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THE STEREOCHEMISTRY of the CATALYTIC HYDROGENATION of Compounds Containing an a S M E T R Ic CARBON ATOM

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THE STEREOCHEMISTRY of the CATALYTIC HYDROGENATION of Compounds Containing an a S M E T R Ic CARBON ATOM THE STEREOCHEMISTRY OF THE CATALYTIC HYDROGENATION of compounds containing an a s m e t r ic CARBON ATOM By TERENCE JOHN HOWARD A T hesis submitted to the University of London for the Degree of Doctor of Philosophy in th e Faculty of Science The Organic Research Laboratories, Battersea College of Technology, Sept. i 960 London, S.W .ll. ProQuest Number: 10804653 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10804653 Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346 2 ABSTRACT OF THESIS 4-Phenyl pen t-3-en-2--one has been prepared by the reaction of dimethyl cadmium with j3~methylcinnamoyl chloride, and its structure confirmed by a haloform degradation to trans - Q - methylcinnamic acid. Reduction of the ketone with aluminium isopropoxide gave (i)-4“Pbenylpent-3-en~2~ol, characterised by the preparation of the 3J-a-naphthyl and R-4-diphenylyl-carbamates. On catalytic hydrogenation (-)-4“-phenylpent-3-en-2--ol gave a mixture of the two diastereoisomeric racemates of (-)~4~phenylpentan-2-ol in which a new centre of asymmetry has been generated at C^. On vapour-phase chromatography the two racemates separated§ from the chromatogram the ratio in which they are present has been determined, and hence the degree of asymmetric synthesis calculated and found to bes ( i ) 50$? (ii) 57$• By oxidation the original centre of asymmetry at has been removed to yield (~)-4“Pbenylpentan~2-one• The stereochemistry of the hydrogenation is discussed. (+) -a-Pinene has been hydrogenated over a Raney nickel catalyst to give almost exclusively (+)-ci s~pinane, and the stereochemistry of this hydrogenation is also discussed. The possibility of purifying (+)-a-pinene by the technique of progressive freezing has been examined. 3 (-)- (3 -Raphthylmethylcarbinol has been hydrogenated over a platinum oxide c a ta ly s t, and over a ctiv e and s ta b iliz e d Raney nickel catalysts. In all cases a mixture of isomers of 1,2,3,4- tetrabydro-2-ethylnaphthalene and 1,2,3,4-tetrahydro-6-ethylnaphthalene was the exclusive* or predominating, product. In the hydrogenation with a stabilized catalyst a small quantity of a tetrahydro-p - naphthylmethylcarbinol was isolated, and the presence of two isomeric 2-ethyldecalins was also detected. The hydrogenation of |3-naphthylmethylcarbinyl acetate, and of the methyl ether, produced in each case, exclusively, a mixture of the two isomeric ethyltetralins» p-Cymene has been acetylated to give a mixture of two acetyl cymenes in which 2-acetyl-p-cymene predominates. Aluminium isopropoxide reduction gave a mixture of two cymyl alcohols, the hydrogenation of which, under various conditions? gave in all cases an isomeric mixture of ethylcymenes, generally as the major product. With a stabilized Raney nickel catalyst a small quantity of the menthyl alcohols was obtained, and vapour-phase chromatography showed that hydrogenation had produced a mixture of four diasterio- isomeric racemates of the menthyl alcohols, which were present in unequal amounts, indicating that an asymmetric hydrogenation had occurred. The stereochemistry of the hydrogenation is discussed. ACOOWLEDGMEUTS The work described in this Thesis was carried out in the Organic Chemistry Research Laboratories of the Battersea College of Technology under the supervision of Dr. C.L. Arcus. The author wishes to express his sincere thanks to Dr. Arcus for his constant help and encouragement throughout the work. Thanks are also due to Dr. J .R. Haresnape and Mr. D.H. Desty of The B ritish Petroleum Company Research Centre9 Sunbury-on- Thames3 for the use of a vapour-phase chromatograph. PREFACE The work described in-this Thesis has been divided into four parts, each dealing with the hydrogenation of a different compound. Each part is complete in itself and contains two sections^ in one section the experimental results are given, and in the other the interpretation of these results is discussed. The whole is preceded by an introductory review of catalytic hydrogenation. 