5&9: {IIIUHIHIUJIWINIWINHJIHHIIIUHIHllllHllHHl/li‘ LIBRARY Michigan State University This is to certify that the thesis entitled THE INITIAL INVESTIGATION OF THE CHEMICAL REACTIVITY OF OCTAHYDROXYCYCLOBUTANE presented by Kenneth C. Fey \ =fia§bgen accepted towards fulfillment EXAR, x of the requirements for Masters degree in ChemistrL max/[W Major professor, Date #97 EA /%7/ 0-7639 m: 25¢ per day per 1t- RETURNIm LIBRARY MATERIALS: Place in book return to remove charge tron circulation records THE INITIAL INVESTIGATION OF THE CHEMICAL REACTIVITY 0F OCTAHYDROXYCYCLOBUTANE by Kenneth C. Fey A THESIS Submitted to Michigan State University in partial fullfillment of the requirements for the degree of MASTER OF SCIENCE Department of Chemistry 1981 ABSTRACT THE INITIAL INVESTIGATION OF THE CHEMICAL REACTIVITY OF OCTAHYDROXYCYCLOBUTANE By Kenneth C. Fey The intent of this program was to determine the utility of octahydroxy- cyclobutane as at C-4 synthon for the synthesis of multicyclic highly conjugated ring systems. These compounds would then be evaluated as organic conductors. A prerequisite for such an organic material is that it be symmetrical and contain a high degree of conjugation. Octahydroxy- cyclobutane is a prime candidate for such a synthon because it contains abundant functionality as well as the ability thru elimination reactions to form carbon-carbon double bonds resulting in an unsaturated internal C-h fused ring. However, evaluation of octahydroxycyclobutane in this role proved dis- appointing since its reactions with 3-keto structures, 1° alcohols, acid anhydrides, acid chlorides, and o-phenylenediamine were all charac- terized by poor yields and complex product mixtures. With 2° amines it produced, via ring opening, satisfactory yields of bis(dialky1amino)-2, 3-dihydroxy-2-butenedioic acid salts. ACKNOWLEDGEMENTS The author would like to acknowledge the valuable insight, advice, and encouragement of Dr. E. LeGoff during the term of this research project. The author also desires to acknowledge the cooperation of The Dow Corning Corporation for their advance of time and financial as well as moral support. ii TABLE OF CONTENTS PAGE INTRODUCTION 1-2 RESULTS AND DISCUSSION 3-16 A) Synthesis of Octahydroxycyclobutane and Other Reactive 3-4 Intermediates from Squaric Acid B) Attempts to Synthesize Multicyclic Ring Compounds from 4-6 Octahydroxycyclobutane and Substrates Containing a 3-Keto Structure C) Reaction of Octahydroxycyclobutane with Alcohols, Acid 6-10 Anhydrides, and Acetals D) Reaction of Octahydroxycyclobutane with o-Phenylenediamine 10-13 E) Reaction of Octahydroxycyclobutane with 2° Amines 13-16 CONCLUSIONS 16-17 EXPERIMENTAL 18-23 BIBLIOGRAPHY ' 24 APPENDICES iii LIST OF TABLES PAgg TABLE I IR COMPARISON 0F 11 WITH 2,3-DIHYDROXY-2-BUTENEDIOIC 3 ACID, DIME'I'HYL ESTER TABLE II REACTIONS OF _1_ WITH 2° AMINES 14 TABLE III COMPARISON OF _2_7_g DECOMPOSITION POINTS 15 iv LIST OF FIGURES PAGE FIGURE 1 ATTEMPTS TO SYNTHESIZE MULTICYCLIC 5 STRUCTURES USING OCTAHYDROXYCYCLOBUTANE FIGURE 2 REACTION OF OCTAHYDROXYCYCLOBUTANE WITH 7 1° ALCOHOLS, ACID ANHYDRIDES, AND ACETALS FIGURE 3 REACTION OF OCTAHYDROXYCYCLOBUTANE WITH 12 o-PHENYLENEDIAMINE INTRODUCTION The synthesis of fused multicyclic ring structures having a high degree of conjugation for use as organic conductors has been of interest to this lab for some time. One proposal for arriving at such structures was to use octahydroxycyclobutane l as a synthon so that a multicyclic compound might be constructed about a central unsaturated cyclobutane ring. The first reported efficient synthesis of l was carried out by westl, and involved the oxidation of squaric acid (1,2-diketo-3,4-dihydroxy- 3-cyclobutene) with either nitric acid or bromine. Infrared (IR) analysis revealed that no carbonyl groups were present indicating a fully hydrated structure rather than. one having carbonyl and ‘water groups equilibrated. Several other papers were published in the next decade which supported West's findings and elaborated further on the structure of 1. Skujins2 reported from its mass spectrum that mass fragments at m/e 184 and 166 were not observed indicating the ease with which the parent molecule can lose two moles of water. But the fully dehydrated tetrone (m/e = 112) is a1So absent implying that ring fragmentation occurs prior to complete dehydration. Though West believed I decomposed to carbon monoxide at 140°C, Skujins showed that water and carbon dioxide as well are major decomposition products. Bock3 studying its crystal structure and Miller4.its IR and Raman spec- tra both concluded that the structure of l was rigidly planar due to hydrogen bonding of the compound's eight hydroxyl groups. This finding is in contrast to the structure of octachlorocyclobutane as reported by Owens. The latter has a puckered ring structure as one might expect. C13 Nuclear Magnetic Resonance (NMR) analysis of l was carried out as part of this study to confirm the earlier IR and Raman spectra which imply the presence of only one carbon species. The spectrum, run in D20, revealed a lone sharp signal at 6 = 87.04 ppm. By comparison, one would expect to find the BC-O- structure at 6 = 73-85 ppm. 2 Only Scharf and Seidler‘5 reported any investigation of the chemical reactivity of _1_. They isolated it by hydrolysing a photochemical cyclo- addition product _2_. IR and H'NMR analyses of the hydrolysis product matched the structure for 1 found by West. ' 0 Yo c. 0 CI 0/40 2 When _1_ was reacted with semicarbazide-hydrochloride, compound g was isolated. ' The authors make no suggestion, however, as to the mechanism Of this reaction: substitution of hydroxyl followed by dehydration, or dehydration of 1 followed by addition to the resultant carbonyl and finally elimination of water. R N OH OH I R=NHCONHZ RN NR é Limited solubility of l in most common solvents would make its reaction study quite difficult at times. Dimethylsulfoxide, dimethylformamide, and water would prove to be the only solvents in which 1 could be readily dissolved. Other solvents (i.e. CHC13, CC14, aromatics, ethers, ketones) were incapable of dissolving 1, while materials such as pyri- dine and alcohols caused significant decomposition to occur within a few hours. RESULTS AND DISCUSSION A. Synthesis 0f Octahydroxycyclobutane And Other Reactive Intermediates From Squaric Acid To synthesize 1, West1 oxidized squaric acid 5 in an aqueous medium with either nitric acid or bromine, 84%,or 70% yield respectively. During this study, that synthetic procedure was improved by incor- porating acetone.into the reaction medium. The’increased yield (now >902) likely is attributable to acetone's ability of rapidly precipitating I from the reaction solution as it is formed thus minimizing any oxidative degradation of the product. Speculation concerning the mechanism for this reaction pointed to- ward an oxidation of 5 to some intermediate which then was reduced via hydrolysis. Should this-be operative, one might expect a methylated adduct of 1 if water is replaced with methanol. This was attempted using bromine as the oxidant, and a few off-white crystals hm; = 169-171°C) were isolated, é. Mass spectral data indicated the largest fragment to be m/e = 176. This corresponds to two possible isomers: S3, Sb. CH oc co,CH, }o>,_ “vi. . Ho 0H cu,o cuao .53 a Product S was also made via another procedure and this will be dis- cussed in Section C, Results and Discussion. At‘this time, let it suffice to say that water is by far a more efficient reactant than methanol for converting the oxidized intermediate of 5 to products. 