33°52 IIUHIWIIW”WWWWWWW I‘ll-l3 z , i . . x \y i . n . E 1 I ‘i.‘\1r I n11 L. . . \‘ «L‘xvl. -rqcfllhuul: u. “an“!!! .._ . , . . L J 8 . , .Y ”Y . . R mum . u, , . A n a . “n R Manny . m 8. kW. ‘ , , x I C . ,.. L M _ 1.] ..\ 3L1. . ow: zTaunria . a}; . ,PH 4 . . x #22233... a ... .2... ~2::2:==:a:=a.222“,Nu w n::: a a a: :2:::::::, ,, :z¢...:.-.::z-nfizg: ::.::::2:.:::::; ¥ ‘ . . . A mh::_:F:Z:5::::.:::::::::_::::_J X I CONDENSATION OF SOME OCTYL ALCOHOLS WITH BENZENE IN THE PRESENCE OF LLUfiIR’d CHLORIDE METHYL DI PRDPIL CLRBINOLS by Kenneth Dale Cline A THESIS Submitted to the Graduate School of Michigan State College of Agriculture and Applied Science in partial fulfilnmnt of the requirements for the degree of EASTER OF SCIENCE Department of Chemistry 1939 Acknowledgement The writer wishes to express his sincere appreciation to Dr. R. C. Huston for his helpful suggestions and advice which made possible this work. 33163.3() Contents Introduction ...................... History —.- - - - .................... Preparation of Carbinols Methyl d1 n—progyl carbinol ——————————— Eethyl n-progyl iso—propyl carbinol — ~ - - ~ - - methyl di iso-propyl carbinol .......... Condensatione General Procedure ---------------- hethyl d1 n—propyl carbinol plus benzene — ~ ~ — Methyl nopropyl iso~propy1 carbinol plus benzene 1 Methyl di iso—propyl carbinol plus benzene - — - - Data and Physical Constants ............... Data sheets ................... Summary - ------------------------ Reagents Used ..................... Bibliography ...................... Page 14 15 16 17 19 22 23 INTRODUCTION INTRODUCTION The process of condensation is connected with the early history of organic chemistry and was the outcome of the first systematic at- tempts at organic chemistry. Condensation may be defined as "the union of two or more organic molecules or parts of the same molecule (with or without elimination of component elements) in which the new combination is effected between carbon atoms”. There are two types, external condensation in which two or more different molecules become linked together and internal condensation in which carbon atoms in the same molecule combine, leading to ring formation. It will be observed that union between molecules or parts of a molecule is nearly always determined by unsaturation and by a conse- quent tendency for the unsaturated atoms to saturate themselves. There are two groups: those in which the combining molecules are induced to unite by being rendered, as it were, artificially unsaturated as the result of withdrawing certain elements and those which, being already unsaturated, combine either spontaneously or with the help of a re— agent or catalyst. Condensation by the separation of the elements may be divided into catalytic and dehydrative reactions. However, these may be united again when the reagent used may serve both purposes in the same reaction. The workers in this laboratory, however, have been especially interested in the condensation reactions in which water is apparently Split from the alcohols. These are three mechanisms for the explanation of the catalytic action of aluminum chloride: First, proposed that the formation of an unsaturated compound (dehydration of the abohol) is the easential intermediate in the catalytic action. Second, states that the formation of an alkyl halide is neceseary for aluminum chloride to act as a catalyst. Third, suggests that the preliminary action of aluminum chloride followed by rearrangement is the true explanation. The Lewis-Kossel theory (1) offers the best explanation al— though it is somewhat indefinite. The catalyst unites with the sub- stance catalyzed through some of the electrons of the outer shell of the atoms of the molecule. The new arrangement of atoms and electrons is unstable at the temperature of the reaction. Rearrangement of the atoms and electrons then takes place to form more stable systems. HISTORY filSTJRY many dehydration agents have been employed in the condensation of various compounds to give a new field of organic chemistry. Catalyst which have been used are; sulfuric acid, phosphoric acid, phoSphorous pentoxide, magnesium chloride, zinc chloride, phosphorous pentachloride, aluminum chloride, ferric chloride, (both anhydrous and Fe013'6320), stannic chloride, acetic acid, sulfuric and acetic acid mixture, and hydrogen