper(II) perchlorate complex with l,3—bis(5- tetrazolyl)-nfpropane (Nujol) . o 56. Infrared spectrum of bis(trimethylene- tetrazole)€ilver(l) nitrate (Nujol) . 57. Infrared spectrum of bis(tetramethylene— tetrazole)silver(l) nitrate (Nujol) , II. Computer Program of Ketelaar Equation for the Calculation of Formation Constants a . III. Determination of Pharmacological Properties of the Various Cyclopolymethylenetetrazoles xii o Page‘ 194 195 196 197 198 199 200 201 202 203 204 208 ._. __.'-|._‘L. . There physicochemj biology . W1 than those 1 tigations it Bechniques 5 including 1;} The bj INTRODUCTION There is a growing awareness of the importance of the physicochemical approach to the problems of molecular biology. While biological systems are much more complex than those usually studied by the chemist, numerous inves- tigations in recent years have applied physicochemical techniques and concepts to various biological processes, including the mechanism of drug action. The biological mechanism of drug action is one of the most interesting and important phases of modern research. Because a drug molecule must attach itself to a cell membrane, some type of mechanism must exist which would involve physical and chemical interactions. These inter— acting forces could be in the form of charge-transfers covalents and hydrogen bondings as well as steric hindrance and London forces. The importance of charge~transfer complexes in drug action has been illustrated in the publications of A. Szent—Gyorgyi (1,2). He states that the charge—transfer reaction may be one of the most important9 frequent, and fundamental biological reactions. Pullman and Pullman (3)5 recognizing that purines are important growth factors in biogenetic processes, have investigated their respective electron donor and acceptor properties. Russian workers (U) have recent] materials wi concluded tr biomycin, ar tron donors biological a chemical fac have recently studied complexes of biologically active materials with electron spin resonance spectroscopy. They concluded that antibiotics such as penicillin, streptomycin, biomycin, and similar related antibiotics are strong elec— tron donors and that this property is related to their biological activity. Recently, the importance of physico- chemical factors in convulsant disorders has been ably illustrated by D. B. Tower (5) while Friess, Standaert and Reber investigated the influences of stereochemical factors in convulsant activity of aminocyclanol derivatives (6). It is known that pentamethylenetetrazole increases the electrical activity in the brain and that the action is due directly to the compound itself rather than to its metabolic product (7). It is, therefore, not inconceivable that physicochemical propertieslof pentamethylenetetrazole and of similar tetrazoles are related to this pharmacol— ogical activity. In particular, it was of interest to study the complexing abilities of tetrazoles. It should be noted that these compounds have four nitrogen atoms, each capable of donating a pair of electrons to form 0 bonds. Because of their conjugated double bond system, they could also be capable of forming weak n type complexes. Many of the studies of tetrazoles have been done because of their pharmacological properties. Pentamethyl— enetetrazole (hereafter abbreviated CBMT) is known to be a Strong convulsive agent with a long clinical history. Less well-kn tetrazole de tetrazoles a cologically gated substi the addition increased th Furthermore , "Symmetric a1 Less well—known are the substituted pentamethylene- tetrazole derivatives and other 1,5—cyclopolymethylene— tetrazoles and bitetrazoles although they are also pharma- cologically active. Gross and Featherstone (8—12) investi— gated substituted pentamethylenetetrazoles and found that the addition of a methyl group to the pentamethylene chain increased the stimulating action of the parent compound. Furthermore, as the methyl group is moved toward the "symmetrical" 8—position, the activity becomes more pro— nounced. An increase in the size of the substituent group in the 8~position shows a variable effect in that 8- isopropylpentamethylenetetrazole has a minimum convulsant dose of 3 mg/kg (compared with 50 mg/kg for pentamethy— lenetetrazole). On the other hand, 8—sgg—butyl and 8-:- amylpentamethylenetetrazole show a depressant rather than a stimulant activity. Substitution of larger groups in other positions of the pentamethylene chain also decreases the convulsant activity of pentamethylenetetrazole (8). Thus, pentamethylenetetrazole has a wide range of physiol— ogical activity. The specific activity depends on seemingly minor changes in the nature and/or the position of the substituent group. In this research problem the factors affecting the nucleophilic properties of tetrazoles, particularly the influence of substituent groups on the formation and strength of charge—transfer complexes, are investigated. Hhile a slum physicochend ogical activ to form char determine wt factor in st Previc 17)showed t While a simple correlation cannot be expected between the physicochemical property of a compound and its physiol— ogical activity, the ability of the tetrazole derivatives to form chargentransfer complexes must be established to determine whether or not this ability is_an important , factor in such mechanisms. Previous research conducted in this laboratory (13— 17) showed that pentamethylenetetrazole acted as a fairly strong ligand toward the first row transition metal ions in non—aqueous solvents like 2,2—dimethoxypropane (here— after abbreviated DMP). Solid complexes of pentamethy— lenetetrazole were prepared with manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II) perm chlorate according to the following equation: II II M (ClOu)296H2O + 605MT DMP M (CSMT)6(C10H % )2 The characteristics of a ligand which influence the stability of a given complex are: basicity of the ligand, number of metal chelate rings per ligand, size of the chelate ring, steric effects, resonance effects, and the ligand atom (18). Among these, a major factor influencing the stability of coordination compounds is the Bronsted basicity of the ligand. Whereas pentamethylenetetrazole forms an octahedral complex with a copper(II) ion, attempts to prepare complexes with pyridine and substituted pyridines have been unsuccessful (19). . . as. J“...- The cc ligand shou] proton affix however, thi nethylenetet aqueous solL The coordinating properties of a nitrogen—containing ligand should be reflected, to a large extent, by its proton affinity. In the case of pentamethylenetetrazole, however, this parallelism does not exist because penta- methylenetetrazole does not possess a basic character in aqueous solution and only acts as a weak base in glacial acetic-acid (20). Therefore, exploration of the factors affecting the nucleophilic properties of substituted tetrazoles with varying convulsant activity can add to the study of this aspect of chemistry in the following areas of consideration in this research project. 1. The synthesis of molecules which contain two tetrazole rings bridged by a methylene chain and which would act as polydentate ligands. 2. The synthesis of other 1,5—cyclopolymethylene— tetrazoles. 3. The investigation of respective donor properties of these new tetrazoles by determining at various tempera- tures their respective complexing abilities with appro— priate Lewis acids. Thermodynamic values obtained for the complexation reaction are then related to the donor and, where possible, the physiological properties of the respective tetrazole. Special emphasis is placed on the following variables. . 'F. -. .n‘LQ; tetrazole h1 complex for: 2. T1 oftetrazclt ties. l. The influence the substituted group onva given tetrazole has on the free energy, enthalpy, and entropy of complex formation. 2. The relative donor strength of a homologous series of tetrazoles to their respective pharmacological proper- ties. Tetra compounds it HISTORICAL PART Tetrazoles arefive membered, heterocyclic ring compounds which contain one carbon and four nitrogen atoms linked by three single and two double bonds. The tetra- zole ring is numbered so the nitrogen single bonded to the carbon is the lmposition. The remaining three nitrogens are then numbered consecutively two through four with the carbon at the Buposition. The parent compound may exist in tautomeric forms (I) and (II) (21,22). H H H \1 5/ 1 5/ N_~ C N:::Q / \\ 2 / \ 2N Nu H—N Nh \\\\N / \N’// 3 3 (I) (II) It has been found that 97% of an equilibrium mixture of (I) and (II) exists in the form (I) (23). The tetrazole ring is unusual among cyclic systems in that it offers only two points of substitution, in position 1 or 2 and in position 5. A great number of sub— stituted tetrazoles are known with a variety of organic substituents that replace the respective tetrazole protons. F. R. Benson (2A,25) has extensively reviewed the literature 1 organic chel limited to i particular 1 The c; special cla: which the pl to the tetr; literature pertaining to the preparation of tetrazoles in organic chemistry. Therefore, this discussion will be limited to the aspects of the subject relevant to this particular research project. The cyclopolymethylenetetrazoles (III) represent a special class of substituted tetrazole derivatives in which the polymethylene chain forms a second ring fused to the tetrazole ring. 6+n (CH 2)n / \ 6 HCH HCH 7+n / C-—-N l 5 A Wyl \N 2 \N/ 3 (III) where n = l,2,3,A,5,6,7, etc. The reaction between equimolar quantities of carbonyl compounds and hydrazoic acid in the presence of a strong mineral acid was studied in detail by K. F. Schmidt (26—28). He found that organic acids were transformed into primary amines, that aldehydes yield nitriles and formyl deriva— tives of amines, and that ketones yield amides. With the hydrazoic acid present in large excess aldehydeS and ketones yield substituted tetrazoles. Cyclic ketones react normally, and the firs was pentamet cyclohexanor It is powerful sti in chemothei nor the lows been investi literature 5 on the prepz and the first cyclopolymethylenetetrazole to be synthesized was pentamethylenetetrazole obtained form the reaction of cyclohexanone and two or more moles of hydrazoic acid. It is well known that pentamethylenetetrazole is a powerful stimulant and convulsant that has been widely used in chemotherapy. Surprisingly, however, neither the higher nor the lower homologues of pentamethylenetetrazole have been investigated to any significant extent. In fact, a literature search indicates that only two reports exist on the preparation of tri- and tetramethylenetetrazole (29,30), and two other reports on the corresponding hexa— and heptamethylenetetrazoles (31,32). Ruzicka gt a1. (31, 32) have applied the Schmidt reaction to higher cyclic ketones and have prepared the respective cyclopolymethyl- enetetrazoles: hexa—, hepta-,and tetradecamethylene— tetrazole. They were synthesized from cycloheptanone, Cyclooctanone, and cyclopentadecanone. Von Kereszty (29,30) patented an interesting internal condensation of an azidoalkanenitrile used to prepare tri— and tetramethylenetetrazoles. For this purpose, A— azidobutyronitrile and S—azidovaleronitrile were treated with chlorosulfonic acid. Syntheses of 6—methyl-8— ethyltrimethylenetetrazole, 7,9—dimethyltetramethylene— tetrazole and 6—carbethoxytetramethylenetetrazole, are also claimed in this patent. Carpenter (33) attempted to prepare penta— and hexamethylenetetrazole by condensation of 6-azidocapron‘: to extend von the series. 1 reactions for penta- or hex: by careful chi products. Ca] mechanism. A azido groups : cyclization p] pPepared by h: alkyl derivati (30). Recent: over Palladium methi'lenetetrg 10 6-azidocapronitrile and-7-azidoheptanonitrile in an effort to extend von Kereszty's cyclization to higher members of the series. Carpenter readily duplicated von Kereszty‘s reactions for tri— and tetramethylenetetrazole, but no penta— or hexamethylenetetrazoles could be detected even by careful chromatographic analysis of the reaction products. Carpenter explains these results by the following mechanism. A high degree of orientation of the cyano and azido groups is required in the transition state of the cyclization process. Tetramethylenetetrazole was also prepared by hydrogenation of pyridotetrazole and its C— alkyl derivatives in the presence of a noble metal catalyst (30). Recently, Boyer a: a1. (3A) reduced pyridotetrazole over palladium in the presence of acetic acid to tetra~ methylenetetrazole in nearly quantitative yields. Because tetrazoles offer two nonequivalent positions for the attachment of substituent groups, compounds con_ taining two tetrazole rings joined by a methylene bridge can be of the d,w~bis(Sosubstitutedal—tetrazolyl)eg- alkane type (IV) or the d,w-bis(l-substitutede-tetrazclyl)e n—alkane type (V). R-C-N—(CH)-N~C-—R (/ i. “N/ \b \N/ \N/ (IV) where R = C The a type compou and referen p—alkane co (35) first cyanotetraz R — N — C — (CH ) — C - N — R / \ 2 // \ N N N N \N/ \N/ (V) where R = C6H5, H, CH3 and n = O,l,2,3,4, etc. The d,m—bis(5—substituted—l-tetrazolyl)—nfalkane type compounds (IV) are not recorded in the literature, and references to the d,w—bis(l—substituted—S—tetrazolyl)- n—alkane compounds (V) are very sparse. Oliveri—Mandala (35) first prepared 5,5'—bitetrazole by reacting 5— cyanotetrazole with hydrazine hydrate in alcohol, followed by successive treatments with sodium nitrite and hydro- chloric acid. Because this compound behaves as a weak acid, the corresponding heat sensitive sodium, copper (II), and shock sensitive mercury(ll)salts were easily prepared (36). Cohen et 31. (37) modified the high pressure method of Mihina and Herbst (38) for the conversion of alkane nitriles into 5—substitutedtetrazoles and prepared l,A—bis(5—tetrazolyl)-n~butane from adiponitrile. Recently, Wehman (39) of this laboratory used the same method to prepare 5,5'-bitetrazole, 1,3—bis(S—tetrazolyl)—g—propane, and 1,4—bis(S—tetrazolyl)—n—butane. Kauffmann and Ban (A0) prepared l,A-bis(5—tetrazolyl)—n—butane, l,6-bis(5-tetrazolyl)l gehexane, and 1,8—bis(5—tetrazolyl)-g—octane by a novel method. Aliphatic diamidrazones of the type H2NN = C(NH2) - (CH h 2’n I C(NH2) = NNH were prepared by treating the corresponding 2 dinitriles with sodium hydrazine in a hydrazine—diethyl ether mixture: acid yie'l'de could not p tetrazolyl) these compo Thus substituted l,1'-dimethy of diazomet (35). The p l2 ’mixture.’ Treatment of the aliphatic diamidrazone with nitrous ,acid yielded the corresponding:bitetrazoles The authorS' mould-not-prepare~bis(Setetrazolyl)methane,or l,2—bis(5— tetrazolyl)ethane by this method, nor have preparations of these compounds-been reported by any other method. Thus far, only three syntheses for the d,w-bis(l— substituted—S-tetrazolyl)-gfalkanes have been reported. l,l'-dimethyl-5,5'-bitetrazole was prepared by the action of diazomethane on 5,5'—bitetrazole in an ether medium (36). The preparation of l,A~bis(l~methyl—5-tetrazolyl)- nebutane was accomplished by treating a warm aqueous solution of the sodium salt of l,A—bis(5—tetrazolyl)-ne butane with dimethyl sulfate (37). Stolle (41) prepared l,l'—diphenyl—5,5V-bitetrazole by the reaction of N,N‘- diphenyloxalimidyl chloride with sodium azide in boiling ethanol for about twelve hours. The physiological activity of various substituted tetrazoles is well—known and has generated a great deal of research seeking to understand the nature of the drug- receptor, physicochemical interactions. Determining the properties of these drugs which are responsible for or related to their respective pharmacological activity would be invaluable in the study of the physiological effects of these drugs on the central nervous system as well as being a guide for the synthesis of new, more active drugs. Gross of a large that the ph central ner general typ that larger depression 0 nervous syst substituent Von Is the effect 0 nervous syst Wins a met the methyl g Position. Q; 13 Gross and Featherstone (9) studied the pharmacology of a large number of substituted tetrazoles and concluded that the physiological activity of these drugs on the central nervous system appeared to be a function of the general type of substitution on the ring. They concluded that larger alkyl substituents in position 5 diminish the depression of the electrical activity of the central nervous system whereas increasing the size of the alkyl substituent in position 1 increases stimulation. Von Issekutz, Leizinger, and Novak (U2) noted that the effect of pentamethylenetetrazole on the central nervous system was increased two or three fold by intro— ducing a methyl group in the 6 position and 20—30 fold if the methyl group was substituted on the "symmetrical" 8 position. Gross and Featherstone (8) confirmed the findings of von Issekutz and his co—workers and extended the study by including 23 additional alkyl substituted pentamethyl— enetetrazoles. In order to determine the maximum enhance- ment of activity, the structures of the alkylated penta- methylenetetrazoles were varied systematically, and an effort was made to correlate these structural changes with changes in the pharmacological activity. The authors concluded their study with the following observations. The introduction of a single substituent on the 8 position of the pentamethylenetetrazole structure enhances the analeptic and convulsant activity of the parent substance only when the group methyl, is groups in the formati of the comp unique bec ciated with As e correlate t stituted te convulsive respective those subst and that ex absorption tives With l” the group is small or closely packed as in the case of methyl, isopropyl, or tert-butyl. Substitution.of alkyl groups in any other position, di— or tri—substitutions, or the formation of quaternary salts decreased the activity of the compound. The isopropyl group appeared to be unique because, in any given case, it was generally asso- ciated with the most active compounds. As early as 1949,Schueler gt 3;" (A3) tried to correlate the pharmacological activity of a series of sub- stituted tetrazoles with an activity range from severe convulsive stimulation to deep depression with their respective ultraviolet absorption spectra. Generally, those substituted tetrazoles that have alkyl substituents and that exert stimulative action showed little or no absorption in the region of 220 mu. The tetrazole deriva- tives with aryl substituents which exert a depressant activity showed two absorption bands in the regions of 290 and 225 mu respectively. The 225 mu band has an absorption ten times greater than that of the 290 mu band. As the depressant activity of the series of tetrazoles decreased, it was accompanied by a hypochromic effect of the band at 225 mp only. On the other hand, for increasingly stimu- lative activity, both absorption bands underwent the hypochromic effect. Apparently, there is some correlation between the physiological activity of the tetrazoles and their respective absorption spectra. Pent tetrazoles , weak basic of the basi distributio that the di larger for methylenete Hold (20) t cally in g1 sane solven possess wea investigate 15 Pentamethylenetetrazole, substituted pentamethylene— tetrazoles, and 1,5—dialkyltetrazoles have surprisingly weak basic properties in aqueous solutions. The first hint of the basic character of these compounds came from the distribution studies performed by Dister (7). He noted that the distribution coefficient (organic)/(aqueous) was larger for basic media. This would indicate that penta- methylenetetrazole can behave as a weak base. Popov and Holm (20) titrated pentamethylenetetrazole potentiometri— cally in glacial acetic acid with perchloric acid in the same solvent and found that pentamethylenetetrazole does possess weak basic properties in acetic acid. Golton(44) investigated the distribution of pentamethylenetetrazole between various aqueous solutions and carbon tetrachloride as a function of pH. A value of lO_lu was obtained for the apparent protonization constant of pentamethylenetetrazole in water. The above results, as well as the titratability in glacial acetic acid, confirmed the extremely weak basic nature of pentamethylenetetrazole. A more detailed treat— ment of the proton affinity of pentamethylenetetrazole, substituted pentamethylenetetrazoles, and 1,5—dialkyl— tetrazoles by POpov and Marshall (A5,”6) was carried out in anhydrous formic acid to enhance the basic character of these weak bases. They determined potentiometrically the pr values of these tetrazoles in this solvent to be of intermediate strength, around 2, with very slight differences the tetrazol The overall Nonetheless : compound te: pound was 14 As pa] Properties < Holm (117) (it tetrazole, 1 in benzene ‘ l6 differences and attempted to relate the base strength of the tetrazoles to their respective physiological activityo The overall correlation of their study was not definitive, Nonetheless, it showed significantly that the most active compound tested was most basic and the most inactive com— pound was least basicq As part of a general investigation of the physical properties of certain nervous system stimulants, Popov and Holm (47) determined the dipole moment of pentamethylene— tetrazole, B—Egbutyl- and 8—§§2fbutylpentamethylenetetrazole in benzene solution to be 601A, 6020, and 6.18 Debyes respectivelyo Because 8~tgbutylpentamethylenetetrazole has a minimum convulsant dose of 3 mg/kg of body weight com— pared to 750 mg/kg for 8—sec—butylpentamethylenetetrazole (8),they concluded that there was no simple correlation between the physiological activity of the compounds and their dipole moments, Person 33 El” (48), in their infrared spectra study of iodine monochloride charge transfer complexes, found that the spectrum of the l-Cl fundamental stretching vibration was very sensitive to the strength of the inter» action between the halogen and the donor molecule with which it is complexed° As the formation constant of the complex increased, the fundamental band shifted to lower frequencies while the intensity of the absorption band increasedo Pentamethylenetetrazole caused a shift of the 3. d ..l n' ' l 101 peak frOI respective to El peak to ‘ concluded th: strong donor tetrachlorid‘ Person far-infrared that it form: 17 101 peak from 375 to 310 cm—1. Benzene and pyridine formed respective weaker and stronger complexes that shifted the ICl peak to 355 and ~270cm—l respectively° Therefore, they concluded that pentamethylenetetrazole is a moderately strong donor molecule in a mixture of equal parts carbon tetrachloride and l,2-dichloroethane. Person gt i£° (A9), found similar changes in the far—infrared spectrunlofiodine cyanide which indicates that it forms chargeutransfer complexes with electron donor molecules of different strengthso These changes in the lac stretching motion were reflected by a decrease in frequency with an accompanying large increase in intensity and some increase in the half-intensity widths of the respective absorption bands, The decrease in frequency resulting from complexation was correlated with the donor strength of the molecule complexing with iodine cyanideo The electron donor nature of pentamethylenetetrazole was again indicated in the shift of the I-C asymetrical stretch of ICN from 486 to M53 cmfll in benzeneo Because the absorption maximum of the ION-pentamethylenetetrazole charge—transfer band occurs in the ultraviolet region not easily studied by conventional spectrophotometric techniques, Popov SE ii° (50) modified the approach developed by Benesi and Hilde- brand for use in the far-infrared regiono They calculated formation constants of 1,2: 0,4, 15$ 3, and 5li 5 for the dioxane—ICN, pentamethylenetetrazole~ICN and pyridine—ION complexes in benzene respectively, i_.‘_-.- -3254. . , . . "1.... - -_-_. 