4 Dimethyl squarate 6 was also used during this study as an inter- 7 had synthesized §_via treat- mediate in several reactions. Cohen ment of g with diazomethane, or by reaction 0f.§:§ silver salt with methyl iodide. A less hazardous and more rapid procedure was used to generate 6 for this study. Methanol, g, and an excess of 2,2'-dimethoxypropane were refluxed for 24 hours, concentrated, and the residue recrystallized from boiling ether. The resulting light yellow crystals melted at 55-56°C and the IR analysis was identical to that reported by Cohen. Attempts To Synthesize Multicyclic Structures From Octahydroxycyclo- butane And Substrates Containing A 3-Keto Structure Weiss had reported8 that dimethyl -3-ketogflutarate and a number of 1,2-dicarbonyl compounds could be reacted at room temperature in aqueous solution to yield fused ring systems (eq. 1). cogs 902C coza CHO <— H I -+ 2. C) .:21§h§h. () () CHO (- H , (eq- 1) COzR no,c C ozR It is likely that the mild acid conditions favor formation of the glutarate's enolate, and that the now slightly anionic methylene carbon attacks the glyoxal carbonyl carbon. Elimination of water leads to the final product. Our intent of replacing glyoxal with l presupposed that these enolates would also attack the election difficient cyclobutane ring carbons as depicted by eq. 2. C02.“ R0 C C02.“ _1_L_*Z <(’°""0 : 9 0M CO,R l~a 0 he a) No.09c /Qc,_0 80°C. 2) {kn ) co 85°C HO \\O ( z ‘ i 01,0 0 ° Cn,o 0 IO\ FIGURE 1 ATTEMPTS TO SYNTHESIZE MULTICYCLIC STRUCTURES USING OCTAHYDROXYCYCLOBUTANE 6 Figure 1 summarizes these experiments. In each case, the reactions were extremely slow and only a small amount of product could be isolated. Products 1 and g were orange-yellow solids which melted at 85-6°C. Their mass spectra indicated the presence of glutarate fragments though it cannot be determined if they result from forma- tion of the desired products or contamination by starting material. The reaction of _1_ with 1,3-diphenyl-2-propanone fared worse, as only starting materials could be recovered. But since 1,3-diphenyl- 2-propanone is more stable than. the glutarates, it.7was chosen to be used in further attempts to make a multicyclic product. In one case, the diacetyl derivative of g was generated in EIEB by use of sodium acetate/acetic anhydride; the other employed di- methyl squarate 6 in sodium ethoxide/ethanol, an adaptation of the procedure of Schmidt and Reid.9 Respectively, products 3 and 19 were recovered. Unfortunately, these reactions also yielded small quantities of products. Tarry reaction mixtures made any straightforward iso- lation difficult, and consequently those few crystals obtained were only analyzed by elemental and mass spectral methods. Both have similar mass patterns Showing diphenylpropanone type fragments while 2 in addition displayed species corresponding to acetyl. Not surprisingly, their elemental analyses revealed no empirical for- mula which matched any of the observed mass fragmentation patterns. This concept was as a result abandoned since it was apparent that products obtained wouLd be both quite difficult to purify and in very low yield. Reactions Of Octahydroxycyclobutane With Alcohols, Acid Anhydrides, And Acetals Assuming l behaves as an alcohol, then reaction with other alcohols, acid anhydrides, and acid chlorides should be expected. Consequently, ILP. NJK NJfi CH,C(C;H,O)2.C H, I “4'. NmH/CflaI - cuaoH/H't CH3C(°CH3)._CH3 /H+ . Naonc / Heto ’ OH one (no)1 0 ° O\\ cuao,c Color-I, —OH one >< ; 123m». \ ; , Ho °“ (“30). o ‘o o’ ‘o 11’ 33 FIGURE 2 REACTION OF OCTAHYDROXYCYCLOBUTANE WITH 1° ALCOHOLS, ACID ANHYDRIDES.AND ACETALS 8 several attempts were made to replace the hydroxyl hydrogens of l with methyl or ethyl groups (See Figure 2). Refluxing l in methanol with acid present succeeded in only causing a slow decomposition to occur, while Brown's procedure10 for methyl- ating glycols (sodium hydride/methyl iodide) yielded what appeared to be an insoluble polymeric substance. Success was achieved by adapting the procedure used to synthesize 6. Overnight refluxing of _1_ and 2,2'-dimethoxypropane in dry methanol yielded a methylated product 11. These fine white crys- tals melted at 171-4°C and produced the same mass spectral frag- mentation pattern as § (mp = 169-171°C), the material isolated from the bromine oxidation of‘fl in methanol. Elemental analysis of 11 also confirmed that its empirical formula matched that of the pro- posed structures 5a, 5b. Despite that only very small amounts of § or 11 were isolated, an attempt was made to determine if either i". or §_b_ could alone be identified as the correct structure of these products. Structure §a could not be found in the literature; however, éb is known and a wide range of melting points is reported: 165-173°11, 157-165°12,. 178-180°13, 174-174°14. But only Goodwin11 reports spectral data for these derivatives of 2,3-dihydroxy-2-butenedioic acid, among them the dimethyl ester £§bl. He reports IR bands that are quite like those obtained from a sample of 11 (See Table I). TABLE I IR COMPARISON 0F 11 WITH 2,3-DIHYDROXY-Z-BUTENEDIOIC ACID, DIMETHYL ESTER 11 2,3-DIHYDROXY-2-BUTENEDIOIC ACID, DIMETHYL ESTER 2.8-3.3w - 3.39 3.18 6.003 5.983 6.903 6.948 7.20 7.29 8.003, br 8.038 9.803 9.825 11.40 11.41 13.00 - 14.60 - 9 This data suggests that §b is the correct structure, but it does not completely eliminate §__a_. One isomer of is is 1,2-diketo-3,3' , 4,4'-dihydroxy-dimethoxycyclobutane, and such 1,2-diketo com- pounds display a sharp band at ~6.0 microns. C13 NMR could be used to resolve _this question since §_a_ would show (C (C = C) carbons. Unfortunately the yields of both reactions _(_5_ and 0) and (3°) carbon species while _5}; would display (C = 0) and E) are so poor that far too little of the product could be isolated for 013 analysis. An attempt was made to make the ethylated derivative of 1 using 2,2'- diethoxypropane in refluxing ethanol. Unfortunately, a very complex product mixture results as well as significant decomposition of _1_, and no product could be isolated. Numerous attempts were made to substitute acetoxy groups into com- pound _1_, but all met with only limited success at best. Reagent combinations such as acetic anhydride/4DMAP (4-dimethylaminopyri- dine)15, sodium acetate in acetic acid, trichloroacetic acid/acetic anhydride and sodium acetate in acetic anhydride, were employed. The most successful of these combinations 'was the last. The yellow oil that resulted could be chromatographed to yield a frac- tion which when analyzed by mass spectroscopy indicated fragments corresponding to structures 123:2. Other (analyses could not be performed however because the sample was impure and of a very small amount. CHQc CHac —-OHc 0" 10 Thionyl chloride was used to attempt chlorination of 1, according to the procedure for generating dichlorosquaratels. These reactions easily generated black tars while surprisingly a signi- ficant portion of unreacted 1 could be recovered. Silylation of 1 using Me3SiC1/4-DMAP/(Et)3N was also attempted, the 4-DMAP reportedly being very effectively in