6 C d M T S Title of Thesis 1 A b stract 2 Acknowle dgmen t s 4 P reface 5 THE MECHANISM AND STEREOCHEMISTRY OP CATALYTIC HYDROGENATION Introduction 12 Historical Survey 12 Steric Interaction between Substrate and Catalyst 30 Optical Activity and Catalytic Hydrogenation 35 Conclusion 44 PURPOSE OP THE V/ORK 45 PART 1 DISCUSSI0N_0P RESULTS R eaction Scheme 49 4-Phenylpent-3-en-2-one 49 The geometrical configuration of 4-pbenylpent-3-en~2-one 53 4-Phenylpent-3-en-2-ol 54 The catalytic hydrogenation of 4-pbenylpent-3-en-2-ol 56 The oxidation of 4“Pb©nylpentan-2-ol 58 The stereochemical course of catalytic hydrogenation of 4-phenylpent-3-en-2-ol 59 Conclusion 65 7 Preparation of ethyl bromoacetate 67 Preparation of ethyl p-methylcinnamate ■ 67 Preparation of j3-methylcinnamic acid 69 Preparation of (3-methyl cinnamoyl chloride 70 Preparation of 4-pbenylpent-3-en-2-one 70 4-Phenylpent-3-en-2-one semicarbazone 72 4-Phenylpent-3-en-2-one 2?4~&initrophenylhydrazone 73 Oxidation of 4~pbenylpent-3-en-2-one with sodium hypochlorite 73 Preparation of 4-pbenylpent-3-en-2-ol 73 l-Methyl-3-phenylbut-2-enyl N-a-naphthylcarbamate 'JS 1-Me thy 1-3-phenyl but-2-enyl N-4-diphenylylcarbamate 76 Preparation of Raney Nickel W-3 catalyst 76 Hydrogenation of 4-pbenylpent--3-en-2-ol I 77 Oxidation of 4-pbenylpentan-2-ol I 79 4-Phenylpentan-2-one semicarbazone 83 Hydrogenation of 4-pbenylpent-3-en-2-ol II 84 Oxidation of 4-pkenylpentan-2-ol II 85 PART 2 DISCUSSI0N_0P RESULTS (+)-a-Pinene 90 The catalytic hydrogenation of (+)-a-pinene 93 The purification of (+)-a-pinene by progressive freezing 100 Conclusion - 103 8 Greek (+)-a-pinene 104 Hydrogenation of (+)-a-pinene 105 Purification of (+)-a-pinene by progressive freezing 109 PART 3 Introduction to Parts 3 and 4 111 ^SCUSSIOE^OP RESCJLTS The attempted hydrogenation of p-naphthylmethylcarbinol 113 The attempted hydrogenation of p-naphthylmethyl- carbinyl acetate 116 The attempted hydrogenation of p-naphthylmethyl- carbinyl methyl ether 117 Further attempted hydrogenations of (3-naphthylmethyl~ c arb in o l 118 Conclusion 120 Preparation of (3-naphthylmethylcarbinol 121 Hydrogenation of j3-naphthylmethylcarbinol I, Using a stabilized Raney Uickel catalyst 122 Identification of the low-boiling products of hydrogenation 123 1. Examination of the hydrocarbon product 124 2. Examination of the alcoholic product 124 Preparation of (3-naphthylmethylcarbinyl acetate 126 Hydrogenation of (3-naphthylmethylcarbinyl acetate 127 9 Preparation of p-naphthylmethylcarbinyl methyl ether 128 Hydrogenation of (3-naphthylmethylcarbinyl methyl ether 130 Hydrogenation of p-naphthylmethylcarbinol II. Using an active Raney Uickel W-3 catalyst 132 III. Using Adam’s platinum oxide catalyst 133 PART 4 DISCUSSI0I\r_0P RESULTS Introduction 137 The preparation of 2-(p-cymyl)methylcarbinol 137 The hydrogenation of the cymyl alcohol 140 The stereochemical course of catalytic hydrogenation of 2-(p-cymyl)methylcarbinol and 6-(m-cymyl)methylcarbinol 142 Further attempted hydrogenations of the cymyl alcohol 145 Conclusion 146 E M m A L Preparation of 2-methyl-5-isopropylacetophenone 147 Preparation of 2- (p-cymyl)methylcarbinol 148 a-(2-p-Cymyl)ethyl H- 4-diphenylylcarbamate 151 Preparation of 2-(p-cymyl)methylcarbinyl hydrogen phthalate 151 Preparation of 2-(p-cymyl)methylcarbinyl acetate 152 Hydrogenation of 2-(p-cymyl)methylcarbinol I. Using a stabilized Raney Uickel catalyst 153 a - ( 2~p-llenthyl)ethyl H- 4-diphenylylcarbamate 156 10 Hydrogenation of the cymyl alcohol II. Using a Raney Hickel ¥-3 catalyst of low activity 156 III. Using an active Raney Uickel W-3 catalyst 158 Vapour-phase chromatography Experimental conditions 163 GENERAL INTEODUCTI ON Tlie Mechanism and Stereochemistry of Catalytic Hydrogenation 12 INTRODUCTION The use o f a s o lid c a ta ly s t i s e s s e n tia l in many modern industrial syntheses* Without the use of such catalysts many processes would require such extremes of pressure, or temperature, that they would no longer he economically feasible. For this reason the study of heterogeneous reactions has attracted much attention* Nevertheless knowledge of the mechanisms involved is s till far from complete. This is not surprising when it is .remembered that in a heterogeneous system all the problems associated with a homogeneous reaction are present plus the added problems due to the introduction of a surface. There is however one heterogeneous system, namely catalytic hydrogenation and the closely allied exchange reaction, for which a mechanism accounting for most observed experimental facts can be postulated. A survey of the work carried out in this field fo llo w s. HISTORICAL SURVEY Present-day knowledge of the mechanism of catalytic hydrogenation dates mainly from the work of Farkas, Faikas, and Rideal (Proc. Roy. Soc., 1934? A? 146? 630). Prior to this date it was generally assumed that catalytic hydrogenation of olefinic linkages simply involved the addition of a molecule of hydrogen across the double bonds this postulate being based on the observation that in such hydrogenations predominantly cis products were obtained. 13 Farkas? Farkas? and Rideal (loc. c it.) suggested? however? that in view of the fact that chemi-adsorbed hydrogen on catalytically active metallic surfaces is in the atomic form? it would seem possible that the reaction was considerably more complex than the simple one postulated.
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