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Acid Catalysed Dimerisation of 2,3-Dimethylbutadiene By ACID CATALYSED DIMERISATION R H C. 1L I ^ A R Y CLASS c c OF No. 2,3-DIMETHYLBUTADIENE —ACC.---- No.f (>ll^SS o Date ACQ. | N a r f L BY GEORGE METRY GUIRGUIS DIMITRIOUS THIS THESIS IS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF PHILOSOPHY IN THE UNIVERSITY OF LONDON ROYAL HOLLOWAY COLLEGE'(UNIVERSITY OF LONDON) THE BOURNE LABORATORY CHEMISTRY DEPARTMENT EGHAM HILL, EGHAM, SURREY, TW20 OEX r\i DECEMBER 1981 RHC b llS û D 3 a3021U 006 115803b ProQuest Number: 10096446 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 10096446 Published by ProQuest LLC(2016). 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 48106-1346 ^ J . 1 |V-^J ^ y . Q I I ^ l_a ^ I zj LvJjJ I Ô Â-i u? ClJ ij la j .iLj t IjrCj^ I (_y9 ^ J ^ Ij J Oyls J j^Jv^ l<^^ l_^ SLj^ L ^cJ la j^SjUjJl ôi^ Ô -^Io ^ ^ ^ j U hJI ^ k_) I -i— I y j b b-jb. O A». CXH ^ LT^^i û-b^ (jJ (J ■■■ ■■ ' -1 i=-3— (_pb <Sj^ JJ^3 * ^ b>Qa LÜI U-2» <L——rxv/OÙ J b%_w, 0 Al bb^b Û bi>«-j b-^J^ J j b ^ ^ OjaZwaJ I 1 jp J j ♦ *L— iJbj 5 Dedication Q To M u m and Dad This Thesis is dedicated to m y beloved parents;in which I should like to thank them for being very patient in not seeing m e during the years of m y doing the work in this thesis, and for their endless encouragement and prayers for me. I wish them a very happy and long life. o George ^ H . c . .flB/TRflCT- The acid catalysed dimérisation of 2,3-dimethylbutadiene has been carried out using sulphuric acid in acetic acid as solvent. Analysis by gas chromatography, mass spectroscopy revealed that the product, b.p.46 - 120° at O .5 mm consisted of at least thirteen compounds. Of the eight major components (hydrocarbons), five have a molecular weight of I64 and three 162. No acetates appeared to be formed during the reaction and only one compound was found to be a solid (m.p. 87°)* The major compounds were separated in a pure state using preparative 1 13 G.l.c. and their molecular structure investigated using H and C n.m.r. and open-chain, mono-cyclic, bicyclic, tricyclic and aromatic structures have been found in these compounds. The following compounds were suggested; 3-methylene-2,6,7-trimethyl- 1 ,6-octadiene or 4-methylene-2,],7-trimethyl-2,7-octadiene, 1,2,4- trimethyl 4-isopropenyl cyclohex-1-ene, 2-methylene-1,3,3,4-tetramethyl- bicyclo[2,2,1 ]heptane, 2-methylene-1,4,7,7-tetramethylbicyclo [2,2,l] heptane (solid), 2 ,4-dimethyltricyclene or 1,2,4,7,7-pe%tamethyltricyclo 2—6 (2 ,2,1,0 ) heptane, 2,4-2,5- and 3,4-dimethyl t-butylbenzene. The kinetic study of the reaction has shown that it is second order in 2,3-dimethyl-1,3-butadiene. c Ik fl © yj) Il @ d Q ® m ® û t / I wish to express my deep gratitude and indebtedness to Professor T G Bonner for his encouragement, support and advice. His kindness and help, which words can hardly express, have enabled me to carry on with my studies at Royal Holloway College. I would like to thank Dr R A Hancock for supervision and acknowledge his guidance throughout this project and for his help with interpreting the results reached as well as for many useful discussions. I also wish to express my appreciation to Mrs E Summers at King’s Collège (London University) for recording the 1 3 C n.m.r. spectra, and the staff of the n.m.r. laboratory at the Physical Chemical Measurements Unit (Harwell) for recording 1 the H n.m.r. spectra. Special thanks, are also extended’ to IAl s s J L Hurn the Registrar of the Royal Holloway College, to the administration and to the Bourne Laboratory staff for unfailing help and the British Council for financial assistance. Finally I wish to thank Mrs E I Kearsey for her neat typing of the present Thesis. Chanter I Introduction Page I . The Chemistry of Acyclic Hydrocarbons Containing 1 Two Double Bonds. II. Conjugated Dienes. 1 A. Methods of Formation. 1 (i) From hydrocarbons. 1 (ii) By dehydration of the saturated 1,2-^1,3- or 4 1,4-diols and by pyrolysis of their diesters. (iii) By addition reactions. 7 (iv) By Grignard reactions. 9 (v) By 1,4- elimination reactions. 10 (vi) Lebedev’s process. 1C B. Bonding and Stability. ' 11 (i) Bonding Characteristics. 