these applications.17 However little product was isolated and no unreacted 1 could be re- covered leading to the conclusion that decomposition was occuring rapidly. Reaction 0f Octahydroxycyclobutane With o-Phenylenediamine One goal of this project was to determine if 1 could be used as a cyclobutane synthon for multicyclic fused ring systems. The prin- ciple approach used toward achieving this goal was the reaction of l with o-phenylenediamine (eq 3). HO OH NH ‘ HO OH 1 N N +2 ¢~©In© HO OH NH, N N Vic> (3&1 ' l 13 Although a synthesis of 13 is not mentioned in the recent litera- ture, a number of analogous reactions using squaric acid _4 and o-phenylencdiamine (o-PD) are reported. From 4 and o-PD, Erhardt18 and Skujins19 both synthesized 14, from which Erhardt obtained the aromatized adduct 1Q by use of benzoquinone/DMF. The reactions of lg with aniline or a second equivalent of (o-PD) yielded 11 and 16 respectively, the suggestion being that the second equivalent of (o-PD) cannot cyclize with the C-4 ring before the latter is opened. Erhardt also reports a number of cases when water is 11 observed to hydrolyze and (nun) the C-4 ring of l; presumably by nucle0philic attack at the carbonyl. But attempts to arrive at 13 by reaction of 4 with two equivalents plus an excess of (o-PD) do Oh /:@?© CI:11°©I:I<::'_ @@::l:-u—© .11. not appear successful. Replacement of‘4 with l was contemplated as a means of synthesizing 13 since initial attack by the amine groups conceivably could occur at a greater number of ring carbons than with 4. This was at- tempted using two reaction media (Figure 3). Products from each system form rapidly. A very intense deep red to dark violet color also emerges almost immediately upon mixing of the reactions. Unfortunately, the products obtained are spar- ingly soluble in most common solvents and as a result purification was difficult. The 1:1 adducts, 14 or the isomer 18, were found by IR to contain NH (3.23p) and 1,2-dicarbony1 (5.55-5.65p) groups, but no hydroxyl was noted. The mass spectral analysis matched that reported by Webb.” 0.: the strength that no .hydroxyl bonds were found in IR analysis, structure 14 was deemed the correct configuration. In attempts to produce 13, (o-PD) was reacted with l in 2:1 and 3:1 ratios. In the former case, a mass spectrum showed a fragmentation pattern corresponding to the presence of 12 or its isomer 14 which was isolated by Erhardt.18 An IR analysis indicated NH groups, no OH groups, and was inconclusive on the presence of >0 = 0 species. Since the solubility of this material was quite low, no H'NMR could 12 N 0 N§ 0H 3:: r + ~ I H 15 18 gnu, @NHz 1000 V1 “PVC 7. XS @3ij (151:1) mix—C) _ _ _2___0 +_1_4,_1__6 FIGURE 3 REACTION OF OCTAHYDI‘ \OXY CXCLCB L'T;\.\'E LIT}! o-FHENYLENEDI .nL‘IIwT 13 be run to aid in resolving the structure. The purity of the sample itself was questioned when elemental analysis revealed a chemical composition not consistent with the other structural data. H .0 N '3 ~ o~ K) ‘ (01 Li "‘ "‘ "W “' OH :4’ @fi 18 19 ‘ 20 II \} The 3:1 adduct also was a victim of its inability to be purified. Mass spectral data suggests that fragments corresponding to _1_6, 14, and 22 are present, and not surprisingly IR and elemental analyses prove inconclusive. Two comments should be made.‘ First, the initial substitution of _1_ by (o-PD) must also promote dehydration of the remaining adjacent hydroxyl groups since the products- formed are identical to those found from the reaction of 4 with (o-PD). Secondly, since yields are significantly higher when 4 is used, one can conclude that _1_ is more susceptible to C-4 ring opening processes than is 4 or 1;. Reactions Of Octahydroxycyclobutane With 2° Amines The reaction of _1_ with o-phenylenediamine indicated the instability of _1_ in a concentrated 1° amine solution. This, in spite of the fact that Scharf° had isolated the imine product of 1 and semicaribazide-hydrochloride. Thus it would appear that imine- containing derivatives of _1_ can only be synthesized under mild and/or specific reaction conditions. The decision to investigate reactions of l with 2° amines is pre- dicted on the basis that these reagents will not form imine struc- tures, thus hOpefully permitting isolation of more stable deri- vatives of _1_. This was found to be an accurate assumption as slow addition of 2° amines to aqueous solutions of _1_ at 0°C lead to good yields of stable products (Table II). 22L II REACTIONS or ;_WITH 2° AhINES DECOMPOSITION POINT(°C) # AMINE YIELDa * .22 Diethyl 43.74 166.5-167.5° 23 Diisopropyl 47.58 l93.5-l94.5° 24 Dimorpholino 57.74 194° 25b Dicyclohexyl 2.16 201-202° 26 Diethyl 8.75 l75-177° ; Based on 1, recrystallized product. However, since a saturated, 4 used instead of l. amine-substituted cyclobutane product was anticipated, it was surprising to find that 2_2, 2.3, _2_4, and 25 all possessed a strong IR band at 6.2311 indicating the possibility of the carboxylate ion group. Having noted that the reaction of _1_ with o-phenylenediamine resulted ,in. produCts similar to those obtained from 4 and o-phenylenediamine, the suspicion arose that _1_ may have been reduced to a squarate-type intermediate in this reaction as well. As noted in Table II, this hypothesis was dis- proven when squaric acid and diethylamine were reacted _(_2_6__). Product 24 is not the same material as 22. Elemental analyses of 22-25 reveal each product has the same empi- rical formula: group . correspond to the empirical formula. (02H303NR2)n where R is the appropriate alkyl Structures 27a,b represent those 4-carbon amine salts that p- .- . + o OH I r- "1 o- + HO OH (NHIRL) ' (NH R ) . U 2. HO 1 2 2. / \ .- o" 0 _1 :05: CO; d 27a _2_7_13 But only 27b contains a carboxylate structure, as suggested by the IR, and 213 is likely to be unstable. l4 15 C13NMR analysis of g and _2_3 reveal a low intensity pair of signals at 6 = 174: 0.05ppm (C = O) and 6 = 137 1 0.05pm (C = C) as well as the amine carbon signals which are quite strong.8 If these signals do correspond to (C = O) and (C = C) as represented in _2_Z_b_, then their low intensity would be expected because no hydrogen is bonded directly or adjacent to these carbons. Proceeding on the assumption that _2__7_b_ is the correct structure, a neutralization equivalent was performed on 2_4. The actual molecular weight of _2_4 is 322.31g, and the test value obtained was 323.51g. Following this, the free acid was isolated 421) by neutra- lization using concentrated hydrochloric acid; IR analysis of the product matched the bands reported for 2,3-dihydroxymaleic acid21 (2.353, 3.24w, .s.2m, 6.14s,‘ 6.40w, ’6.75-6.853, 8.0-8.4s, 9.6w, 10.6m, 12.8m micron). A subsequent literature search for related compounds revealed that the tra—us form of _2_2 and Q had been previously’reported.22 Table III shows the comparison of reported decomposition points. Com- parison of the infrared spectra suggests 2_2 has the 3313 form, but the conformation for _2_3 is not so implied. Yet in either case, this data is not conclusive evidence for the correct conformation. TABLE I I I COMPARISON OF 2.113 DECOMPOSITION POINTS DECOMPOSITION POINTS (°C) _fi_ AMINE OBSERVED REPORTED 22 Diethyl l66.5-167.S 168-169 23 Diisopropyl 193.5-194.5 183-184 a Analogous structures and their C13NMR values taken from ref.23 are: 0 O 0 [8‘1 :87 ./ J ”9.8” "A,” \ I O O 