4.... Brubak line forms a method of co 1:2 metal to hypsochromic suggest coor Spectrophoto equilibrium complex. Fu Observed m1 . l8 Brubaker (51) prepared and Characterized two crystal— line forms of bis(5-aminotetrazolato)copper(II)o The method of continuous variation clearly indicated that a 1:2 metal to tetrazole complex was formed in solution, The hypsochromic shift and accompanying hyperchromic effect suggest coordination rather than simple salt formation, Spectrophotometric studies in aqueous solution gave an equilibrium constant of 1012 for the formation of the complex° Further studies showed that similar behavior is observed with ‘tetrazole, 5-pheny1tetrazole and 1— ethyltetrazole, Brubaker found that there is very little interaction between the copper(II) ion and 1,5- dimethyltetrazoleo This fact, together with the rela-3 tively low formation constant values for Ag(CSMT)2NO3 (~102)(2O), indicates that a replaceable ring hydrogen is required to form this type of complexo Brubaker and Daugherty (52) found that nickel(Il) 'forms only impure and poorly characterized complexes when its salts react with various 5=substitutedtetrazoleso Copper(II) complexes (53) with 5~substitutedtetrazoles are obtained in good purity simply by mixing aqueous solutions of the reactantso Brubaker and Gilbert (5A) prepared various dichlorobis- (l-substitutedtetrazole)cobalt(ll), nickel(II), platinum(II), and zinc(II) complexes, The solid complexes, with the exception of the zinc complex, are insoluble in common solvents. '1 suggests the early as 196 possible met tetrazoles. 1. 0r a< el 2. T1 n. 3. S:‘ ti c< b< t! Recem Vibrational 19 solvents. They decompose upon_heating. This property. suggests the possibility of polymeric structures, As- early as 1961 Brubaker (53) suggested the following three possible methods of coordination between metal ions and tetrazoles. 1. One of the nitrogens of the tetrazole ring acts as a Lewis base and donates its pair of electrons to the central metal iong 2. The central metal ion may coordinate to the reelectron system of the tetrazolate anion° (J) Since the tetrazolate anion seems to satisfy two coordination sites on the copper ion, coordination could occur by the formation of bonds to two different nitrogen atoms of the tetrazole ringo Recently, Garber ii gi. (55,118) performed a Vibrational analysis of sodium tetrazolateu By means of a normal coordinate analysis calculation on the tetrazolate ion, they made the vibrational assignments for the molecule, From these results, the assignments of the genuine vibra- tional modes of l-methyltetrazole were madeo The complexes of bis(l—methyl-5—tetrazolyl)nickel(II), bis(lwcyclohexy1_ 5—tetrazolyl)nickel(II), bis(tetrazolate)copper(II)mono- hydrate and l—methyl-S-tetrazolyllithium O.5THF(tetra— hydrofuran) were also prepared. The fact that the tran— sition metal complexes were insoluble in all common solvents suggested a heated, and atmosphere. respective : are in an of fore, are 3: data, the 3.1 each nickel bonds. The Wk molecu Ni-N bonds I the 2- or 3. Durinl atory (13,11 tetraZOle w' 20 suggested a polymeric structure. They decomposed when- heated, and the nickel complexes weresensitive to the atmosphere. The reflectance spectra indicate that the respective nickel(II) and copper(II) atoms of the complexes are in an octahedral or tetragonal environment and, there— fore, are six coordinate. To account for these Spectral data, the authors suggest that two of the six bonds to each nickel are Ni-C bonds while the other four are Ni—N bonds. The only arrangement found possible with frame- work molecular models has the two Ni—C and each pair of Ni—N bonds trans forming an infinite array. The A—N and the 2= or 3—N would then be bound to the nickel atom. During previous research conducted in this labor- atory (13,15), anhydrous complexes of pentamethylene- tetrazole were prepared with iron(II), manganese(II), cobalt(II), nickel(II), and zinc(II) perchlorates by treating the ligand with the respective hydrated transi— tion metal perchlorates in 2,2_dimethoxypropane solutions. Pentamethylenetetrazole is a weakly coordinating ligand and cannot effectively compete with water for the coor- dination sites of the central metal ion. For this reason, 2,2—dimethoxypropane was utilized to dehydrate the metal perchlorates in solution and, therefore, to exclude water as a competing ligand (57—62). In all cases, six moles of pentamethylenetetrazole were coordinated to the central metal ion. This was not expected because pentamethylene— tetrazole is a rather bulky ligand. Powder X—ray diffractior properties isomorphou: Far-i the appear: 236-198 cm' assigned t< bending vii compositior diffraction studies as well as the magnetic and spectral properties of these complexes indicate that they are isomorphous and have an octahedral configuration. Far-infrared studies (17) of these complexes show the appearance of two new bands located in the 302—276 and 236—198 cm.1 regions. These bands were tentatively assigned to the metal—nitrogen asymmetrical stretching and bending vibrations. Three copper complexes (16) with the compositiomsCu(CSMT)2ClOu, Cu(C5MT)u(C10u)2 and Cu(CSMT)6— (010,), were also isolated and characterized. And the electron spin resonance spectra for Cu(CSMT)6(ClOu)2, Cu(C5MT)u(ClOu)2 and Mn(CSMT)6(ClOu)2 were obtained (14). For hexakis(pentamethylenetetrazole)manganese(ll) perchlorate dispersed in hexakis(pentamethylenetetrazole)— zinc(II) perchlorate, the data indicate that the metal— ligand bonds are 91 per cent ionic with essentially octahedral symmetry. For the copper complexes, high resolution spectra of the copper nuclear hyperfine splittings were obtained in the undiluted sample. The symmetry for CU2 is tetragonal with distortion from the octahedral symmetry influenced by both a local Jahn—Teller effect and lattice distortion. The Cu(05MT)u_ (ClOu)2 exhibits a definite tetragonal symmetry, and the copper—pentamethylenetetrazole complexes are approximately 80 per cent ionic. The bonding of the pentamethylene— tetrazole ligand appears to be similar to that of pyridine .V .ui “j with the b0] pyridine n11 Recem complexes 0: sition metal II ( CS] were insolul type M 22 with the bonding nitrogen slightly less basic than the pyridine nitrogen in Mucyanopyridine. Recently, Bowers and Popov (63) prepared anhydrous complexes of pentamethylenetetrazole with first row tran- sition metal chlorides and bromides. Complexes of the type MII(05MT) x2 and MII(C5MT)2X2 were isolated. They were insoluble in polar and non—polar solvents and have high melting or decomposition points. Magnetic and specm tral evidence indicate that the metal ions in the MII(C5MT)X2 complexes are in octahedral environments while the MII(C5MT)2X2 complexes may be tetrahedral. The MII(CBMT) X2 compounds are probably polymeric and contain halogen bridges whereas complexes containing two molecules of the ligand are probably monomeric and have a tetra_ hedral structure. In order to study the electron donor properties of pentamethylenetetrazole complexes, Popov g; 31. (6A) determined spectrophotometrically the formation constants of the 1:1 C Mchmplexes with iodine monochloride, iodine 5 monobromide, and iodine in carbon tetrachloride solution to be 2,000, l50, and7.5 respectively. Only the pentamethylenetetrazolexlCl complex could be obtained as a solid crystalline form which could be purified by recrystallization from chloroform. Vaughn :3 ii“ (65) extended this work by the spectrophotometric investigation of the complexes of iodine monochloride with 7-methyl, ‘=¢£me———— -. . .'.._._.u.. | l l S-EE-butyi Repeated a1 solid iod11 tetrazole < decomposed constants ( all cases 1 correSpond; enetetrazo; 23 8—sggebuty1, and8—tfbutyl pentamethylenetetrazole. Repeated attempts were made to isolate the respective solid iodine monochloride complexes of these pentamethylene— tetrazole derivatives; however, only oily residues which} decomposed on standing were obtained. The formation constants of the three complexes were determined, and in all cases-the complexes were slightly stronger than the corresponding complex for the unsubstituted pentamethyl- enetetrazole. Rheinboldt and Stellinger (66), Dister (7), and Zwikker (67) have reported the preparation of pentamethylenetetrazole-silver complexes, however, the stabilities of complexes in water were never determined. Popov and Holm (20) prepared silver complexes in acetonitrile with the general formula (Tz)2AgN03, with pentamethylene— tetrazole substituted pentamethylenetetrazoles and l— Cyclohexyl—5-methyltetrazole. The stabilities of these complexes were determined potentiometrically in acetoni-‘ trile, and the approximate formation constants were of the order of 102. Only the Ag(CSMT)2NO3 complex was obtained in the crystalline form by the slow evaporation of an aqueous solution of the complex. The above results demonstrate that loss of the ring hydrogens is not neces— sary for coordination to occur. The coordination probably occurs, as will be discussed later, through one of the nitrogen atoms of the ring. They also determined polarograp with cobal essentiall Harr of iron(II zolato) -2 2 5-trifluor infrared a 2A polarographically that the pentamethylenetetrazole complexes with-cobalt(II), thallium(l), and cadmium nitrate were essentially completely dissociated in aqueous solution. Harris 23 a1. (68) prepared microcrystalline complexes of iron(II) conforming to the general formula Fe(tetra— zolato)2o2H 0. They used the anions of 5-chlorotetrazole, 2 5-trif1uoromethyltetrazole and 5—nitrotetrazole. With infrared and Mossbauer studies, they proposed the forma- tion of an analog to ferrocene when the tetrazole has strongly electronegative groups on the carbon. Harris ‘3 _i. (69) obtained the reflectance spectra of divalent metal complexes with the 5—trifluoromethyltetrazolyl anion. Based on the correlation of these reflectance spectra with previously obtained magnetic susceptibility and spectral data in the visible region, they re—evaluated the proposed structure of the Fe(tetrazolato)2n2H20 com— plexes. The new experimental evidence indicated that the structure of the iron(11) and respective copper(II), cobalt(II), and nickel(ll) 5—trifluoromethyltetrazole complexes are octahedral or distorted octahedral o—bonded complexes involving coordination by tetrazolyl anion and water. Wehman and Popov have extended the evidence that complexation occurs (70) through one of the ring nitrOgen atoms. A study of the charge—transfer complexes of mono— and disubstituted tetrazoles with n—electron acceptors has shown that, while such complexes do exist in solution, they Ii are extreme: concentrate of the bent tetracyanoe tion consta tetrazole i of the hen: indicate t1 methylenete nitrogen at CI‘ystal anc' 25 are extremely unstable and are largely dissociated even in concentrated solution. Furthermore, the formation constants of the benzene—tetracyanoethylene and pentamethylenetetrazole— tetracyanoethylene complexes are comparable, but the forma— tion constant of iodine monochloride with pentamethylene- tetrazole is larger by three orders of magnitude than that of the benzene—101 complex (6“). The above results seem to indicate that in the iodine monochloride complex of penta- methylenetetrazole, complexation occurs through one of the nitrogen atoms on the tetrazole ring. Recently, the crystal and molecular structure of the iodine monochloride complex of pentamethylenetetrazole was carried out with X—ray crystallographic techniques (71). Pentamethylene— tetrazole acts as a unidentate ligand. The planar tetrazole pentagon with the linear 101 group is bonded to the number four nitrogen atom and is essentially co—planar with the tetrazole ring. This configuration precludes the n—electron bonding suggested by Harris at 31. (68). The crystal structure of dichlorobis(l—methyltetrazole)zinc(ll) complex has also been determined (72) and gives further support to o-type bonding. Crystals of this complex show the zinc atom in an approximately tetrahedral environment but co— planar with the tetrazole rings and with coordination through the four position of the tetrazole ring. ..-_s_._ _- . on a Fishe: brated wit} Pa.) micro- B- l out by the Ifichigan° 0. m magnetic re llodel 11-60 int ernal St EXPERIMENTAL PART I. General A. Melting points.—-The melting points were measured on a Fisher—Johns melting point apparatus which was cali- brated with the Arthur H. Thomas Company (Philadelphia, Pa.) micro—melting point standards. B. Microanalysis.——The microanalyses were carried out by the Spang Microanalytical Laboratory in Ann Arbor, Michigan. C. Nuclear Magnetic Resonance Spectra.——The nuclear magnetic resonance spectra were all recorded on a Varian Model A—60 NMR spectrometer and calibrated relative to an internal standard of tetramethylsilane. 0. Mass Spectra.—-The mass spectra were all obtained on a Consolidated Electrodynamics Corporation Model 21—103C spectrometer with an ionizing voltage of 56 volts. E. Infrared Spectra.——Infrared spectra in the 5000- 550 cm_1 region were recorded on a Unicam SP. 200 spectro— meter with potassium bromide discs or with Nujol between sodium chloride plates. The spectra in the 650—100 cm—1 TEgion were obtained on a Perkin—Elmer Model 301 Far— Infrared Double-Beam Spectrophotometer with various choppers, mirrors, and filters. Spectra were obtained with Nujol 26 mulls betwe1 Below 300 01 Contact wit] F. N! tion Spectrz 114 recordin; G. C< constant tex Anderson C01 27 mulls between cesium bromide or polyethylene plates. Below 300 cm-l~polyethy1ene plates were used exclusively. Contact with water vapor was carefully avoided. F. Near Infrared, Visible, and Ultraviolet Absorp- tioanpectra.-—These spectra were recorded on a Cary Model 14 recording or Beckman DU spectrophotometer. G. Constant Temperature Bath.—-A Waco refrigerated constant temperature bath designed by the Wilkens- Anderson Company, Chicago, Illinois, was used. H. Reflectance Spectra.——The reflectance spectra were all obtained on a Beckman model DK—2 Spectrophoto- meter equipped with a diffuse reflectance attachment located at the Dow Chemical Company in Midland, Michigan. II. Chemicals A. The following chemicals were used and purified as described herein. 1. Pentamethylenetetrazole: All CSMT was obtained from the Knoll Pharmaceutical Corporation under the registered name "Metrazol." The CSMT was purified by recrystallization from anhydrous ether. The crystals obtained were washed with small volumes of chilled ether. Residual ether was removed under vacuum, and the crystals were stored in an evacuated desiccator over phosphorus pentoxide. The melting point of the crystals was 60.5—610 o The literature value is 610 (6N)o prepared Ci impurities reaction 11 ties prese: forms many tional dis1 formed wit] carbon tet] 28 2. l,2—Dichloroethane: l,2—Dichloroethane is usually prepared commercially by adding chlorine to ethylene. The impurities were primarily produced by a substitution reaction involving chloroethane as well as by other impuri— ties present in the ethylene. Because l,2—dichloroethane forms many azeotropes it is difficult to purify by frac- tional distillation. For example, binary azeotropes are formed with water, ethanol, methanol, trichloroethylene, carbon tetrachloride,and 2-pr0panol (73). The fractional distillation method described by Vogel (6A) was followed. The crude l,2-dichloroethane (5 liter batches) was first washed with 600 ml of a 5% aqueous sodium hydroxide solution followed by three washings with 500 ml portions of distilled water. The solution was stored over anhydrous calcium chloride for twenty—four hours. The washed l,2—dichloroethane was refluxed over barium oxide for twenty-four hours and fractionally distilled. The fraction which was retained had a boiling point of 82.5° [lit. (7A) 83°]. 3. Iodine: Fisher Certified Reagent grade iodine was sublimed over a mixture of potassium iodide and barium oxide. It was then resublimed over a few lumps of barium oxide to remove any impurities caused by splattering in the first sublimation (75)» _.-L¥QW u! silver nit Rosa and V A. Silver Nitrate: 29 Fisher Certified Reagent grade silver nitrate was purified according to the directions of Rosa and Vinal (76). 5. Water: The water used in the potentiometric portion of this study was prepared by passing distilled water through a mixed bed resin obtained from Crystalab Research Laboratories. water ranged from 5—7 x 10—7 ohms— The specific conductance of such 1 cm‘1 (77). B. The following chemicals were used without further the reagent solutions. 1. Aniline 2. 2-Azacyloheptanone 3. 2—Azacyclohexanone 4. 2-Azacyclooctanone 5. 2-Azacyclotridecanone 6. Barium Oxide 7. Benzamide 8. Benzoic Acid 9. Benzoyl Chloride Bromine t—Butyl Amine Chlorosulfonic Acid 13. A—Chlorobutyronitrile 5-Chlorova1eronitrile Cobalt(II) Perchlorate Hexahydrate purification in the synthesis and preparation of Eastman Organic Chemicals Aldrich Chemical Co. Aldrich Chemical Co. Aldrich Cehmical Co. Aldrich Chemical Co. Barium and Chemicals, Inc. Eastman Organic Chemicals Matheson Coleman and Bell J. T. Baker Chemical Co. Dow Chemical Co. Eastman Organic Chemicals Matheson Coleman and Bell Columbia Organic Chemical Columbia Organic Chemical Co. Co. Co. Co. G. Frederick Smith Chemical Co. 30 l6. Copper(II) Perchlorate G. Frederick Smith Chemical Co. V Hexahydrate l7. Cyclododecanone Aldrich Chemical Co. 18. Cycloheptanone Aldrich Chemical Co. 19. Cyclooctanone Aldrich Chemical Co. 20. Cyclononanone Aldrich Chemical Co. 21. l,4-Diaminobutane Aldrich Chemical Co. 22. l,2—Diaminoethane G. Frederick Smith Chemical Co. 23. 1,6—Diaminohexane Aldrich Chemical Co. 24. 1,3-Diaminopropane Aldrich Chemical Co. 25. 1,3—Dibenzoylhydrazine Aldrich Chemical Co. 26. l,2—Dichloroethane Fisher Scientific Co. 27. Diethyl Malonate Matheson Coleman and Bell Co. 28. N,N-Dimethylaniline Eastman Organic Chemicals 29. N,N'—Dimethyloxamide Aldrich Chemical Co. 30. Ethyl Oxalate Matheson Coleman and Bell Co. 31. Nickel(II) Perchlorate G. Frederick Smith Chemical Co. Hexahydrate 32. Phosphorus Pentachloride Allied Chemical Co. 33. 2—Piperidone Aldrich Chemical Co. 34. Potassium Cyanide Fisher Scientific Co. 35. Potassium Nitrate Allied Chemical Co. 36. Sodium Azide Eastman Organic Chemicals 37. Sodium Bisulfite Fisher Scientific Co. 38. Sodium Carbonate Fisher Scientific Co. 39. Succinyl Chloride . Aldrich Chemical Co. 40. Sulfuryl Chloride Eastman Organic Chemicals t1. Tetrabu A3. Zinc(II Hexah The common 1 further purl . Prepar clopolymet <3 |e| 'LC I 31 41. Tetrabutylammonium Hydroxide (25% in methanol) Matheson Coleman and Bell Co. 42. Zinc(II) Chloride Mallinckrodt Chemical Works 43. Zinc(II) Perchlorate Hexahydrate G. Frederick Smith Chemical Co. The common laboratory reagents and solvents were used without further purification and are not listed here. III. Preparation of Precursors to Cyclopolymethylenetetrazoles A. 4—Azidobutyronitrile.--The method outlined by Carpenter (33) was used. A mixture of 100 grams of 4- chlorobutyronitrile (1.033 moles), 124 grams of sodium azide (1.94 moles),and 500 ml of diethylene glycol was stirred at 100° for 24 hours in a one liter, three— necked, round bottom flask fitted with a stirrer, reflux condenser, and.mialcohol thermometer. The crude product was isolated by steam distillation, and the 4- azidobutyronitrile was separated from the aqueous layer. The aqueous layer was then extracted with three 300 ml portions of ethyl ether for an additional yield of product. The crude product was then dried by filtration through a 3 mm layer of anhydrous sodium sulfate and distilled under reduced pressure (bp 54° at 0.25 mm). The final product (75.4 grams, 70% yield) was a colorless liquid with a refractive index of 1.4574 at 23.50: The infrarec in Appendix B. 5_ chlorovalerc manner prev: 4—azidobuty: was 62° at 57% yield) ‘ index of 1. this compou I’eSpectivel 32 The infrared and nmr spectra of this compound appear in Appendix I as Figures 1 and 2 respectively. B. 5-Azidovaleronitrile.--Starting with 5— chlorovaleronitrile, this compound was prepared in the manner previously described for the preparation of 4—azidobutyronitrile. The boiling point of the product was 62° at 0.5 mm, and the final product (70.0 grams, 57% yield) was a colorless liquid which has a refractive index of 1.4605 at 24.0°. The infrared and nmr spectra of this compound appear in Appendix I as Figures 3 and 4 respectively. C. Hydrazoic acid.—-The method outlined by Braun (78) was used to prepare solutions of hydrazoic acid in benzene. The benzene solution of hydrazoic acid was prepared by suspending 210 grams of practical grade sodium azide (3.23 moles) in the same weight of warm water. The mixture was placed in a 3 liter, three—necked, round bottom flask equipped with a dropping funnel, stirrer, and ther— mometer, and one liter of benzene was added to the slurry. After the slurry was cooled to 0°, 85 ml of concentrated sulfuric acid (1.60 moles) wereadded to the vigorously stirred slurry by means of a dropping funnel. During the addition of the sulfuric acid, the temperature was main- tained between 0° and 10° by means of an external ice bath. After the addition of the sulfuric acid, the . ‘ Era-2‘" mixture was the hydrazoi almost solid hydrazoic ac sodium sulfa solutions oi method. The mined by exi hydrazoic a and titratiz using pheno CAUTI and all rea in a good h in thermome Of the 8X0] In P ;" Penal vyclo\ 33 mixture was cooled to about 5°, and the benzene layer, with the hydrazoic acid dissolved in it,was decanted from the almost solid sludge of hydrated sodium sulfate. The hydrazoic acid—benzene solution was stored over anhydrous sodium sulfate. Whenever necessary, toluene or chloroform solutions of hydrazoic acid can be prepared by this same method. The normality of the hydrazoic acid was deter— mined by extracting two milliliters of the benzene- hydrazoic acid solution into water in a stoppered flask and titrating the acid with standard sodium hydroxide using phenolphthalein as the indicator. CAUTION: Hydrazoic acid vapors are highly toxic, and all reactions involving its use should be carried out in a good hood. The use of heavy metals such as mercury in thermometers or seals should also be avoided because of the explosive nature of mercury(II) azide. IV. Preparation of the Various Cyclopolymethylenetetrazoles A. Trimethylenetetrazole.—-Von Kereszty's method (29) modified by Carpenter (79) was used for this prepar— ation. A solution of 11.0 grams of 4—azidobutyronitrile (0.099 mole) in 100 ml of chloroform dried over calcium chloride was added from a dropping funnel to a well— stirred solution of 11.30 grams of Chlorosulfonic acid (0.097 mole) in 100 m1 of chloroform. The rate of addition was controlled to maintain the temperature of the reaction mixture bets itated from chloroform : a flask for basic with The neutral twenty minu evaporated 100 ml of w sulfuric ac oxidized wi mixture between 20 and 40°. A white, solid complex precip— itated from the solution when the 4-azidobutyronitrilee chloroform solution was added. The mixture was stirred in a flask for 12 additional hours, cooled to 0°, and made basic with 50 m1 of 25% aqueous sodium hydroxide solution. The neutralized mixture was stirred for an additional twenty minutes. The chloroform layer was then removed and evaporated to dryness. The crude product was dissolved in 100 ml of water, made acidic with 15 m1 of concentrated sulfuric acid, and the unreacted 4—azidobutyronitrile was oxidized with a 0.2 M potassium permanganate solution. Trimethylenetetrazole was extracted from the aqueous layer with four 100 ml portions of chloroform. The final puri- fication was accomplished by recrystallizing approximately 10 grams of trimethylenetetrazole from a solvent mixture of 50 ml of carbon tetrachloride and 10 ml of ethanol. The colorless crystals that were obtained melted at 110°, [lit. (29) mp 110°]. The yield of trimethylenetetrazole (total 8.18 grams) based on 4—azidobutyronitrile was 74%. The infrared, nmr, and mass spectra of this compound appear in Appendix I as Figures 5, 6,and 7 respectively. Anal. Calcd. for C4H6N4: C, 43.63%; H, 5.49%; N, 50.88%. Found: c, 43.74%; H, 5.41%; N, 51.04%. B. 2 prepared st (0.089 mole preparatior formed inst 5-azidovale chlorosulfc (6.00 gram: previously recrystall: mixture. melted at grams) has infrared, in Appendi A n 1&1- Cale 35 B. Tetramethylenetetrazole.