chloride. The condensation catalysts listed below have, however, proven more efficient, so at least one example of each is given. Zinc chloride was used by Fisher and Racer (2) to prepare aminotriphenylmethane by the condensation of benzhydrol and aniline hydrochloride. Sulfuric acid was used in 1330 when Becker (3) condensed m—nitrobenzyl alcohol and benzene to give m—nitrodiphenyl— methane. Sulfuric and acetic acid mixtures were used by heyer and Wurster (A) to condense benzyl alcohol and benzene to give diphenylmethane. Stannic chloride was used by Micheal and Jeanpretre (5) when they prepared phenyl trimethylphenylacetonitrile by the condensation of mesitylene with phenylhydroxyacetonitrile. Phosphorous pentoxide was employed by Hemilian (6) to prepare diphenyl p—xylymethane from benxhydrol and p-xylene. Eagnesium chloride was used by Mezzara (7) in the prepara- tion of propyl m-cresol from the condensation of propyl alcohol and m—cresol. Hydrogen chloride has been used as was shown by Noelting (8) in the preparation of p-nitrodimethyldiaminodiphenyl- tolylmethane. Acetic acid was used by Rhotinski and Patzeuitch (9) to condense triphenyl carbinols with pyrrole. The workers in this laboratory, however, have been especially interested in the use of aluminum chloride and the mechanism by which the reaction takes place. Therefore I will elaborate on this con- densing agent to give a more complete picture of its use. Aluminum chloride was introduced as a catalyst in the conden- sation reactions by the works of Friedel and Craft (10) in 1877. /’Their work was held within the bounds of the aliphatic series, however, they stated that it would not hold for the aromatic series. This has been disproven as have many theories by further research. The catalytic activities in Friedel and Crafts reactions of the anhydrous aluminum chloride may be explained'by the production of a temporary combination between the chloride and the organic material. 012 I CéRSH +- A1C13—9 HC]. 4- Al the latter would react 11th the halide. .012 1% «b R'Cl—9 A1013 4- 8'06R5 c635 Her: and Keith (11) condensed phenol with itself to form diphenyl ether by the use of aluminum chloride. wees (12) by condensing dichloroethyl oxide with benzene obtained triphenylethane. It is shown here that undoubtedly the aluminum chloride serves not only as a catalyst but also as a dehydrating agent. Graebe (13) condensed benzene and ly- droxylamine in the presence of aluminum chloride to produce aniline which was obtained, however, in small amounts. Frankforter and co-workers in 191A (14) reported in a series of articles that they had successfully condensed chloral, chloral hydrate, bromal, and tri-oxymethylene with various organic compounds in which there was an elimination of water. They could not obtain all the products by the Baeyer or sulfuric acid reaction, thus Frankforter maintained that aluminum chloride acts primarily as a catalyst and at the same time plays the part of a dehydration agent. Prins (15) in 1927 gave some concepts on the mechanisms of aluminum chloride condensation. He stated that benzene under the influence of aluminum chloride acted as if it had a.mobile hydrogen linkage apparently has undergone ionization under the influence of aluminum chloride's strong positive ion. Daugherty (16) agreed mainly with Prins but believed in an addition comoound betseen benzene and aluminum chloride tith the hydrogen loosely held. WOhl and Werlsporoch (17) were of the same opinion. However, one should not overlook the dehydrative power no matter that its catalytic action is toward aromatic compounds. . Huston and Friedmann (18) were the first to employ aluminum chloride as a condensatinlreagent to the aromatic alcohols. They obtained diphenylmethane as the principle product in the treatment of benzyl alcohol with benzene. The yields of the final product and by-product were found to be a function of the temperature and amounts of reagents used. Later they extended their work (19) to secondary alcohols with benzene and aluminum chloride using methylphenylcarbinol, ethylphenyl carbinol and benahydrol obtain- ing diphenylethane, diphenylpropane and triphenylmethane respectively. A much higher yield and smoother reaction was obtained from the methylphenyl carbinol than from the dzhylphenyl carme which led them to conclude that the ethyl group