0 283 28b "Sc —“ ‘ l6 llartree2M addressed a similar configuration question for maleic acid methyl esters in 1953. He resolved that the free acid is in the trans form in solution, a form he trapped by using diazomethane to form the corresponding methyl esters. Gupta25 later confirmed Hartree's conclusions from Xfiray studies of the acid’s crystalline dihydrate. Since 22:25 are quite closely related to maleic acid, their X-ray analyses should also be capable of satisfactorily verifying their configurations. Finally, these unexpected products' formation might be explained by the following mechanism. Following an initial loss of one proton, the formation of a carboxylic acid group and ring opening take place. This is accompanied by the loss of a mole of water. A subsequent rearrangement to form the second acid group followed by the elimi- nation of another mole of water yields the free acid. no on .40 OH no on "'\ OH H OH HO OH - 693E ———=» -——- l --—5 I I l”- ‘ HO IQ" "OJ—:0 O-l O H o OH HO OH HO OH 44,0 NHR‘ H010 COzH FHTHliE Sfimfi' «f—-—-' ’/----N\ ' . |*C) (DFI CON CLUS ION The principle goal of this project was to use _1_ as a cyclobutane synthon to synthesize fused ring systems. That this goal was not achieved is probably due to _1_‘s unique cage structure of hydrogen bonds, 8 structure influential enough to render _1_ planar and quite stable. This stability, however, is lost upon disruption of the hydrogen bonding configuration. The low yields, high reactivity, and low degree of specificity displayed by _1_ are indications of this unique molecular structure. 17 Generally, many of 1's reaction products are those same materials iso- lated from reactions of squaric acid, the reduced form of _1_. This implies that 1 can easily be reduced to squaric acid-type intermediates. An unexpected result of this study was the identification of the unique reaction products of _1_ and 2° amines. This facile route to aliphatic C-4 unsaturated dicarboxylic acids might be considered in the following sequence for introducing acid groups into cyclobutane rings. Such a sequence would enable the subsequent formation of additional fused rings via the acid groups. HO OH ”III: “fl. x: HO OH The author would like to see X-ray analysis of the C-4 acid salts to confirm their geometric configurations. . Also an effort to improve the yields of reactions 5 and 11 would be in order so that 013NMR analysis could be used to elucidate the structure of these materials. EXPERIMENTAL Octahydroxycyclobutane was recrystallized from water-acetone and o-phenylenediamine from methanol prior to being used. All other rea- gents were used as received. 2,2'-dimethoxypropane was prepared by the procedure of Hured and Pollack.26 Analytical data was obtained from the following: H'NMR, Varian T-60 spectrometer; C13NMR, Varian CST-20 spectrometer; IR, Perkin-Elmer 237D; mass spectrometer was manufactured by Hitachi. Elemental analysis were determined by the Analytical Labor- atory of the Dow Corning Corporation, Midland, MI., 48640. Melt points were run on a Hoover-Thomas apparatus and are uncorrected. Octahydroxycyclobutane 1 Squaric acid (4, 10g., 87.7mmol) was dissolved in 100ml Ego-50ml ace- tone. Bromine added dropwise at 0°C until yellow color persisted. Product spontaneously precipitated from solution during bromine addition after which cooling for 30 minutes in a Dry Ice-acetone bath was main- tained. Additional acetone added (100ml) prior to filtration. White crystals (15.2g (94.17% based on 4) mp: 138-139°d). Recrystallized from a minimum of H20-100m1 acetone, mp: 140°d. IR (Nujol, microns): 3.005, br; 8.605; 9.25; 11.205h Mass spectrum identical to literature.1 Calculated for C4H303: C, 26.09; H, 4.35. Found: C,26.l3; H, 4.36. Dimethyl Squarate 6 Squaric acid _(_4, 103, 87.72 mmol) was charged to dry MeOH (100ml) and 2,2'-dimethoxypropane (50ml, Eastman). After 10 hours of refluxing, and every 3 hours afterward, 25ml of condensables were removed using a Dean Stark trap. After 19 hours, the remaining condensables were removed. The resulting residue was dissolved in boiling pet ether (250ml), fil- tered, then allowed to crystalize. The light yellow crystals obtained were washed with hexane and vacuum dried. (7.913, 63.5% yield, mp: 55-6°C). IR(KBr, microns): 3.36m, 4.44w, 5.555, 5.755, 6.285, 6.755, 7.055, 7.305, 8.15m, 8.70m, 9.205, 9.655, 10.805, 12.155. 18 19 Product 5, Reaction of 4 with Bromine in Methanol Squaric acid ( 4, 0.5g, 4.38 mmol) was dissolved at 35°C in dry MeOH (50ml) and then bromine was added until a faint yellow color persisted. Removal of volatiles yield a beige-colored paste which upon suspension in cold MeOH yielded a small amount of white crystals (mp: 169-171°). Chemical analysis was limited to a mass spectrum, largest fragment: m/e = 176. Product 2, Reaction of 4 with 1,3-Diphenyl-2-Propanone Squaric acid ( 4, 2g, 17.54mmol ) was mixed at 80°C with acetic an- hydride (50ml) and a small amount of sodium acetate. The resulting squaric diacetate was combined in gill; with 1,3-diphenyl-2-propanone (2.46g, 11.75 mmol). After 36 hours at 80-85°C, the remaining acetic anhydride was removed using a rotary evaporator. The residue was taken up in ether and a small amount of hexane; the unreacted squarates being insoluble were filtered. The ether solution was washed twice with H20 (50ml), then concentrated in) a thick dark oil. Redissolution in cold ether (10m1)-hexane (2ml) yielded a few milligrams of an orange powder (mp: 180-6°C). Mass spectral analysis showed fragments of diphenyl- propanone; however, little else could be deduced. Elemental analysis: Found: C, 83.3; H, 6.80. Product 1, Reaction of 1 with Dimethyl-3-Ketoglutarate Octahydroxycyclobutane ( _1_, 1g, 5.43 mmol) was dissolved in H20(75ml), then dimethyl-B-ketoglutarate (0.953, 5.43 mmol) was added, and the pH adjusted 1x) 4-5 with dilute potassium carbonate. Mixture stirred at 25°C for 96 hours during which time it turned a deep yellow. Removal of the water resulted in 0.8g of an orange paste which was taken up in H20 (50ml) and extracted with several portions (50ml) of CHC13 to remove unreacted glutarate (0.35g removed). The aqueous extract. was then saturated with salt, and bit of acetone added. Orange crystals isolated (0.103, mp: 85-6°d). IR (Nujol, microns): 2.8-3.2w, br; 5.705; 5.885; 6.105; 6.355; 7.8-8.8w5 br. Mass spectral analysis shows fragments corresponding to decomposition of l and glutarate. Elemental analysis: Found: C, 24.5; H, 2.60. § 20 Product _8_, Same Reaction as Product 1 but with Different Isolation Procedure The orange paste was taken up in MeOH, unreacted 1 remained insoluble and was filtered off. The MeOH was then removed and the yellow solid was extracted with equal volumes of CHCl3/H20, the former removing glutarate impurities. The aqueous portion was then evaporated and the residue taken up in acetone from which 0.4g of yellow crystals were recovered (mp = 86-7°C). Mass spectrum shows m/e = 198 fragment which corresponds to the mono-methyl derivative of 1; the remaining fragments are identical to those found for product _8__. Elemental analysis: Found: C, 30.2; H, 4.0. Product 11, Reaction of 1 with Acetic Anhydride/Sodium Acetate Octahydroxycyclobutane ( 1, 0.58g, 3.15mmol) was mixed with acetic anhy- dride (50ml) and a catalytic amount of sodium acetate, brought to 50°C, and let