11 (ii) 1,2- and 1,4- addition. 12 (iii) Valence bond approach and thermodynamic 13 stability. Ill. Addition Reactions of 1,3-Butadiene. 15 A. Addition of Hydrogen. 16 B. Electrophilic Additions. l8 (i) Acids as electrophiles for addition. l8 (ii) Additions with other electrophiles. 19 C. Addition of Sulohur Dioxide. 21 D. Reactions with Organic Peracids. 22 E. Addition of Carbenes. 22 P. Hydroboration of Dienes. 23 G. Coupling with Diazonium Salts. 24 H. Reactions with Transition Metal Complexes. 24 I. Additions to other Dienes. 25 J. Ring Forming Reactions of Dienes. 26 IV. The Polymerisation of Conjugated Dienes. 26 V. Carbocations and their Rearrangements. 31 A. Simple Rearrangement of Carbocations. 31 B. General Concepts of Carbocations. 34 C. Non-Classical Ions. 35 D. Evidence for Non Classical Ions. 37 E. The Naming of Carbocations. 46 VI. Nuclear Magnetic Resonancv Soectroscorv. 47 -J A. Proton ( H) n.m.r. Spectroscopy. 47 (i) Introduction. 47 (ii) Spin-Spin Coupling. 49 (iii) Field-Frequency Lock Systems. 50 (iv) Nuclear Magnetic Double Resonance. 51 B. Carbon-13 n.m.r. 52 Chapter II Results and Discussion Page I. The Reaction of 2,3-Dimethyl Butadiene with Sulphuric 57 Acid in Acetic Acid Solution. A. The preparation of 2,3-Dimethyl Butadiene hy Acid 57 Dehydration of Pinacol. B. Acid Catalysed Reactions of 2,3-Dimethyl Butadiene 58 in Acetic Acid. C. Alternative method of examination of Reaction Products 60 from the Reaction of 2,3-Dimethyl Butadiene with Sulphuric Acid in Acetic Acid. II. Structure Determination of Hydrocarbons Resulting from the 62 Reaction of 2,3-Dimethyl Butadiene with Sulphuric Acid in Acetic Acid. A. Gas chromâtography-Mass Spectrometry of Reaction 62 Products. B. Separation and Purification of Products. 74 C. N.M.R. Spectroscopy as an Aid to structure elucidation. 76 (i) Determination of the structure of compound E by 77 1 13 H and C n.m.r. spectroscopy. (ii) Determination of the structure of compound D by ^H and 1 3C spectroscopy. (iii) Determination of the structure of compound B by ^H and spectroscopy. (iv) Determination of the structure of compound F by ^H 94 and ^spectroscopy. (v) Determination of the structures of compounds G , H 1^1 1 13 and I by H and C spectroscopy. (vi). Determination of the structure of compound A by ^H 1 ^^ and 1 3C spectroscopy. 1 1 ^ (vii)H and C n.m.r. spectra of compounds A, B, D, 118 E, F, G , H and I. Page III. Kinetics of the formation of dimers of 143 2 ,3-DimethyIbutadiene. (i) Determination of reaction rate of acid 143 catalysed dimérisation. (ii) Kinetic analysis of the reaction of 145 2.3-Dimethylbutadiene with sulphuric acid. (iii) The reverse of the reaction of 1 55 2 .3-DimethyIbutadiene and sulphuric acid in acetic acid. (iv) Variation of Experimental Rate Constants with 155 Concentration or Acid. IV. Suggested Mechanism of the Formation of 157 ^ 12^20 ^12^18 Products. Chapter III Page Experimental I. General Techniques 163 A. Gas-Liquid Chromatography (G.L.C.) B, Mass Spectrometry. 169 C. Nuclear Magnetic Resonance (n.m.r.) 169 II. Experiments 170 A. Synthesis of 2,3-Dimethylhutadiene. 170 B. The oligomerisation of 2,3-Bimethylbutadiene. 170 C. Kinetic Experiments. 171 (i) Materials. 171 (ii) Determination of calibration graphs for 1 72 2-methylene. 1 ,4 ,7.7 ,tetramethyl [2 ,2 ,l]- bicycloheptane and 2,3-DimethyIbutadiene. (iii) Procedure for a typical kinetic experiment. 1 72 (iv) Kinetic Experiment to study the 175 dedimerisation reaction. (v) Determination of the loss of 2 3-Dimethyl- 176 butadiene during the experimental work. (vi) Extraction coefficient of 2,3-Dimethyl- 176 butadiene from Acetic Acid solutions. 1 13 • List of H and C n.m.r. spectra of compounds A , B , D , E , ? , G , H and I. Page No Spectrum 1) H. n.m.r. of compound "A". 118 Spectrum 2) H. n.m.r. of compound "B”. 119 Spectrum H. n.m.r. of Tricyclene. 120 Spectrum 4) H. n.m.r. of compound ”D”. 121 Spectrum 5) H. n.m.r. of compound ”E". 122 Spectrum 6) H. n.m.r. of Camphene. 123 Spectrum 7) H. n.m.r. of compound "F", 124 Spectrum 8) H. n.m.r. of Limonene. 125 Spectrum 9) H. n.m.r. of compound "G-”, 126 1 Spectrum 10) H.
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