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STEREOSPECIFIC SYNTHESIS of GEO METRIC ISOMERS of ACYCLIC Cg- CONJUGATED DIENES and THEIR REACTIONS. University Microfilms, In This dissertation has been 65—3913 microfilmed exactly as received ROY, Bhairab Nath, 1936- STEREOSPECIFIC SYNTHESIS OF GEO­ METRIC ISOMERS OF ACYCLIC Cg- CONJUGATED DIENES AND THEIR REACTIONS. The Ohio State University, Ph.D., 1964 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan STEREOSPECIPIC SYNTHESIS OP GEOMETRIC ISOMERS OP ACYCLIC 'Cg- CONJUGATED DIENES AND THEIR REACTIONS DISSERTATION Presented In Partial Pulflllment of the Requirements for the Degree Doctor of Philosophy In the Graduate School of The Ohio State University By Bhairab Nath Roy, B. Sc. (Hons.) M. Sc. (Tech.) ****** The Ohio State University 1 9 6 4 Approved by Adviser Department of Chemistry ACKNOWLEDGMENTS The author wishes to express his sincere appreciation and deep gratitude to Dr. Kenneth W, Greenlee and to Professor Harold Shechter, under whose scholarly guidance this investigation was undertaken. ■ Acknowledgment must also be made to Mr. Vincent G. Wiley for his untiring technical assistance for the last four years. The financial support of this work by the Goodyear Rubber and Tire Co., Akron, Ohio, is gratefully acknowledged. ii VITA January 1, 1936 B o m - Taipur, Burdwan, W. Bengal, India 1955 ........ B, Sc. (Hons,), Calcutta Iftiiversity, Calcutta, India 1958 ........ M, Sc. (Tech.), Calcutta University, Calcutta, India 1958-1960 . C.S.I.R Research Fellow at I.A.C.S, Calcutta-32, India 1960-1963 . Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1963-1964 . Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio FIELD OF STUDY Major Field: Organic Chemistry iii CONTENTS Page I. Introduction................................. 1 II. Statement of the Problem ............................. 3 III. Historical . ...................... 4 17. Discussion and Results ................................ 11 V. Experimental......................................... 54 A. Determination of Physical Constants. .......... 54 1. Cryoscopic constants ................ ..... 54 2. Gas-Liquid Partition Chromatography (G.L.C.) . 56 3. Cottrell Boiling Points.................... 56 4. Refractive Indices ......................... 56 5. Densities ......... • . 57 6 . Infrared Spectra. ............. 57 7. Nuclear Magnetic Sprctra (NMR) ............ 57 B. Experimental Procedures ...................... 58 Rearrangement of biallyl ........ .......... 58 trans-4-Hexene-3-ol................... 58 3-AcetoQcy-trans-4-hexene ........... 59 Pyrolysis of 3-acetoocv-trans-4--hex:ene. ........ 60 3“Hexyne-2-ol ........................ 6l 3-Hexene-2-o l ..................... 6l 2-Acetoxy-3-hexene , ........ .. ............ 62 4-Methyl-3-pentene-2-o l ......... 62 2-Acetaxy-4-m®thyl-3-pentene « ........... 63 iv CONTENTS (contd.) Page Pyrolysis of 2-acetoxy-4-m«thyl-3-pentene .................. 63 2-Methyl-3-pontene-2-ol ...... 63 2-Acetoxy-2-mothyl-3-pentene 64 2-Methyl-2-pentene-l-ol . 64 1-Aceto%y-2-methyl-2-pent@ne and its pyrolysis.............. 64 2-Methyl-l-pentene-3-ol and 3-acetoxy-2-methyl-1- p e n t e n e ................................................. 65 N-Phenyl carbamate of trans-4-hexene-3-ol and its pyrolysis............. 65 trans-4-Hexene-3-yl xanthate and its pyrolysis.............. 66 4-Hexyne-3-ol ........... 67 3-Acetoxy-4-hexyne and its pryolysis............... 6? 3-Chloro-4-Hexyne.......................................... 6? cis; trans-2-Hexene-4-yne..................... 68 cis, trans-2,4-Hexadiene............ '■...................... 68 2,4-Hexadiyne . J ...................... 69 cis, cis-2,4-Hexadiene................................. 69 1,3-Hexadiene and sulfur dioxide adduct and its 70 thermolysis ............................................... l-Hexene-3-yne 70 ci s-1.3-Hexadiene . 71 1-Hexene-4-yn e ................... 71 ci s-1 .4-Hexadiene......................................... 71 3-Methyl-3-pontene-2-ol................ .................. 72 Acétylation of 3-methyl-3-pentene-2-ol and pyrolysis of 2-acetoxy-3-methyl-3-pentene. .......................... 72 V CONSENTS (contd.) Page Diels-Alder adduct of higher boiling 3-niethyl-l, 3-pentadiene ..................................... 72 Dehydration of 2-methyl-2,4-pentanediol by iodine. 72 2-Methyl-l-butene-3-yne 73 2-Methyl-l-pentene-3-yne....................... 73 Sodium in liquid ammonia reduction of 2-methyl-l- pentene-3-yne ..... ........................... 73 Hydrogenation of 2-methyl-l-pentene-3-yne..... 74 Rearrangement of cis-2-methyl-l, 3-pentadiene by- acid and heat ......... 74 Hydroboration of 2-methyl-l-pentene-3-yne...... 75 Crotyltriphenylphosphonium chloride .... .... 75 Reaction of crotyltriphenylphosphorane and ethanal: Preparation of 2 ,4 ~hexadienes . ................... 