stir for 24 hours. No reaction appeared to occur, so tempera- ture was raised to 80°C, and let stir for 9 hours after which the re- maining acetic anhydride was removed. The resulting dark, thick oil was chromatographed on silica gel, 60 mesh (5" x 6" columns). A 2/1 v/v hexane/ chloroform solvent eluted a fraction of product having a strong acetic anhydride odor. Upon setting for several days this solution yielded a few milligrams of light yellow crystals. Mass spectral analysis shows fragments at m/e = 172 and 214, corresponding to (triketo-hydroxy-acetoxycyclobutane) and (triketoediacetoxycyclobutane) respectively. Product 11, Reaction of 1 with 2,2'-Dimethoxypr0pane Octahydroxycyclobutane ( 1, 1.55g, 8.42 mmol) was refluxed with 2,2'-dimethoxypropane (20ml, 192 mmol, Eastman), dry MeOH (50ml), and a catalytic amount of p-toluenesulfonic acid. After 12 hours 10ml of volatiles were removed via.za Dean Stark trap, and an additional 10ml were removed every 3 hours afterward. When 24 hours of reflux had been completed, all remaining volatiles were removed. The residue was taken 21 up in a minimum of acetone with gentle warming; cooling yielded 0.083 of fine white crystals (0.05% yield, mp: 171-173.5°). IR (KBr, microns): 3.08w; 3.18w; 3.405h; 6.005; 6.895; 7.225; 8.00; 9.805h; 11.48sh; 13.005h; 14.505. NMR (DMSOs): 6 = 3.60 (5, 1.23, 0CH3), 3.75(s, 1.00, OCH3). Mass spectrum: m/e = 176 which corresponds to diketo-dihydroxy- dimethoxycyclobutane or dimethyl-2,3-dihydroxymaleate. Elemental anal- ysis: Calculated for C6H306: C, 40.91; H, 4.55. Found: C, 40.83; H, 4.72. 3,8-Dihydro-1,2-Dioxo-Cyclobuta[b] Quinoxaline 14 Procedure (3): Octahydroxycyclobutane ( 1, 1.433, 7.77 mmol) was dis- solved in H20 (10ml) while o-phenylenediamine (0.843, 7.77 mmol)was dissolved in DMF (2.5ml) - H20 (215ml). With agitation at 25°C, the diamine solution was quickly added to 1. Immediately, a dark red solu- tion emerged and precipitation of products began. The temperature was raised to 90°C, and then after 2 hours, it was cooled and the products filtered off. The fine black crystals were sparingly soluble in most organic solvents, and their dilute solutions in water or acetone yielded intense red/orange color. Purification was carried out by refluxing in methylene chloride/ methanol (1/1). Impurities were dissolved, and the products filtered off: reddish brown powder (mp >300°, 15.22% yield). IR (Nujol, microns): 3.25w; 5.57-5.605h; 6.055; 6.205; 6.405; 13.0w; 13.75w. Mass spectrum corresponds to that reported by _W_e_b_b.19 Ele- mental analysis: Calculated for C10H6N2023 C, 64.52; H, 3.23; N, 15.05. Found: C, 64.20; H, 3.38; N, 15.30. Procedure (b): Octahydroxycyclobutane ( 1, 1.0g, 5.43 mmol) was dis- solved in 30ml 2N H2804; o-phenylenediamine (0.593, 5.43 mmol) was dissolved in 30ml of warm 2N H2304. Upon mixing at 25°C, a dark red solution formed. Then more 2N HZSO4(50ml) was added and the tempera- ture raised to 90°C for 5 minutes. Finally the solution was cooled at 0°C for 8 hours. A dark green solid was first gently filtered and taken up in 150°C 1,2,4-trichlorobenzene to dissolve contaminants. The fil- tered powder was orange in color (0.123, 11.88% yield, mp >300°). IR 22 and mass spectrum were identical to those obtained for powder made by procedure (a). Elemental analysis: Calculated for C10H6N202= C, 64.52; H, 3.25; N, 15.06. Found: C, 64.6; H, 3.38; N, 14.70. Product 12, Reaction of 1 with 100% Excess of o-phenylenediamine Procedure (a) used, see compound 14: ( 1, 1.03, 5.43 mmol) and o-phenylenediamine (1.173, 10.82 mmol). The solids filtered from the reaction solution were purified by dissolving contaminants in 200ml of refluxing acetone. A sparingly solution red-brown powder was isolated (0.253, mp: 198°d). IR (Nujol, microns): 3.17m; 3.38m; 5.60w; 6.055; 6.22 db, m; 6.40m; 7.70w; 7.85w; 9.67w; 12.75w; 14.10m. NMR(DM806): 6 = 9.67(1abile), 6.48 (complex, aromatic). Mass spectrum: m/e = 274, 246 (largest fragments). Product _2_9, Reaction of 1 with a 200% Excess of o-phenylenediamine Procedure (a), per compound 14: o-phenylenediamine (4.03, 37.0 mmol) and ( 1, 2.263, 12.33 mmol). The red-brown solids isolated were further purified by dissolving the contaminants in refluxing ethyl acetate. The residues were filtered and dried yielding a brown powder (0.423). IR (Nujol, microns): 2.80w; 3.105; 3.15m; 6.005h; 6.20-6.25m; 6.43m; 6.57m; 7.60m; 7.80m; 9.55m; 13.60m. Mass spectrum: parent fragment m/e = 234. General, Procedure for Preparing Bis(dialkylamino)-2,3-Dihydroxy-2- Butenedioic Acid Salts Octahydroxycyclobutane ( 1, 1.03, 5.43 mmol) was dissolved in water (Sml), and cooled to 0°C. With stirring over a 5 minute period, the secondary amine was added dropwise. While product precipitated from the solution after several minutes, the reaction solution was kept at 0°C for 1.0 hour. Then 25ml of acetone was added, and the solids filtered off. Purification consisted of dissolving the crude solids in H20 (20ml) - acetone (100ml) followed by the further addition of acetone (100ml) to precipitate the product. 23 (a) Bis(morpholino)-2,3-Dihydroxy-2-Butenedioic Acid Salt 24 Morpholine (Eastman, 3.503, 40.11 mmol). White crystals (0.603, mp: 196.5-197.5°d). IR(KBr, microns): 3.1-4.55, br; 6.25h; 6.755h; 6.905h; 7.4-7.65; 8.155h; 8.505h; 9.105h; 9.55-9.655; 10.40m; 10.80m; 11.505; 12.25; 13.15h. NMR (CF3C(OH)2CF3 ° 15H20): 6 = 3.38(qt, CH2N,1.00), 4.00(qt, CHZO, 1.00). Mass spectrum: parent m/e = 148(low intensity) plus morpholine fragmentation pattern. Elemental analysis: Calculated for C12H22N208: C, 44.72; H, 6.83; N, 8.70. Found: C, 44.80; H, 6.92; N, 8.45. (b) Bis(diethylamino)-2,3-Dihydroxy-2-Butenedioic Acid Salt 21 Diethylamine (Eastman, 3.493, 47.87 mmol). White crystals (0.703, mp: 166.5-167.5°C d). IR(KBr, microns): 0.7-3.25, br; 3.4-3.65; 6.105; 7.105; 7.555; 8.55m; 9.8w; 10.45w; 11.75m; 12.5m; 13.55. NMR(CF3C(OH)2CF3. 131120): 6 = 3.18(db, 0.67, NCHZ), 1.39(t', 1.00, CH3). C13NMR(D20): 6 = 174(C = 0), 137.5(C = C), 48.3(CH2), 19.4 (CH3). Mass spectrum: parent m/e : 148 (low intensity) plus diethylamine fragmentation pattern. Elemental analysis: Calculated for C12H26N205: C, 48.98; H, 8.84; N, 9.52. Found: C, 48.90; H, 8.80; N, 9.41. (c)Bis(dicyclohexyl)-2,3-Dihydroxy-2-Butenedioic Acid Salt 15 Dicyclohexylamine (Eastman, 8.653, 47.78 mmol). Off-white crystals (0.023, mp: 207-207.5°d). IR(KBr, microns): 3.2-3.45br,s; 6.28s; 6.59m; 6.905h; 7.40br,s; 8.605; 9.405; 10.5w; 11.55; 13.505. Mass spectrum: dicyclohexylamine fragmentation pattern. NMR (CF3C(OH)2CF3 ° IEHZO): 6 == 2.20-1.0, complex. Elemental analysis: Calculated for C28H50N206: C, 65.88; H,,9.80; N, 5.49. Found: C, 62.70; H, 9.36; N, 5.39. \OmNO‘U‘ J-‘wNv-I R. S. C. F. BIBLIOGRAPHY West and H. Y. Niu, J. Am. Chem. Soc. 85, 2584 (1963). Skujins et al. ,Tetrahedron, 24, 4805- 4817 (1968). Bock, J. Am Chem. Soc. , 9__0(1TS, 2748- -51 (1968). A. Miller and R. Capwell, Spectrochim Acta Part A, 11(7), 1113- 31 (1971). B. Owen and J. L. Hoard, Acta Cryst,4,172-6 (1951). D. Scharf and H. Seidler, Chem Ber, 104(10), 2995-3015 (1971). Cohen and S. Cohen, J. Am. Chem. Soc. , 88(7), 1553(1966). Weiss and J. M. Edwards, Tetrahedron Letters, 47, 4885 (1968). Schmidt and W. Reid, Synthesis, Jan. 1978, 2122. . A. Brown and D. Barton, Synthesis, 434 (1974). Goodwin and B. Witkop, J. Am. Chem. Soc. , :flé, 5599 (1954). Fenton, J. Am. Chem. Soc. , 65, 899 (1894). Hartree, J. Am. Chem. Soc. , 75, 6244 (1953). Fox, J. Org. Chem. , 12, 535 (I947). Hofle et al, Agnew Chem. Int Ed, 17, 569-83 (1978). C. DeSelms and R. C. Fox, Tetrahedron Letters, 10,78 (1970). Larson and S. Monti, J. Am. Chem. Soc. ,9_9(24), 8015 (1977). Ehrhardt, S. Hunig and 11. Puter, Chem Ber, 110, 2306 (1977). Skujins and G. Webb, Chem Comm, 598- 600 (1968). Ried and W. Kunstmann, Chem. Ber, 102,1439 (1969). Aldrich Library of Infrared Spectra - 2nd Edition, #277A. Japanese Patent No. Sho 48 [1973]- 32, 332. L. F. Johnson and W. C. Jankowski, "C13NMR Spectra", Ref. No 366 (283), 151 (28b), 171 (27c). E. M. S. F. Hartree, J. Am. Chem. Soc., 15, 6244 (1953). P. Gupta, J. Am. Chem. Soc., 15, 6312 (1953). Pollack, J. Am. Chem. Soc., 59, 1905 (1937). APPENDI CES APPENDIX FOR SECTION A SYNTHESIS OF OCTAHYDROXYCYCLOBUTANE AND OTHER REACTIVE INTERMEDIATES FROM SQUARIC ACID 1 Ho «0.. . ._ he. .0“ mass SPEC-flu.