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Reactions of Organosilylmetallic Compounds with Some Halides Dan Kazumi Aoki Iowa State University

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Reactions of Organosilylmetallic Compounds with Some Halides Dan Kazumi Aoki Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1961 Reactions of organosilylmetallic compounds with some halides Dan Kazumi Aoki Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Aoki, Dan Kazumi, "Reactions of organosilylmetallic compounds with some halides " (1961). Retrospective Theses and Dissertations. 1958. https://lib.dr.iastate.edu/rtd/1958 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. REACTIONS OF ORGANOSIIHMETAL1ZC COMPOUNDS WITH SOME HAHDES by Dan Kazumi Aok± A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHIIOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. In Chargé of lfe.jor.Mbrk Signature was redacted for privacy. Head of Major Depa: Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1961 il TABLE OF CONTENTS _. - Page I. INTRODUCTION 1 II. HISTORICAL 3 A. Reactions of Grignard Reagents with Organic Halldes 3 B. Reactions of Organblithlum Compounds with Organic Halldes 9 I# The condensation reaction 10 2. The halogen-metal interconversion reaction - 11 3» The metalation reaction 16 G# Reactions of R3EIA Compounds with Organic Halldes 20 le Reactions of tripheqylsilyllithium with aryl halldes 20 2. Reactions of triphenylgermyl 11 thium with organic halldes 20 3# Reactions of triaryl- and trialkyltin-lithium with organic halldes 21 Reactions of trlphenyllead-llthium with organic halldes 23 HI. EXPERIMENTAL 24 Ae General Considerations 24 B. Reactions of Trlpherylsilyl lithium with Alkyl Halldes 2? le Reaction of triphenylsilyl 1 i thiam with n-butyl chloride 2? 2e Reaction of trlpherçylsilylli thium with g-butyl bromide 2? 3. Reaction of triphecylsllylllthlum with n^dodecyl chloride 2? 4e Reaction of tripherylsilyllithiym with allyl chloride 28 5• Reaction of tripheryisilyllithium with cyclopentyl chloride 28 6. Reaction of trlphenylsilyllithium with l,3~dichloropropane 29 7. Reaction of trlphecylsllyl 11 thium with 1,3-dibromopropane 29 iii Page 8. Reaction of tripherylsilyllithium with methylene chloride 30 a. No mal addition 30 (1) Run 1 (1:1) 30 (2) Run 2 (2:1) 30 (3) Run 3 (2:1, in the presence of cyclohexene) 31 (4) Run 4 (512) 31 be Reverse addition 32 9. Reaction of triphenylsilyllithium with methylene bromide 32 a. Normal addition 32 (1) Run 1 (2:1) 32 (2) Run 2 (2:1, in the presence of cyclohexene) 33 be Reverse addition 33 10. Reaction of triphenylsilyllithium with methylene iodide 33 lie Reaction of triphenylsilyllithium with chloroform 34 a. Normal addition 34 (1) Run 1 (1:1, room temperature) 34 (2) Run 2 (2:1, -60») 35 be Reverse addition 36 12. Reaction of triphenylsilyllithium with bromofom 36 a. Normal addition 36 (1) Run 1 (2:1) 36 (2) Run 2 (8:3) 37 be Reverse addition 38 iv Page 13• Reaction of triphenylsilyllithium with iodoform 38 a. Normal addition 38 (1) Run 1 (until positive with Color Test I) 38 (2) Run 2 (2:1, in the presence of triphenylsilane) 39 b. Reverse addition 39 14. Reaction of triphenylsilyllithium with carbon tetrachloride 40 a. Normal addition 40 b. Reverse addition 41 15 • Reaction of triphenylsilyllithium with carbon tetrabronti.de 41 a. Normal addition 41 b. Reverse addition - 42 16. Reaction of triphenylsilyllithium with chloromethorltriphenylsilane 43 17. Reaction of triphenylsilyllithium with dichloronetiyltriphenylsilane 44 18. Reaction of triphenylsilyllithium with chloromethyltrimethylsilane 45 19» Reaction of triphenylsilyllithium with chloromethyldimetbylvixylsilane 45 20. Reduction of dichlo romethyltriphenyls ilane with lithium aluminum hydride 45 21. Reduction of diiodomethyltriphenylsilane with lithium aluminum hydride 46 22. Reaction of bromcmiethy 1triphenylsilane with lithium in THF 46 23. Reaction of triphenylsilyllithium with 1,1-dichlorobutane 47 a. Normal addition 47 b. Reverse addition 47 24. Reaction of triphenylsilyllithium with 1,l~d±bromoethane 48 Reactions of TripheiQrlsilyllithium with Alkenyl Halldes 1. Reaction of triphenylsilyllithium with 1-chloropropene a. 1:1 ratio be 2:1 ratio, followed by addition of chlorotriphenylsilane Ce Reaction of triphenylsilyllithium with 1-triphenylsilylpropene d. Reaction of prcpenylHthium with triphenylsilane e e Reaction of properyHi thium with chloro triphenylsilane 2. Reaction of triphenylsilyllithium with 1-chloro-l-bti.tene a. 1:1 ratio at room temperature be 1:1 ratio at reflux c. 1:1 ratio at room temperature, followed by addition of chlorotriphenylsilane 