had a greater retarding effect than did the methyl group. Huston (20) extended his work when he condensed benzyl alcohol with phenol in the presence of aluminum chloride obtaining para— benzylphenol. Good yields of the methylethyl ethers were obtained upon condensing benzyl alcohol with anisole and phenetol. Thereby showing that the phenolic hydroxyl group did not interfere with the substitution of the bensyl group into the benzene ring. Huston and Bartlet (21) condensed phenylbutyl carbinol and phenol to give p-hydroxyl l, 1 diphenylpentane. The hypothesis that unsaturation of carbon atoms adjacent to the alcoholic group in- creases the reactivity of the hydroxyl group was confirmed by the large yield of p-hydroxytriphenylmethane. Huston, Lewis, and Grotemut (22) obtained p-hydroxy l, l diphenylpropane, and p—hydroxytriphenylmethane by condensation. p—Hydroxy 1, 1 diphenylbutane was added to this list later by Huston and Stickler (23). ethyl, iso—prooyl, butyl, ice-butyl, and iso-amyl alcohols would not condense with benzene in the presence of aluminum chloride. However, by a modification of the former's procedure Hsieh (25) did condense iso-propyl, isoébutyl, and iso-amyl (but not the normal) alcohols with benzene. Huston and Fox (26) condensed tert-butyl alcohol, tert-amyl alcohol, dimethyl n-propyl carbinol and dimethyl iso-propyl carbinol with benzene in the presence of aluminum chloride to form tert~butylbenzene, tert—amylbenzene, dimethyl n-propylphenyl— methane, and dimethyl iso-propylphenylmethane in good yields. Huston and Binder (2?) prepared several heptyl benzenes by this method. The alcohols used were dimethyl n-butyl carbinol, dimethyl iso~butyl carbinol, dimethyl soc~butyl carbinol, methyl- ethyl n—progyl carbinol, methylethyl iso-propyl carbinol, and triethyl carbinol which were condensed with benzene giving good yields of the alkyl benzene. Hradel (28) was reported to have had no condensation of di- phenylethyl or diphenylpropyl Carbinols with benzene in the prev sence of aluminum.chloride. Instead there was noted a great ten- . dency for the splitting off of a molecule of water from the carbinol to fern an unsaturated’hydrocarbon. Fox (29) reported no condensation of diethylphenyl carbinol. The inability of these latter carbinols to condense may be explained by the fact that the OH group is drawn closely to the carbon atom thereby inhibiting it from being split off. Macomber (30) attempted to condense diethylphenyl carbinol, dimethylohenyl carbinol, and methylethylphenyl carbinol with.benzene in the cresence of aluminum chloride to give the corresponding hydro- carbon. Methylethylphenyl carbinol and dimethylphenyl carbinola did give the predicted hydrocarbons but the diethylphenyl carbinol did not condense with benzene. Huston and Sculati (31) condensed dimethylamyl carbinola (n—amyl, active amyl and sec-emyl) with benzene in the presence of aluminum chloride to for! the alkyl benzene and also found that the branched chain carbinols showed decreasing readiness to condense with benzene as the branching approached the carbinol groun. Rheton and Breining (32) in 1938 reported good yields when they condensed diethyl n—progyl carbinol and diethyl iso—pronyl carbinol with benzene in the presence of aluminum chloride to give diethyl n-propylphenylmethane and diethyl iso—pronylphenylnethane. Huston and Guile (33) renorted having obtained condensation products of 2-methylheptenol—2, 2, 3-dimethylhexanol-2, 2,3,3-tri- methylpentanol-Z, 2,4—dimethylhexanol—2, 2,5—dimethylhexanol-2 2,3,A-trinethylpentanol-Z, end 2,4,A—trinethylpentanol-Z with phenol in the presence of aluminum chloride. The yields of the resulting p—t—alkylphenols ranged from 2.1 to 69.5 per cent. PREPARATION OF CABBINOLS Methyl di n-propyl carbinol Methyl di n-propyl carbinol was first prepared in 1886 by Gortalow and Saytzeff (34) when they reacted butyron and methyl iodide in the presence of zinc to give the desired carbinol in a 30 per cent.yield. Later Halse (35) prepared the same carbinol by treating n—propyl magnesium bromide with ethyl acetate. It was also prepared by Stadnikov (36) when he used benzhydryl acetate and n—propyl magnesium bromide to give a 40 per cent yield. Preparation of Grignard reagent Into a 3-liter 3-necked round bottomed flask equipped with a glycerine sealed stirrer, a reflux condenser and