“- $0 0“ . Fm - . .~..' 58 — 7* V - I I . . ‘02 I30 ' -l - . . . “.C‘3NmV- Owlwlpzbl: . .- _ " SISV‘OI‘If’r-n‘ ' 3,413,715,, {99 sdPrm [III/III IIIII'I IIIWII II III I {1 IIIIIIIIII IIIé III IIIII III I III I IIIIII m IIIIIII .E .E. E.E .EEEEE E. J OerDu Eu E.E EEE EEEEEEEEEE EE. 2% E.EEEE: OMEDch 7: “I“! no NEE-40.0 .52. 5.2me E 2: EEEEEE. 3., E.E E.EE .E E E. E....EE E..EE r E.E.EEE... EEEME EEEEEEEEEHEEE ..EE .EEEE E.E. E.EEE EE..EE.EE..EE.E m m a a n . MODEL 700 Sane-re Focua 90° IOVO lwo "“9 NI" _ "' cwmum 32.50 (on) 3350 wan __ an: __Jz:fl=‘lI________' ”QUINCY {CM'I 2‘00 2006 "00 1600 mo um I L . . . u n ' u u n. III A. u u u . .. _ ...... I ...qu ...... ...... ' mu on"... _ O __ M» mum m. _. , vac warn-.0. $,,__ ‘Mv won- P-n .. :Lv'A: 'yn ‘ _ J D So MIG-l A—nm.‘ _ ‘o ___ ~ nu ”I. a - - . i .. I " m v—o-t-h'lI-m 31. . Iranian-.33. . 5' {cu-rugs“ ' 1" - a“? ...-... .. am w-u -u- _.-... . “Lam- ...-..._ .-...LLLT: 1- hVN IOC‘) IS-SO‘H ' - ' . ' 'HO OH ; ~ . . mass spec-rpm . meotrficozmg (CIS‘TIEQNS) Pmooucr 5' z . _ . ' — on. ‘ ' (03):. (9?). - @mQ1 “'33" ' :15 .49! .ll 'W 'm - ‘8 L lfia _ I _‘-l l l I’LLL I”, 'hrl l 1 m +1.11 :1: IIll :Tiéiil :l E 11“. 1;: I I 0 #fi :a'uuu 6.) *; ‘ 3.2L ‘ t; " fl EXPEG'ED ()4 I ' as (to! - - S-l" 1“.) .V ‘- [JO :3 _'__ ' TH no (cm) ms -: , ' :3 0..” (etc) . ' L-‘LS '_:\ . _ ‘ I _ _____o 4000 ‘1 3590 - __ , 3900 _ . 132.500 . . _ 'gooojzn‘ - _1500 C=C¢.¢ cm“ - (vuuyucc-o) 1s ' n CC-O) 2000 1800 1600 1400 ‘ ' 1200 1000 800 ll:au¢~<7 [00) _°|m§.w'=, S‘ly.BE~LL.._ no _~_ __ OumPou u b l. KB!- APPENDIX FOR SECTION B ATTEMPTS TO SYNTHESIZE MULTICYCLIC RING COMPOUNDS FROM OCTAHYDROXYCYCLOBUTANE AND SUBSTRATES CONTAINING A 3-KETO STRUCTURE 2.5 3.0 3.5 4.0 “'0‘?” .5.0 0.0 ' 0.0 :00 4130-130 fi (0“) 80 20. 0 . _ . 4000 3500 . 2500 — 2000 . 1500- "!M"? Kl'l ,,,,,,,,,, _ ml... -- , noun}! r ' 5.0 ‘ ' ' 00 7.0 0.0 “'CRONS 10.0 11.0 12.0- - 10.0 100 ‘ 100 a. 50?; \Es - 750. b 5282’ . . 'L 0) LJO KeTouE .. 8° ' «H.313 .. s . 8° 40 4O 20 '. 20 o ' ' ' 0 2000 1800 1600 1400 1200 1000 800 manage-5 . won! opocr (mu ~o . ... . - -..-.. _. manta” camc- - _ ' .. I“. .-. -...L--. 00-0 . . . . . ... ,2- ° «Lid - 0v, . .. - . uu M" .-..-. _._.__-_. Hunt .. . . .....-._... . y“... NUEDL . . «mo-N , . . ..-. ._ 19' S1. .150 mass sue-morn ‘I‘! P300007 _3_ ’55- QB L -' I‘ll [ll . ; .. . ‘ . . . ['“1* .. IL InlL “10.1."; m LL; 1 1 i 2 '3‘! - 4B". J8 3 I- . . H4, mass ”sand“ 38 ‘ [l LII“ -’ _ .9! ' GLwanm'E ensign-nears. . P800007 ‘5’ 5°: . . 10! L9 '1'! '11 3'1 'soq ' .‘3q ‘ m. N: .1 H0 lju'mhl Cl 1 l n 1 in ....m. banana. 53.5.00 m mmmE 18 7.0” 43 mass 9300-3005 .50 ' _fiffiouum' IO - .77 l 9(- _ 105' L- H‘" ' ‘ I. . h LI. Ll. ; I. . h all .&’| H. A APPENDIX FOR SECTION C REACTION OF OCTAHYDROXYCYCLOBUTANE WITH ALCOHOLS, ACID ANHYDRIDES, AND ACETALS 45 "5‘ 33 I3 43 00 mass sue-rum moucrlL h {Ah 32. 18 ['11 [I ' 101' l '10 rm 88% P ["70 - "53333510110311 PRoooc'r ,5' ' LO "1 ma _: 9: 9L J . 0.. ones? . . -- , . c "r '3 ITI ' “I I D} '1. ~ ‘ o .g. a on .... ::""‘ ..‘..._. hot-car; '5": I i _- W . .— HO ~~~ - o .310 .- "-—‘="~-“- 3- :" mil-=19 - - I :9: ““90 Pnovue'r u OHIO-venue, 0'." -.. - “C'- 0- O Q \:'0.;:.;’:‘:.::...n .‘ Jinx- —l(LL—__:-::ao 0318-33 OH 0339' .CH3 runsmnmcsm) PRODUCT _u_ 2500 2000 -. ‘500 may) sum- -...._._.-.- cum-o. _."._.._ -- - “mum-v¢nu“.._ _-.——. .. - ‘M — .-‘... _——.._ -... -- D. on mg,“ .' _.__L____, an mm _o ,,_._ _ __ _ _ MLLZJ‘. ._ 5am" ”I... mama . _‘__. '. - - c)0.o c=o ansc ‘09 d)LS¥ CH3 +JIL4 . e)7.Z cu: than 98.0 CH fim IRANSMIIYANCE(%) 1000 1400 1203 -‘ woo 800 FUNKY Kn ') - mass spec-mam P309007 IQ. _ L0 ' ’ h, 1’. m I I‘ll”! [[lhl 'll :1 "3|; 11‘. :h' 2H1.- APPENDIX FOR SECTION D REACTIONS OF OCTAHYDROXYCYCLOBUTANE WITH O-PHENYLENEDIAMINE mnss srecrzom H “3° [8 29 ‘ I ‘H - i '76 '03 . . 68 '9‘, . . ‘ _- m. 254 '-_. l.lLLIJ.UL“ILU--I-l’_J|ll LJJ 1. J1 . . i _ _ .l __ meters 3500 . 3000 2300 2000 M‘- I300 1 MICHONS b) 55135.“) C-O :) L.O'L C‘C d) h 2" c-0Sm e) 0.30 5) the; MOM I 1.15 I I800 1000 I400 I201) IND 000 ”Ion-(v ‘lj .. WM If"... :0: . _ ‘-—N .... ".HHL mnss we crmm .Ii . Pnoceourua a . . I30 1.9 ' ' ' 103 MICRONS 7500 non-a us 2000 I300 MICRONS b) 0.03 69.21. C a) 0.43 e) ("S-(.3 noun, 5) Int. 5) ILIS h) IJ-IO I400 12001000 man-u cu, “'4’ .. ..I- .__-__... l-stwou-K‘ “F ~'_ - “ml: -_N_..J-.~.~. 1&1} "...-'1 _ _‘_ f P03050022. 0.. . .. moans; ' - "Inuit .- 18 Ill! mass Spam-mm” 93.00001" . l‘I - '13 130 44‘ l hhdLLflLJ ' 3‘“. 1.34 ' 2.04 @Qfim ( 0:01 a rule 3500 3000 2500 2000 I500 mm «on '1 ' ‘ -Pl‘zpnysLJs .- _ .. --.——-__. “$.00 (2'0 3‘ ".3! 100 name CsN 00.095130 410.15 C ICM (Mano .) 5.)! Humoo é' “LAO 2000 1800 1600 1400 120') I000 800 [lacuna K- 'I .mm_ M" "°-— --’—--— —-----—_..-..._. .(ODK. tum! sun vuu Shag? amulet f” _ - ._ ....-__.__——_._ r_ O"! 1 o:-c-u___,,—,__* ' _(lll Mlu ... _-_____,__.....-._ ...._ Ill-All! .____----.-.. - . .— Ltnz-nLNUnL . fill-ma ,-. _ . .. . . . -.-..- mass SPEO‘I'EUM gene-no.4 OF _._1_L4-v-¥PD(ZO°%XI) l’ ‘13 5'1 10: . '13 10 ' us M m a” .14. ii' ’ h ' 11.0303?" L'ngth, ”ll uHLuMJJhI .mJILu. I .l J .. 3““ I ll. I 5.1 muons I men»: 93.00001: 1 0v o-PD a.) 3.0 -3.3 01-1 3500 2500 we ‘I‘ 2000 1500 wczom ' who cm 7.11 00.. 7.6! mass SPEG‘lem REBCTION 0F 2:. +e.PI> (7.00%)“) w W . . ' 7.34 gm was suit-nun 14L ' 3:. mmno'rmmlli j '13 m ._ 9' 3 f 94 m m Lima - _J 11 l llhglflmul...m.uln.. ‘1 . l 1‘: l, . ‘ . MICRONS . I 2500 non-o on MICRONS 2.69ch Pit-covers é. "~10 1.3 nuns-Lao - ' 0 I600 “00 u-ou . .lnau-o" -_..__.,.-_:Fa- ”Si-Di an: E- II ' Z:::"' 1mm”? 33.2“." APPENDIX FOR SECTION E REACTIONS OF OCTAHYDROXYCYCLOBUTANE WITH 2° ANINES MESS svec'mum 22 _ _- 4 i 58 and» g * . _ . "‘ . _. 1'] -' I ll Ill“. IL I. . fighfiim er mums Men-nan.“ aniu'r - '2, H13 (E eh] C‘s 0 IL 1'13"! n—m anon-u _, o__ "03...,0‘“ ' 5:5 I u“ ”u“ 3...): («5) WIN- Ammu- JO _. HI! ~00: 1.... Ef-qu ‘ S . 1J° (c...) “a“ -‘--w . .__ In!“ A: . : .1. I c" “.1:;£’:;':;'!L a on- mu..;!..._.__.-— .0. Ion-n. CF, C(OHLC F, . 'I‘"‘° I/"‘n ' 12.2%:1 M. ’" bun-.343" ._.'__ ...... _ IF '3; 33- _ u \m 7309' 'I's-oon 2.5 0 (D O O ‘ TRANSM!TTANCE(%) A O 3.0 3.5 o 8.0 ' on . - \—/ /—\ - 2[H1&(Et)l.] ‘ Co; . ' Cl: cam-as 331-3.! 3 when“ 3500 3000 . . 2500 2000 . 1500 . TRANSMIII mam - £_.__-. mm. __-...___‘;_-....__ act-mow -. crime-u- .. V -_ c 0 ya Ir an: tax-11 oar-cu - .-._._'___. __ rm rm __.-,_-_____. ... _. Imus '....‘.--..._ -.__ .. :owIn-l Kflr . __ _._ _ _., '_-~_ flMNNCI . - -..