——The above compound was prepared starting with 11.00 grams of 5-azidovaleronitrile (0.089 mole) in the manner previously described for the preparation of trimethylenetetrazole. However, an oil formed instead of a white solid precipitate when the 5-azidovaleronitrile-chloroform mixture was added to the Chlorosulfonic acid-chloroform solution. The crude product (6.00 grams, 54.5% yield) was purified in the manner previously described for trimethylenetetrazole. It was recrystallized from a carbon tetrachloride—ethanol solvent mixture. The colorless crystals which were obtained melted at 1170 [lit.(29) mp 115°]. The yield (total 4.80 grams) based on 5-azidovaleronitrile was 43.5%. The infrared, nmr, and mass spectra of this compound appear in Appendix I as Figures 8, 9,and 10 respectively. Anal. Calcd for c H8Nu: c, u8.37%; H, 6.50%; N, 45.13%. 5 Found: c, 48.46%; H. 6.41%; N, 45.20%. C. Pentamethylenetetrazole.——This compound is commercially available and was not prepared in this laboratory. As a matter of completeness, however, and for comparison purposes, the infrared, nmr, and mass Spectra appear in Appendix I as Figures 11, 12, and 13 respectively. D. Hexamethylenetetrazole.—-A mixture of twelve grams of cycloheptanone (0.107 mole) and 20 grams of hydrazoic acid (0.466 mole, 188 ml of 2.5 N hydrazoic acid—benzene solution) v to make a t mixture was well-stirre sulfuric ac was complet mixture. T cooled to E hydroxide 5 yield) was ether, purj tetrazole, 36 solution) was added to 100 m1 of freshly distilled benzene to make a total volume of approximately 300 ml. This mixture was then added over a period of 45 minutes to a well-stirred, ice cooled mixture of 60 ml of concentrated sulfuric acid and 100 ml of benzene. After the reaction was completed, ice and water were carefully added to the mixture. Two layers were formed. The aqueous layer was cooled to 0° and neutralized with 50% aqueous sodium hydroxide solution. The crude product (12.0 grams, 79.5% yield) was extracted from the aqueous layer with ethyl ether, purified in the manner described for trimethylene- tetrazole, and recrystallized from hexane. The melting point of the crystals was 68° [lit. (31) 68°]. The yield of the product (total 6.80 grams) based on cycloheptanone was 46%. The infrared, nmr, and mass spectra of this com- pound appear in Appendix I as Figures 14, 15, and 16 respectively. Anal. Calcd for C C, 55,24%; H, 7.95%; N, 36.81%. 7H12N14: Found: C, 55.32%; H, 7.93%; N, 36.61%. E. Heptamethylenetetrazole.-—Eighty ml of concen- trated sulfuric acid were added to an ice cooled mixture of 20.80 grams of hydrazoic acid (0.484 mole, 323 ml of 1.5 N hydrazoic acid—benzene solution) in a one liter, three—necked, round—bottom flask equipped with a mechanical stirrer, drOpping funnel, and thermometer. A solution of 20 grams of cyclooctanone (0.159 mole) dissolved in 80 ml of benzene ‘ mixture was poured into liquid laye to approxim sodium hydr by three su benzene lay the product was added t recovered < 37 of benzene was added from a dropping funnel. The reaction mixture was stirred for an additional 20 minutes and then_ poured into an ice-water mixture, at which point two liquid layers were formed. The aqueous layer was cooled to approximately 5° and neutralized with 50% aqueous sodium hydroxide solution. The neutralization was followed by three successive extractions with ethyl ether. The benzene layer, which contained only a small fraction of the product, was also evaporated, and the oily residue was added to the evaporated ethyl ether residue. The recovered crude product (23.90 grams, 90.5% yield) was an oil which was purified further by distillation under vacuum. The fraction with a boiling range of l40-l50° at 0.5 mm was collected [lit. (31) l45-l46° at 0.1 mm]. The oil was difficult to crystallize, and seed crystals were first obtained by freezing a small sample at 0° for approximately 30 days. These crystals were used to induce crystallization of the oil. The first product had a melting point of 40-55°. The crude heptamethylenetetrazole (20 grams, 0.12 mole) was dissolved in 200 m1 of a mixture of equal parts of ethanol and water, and the solution was made acidic with 50 ml of concentrated sulfuric acid. Sufficient amount of 0.2 N potassium permanganate (about 25 ml) was added to oxidize the azide impurities. The crude product was then extracted with four 100 ml aliquots of chloroform. Evaporation of the chloroform solution left a residue i1 dissolved i: heptamethyl temperature four recrys the chilled The purifie and the cry cyclooctanc only previc sound (31) ,4 ,4 'ze. The appear in 1 Anal. Calc< \ Founc () fl) 38 a residue in the_form of a yellow oil. The oil was» dissolved in 400 ml of ethyl ether, and crystallization of heptamethylenetetrazole was induced when the solution temperature was reduced to approximately —60°. Three or four recrystallizations were required before seeding of the chilled, saturated solution was no longer required. The purified heptamethylenetetrazole was dried in vacuo, and the crystals melted at 42—43°. The yield based on cyclooctanone was 75%. It-is interesting to note that the only previously published literature report on this com— pound (31) describes it as an oil impossible to crystal— lize. The infrared, nmr, and mass spectra of this compound appear in Appendix I as Figures 17, 18,and 19 respectively. Anal. Calcd for C8Hl4N4: C, 57.81%; H, 8.49%; N, 33.70%. Found: c, 57.9Am; H, 8.47%; N, 33.74%. F. Octamethylenetetrazole.—-Starting with 5.5 grams of cyclononanone (0.039 mole), this compound was prepared in the manner described for the preparation of hepta— methylenetetrazole. The crude product recovered by the evaporation of the ethyl ether was purified as previously described and then recrystallized from a solvent mixture composed of one part benzene to fifty parts hexane. The purified octamethylenetetrazole was obtained as colorless crystals and had a melting point of ll7-1l8°. The yield, based on the cyclononanone, was 73.5% (4.8 grams). The infrared, r Appendix I Lug} Calcc‘ Founc' G- i of cyclode< was prepare of heptame‘ was I‘ECOVGI layer was 39 infrared, nmr, and mass spectra of this compound_appear in Appendix I as Figures 20, 2l,and 22 respectively. Anal. Calcd for 09H16N4: C, 59.97%; H, 8.95%; N, 31.08%. Found: C, 60.09%; H, 8.90%; N, 31.08%° G. Nonamethylenetetrazole.--Starting with 5.0 grams of cyclodecanone (0.031 mole), nonamethylenetetrazole was prepared in the manner described for the preparation of heptamethylenetetrazole. Most of the crude product was recovered from the benzene layer. However, the aqueous layer was extracted three times with 100 ml portions of ethyl ether in order to recover an additional small fraction of the product. The crude product was recrystal- lized from a solvent mixture composed of one part benzene to twenty parts hexane. The purified nonamethylene- tetrazole was obtained as colorless crystals with a melting point of 90—91°. The yield of the reaction (4.8 grams) based on cyclodecanone was 80.0%. The infrared and nmr Spectra of this compound appear in Appendix I as Figures 23 and 24 reSpectively. Anal. Calcd for c NM: 0, 61.82%; H, 9.34%; N, 28.84%. 10Hl8 Found: C, 61.93%; H, 9.31%; N, 28.82%. H. Undecamethylenetetrazole.—-This compound was prepared by adding from a dropping funnel a solution composed of 22.0 grams of cyclododecanone (0.137 mole) dissolved in 50 ml of dry benzene to an ice-cooled mixture __—‘ of 20.8 gr 2.2 N hydr centrated cyclododec the reacti After this continued tion mixtu methylenet ether to e of 20.8 grams of hydrazoic acid (0.484 mole, 225 m1 of a 2.2 N hydrazoic acid-benzene solution) and 80 ml of con- centrated sulfuric acid (1.50 mole). The mixture of cyclododecanone was added at a rate adjusted to maintain the reaction mixture temperature at approximately 10°. After this addition was complete, the stirring process was continued for 36 hours at 25°. From this point the reac— tion mixture was treated in the manner described for hepta— methylenetetrazole, but benzene was used instead of ethyl ether to extract the product. The crude product was recrystallized three times from a solvent mixture composed of equal parts of water and ethanol. The purified undecamethylenetetrazole was obtained as colorless crystals in a 66.2% yield (20.1 grams) based on cyclododecanone and had a melting point of 66-670. The infrared and nmr spectra of this compound appear in Appendix I as Figures 25 and 26 respectively. Anal. Calcd for Cl2H22N2u: c, 60.83%; H, 9.97%; N, 25.20%. Found: C, 64.84%; H, 9.88%, N, 25.23%. V. Preparation of Precursors to 6,6— Dihalocyclopolymethylenetetrazoles A. 2—Benzoyl—2—azacycloheptanone.--A mixture of 135.6 grams (L20 moles) of 2—azacycloheptanone and 170.1 ml (1.32 moles) of N,N-dimethylaniline was prepared in a 3—liter, three-necked, round—bottom flask equipped with a stirrer, dPopping funnel, and an alcohol thermometer. To the vigorousl benzoyl c the tempe heated an and poure acid in 1 41 vigorously stirred solution, 185.7 grams (1.32 moles) of benzoyl chloride were added drop—wise at such a rate that the temperature did not rise above 80°. The mixture was heated and stirred at 90° for three hours, cooled to 70°, and poured into a solution of 24 ml of 2.5 N hydrochloric acid in 1200 ml of distilled water. The oily blue material crystallized after approximately five minutes. The lumps were broken up and collected on a filter, washed with distilled water, and air dried to yield 260 g of the product (99% yield) mp 67—690 [lit. (80,81) 67—69.5°l. B. 2-Benzoyl—7—chloro-2—azacycloheptanone.——A suspension of 217 g (1.00 mole) of 2—benzoyl—2— azacycloheptanone in 55 ml of carbon tetrachloride and 165 ml of cyclohexane was prepared in a 2-liter, three— necked, round—bottom flask equipped with a mechanical stirrer, dropping funnel, and thermometer. To the stirred solution, 85 ml (1.05 moles) of sulfuryl chloride were added. The yellow slurry was maintained at 5—10° by external cooling while the sulfuryl chloride was added. The mixture was then slowly heated to 40° over a period of thirty minutes. When the temperature of the reaction slurry reached approximately 15°, the suspension dissolved completely. The reaction mixture was stirred and its temperature was maintained at 40-42° for 28 hours followed by evaporation to dryness lg vacuo. During the 28 hours the yellow reaction mixture turned green and then back to gold. The alcohol at to 0-5° fc isopropyl was obtair 123°]. 42 gold. The residue was then stirred with 250 m1 of isopropyl alcohol at 70° for a few minutes. The suspension was cooled to 0—5° for one hour, filtered, and washed with chilled isopropyl alcohol. The white crystalline product (134 g) was obtained in a 54% yield, mp l2l-l22° [lit. (82) 122- 123°]. C. 2-Chloro-7—azacycloheptanone.--A 500 ml three— necked, round—bottom flask equipped with a stirrer, thermometer, and Side arm for sample addition was charged with 168 m1 of concentrated sulfuric acid. Dry 2—benzoyl— 7—chloro-2—azacycloheptanone (125 g , 0.5 mole) was gradually added to the concentrated sulfuric acid at a rate sufficient to maintain the temperature of the reaction mixture below 25°. The mixture was stirred for one hour without external heating, and the temperature rose to 35°. It was heated to 50° and stirred for two additional hours. The-mixture was cooled to 25°, poured into 1 kg of ice in a 4 liter beaker, neutralized with concentrated ammonium hydroxide solution, and extracted with four 500—ml portions of chloroform. The chloroform solution was evaporated to yield a yellow product which was recrystallized from a 10% benzene and 90% ligroin mixture. The white crytalline product (50 g) was obtained in a 68% yield, mp 91—93 [lit. (82) 92.5-93.501 D. of 260g( liter of b round bott stirrer, d azacyclohe added from minutes. maintained tion, and tinuous st D. 2,2-Dichloro-6—azacyclohexanone.—-A stirred slurry of 260 g (1.25 moles) of phosphorus pentachloride in one liter of benzene was prepared in a 2—1iter, three—necked, round bottom flask equipped with an efficient mechanical stirrer, dropping funnel, and thermometer. To the stirred slurry a solution composed of 42 g (0.42 mole) of 2— azacyclohexanone (2-piperidone) in 100 ml of benzene was added from the dropping funnel during a period of 20 minutes. The temperature of the reaction mixture was maintained at 30=35° by external cooling during the addi— tion, and then the mixture was heated to 80-85° with con-- tinuous stirring for an additional hour. The reaction mixture was concentrated by distillation under reduced pressure on a steam bath. After all the volatile materials had been removed, the oily residue was added to 500 ml of a 10% sodium carbonate solution with vigorous stirring. The Sludge wasfiltered, washed with 200 ml of water, and then washed with 100 ml of chilled ethanol. The crystalline product was recrystallized from boiling ethanol and dried 12 vacuo to give 30.0 grams of well-formed prisms of 2,2—dichloro—6—azacyclohexanone (42.5% yield) mp 166° [lit. (83) 166°“. The infrared spectrum of this com— pound appears in Appendix I as Figure 27. E. 57 e (0.5 this comp: preparatii product w: i_n vacuo ‘ dichloro- (lit. (83 appears 1 44 E. 2,2—Dichloro-7-azacycloheptanone.--Starting with 57 g (0.5 mole) of 2—azacycloheptanone (e—caprolactam), this compound was prepared in the manner-described for the preparation of 2,2-dichloro—6—azacyclohexanone. The product was recrystallized from boiling ethanol and dried EH vacuo to give 62.8 g of well—formed prisms of 2,2— dichloro-7—azacycloheptanone (34.0% yield) mp l26—127° [lit. (83) 125°]. The infrared Spectrum of this compound appears in Appendix I as Figure 28. F. 2,2—Dichloro—8—azacyclooctanone.——This compound was prepared in 75.8% yield from 25 g (0.197 mole) of 2-azacyclooctanone and phosphorus pentachloride following the procedure described for the preparation of 2,2—dichloro— 6-azacyclohexanone. The product was recrystallized from boiling ethanol and dried 12 vacuo to give 29.2 g of well— formed prisms of 2,2-dichloroa8—azacyclooctanone mp 96—97°° The,infrared Spectrum of this compound appears in Appendix I as Figure 29. G. 2,2—Dichloro—13~azacyclotridecanone.—-Starting with 100 grams (0.506 mole) of 2—azacyclotridecanone, this compound was prepared in the manner described for the preparation of 2,2-dichloro—6—azacyclohexanone. The crude crystalline product was recrystallized from boiling ethanol and dried lg vacuo to give 95 grams of well—formed prisms of 2,2—dichloro-l3—azacyclotridecanone (70.2% yield) mp 13V 159°. The “ Appendix I 2 s. 2 solution of (2-piperid01 in a l-lite: with a mech. Erlenmeyer Of a large Phosphorus quickly wei nLA coached to 45 159°. The infrared spectrum of this compound appears in Appendix I as Figure 30. H. 2,2-Dibromo—6—azacyclohexanone.-—A stirred solution of 58 grams (0.58 mole) of 2-azacyclohexanone (2-piperidone) in 400 m1 of dry chloroform was prepared in a 1-liter, three-necked, round-bottom flask equipped with a mechanical stirrer and thermometer. A small Erlenmeyer flask was attached to the third opening by means of a large diameter rubber tubing slipped over the opening. Phosphorus pentachloride (242 grams, 1.16 moles) was quickly weighed into the Erlenmeyer flask which was then attached to the apparatus. The phosphorus pentachloride was added to the reaction flask in about one or two gram portions during a period of one hour. Throughout this addition, the reaction mixture was maintained between 3° and 10° by external cooling. After all the phosphorus penta- chloride was added, the resulting slurry was allowed to return to room temperature, 1.5 grams of Zinc(II) chloride was added, followed by 96 grams (0.6 mole) of bromine. The stirring was continued for five hours. The solvent was removed by vacuum distillation at 40° and 20 mm. The resi— due was poured into an ice—water mixture, the solid product was dissolved in chloroform, and the solution was treated with 10% aqueous sodium bisulfite solution to remove the last traces of bromine. Evaporation of the chloroform solution from etha 2,2-dibro based on spectrum Figure 31 46 solution left a solid residue which was recrystallized from ethanol to yield 80 grams of well-formed prisms of 2,2-dibromo~6-azacyclohexanone, mp 186°. The yield, based on 2-azacyclohexanone, was 53.7%. The infrared spectrum of this compound appears in Appendix I as Figure 31. I. 2,2—Dibromo—7—azacycloheptanone.—-This compound was prepared in 91.5% yield from 33.9 grams (0.30 mole) of 2—azacycloheptanone (e-caprolactam), phosphorus penta— chloride, and bromine following the procedure described for the preparation of 2,2—dibromo-6—azacyclohexanone. The product was recrystallized from boiling ethanol and dried lg vacuo to give 74.10 grams of 2,2—dibromo—7— azacycloheptanone mp 162—163° [lit. (80) 162—163.50], The infrared spectrum of this compound appears in Appendix I as Figure 32. J. 2,2-Dibromo—8-azacyclooctanone.-—Starting with 50 grams of 2-azacyclooctanone (0.394 mole), this compound was prepared in the manner described to prepare 2,2—dibromo- 6-azacyclohexanone. The crude product was recrystallized from ethanol to give 32 grams of well—formed prisms of 2,2—dibromo-8—azacyclooctanone mp 150—151°. The yield based on 2—azacyclooctanone was 28.6%. The infrared spectrum of this compound appears in Appendix I as Figure 33. 47 VI. Preparation of the Various 6,6- Dihalocyclopolymethylenetetrazoles A. 6,6—Dichlorotetramethylenetetrazole.--A stirred solution of 16.8 grams of 2,2—dichloro—6—azacyclohexanone (0.10 mole) in 300 ml of dry benzene was prepared in a l-liter, three-necked, round—bottom flask fitted with a stirrer, reflux condenser, and surmounted by a calcium chloride drying tube. The third opening was connected to a 500 ml Erlenmeyer flask containing 22.88 grams (0.11 mole) of phosphorus pentachloride. The benzene solution was stirred and heated to 40° while the phosphorus penta— chloride was added in ~0.5 gram portions over a period of one hour. The reaction was acoompanied by the Vigorous evolution of hydrogen chloride. When the formation of the imide chloride was complete, as evidenced by the disappear— ance of solid phosphorus pentachloride, the reaction mixture was cooled to 20°. The Erlenmeyer flask was then replaced by a dropping-funnel through which 10 grams (0.233 mole, 137 ml of 1.7 fl hydrazoic acid—benzene solution) of hydrazoic acid—benzene solution was added, maintaining the temperature of the reaction mixture between 20 and 30° by means of external cooling. After the addi— tion of the hydrazoic acid, the reaction mixture was allowed to stand at room temperature for two hours. It was then gradually warmed to the boiling point on a steam bath and maintained at this temperature until hydrogen chloride evolution ceased (about three hours). The solVent was remox with ice phosphorL ate was 1 presence The prodt portions lized tw: 48 was removed by air evaporation, and the residue was treated with ice and water (100 grams of each) to decompose any phosphorus oxychloride that was present. Dry sodium carbon— ate was then-carefully added to neutralize any acid, the presence of which caused the oily residue to solidify. The product was extracted from the mixture with four 100 ml portions of chloroform, evaporated to dryness, and recrystal- lized twice from ethanol. On cooling, 13.5 grams (70% yield based on the 2,2—dichloro-6-azacyclohexanone) of 6,6-dichlorotetramethylenetetrazole precipitated. The colorless crystals that were obtained melted at 84°. The infrared and nmr spectra of this compound appear in Appendix I as Figures 34 and 35 respectively. Anal. Calcd for C5H6N4012: C, 31.11%; H, 3.13%; N, 29.02%; C1, 36.73%. Found: c, 31.77%; H, 3.26%; N, 28.86%; Cl. 36.90%. B. 6,6—Dibromotetramethylenetetrazole.——This com— pound was prepared in the manner previously described for the preparation of 6,6-dichlorotetramethylenetetrazole. Starting with 25.69 grams of 2,2-dibromo—6—azacyclohexanone (0.1 mole), 12 grams of crude product were obtained and recrystallized twice from boiling ethanol. 0n cooling, 10 grams (36.5% yield) of 6,6—dibromotetramethylenetetrazole precipitated. These colorless crystals melted at 91°. The infrared and nmr spectra of this compound appear in Ill Appendix I 1113;. Ca1< Foul 49 Appendix I as Figures 36 and 37 respectively. Anal. Calcd for 05H6N4Br2: C, 21,30%; H, 2.15%; N, 19.87%; Br, 56.68%. Found: C, 21.30%; H, 2.19%; N, 20.08%; Br, 56.48%° C. 6z6-Dichloropentamethylenetetrazole. .1. Method I: This compound was prepared starting with 18.2 grams of 2,2—dichloro—7-azacycloheptanone (0.10 mole) in the manner previously described for the prepara- tion of 6,6-dichlorotetramethylenetetrazole. The crude product was recrystallized from boiling ethanol twice. The resulting colorless crystals melted at 81—82°. The yield (total 17.48 grams) based on 2,2—dichloro—7— azacycloheptanone was 84.5%. The infrared and nmr spectra of this compound appear in Appendix I as Figures 38 and 39 respectively. Anal. Calcd for C6H8Nu012: C, 34.80%; H, 3.94%; N, 27.06%; 01, 34.24%. Found: c, 34.77%; H, 3.81%; N, 27.11%; 01, 34.22%. 2. Method II: Phosphorous pentachloride (31.4 grams, 0.15 mole) was dissolved in 200 ml-of hot, dry benzene (50—60°) in a one-liter, three-necked, round— bottom flask equipped with a mechanical stirrer, a reflux condenser surmounted by a calcium chloride tube, and a side arm for sample addition. Dry 2—chloro-7-azacycloheptanone (14.7 grams, 0.10 mole) was gradually added to the hot _ u, _. ~_ benzene-p arm. The of the by all of ti mixture v hydrazoi< acid-hen: funnel 0‘ hydrazoi allowed ‘ ceased i under re ml 0f we 50 benzene-phosphous pentachloride mixture through the side arm. The reaction was accompanied by vigorous evolution of the hydrogen chloride for a period of one hour. After all of the 2-chloro-7-azacycloheptanone was added, the mixture was cooled to approximately 10°, and 12.9 grams of hydrazoic acid (0.3 mole, 108 ml of a 2.79-fl_hydrazoic acid—benzene solution) were added by means of a dropping funnel over a period of one hour. After the addition of hydrazoic acid was completed, the reaction mixture was allowed to stand at room temperature for one hour before it was gradually warmed to the boiling point and maintained at this temperature until the hydrogen chloride evolution ceased in approximately two hours. The solvent was removed under reduced pressure, the residue was diluted with 300 m1 of water, and the product was extracted with four 200 ml portions of chloroform. The chloroform solution was evaporated to yield ablack, viscous oil—like substance. The crude product was purified by sublimation (1 mm at 170°) to yield an impure white solid (mp 42-580) which was purified further by a second sublimation and then recrystalm lization from carbon tetrachloride and absolute alcohol respectively, mp 80—82°. The yield of the product (total 10.35 grams) based on the 2—chloro—7—azacycloheptanone was 50%. This compound is identical with the 6,6— dichloropentamethylenetetrazole. Because the preparation of 6-chlor0pentamethylenetetrazole was attempted, 41V 6,6-dich2 product. 