76 AUyltriphenylpho sphonium chloride............. 76 Reaction of allyltriphenylphosphorane and propanal: Preparation of l,3-hexadienes ......... ...... 76 Reaction of 3-chloro-l-butene and triphenyl- p h o s p h i n e..................................... 77 Reaction of mixture of crotyltriphenylphosphorane and l-methyl-2-propenyltriphenyl phosphorane with e t h a n a l ....................................... 77 Reaction of ethylidenetriphenylphosphorane and methyl vinyl ketone ............... 78 Methallyltriphenylphosphonium chloride ............ 78 Reaction of methallyltriphenylphosphorane and eth­ anal; Preparation of 2-^nethyl-l, 3-pentadiene s. .. 78 Reaction of methylenetriphenylphosphorane and 2-methyl-2-butenal: Preparation of 3-methyl-l, 3-pentadienes . ..................... 79 Vi CONTENTS (contd.) Page Diels-Alder reaction of trans. trans-2,4-hexadiene and acrolein: Preparation of I .................... 79 ci8-2-MBthyl-cis-5-aafltharl-4-cyclohexene-cis-l- methanol and ci8~2-giethyl-ci8-5-niethyl-4- cycloheocene-trans-l-methanol: Preparation of II . .. go ci3-2-ineth.yl-ci8-5-iBSth.Tl-4-cyclohexene-ci8-l- methanol-2-toluene sulfonate and cis-2Hpethyl- cis-S-msthyl-A-cyclohexene-trans-l-methanol-p- t oluene sulfonate ........................... go 3 ,cia-4 .ci8-6-trimethylcyclohoixene and 3 .cis-4 . tran8-6-trimethylcyclohexene...................... gl 1 .cis-2 .cis-4-trimethylcyclohexane and 1 ,cis-2 , tran8-4-cyclohemne ......................... gl 3-methyl. cis-6-methyl,4~methylenecyclohexene (IV) . 82 Hydrogenation of I V ......... 82 Diels-Alder reaction of cis. trans-2,4-hexadiene and acrolein ...................................... g3 cis-2-methyl-trans-5-niethyl-4-cyclohexene-ci3-l- methanol and ci3-2-methyl-tran8-5-methyl-4-cyclo- hexene-trans-l-methanol (VI) . ............ g3 3-methyl, 6-trans-methyl, 4-^nat hylenec yc lohexene : Preparation of VIII .............................. g3 Hydrogenation of 3-methyl.6-tran3-methyl.4- methylene-cyclohexene............................. g4 Co-dimere of trans. tram8-2,4-hexadiene and 1,3- butadiene......... 8U Isolation of co-dimers of trans. trans-2.4- g$ hexadiene and 1,3-butadiene: Isolation of A, B, C. Dehydrogenation of A, B, C ..................... g$ 3-methyl.cis-6-methyl. cis-4-vinyl-cyclohexene and 3-methyl, cis-6-methyl. trana-4-vinyl-cyclohexene. 86 vii CONTENTS (contd.) Page Hydrogénation of C: cl3-l-methyl-2-n-propylcyclo- h e x a n e ........... 86 Co"dimerization of cis. cis-2 .4-hexadiene and 1, 3-butadiene 86 Isolation of co-dimers of cis. cis-2.4-hexadiene and 1,3-butadiene; Isolation of D, E and FG ........... 86 Dehydrogenat ion of D .... ...................... 8? Hydrogenation of D: l-methyl, trans-2-n-propyl- 87 cyclohexane...................................... Co-dimerization of cis. trans-2 ,4-hexadiene and 1, 3-butadiene 8? Co-dimerization of trans-3-methyl-l.3-pentadiene and 1,3-butadiene.................................... 87 Dehydrogenat ion of Co-dimer of trans-3-methyl-l. 3-pentadiene and 1,3-butadiene ...................... 88 Relative rates of exchange of Grignard reagents with 1-hexyne........................................ 88 Materials................................................... 88 Equipments ..... ........................................ 88 Kinetic runs ............................................... 88 R e s u l t s ...................... 89 VI. Infrared Spectrograms..................................... 91 viii LIST OF TABLES Table Page 1 2,4-Hexadienes.................................. 22 2 Ij3-Hexadienes ................ 25 3 3-Methyl 1,3-pentadlenes ............................. 26 4 2-Methyl 1^3-pentadienes ............................. 30 5 1,2,4-Trimethylcyelohexanes ........... 36 6 Relative rates of exchange of 1-hexyne with 44 acyclic Grignard reagents ............................ 7 Relative rates of exchange of 1-hexyne with 45 aryl Grignard reagents ...................... ....... 8 Relative rate of exchange of 1-hexyne with 50 acyclic Grignard reagents ............................ 9 Relative rate of exchange of 1-hexyne with 50 cyclic Grignard reagents ............................ ix I. INTRODUCTION The synthesis, purification and study of properties of pure hydrocarbons have long been in progress at The Ohio State University From 1938, almost to the present, this research has been under the sponsorship of the American Petroleum Institute, The program originally called for an extended series of motor tests on each hydrocarbon included in gasoline. In more recent years, the emphasis has been on the preparation of very pure hydrocarbons on which determination of the physical and thermodynamic properties are made. These same hydrocarbons are also made available as standard samples for calibration of analyti­ cal instruments
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