- ' .... ...- --.-.. --....‘ . ' ... _ _- ‘ 7 MICRONS ‘.'5'~ 1,2-Otow.so,. was,» \Cu'o“||ns,~ 'LLOIs I |3.£°'- v.55- c-o Mao» 1.05,. .1800 1600 I400 I700 . . 3000 800 "lam—(v [0- '. -____ ‘0"?- -.__-_-..-. ._'_._-_. m! .. _____.__. , °"G"‘ -_ - . —— .. ... sum-u KB,- _ . .. .. . ll'lihccl _ _ _ . -. jh.__-.- (9"! ’0. -....._-. --._._..-_ “many-o-J— annual K‘V_.__- t on" inn-"1 _-_ _ __._'-.-_ Ifunut - -. , '. ..... a... ll ...-‘0 ...-(.....sol 0.1... pl! arm-APJIp-va l . C v.5 . lb. 3. .2: 325:. o G slloi .2 :6» 10.3; N.“ o lal a: .25 .0 02. b {5 -03. :30 B 593 M. I... 5. .0: .0 oz. ou‘oxm-‘ E: .0: .o 1.93 QM. .55. 53023.2. 53 >338 60s 2:32.285823 3.02 Duallifio. :25 .3593 s .2980: .3538 9 6.. 220 32.3- 9 .39.!ig . .9226... u.“ .0:— ..O 3.333;. . Vs“: . . to. 22.9 (.(o H” 0 . ...-Ill 5;. >(awo ~32 I’M 91.1.93 3:: mN¢ $1.42. 92: 20.3503 .0 . i ..z_=z..w2<: no .02 gm “ nlésc 2.93 7:83 ZO$3509¢ «Mesa—Ill... .Ill. :5 25 I I 2293 .09 4.52 so I I. ldméa :(OOEI. .. ul¢0p—. : .m 3.3 .h. Liv... _ 11.96“. . —.- o a. 31:... ‘ .um...«.u._fiw__w_._um_.3...: ......zfis. . 2”..me .. 0....- o . . o _ -I-.. ..-. ...... a . So . _ E; cub coo. _ r 1 z _. SON x...,_2_m . .18.? . . . _ A. v ‘ 1" ."1 uh' 'I U h ma 3: swam-gum :13. ‘ . Li IO! % Tm file-HS 9% lumen-ms DInSoPcoWann-IE Fandmems - 2 [H 1:. on] CI: 01?. ‘I‘RBNS u u u u pt‘li' u n u I ll numraz -- in. i M M .- A ”"1“” Mun-cup. m: n z {-3.43 (cl) i :1: I .flflfll. CFJC(°¥)\C‘3 - 7‘th 'I'Ihl'fi‘I' snail]. nun- ..XF.‘__, :22: ’ OH ‘a Z ulfiafik] C|s eq.-man's " noun H" "‘"FD .-O.._.. Mu N m C7" m. u— ’ "'- an ' C‘hku 0L0 1101.11 :0: It“ CF: C(Ou)‘c F: ~1l|h° ¢“.I‘- 'L‘ .‘YUCL -“u mn— A-.. _...0. 0mm .--..V ... . - ... VN 1009 «s-Ion 2.5 3.0 3.5 o 5-0 L0 8.0 100 _ _ HO ,OH 1. .- /_\ -_- ' 2' “15‘6““ 01¢ co,_ . 8° . cu: ca. Tums 3-U-3.35-3-SOo- ' ~¢H‘- .CHJ_ .50 14.0 w OH .-!-;..*s- ..> ”.00 40 40_ 20 ' 20 O f g '. ’i' . . , _ . . - . . . , 4000 3500 3000 2500 . 2000 1500 ‘ . 0.0011“? KN.) . Sum .....21.-.--_ (00" ~01 ._ .....'........__...- an. 9109 ’¥0~3__‘ onnxon 10'— -.....-.,.... ..--_...__...----_'. conc-....’... .-. -....-. ,2: 0‘ Ln! 34.01% on“ " ._, ,, , , , _ I!“ ”In ‘ nuns .. -.. q . . , .. 56mm Kno- - . ._ - .. mama - . .. . . . - . .. J; . _._ ' 5.0 'f‘ 6.0 7.0 ‘ . 3.0 M'CRONS 10.0 11.0 12.0 16.0 ' ' 0 ' ' ' 100 111:1 . o . ___ 100 so '_‘ so 60 . . . , 00 . Lou’s ht‘cgo 115-155,. 0“ 5‘ : 0 , .0..-. .5 ' a“ '5; . .'-' - .: ‘ '; ~s - ff -'. 3 .... 9L0» c .. . :. .1. : - .- ‘ ‘ ' 5. . _ ... ' 40 b 403 __ "9.10,. W 1: .; ”-50,... 20 14.00,. 20 1600 1400 1200 , mount. 101'. . um: 3L. ____,__ (who no... 32..., -- ___,-____ K00 9110!...- ” mum-D Iu' _ 9.10 C. out 3-3-11 " (mum ......;.-__ ONO-fl..- °.- -.. - 0"”. .— . —-.-.—--————- —" so.-!~l KB;- . .. , mm~cu - ~ IOOO 800 O .‘5 I '. 2000 .1300 -——-c—- -. - .- ..-——.,—_ (M -—-- -—- -—.————o HO 1! [q .z["‘§(ip"t] 1 . a “I“! 0.0,; co; ‘ cm PERKlN-ELMEFI C13 0!. Wu: MODEI. 700 m ILA—_— ' am 1 3.15”“.80" OH’CH ' . L-13 p ' \‘1- C30 m NWOL 0.55,. OH.CH continuum ~ . ~ 955,- c - 0 am a g $00,. w 'l-I’I-W‘I 10.40.. ' 11.30,... onwa- ‘K. F. | ‘0 “a” ‘H.°°» . IRIOUENCY COA'I ‘4000 3600 3200 2:00 2100 2000 1:00 1600 1400 1:00 1000 .00 m '8' 88383 mun-13m nmsmmnc: 11.1 b O H O 3 ....... SPECIRUM NO. OPEIAIOI I . DAI . ...I" 19.1.1: ACQUISITION 9111 was 10C! SIGNAL ... [192-_- I (IOI .. .l .909 .-.- 0.- .01.. id mu: own! 1101 .-.... O - NO. or IRANSIENIS mu OAIA 1011061011.-.. ACOUISIHON "ME (A!) SPECIAL WIOW (SW! . 'UISE wmm (PW)- - _ 0' U IO. .7} mum am 11617.-- .. ’1 IIANSMIIIII 0" HIGH nuo ..4 N011: unowmm INI you DISPLAY “COIN!" MOO! IM— I DECOUOIII 0"“! I00! ... 2121!; ‘43:: mom 0! (11111qu ... (NO OF CHM" (EQ .... won: 01 1101 M... mo 01 nor my .. . vunou sou! (vs; ...”le «mama uni 1m .. .. ..0. ._ 11m. (Mum on Ir? i! .l .IALAAAAA l I i d .-.4-_——. ....__. -.m _-_.._. . ....--,.._ hA—A . i ‘l —--'o — -... ‘.v -1 _—_.——- 0 ...-__.--. . _. l -A1. ‘1 'IL ‘3 I I I I «W I , . n T“... O 0 2. a“ "I“ 5‘" «m III"; a .... o o~.- . ...“ I l‘.“ Al‘. I I “I ....A *1“ '7" "TV? ' If" -;n.o‘-’-.-; ‘00 I 7" rv-v‘r' ‘l‘l I IA‘J-u LAAAILAAL I '1” “2° (.00 00 O 0 O finmsmrumsmi. YRANSMITTANCE(%) I“ "0 V0“ . 2E“: 3] I 'qc “1’. en en. flat-6 3. I 41.5,. on 40000 3500 3000 2500 2000 I500 ' . ‘. V momma (cu-'1 ' 9w ' ‘ fi ' . cum nu__?___._._ KM 91w SL931.) Utmo- RE-.. . . - - 1 ‘0‘ .. - out 141’“ one-u ...- '2... .._-.__- H (ll-I ""0 ... W6 . ' yam-n _._JBC..- ... -.'_ unmet - ......_.- ._ --._. _ _.:.-.. . _ -_'. -__-._'.___ _ III C=o ("7.4.31- 11. '7‘» LI 9 p 2.50... 9.LOI4I.~ 10(1)“ 1800 1 1600 I400 l200 "INK! ACI'I IOOO 800 ““91":me O‘I'N'GKF .— '- 1.11 11: mm -4. .... sum ' 3“. . . cum to .."' ....-.._. _._- -_ . _ -- .— . (on: . ..- . ..-.. -.....- 1m b an! 44:41 cac-I _ f' _ ________ _ an un- ..-\ _____ _ llufil|~-... ...-.- .. _. .... _— zm-tuv _. “Br _ _ -_, . mama .. _ ‘ _ _ __ , , _ _ __ -_ , . ("tutu-:u‘l'u gut—c [H'~,I ww- wo.n~--— . mass SPEC-rum . as ‘ . . 2.5.. _._L. *1 ' . . . e 18 | - j 3 .1 . . .- . we LL1|1 l [I .IJ ll Ll LI 8 ' ' '. . «151110101113 3 1000mm: menr‘ . ,- HO ou * H 11:03 'o‘c °°1 C13 0!. Tums u u u 10 av— _ u u u 10 w t WIDE M M N’cug 3.3.38 hm cum!» .0. . ...... M" "-1 NC. ‘7'?” .4 3 mo { . ' v. 1 mm. , 0 fl. M” . :1.Ig_:.'t_- E :- u:co.::»ma :1: ,__. qu. “NEE-C Hal-11) g :10: I 0 cu‘ .s' ”.00 ”mamrgam ' ..... --°"~ ------------ * ... ‘ ...... CF: C(WLCH- Ywao “Jae-‘0.“«m - O II. n a .233... 3- ‘ 0n; .2'_I,"_______ Mum "If. Inc-u- no- I. VN I009 IS-‘OYI NO. 007-106! ' - . ”nu-.4: Ho ‘ m PERKIN—ELMER \ffl . - 010021.700 . ‘ n ' .2[H‘NG] . mun—£— 0,; co‘ 1 mm _ . . ca acts-gnu: ; m 1 A 30"“OO|§ OH 3 - - . . (”7.09:— C-0 10.11.... 3 m NUJ'OL 8.10m C’? 103» ‘ «mum 9.45 r~ c-D II-‘I n m _ M: q. 00,. ' IL'I ... 0A?! 147—19 9.00... . 11.5}. OHM?“ IF "Ll-5 ”EWING ICM'I I00 "msmuncz 11.1 3 ‘6 8 ‘6 8 3 3 - ~ . . £000 3600 3100 2000 2400 20” I000 I600 I“ 1300 1000 000 030 ‘0“ WI)!“ mnss SPecmwm. * . L5; . _ 'm 1. . am Is , 28' - ~ _ . ' . 82. , goo . . , JJ ‘~ 7|“! "J ll . a7.5” ill I.” 1'"? ' I 1'" it Ichn-res mcycwuexymmmi muniflrs ”>51" -, z[uM©)‘] 7‘19 c°1. . ‘cns on. runs M "mo—unn- "9,... r.— ' yum- nan-... . .-’32.. um nu t—u GET—'3 l-I-I 3" LO YO 1". ((1‘“ ct"!) um.m ...-:0, ._ . . r3773. ‘" ...—.unwu ..19... a... ,5___"_._ I») . m- CFJCCOH) tQFJ- 'I‘ up ......3.’1’.’.7........ . out-u...” ...-1:47;... “0%....“- 2.5 3.0 3.5 4.0 5.0 0.0 3.0 100 80 60‘ .Z[H1."5{®Lj .3 p .. * _ i._.:~ 1'40 Cl: 011. T161149 1.9—5.50,“ (on-1314‘) b. ’0 . f. . I: :f' ‘ I. ' '. 2c 0 _ . . I! ‘ . . . ‘ ' . ‘ ' ' . ' ’ 4000 - - 3500 3000 2500 . 2000 I500 ' A - ' 1110011101 101') . ' ' ’M‘ 2 g- o-OO-o ...c (‘M m‘ -o I .-. -'- o. .- -- . — gu- use,” mum” ..-- ., _ _ .... 3:1-'11 . cu. -.-. ..--..- u-u..— (0" ’~_‘ ...-~- a -_.—0. 0"" - —-o-o—..o-o.—-- --- ("‘ "m- ... .o— — u— — M.-- ...-.- - a u- h. »- ’ - - “‘1". w . .1 a -u — . .. 7::. ‘0’fitg ..‘.-o o -. n o: '. o: 3 '0. 0- . .- .‘ ‘ ...“ g ._. 5.0 6.0 “ 7.0. 3.0 M'CRON5.10.0 110120 16.0 100 ' ' ' , ‘ , 100 \ 1'80 I‘M (n O 60 O O 1.25,. 1.1-0» LJpop _ g 1 . . . L30" . . . . . . - : ‘ . I, 40 14.0,. - " ‘ ‘ ' -': - . - 3.1.0,. c.o. ¢1.110... , _.. _ , , , » .. 20 . 0,50” ' g . z . _ . ‘ E 20 11.50,. , ' . - ‘ 111.00,. . ’ — . . , I; IKANSMII IANCE 0. O O 0 . . . ‘ ; LI _ . . 2000 I800 » I 200 I000 300 [IIOUCNCI Km '1 0 “N“ "" u-‘ai . . (awn-o .- ....”.. . -..-. ... match“ .. OHM-0' U ._ - -' ‘-—" -‘."_- .