7-azacycl benzene r 2 positic 2,2-dich2 hydrazoi< produce E 0 N ”f V, 51 6,6-dichloropentamethylenetetrazole was an unexpected product. In all probability, the addition of dry 2-chloro- 7-azacycloheptanone to the hot phosphorus pentachloride- benzene mixture resulted in a further chlorination of the 2 position to cause an imidyl chloride intermediate of 2,2-dichloro-7—azacycloheptanone which, when reacted with hydrazoic acid, added an azido group that rearranged to produce 6,6edichlorOpentamethylenetetrazole. a 0.1 Cl J‘ + ”g \\\\ . a J C N H 19015 01 l“ HzN — N 2 N: -——-—> —-——> Benzene 80° . + ” N if. 8‘" . 51%;4'51‘6: N/ \N :N——NEEN° I C. Cl \\\\N: Cl L::§: Cl “ // C1 C1 C1 _===§> _a_;> This mechanism is supported by the experimental evidence that all efforts to convert 2~azacycloheptanone directly to 2-chloro-7—azacycloheptanone result only in the formation of 2,2—dichlorou7—azacycloheptanone (80, 82, 84). Therefore, the more efficient way to prepare 6,6-dichloropentamethylenetetrazole would be with 2,2— dichloro—7-azacycloheptanone as the starting material, method I outlined above. D. ation of dibromo-' previousl tetrazole 52 D. 6,6—Dibromopentamethzlenetetrazole.——The prepar— ation of this compound started with 27.10 grams of 2,2— dibromo-7-azacycloheptanone (0.10 mole) in the manner previously described to prepare 6,6—dichlorotetramethylene— tetrazole. The crude product was recrystallized from boiling ethanol . Upon cooling, 22.35 grams (75.4% yield) of 6,6—dibromopentamethylenetetrazole precipitated. The colorless crystals thus obtained melted at 117—119°. The infrared and nmr spectra of this compound appear in Appendix I as Figures 40 and 41 respectively. Anal. Calcd for C6H7NuBr2: C, 24.35%; H, 2.73%; N, 18.93%; Br, 54.00%. Found: C, 24.38%; H, 2.72%; N, 18.95%; Br, 54.03%. E. 6,6-Dichlorohexamethylenetetrazole.——Starting with 19.6 grams of 2,2—dichloro-8—azacyclooctanone (0.10 mole), this compound was prepared in the manner described for the preparation of 6,6—dichlorotetramethylenetetrazole. The crude product recovered by evaporating the chloroform was purified by two recrystallizations from ethanol. On cooling, 12.20 grams (55.2% yield) of colorless crystals of 6,6-dichlorohexamethylenetetrazole (mp 63-64°) pre~ cipitated. The infrared and nmr spectra of this compound appear in Appendix I as Figures 42 and 43 respectively. Anal. Calcd for C7H10N4012: c, 38.03%; H, 4.56%; N, 25.34%; Cl, 32.97%. Found : c, 38.56%; H, 4.61%; N, 25.80%; 01, 31.23%. F 6,6-dicl attempt startim and inf: the em 53 F. Attempted Preparation of 6,6-Dibromohexamethylene— tetrazole.-—The procedure previously described to prepare 6,6-dichloropentamethylenetetrazole was also used in an attempt to prepare 6,6—dibromohexamethy1enetetrazole, starting with 2,2—dibromo—8—azacyclooctanone. The nmr and infrared spectra of the isolated product showed that the expected product was not obtained. G. Attempted Preparation of 6,6-Dichloroundeca- methylenetetrazole.-—The procedure previously described to prepare 6,6-dichlorohexamethylenetetrazole was also used in an attempt to prepare 6,6-dichloroundecamethylenetetrazole starting with 2,2—dichloro—l3-azacyclotridecanone. However, only starting material could be recovered from the reaction mixture. VII. Preparation of Precursors to l,1'—Diphenyl~5.5l=bitetrazole A. N,NV—Diphenyloxamide.——A mixture of 73 grams of ethyl oxalate (0.50 mole) and 100 grams of aniline (1.07 mole) was heated at 150° for 30 minutes in a 500 m1 three— necked, round-bottom flask equipped with a thermometer, reflux condenser, and stirrer. After the ethanol produced during the reaction was removed by distillation, the remaining material solidified as it cooled. The crude product was recrystallized from benzene. Upon cooling, 100 grams of N,NV—diphenyloxamide mp 245° [lit. (85) mp 1_flp 244°] pr grams) 0 trum of B. was prep of N,N'- phosphor 240 ml c 54 244°] precipitated. The yield of the product (total 102.6 grams) based on ethyl oxalate was 85%. The infrared spec: trum of this compound appears in Appendix I as Figure 44. B. N,NV-Diphenyloxalimidyl Chloride.--This compound was prepared by Bauer's method (86). Eighty-five grams of N,N'—diphenyloxamide (0.354 mole) and 170 grams of phosphorus pentachloride (0.817 mole) were suspended in 240 m1 of freshly distilled toluene in a 500 m1 three- necked, round-bottom flask equipped with a stirrer, a reflux condenser surmounted by a calcium chloride tube, and a thermometer. As the stirred solution was heated, the phosphorus pentachloride dissolved, and a clear yellow solution resulted when the temperature reached 90°. The solution was then refluxed for an additional three hours, and 200 m1 of toluene were distilled off. The crude product in the flask solidified when it was cooled to room temperature and then was recrystallized from ligroin. Straw yellow needles of N,lediphenyloxalimid 1 chloridenm3115° [lit. (86) mp 115°] were obtained. The reaction yield (total 44.2 grams) based on N,Nlmdiphenyloxamide was 45%. The product is gradually hydrolyzed back to N,NV- diphenyloxamide by atmospheric moisture. However, if the preparation is carried out rapidly, a dry box is not required. The infrared spectrum of this compound appears in Appendix I as Figure 45. VIII. ] a,m-Bls alkanes A grams 0: in one g solutio; 55 VIII. Pre aration of Precursors to d,w—Bis'Bephenyleletetrazolyl —n— alkanes A. Bis(d—chlorobenzylidene)hydrazine.——Twenty—four grams of dry 1,2-dibenzoylhydrazine (0.10 mole) were added in one gram portions, over a period of one hour to a solution of 50 grams of phosphorus pentachloride (0.25 mole) in 100 ml of freshly distilled toluene at 90-100°. During the reaction the solution was stirred vigorously and after the reaction was completed, the volatile reaction products and most of the solvent were distilled off at 760 mm. 0n cooling, the residual liquid yielded 20 grams of crude product which was recrystallized from 300 m1 of ethylene glycol monomethyl ether and 18 grams (65% yield) of bis(d—chlorobenzylidene)hydrazine [mp 121—122°, lit. (87) 120-122°] were obtained. B. N,Nl-Dibenzoyl-l,3udiaminopropane.x—Benzoyl chloride (140 g, 1.00 mole) was added over a period of 55 minutes to a well-stirred solution of 29.6 grams (0.40 mole) of 1,3wdiaminopropane and 60 grams (1.50 mole) of sodium hydroxide in 600 m1 of water. An ice bath held the temperature of the reaction solution below 10°. After stirring the slurry for an additional one hour, it was filtered. The solid white product was washed with a large amount of water and then air dried. The crude amide was dissolved in 300 m1 of a 1:1 mixture of boiling ethanol 1V and ben benzene diamino reactio propane 56 and benzene, and this solution was diluted with 300 ml of benzene. On cooling, 86.2 grams of N,N'—dibenzoyl—l,3— diaminopropane mp 147° [lit. (88) 147°] precipitated. The reaction yield (total 95.5 grams) based on 1,3—diamino- propane was 85%. C. N,NV-Dibenzoyl-l,4-diaminobutane.-—This compound was prepared starting with 35.2 grams of 1,4—diaminobutane (0.40 mole) in the same manner as the corresponding propane derivative. The melting point of 177° agrees well with the literature value (89). The yield (total 102.0 grams) based on 1,4ndiaminobutane was 86.5%. D. N,NV=Dibenzoyl=l,2—diaminoethane.~—This compound was prepared starting with 24 grams of ethylenediamine (0.40 mole) in the manner previously described for the corresponding prOpane derivative. The melting point of 249° closely corresponds with the literature value (90). The yield (total 91.0 grams) based on l,2-diaminoethane was 85%. E. N,NV—Dibenzoyl—l,6mdiaminohexane.--This compound was prepared from 46.5 grams of 1,6-diaminohexane (0.40 mole) in the manner previously described for the corres— ponding propane derivative. The melting point of 165-166° corresponds closely with the literature value (90, 91). The yield (total 104.3 grams) based on 1,6mdiaminohexane was 81%. 1“»! (I) ,1 c r (D Q. In ‘nal '\ \;: \\ \M 4x 57 F. N,N'—Dibenzoy1diaminomethane.——This compound was prepared by stirring together 20 grams of benzamide (0.165 mole), 40 m1 of 40% aqueous formaldehyde (0.531 mole) and 20 m1 of 15 g sulfuric acid. As this mixture was heated, dissolution occurred. On further heating, a precipitate formed. The solution was cooled to ice-bath temperature, and then the product was recrystallized twice from absolute ethanol. 0n cooling, 8.93 grams of N,N‘- dibenzoyldiaminomethane [85% yield, mp 225°, lit. (92) mp 220°] were obtained. IX. Preparation of 1,1'-Dipheny1- 5,5'—bitetrazole Twenty—eight grams of N,N‘—diphenyloxalimidyl chloride (0.100 mole) and 26 grams of sodium azide (0.400 mole) were added to 200 ml of 95% ethanol. The mixture was caused to refluxed and stirred for 12 to 14 hours. After the reaction was completed, the white, solid precipitate was filtered, washed with water, and recrystallized twice from absolute ethanol. The white crystalline material melted sharply at 2120 [lit. (41,93) 212°]. The infrared spectrum of this compound appears in Appendix I as Figure 46. The nmr spectrum was not obtained because this compound does not possess sufficient solubility in any suitable solvent. Anal. Calcd for c c, 57.93%; H, 3.47%; N, 38.60%. 17H10N82 Found: C, 57.94%; H, 3.55%; N, 38.51%. U‘J X. Pre aration of a waBis(5— henyl—l— t e t ra‘ Z011. 1' 443-48. l'kan e S ~ A. 5,5”—Diphenyl—l,1"-bitetrazole.——Bis(d— chlorobenzylidene)hydrazine (14.0 grams, 0.05 mole) and 20 grams of sodium azide (0.305 mole) were added to 100 ml of 95% ethanol and then refluxed and stirred for approxi— mately 12 to 14 hours. On completion of this process, the unreacted azide was removed by filtration, and upon cooling, crystals of the product precipitated. The crude product was then recrystallized from 95% ethanol. It decomposed at 203°, and,if more than a few milligrams were heated, the product exploded. The infrared Spectrum of this compound appears in Appendix I as Figure 47. The nmr spectrum was not obtained because this compound does not possess sufficient solubility in any suitable solvent. Anal. Calcd for c. H N8: 0. 57.93%; H, 3.47%; N, 38.60%. 17 10 Found: C, 55.05%; H, 3.56%; N, 41.32%. B. 1,4wBis(5~phenylelutetrazolyl)~n-butane.-— N,NV-dibenzoyl—l,4—diaminobutane (29.6 grams, 0.100 mole) was added in one gram portions to a stirred, heated (90- 100°) solution of 50 grams of phosphorus pentachloride in 150 ml of freshly distilled toluene for an hour. The reaction was completed by allowing the solution to reflux for an additional hour after which 26.6 grams of dry sodium azide (0.400 mole) were added directly to the hot mixture in one gram portions over the period of one hour. The mix The sol was was in wate 1.89 gr (mp 225 N,N'-di spectru 48. Th 59 The mixture was then refluxed and stirred for 12 to 14 hours. The solvent was evaporated, and the crude product recovered was washed with 200 m1 of water. The material, insoluble in water, was recrystallized from glacial acetic acid, and 1.89 grams of l,4-bis(5—pheny1-l—tetrazoly1)—p7butane (mp 225-226°) were obtained. The reaction yield based on N,N'-dibenzoy1—l,4—diaminobutane was 3.44%. The infrared spectrum of this compound appears in Appendix I as Figure 48. The nmr spectrum was not obtained because this com— pound does not possess sufficient solubility in any suitable solvent. Anal. Calcd for C18H18N8: C, 62.41%; H, 5.24%; N, 32.35%. Found: C, 62.34%; H, 5.14%; N, 32.41%. XI. Pre aration of Precursors to d m— Bis(l-pheny145—tetrazolyl egralkanes A. N,N'—Diphenylmalonamide.—-Diethyl malonate (320 grams, 2 moles) and aniline (400 grams, 4.30 moles) were mixed together, and N,N'—dipheny1malonamide was prepared in the manner previously described for N,N'—diphenyloxamide. The crude product was recrystallized from methanol, and, upon cooling, 502 grams of N,N'—diphenylmalonamide [mp 225°, lit. (94) mp 224—225°] precipitated. The reaction yield based on diethyl malonate was 93.6%. The infrared spectrum of this compound appears in Appendix I as Figure 49. B of anil benzene bottom droppin bath. mole) a added t. of two ] aniline residue 60 B. N,N'—Diphenylsuccinamide.--A mixture of 93 grams of aniline (1 mole) and 1 liter of freshly distilled benzene was prepared in a two liter, three—necked, round— bottom flask equipped with a stirrer, thermometer, and dropping funnel. The flask was cooled by a water-ice bath. A solution of 25 grams of succinyl chloride (0.25 mole) and 200 ml of freshly distilled benzene was slowly added to the well—stirred, cooled solution over a period of two hours. After the reaction was completed, the aniline hydrochloride was extracted with warm water. A residue was left which consisted of almost pure N,N‘— diphenylsuccinamide. The crude product was recrystal- lized from methanol [mp 229°, lit. (95) at 228—229°] and the yield of product (39.0 grams) based on succinyl chloride was 90%. The infrared spectrum of this compound appears in Appendix I as Figure 50. XII. Attempted Preparation of u u)— Bis(l—phenyle5—tetrazolyli—nralkanes Preparations of bis(l-phenyl-5-tetrazolyl)methane and 1,2—bis(l—pheny145-tetrazolyl)ethane were attempted from N,N'-diphenylmalonamide and N,N'-dipheny1succinamide according to the following reaction procedure. 2PCl 5 _ _ ¢-w-;—.-fi-N- .—.——.—-...> -N-aJ—.-$—N-¢ H O O 8 C1 C1 where n spectra expecte; 5,5'-b11 (see p. bridged plausibl 61 2HN3 2 -N=C— CH —C=N— —N—C— CH —C—N— ()<1>l(2)1r1| ¢—-——-—>¢'”(2)nul¢ 01 01 N N N N 8’ \” N N where n = l and 2, 0 e C6H5. In each case, the respective nmr, infrared, and mass spectra of the isolated reaction product indicated that the expected compound was not obtained. Because 1,1'-dipheny1— 5,5'—bitetrazole can be prepared from N,N'—diphenyloxamide (see p. 57), it is surprising that the related methylene bridged bitetrazoles could not be prepared. The most plausible explanation for the failure of the synthesis is the availability of methylene hydrogens which could facil— itate a possible rearrangement. Von Braun and Rudolph (96) applied the foregoing sequence of reactions only to imide chlorides in which R? was aromatic and R was either aliphatic or aromatic groups. The restriction to imide chlorides derived from anilides was based on earlier work by von Braun and his co-workers (97- 99). These authors have shown that the chlorides of ali— phatic amides of the type R-CH2—C(Cl)=NR', where R was either hydrogen or an aliphatic group and R' was either an aliphatic or aromatic group, were so reactive that they could not be isolated. Such imide chlorides readily formed amidine—like condensation products, apparently because of a primary shift of hydrogen from the alpha carbon to the nitrogen atom, followed by a reaction between the tautomeric forms with the elimination of hydrogen chloride. if R P! repres; applim | . chloric ‘ on atte Chlori< appear HoweVe: Dressu: benzon tx: I—I I—' HI —- [A l _ t3 62 (l) R4CH2C(C1) = N—R'—>R-CH = C(Cl) NHR' (2) R-CH2C(C1) = N-R' . R-CH2—C = N-R' + _ —> . R'CH = C(Cl)NHR' R—CH = C(Cl) N—R‘ + HCl if R represents the ¢-N = C(C1)- fragment and R' represents a phenyl group, this reaction sequence is applicable. Although von Braun concluded that most imide chlorides were highly unstable, this conclusion was based on attempts to isolate these compounds. The imide chlorides of the d,w-bis(5—pheny1-latetrazolyl)—p—alkanes appear to form in solution with complete stability (100). However, they could not be isolated even under reduced pressures because they decompose into two moles of benzonitrile and the corresponding a,w-dichloroalkane. XIII. Preparation of the Precursor of 1,1'—Di—tert-buty1—5,5'—bitetrazole N,N'-Di—tert-butyloxamide.--A mixture of 146 grams of ethyl oxalate (1.00 mole) and 150 grams of p—butylamine (2.06 moles) was heated at 100° for 24 hours in a l—liter, three— necked, round—bottom flask equipped with a thermometer, reflux condenser, and stirrer. After the ethanol produced during the reaction was removed by distillation, the remaining material solidified as it cooled. The product was recrystallized from a solution consisting of equal parts of water and ethanol product infrare as FigL XIV. g Dimethy the iso bitetra Peactiv ethanol. When the mixture was cooled, 150 grams of pure product [mp 176°, lit. (101) at 176°C] were recovered. The infrared spectrum of this compound appears in Appendix I as Figure 51. XIV. Attem ted-Pre aration of 1 1'— Dimethyl—”and"1,1‘ADIAtert-butyl—5, "S'Abitetrazole ' A slurry of N,N'—dimethyloxamide or N,N'-di—tert- butyloxamide in benzene reacted with phosphorus penta— chloride and then was successively treated with hydrazoic acid in the following manner. (1)R—N—C—C-N—R+2P01 ._.R—N=/C_(|3=N_ 488%; 5 Cl 01 (2) R-N=C—C=N_R+2HN3 IR_I}I_fi-fi-I\|I-R I ' N N N N Cl Cl \\/ \/ N N In each case, the nmr, infrared, and mass spectra of the isolated reaction product showed that the expected bitetrazole was not obtained. It appears that the reaction scheme failed to yield the expected product because of the reactivity of the diimidchloride intermediate. There is evidence of an intramolecular rearrangement (96) in which the diimidchloride eliminates one HCl molecule and an inter- molecular rearrangement (96-99) in which a proton shifts from a carbon atom to a nitrogen atom followed by the subsequent elimination of HCl between one molecule each of the invest i pursue ‘ effort l explor I periph XV. § Measur consta that a with tj COmpon polyme‘ range Concen Weighix to the 64 of the rearranged and nonrearranged compounds. The further investigation of the mechanisms of these reactions was not purSued because, while highly significant in itself, the effort to prepare these compounds necessitated a detailed exploration of an area of fundamental organic chemistry peripheral to the main goals of this research project. XV. Spectrophotometric Studies A. Irocedure for Carrying Out Spectrophotometric Measurements.—-The method used to evaluate the equilibrium constants for the reaction CnMT + IZjELCnMTnI2 requires that a series of solutions be prepared in an inert solvent with the initial concentration of the absorbing iodine component held constant and the concentration of cyclo- polymethylenetetrazole varied over a ten to fifteen-fold range, always in large excess compared with the iodine concentration. B. Preparation of Solutions.——Stock solutions of the respective cyclopolymethylenetetrazoles were prepared by direct weighing of the compound into a volumetric flask and dilution to the calibration mark with 1,2—dichloroethane at the appropriate temperature. Stock iodine solutions were prepared by accurately weighing the solute into a volumetric flask and diluting to the calibration mark with l,2-dichloroethane at the appropriate temperature. C. Spectrophotometric Techniques.—~All measurements were made in stoppered one cm matched silica cells with a Beckman 130 spectrophotometer equipped with Beckman thermospacers to control the temperature of the sample compartment. The desired temperature was maintained by circulating water from a constant temperature bath (Waco refrigerated constant temperature bath, Wilkens-Anderson Company, 4525 W. Division Street, Chicago 51, Illinois) through the thermospacers. By controlling the temperature of the bath, the temperature of the cell compartment was regulated to within iO.l° for each of the following four temperatures: 5.0, 15.0, 25.0, and 35.0°. Dry nitrogen circulation through the cell compartment was essential during the absorbance measurements at the lower temperatures in order to remove moisture and to prevent cell fogging. The absorbances of each of the iodine solutions of a given cyclopolymethylenetetrazole were measured at several of the wavelengths near the complex absorption maximum. D. Spectrophotometric Measurements.——Solutions with known concentrations of iodine and of the respective cyclopolymethylenetetrazole were prepared at 5.0, 15.0, 25.0, and 35.0° 10.10 respectively. The iodine concentra— tions of these solutions were such (approximately 10—3 M) that the absorbances in the region of the complex absorption maximum were approximately 0.5. Measured amounts of these stock solutions were mixed in 25 ml volumetric flasks so ature i solutio absorpt compart attaine measure dichlor 66 as to obtain the desired final concentrations. The solutions were diluted to the mark with 1,2—dichloroethane which had previously been brought to the respective temper- ature in the constant temperature bath. Samples of these solutions were transferred to l—cm glass stoppered silica absorption cells and placed in the thermostatted cell compartment. After the temperature equilibrium was attained (~fifteen minutes), the absorbance values were measured at 430, 420, 410, and 400 mu. Pure l,2- dichloroethane was used as the reference solvent. B. Recovery Procedures for the Cyclopolymethylene— tetrazoles.—-The recovery techniques for all the cyclOpoly— methylenetetrazoles are essentially the same. Solutions containing the water soluble cyclopolymethylenetetrazoles were first treated with an aqueous sodium thiosulfate solution in order to reduce the iodine. The respective cyclopolymethylenetetrazole was then extracted from the aqueous phase with chloroform. The tetrazole recovered by evaporation of the chloroform was then purified further by recrystallization from an appropriate solvent. The cyclopolymethylenetetrazoles which were insoluble in water were dissolved in a one to one ethanol—water solvent solution before the above purification procedure was carried out. I Functic Benesi- \ calcule reactio where F. Calculation of Equilibrium Constants as a Function of the Temperature.--The formation constants were calculated using Ketelaar‘s (102) improvement of the Benesi-Hildebrand method where, in the case of an addition reaction between iodine and a cyclopolymethylenetetrazole 0 MT + I -——>C MTUI n 2 n 2 the formation constant is given by K ._ n _ 2 . l f _ __________ _ ________ .__ [CnMT][12] so — at CB where EI = the molar absorptivity of pure iodine in the 2 pure solvent. m H t the apparent molar absorptivity, calculated by dividing the total absorbance at the appropriate wavelength by the total iodine concentration. 8c = the molar absorptivity of the cyclopolymethylene— tetrazole—iodine complex. CE = equilibrium concentration of the cyclopoly— methylenetetrazole. If 0 total >> C total then C x C total 3 B I2 B B This equation can be rearranged to II + The or lg. the SI and mc respe< cyclo; sever; culah oomph Where AH° i is th of 10 0f ~A 68 The only unknown factors here are so andlgq aplotof -—e t I2 Ki? 6; should therefore produce a straight line. From the slope and intercept of this line, the formation constant and molar absorptivity of the complex can be determined respectively. Once the formation constants for the respective cyclopolymethylenetetrazole-iodine complexes are known at several different temperatures, they may be used to cal— culate the free energy, enthalpy, and entropy for the complexation reaction from the well known relationships AG° - RTan f AG° = AH° — TAS° 0 log K = —AH + AS f 2.303 RT 2.303 R where AG° is the standard free energy change in cal/mole, AH° is the standard enthalpy change in cal/mole, and AS° is the standard entropy change in cal/mole deg. A plot of log K lppl/T should give a straight line with a slope f of -AH°/2.303R and an intercept of AS°/2.303R. G. Treatment of the Spectrophotometric Data.