dropping funnel was placed 50 gms (2.06 moles) of dry magnesium turnings and one hundred m1. of anhydrous diethyl ether. To this was added a mixture of 246 gas (2 moles) of the halide (n—propyl bromide) and 500 ml. of ' anhydrous diethyl other. A small amount of the mixture was run into the flask through the separatory funnel to start the reaction; the reaction was continued by the addition of the rest of the mixture at the rate of one drop per second or less. Preparation of the carbinol To the Grignard reagent 88 gms (1 mole) of freshly distilled ethyl acetate was added at a rate such that the éher refluxed gently. Stirring was continued for two hours after the last of the ethyl acetate had been added. After standing overnight the mixture was hydrolyzed by pouring 10 the contents of the flask onto ice and treating the resulting mix- ture with reagent hydrochloric acid until the water layer became clear. The ether-water layers were separated by the use of a separatory funnel and the water layer was extracted three times with ether. The ether extracts were combined and anhydrous sodium sulfate was added and allowed to set overnight to dry. The other was distilled off on a water bath and the product was subjected to a distillation under reduced pressure. Hethyl di n-propyl carbinol was collected between 52 - 53.5°C. at 3.5 mm. Methyl n-propyl iso-proqyl carbinol It was first prepared by Clarke in 1911 (37) when he added 2-methy1 3—butanone to the Grignard reagent, n-propyl magnesium bromide, to give a 1.5 per cent yield of the carbinol. Preparation of Methyl n—propyl iso-propyl carbinol To the Grignard reagent was added 172 gms. (2moles) of :1er iso-propyl keto'ne. The rate of addition was such that the ether refluxed gently. The stirring was continued two hours after the last of the methyl iso-propyl ketone had been added. The resultant product was hydrolyzed in the usual manner. Methyl n—propyl iso-propyl carbinol was collected between 1.4.5 - 1.6.5°C. at 3.5 mm pressure. l2 Eethyl di iso-propyl carbinol Hethyl di iso—propyl carbinol was prepared in 76 per cent yields from di iso~propy1 ketone and methyl magnesium chloride by Whitmore and Laughlin (38) in 1932. Preparation of Methyl magnesium bromide The methyl bromide generator (by a modification of the pro- cedure given for methyl chloride (39))consists of a 3-liter 3-necked round bottom flask resting on a sand bath and fitted with a reflux condenser with a delivery tube running from the top of the condenser to a train of wash bottles, three containing a saturated solution of sodium hydroxide, three containing conc. sulfuric acid, and three safety bottles (one at each end of the train and one between the sodium hydroxide and the cone. sulfuric acid bottle). It was charged for a 12 mole (theoretical) of methyl bromide. 53 gms of water and 586 gms (320 cc.) of cone. sulfuric acid are placed in the flask and 370 gms (470 cc.) of methyl alcohol is added, with cooling, at such a rate that the temperature does not rise above 70°C. Then 1130 gms of sodium bromide is added, the apparatus is tightly connected, and the flask heated on the sand bath so that the gas is evolved at a fairly rapid rate. It has been feund in practice that, using materials of the commercial grade, the yield of methyl bromide is about 55 - 65 per cent of the theoretical amount. The methyl bromide is passed through the wash bottles into a 3-1 B—necked round bottom flask into which 75 gms (3.09 moles) of magnesium, a few crystals of iodine, some ethyl bromide to start the reaction and 600 ml of 13 an rdrous di ethyl ether have been placed. The reaction takes place smoothly - taking about two hours to use up the magnesium. The re— action was carried out under the hood as the methyl bromide is a poisonous gas. To the Grignard reagent was added 296 gms (370 cc.) of di iso~progyl ketone in 400 cc. of anhydrous di ethyl ether. It was added at such a rate that the ether refluxed gently. The resultant product use hydrolyzed as instructed under methyl di n-propyl carbinol. methyl di iso—propyl carbinol was collected between 53 - 54°C. at 13 mm. pressure. CONDENSATIORS Condensations General Procedure: A 500 ml 3—necked round bottom flask was provided with a glycerine sealed mechanical stirrer, a reflux condenser with a thermometer inside, and a separatory funnel. Benzene (5 equiv.) was placed in