--- . _ -— - (0&7 — - .- . . --—-.---...-. 0 “' J ‘ 0" "1.7‘ cm“ ' —_.00— --.-o o -..-o ‘.‘| "'” ...—o—‘o-o - .... . 1w!- C..— ""m‘ 0‘ “‘ sown" ”1’ . , 111nm“ '- mas; Spam-um . 39 * - ° 1.8-“). A - I8. I. ' =1! - .l "u eh "uncut-s: 91mm“: 611901110111; I I» CF,C (ouI‘CF, w , 4 o nu‘Et‘ o - g - 52-3 .0 I. 00 I. 00- ' 10 u . M1: 011mm ”0...... M00 m 11K- (:2 2 11101 I ‘ “v”, mm.- m. ,1..- MI! nun-u (EL: "'_ i m- ” w t m»- ......o. - ...- .... 2:1-1111:1311 - . . i M can on» 40 .. u to." m... 0’ .......-... I .011 ' 00-4-1. D‘Ithj-su-T'J . ”tn-a1 coco-F. ' . Oahu-l u... m- - 0.11 3 ”1.11 . 0...... _0 mm- “. .....- no. VN 3009 IS-GO“ 8'0 I00 3.0-50 r1, ' 9 o o “”19“ Ii 0 0' 'NH‘E“ 20 3500 3000 2500 ' 2000 ,‘ 1500 111.0qu .01 ‘1 sum £3.— .,_--. cww....-.-'_...-. -...... mama-6.. amne- “v . .. .. . . - ..-.__. -... (M . _. .-._......_'.__... ._ 1m " cu! 3-13-‘19 one-u ’ _ ' _ _ (In "M -. ~........_._.____.. “and- - ...- .. - -..- -. - "II'INCI , -. _ _ -... .- . . ' MICRONS 1400 INOWVCI :01" 1800 I600 I200 IOOO 800 “M“ Ia - (14M no .. . ." . . . Kn: vu- Isoa gnu-o. FEV .... . - . ...---.——_-_. ..... .. to~< ... _ -_‘ .. . .. .:.. ...—-1 . 1111 u an! 33:19 "’3‘“ . " . . — ._...__. __,., (111 um. . .-. . .. I" _ 01-11.: _ 1:11.:‘1 . “any,“ ‘ 2.5 3.0 3.5 4.0 5.0 1.0 0.0 100 - o- O NulEg‘ o 0 *NH‘Et" - - 330-1130” . .1: _ . , . 80 60 40 20 0 . . . . . 4000 . 3500 3000 - 2500 .. 2000 - 1500 . mouucv .015 ‘m L- .‘O.. .‘C- (W. u-0.l.- .. ..-~-.— .m “‘9"Q. m a -- .:-_ U...“ . “.--.C— .."-:¢ c“ -— --- .....L. a": ‘; AAA -AA $.a1'L‘ omen -.....— -. -. ...... cmum...-..-. ....... ...... .. ”Mill—-...-. . . .....J ”Va" "‘ ° ’ ' .‘ ‘ I ' "HRH“ 1'. - ..'.'.:. ---~-- -' ° — '-—°:.°.-. "12.5.; ~. a .. ' 3.0 M’CRONS 100 ‘1').0 12.0 16.0 5.0 ’ 6.0 1 - ‘ 7.0 , . .100 5.1.0- 11.00,. ‘LLO 1‘" ‘ 8.50 ..., ' .. ; . _ __ 3 11.36 41-50»- . . . ' 80 11.05... 1 '-i':- 3 .‘ . 60 60 40 i 40 2O 0 ‘- 3 ' 'I ' 7 t ‘ - A'i 3 " 1 .~ . 2000 I800 I600 I400 I200 I000 800 1010111610 10101 Sun-'11 ...—3.1L.-- . ....-- com ~o.._..._. -.- -....._.. 1011111100») -- canto-3‘ -4-.. . (“u ... __-___ “g ‘ u 0." ’°."” ‘.l~ 0- ---0 h—w— oocu-."..-_......-...._... .....- (111 mu---- ' gJ.o‘~' tar . .‘.!':~(‘ .. o .. , O ' - --.-..- ----~OOC— -- ...m’ - ..~o .‘ooom- .- -.... mass SPEC-mum . 2:1... .8 . "j .. ' . r .' 4 411116161113 11 11101101101111: smug»..- ..... u M o 0 1 0 ~- _ u u 8 0 I. w ‘ unoDE m ...... N- 011 km 0111111» .o.. ...... M10 11.11111. F7! § 11101 I I. . 3.3.3.8 1911111.- 61-00110...”an ..- M o . "G"??? : _ ...... -..... -..: ..- ....l "h baffling i I”: i °'°”‘ 3' “'°° II a 0 ' E . M2.0l(".:;33r57'm. ' w. i .8 no. -..---uo-u- . .~ 5 a”.' CF, C(ouKC". Y‘H‘O $2.920 not. u- ‘ I n a. I... —-- - - .. 0m. .2'.‘.:.?.'..__.._ 0mm ....(f. nova- no- I. VN I009 IS-‘Ofl NO. 007-10“ ' 0 “DH_ Ho ' " «on PERKLxszéBMEn 1 ‘ E17 . )‘Wpfi: '2["1"O] 9101—11111 L4" . ‘0‘; co‘ 1 1mm . 3.I-‘I.O,:"o°£ “a“, ; .. m 1 g L.7.0M— C-0 10.1“... ; Ml - NUIOL 8.!01-15 3'0 16:1“ ‘ (cum-111611011 9.45 p c-O IwI rs 1111mm wan 9.00... ‘ I13» 0.111 I-fl'fl 0.60,.- 12.5}... OHM!“ ‘F I'LI A "(QUINCY ICM'I 4000 3600 3200 2300 2400 2000 I 000 I600 I“ '10 1000 000 650 YIANSMIIIANC! PM NI H g u o N o o o o o o _- O '0“ WI)!“ mass, SPECTzOm. 2.5. [51. 1m . av 18 .. 21 - 1. . . 1‘2. .-a'°° _. . [I -- 1m, 'Hl -. 13° “In .H ."9 1" 151110101116: PICYCLOHEXYLHMINO mecm: o . . u v o. u .- H0 011 >4 - -. z [10%).] '12.}: co; . ‘ .015 on. mus to u ‘0 M "'“I u .. u u . OM . m ' M w 0 ”no-«11 1 ....... ~1- -.. : M I . ”In... 0.51;... ..".,!.. NICO '70-‘25 E3113 : I; i x .'o TO ‘.‘* (c“.. qu,) urn-“6m ...‘f... CI- ' ‘ 7' ° ' ' ' I 'I : I I ‘ run—0161111!» .39... van-M "105..."... I (u) ' um CFJCQDH)‘CFJ ' [\"10 un..3.‘1fl........ . ”on...” .......... . ............ :«2-2... ....g... 100 2.3? - 5.50 ,... (0+5qu 2.5 3.0 3.5 4.0 5.0 6.0 9.0 H -80 60. . z [EMCéLj Cl: 08.70149 .'.'40 2C .- u- ... . - O . ‘.2‘ "1..- .' '. . - 4000 . . 3500 3000 2500 2000 1500 5.0 6.0 . 7.0 0 100 (‘70) IRANSMII IANCE 80 5 O 20' RINK? K‘l') _ . o , ' . . C T . ' 2000 - I400 1200 1000 sum 7 .2: ..-.-. ---. «M No. .. . .'. ..'.... .. ... KI- vflchfi- mumKF ..-; . -. -..-. ..-.._— ......— cm -..-_r-oov—m I -.--o—.o “ ‘ 4A A 9." "7-q‘ ’ O ”m - -I.-.---.-n.—I --. "“ "m- -~_—-“— _ M. C- O... 0. _.GO- .. - . . . smut K5? .. .. - -... .....- «:2.ng 3..., ... .... . .. . . ...... ;..-.-= g . . 3.0 M'CRONS. 10.0 11.0 12.0 ,"so 60 2 1.15,. n.1-c=0 ' 4.4.0.. _ , . . . . . . LAO" . ' . . .. . t - : .: . ' . 40 '-’.or u. . M’ ' 2'. ..- ' ' T; ‘ ‘ ' 8.1.0,. c-0::" q.‘l0,.. ' 0.50,. ”.50.. -. m.oo,. 20 3 I "IOUQNC! (CA. ‘| -.--_o-...o-----a -—- ‘--'— O "W“ ”-35. . . .. (um '40 .- ......“ .. . -.... ... mm “003"“ - 0mm” b" -... o (0* - ‘ . ~.‘-:-.-...-. . “fl . ‘ 0" 3-1-7‘ . om“ ‘ —-.-._ 0.... c .0... (.“ "'~ 0 'C 0 D . " SOsol'fl Xflr . , mam-wt 3 a I I 1 ’ | «nu-s . . .- mas; Spec-mum ' } ac * . u. . ‘8. _ . 1‘ |_ " IJIL. “LI. ale INMCM‘SS‘ mew/Lamas Panama-I: °‘j l 9 o‘ 0' NH‘Et‘ I“ CF,C (001.0% u . u 0 m ’ MOD 1 m M M“ coo-10m , ..O .-.. MN m me. (:7 ‘ E m. 3 cu, I“. ’h ”"3“ W“. .I O .. MID vou- Ho WEE ; mg H‘W'Vmit ..w. .wm ...“; .._ an. zgqm i . . I M 0"! an. a l O'Jct-J-puc‘tqh' I noun my; .......--.. can 00-4-0. . ”(th'Q‘CMo- ' . ..~~‘ L "2°C.? .... on! 3'01'1‘_-____ o-nuc- _U mm.- .4-_a...__- ... VN 1009 (S-GOTI') 3.0 40 3.0-50 F, O 20 O . J . 0' ’N utEt ‘ J :0. .NH‘ES‘ 3.5 5.0 0.0 I 00 80 "60 .10 20 4000 3500 3000 2500 2000 1500 ‘ 11110011.:va m1 £9..— ..-..-_ cwm-,.-.-__.. .. -..-.. mm&u_ ouuvon “v— .. ....-. .. . - ..-.---- .. (cu-ac . -. .-.—......_-.._...- _s:_11 " L --. c. auzns onen- c- - ._ _ (a; 0"" _. . Imus- - ...--- -..- -. - vum~<1_.-. - .. .- . .. --.-.. 5.0 6.0 7.0 8.0 M'CRONS 10.0 11.0 12.0 16.0 - 5.9- 1.40 ,. 40: 'LLO r0. '.3’- '.L°r~ $20-$40... 13.50 ,1... '1 100 80 60 20 f o ‘ ', . '7 ’ I ' 7000 1800 I600 1400 1200 1000 500 "1001'va :tn'o W0“ _.i‘..- can: no. ." . . . KM vuo 3503 0'1“"). ‘0’ 5.. . ..-....._._--. ...... co~c .. . -..- ... .- ..-- . .... ~ 3:32;. CW)»: . " . . .. .-....____- __ __. (111 um, _ ." . . 01...»: 131.:s1 NW 1:409.“ - . —_ 2.5 3.0 3.5 4.0 5.0 1..0 0.0 10 :0' ‘NH‘Et‘. T. O . . . . ’ ‘ ' .1 2.10 - "08°” ' 1 ‘ ' . ‘ o. 80 80 60 00 40 40 _ 20 20 3100 I 3500 3000 - 2500 _. ‘ 2000 1500 "(01.1010 101') ‘ ' .- ‘ "a M i- .—O on ‘n.- (UM m -- o..- .a-o ..-—.... m m'.‘ C. "no: :— ‘z . c“ -—.-o ..---51- hfl' ‘ A AA AA. 0‘1 . o W - ......— - u - - ...— n. c.“ "m-oo-o‘- - u .0 . -.. .. I.“ n. M-— O a o -0 - n .0 u .0... 30mm 1'."- . .. . . . 111mm .. '3 _..... ..----.. __-_,_.....,_, ,, ~~ , ...0 .._—D— . 5.0 ' 5.0 7 .0 100 ' 8.0 M'CRONS 100 11.0120 16.0 ' ' . 100 1 - ; - _ .1: .: 5&0-730» 7.1.0 p _. : 8.50 .. ' .1 . -- .. .. .3 -- 80' ' ' z' " 9-’°"'“°1*- ‘. .. .. . .'- i . 80 12.75 p. ‘ , . ‘ .‘ .‘ . 1 1- 60 ' 60 40 40 2O 2%00 1800 1600 1400 1200 ' 1000 800 '.|OU.K' SCH.) MI .._-'21.... . ....-- (on: no. .._. .-.- -_.__., 000911051»: -- omuou“ .4... . (01¢. .. ----.. s10 ‘ 0“. ”n’” 0.“...- .‘--..‘0.---—-00- Coo—- "“ '.'”-—-- VAN-0' [Bf ' 01111:“! .. . .. . . - - M Glut-0‘ . .. - .~-o. .- o 0- -~-.. 0.. O O O O O N ‘0 '0 V :1 VI.) 33Nv111wsr~1v111 0 CD 00 02 . 82 80a 82.. 83 8% 88 88 . £20. 52302: . _ Johaz _ 0N OraanoO v one cow 000— camp 00:. 000— gag .. 'OIUIQ-Hvlm-o. & co 0 ..................... fit: .2. ...I 35.5. x623. 5.836.. .2: 3: .S ...n . .15 61 .n :- 42: 2.3!»...6-53 u... 3.11.2155 ...—1.8 UOJQFQU N‘H .30-~qu u wuzmdmumk 312 M SW NW AW ...” m