——The respective formation constants were determined by using the spectrOphotometric data taken at each of four temperatures for the cyclopolymethylenetetrazole solutions in 1,2— dichloroethane. These data, given in Tables I through VI, CDC 36 tions 1 writte in the and l/ l 3 were t: l 1 i l l l ; a valu subtra \ proces I agreed 69 were treated using a regression analysis performed on a CDC 3600 computer with points over three standard devia- tions off the line being rejected. The program was written by W. J. McKinney and is listed in Appendix II. The iteration was performed on the Ketelaar equation in the following manner. The experimental values of l/CB and 1/et-eI were used in Ketelaar's equation to calculate 2 a value for the concentration of the complex which was subtracted from each value of CB to give a new array. The process was then repeated until successive values of Kf agreed within 0.1%. The iteration procedure for solving Ketelaar's equation offers a distinct advantage in the evaluation of formation constants from experimental data. The values converged rapidly and reproducibly at all wavelengths. This method made it possible to use lower concentrations of the donors to avoid the possibility of a change in the physical properties of the solvent in solutions with high concen— trations of the base. It is assumed that the activity coefficients of uncharged species equal the unity at the concentrations of iodine and cyclopolymethylenetetrazoles that were used (CnMT°I2 in l,2-Dichloroethane Solutions at 25°. Temp. 35»0° 25.0° 15.00 5.00 35.0° 25.00 14.80 5.10 35.00 25.0° 15.00 5.00 36.00 25.00 15.00 6.50 35.10 25.00 15.10 5.l° —l Kf 1.16:0.06 1.42:0.09 1.63:0.04 2.10:0.03 .05 .05 .05 .22 0 l--‘ owm POO—1:0.) 1+ H H- l+ 4‘:me a o 9 0000 .04 .04 .07 UJNNH 0 0 OD Jl‘\1|—'O\ O\U‘|CI)\O 1+ 1+ 1+ H- 0000 1.78:0.04 2.4410.05 3.14:0.08 4.0110.22 2.08:0.05 2.64:0.05 3.42:0.10 4.23:0.08 AG°(cal/mole) AS°(eu) Trimethylenetetrazole _ 91 —10.8 —215 —299 —454 Tetramethylenetetrazole —318 —15.2 -504 —644 -782 Pentamethylenetetrazole ~32l —l2.3 —461 -579 -686 Hexamethylenetetrazole —354 —14.2 —529 -655 -772 Heptamethylenetetrazole —446 -575 —704 -797 .-ll.9 AH(Kcal/mole) -5.0 —4.1 —4.1 I .Lt/1 co \) 1. .0 .1 .11 33 0.. P1 .1/\ a: log Kf 3-30 3-50 3.50 l/T x 103 Figure l.——The relations between log Kf and l/T for (l) trimethylenetetrazole, (2) pentamethylenetetrazole, (3) tetramethylenetetrazole (4) hexamethylenetetrazole, and (5) heptamethylenetetrazole. band a ferenc tetraz acid m lizati ion we not ex tetraz obtair 84 band at about 430t5mu. In order to eliminate the inter— ference from_the residual azide, crude cyclopolymethylene- tetrazole was treated with potassium permanganate in an acid.medium pricrto the final purification by reCrystal— lization. After this treatment,ru3evidence of the triiodide ion was found in the spectra of the respective complexes, not even when the concentrations of cyclopolymethylene- tetrazole were four times greater than those used to obtain the needed data. The solvent, l,2—dichloroethane, was selected because all the cyclopolymethylenetetrazoles were soluble in it at concentrations greater than one molar, and its vapor pressure at 35° was sufficiently low to allow convenient handling. In l,2—dichloroethane solutions, molecular iodine has an absorbance maximum at 495 mu. The cyclopolymethylenetetrazoles essentially do not absorb in this spectral region. In all cases the concentrations of tetrazole were kept below 0.5 M. With the increasing tetrazole/I2 ratio the absorption maximum gradually shifted from 495 to 430 i 5 mp. A series of each of the respective cyclopolymethylenetetrazole—iodine mixtures was run on the Cary model 14 spectrophotometer at room temperature to monitor the isosbestic point. The very slight shifting of the isosbestic point can be attributed to the changing character of the solvent as the concentration of the cyclopolymethylenetetrazole was incre signi spect increased (104).~ This shift,however, was too small to significantly influence the results. A typical set of spectral curves is illustrated in Figure 2. I. Complexation Studies of l,l'-Diphenyl—5,5'- bitetrazole.--Attempts to prepare solid complexes of l,l'—diphenyl—5,5'—bitetrazole with copper(II) perchlorate hexahydrate dehydrated with l,2—dimethoxypropane in various solvents were not successful. In each case the starting material was recovered unchanged. Therefore, the complexing ability of l,l-diphenyl-5,5'—bitetrazole in solution was studied spectroscopically by the method of continuous variations. The absorbance of solutions in which the total analytical concentration of bitetrazole and iodine in purified l,2—dichloroethane was 10_3 g were determined with a Beckman model DU spectrophotometer. The measurements were carried out at three different wave— lengths. The fact that the concentration of free iodine was not decreased by the addition of l,l-diphenyl—5,5'— bitetrazole indicated that complexation did not occur. The same experiment was repeated with copper(II) perchlorate hexahydrate (total analytical concentration 0.015 M) in purified nitromethane with the same results. .4 92 1 920 .<\/\/ . . . :1 AU 71 11 71 O P.16L {\I\ 08 0.7 06 0 0 O O ®OCGQLOWD< 86 0. 0. 0. 0. 0. Absorbance 0. 0. 0. 350 400 . 450 500 550 Wavelength—~millimicrons Figure 2.-—Absorption spectra of tetramethylenetetrazole— iodine system in l,2—dichloroethane solutions. — *4 C12“ 8.89 x 10 M CC.MT(M) (1) 0.00 (2) 0.042 (3) 0.084 (4) 0 126 (5) 0.168 (6) 0.210 (7) 0.252 (8) 0.294 (9) 0.337 (10) 0 379 (1) 0 425. XVI. scale was a 31176 cons1 recal Bidd: this junc1 e1e01 W 8188: sodi' appat trod. give: XVI. Potentiometric Studies. A. Instrumentation.--A Beckman model 76 expanded scale pH meter with a sensitivity of 10.3 millivolts was employed in the potentiometric determination of the silver-cyclopolymethylenetetrazole complex dissociation constants. The 0-200 mv full scale was extended by recalibration of the scale against the output of a Biddle-Gray portable potentiometer. B. Electrodes.——The indicating electrodes used in this study are listed below. A standard Beckman fiber junction calomel electrode was used as the reference electrode in all the potentiometric studies. 1. Corning NAS ll—18 Sodium Ion Electrode (Catalogue Number 476210): The Corning sodium ion electrode is a glass membrane electrode which exhibits high specificity to sodium and some selected univalent ions. The very high apparent selectivity toward silver ions allows this elec— trode to be used in making direct quantitative determinations of silver ions in solutions. The electrode reSponse is given as follows. ENE . 23M F log (48a+ + dd&+) where the 1 Tech] Tabll TABL 88 where M+ is any univalent cation. The values of 0 define the apparent selectivity referred to in the Corning Technical Information Bulletin EL - l4 and reproduced in Table VIII. TABLE VIII-—Approximate Ion Apparent Selectivity of the “Corning NAS ll—l8 Sodium Ion ElectrOde at.pH 7. WW Na+/K+ 1000 Ag+/Na+ 1500 Na+/Li+ 250 Na+/NHu+ 3000 Thus, sodium has an apparent selectivity over potassium ions at pH 7 of 1000 or d = 0.001 in the equation when M+ is a potassium ion. Furthermore, since the apparent selectivity at pH 7 of Ag+/K+ is 1.5 x 106, 0.1 and 0.4 M solutions of potassium nitrate were used as the inert electrolyte to maintain a constant ionic strength. It was important, therefore, to verify the high selectivity of the Corning NAS ll-l8 sodium ion electrode to silver ions over potassium ions. In Figure 3, the potentials are given for mixtures of silver and potassium ions as one is varied relative to the other. It can be seen that even a thousand fold excess of potassium over silver ions has very little effect on the response of the electrode toward silver ions. The cm i of w fuse clea for atic plat near 89 2. Silver Electrode on Platinum~Base, a. Construction and cleaning of silver electrode: The electrode base was made of platinum wire-0.040 to 0.045 cm in diameter fused into glass tubes, leaving about 1 cm of wire outside the tube. The end of the platinum wire is fused into a small ball. The finished electrode was cleaned prior to electroplating by dipping the electrode for five minutes in boiling concentrated nitric acid. b. The silver—plating solution: In the prepar- ation of the electrode, the salt used for the silver- plating solution was potassium dicyanoargentate(I). The nearly pure salt KAg(CN)2 was obtained as colorless crystals by the addition of an excess of silver cyanide (45 gm) to a boiling aqueous solution of potassium cyanide (20 grams of KCN dissolved in 90 ml of water) (105). After stirring the solution for about 30 minutes, the undissolved silver cyanide was filtered off, and the solution was cooled. The precipitated potassium dicyanoargentate(I) was purified further by a double recrystallization from water. The silver—plating solution was 0.05 M potassium dicyanoargentate(I) (10 g/l). Because cyanide ions tend to be absorbed in the silver—plated electrode and influence the potential (106), the cyanide concentration was reduced to a minimum by adding enough 0.1 M silver nitrate '"pl 1 _ _ _ _ 1. F .1 .1 .1. 1 .1. >E .HEmu _ D. A v TpAg = 2 0 i pK varied - A v) . u V T pAs=3 pK varied emf mv O —20 pK = l ‘40 pAg varied (ion) Figure 3.——Response of the corning NAS ll—18 sodium ion electrode to silver ions relative to potassium ions. solu prec H-ty and poro the cyan he s L thro plat read 91 solution to produce a faint cloud of silver cyanide. The precipitate was filtered off. 0. Electrolysis of the silver electrode: An H-type electrolysis cell (Figure 4a) in which the anode and cathode compartments are connected with a fine porosity glass frit was used to prevent contamination of the electroplating solution by the oxidation products in the anode reaction, principally precipitated silver cyanide and hydrocyanic acid. The platinum electrode to be silver plated was inserted into the cathode compartment through a hole drilled through a teflon stopper. A platinum anode was used since silver anodes polarized too readily (107). The source of current was a Heath constant current module attached to a Heath operational amplifier system (model EUW 19B). The platinum wire was silver plated by electrolysis for approximately 15 hours at a total current of 0.2 milliampere. A layer of about 1.12 x 1074 equiva— lent of silver was deposited on the platinum wire. After completion of the electrolysis, the electrode was washed in distilled water and then immersed in 6 M ammonium hydroxide for one hour to dissolve the outer layers of the silver plate and free as much of the absorbed cyanide ion as possible. Finally, the electrodes were washed for four hours in distilled water. The water was changed GVGI was NEEE empl has elec mini 92 every twenty minutes during the process. The electrode was stored in distilled water in subdued light. 3. Beckman Silver Billet Electrode (Catalogue Number 39261): The Beckman silver billet electrode was employed to measure the free silver ion. This electrode has_a large area of silver metal which provides more rapid electrode response, increases thermal stability, and minimizes polarization effects. The electrode was prepared by cleaning the metallic surface with a mild detergent and scouring power. The surface was rinsed in distilled water and then immersed in a beaker of stirred, distilled water at 50° for two hours, and then it was again repeatedly rinsed in cool, distilled water. Prior to immersion of the electrode in the solution to be measured, it was washed in distilled water and dried with tissue paper. Finally, the electrode was stored in distilled water in subdued light. C. The Cell Used in the Potentiometric Measurements.—- All of the potentiometric measurements were carried out in the cell shown in Figure Mb. To alleviate the errors caused by the precipitation of silver as a result of the potassium chloride leaking out of the calomel reference electrode, the experimental silver solution was separated from the reference compartment by a bridge filled with l M potassium nitrate. Prior to each measurement, the cell was cleaned and 93 ua.—-Silver Electroplating Cell cathode compartment anode compartment fine porosity glass frit platinum wire to be silver plated platinum electrode teflon stopper 0 o o o o HaCDQJOO‘SD 4b.——Silver Potentiometric Cell silver electrode half cell reference electrode half cell $‘lA/2O joint fine poroSity glass frit electrolyle chamber calomel electrode teflon stopcock respective silver electrode teflon stopper 0 a o HWTW w(no.ocrm er plated mll 4a. Silver electroplating cell. Mb. Silver potentiometric cell. rims hydr thro cell l l ::: l l tami pot thr 95 rinsed with distilled water. Then 50 ml of l2.M ammonium hydroxide followed by 200 ml of distilled water was passed through the frits of the electrolyte compartment. The cell was prepared for a potentiometric measurement by passing 25 ml of acetone through the frits followed by a dry air stream to eliminate the bulk of residual acetone and drying for two hours in an oven at 110°. D. Potential Measurements.—-To insure minimum con— tamination of the silver solution under investigation by the reference electrode solution, the following procedure was used. Fifty milliliters of each silver solution was measured into the silver electrode half cell; and its level was adjusted so that it was at least l/2" higher than the level of the l M potassium nitrate in the reference electrode half cell. The equilibrium potential usually stabilized after ten minutes and if, after this period, three successive potential measurements taken at five minute intervals corresponded to within 0.5 mv, the mean value was recorded. The liquid junction potential is included in the fixed "standard potential" of the reference electrode. It has been assumed that the liquid junction potential and the potential of the reference electrode remain constant throughout the measurements. ever, in t conc obta meas elec cali solu nitr: yiel< 96 A variation of i 0.3 mv was found to be inherent in every potential reading listed. This caused an uncertainty in.the pKi values of i 0.02 pKi units. E. Response of Respective Electrodes.——To measure the concentration of free silver ions, a calibration curve was obtained by varying the concentration of silver ions and measuring the potential of the respective silver indicating electrode versus the reference electrode. Table IXlists the data used to form the working calibration curves of each of the respective electrodes for solutions of silver nitrate in 0.1 and 0.4 M potassium nitrate. In all cases the potentiometric measurements yielded a straight line plot of emf versus the silver ion concentration. The slope of the line was 0.059 i °002 as predicted by the Nernst equation. The measurements were carried out over a pAg range of 2 to 5. Figures 5 and 6 depict the respective working calibration curves. F° Calculations of the Instability Constants.-— The results of instability measurements on the 2:1 cyclopolymethylenetetrazo1e-si1ver(I) nitrate complexes have been calculated on the basis of the following equation. + + Ag(CnMT)2 :;:?Ag + 2CnMT and the instability constant for the complex is given by [V TABI 97 TABLE IX—-Silver Nitrate Working Calibration Curves for the Respective Silver Electrodes. W Silver Molar Electrode Beckman Silver Corning NAS Concentration on Billet 11-18 Sodium of Silver Ion Platinum Electrode Base x10)1l mv mv mv a. 0.1 M Potassium Nitrate as the inert electrolyte 100 UAl.3 433.0 +92.5 50 423.0 415.1 +72.0 10 385.0 374.3 +31.0 5 368.5 357.0 + 7.5 1 325.5 314.0 —28.3 0.5 304.1 300.5 —44.0 0.1 ——- -__ -66.0 0.05 ——— ——— —86.0 b. 0.A M Potassium Nitrate as the inert electrolyte 100 431.2 433.0 +91.5 50 414.0 415.1 +71.2 10 377.1 372.2 +31.5 5 361.9 356.1 + 8.5 1 317.8 318.5 -30.0 0.5 301.0 299.8 -43.3 0.1 ——— ——— -66.2 0.05 ——— ——— ——- 100 460 80 440 60 420 40 400 20 380 :> s a 0 360 s (D —20 340 —40 320 —60 300 -80 280 260 —100 Figure 5.——Si1ver nitrate working calibration curves 0.1 M aqueous potassium nitrate solutions. (A) Corning NAS 11—18 sodium ion electrode (left scale); (B) Silver plated on platinum electrode (right scale); (C) Beckman silver billet electrode (right scale). emf mv 99 100 460 80 440 60 420 40 400 20 380 E c. O 360 s (D -20 340 ‘40 320 —60 300 —80 280 —100 260 Figure 6.—-Si1ver nitrate working calibration curves 0.4 M aqueous potassium nitrate. (A) Corning NAS 11—13 sodium ion electrode (left scale); (B) Silver plated on platinum electrode (right scale); (C) Beck— man silver billet electrode (right scale). emf mv wheJ COH cie sam Spe Equ Whe 100 2 f + f C MT n [42+] [CnMTJ2 Ag K. — 1 o [Ag(chT)2+1 ng(CnMT)2 where + [Ag 1 = equilibrium concentration of free silver ion ll equilibrium concentration of free cyclopoly— [CnMT] methylenetetrazole [Ag(CnMT)2+] = equilibrium concentration of the respective cyclopolymethylenetetrazole- silver(I) complex ng+, fchT, and ng(CnMT)2+ = the activity coeffi— cients for the respec- tive species The instability constant equation is derived from consideration of the equilibrium in aqueous solutions and is simplified by the assumption that the activity coeffi— cients of ions of the same charge are approximately the same at any given ionic strength while those of uncharged species equal unity. From the mass balance relationships the following equations are obtained. [CA5]t = £4g+1 + [Ag+1 + [Ag2+1 [0 = [chT] + [Ag(CnMT)+] + 2[Ag(CnMT)2+l C MTJt n where [C ] = the total analytical concentration of silver Ag+ W aSSL' .l_. 9 Ti 3 it_Tt .. w .. LL ,1,. 1 'r_-a~ ; 7:7. , 32‘: 101 [CC nMTJt = the total analytical concentration of the respective cyclopolymethylenetetrazole [.Ag(CnMT)+ ]— ‘ the 1:1 cyclopolymethylenetetrazole— silver(I) complex If [C >> [C +]t then concentration of the 1:1 ChMTJt Ag cyclopolymethylene-silver(I) complex in solution is assumed to be small and may be neglected. Therefore, the instability constant expression becomes [Ag*1 (ICC MTlt _ 2ECAg+lt - 2£Ag+1)2 n K.= _ l [CAg+l £4g+1 . + The overall formation constants of the reaction Ag + 2 CnMT ;: Ag(CnMT)2+ was then calculated by taking the reciprocal of the instability constant. The data used to calculated the respective insta— bility constants of the various cyclopolymethylenetetrazoles are listed in Tables X and XI. XVII. Preparation and Characterization of Transition Metal Complexes with 1 ,3- bis(5~ tetrazoly15-p- ropane and l H—bis(5— tetrazolyliwp—butane A. Purification of the bitetrazoles.—~The author is indebted to Mr. T. C. Wehman of this laboratory for samples of 1,3—bis(5—tetrazolyl)=Q-propane and 1,M-bis(5— tetrazolyl)—M—butane (hereafter abbreviated PBT and BBT respectively). The bitetrazoles (hereafter abbreviated 102 TABLE X.—-Experimenta1 Data from the Potentiometric Studies in 0.1 M Potassium Nitrate Solutions at 25°. ’ W +, E1ectrode* ' pK x10“, x102 mv X10” x10)4 x10'3 f ‘ wTrimethylenetetrazole Na 100.2 8.71 48.2 18.3 7.48 1.34 -3.13 Na 75.1 9.10 38.0 10.5 8.87 1.13 ~3.05 AgB 100.2 8.71 391.0 . 19.7 9.75 1.03 -3.01 AgB 75.1 9.10 377.5 11.2 9.53 1.05 -3.02 AgP 100.2 8.71 401.5 19.9 9.86 1.01 -3.00 AgP 75.1 9.10 388.3 ‘ 11.8 10.01 0.990 -2.99 Tetramethylenetetrazole Na 109.4 11.06 31.1 9.9 7.49 1.34 -3.13 Na 60.5 6.50 44.7 14.4 7.81 1.28 -3.11 AgB 109.4 11.06 374.0 10.2 7.73 1.29 -3.11 AgB 60.5 6.50 384.5 16.1 8.95 1.12 -3.05 AgP 7 109.4 11.06 386.7 10.9 8.29 1.21 -3.08 AgP 60.5 6.50 385.4 16.4 9.16 1.09 -3.04 Pentamethylenetetrazole Na ' 103.0 ' 11.58 28.0 9.5 8.84 1.13 -3.05 Na 82.5 10.15 30.0 8.2 7.67 1.30 —3.11 AgB 103.0 11.58 375.0 10.4 9.74 1.03 -3.01 AgB 82.5 10.15 371.0 ' 8.7 8.17 1.22 —3.08 AgP 103.0 11.58 385.3 10.3 9.64 1.04 —3.02 AgP 82.5 10.15 380.5 8.5 7.97 1.26 -3.10 Hexamethylenetetrazole Na 105.0 6.72 69.2 38.1 8.48 1.18 -3.07 Na 121.7 12.05 33.0 10.3 8.19 1.22 -3.09 AgB 105.0 6.72 409.2 39.1 8.74 1.14 ~3.06 AgB 121.7 12.05 377.5 11.2 8.94 1.12 —3.05 AgP 105.0 6.72 418.0 39.5 8.85 1.13 -3.05 AgP 121.7 12.05 387.5 11.6 9.28 1.08 —3.03 Heptamethylenetetrazole Na 48.1 3.15 69.1 38.0 7.69 1.30 —3.11, Na 30.4 3.31 47.0 17.4 7.45 1.34 —3.13 AgB 48.1 3.15 409.3 39.3 8.80 1.14 -3.06 AgB 30.4 3.31 388.5 17.7 7.72 1.30 —3.11 AgP 48.1 3.15 417.8 39.4 8.90 1.12 —3.05 AgP 30.4 3.31 398.0 17.5 7.54 1.33 -3.12 * Na = Corning NAS 11—18 sodium ion electrode. AgB = Beckman Silver Billet electrode. AgP = Silver plated on platinum base electrode. 103 TABLE XI.--Experimental Data from the Potentiometric Studies in 0.4 M ’ Potassium Nitrate Solutions at 25°. m . + _ * [CAg+]t [chMT]t emf [Ag 1 1 f Electrode pK ~ x101l x102 mv x10” x10” x10 3 f Trimethylenetetrazole Na 104.3 8.60 44.5 ‘21.0 9.36 1.07 -3.03 Na 70.7.44 33.0 13.1 7.68 1.30 —3.11 Na 82. 4 10.11 24.0 9.2 8. 41 1.19 -3.08 AgB 104. 3 8.60 395.0 23.5 10. 64 0.940 -2.97 AgB 70.0 7.44 384.0 15.2 9 13 1.11 «3.05 AgB 82. 4 10.11 375.5 11.0 10.05 0.995 —3 00 Ag? 104. 3 8.60 400.5 25.0 11.40 0.877 —2. 94 AgP 70.0 7.44' 389.8 16.1 9.77 1.02 -3. 01 Ag? 82.4 10.11 382.2 12.1 11.63 0.860 -2. 93 Tetramethylenetetrazole Na 114.2 8.86 43.5 20.0 8.07 1.24 —3.09 Na 56.4 5.76 39.6 17.1 8.01 1.25 -3.10 Na 27.4 5.85 15.0 6.3 8.12 1.23 -3.09' AgB 114. 2 8.86 394.5 23.0 9.44 1.06 -3.03 AgB 56.4 5.76 388.0 18.0 8.56 1.17 -3.07 AgB 27.4 5.85 363.8 7.1 9.31 1.07 —3. 03 AgP 114. 2 8.86 399.1 23.6 9.71 1.03 —3. 01 AgP 56.4 5.76 393.4 18.7 8.99 1.11 —3. 05 AgP 27.4 5.85 370.0 7.5 10.00 1.00 —3. 00 Pentamethylenetetrazole Na 120. 6 12.19 27.2 10.4 8.64 1.16 -3.07 Na 81. 3 9.07 25.8 9.7 7.11 1.41 —3. 15 Na 20. 5 5.40 10.7 5.3 8.32 1.20 —3. 08 AgB 120. 6 12.19 378.0 12.2 10.23 0.978 —2. 99 AgB 81.3 9.07 376.2 11.3 8.41 1.19 -3. 08 AgB 20.5 5.40 368.0 , 6.8 11.70 0.855 -2. 93 Ag? 120. 6 12.19 384.0 13.0 10.95 0.913 -2. 96 Ag? 81. 3' 9.07 380.0 10.9 8.08 1.24 -3. 09 AgP 20. 5 5.40 367.5 6.7 11.45 0.873 -2.94 Hexamethylenetetrazole Na 119.5 6.98 66.0 50.0 9.27 1.08 -3.03 Na 51. 7 3.98 54.0 31.1 8.10 1.23 —3. 09 Na 68. 4 6.58 41.4 18.4 8.63 1.16 —3. 07 AgB 119. 5 6.98 417.0 55.6 10.52 0.951 —2.98 A38 51. 7 3.98 407.1 37.1 12.31 0.812 -2. 91 AgB 68.4 6.58 393.5 22.0 10.85 0 922 —2. 97 AgP 119.5 6.98 420.2 54.5 10.30 0.971 —2.99 AgP 51.7 3.98 409.1 35.3 10.81 0.925 —2.97 AgP 68.4” 6.58 396.8 21.5 10.48 0.954 —2.98 Heptamethylenetetrazole Na 64.1 3.66 60.0 39.2 4.00 2.50 -3.40 Na 60.2 3.54 57.0 35.0 3.72 2.69 —3.43 Na 41.7 3.28 43.8 20.3 4.47 2.24 —3.35 A38 64.1 3.66 412.0 45.3 5.22 1.92 —3.28 AgB 60.2 3.54 409.1 40.2 4.72 2.12 -3.33 A38 41.7 3.28 395.3 23.7 5.12 1.95 ~3.29 AgP 64.1 3.66 414.3 43.1 4.72 2.12 —3.33 AgP 60.2 3.54 419.2 38.4 4.33 2.31 —3.36 AgP 41.7 3.28 397.6 22.1 4.53 2.21 —3.34 * Na = Corning NAS 11—18 sodium ion electrode. AgB - Beckman Silver Billet electrode. A3? = Silver plated on platinum base electrode. .U .1 DD abSI app' n-p: in: cal tet pur pot zol wei tet the and 104 Bitz) were purified by recrystallization from boiling absolute alcohol. The infrared spectra of these tetrazoles appear in Appendix I as Figures 52 and 53 respectively. B. Potentiometric Results.——l,3—bis(5-tetrazolyl)- n—propane and 1,4—bis(5—tetrazoly1)-nfbutane were titrated in methanol with a standard glass electrode and sleeve calomel electrode as the reference. The titrant was tetrabutylammonium hydroxide in methanol, standardized with purified benzoic acid° Since only one equivalence point is noted in the potentiometric titration curves of the respective bitetra— zoles (Figure 7). it is apparent that acidity constants~ of the two protons on the bitetrazole molecule are within 2 pK units of each other. The calculated equivalent weights of l,3—bis(5—tetrazoly1)—nfpropane and 1,4-bis(5— tetrazoly1)~2-butane are 91 and 97 respectively. The theoretical equivalent weights for the respective propane and butane bitetrazoles are 90 and 99. Although the overall dissociation constants of these bitetrazoles have not been determined, it appears that they should be of the same order of magnitude as the acidic proton of tetrazole, i.e., Ka = 1.3 x 10.5 (108). C. Preparation of the Respective Transition Metal Complexes.——The complexes were prepared by the following procedures. The respective bitetrazole (0.02 mole) was 105 .Hocmgumfi CH mUMxozozg SoficoEEmfihpSQMmep sows mcmpzolmlflflafiomospoplmvmflhlq.finm use ocmoosd Icnfiazaomwppmplmvmflolm.a .