the flask and the stirrer was started. The entire amount of aluminum chloride (l/2 equiv.) was added to the benzene and uniformly suspended in the benzene. The carbinol (1 equiv.) was added by means of the separatory funnel, fitted with a CaClz tube, at a rate of 1 drop every 3 or 4 sec. so that the tempera- ture didn't rise above 30°C. A considerable amount of hydrochloric acid fumes were evolved during the process of the addition of the carbinol. If the temperature went above 30°C. it was cooled by means of a ice bath, the temperature remained between 25 - 30°C. The mixture was stirred for 4 hours after the last of the carbinol had been added. It was allowed to stand overnight and then de- composed hy ice and reagent HCl. The benzene layer was separated and the water layer was extracted three times with ether, the benzene other layer was then washed with sodium carbonate to remove any excess acid and allowed to dry overnight over anhydrous sodium sulfate. The ether and benzene were distilled off from a water bath and the remaining solution was distilled under reduced pressure. l5 Methyl di n—propyl carbinol, benzene and aluminum chloride Following the above procedure the following amounts were used: Run ’1 grams Equivm mg Carbinol 32.0 1 1/4 Benzene 97.5 5 1 1/4 Aluminum chloride 16.6 1 1/4 The following fractions were obtained: Up to 112°C. - - 12 mm 5 gms 112 -115°C. - - 12 mm 12 gms Above 115°C. - - 12 mm 7 gms The second fraction was redistilled and purified and final]: collected between 109 - 111°C. at 10 mm. (011 bath at 134 — 1390c.) and was found to be 4—methyl A-phenylheptane. The boiling point at 749 mm. was found to be 242 - 243°C. Iield 25.7 per cent. On the second trial a 1/2 mole run was made which gave about a 10 per cent higher yield. Yield 37.9 per cent. A-methyl L—phenylheptane was prepared originally by Halse (40) from A-chloro Lemethylheptane and benzol in the presence of aluminum chloride. Later it was prepared by the same author by the reduction with 32 in the presence of black platinum in glacial acetic acid of methyl X cylobenzylheptane (41). 16 Methyl n—propyl iso-propyl carbinol, benzene and aluminum chloride Following the general procedure the following amounts were used: M Emma Wuiv nt 11916.11 Carbinol 32.0 1 1/4 Benzene 97.5 5 1 1/4 Aluminum chloride 16.6 1 1/4 The following fractions were obtained: Up to 102°C. - - 11 mm 11 gms 102 - 107°C. - .- 11 mm 8.4 gms Over 107°C. - - 11 mm . 5 gms Yield 18 per cent The second fraction was redistilled and purified and finally collected between 104.5%. - 106.5%. at 11 mm and was found to b. 2,3—dimethyl 3—phenylhexane. The boiling point at atmospheric pressure was 237 - 238°C. at 748 mm. 0n the second trial a 1/2 mole run was made which gave about the same yield. Yield 18.8 per cent. 17 Methyl di iso-propyl carbinol, benzene and aluminum chloride A modification was made in the general procedure due to the formation of bi products in that procedure. The benzene and aluminum chloride were snapended in petroleum ether and the contents cooled to a minus 30°C. The carbinol was then added at such a rate that there was no noticeable change in temperature. In trial number one after the alcohol had been added the product was allowed to warm up at room temperature while in trial number two it was placed in the ice box fer 24 hours and then allowed to come to room temperature. It was decomposed and treated as under the general procedure. §¥££; Egggg Ecuigglents lgglgg Carbinol 64.0 1 1/2 Benzene 60.0 3 3/! Aluminum chloride 33.0 1 L/Q The following fractions were obtained: Up to 108°C. — - 14 mm 34 gms 108 - 115°C. - - 14 mm A gms Over 115°C. - - 14 mm 9 gms The second fraction was redistilled and purified and finally collected between 104 - 106°C. at 13 mm. (oil bath 134 - 136°C,) and was found to be 2,3,4—trimethyl 3-pheny1pentane. The boiling point at atmospheric pressure was 234 - 236°C. at 713 mm. Yield 4.33 per cent. 0n the second trial a 1/2 mole was also ran and a 7.57 per cent yield was obtained. 18 The low fractions were combined and a chloride was distilled over which was found to be 3-chloro 2,3,4-trimethylpentene which boiled between 53 - 56°C. at 11. mm. DATA AND PHYSICAL CONS-TAKES 19 Determination of Physical Constants The density was determined by using a small pycnometer. The weighings were all made at 20°C. and compared with water at 4°C. Measurements of the index of refraction were made on a Abbe refractometer. 