3» Reaction of triphenylsilyllithium with 1-bromopropene a. 1:1 ratio be 4:3 ratio, followed by addition of chloro triphenylsilane Ce 8:5 ratio, followed fcy addition of chlorotriphenylsilane de 3*1 ratio 4e Reaction of triphenylsilyllithium with l~bromo-l»-butene 5 e Reaction of triphenylsilyllithium with 2-bromo-l-.bu.tene, folio wed-ty addition of chlorotriphenylsilane 6. Reaction of triphenylsilyllithium with 1,1-dichloropropene a. At -60° (1) Run 1 (2:1) (2) Run 2 (3:1) vi Page b. At roam temperature 59 (1) Run 1 (1:2) 59 (2) Run 2 (2:1) 60 (3) Run 3 (2.5:1) 60 (4) Run 4 (3:1. followed by addition of chlorotriphenylsilane) 61 7. Reaction of triphenylsilyllithium with 1,2-dichloropropene 62 8. Reaction of phenyllithium with 1.2-dichloropropene 62 a. 1:1 ratio, followed by addition of triphenylsilyllithium 62 b. 2:1 ratio, followed by addition of chlorotriphenylsilane 63 9e Reaction of phenyl lithium with trichloro ethylene 63 a. 1:1 ratio, followed by addition of chlorotriphenylsilane 63 b. 1:1 ratio, followed by addition of triphenylsilyllithium 64 10. Reaction of triphenylsilyllithium with 1.3-dichloropropene 64 a. 1:1 ratio 64 b. 2:1 ratio 65 c« 3:1 ratio 66 d. Reaction of triphenylsilyllithium with a mixture of compounds (I) and (II) 6? e. Reaction of phenyl 11 thium with a mixture of compounds (I) and (H) 67 f. Reaction of triphenylsilyllithium with 1,3-bis( triphenylsilyl)propene, followed by addition of chlorotriphenylsilane 68 lie Reaction of triphenylsilyllithium with 2,3-dichlo ropropene 68 a. 1:1 ratio 68 b. 2:1 ratio, followed by addition of chlorotriphenylsilane 70 vii Page Ce 8:3 ratio, followed ty addition of chlorotriphenylsilane 70 d. Reaction of triphenylsilyllithium with compound (ill) 71 De Reactions of Triphenylsilyllithium with 1-Triphenylsilylpropyne and Related Reactions 71 le Reaction of triphenylsilyllithium with L-tiiphenylsilylpropyne 71 at Without addition of chlorotriphenylsilane 71 b« Followed by addition of chlorotriphenylsilane 73 (1) Run 1 (in a mixture of ether and THF) 73 (2) Run 2 (in THF) 74 2, Reaction of phenyl 11thium with 1-triphenylsilylpropyne 75 a. Followed by addition of triphenylsilane 75 (1) Run 1 (5 hours) 75 (2) Run 2 (24 hours) 75 be Followed by addition of chlorotriphenylsilane 76 3e Reaction of triphenylsilyllithium with tris( triphenylsily 1 ) propadiene 76 a. Without addition of chlorotriphenylsilane 76 be Followed by addition of chlorotriphenylsilane 77 4e Reaction of phenyllithium with tris( triphenylsilyl)propadiene 78 a. Followed by addition of chlorotriphenylsilane 78 be Followed by addition of methyl iodide 79 Ce Followed ty addition of deuterium oxide 80 5. Reaction of triphenylsilyllithium with l,3-bis (triphenylsilyl)propyne followed ty addition of chlorotriphenylsilane 80 viii Page 6. Reaction of phenyllithium with 1,3-bis( triphenylsilyl)propyne 81 a. Followed ty addition of chlorotriphenylsilane 81 b. Followed by addition of methyl iodide 82 (1) Run 1 (2:1) 82 (2) Run 2 (1:1) 83 7» Reaction of triphenylsilyllithium with Imtriphenylsilyl-lmbatyne 84 8. Reaction of phenyllithium with L-triphenylsilyl-lfbutyne 85 a. Followed by addition of triphenylsilane 85 be Followed ty addition of methyl iodide 86 9. Reaction of phenyllithium with a mixture of 1,3-bis(tripherylsi]yl)-l-butyne and 1,3-bis( tripbenylsilyl) -1,2-butadiene, followed by addition of methyl iodide 87 10. Reaction of triphenylsilyllithium with allyltriphenylsilane 88 E. Reactions of Triphenylsilyllithium with Polyhaloethylenes and Related Reactions 89 1. Reaction of triphenylsilyllithium with cjs-1.2-dlchloroethylene 89 2. Reaction of triphenylsilyllithium with trichloroethylene 90 a. 1:1 ratio 90 b. 2:1 ratio 90 3. Preparation of bis(tripbenylsilyl) acetylene 91 4. Preparation of chlorotriphenylsilylacetylene 92 a. From trichloroethylene 92 b. From cis-1.2-dichloroethylene 92 (1) Run 1 (in ether) 92 (2) Run 2 (in a mixture of ether and THF) 93 is Page 5. Preparation of brmotripherylsilylacetylene 94 a. From pentabromoethane 94 (1) Run 1 (in ether at -60°) 94 (2) Run 2 (in a mixture of ether and THF at -60°^ room temperature) 94 (3) Run 3 (in a mixture of ether and THF at -60O) 95 b. From tetrabromoethane 95 (l) Run 1 (in ether) 95 (2) Run 2 (in a mixture of ether and THF) 96 6. Reaction of triphenylsilyllithium with chloro triphenylsilylacetylene 96 7. Reaction of triphenylsilyllithium with bromotriphenylsilylacetylene 97 8. Reaction of triphenylsilyllithium with bis(tripbenylsilyl)acetylene 98 9. Reaction of phenyllithium with chloro triphenylsilylacetylene 98 10. Reaction of phenyllithium
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