< mo mo>szo cowpmppwp , ocmsoap no as mm om ma OH ) .k wsp®E0flpCop0Q oSBI1.N oaswflm M... d dr< tr: tr: pm pm f1: .401 0112 00] Th: 5e} 8X( 80 106 dissolved in 50 ml of absolute ethanol to which was added dropwise an absolute ethanol solution of the hydrated- transition metal perchlorate (0.01 mole). The respective transition metal complex of either l,3-bis(5—tetrazolyl)-n— propane or 1,4-bis(5-tetrazolyl)—ngbutane immediately precipitated out of solution. The complexes were then filtered, extracted with ethanol for approximately 12 hours in a Soxhlet extractor in order to remove any unreacted bitetrazole and dried at 110°. The cobalt(II), nickel(II), copper(II), and Zinc(II) complexes of propane and butane bitetrazole were prepared. They are all nonhydroscopic microcrystalline, shock sensitive powders which have decomposition temperatures in excess of 250° and are insoluble in polar and nonpolar solvents. The results of the elemental analyses performed on these complexes are listed in Table XIIand indicate that the most probable composition is MII(BitZ). The results of the analyses are rather poor, indicating a moderate degree of contamination. D. Magnetic Susceptibilities._-The magnetic moments of the complexes were determined by the Gouy method pre— viously described (13) and are listed in Table XIII. The magnetic moments obtained were much lower than the expected Values which again indicates the impurity of the complexes. 107 mm.mm m0.m 0m.mm III 00.00 00.0 00.00 00.00 00.00 00.0 00 00 00.00 00.000 0000000 00.00 00.0 00 00 00 00 00 00 00.0 00.00 00 00 00.000 0000000 00.00 00.0 00.00 00.00 00 00 00.0 00.00 00.00 00.000 0000000 00 00 00.0 00 00 --- 00.00 00.0 00 00 --- 00.000 000000-0-. Aamaommppmplmvmflhlq H 00 00 00.0 00.00 00 00 00.00 00.0 00 00 00 00 00 000 0000000 00.00 00.0 00 00 00 00 00 00 00.0 00 00 00.00 00.000 0000002 00.00 00.0 00.00 00.00 00.00 00.0 00.00 00.00 00.000 0000000 00.00 00.0 00.00 In: 00.00 00.0 00.00 :1: 00.000 mcmgo0guml ZR ER 0& 20m 20 0 0 0 |II||I|IIthlIIMWWIIIIIWWIIIIIWWI 03 00E Q00pflmomEoo 00000000 0000 oczom 0000050000 EEK: .oCMpSQLmlflamflommppopnmVmHmnzna I I 0 . 030 mswaopglc10000000ppmplmv00m 0 0 0003 000000000 00002 0000000000 0000 00 00000000 000000000-0000 00000 108 TABLE XIII—Calculated Magnetic Moments and unpaired Spins of :ome Transition Metal Comfilexes with l,3—Bis(5- Tetrazolyl)—nypropane and l 0 Bis(5-tetrazolyl)-n—butane.. } Most X ngggggtion Exg3 0:2r. ogs. ‘" ung x10 XlO3 Co(PBT) 5.36584 5.46479 2.77 3.64 Ni(PBT) 1.60913 1.71015 1.27 2.03 Cu(PBT) 0.96518 1.06334 0.89 1.62 Zn(PBT) 0.08945 0.00939 0.01 0.15 Co(BBT) 5.45371 5.57384 2.81 3.68 Ni(BBT) 1.53605 1.64940 1.23 _2.01 Cu(BBT) 0.45781 0.57036 0.54 1.18 Zn(BBT) 0.09399 0.01935 0.03 0.20 E ground 1 into 0.! attempt compleXt crystal diffraci was nott 110). ( of theiJ Appendi; Chlorim 109 E. X—Ray Powder Pattern.—-The samples were first ground to the consistency of fine powder and then packed into 0.5 mm thin-walled glass capillary tubes. The attempt to cempare the crystal character of the above complexes was unsuccessful because the respective complex crystal size was too small to permit satisfactory powder diffraction diagrams to be obtained. This same condition was noted for other types of tetrazole complexes (109, 110). Grinding these complexes is not recommended because of their shock sensitive nature, F. Spectral'Measurements. 1. Infrared Spectra: The spectra in the 5000—680 cm‘ region were obtained with the samples dispersed in Nujol. The infrared spectra of the transition metal complexes of the type MII(PBT) were essentially identical as were the spectra of the MII(BBT) type complexes. A representative spectrum of each type of complex appears in Appendix I as Figures 54 and 55. The strong perchlorate band at ~llOO cm“1 was absent in all of the spectra indi- cating that the complexes do not contain the perchlorate group as the counter ion. However, one obtains a positive test for the perchlorate ion when tetraphenylarsonium chloride is used, indicating the presence of some occluded perchlorate ion. _——_—_——‘ variatic tion of tive bi1 8). Ma: 0.5, whf copper(I 1,4-bis measurex and a s1 LS. molt due to ‘ reSpect: 110 2. Visible and Near Infrared Spectra of the Copper— Bitetrazole Complexes in Ethanol. a. Method of continuous variation; The bitetrazole complexes were investigated with the method of continuous variation (III) in which the total analytical concentra— tion of Copper(II) perchlorate hexahydrate and the respec— 3 tive bitetrazole was 2.0 x 10' in purified ethanol (Figure 8). Maxima were obtained at a ligand mole fraction of 0.5, which clearly shows that the stoichiometry of the copper(II) complexes of 1,3—bis(5—tetrazoly1)—nrpropane and 1,4—bis(5-tetrazolyl)—n:butane is given by Cu(Bitz). The measurements were carried out at four different wavelengths, and a small shift of the maxima in the plot of absorbance Ks. mole fraction of ligand was noted. This shift may be due to the formation of a colloidal precipitate of the respective complex. b. Mole—ratio study; A mole—ratio study of the 1,3-bis(5—tetrazolyl)-nfpropane and 1,4—bis(5—tetrazolyl)- Q—butane with copper(II) perchlorate hexahydrate in puri— fied ethanol is shown in Figure 9. These data confirm the results obtained with the continuous variations study. The formation constants of the complexes were calculated from spectrophotometric data (112) and the values varied from 6.63 to 14.90 x 10Dr depending on the wavelength at which the measurements were obtained. The relatively large variation in the results is probably due to 0.300 0.250 0.200 0.150 Excess Absorbance 0.100 0~050 Excess Absorbance 111 0.300 0.250 0.200 0.150 0.100 0.050 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Mole Fraction OfLigand Figure 8.——A continuous variations study at 680 m0 of copper (II) perchlorate hexahydrate with A,l,3-bis(5— tetrazoly1)—n—propane and 8,1,4—bis(S-tetrazoly1)—n-butane in purified Ethanol. The total analytical concentration of copper (11) ion and ligand is 2.0 x 10‘3 4. 112 .as osm palaocmcpm ncflafl . . Aaaaommspcplmvmflnun H nmvmapnm.a.m eca ccapspuen mpMMOHzoch AHHV amggoo E m|0 h+NSOQ\mN 0.m L a x fl 00 >030m oflp pfimw 0.m 0. 6L fimHOElI H omfi.0 00m.0 0mm.0 00m.0 omm.0 003.0 acueqaosqv a colloi the Tynd 4 x 10‘“ methanol a 001101 of the t and 11) photomet The absc expectec hedral C 113 a colloidal precipitate observed-in the solution by the Tyndall effect. Complex concentrations as low as 4 x 10—4 M were tried in various solvents such as' methanol, ethanol, n—butanol and nitromethane; hoWever, a colloidal precipitate of the complex always formed. G. Reflectance Spectra.--The electronic spectra of the transition metal bitetrazole complexes (Figures 10 and 11) were recorded on a Beckman model DK-2, spectro— photometer equipped with a diffuse reflectance attachment. The absorbance values are given in Table XIV. TABLE XIVr—Electronic Absorption Spectra (cm-l) of the Transition Metal Complexes of l,3—Bis(5—tetrazclyl)- n—propane and 1,4-Bis(5—tetrazoly1)-n—butane. Complex Vmax Ni(BBT) 10,000, 18,200, 28,100 Ni(PBT) 10,200, 18,200, 28,600 Co(BBT) 9,530, 21,100 Co(PBT) 9,530, 20,800 Cu(BBT) 13,500 Cu(PBT) 14,700 ——————_—————————-—-———————————_"— The reflectance spectra are essentially those expected for the respective transition metal ions in octa— hedral configurations, and the absorption maxima appear 114 lmlfiazaoamnucplmvmwbl .mcmmoaq ‘ 1 q. «a nxglufl mnfl spas mmxcfidsoo mpmpoagocoo AHHV smocoomov.es cnmmmW pamnooflmv .AHHV meOHc A<0 o>wpomgwms on» 00 mspomam cocmuoma0mml| 0H . : wCOLOflEHHHHE CH cpmcmflc>w3 oomH oooH 000 00w 000 0mm oom om: eoueqaosqv 3A13PTQH :mnAHzHOch pamcoo Amv ooma 000a a 6.0-mvmfls- .cCMpsn ace .AHHV .HH magmas eouequosqv eAtgeteg to be 1 conflic spectrc salt-11 visuali hedral stoichi this wc XVIII. tetraz: \ enetetI \ A solut nitrate taining 116 to be independent of the ligand. These results are in conflict with the proposed elemental analyses and the Spectrophotometric study which indicates a one to one salt-like complex. Therefore, it is difficult to visualize the central transition metal ion in an octa- hedral environment. Because of the obviously non— stoichiometric and explosive nature of these complexes, this work was discontinued. XVIII. Pre aration of Bis(trimeth lene- tetrazoleSsilveriIS and Bisitetrameth 1- enetetrazoleSSilverZIS Nitrate A. Bis(trimethylenetetrazole)silver(I) Nitrate.-- A solution containing 8.50 grams (0.05 mole) of silver(I) nitrate in 100 m1 of water was added to a solution con— taining 12 grams of trimethylenetetrazole (0.11 mole) in 100 ml of water. The solution was concentrated to a very viscous liquid by air evaporation in a hood over a period of two weeks. Crystals were very difficult to obtain, and the covered syrup residue was allowed to remain in the hood. After approximately thirty days crystals appeared in the syrup. They were allowed to grow for an additional two weeks until they were approximately 3 mm.X15 mm. The larger single crystals were then removed from the syrup residue and quickly washed with cold water to remove the remaining syrup residue. The crystals were then dried with tissue paper. The melting point of the complex was 58-600. lizatio cessful removed as Figu mac This 00 tetrazo for his procedu Which h Of this 117 58—60°. All efforts to purify the complex by recrystal- lization with seeding from various solvents were unsuc- cessful because syrup resulted when the solvent was removed. The infrared spectrum appears in Appendix I as Figure 56. c, 24.63%; H, 3.10%; Anal. Calcd fdrAg(C3MT)2NO3: N, 32.31%. Found: 0, 23.80%; H, 2.90%; N, 31.60%. B. Bis(tetramethylenetetrazole)silver(I) Nitrate.—- This complex was prepared from 13 grams of tetramethylene— tetrazole (0.105 mole) in the manner previously described for bis(trimethylenetetrazole)silver(I) nitrate. The same procedure was followed to obtain and purify the complex which has a melting point of 108°. The infrared spectrum of this complex appears in Appendix I as Figure 57. RESULTS AND DISCUSSION I.~ The Mechanism of the Intramolecular Rearrangement of w-Azidoalkanenitriles in the Pre aration of Tri- and Tetramethylenetetrazole Von Kereszty's work describes the acid-catalyzed cyclization of 4—azidobutyronitri1e and 5-azidova1eronitrile to form the respective bicyclictetrazoles (29). The synthesis takes place according to the following equation. CE-N C;N N / (CH2)I’1 + NaN3 ____> (CH2 n 2m (CH2) 1 N \ \ CHél I‘S.. 1’1 / Cl N3 3 VN \N where n = 3, 4 The following mechanism involving acid—catalyzed intramolecular condensation is proposed. In the highly acidic Chlorosulfonic acid—chloroform mixture, the nitrile nitrogen is protonated (I) causing a polarization of the nitrile triple bond and the 118 CVClOpc 119 shifting of a pair of electrons toward the protonated nitrogen, leaving the nitrile carbon electron deficient (II). The next step involves a nucleophilic attack of the electron deficient carbon atom by the electron rich nitro- gen attached to the methylene chain (III). /C = RIB-H /C — N—H (CH ) —————4> (CH “‘0‘ 5+ N - N E N: (II) (III) The tetrazole ring closure could take place when a pair of electrons are shifted from the azide triple bond to the electron deficient center nitrogen (IV). This shift causes the terminal azide nitrogen to be electron deficient, and ring closure may take place through a nucleophilic attack by the nitrogen atom which is attached to the hydrogen (V) to form the respective protonated 0 H /// _ _ :;:N ‘///////C = N—H ///////C — N H ///////C \\\ (CH2)n 6+ —>(CH2)n \5+—> (CH )n N + H69 / 2 // (VI) (VII) II. The Mechanism of the Schmidt Reaction in the Preparation of the 1 5-C 010 01 meth lene— tetraz01es The stoichiometry of the preparation of tetrazoles with hydrazoic acid, present in great excess in a highly acidic medium, is represented by the following equation. A H230, bcélk (CH2)n C=O + 2HN V 3 W VIN” By analogy with the mechanisms which have been proposed for the Schmidt reaction, it is possible to postulate the following mechanism for the above reaction. The concentrated sulfuric acid transforms the hydrazoic acid(I) to its active form (II), and, at the same time, the carbonyl oxygen becomes protonated, thus converting the cyclic ketone(III) into a hydroxycarbonium ion (IV). -~—,"‘ “firs, , ,, ”,4”, -:r—-——~ -2, , fi—z ex, 7. 7.: _~. ,_ 121 (I) (II) 5+ .9 9H r A H230, A A _—> ——> (III) (IV) The general mechanism for the reaction appears to be a nucleophilic attack on the cyclic hydroxycarbonium ion (IV) by the activated hydrazoic acid molecule to form a transitory intermediate (V). H 6+ OH HO N—NEN A __. as 69 + N=NEN _ H (IV) (V) The intermediate compound loses one mole of nitrogen and undergoes a Beckmann type rearrangement which results in ring expansion and the formation of a second hydroxy- carbonium ion (VI). illiiii,il;: Beckma which mediat a prot (VIII) (VI) 122 H + H N-NEN O N :6 O\ A + N . ‘/EB\N—H , I 2 I (V) (VI) A second nucleophilic attack of hydrazoic acid on the Beckmann transient adduct (VI) produces intermediate (VII) which loses a mole of water to give two possible inter— mediates. Each of these, on ring closure and ejection of a proton, yields the respective cyclopolymethylenetetrazole (VIII). 123 N H II|\T// §§N N /.N\\\\N + / \1‘3'3; \“gf/ ; ‘ l -H+ -fi{ \ N/ N ’/ || \\ N '/\N/ - l (VIII) III. Evaluation of the Nuclear Magnetic Resonance Infrared and Mass Spectra of the VariouS'l 5—Cyclo 01 met ylene— tetrazoles A. Nuclear Magnetic Resonance Spectra.--The proton magnetic resonance spectra of the cyclopolymethylene— tetrazoles are essentially the same with the exception of trimethylenetetrazole which shows a more complex spectra due to spin—spin splitting. A typical spectrum of the remaining cyclopolymethylenetetrazoles has two triplets of unit area at about 5.5 and 6.9 T respectively and a third or fourth complex peak, depending on the cyclopoly— methylenetetrazole, at about 8.0 and 8.6 T respectively which are integer values of the first two peaks. The assignments of the cyclopolymethylenetetrazole resonance peaks were based on the nmr of 1-methy1, 5-meth peak I C-CH at 7.4 tetraz the N- 7.42 T cyclop proton 124 5—methy1, and 1,5—dimethyltetrazole. The N—CH3 resonance peak for 1-methyltetrazole was observed at 5.7 T, and the C—CH3 resonance peak for 5-methyltetrazole was observed at 7.4 T. Proton nmr spectra obtained for 1,5—dimethy1- tetrazole showed two sharp peaks in the ratio of 1:1 with the N—CH3 resonance at 5.95 T and the C—CH3 resonance at 7.42 T (113). Therefore, the 5.5 T triplet of each cyclopolymethylenetetrazole was assigned to the methylene protons adjacent to the 1—nitrogen of the tetrazole ring and the 6.9 T triplet to the methylene protons adjacent to the 5-carbon atom. The single peak that was obtained in the spectra of tetra— and pentamethylenetetrazole at about 8.0 T arose from the remainder of the methylene protons. As the number of methylene groups in the ring were increased beyond five, two bands became discerible in the regions of 7.9 and 8.75 T. The resonance peak at about 7.9 T with twice the unit area was due to the almost equivalent methylene protons adjacent to the methylene groups which gave rise to the two triplets. The resonance peak in the 8.6 T region was due to the remaining methylene protons. Since these protons are most distant from the tetrazole ring, their chemical shift approached the position expected for methylene protons of a hydrocarbon. The nmr spectra of the respective 6,6-dihalocyclopoly— methylenetetrazoles show essentially the same patterns with complex triplets in the regions of 5.3 and 7.0 T which are assigr and 5- methyl rise t 8.0 I. 6,6-di 125 assigned to the methylene protons adjacent to the l—nitrogen and 5-carbon atoms respectively. The remainder of the methylene protons of each cyclopolymethylenetetrazole give rise to a very complex singlet in the region of 7.4 to 8.0 T. This singlet is split into two peaks in the case of 6,6-dichlorohexamethylenetetrazole as described above. B. Infrared Spectra.—-The infrared spectra of the various 1,5—cyclopolymethylenetetrazoles, 6,6—dihalccyclo— polymethylenetetrazoles, and bitetrazoles were determined in the 5000—670 cm'lregion. The absorption bands charac- teristic of the tetrazole ring were observed in all the compounds (55,56). The spectra of the various 1,5— cyclopolymethylenetetrazoles are very similar except for slight shifts and variance of intensities of some absorptions bands. The spectral features of the 1,5—cyclopolymethy1ene— tetrazoles ameretained in the corresponding 6,6—dihalo— cyc1opolymethylenetetrazoles butwith slight positional shifts and changes in the intensities of the absorption bands. A new band appears in the region of 760-780 cm”1 in the spectra of the 6,6—dichlorocyclopolymethylenetetrazoles which is attributed to the C—Cl stretching frequency. A direct correlation of the various tetrazole bands was not attempted because weaker bands may not be discern— ible in poorly defined spectra, and the inability of the spectrometer to resolve closely spaced absorptions must also be taken into account. patteI essent spondi of eac tive c respec or abs backgr o O l—l o < O n '1 0. Hun/J <<: (D I——‘ O *C) 126 C. MaSS’Spectra.--The mass spectra fragmentation patterns of the various cyclopolymethylenetetrazoles are eSsentially the same with the most common fragments corre— sponding to C2H5, CH2N, CHZNé, and N2. The relative abundance of each of these fragments varies and depends on the respec— tive cyclopolymethylenetetrazole. The parent peak of the respective cyc10polymethy1enetetrazole is either very weak or absent. All the spectra were corrected for instrument background. IV. Spectrophotometric Study of the Coordination Ability of the 1,5— Cyclopolymethylenetetrazoles The results obtained in the spectrophotometric part of this investigation are shown in Table VII. It has been noted previously that the donor properties of the cyclo— polymethylenetetrazoles are rather weak and the formation constant values for the iodine complexes in 1,2— dichloroethane at 25° ranged from 1.42 to 2.64 liter mole—l. The formation constant for the pentamethylenetetrazole— iodine complex was reported as 7.5 in a previous publica- tion (64). However, that work was done in carbon tetra— chloride solutions. Keefer and Andrews (114) determined that the formation constant of the benzene-iodine complex in carbon tetrachloride solutions at 25° was 1.55 liter mole—1. Therefore, toward iodine the donor properties of the tetrazole ring are of the same order of magnitude as those of the benzene ring. and di shown they 2 even i stants tetraz 127 A study of the charge—transfer complexes of mono— and disubstituted tetrazoles with w-electron acceptors has shown that, while such complexes do exist in solution, they are extremely unstable and are largely dissociated even in concentrated solutions (70). The formation con— stants of the benzene-tetracyanoethylene and pentamethylene— tetrazole-tetracyanoethylene complexes are comparable, but the formation constant of iodine monochloride with penta- methylenetetrazole is larger by three orders of magnitude than that of the benzene-iodine monochloride complex (64). Moreover, it has been recently shown that in the solid pentamethylenetetrazole—iodine monochloride complex the bonding occurs through one of the nitrogen atoms (71). Therefore, it appears that the tetrazole—iodine inter— action involves 0 type bonding. Under these conditions, the inductive effect of the polymethylene ring would not be too significant. The formation constants seem to increase with the increasing length of the hydrocarbon chain with the exception of pentamethylenetetrazole which does not fit into the series. This irregularity may be due to difference in the solvation of pentamethylene- tetrazole as compared with the other homologues since this compound is, by far, the most soluble of the series, both in water and in nonaqueous solvents. Physicochemical properties of other cyclopolymethylenetetrazoles are practf invesi the d5 VariOL photor bitetl Prepaz 128 practically unknown at this time and will have to be investigated more thoroughly before possible reasons for the discrepancy can be advanced. V. Spectrophotometric Study of the Coordination Ability of the Various Bitetrazoles The following studies include the preliminary spectro— photometric determinations of the complexing ability of bitetrazoles. A. 1,1"—Diphenyl—5,5'—bitetrazole.—-Continuous variation studies of the reaction of l,l'—dipheny1—5,5'— bitetrazole with copper(II) perchlorate in nitromethane or iodine in 1,2-dichloroethane indicate that no reaction occurred between the bitetrazole and the respective Lewis acid. These results suggest a deactivation of the coordi- nation ability of the tetrazole ring. Because solid complexes of 1,5-dia1kylasubstituted tetrazoles have been prepared (13), it would appear that the phenyl rings may be responsible for this deactivation. Transition metal complexes with 5-aryltetrazoles have been isolated as crystalline solids (51-53). However, analytical results and infrared spectra indicate that the 5—substituted tetrazoles coordinate as anions and not through the tetrazole ring electrons as must be the case in 1,5—dialkyl-substituted tetrazoles. crysta l-pher platir of the were 0 some c result comple i Condit i VETS?" 129 Gilbert and Brubaker (54) prepared the respective crystalline complexes of 1-methyl,.l-cyclohexyl, and l-phenyltetrazole with nickel(II), Zinc(II), and p1atinum(II) chlorides. Stability constant measurements of the 1-phenyltetrazole nickel complex in tetrahydrofuranv were calculated to be of the order of 10“. However, since some of the data were rejected, the authors feel that these results may not be significant. Nevertheless, since solid complexes of l-phenyltetrazole can be isolated, a sig- nificant interaction occurs between 1-phenyltetrazole and the transition metal ions in ethanol or tetrahydrofuran. In a later study Garber and Brubaker (56) prepared bis(1—methy1—5—tetrazolyl)nickel(II) and bis(l-cyclohexyl— 5—tetrazoly1)nicke1(II) complexes containing nickel-carbon bonding by reacting 1-substituted—5—tetrazo1yllithium intermediate prepared 33 situ in tetrahydrofuran with dichlorobis(triethylphosphine)nickel(II). When the same conditions were used to prepare the corresponding bis(l- phenyl—5-tetrazolyl)nickel(II) complex, the l-phenyl-5- tetrazolyllithium intermediate was recovered unchanged. It is clear that the coordination ability of 1,1'— diphenyl-5,5'—bitetrazole was deactivated. It is unlikely that the phenyl groups caused this deactivation because they tend to increase the Lewis basicity of the tetrazole rings. Also, complexes with l-phenyltetrazole have been prepared (54). A more satisfactory explanation is that with relat activ subst the n a ver; specti howeve vatior 130 with two tetrazole rings adjacent to each other, the relatively large iodine molecule is unable to approach the active coordination site of the tetrazole ring to form a ‘ substantial bond. Therefore, the complex formed between - i the respective Lewis acid and the bitetrazole may have i a very small formation constant (<1) and cannot be detected spectrophotometrically. A possibility also exists, however, that adjacent tetrazole rings may cause deacti— vation of both rings. B. d,w—Bis(5-tetrazolyl)-n—alkanes.