1_Du Rouy Tensiometer was used to determine the surface tension. A standardisation of the instrument was necessary which was accomplished by means of the following cééE‘éen: Wt; Ciel). Wirg 5 28; 2 x 4 x dial reading The molecular refractions were calculated by using the Lorena- Lorentz formula: 3,. M d .n_:;L / x [“2 a“ MD = Molecular refraction u = Molecular weight d := Density n. = Index of refraction The theoretical molecular refractions were calculated from the following atomic refractions: (Zeitschrift Physicalische Chemie, 7, 140, (1891) ' 0.11: 1.705 0-0:: 1.209 C = 2.418 H - 1.100 Double bond = 1.733 The observed parachor was calculated by the formula: 1 13:de X‘ P = Parachor of compound M : Molecular weight (1 .2 Density 1 X 4:.- alrface tension Where: The molecular weights were obtained by observing the lower- The solvent was pure benzene into which the ing of freezing point. compounds were placed. . . . . . . . . .. . . . . a I. nflk . a: m.” \ . Savannahnenalm 33.0 . 3&4.” . 8.34 . 3.79.... . . . \emw .. .5. . \SH .. 3a . Aafioflstfid . . . as . . a . . u . . 1 . a a . . . . . w . . . aw 3Q . as .3 \ . cosmonagndun nowod . 8.?” a $3.4 . 0.3.33 . . . \ann .. bmu . \nooasméoau 1152. Sun.“ _ 1am . . . . tr . . . i. . . . . . . . _ .1. ..._ c. . ... . .- i «a \ . II 3Q . 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Ethyl Acetate: Baker’s U.S.P. from the stockroom. Methyl iso—Pronyl Ketone: Prepared by brominating tert.—amyl alcohol and hydrolyzing to Obtain the desired product. (1.2) Yield 55 - 70 per cent. Magnesium: Fresh magnesium turnings were obtained from the stockroom and were placed in a desiccator over Ca012 until ready fer use. Anhydrous di Ethyl Ether: This was obtained from the stockroom and allowed to stand over fresh cut metallic sodium until ready for use. I Benzene: Thiophene free benzene (C.P.) was obtained from the stockroom and allowed to stand over fresh cut metallic sodium until ready for use. Anhydrous Aluminum Chloride: (Tech.) This was obtained from the stockroom. Di lea-Propyl Ketone: (Pract.) Was obtained from Eastman. It was redistilled and collected over a two degree range. 25 Petroleum Ether: (C.P.) Obtained from stockroom and was dried over CaCl2 until ready for use. Anhydrous Sodium Sulfate: This was obtained from the stockroom and was of a good quality. Sodium Bromide: Obtained from the stockroom and was of a com. mercial grade. Methyl Alcohol: was obtained from stockroom. BIBLIOGRAPHY (1) (2) (3) (A) ( 5) (6) (7) (8) (9) (10) (11) (1?) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) Bibliography Lewis and Kossel Fisher and Roser Becker Meyer and fiurster Micheal and Jeanpretre Hemilian Mascara Hoelting Rhotinski, Patzewitch Friedel and Craft Her: and Weith Hess Graebe Frankforter and coworkers Prins Dougherty WOhl and fierISporoch Huston and Friedmann Huston and Friedmann Huston Huston and Bartlet Huston, Lewis, and Grotemut Euston and Sticker J. Am. Chem. Soc., 46, 137, (1924) Ber., 13, 674 Ber., 15, 2090 Ber., 6, 964 Ber., 25, 1615 Ber., 16, 2360 Gaza. Chim. Ital., 12, 505 Ber., 24. 553 Ber., 24, 3104 Comp. Rend., 84, 1392 Ber., 14, 187 Ber., 15, 1128 Ber., 34, 1778 J. Am. Chem. 800., 36, 1911 37, 385 Chem. Weekblad., 24, 615 J. Am. Chem. 8°C., 51, 576 Ber., 64, 1357 J. Am. Chem. Soc., 38, 2527 J. Am. Chem. soc., 40, 785 J. Am. Chem. Soc., 40, 2775 (Master's Thesis 1926) J. Am. Chem. 800., 49, 1365 J. Am. Chem. Soc., 55, 1.317 (24) Huston (25) Huston (26) Huston (2'7) Huston (23) Huston (29) Huston (30) atom (31) Huston (32) Huston (33) Huston and and and and and and and and and and Sager Hsieh Fox Binder Hravel Fox Macomber Sculati Ereiaing Guile (34) Gortalow and Saytseff (35) Hales (36) Ftadnikou (37) Clarke (38) Whitmore and Laughlin (39) Organic Synthesis (40) False (41) Halse (42) Organic Synthesis 27 J. Am. Chem. Soc., 4%, 1955 (Doctor’s Thesis 1935) (Master's Thesis 1934) (Master's Thesis 1935) (Master's Thesis 1934) (Bachelor's Thesis 1933) (Master's Thesis 1935) (Master's Thesis) (master's Thesis 1938) J. Am. Chem. Soc., 61, 69 (1939) J. prakt. Chem. 33. 203 J. prakt. Chen., 89, 453 Ber., 47, 2137 J. Am. Chem. 806., 33. 528 J. Am. Chem. 8°C., 54, 4392 Vol. X, 36 J. prakt. Chem., 89, 453 J. prakt. Chem. 92, 44 Vol. XllI, 68 I “1 ”(I H H