—-Continuous variation and molar ratio studies of 1,3—bis(5—tetrazolyl)— g—propane and 1,4-bis(5—tetrazoly1)—E—butane in ethanol with copper(II)perchlorate hexahydrate indicate the existence of a 1:1 copper-bitetrazole complex in solution. Although the elemental analyses of the solid complexes are poor, they indicate that the most probable composition corresponds to the 1:1 transition metal-bitetrazole species. The reflectance spectra of the corresponding nickel(II), copper(II) and cobalt(II) bitetrazole complexes are those expected for the respective transition metal ions in an octahedral environment. These results are in an apparent conflict with the proposed elemental analyses and the spectrophotometric study which indicates the formation of a one to one salt—like complex. A possible explanation seems to be that in View of their relatively acid protons, these 5-subs as ani charac occasi 131 these bitetrazoles behave in a manner similar to the 5-substituted tetrazoles (51-53) and are coordinated as anions. VI. Potentiometric Study of the Coordination\Abilit of the l 5— Cyclopolymethylenetetrazoles The silver(I) ion is usually considered to have a characteristic coordination number of two although occasionally complexes with coordination numbers of three and four have been reported (115‘117). Usually, where successive stability constants have been determined, the first two monodentate ligands are strongly attached to the silver ion. In the few cases where additional ligand molecules are taken up by the silver ion, the ligand— metal bonds are quite weak. In the case of the cyclo- polymethylenetetrazoles, the complex formation appears to be complete after two ligand molecules are added to the silver ion. Bis(pentamethylenetetrazole)silver(l) nitrate was isolated by Popov and Holm (20) and bis(trimethylene— tetrazole)silver(I) nitrate was prepared in this investi— gation. All calculations of the respective instability constants were made on the assumption that the complex formed in solution contained two molecules of the respective cyclopolymethylenetetrazole per silver ion. Because a large excess of the ligand was used in these studie of the this i format 1250 1 pKf vs the v5 elect: 132 studies, it can be assumed that only negligible amounts of the 1:1 complex were present. The results obtained in the potentiometric part of this investigation are shown in Tables X and XI. The formation constant values at 25° ranged from 1070 to 1250 liter mole-l. The data show some reproducible differences in the pKf values obtained with the three electrodes. For example, the values obtained with the Corning NAS 11-18 sodium ion electrode are ~0.1 higher than values obtained with the TABLE XV.—-The Average pKf Values for the Reaction + , + Ag + 2 CnMT _——-Ag(CnMT)2 Tetrazole pKf pKf (0.1 M KNOB) (0.4 M KNO3) Trimethylenetetrazole ~3.0li0.01 -2.98i0.05 Tetramethylenetetrazole —3.07i0.03 -3.03i0.03 Pentamethylenetetrazole -3.05i0.04 -3.00I0.05 Hexamethylenetetrazole -3.05t0.01 —2.98i0.03 ‘Heptamethylenetetrazole —3.08i0.04 —3.32i0.03 As shown on page lOO,the pKf values should not be influenced by the ionic strength if the Debye—Huckel limiting law is obeyed. At the higher ionic strengths used Debye check ionic that tetra is a) hepta cant . varim 133 used in this investigation, however, deviations from the Débye-Huckel limiting law may be significant. In order to check this, the measurements were carried out at two ionic strengths, 0.1 and 0.4. Tables X, XI, and XV show that the results for tri, tetra, penta, and hexamethylene— tetrazole were independent of the ionic strength. There is a difference of about 0.3 pK unit in the case of f heptamethylenetetrazole. From the data listed in Tables X and XI, no signifi— cant change is observed in the formation constants of the various 1,5-cyclopolymethylenetetrazoles; and, once again, no simple correlation appears to exist between the length of the hydrocarbon chain and the stability of the respec— tive silver(I) nitrate complex. synth ties dibro in th 134 RECOMMENDATIONS FOR FUTURE STUDIES I. The following substituted tetrazoles Could be synthesized and their respective physicochemical proper— ties investigated. A. The syntheses of the 6,6-dichloro and 6,6— dibromocyclopolymethylenetetrazoles not already prepared in this investigation could be extended. B. The synthesis of the corresponding 6,6- diiodocyclopolymethylenetetrazoles could be attempted starting with 2,2-diiodoazacycloheptane prepared by reacting 2,2—dibromoazocycloheptane with sodium iodide in a stainless steel reactor at 100° for 24 hours (84). C. The synthesis of monochloropentamethylenetetrazole should be attempted starting with 2—chlorocyclohexanone. The method described in this thesis for hexamethylene- tetrazole can be followed, and the final product may be either 6—chloropentamethylenetetrazole or 10— chloropentamethylenetetrazole depending on the result of the ring expansion step (i.e.) 135 I? 0 Ho N—NEN: /1 Cl HN3 Cl H+ Ho Na 01 OH g 2 H\N/ 01 8:3 N A7 ‘\\N N I \\ 01 6—chloropenta- methylenetetrazole Cl lO-chloropenta- methylenetetrazole could thesi tetra 136 D. Other d,w-bis(5-phenyl-1-tetrazolyl)—E-a1kanes could be synthesized with the method described in this thesis for the preparation of 1,4—bis(5~pheny1—1—. ‘tetrazoly1)-§-butane. E. Various d,w—bis(l-methyl—S-tetrazolyl)-n—alkanes could be synthesized by treating a warm aqueous solution of the sodium salt of the respective d,w-bis(5—tetrazolyl)— g—alkane with dimethylsulfate as described by Cohen 23 g. <37). II. A further investigation of the reasons why l,1'-dipheny1—5,5'—bitetrazole does not complex Lewis acids should be initiated. The most logical reason for steric hindrance could be resolved by investigating the coordin- ation ability of 5,5'—dipheny1—l,1'—bitetrazole, 1,4-bis (l-methyl—S—tetrazolyl)—E-butane, and 1,4—bis(5-pheny1- 1-tetrazoly1)-E—butane which are presently available in this laboratory. The study could be extended further to include the d,w—bis(5-phenyl-l—tetrazolyl)—fl—a1kanes and d,m-bis (l—methyl—S—tetrazolyl)-Q-alkane which could be synthesized as described above. III. A study similar to that done with pentamethylene— tetrazole (13, 15—17, 63) could be instituted to determine the complexing ability of the other 1,5—cyclopolymethylene— tetrazoles prepared in this investigation with transition metal salts. LITERATURE CITED 137 10. 12. 13. ,1) Jr: ,4 \J? ,4 ON LITERATURE CITED 1. A. Szent—Gyorgyi, "Bioenergetics," Academic Press, New York (1957). 2. A. Szent—Gyorgyi, "Introduction to Submolecular Biology," Academic Press, New York (1960). 3. B. Pullman and A. Pullman, Proc. Natl. Acad. Sci., fl, 1197 (1958). “ ‘ 4. N. E. Ainbinder, V. B. Grechishkin, and G. I. Subbotin, Optica i Spectroscopia, $8, 1081 (1965). 5. D. B. Tower, Epilepsia, 8, 141 (1965). 6. S. L. Freiss, F. G. Standaert, and L. J. Reber, Proc. Soc. Exptl. Biol. Med., 29, 277 (1958). 7. A.-Dister, J. Pharm. Belg., 8, 190 (1948). 8. E. G. Gross and R. M. Featherstone, J. Pharmacol. Exp. Therap., 81, 291 (1946). 9. E. G. Gross and R. M. Featherstone, ibid., 81, 299 (1946). 10. E. G. Gross and R. M. Featherstone, ibid., 88, 353 (1946). 11. E. G. Gross and R. M. Featherstone, ibid., 98, 323 (1948). 12. E. G. Gross and R. M. Featherstone, ibid., 28, 330 (1948). 13. F. M. D'Itri, Master's Thesis, Michigan State University, East Lansing, Michigan (1966). 14. H. A. Kuska, F. M. D'Itri, and A. I. POpov, Inorg. Chem.,_5, 1272 (1966). ‘— 15. F. M. D'Itri and A. I. Popov, ibid., 8, 1670 (1966). 16. F. M. D'Itri and A. I. Popov, ibid., 6, 597 (1967). 138 7. 1 18. 19. 20. 21. 22. 23. 24. 25. 26. 30. 17. 18. 19. 20. 21. 22. 23‘ 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 139 F. M. D'Itri and A. I. Popov, ibid., 6, 1591 (1967). F. Basolo and R. G. Pearson, "Mechanisms of Inorganic Reactions," John Wiley and Sons, Inc., New York, No Y-, 1960, p. 170 R. V. Biagetti, W. G. Bottjer, and H. M. Haendler, Inorg. Chem. 8, 379 (1966), and references listed therein. A. I. Popov and R. D. Holm, J. Am. Chem. Soc., 81, 3250 (1959). "““““'— E. Olivera—Mandala, Gazz. Chim. Ital., 88, 175 (1914). D. W. Moore and A. G. Whittaker, J. Am. Chem. Soc., 88, 5007 (1960). J. B. Lounsbury, J. Phys. Chem., 67, 721 (1963). F. R. Benson, Chem. Rev., 41, l (1947). F. R. Benson, "Heterocyclic Compounds," 39, Interscience Publishers, New York, N. Y., 1967. K. F. Schmidt, Z. Angew. Chem., 88, 511 (1923). K. F. Schmidt, Acta Acad Aboensis Math. et Phys., [2] 38 (1924). Chem. Abstr. 18, 3248 (1925). K. F. Schmidt, Ber., _1, 704 (1924). R. T. Chinoin Gyogyszer es Vegyeszeti Termekek Gyara (Kereszty es Wolf) German patent 611,692 (1935); Chem. Abstr., 88, 5995 (1935); 0.8. patent 2,020,937 (1935); Chem. Abstr., 39, 575 (1936). R. T. Chinoin Gyogyszer es Vegyeszeti Termekek Gyara (Kereszty es Wolf) German patent 613,123 (1935); Chem Abstr. g9, 5604 (1935); 0.8. patent 2,008,536 (1935 ; Chem. Abstr., g9, 5994 (1935). L. Ruzicka, M. W. Goldberg, and M. Hurbin, Helv. Chim. Acta 18, 1335 (1933). L. Ruzicka, M. Hurbin, M. W. Goldberg, and M. Furster, ibid., 18, 662 (1935). W. R. Carpenter, J. Org. Chem., 81, 2085 (1962). 34. 35. 36. 37. 38. 39. 40. 41. 42. 46. 47. 48. 50. 51. 52. 140 J. H. Boyer, M. S. Chang and R. F. Reinisch, _8; Org. Chem., 25, 286 (1960). E. Oliveri—Mandala, Gazz. Chim. Ital., 55, 776 (1921). E. Oliveri—Mandala, ibid., 50, 260 (1917). J. Cohen, W. G. Finnegan, and R. A. Henry U. S. Patent 3,073,731, Chem. Abstr., 58,11164a (1963). J. S. Mihina and R. M. Herbst, J. Org. Chem., 18, 1082 (1950). —'_'_“"” ' T. C. Wehman, private communication. T. Kauffmann'and L. Ban, Ber., 22, 2600 (1966). R. von Stolle, ibid., 28, 1296 (1922). B. von Issekutz, M. Leizinger, and E. Novak, Archiv. exper. Path. Pharm., 177, 397 (1935); CEEhT‘KBEEE.j29T‘372I‘(1935). F. W. Schueler, S. C. Wang, R. M. Featherstone, and E. G. Gross, J. Pharmacol. Exp. Therap. 21, 266 (1949). W. C. Golton, Master's Thesis, State University of Iowa, Iowa City, Iowa (1959). A. I. POpov and J. C. Marshall, J. Inorg. Nucl. Chem., 12, 340 (1961). A. I. Popov and J. C. Marshall, ibid., 24, 1667 (1962). A. I. Popov and R. D. Holm, J. Phy. Chem., 88, 158 (1952). W. B. Person, R. E. Humphrey, W. A. Deskin, and A. I. Popov, J. Am. Chem. Soc., 80, 2049 (1958)° W. B. Person, R. E. Humphrey, A. I. Popov, ibid., 8 , 273 (1959). A. I. Popov, R. E. Humphrey, and W. B. Person, ibid., 88, 1850 (1960)° C. H. Brubaker, Jr., ibid., 82, 82 (1960). C. H. Brubaker, Jr., and N. A. Daugherty, J. Inorg. Nucl. Chem., 88, 193 (1961). 53. 60. 61. 63. 64. 66. 67a 68. 69. 70. 71. 141 C. H. Brubaker, Jr., and N. A. Daugherty, J. Am. Chem. Soc., 83, 3779 (1951). C. H. Brubaker, Jr., and G. L. Gilbert, Inorg. Chem., 8, 1216 (1963). L. L. Garber, Ph.D. Thesis, Michigan State University, East Lansing, Michigan (1967). L. L. Garber and C. H. Brubaker, Jr., J. Am. Chem. Soc., 22, 309 (1968). D. W. Meek, R. S. Drago, and T. S. Piper, Inorg. Chem., 8, 285 (1962). G. Franz, J. Inorg. Nucl. Chem., 28, 737 (1963)- D. Earley, Anal. Chem., 82, 1564 (1957). K. Starke, J. Inorg. Nucl. Chem., 81, 77 (1959). D. W. Meek and S. A. Ehrhardt, Inorg. Chem., 8, 584 (1965). L. L. Quill and G. L. Clink, ibid., 6, 1433 (1967). D. M. Bowers and A. I. Popov, ibid., in press. A. I. Popov, C. C. Bisi, and M. Craft, J. Am. Chem. Soc., 82, 6513 (1958). J. W. Vaughn, T. C. Wehman, and A. I. Popov, g. Inorg. Nucl. Chem., 88, 2027 (1964). H. Rheinboldt and H. Stattiner, Bol. fac. filosof. cien. lettrus, Univ. Sao Paulo, Quimica IE, 27 (1942). Chem. Abstr. 22, 1502 (1946). J. J. L. Zwikker, Pharm. Weekblad, Z}, 1170 (1934). A. D. Harris, R. H. Herber, H. B. Jonassen, and G. K. Werthein, J. Am. Chem. Soc., 82, 2927 (1963). A. D. Harris, H. B. Jonassen, and R. D. Archer, Inorg. Chem., 4, 147 (1965). T. C. Wehman and A. I. Popov, J. Phys. Chem., 12, 3688 (1966). “——‘“——————- N. C. Baenziger, A. D. Nelson, A. Tulinsky, J. H. Bloor, and A. I. Popov, J. Am. Chem. Soc., 82, 6463 (1967). I 2 7| 73. 72. 73. 74. 75. 76. 77. 79. 80. 81. 82. 84. 85. 87. 88. 90. 91. 142 N. C. Baenziger and R. Schultz, unpublished results. A. Weissberger, Ed., "Technique of Organic Chemistry“ Vol. VII, Interscience Publishers, Inc., New York, N. Y., 1965, p 196. A. I. Vogel, J. Chem. Soc., 644 (1948). ————————& A. I. Popov and W. A. Deskin, J. Am. Chem. Soc., 8_0. 2976 (1958). ——'———“‘ E. B. Rosa and G. W. Vinal, Bull. Bur. Stand., 82, 479 (1916- 1917) J. A. Caruso, Ph.D Thesis, Michigan State University, East Lansing, Michigan (1967). J. von Braun, Ann., 490, 125 (1931). W. R. Carpenter, private communication. R. Tull, R. C.O'Ne111, E. P. McCarthy, J. J. Pappas, and J. M. Chemerda, J. Org. Chem., 29, 2425 (1964). H. K. Hall Jr., M. K. Brand, and R. M. Mason, J. Am. Chem. Soc., 8 , 6420 (1958). R. J. Wineman, E. T. Hsu, and C. E. Anagnoslopoulos, ibid., 82, 6233 (1958). J. von Braun and H. Silbermann, Ber., 63B, 502 (1930). W. C. Francis, J. R. Thornton, J. C. Werner, and T. R. Hopkins, J. Am. Chem. Soc., 82, 6238 (1958). R. Meyer and A. Seeliger, Ber., 82, 2640 (1896). R. Bauer, ibid., 82, 2653 (1907). A. G. Haco, British patent 970,480; Chem. Abstr. 63, 567 (1965). """‘"“‘ H. Strache, 223-, 31, 2365 (1888). L. Von Udransky and E. Baumann, Z. Physiol. Chem., 13, 574 (1889). A. W. Hofmann, Ber., 2, 246 (1872). Th. Curtues and H. Clemm, ibid., 82, 1167 (1896). o 2 9 93. 99. 100. 101. 102° l03. L04. ~05. -06, ~07. -08. 92. 93. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 143 A. von Einhorn, 223., 233, 226 (1905). R. von Stolle and Fr. Hanasch, J. Prak. Chem., 136, 14 (1933). A. Reissert and A. More, Ber., 82, 3298 (1906)» G. F. Morrell, J. Chem. Soc. Lon., 105, 1733 (1914). J. von Braun and W. Rudolph, Ber., 13, 264 (1941). J. von Braun, F. Jostes, and A. Heymons, ibid., 99. 92 (1927). J. von Braun, F. Jostes, and W. Munch, Ann., 453, 113 (1927). J. von Braun, H. Silbermann, Ber., 63, 498 (1930). 8, 2346 (1905). J. von Braun, C. von Muller, ibid., M. M. Brander, Rec. Trav. Chim. Pays—Bas, 21, 79 (1918). J. A. A. Ketelaar, C. Van deStolpe, A. Gaudsmit, and W. chubas, ibid., 11, 1104 (1952). R. E. Buckles, J. P. Yuk, and A. I. Popov, J. Am. Chem. Soc., 13, 4379 (1952). R. S. Drago, R. L. Carlson, N. J. Rose, and D. A. Wenz, ibid., 82, 3572 (1961). H. Bassett and A. S. Corbet, J. Chem. Soc., 1672 (1924). W. R. Carmody, J. Am. Chem. Soc., 51, 2901 (1929). A. S. Brown, ibid., 56, 646 (1934). E. Lieber, S. H. Patinbin, and H. H. Tao, ibid., _2, 1792 (1951). L. L. Garber, private communication. R. D. Holm and P. L. Donnelly, J. Inorg. Nucl. Chem., 28, 1887 (1966). P. Job, Ann. Chim., [10] 2, 113 (1928). 112. 113. 114. 115 a 116. 117. 118. luu 1120 F9 Jo Co Rossoti and Ho Rossotti, "The Determination of Stability Constants,“ McGraw«Hill Book Company, Inca, New York, No Yo, (1961), pa 52a 1130 Jo Ho Markgraf, Wu To Bachmann and Do Po Hollis, J° Org“ Chemo, go, 3u72 (1965)o 114, Re Mo Keefer and Lo Jo Andrews, Jo Am, Chemo 8000, E} 21614 (1955)0 1150 R, Co Cass, Go E0 Coates and Re Ga Hayter, J, Chemo Soc.,, 4007 (1955), __..._._. 1160 F0 Go Mann, Ao Fo Wells and D0 Purdie, Jo Chem, Soon, 1828 (1937)° 1176 I0 Leden and Cu Parok, Acta Chemo Scandp, 19, 535 (1956)“ 1180 Lo Lo Garber, L0 B0 Sims and Co Ho Brubaker, Jro, Ja Amc Chemo 8001, 90, 2518 (1968), 1‘11‘1 .I APPENDICES 1H5 APPENDIX I SPECTRA 146 09— ”114 . . m . . . m ll:— . Fli.’ 04.. 1» .9. 9.1.25.1 . 0.. c mm F... -l Izril‘LLlaw 11111-.." -1, 115111;} n. m.» a ‘ .1 P111] ll 11 1L1: 1 111111 1 :u 11. lixlk 0(— vlll!| [-mlllflxu 1 E 1;th (MTG. Lemon-v oH-mhpfinonhpSQoUHp-wn: ,wo 2900mm 66.39ng in madam-Tm .— 03 E 3 c u>d.§ 003 009 009 000m 000m .000? 0009. nllql-flll-Iinfilil-fil-iil41:}! 1.}:- - “I.“ ! .3 .- - .i-JM-IIII I «81.-9|I31i. 5.3.1“ O M. .,l ~Mmm m .9. n. 113-: . . _ . 1.7- IJIJLI-l-J-n-J-nclcll O» 11 A _ m m m w m .4 p rum-H _ . I . ...-,.-.i...-.v-- - 1.18-.41-- . .. . A i 1. I f) i l _ _ n w n. P. 1 1 z m _ _ . . _ , 1 u M I . . . . . I . .. _ H. . - w-“ .. 111;. I- 1 I- w 8 - m O,w . w - - «if. to- - I- 88.-c,- -..-.-- 1 Gnu m “%.l _ M _ .1 w m n . H. n m _ _ U m _ . m m I m M s L- :- rwf -_- I...- .._-.._...-m3nfl. u. ... ..... .-?-a-.-ila|l-T9:s-.hEmu . w . . . - M. . 4 d _ , . . . M a - . a} . . u T I u t . _ _ I : u n, . . a 3 ~ _ . . . 1 . _ . ._. _ . a n l i 7.. . U _ . . w . _ i . . N .. . u a. H _ H a“ .n. u . u _ T M.- . . . i a _ a .- - 511.99 . .1811...- 1£ r-f . - - 4 7 ill-.1 Av 1!. «all I lit: PA. _ . . . T m i; m .... m I _ I w m H - 1.. I : n M m _ _ _ n . .1 . i . _ n .- . . .N _ H...“ . m .-.--.“--¢-..-.-..--UOJ: h :tr':__,--_...- 0 1 5.“ «——~.. 1-- 0,—— -- ‘- v .‘ . . .-.... 4"...“ _._.. _ ,-_ . .. .W-My f . l , 1 _ “ a . . _ . I _ _ M . .7 - - n . l .h 7.. i. . u u . .. . ._ m n __ u 0 . . . u ._ N _ 1 . I l i l m m .7 m:- m. - 1:- Wei-1.11.4 3 . M M w I U _ i i u . . w . m I m H n s . 1 i n l - _ 1r! -L..l-lpll1-l111-1rl-tw-Hrlluwr41-WWHH-llq 00p 1.1ail111111:1.l!»l.11 _ 5:. .332?) T.“ . o w r [Inn-xii- ....... .- c .3135 oH-mhpwgohhpsnoddnwn: .Ho HES-comm ocean-domes oflpanmda 283652” .N mhfiwfim 8 y la.- “ )\. . . n «J ‘H\ m 1 .-. lam ;--u . m-nmmmzm .. e,“ 1‘»- Anna-05 odfihpwflonoH-mboufiuulm .Ho 23.30on dohwanH .m whim-E Luagfiflms’flmfi 000? 0000. . . . . . . . . « . . . 0 . u n m - _ c . . . n u :u .3 23...: . . n u . n .. . . . . . . . . . . . . . - .v . . . . . . _ n n . u . . . . . . _ . . - . O L”! n U o _ o... . 0.“ o." . . 3. .32.: o...- 95 o...“ , are 150 r\,_.,_17: ,_, ._w*fl-,wm~_m‘~_ualw.;-v~—‘- w .- .- . ,- ’ ._,‘ I" iv o 8. 8« con 03 m w AKIA ... .- -. U IrIl-lnllilltrlvlls. {align-3511......- ...-.q .1... .21.." .b rift-1'11}... -_- - E 0% , 06 0.6 6.5 6.6 TS EL 0.6 Gd 6......- . . 1.1 «- FELL .09 11Pi111~1 e18” -. .-11»-11|-1.1-1-.. 1.11 .1L11-11rxz- 18.. 111- 1111L1.1- r1: ., - .. 1 11.1- »1-1 1.7-.181. -1 v 1111. r1 - {11-1.1111111811-1 Taxi: vie-3f. .1. x m: 1r nw Nr 3 Or a a x- . 0 r- ? n .l1111111.-...:11L .- . Tummy odouukpopoqQthpoP-th .Ho Edna-comm cohmnmfiH .m ohsmwm 22.-5...: . . . ,. 39:35.22... Ono 000 00mm. . OOON OOOn OOOV 000m. o J 1 :11. M . .4.-. .fl - . 3.1.1.7141-11-H.11- 1711- M-11.1-,. O . m m. _ m m _ m E m w .2 2.1.2:. _ a i n u . n u _ l u . I u _ l m _ U I i w , . .9 .1-11 ..11 . $1 - . 1a - J - - . a . ..- 8.“ 9 71-1;- .- -. . .. - . .-. - -.-1.....1-1..1_ .r... 2 . . q _ I . .. ._ M u w I a I ”a. I . ., . i . l . . . a . u H. . l . . _ . . . .x. H M .1 _ .. . 1 j m I W .1 u.- on - 1.. : f, f 1 2x. + .- .. - I. can . _ .. H u .. _ _. i 1 n . I u u _ _ N . n m m m . . m m m m H n. S 1.1. m u L. .. 3.? . T -.;,.-,.-....-...:.m m u n h . . ._ m n I 1 H .1. . .1“ U n l m H . I I . :- . . x .- . n u n . . __ m .1 _... a n . n . .. n . . . 9‘11- -1 -- 11H. a i a - ..... .1 4.14.1...“ -.-.m:-11-3... . . . . . . _ I . _ o . . . . . . . . . . l _. . . m . I .. u . _ n . i . u m _ l , n m u i .. u u . .. .1 I u w C ... “1.11M-x1- -1.1111. 0.. v i .m l H _ n h .. . a U m H. . m u. . . . ,. . m . . n _ m I m f _ I . I _. ._ H _ _ l -1 _ - .. ---. .-. n .811.- " w l m 1 _. m w n n I u . _ . _ . _ .. . .. I I . n n m . . I . . . w "I . -M q- 11... 12.1-- 8.... . 141 .1" -11- .. On 1.. 14111-111114,- , . . - 119-1. 00 h . . I u i . fl . .- ~ fl 1 . . . I _ . . _ _ W l _ W _ m I .. ._ . l w 1, . _ m _ I . I M m _ w u . , - , . . . . 41-11 a 1 - 8.. 1-1-1- 11141-1-.. Go a1 1111-4 -1.--- .- E n _ N u w w . w . _ . N .. . U i n ._ I . i . _ n i _ m u M n m m m _ . n _ 1 m m I m .09 1 -11L-r.-1rw .111 F111L11-1lr1 .l.»11-1.r.1.1-.. 111.711- .1 1. - M 1.1L11L.-.-“-1-.11.w1111m..1111H1111w m, E r «r a 9 e 1a s o a .1”.- x--1m1ruw1...~,mmwmo..fin- m A Homov maouwhpoponoahflpoawhp .Ho €5.30QO ooqmnnvmoh caposmwg nmoaosz .o madam-E O 3 x . :o I: T141111 .151.- . Hindi. fl}!!- §.Wunfimx.... [5133} In! at! :5th . _ _ ‘311‘h:<'.' A ... 7... n: _-.: ”a... :-"»t y. -._._.. ..... ,‘. I k 1. w. 3 . - . .r... . .... u; .5 g 6 o. 9— a 0.6 III- wt’ia‘nllllnvlr ... Elk-FEETIVtfiiaLZAxrimz . 1153 .nHH mo mo=Hm> w\a um munmsmmumv oom . o-H AhuflHSQEH anomouoasu ou msw mum HNH was mHH .mHouwhpop¢QmHhflpoSfiHP Ho Ednpommm mmwz .w ohfimdh 3&0 H on . . I W HI.I m . w . I I I . I . . . II I . . . I a . _ , I _ I I I I103 (%E <) eouepunqv equgIQH loll-1......i'li-I'I‘ CrCr If ”V. LwnEEIIEE-fi 009 .u OOOH .000. 000..» - . - I11.“ - 11 ..I11.11-1I1. I 1 . 1 1. - I 1 I x . 1.1.1 ..I... .11.--..I C . . I . . . I I . I I I .2 I. .23.... u _ I I I I I I I. I I . I I I . 1. w . . I I . h I I u .. . .I.>......11_..- » .1. I . I , I _ I I u w _ — m # I I . . I . . _ I I I . . I I I I . . I .1. ...-.-d-...I - .ICN - ~11... .-.. - ..I I I . , . I I _ . . I I I I I I _ I I I I I _ _ I _ I I 1.. - I . - . . . ..h-. - . . T. . . . . 1.... n «I . If} . a 1... I .3 .. . ._ I . . I I , I . Id . I I II . . _ I _ I I I I I I v. w - u -------- I 5.». . u . . * - _ I ~ .o I I . m . I . . - . _ I I I h. qW..H.-m»pww~ g.~I.I-I I III 1 1 1 v ...I__ "III. 1 - a 1 T 1 1 1 I C- K ..._-.-I._-__-._II w .._.II--..A.. : 1 1 7 1 -WIIIIIIIII'IIIIII. . III..- II.-. ..._ . 1 1 1 1 r 1 1 P . I I I I m? _ M u .I 7 I I 4 V!) .1” OD . I . I .. . I _ I W ,. OéIr. . I I I. I II .1111 4.111111 . 11 I1.- ..1.. L 11 1.11-I? .- 1 .. 1 11-11.“..- - 1- W11 1 .8 I. . m I . I .I I I .. oQI-Wt . . . I I .I I I .I I 11-11%... - 1. . . .. . . .. 111-11-.- 1-..- -... 1-11--11.? 3.11.1.- r111111. 1.11-n.1, . y . . 1 . L 00. S 3 5 m. ...:....... 9 a . ..:11-.--.1m1-1- e .....1-. £1... 54-. TL N 155 ._ I I I I I I I I I _ I .I I I .. I. . “I I I _ . . . - I I I _ I- ._ I . .. I. I . .I-.. I _ I: I I I _ I I I _. I I _ II II... I .. I I III .A .. .I I I I. . I ..II II .. 7. u 9 IL 8 “*1 Tan A 9 "IV . I . I m- .. .. . .I I I I . . . - om w. I I I I, .I. _ I. I _ I I I I . I-II .. .I. I I I _ I I I I- u I... I I. _ m . .. m. u I .I I. I . . .Il! | \I n I... . ..I I.‘ l .-m- . I" I < .... I... Ii.- - . I I I _ I _ E . _ .. I. I I . .I.. I I I I .-- am, ..I....m. . _ u I I I I . I. .w1 II _ . ( . I I .u... ... . ..H I. _. I I I I in .. . I I I I I. I I I I _ I . .qu .I. I I I I I I. I I . I. I I I I I - . .... I . .. I I. I. .I I I . . I ....I..._I -.--I: ..-.I I _ I _ . I _ I . II. I I I _ -- IsIIIII II. I I I03 I . I I .I. I .. ....I... . I I: . I I -..”..-I-..I..-I..__. . I. III I _. I I _ _ I I I .I . I .I I I . .. . E u I . 1am- . _ - -- -, ...-... m . I 0 -rr- ‘ I . . . . . 1--..-- W—T‘m III... . ‘ TIIIIJ I.II-.+-----._. .ii:;‘.;?;¥il3§il€$ . 158 OOH <) eouepunqv aqueteg . Ahmad caonwhpopofloahnpofimxon ,Ho EPOQQm 60.39th 1”: omfimflm EnEES ac, ooov ,=_‘ Cm. ‘ va- _ ~ . I _ u ril. . w I ~ .u H. ONT ” m om“;” . 1m w m u _ n N n _ ,. _ _ _ Cm TIT: m - y}% I! rl I x _ m _ _ . U u _ _ “ C073“! .Ill‘Ll‘lflilv.llxl.lIL .L ... ‘ .y . . .. , ll ‘I‘E‘ m: Elmwlmrui: CHI .w LI»? 1: ,- Egfi QEKKXEEE 13E E I \L _ w E, refinanflfiavaflwfigq .. c LII! 162 .waouwnp0p0Q0HhflpoEdM®£ Mo SSHpoomm and: .oH mgsmflm m umy;Amwwu..mmmm-v.—.‘=."~mnmw.w..§~_w..m (%S <) eoufipunqv equeteH .393 oaouwhpopoqoahapofiwpmon .Ho Sassoomm vohweflhaH .5” magma—m 535353.“. .\. .. 0009 163 . . H . . .. . ........... . . . nlnt‘ltlliniilul. ‘{)TI¢I.A.I: I llv f . . VJ? l 61; Eu 0 8. 8n . 8n 8‘ AzIA . . o— 0.0 0.» OK 0.0 T: 2.: 0.». oé 06 o.“ um m~mw rial-“M “mmwmfl‘ warm Er. qufl-me m» .wmw—wm— mi OOH (%g < ) eouepunqv e‘xzqetea u“! ‘r 'r ah! : .2"va oHoudmpoponOthpmfimpoo .Ho Epoomm wothMGH .om ohsmfim uaflEDCOsavw 00W» 003 000" 000m 000m 000v 0000 l u ._ ---,Y--. I ( I I I --4i..- 0 w 4 .4. 3- W 4-1.. _I. 114.}.-Jéll-..44{1114: 14‘!!! 111.414 0 m M M m u _ m _ .m .. =~. ,.¢._t:.uvm M .--:g. -.._ _ 2.9 T -iL. H ...“ n m u _ _ m. m n _ 0 4 . M . _ .. _ u . w _ . _ . 4 — w . u ‘ . _ r m . _ H _ . _ W , v. fni v . - w .3. u.-1¢f.g¥v.lkiT.flfl..4 ON “4:11.11 m n M m m w __ . _ V M _ . M _ _ , m w M . . a _ u m . M _ . . 0"! rl : . ._ . . 4 .. .Iu.pl.llnt4..bl\.'blul L11, . m A . _ , w _ N * W 2219.23..-“ 0n _ __ fl ._ 33- 3?! oo ...—..— 6.2:. Car— ... ”.....-“ . . ...—...... ..--..u..- -. . .w _ “ m m w M , . w W . --.r, . raj—L: . il..L3-rl.iLI~it 41.5.3.4. 3.3.1»: .4 : a s o .. 0 ml nullrzhufiéE.._n.....anf.. 167 Eu 0 AI . A9833 oaonwhpopoqodhnpmedpoo .Ho Epoomm $389039 oapmmwwfi .Hwoaosz .HN 93mm. 0.0 8.. 0.» OK 3N 0.0 C. so... 8n Qn 9v 001 o.m .H o .4 .ofiondhpopmnofihflnmsmpoo Ho Esapoomm mud: .NN ohfiwfih o\E ..H . .m _ U . _ u m _ _ _ ~ n . . n _ u _ n _ . n _ . . l ._ u _ _. _ .. _ . _ . . . _ m _ _ . . _ . . a . _ u . _ _ _ _ m _ . _ n a. I, w /_ _ w _ (%g <) eouapunqv GAIQBIGH OOH 2‘34 (H1 fir} .2..va odouwnpOpquHfiMpofiquG 9.0 £5990on .009.“th 1mm 095mflm £113.... . . . . LUQ»C3CO>H.€. 000 009 030, oar... COS 30;. r. .... 00.0,; 090... 000v 000.... O M» l u y . W . ‘ . ”I 4 - , 4 n . . . . . . . 4 . . t 1...! . l.- w . . . . . .. . h 2. 1.1.1.: . w M _ . , . . . 5 _ . . _ 9 T n . . . . A . . .. . . . . . ..... . m u . . m .. m h . m .. _ M H M a M a on ... m . . . .h w M . . . w n u .. . . . m . n .. . QM w . a . .. v . . .. _ M _ h M 4 w . u . .. . 0.44... .7 m . . ...-..”C.‘ . . . g n O/ w m o n l . m . m . . . . v 6 . . . _ ... , H _ 1 Q. 4. .. . m . . . 2 fl. . a . . H . . W . . T: g . . w . . . ‘ . . . . .. . . . . m m . ~ .; d. f w .. C: . _ 4 . . n . t ... . .. . . . . :2. .. , . a... .... _ _ u . I . > L( g . u 0.. .. V. rm ” a . . . ... .. . . . _ .... . U . M _ . .. m m W H . .. .. .m w m m . H .. a H 0.1.7 .m. H. m . .. T. .4 ..... ...-.. _ w M * m . . V U , _. H . w w w u _ .. u H H _ A U u . m m . w _ m m . W m M M. H . W 2.: 7“. m. w W M . m .M W 4.... . . . fl . n .. . _ .. a . n . U U _ H m H h . . m w W “ m w w m u h H M . H m u. m U A 0?. . _ . M . m m a u n . u H h u u m u m m H ril.iylllv'. . I 1"} I‘ll; . [.I‘i.’y 1|. , , y4||8lllltll§rlzlllluallql4il .l‘ull'l‘lilitulillitlf I!..|n|lxl|lllllln.(lp|ll.llrol'.lll 4 . . ... , I . , ....14 i 3 C: D : Q o . .c . . n . o . a 1 n VLM.........I............,.........HL u . m . A Home oHonwhpopwgloflpafidqon Mo 8.9.30on monMQOmmn owpoammfi .waaosz .dm 9443.5 170 gr ‘7 'f .“r z 171 E III-01.3 Ono 000 O _ “_11-44: 3.1.4.- -. m 0 1 I § ' 1 i 3 l L l r W...“— . . 0 g . - --.—m... -.. - """"~"7“‘“""""" ..-”? ... .....- _- o A g 4 n 'lelolAiIMrIIInlI-I! - Q a 8 h '1' hr 000.. Ahmad oflonwnpopofloflhflpoflfimoodg .Ho gupoomm demthH .mm charm-E LUQEUCU>G§ 000.» -cIIL|||-|I.lL-v.ll‘z|- ... ...wr. [It'll-lit. r.-..,:.H§._.. ..wwu....§.u.i..... ’40 00 P‘ ' v v 000.4. 000v - - -.--4.x1.m:- -M--- m H .-. l-m. M .s: .1- ..Miil-imii-IJMO _ m a . u _ n n .. . . .... 113...... u _ _ _ . . _ _ . g. . . u u m m fl ” u A n _ _. _ H _ M m _ .1 ._ _ . W m m . u . w . m . _ _ _. _ . w n _. a _ u . :1 w m _ m . . M . _ w w b _.__;H. . .-H; T m ..... .4....L. .m. ." ..- ...--- f . 1.9.5.”. ...-LN 1-43. .. L _. _ N . h . . m .H. _ . _ L m . fl . w . m . u ... ......_ ...- ... - v .. .....-L...) -- -.anw w _ H m W “ n u . . .. ....... m - . .7... . . . u . . . _ . . M . w m m. m . m _ m .. W . . L n . m . . w w W m . m . . . H m _ w m M . . .1-f 2... ..... ... L. L . m ”I .. n r .. ._ w a. .0 . . . u _ . r. a”. . _ . m m _ . _ . {pa-m . . m 2. a ...-T ._-- mi»..- - .10... . n ” it; u H w u . . _ . . . _ . .. m m m . . . . m _ w m . . ” fl . m _ ,_ n m H " . ...: -.v-vv- .. yrv"!.-M .02.. l- ou-y..:-,-.u. -..-.-o».-f1- ....Ou _ . n _ . _ _ u U . . _ _ . W . M m .. H . . . m _ . . . m m; m u N W m M w W m N . v11- r- 1! 91:- III-A 4.53-...: - -?q.-b.-...T....tfw . .00 .86.?“ - . - 4!. 4 x f“. . o -. . .-. Oc . . . . . . . . . . s W . w W . . w W w . . w W M m W . . u .H.. . . u n . . N a . . . . . _ 091$. -..-s..--r- -z-it-IltPia-yhclL-rtr:rIt-LEILELL-IL .- I.” . --t_.. . l. rrILI-bt . . . 00. ON 05 9.? z. ......E 66 as... .. 3va muonwxmvaIOHohowmale-6.3.30Eulm.N .Ho Esnpowmm 60.3..”qu .wm ogflmwm .IILTIA. . . . boflcmfiufluwflmfi Oak» a 5:0 000» . 002$ . 90...} ..u..«/...c» ... .00.... OOOW .. .0... .-,. Hm .... o m .1: _n m g 4...:...-.-....--?..-..; M ..:...az... N... u .. .1 n .. .. . ‘. . . . u M .Z Z ... u. a . u. q n 4 . . N ‘ .. W . .. . . . .. .M . . .. M . m . . . .... 5e. .M u .L.,_...-.«, f . .. . ...... .... .. _ . m m m . .1... H. .. . u . fl _ n n ..u .. a .. ... m m m . .. .. 4 .. . 4 q . . a _. .. . . . .. fl _ M . . . .... .u . . ._ ” . ...... .. u. . .. ..«.. .- -.. “.OFWA} 33¢. . . - . . p «Ir-u” “ . . _ m _ H . .... . .. . _ .. . . . . fl . . . . . . _ . _ _ . w _. . .r . . . . n . _ . . o . . . _ .. .N.. a... m- u-v. u. ..wl.u9. A ...Ln..\m-¢. -.:-L" y . - N a .... .. o .. t .. n n . u .. . h _ . — . . . _ . . . . .7; H. u « fl . M . . W w . . m _ . . . . . l . . w .. .. u fl 0 H , m u M . .p-.v¢ . u. o m-.-....u..c-‘n.-ntt¢v‘Qm.-v (314.. v .4 - r-... m u M m N u u u. u 0 m . a m , . N . . . .. W 4 n . . u .. . . . .r... a) u .u .. H u . w J. _ M w n m f... . . . . . . u . . . . . . . . .m... .... L. . a.... u. a n.- qu-(c n-.f-m.rt..un.(.v...l-?M 4. . .-. . H w . . . a H .. . . u . . . . . m w . u w . u, L .. . , . . . . . . _. H . . . _ .. .. .. . k . . . . 4 . . . .. . . . . . . u u u .. . . . q . . . . ... ..:. --..-.-.- -i-L- ....ni. .... ..p ...... ... . .. x: W . W .4 w w m 4 W J W fizzyw . . . , ,. .. _ . . .. ... W . m . . H . ... _ . . M . w _ . fl .. , . m . . _ . . W . . . . .. _ H . U . . .+.«......u..4.i.4.tv. X-ri... 0519-7790;...7...-5...»...lt. 9 . .L. . ... n . .. . w . . . . . . . , . w H fl .. H v a .. _ . . . _ _ . . ~ . . _ . . _ M w w. _ . .. u m .. n .. M u .. . M n . .m w .. M . v .. w .. m a w a . w . w w H .. u H .. vor.‘.uvv4Vu .....1:..vv.c..4....r.TL est-$.13 t.v1P-l.40l£.V|O ..vi..o|¢ t u . - 4 . - u - , .. . fl . . . M ... v . u .. w w W M w _ . _. u n m .. m . .. L .. m . . ... H . . . . . N L.” M1 m. m w ” 77,7:w w w ...; ,. .. .. - 0.4;-- ;-..-.,-..r-.-...-.. --L-I;:--r{..!.......7-.ol.t.r..--.r..-r..t-.i.xLl.-_r-.L..Iy-L-nI-Iyx-yt-rhiu... .Li-i-x-L {..:-:3. --.-i s .. - . .. L .5:....!.:1...v.1.1.:l.ll. uric. .a . 3:19-14 Effie-xiifl ...; .... . . . ....- .E 3. r. 9 F Cr a. 1 c . t. C c o. . n ..:... _. Wirimnrl NwlINlelppw'Igllildw lllallmwx ilalillr'tq'll! ii- 11.111... I 1911! k 6 m v 17h ON On CV 06 Q 1...?”- ‘ . 3va ono§#mofl0Hohowuw u< «.1!qu M M ~ M _ . _ , . M _ . . ..: .v.. . M .. n _. M _ M _ . . . . ,. INIOHOHdHOflUImuN .Ho fiahpommm wohwhrfisH .mm @95th . . Loflrcmdzus‘flmfir O .OWQ . , 00.3 00.? . 009 000m 000". 0000 M M ,_ M _ . M . ,MI -2121.“ ..l. 11.. _ M M o: ......3.-:. m M M M M M M I v A I c IIIII _ _ H . v17! llllll w - fiilJ,‘ .... .. h _ M . _ _ “ M M . _ . _ M m . M . _ . M M M M . M ....--3-.-.-...-. . M -. - M . M M M M M M M. M M M M M M _, M M M M M M M. - ..M n . . _ M M . M . M . M w . M . M M _. M . .M ..M . . M ..... M. M. M ......M M 1.3.3; M M. H . ~ M . . . . . .. . M _M .M M : .. .... M M M , _ n M _ u M M M M. . fl . . ... r . v s M M _ . m M M M M ~ M M .M M . _ . . n o . . - . w . 00 W.’!sl:0..»:'i- : . w . _. n M. M . M _ . M M . M I}-quxl._.M 1;. --M... . . M . . _ . , M M M . M M M . M . . M M M 111“}, fl..- :...3!...-1£..$H1H.I..1«Irtlz .Iliirtir. rill: ..:- 5...! ‘ . M . :1, h o 2.4-3.4 Wilmirimmwffié 3., .. -J n; 0..V 8 {v ‘r .1.» rr 7‘! .353 mfiofiwpoooaohgmwuwnomoaflowwlm..N .Ho Egypoomm. dohdawGH .mm ohsmfim 03 003 009 005. 00.... 0?: 009 002 won... 0... ... , _ . . o . M . M . M. M M M . . . .M . M . M , ...... H . M “L M M M _ H M M u _ . M a: 11...... M M M s. M _. M M M M . M . M _ M . 9M....M .M. _. M M M ..... . . M -.. M M M M . M M M . M .... MMM M . M M M M _. M M M m ON. . . M . . . . _~ ..V V. .. ..:... M M M . M M . .M H. M M M M M . M M MM _ — . . . M ~l¢ . M M . M . _ .M MMM M ,. M... on m. M.. m . . . ..... a M... .u «M U I) M . . M M M M.M M _ . 3 M M .. . _ M M MM . M . M . MM . . .. 01M. M..MM:M:_ . MM _M MMMM .M. M M, t... M M MM. Mt... .. MMMM ._ . _ M M 5 M M MMM MM. .M . M MM . M M . 7 M M M .M. M .MMM . ..M M M M M l SaM» MIMMMYLMMM MM M. ,. M Ma... . M . .. M . M . . . . .. M M ..M M _. M M M MM M M. M M ..M M M M M M M M . M .. M M: M M M M ,. M . M M .M: M .M M; . M M M M M r Mr C.. c M. M M M M M M . M M M . _ . M n M M M h M . 2.7.7.... if... M, «-.M. ... M.-. M....M....MC. M M M M . M M M M M M M M. r M M M M M M M M M M .. M M M M M . M M M M M M M _ ., M M M «EM. M. M. . M .. M _M M. .0. U .M M Ms; M M . M . . M . _ M ,, . m M. M M M M M M M .. M M .. M 0AM-.. .. ... .-..I- .--..M. ... -... :9” . .. M . . ...\ . M M M M M . . . H M . . , _ . . . . _ . . M u M w M . M M . m M v M .. . . M M . . M . M M M _ . _ M M . . . . . M 09M - M. F I..- - .M.c»-L.ul..- ‘1: [Lilithrg M ..lx;..----l-.r-i-:.r ...- v- M .anluzia MI .. m. . . M Cur ..: $1.2..- Winn . 0...”le .--o s a!!!i2».iii4.9-5::1.....ttrfllgnltJ..-..:.M..M....u...;M....... fits... 4.55 2883mcflapofiohomwmlfllohoflo..8-m.N we 5.38%. @23qu .om oaswfim H.113?! H . . . . . LufithflCu>flw$ 000 CO: 000. OONM. 003 009 DOC... 0 0.0.. OOOn 000... 00ij OMM.M...M. M .... . . . .. . .. . . M .H 1: ...MO . M M M M M _ M M ...... : . M . M M M M M . M _ M M M M M M M .M M or M.. v" . u . a .v . a . . u M .. ; . .M Q. \Q . _ . . . _ M _ . J M M . . M . .. .. M . _ 8 _ M M . . . . . . .u. M M M N . M . . M ..u M _ M . M M . _ .M... ONM.WI...M. .. a . . . .M .M.... 3.“..vu... M. M M M . M M 3 M M M M M M . .M... M . M _ M .. .. ... On . . . . . p . p . . . M M . . .. .... M M n . _ M M M I .‘4. M. M . M . . M M «.... M M M . .. M .. M . M M 0w. . M. q . . _ in. 176 -W". 1 M1? . . r M M _ M . . M M M M QIM M MM MMMM... M To. M . mMMM M M . .M MM M .. u M M. M. M M . . M M. .. . .M .. 0x M. . M. . .F m . 9 . m. 3.. . M . . . . .. _. L M M M M M . . . m . M M M .. M .M .. M .. EM. . M . . . . . . . m .. M 3:...M. . .M..» . M . .. ..... “MC... . M M . M M . M M M . M ._ M. M M M . M M . . . . _ M . . M. M. . . M M M M M . ._ M M M . .. M M M .ooy.k. M n..r....a....w 4....” w I“. .. M ..\...r. . M . . .M _ . . M . .. M . . M M M M M M M M .. .M .M M . . . M . . . . M M M . _ . M . M . . M . . . M M . M . c.......M.-.- M--M .M». ..r -- 23-..... .M M on. . d..- Simfi-..m.fii...... 2.9-1:-..wsilé. A.» {m mflifium....m.MMM . .31. 5nM 5 :3 fir 03. : 1?? .. Ahmad ofiogxofloaohowNwloloaonohvnm«N .Ho 8.9990on 693933” .Hm ogmunm . On a» 00 a O. UT... CQCH OOCMM OMAV". .o M. M M .M M . ..-. _ if M _ . M . MM _ M9 ..M. . .... .M M M: MM MM M M . I. M M MM . M M 2 MM... . ,. M? M 0 MM M M . M. M_ M. M . M.. _ M _.M... .M. . M y. ..MM 8 .M....MMM .M.. . . . M..M. MM -.. ..MM M.. M . t .. . .. . s 9. M: ...M. . M MT... ..., 5 MM . M. . . M: H M ...M. v . M :M . _ ..M » . . M (...?v . 7.. .. . M f . 4.x . M. . M . «a, M 00 ....... . J _ .. . .\....:..Z. ... M _ M... . M . M M . ... M M. M . M M .3 . . . . cf .. ....awbe.‘ ..--f.-.- _ M M M 938 .- . M M Oh. . . . . . . M M M M M M M M 0e M M M .MMMM-.- ...M.M,... ...M-.-‘M..-_.M...MM-... -M..—-..._.MMM....._...-M-.MM..M... . . M M M M . .. M . M M M . . M M M M M M . M .. .ii.M.v... M .M. «. vm.«l.‘.MMOQMM...:twc..x,t .2 ... M ._ M M M M M M M M M M M M M M M M M M M . M M . _ M M. M M M M M M M M M M M 08.3.7.1...4. ..quv.q M .. .M-»-. . ya»- . ...-M..-.!.M- 5.MOOM...§....M.2 ..4 I -\m.ux.lr':.MV . M M M M M _ M M M M M M _ M M . M M M M M M M M M M M M M M 0? [Mali Mp . .. 1M ..-. .-. M, . ..M . . .5. --.}.-.M. ...i..,.M-.i.i.- .r.!.-..L.I.. .-.LM.-:§I! 5-.....aMri- MztiirL..!i.2 M fa; ......r me : Crimii.i€o.fs--.....3...M...i!.v--..-..ilio m. € F": i .. 1...... . . . .53 53:912.... 3 .y. .1. ... . Lamas ononwpmofioaohowuwlwnofioanwuxm.N Mo Fflnpoomm cmfimnufiH .Nm. ohdmfim in}... . . . . . 5.383553 80 000 009 00.04 003 000* 000.. OOOH 0.00%. 0007 . CCUQ WulA .MO. M 1.4..IAAGIAV Ail“. 4 1. 11.1.1 A 111$.1M‘1\v ... v4 M M. M M .9 M M M M M M . M.....MEM M M; M _ M MMM MMM M? M M M M M M? M M . .M M M M M M .M M M M M M . M .. .. M.. Q . U. "M.. .M. . A «.m .. . .... .. ..... u. . ”Av. ..... MA.. 4.. a. . M .....AKMH.‘ M M MM M M M. M M . M M .M M M M M . M m... . .MZM M M M M M . M .. ......M M M M . m... .M..... .. ....M,1M M ... ..... ...... M MMM. _. M . .M M _ .M . . M M M M H..M. M, M . . M M MM .. . M M . _ M M M m. .. M M M M ,. _ M . . M M M .0n-w...;M .m MR .Mfl. Mn M .... M M _ M M . MOTH.” M M ..M ... _.. .M. M M . M. M M a A. M S M _ M, M M M M . MM M _ M . M M . M M M Ov-MTI-.. .... T. M. M....CM.M M MO... _ . M M MMM M H , M . . M . M 8 M M M M M: M M M M M M M .7. . ... M M.. MMM M M M M M .. M l 00”...-M .M..... ..M: _ MiM . .M.....M M M . . . . .M ... M M . M M MM M . MMM .M M... M . . . M M 8M.......:M :.M. M M M M ..... ..... 8. ....M - . M. M ...x . M M _ M M M M M . ... , . . M _ . . _ M . M . M M M “M M . M . _ On -.....A . ...-.. . . . . . .. T M. . M M M M . M . M M M M . M M M M M . M M M .. M M M M M M . . M M . M M . M .. Om v-4. .M.. .M -.. 291...". .. . .. .. . M .M M M M M . M M M M M M M . M M M M ,M M M M M ooTM. M M-. -.M. ...TZLI M _ M .u M..... M . M M M . M M M M M M M . . M M. M M M M _ M. M M M M M . M 09 -AM.-Ar-MrAA,s hi1: M.---AA.M!§I-. AVAIL..- -...M....-.-. .M-.}-LMAAeMri ....-.MA.-A--A-.-.-%-IAA-.AA ..M iii .01..-. 331.5!!!" ti)! nin‘ii» 53 M: ..u. 2. 9 a c s o. m it ... M... H r'lhhia. .i y M... M M.M-M-_.-- __ M... Y‘ ! ..,.M._._,, -.l-..” v . ......IIA. m on r | ..-...n..l.v \. .THmMV ododdpoooaohowuwlwuofiokpwvnm«N mo ghpoomm 693953” .Mm. omsmfim LuflwchFMU>fi OOON OOOfl COO? 000D, a M . m - .. . M . ...M :1--- M I“-.MI._.-M. . _.J. .M M M M M . o: .2 r....... M M M M M _ q M . _ . . . . M . . ..M o. . 5-1-.- M. Me--- . . M M M M M M M _ M M M M . M M M M .M .M M . . _ . M -18...- M M M . M M M M M .. .. M M M M M M M n M y M. OF. M_ M. .. . . . . . . ... n .. M M _ M M M M M . M M M M M M M A M. O”. . - A M M . M M . M . m M .M M M . . M M M . _ . . . . . . M M _ M M M .M M _ _ .....00. --.- .. b. -- I--.MAAAA. . . M M 3.23. . . . H M M . . M . M.4.¢..-...MW..M M _M _ M....AAL ON. M ..-.AAAAW. -AAA.- .I..!A....ALI..1.. . M . . . M _ M .. . . M M M M .M .. . _ . M . M .M M .. MAAAAALHA L I - .M . M M M . M M M M M M M M. M M . . M ,, 51.! .M . Ii-.-..--.-is..,.-.A-r.. I -A M M M M M M M M M . M . M M M M M . M _ . , M . _ M M M . rAALAAMA..t!TM: -. M A, M n e mi??? .....MM.....MM.....M...H.M.l.rM ‘f ‘f " c. AfimmM .odouwfipopmquhflpmgnpopOMOHfloM610“o .Ho gapommm $0.3..."me ..MMm 9.3me an» l {..:-.5 MunMEncgna 00¢... 05... 009 oofi; 00: 00M: . _ 00M. .....4.:11M~{x. M . .M , ......«IJM O M M . 2. u. 11;... .M M . . . . M M M . . M 1...: 71.7-3 . M . M . . . . . Ll)... .....z. . .... .... 9.. 1.. M . M . . . M I.» M . M M . M .7... M . M M _ u _ M M .3 . .....f . . ._Crm a ti. M. M .... v” 4" MM. M .x;. MMMI 0. _fl MM” 3. ._M ; ... MMM MM. OW M.. . M __ m 1 .9 .... g ......M 9...“ 181 m .M Homov oaonwhpopafloahfipofimhpopOhoaflowvlo«o .Ho Empoomm mogaomoh 3.50:me .HGOHosz .mm ohsmflh 2o 0 8. 8a 000 8‘ ac“ Ali 4 M..? or 0.0 06 OK 0.0 T: <5: , o.“ 0.? QM 0.6 . A953 oaouwhpogchflhflpofimapopofionn’ficnono ho Snapoomm voawkwnH .om ondmwm L0£Pp~fl€0>flx> 00.06 . all..|..£.....n O ...: ..: 1.11.. _. I . $ . - *~-_._..N._.__M--j v i i --.-.1._-- L .M .2 M “m m _- m . .A Homov oaoumApopodloflpmaanpmpoSohnawlo.0 .Ho Ednpoomm oonwnowon ofiponwmfi mwoaosz .NM 93me <§§Ez§.§§§§+ 183 .3va 0H0NapsoponoahflpogpqmumonoafloHalo6 .Ho 59.30on won-«92H .wm afipwflm AupEscggM 000M 000“ 000m 000v GOOD m - W. .... 1-. M I ‘ I; H . . vi.“ 51.76 «i. A 1...! A 45:2.- A111-.l...AI-J.. 11.}.- 1Ji4ll.1xllilw.-....l1:“;-0.v4 21% i.l.11.ut-.. u : 1,111.14 o W W A W m W W A W W W. W . .... .M....Z ‘M.1.Z..: ... A A A A A A A A A A A . _ . . . A . _ _ -..A.-.-W-.-.A-1-W-- W - flgw- A- .3-IAAOM 11611-3112.... A A A A. A A A A A A . A . A . . A ... A . _. . A . A A A A AA A A A . . A A A A _ A . _A A A . A A A A A A. A A . . A .. . A ..... --.,-..-..W {AW -A.A_ -w. T191.-. 1W--u..W. .AOn.,..-!1+.:;--; A A A A A A . . A. A . AA A A. A A A AA A A ...-. A I; W 2,” ..:-w.-- A A A _. A A A A A A A A r..A . _A. A A A . - AA A A A A . — . . A A. A A A A u . . .u --t .0 W . A A . . A A A A . M “AAKWMAA AAA . ... . A ..... AAA.AAU..AAA WAY. . Ohm .IJJIIIJI-II.I¢.IIIu.|.[lI.rl!-A|!ul.|e|l.14,}vull..01-.-. . . m ...-L ....._A A . A .. AA A h A A A A M.. . . W . . A A A . . _ . .M..... . ..H..._“... A A\. .tillrw...I-I.vl.:-|l. Il‘;lk I 31 .- - 2 9 1. n. a. c o. o a A. limtlllllllllivwlllllc-liulilnii-AWm-EHV-...-..-......c 185 m .- .A Homov orondmpmuofloahnpofimpfimmopoAuflowcno.o .Ho 8.9.30QO oogguomon ofipoawda hwmaosz .mm 8:de 3“ m6 0 8. . 8« 8n 8' OF ALTA A 82 Iii"!!! A 0+— o.o . o w OK 0.0 T5 42.: own 0 ¢ 06 . 0N 186 . 3va .eaoNwhpmpoQloflpogpnomoSOHnfivno«o .Ho Ede-Mpooo-Mm @meHMQH .0: ohswfim AunEaMAEM-r...» , 00m”: 000m 000” 000v 000m ...xc-Wllt «WI-31.0 A T« . \4..1 IAull. r Aiq‘lillAlJ. ll| 'Ill' ‘41; A A . A A A J . A . A A A A A A A A .2 .2 13...: A A _ A . . A . A A A A A A A . .. A. . A2 A.....!-A-11-..- . . i--. _ A . _ . . . . A A A A A A A .. A A . . A A . A A A A - A .. . A on A 21.-«Ari...- I-I-l-l» - - i1... . A A A . A . A . . A A A A . A A . A A A A A A A A . - -..i.-- -z-.- 1.! A A A A . A I A A . Cw. - 1L ..v-«lq .. A. .-. . 3). 15A,. . A A A. . A _ A A . A A . A ..A . A . .A A A . A. A . A . A AA . A A - . M. .. -zlv-J A . A . AA A A A, A A. A . m .. . a . C Lil-11:14.3 «ill-A . . - . A A . . . A . ..... Liar-LA‘SivL. t...” .. ...-0 . A. , A . AA . . . A A . . xiii-Milli!- AAI-ui- ... ...-.- .A A A . .. A A A A . A. .. U .. . .. .. A. A A . AAA.....1A..A _ . . . . ” lili-A-olfrwé-IIVA 00 Iii-1| 0. zll!-;.Ll.ll11..qii.-lr-A . 1-. --A . A . A . . . A . . A _ A A A A . . A A A A A IA g 151-3 9 - [pt-.-:..L.-IL-n,.-»..-i-..- - 1... -.A . 3 E m t 1 £2qu AA :. .IlAA lift-9-5...» an... r or 1.; 187 m ..A Homov :. 0H0thpopofloflhflpofiamemoSOMo’fldlo«o .Ho 983.0QO oofldflomoh owpmnmws nwofiosz .HAAA 089me !1vo- .7-.. o; . .od. o5 oé .9;&; 9n Qo og A1.3.A..H>2 CON— 001. 000— 009 000“ OOOn 0007 _{a ... . - 1.1.1.1 ..---.I..- I--- . 1-4.1.. . ....I. In- .:.-.-.. . .-.. -.. . ...... i . .. 1. . . .. .. . , . . r m _ _ “ “ fl a . _ w M _ 0 a a . . , h _ R u _ .n _ . u «n. g. I. ... . V _ . . . . . _ . . g . . _ . . . . . . _ . m _ . . . . . . _ — . . . _ . . :1 cullw: ..«v. -. n.0». -.. . . . . | A 1 . . . . ‘ . . . . J _ . . . . 3 . . . . h n . pk . n . a m , U . m n _ . . _ r- I-.- I ...I v-“.. -. Om. . . u .......... ...x. ... . , . , H 3. » fl m ‘ n ...4 u w _ _ _ l . n . . U {.55. 6.3!- x- I. . . --. .1... . - . . . _fi . a m _ v .3 n . m w . V . a m _ _ . __ N , .h 4 . . y . . . u _ u _, n n _a. 0.... q. u ......... .. ........ a _ u “ 8 m a _ u 8 . _ u u l _ . . . .q. 4.1-“... . - - . a n a. w u w w _ . . n . . v . . . .u . . _ “ m — . _ ‘ . . . _ ~ m M. ._ _ _ . m . H a ._ . H m m w m m M _ .. .. n . . . ._ . . a N . u _ W . . n . _ .qllll+-lio-p-.. I.-. 154.697.? 71.34-: ...s all}; 00 v m . 2.. I“ .. n M ~ _ _ _ _ . m _“ m . W . w . n m . . m M tiriL --.-.LEE. .1, . .5 . -- -:---..IIPII-.. a. Q .AMHumo V 0.3593opoqofihflpogxofiohogoflwlo6 .Ho 5399009.“. oofimflomon ounpoflwwfi 833.9 3 o." . o.” Qv . e 5% 0.... 0.0 E ! \ki‘. I. .l' \ “ . . W h. w w, h . 81 n . . , . m I “Er-HIE,» 1. IL {PEI .tII'ID-Lt'lrillllri [It . 0.9 g 3 06 EE . on... . c... c..." ,. r. z .3 93E o.“ ,. 52139.43;{isgrzziyffiufling/«..:q. ......a........,..._. ,. PM... . 355 odflgxoahfloflmflvlzqz .Ho Ephpommm doawéfiH 43 ogwfim LQQESCO>fivw 000V 000w. .w.q...m-.fi.na-u1.w-fl3.lnrin_,.0 U _. 2: ... 55:3— ...... . . Lug: I "I . i 190 ngEssgmfi OOON OOOn 000». 0000. . -..!..11W.111.im5!1_.uial,1.44w31”1.4l“34}1.m u .. ...”..wliw431..--..) O 00! _ , a: ..: 1:23. , . . . , a _. .C.‘ 1 3'! “4:4. _ -..-..L _ _ 7)? . . W _ m _ J c) f! ILU‘ 33. 4*."3 '3. a) : HI}! 9 3 nr mt :. on“... . . . EEC OHOanvopHnfi._mnmlahnaflawwn..m..n .Ho £93009” 60.3933 6.: ohsmfim l . Rani... . . . ., . . . 335553...» One 08 009 oow 000w ..ll!!!)ix uuun~u...n:.“w. .... . 2." ..: 31:1,. 192 ._F, _n L“.u_. .u... ... .> . . .7. . . . . .7. .... H .. u...........:.... FtEiF.L:¥riE‘i§p£nriF Mitzi. 45...... h _ , . . . . . ’si.::,l.l.r1-....i...\ ..:... . 10?.9’1‘. . .... a . Nr . 1 II. n u.) D. . .. ._ ax. “ m . . .— :" .:.. _ .... 0.3:; .r. .x _ ‘1. _ (V n m r u .31 . IL _ _ ... _ _ . - ... ...... . _ n - {U $32.... .:...... . .HmM oqusemx HhaoumnpopflhfloSMI n.3,: «H .Ho ghpoomm vohwawnH . opsmfim A . m LOSCEU is 5...? 11. . :va odwfimnoawfiflhnoflmwwlzé .Ho ggpoomm _vohthGH .w: mmfiwfim Bun-Snip. 338353...» 03 com 009 . 00$ 00: 009 009 000m 009. 08.x con... 1§l|i.llll1llllllnllll V‘I nlllnlxlllllill' ..u . M _ _ w _ n . . a . «it?! _ w m _ m w .M . h u w . . H ._ . o: :_1:_..>.. ~ _ . _ _ . _ _ _. . , . . H M .. “a w W M g n. W . _ u . . . . _ _ . _ . t. .... .1! .-.. . .27 IV, vcvxrl . L1! 11 OF . ...... ....-. ...x. III“ It I #21»? I... . .. c .u ...I 115.. ._ m . _ # d _ . m .. N _ u w _m w . W ~ . w . _ m _ m _ m ._liim .. h- . m--- -r- T om w- ..- I, ---. , - W. --: - m -1 --.: 1-. w M ... , ._ “ h A _ _ u , w . fl . m _ . F r W . . V M 5 m _ . . m _ . _ . ., _ , v .. . . M w i b m; M __ . V W W , . _ u , m i“ h - ---. - . - -:.---.. -, - - 3 4 n . n .N u . . w _ n w m 4? ; :.... W M m . m _ _ m . M . . . . _ : _ _ _ I _ k n . h 1.4. u. I x .« . . .. u: I, “lift! .'I I C» ' ul. Ill! '1... I . ll: .14, 1111-113. 1 In.“ :. n T f A“ u , _ M _ _ H _“ M m u u n . m. _” . , . . n . W Q C. a;u::u_;u:g4,1:-;3 Q 196 and at cane—5° 000 0, ON OwW on“ em” om“ . a M o dawn - u . A m v u. flooSmthoAgfiv _z.z ho ssnpoomm uwampwcH .om mnfiwwm LU Meagan-...flsuw #551 ___.........m_:.. ..:. ,_ .l'llllll‘llylk “kg—..: 13...... . , . w . 199 gm“. »~.—._._ . . ............... zszrgtgzmsgtw .. U3 200 .AH0nszv eqmp59-mx Spas Mmfimfioo opwhoaflonom AHHVHommoo map Afihaonwppop-mvmflpuj.fl ho SShpcmmm dedMHQH .dm opfiwfla Loflncuucafidhw 000M, . 000... 000.... . .u..—I..|Il‘.ll.‘ I’lj‘jarqltal .Iltl... J. \. II...~ “a: .5 ::...»... . , . __ ._ ,-...———--"— LO ..AHOnsg oflmnHOQQnm...AHhHoumnpmplmvaofimJ #3”: “3.3980 opanodaonom 3599500 93 .Ho 9.893on cmnwnmnH .mm omsmfim 33855....2... ooom coo... . S. ...unhEscu, ...... 008 00...: .... ..., . .. [fil-Illlllllcl. ll l|4 203 . AHOnSzV opwnpflfi AHVao>§nmAOHONahpopoamahflpoSwhwmpVmfio. .Ho £5.30on 69393.3“ .wm onsmfim .. ... .X. . . . «....n O.- uivaJ . ?_ ._ ., 1...-.. ......S C m; : or m m n o l!) APPENDIX II Computer Program.of Ketelaar Equation for the Calculation of Formation Constants 20H 205 The numerical calculations of the formation con— stants of the respective cyclopolymethylenetetrazole- iodine complexes were performed on a Control Data 3600 digital computer with the program written in FORTRAN. The program listed below was written by William J. McKinney of this laboratory. The author is indebted to him for its use. The following data are read in for the Ketelaar equation computer program. The first data card is the identification card, ID, and uses columns 1 through 56. The second data card contains in columns 1 through 10 the absorbance of iodine, AI, at the wavelength of interest, the molar concentration of iodine, CI, in columns ll through 20, and the number of data sets read in, N, in columns 21 and 22. The third through N data cards contain in columns 1 through 10 the absorbance, A, at the wavelength of interest and the molar concentration, CB, of the respective cyclopolymethylenetetrazole in columns 11 through 20. The last data card contains the end of D statement in columns 21 through 28. wnz 1nd 1n: 11 '19 .1: 1d 731 541 961 951 na- 206 CO‘ST22 1./(“t(FDS”'- l=F—‘§X)) PYFF = A3S7("HIST? - C"NST) YF(DYFF.LF. .n“1¢C“PQT)9°.304 rows? :ccwsva PRINT 11, Fuss. PU‘ST ranAT(,1nv,un:A: ancoupTrVITY = .ra.5. fiXwFDRWATlnN nnNSTANT 110.33 Y ’ rnAcT : ((cuuxv - euwxcsHHY/FN)tn21/(SHMY2 -SUWX**9/FN3 F : CUVYQ - (QIMYt071FM) . FRACT 99 = b/(rm . 7.n\ Q = QQPTV(°?) gAp 3 c2/(cuuxe - (SHMVtOZIFN)) =A : SDPYF(SA9\ :99 : c2.QHMVQ/(rN.sHMv2 - SUMXwaZD gag cngr(cu9\ VA: = (SA/")0." .5 fSD/Q)Oi2 QKFPE c031T (VfiR) QKF = FO‘STtQKFP uptnr 12, e. s~. SO, SVF FOPNATf/10Y¢ crn. or A STNGLE Y = 'F14.11.=X~STD. nEV. 0F 1s|npc = aF14.11./1¢X* QT“. DFV. 0F IMTCRFEDT = 'F14-11.5¥* 997m. DVV. nr «r : .r4n,43 PRVNT 15 rampart/1ny.v chLC T DFVYATI”N*/’ VDPMAlerX. 47<4.RV "n 211 I :10 " YCILF(Y) = roll!) .5 7(1) = AG§F(Y(') - YfiALC(I)) npv(r) = T(13 - 1.3tt . pnvmr «4. Vet»; vcaLfi(1). T(I). DEV FAILNRH =ncths) 9o pcrn 1, 1n e 1 ranATt7nax ) PQYNT 9. 1P 9 FnDMAT (1H1.1nv,7A6) VF»(ID‘E".“HFN“ “F R5 anp F99x = EDSYInv SHR X. C! = IODIME anc, N = NJMQED 0; DATA PFAD 31 AI. rt; " 1 FDPMAT17F1n. I?) FDCX = AY/FI PRYNT A.FPCX.C!.“ 4 FnrMATf/10Y+CP=IIO“X = .r9,3, 5XtI"UYNF FOMC = rr19.1o. SXtN = .12 15 PRINT = . : FnPMAT(/1nV.An=nWRANr nouc BASFiI) 1:1 101 PFAD 6. ’(Y). 'an\. II A FODHAT(?F1H. Ac) PRYNT 7. A(Tfi. nD(Y) , 5 FOPMATI19X)FA.A.4nV,r19.1o) cn3(1) = CD(¥) IFIIJ.CD.RHFMn HF ") 27, 21 91 Y 2 In t 'Ih'T’11n4 25 PRINT 9 a rnPMnTr/1nV.v EPsyLnN To/a no 2n1 1:1;w ' thTtlx = A(I)/CY Y(I) = 1./'FD§T(T) - EDSX) ?n1 PRINT 0.V(Is, cpsTII» ' ° FORMATI1FX.F19.1".1nY.F8.2) 1L = 1 E14 suvx = SUMV = :uka = QUMX? = SUMY? = o.n PR‘NT 29 3° F'nPMATl/16Y.Y.n DO 909 I = 1, “ Y(?) : 1./rn(1\ 090 PRINT 49. y<13 4o FfipMATI1PXvF1S.1") DO 301 I = 1, “ cHMX = SWMY + V(1) envy = SUMV . y(y) elwxv : tuvyv + 1(Y)*Y(I) FUVX9 I CUV¥9 + Y(Y)ta° ‘01 QHVYQ = cUVY’? t V(Y)ot9 FM I N v a (Pvtcuuyv - QU”X¢SHMV)/(FN*SUMV2 - SUMthZ‘ P = (SPMV«CHch - QUMXV.