Reactions of Organo-Silicon Compounds PDF
Preview Reactions of Organo-Silicon Compounds
PURDUE UNIVERSITY THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION by_______Philip Eugene Brumfield_______________ entitled Reactions of Organo-Silicon Compounds COMPUTES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Doctor of Philosophy Professor in Charge of Thesis — ie r £ TW-t-üu Head of School or Department 19£L TO THE LIBRARIAN:-- » THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL. photossor nr charge grad, school FORM 9 REACTIONS OF ORGANO-SILI CON COMPOUNDS A Thesis Submitted to the Faculty of Purdue University by Philip Eugene Brumfield In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy June, 1951 ProQuest Number: 27714212 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 27714212 Published by ProQuest LLC (2019). 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 ACKNOWLEDGMENT The author wishes to express his indebtedness to Dr* Robert A. Benkeser for suggestion of this problem and also for the guidance offered by him during the course of this Investigation. An expression of appreciation is also made to Dr. Nathan Korhblum. for his valuable suggestions pertaining to this problem. TABLE OF CONTENTS Page ABSTRACTS .............................................. i NITRATION OF ORGANOSILICON COMPOUNDS WITH COPPER NITRATE .... i PREPARATION AND REACTIONS OF AMINOARYLTRIALKYLSILANES...... xv SURVEY OF ORGANOLEAD COMPOUNDS, 1920 - 1935 ........»........ 1 Tetraalkyllead Compounds ................ 1 Tetraaryllead Compounds...................... 5 Arylalkyllead Compounds .................. 8 Derivatives of Alkylhydroxylead Compounds ...... 10 Derivatives of Arylhydroxylead Compounds ........ 14 Derivatives of Arylalkylhydroxylead Compounds ..... .. ... 19 Aryllead Compounds Containing Additional Elements. ....... 20 Derivatives of Arylalkyllead Compounds Containing Additional Elements ................ 22 Derivatives of Arylhydroxyle ad Compounds Containing Additional Elements...... . . .. .... .. 23 Organic Compounds of Trivalent Lead ••«...... 23 Organic Compounds of Divalent Lead................... ••• 25 BIBLIOGRAPHY............................................ 26 INTRODUCTION............................................... 30 DISCUSSION.................. 32 Preliminary Nitration Studies ........................ 32 Nitration of Arylsilanes .............. 33 Bromine Cleavage and Bromide Release Procedures .......... 39 Reduction of Nitroaryltrialkylsilanes ». 40 Page Acylation of Aminoaryltrialkylsilanes ............ 41 Diazotieation Studies with Aminoaryltrialkylsilanes .... 41 Halogénation of Arylsilanes ..... 47 Oxidation of Tolylsilanes to Acids .................. 49 Investigation of the Ortho Oxygen Effect ...... 49 Miscellaneous .................. 51 EXPERIMENTAL..................... 54 Nitration of Aniline with Various Metal Nitrates .......... 54 Nitration of Aniline with Lithium Nitrate ................. 54 Nitration of Aniline with Potassium Nitrate 56 Nitration of Quinoline with Lithium Nitrate ...... 56 Nitration of jg-Toluidine with Lithium Nitrate ........ 56 Nitration of ja-Toluidine with Ferric Nitrate .............. 57 Nitration of Phenylacetic Acid with Lithium Nitrate ....... 57 Nitration of Phenylacetic Acid with Ferric Nitrate ........ 57 Nitration of Benzoic Acid with Metal Nitrates...... 58 Nitration of Toluene with Copper Nitrate ..... 58 Nitration of Phenyltrimethylsilane ........ 58 Bromine Cleavage of Nit rophenylt rimet hylsilane s in a Sealed Tube ........ 6l Reaction of o-Aminophenyltrimethylsilane with Bromine 61 Nitration of Benzylt rimet hylsilane ..... 61 Reaction of Nit rob enzylt rimet hyls ilanes with Base ..... 63 Oxidation of o-Nitrobenzyltrimethylsilane ...... 63 Nitration of Phenyltriethylsilane ....... 64 Page Nitration of Hexaphenyldisiloxane • ♦ 66 Mixed hydrolysis of Phenyldimethylchlorosilane and Trimethylchlorosilane .................. 66 Nitration of Phenylpentamethyldis iloxane................ 6? Nitration of 1,3-Diphenyltetramethyldisiloxane .... 68 Bromine Cleavage and Bromide Release Procedures ........ 69 Reduction of Nitroaryltrialkylsilanes ........ 77 Acylation of Aminosilanes........... 79 lodination of Diazotized Aminoaryltrialkylsilanes ..... 79 (f-Naphthol Coupling of Diazotized Aminoaryltrialkylsilanes. 80 Diazonium Fluoborates .......... 83 Deamination of m-Aminophenylt rimet hylsilane ............ 84 Action of Nitrosyl Chloride on o-Aminob enzylt rimet hylsilane 85 Bromination of 2-Thienylt rimet hylsilane ......... 85 Aromatic Bromination of jg-Tolyltrimethylsilane ........ 86 Aromatic Chlorination of jd-Tolyltrimethylsilane .....••• 86 Aromatic Bromination of Phenylt riethyls ilane .............. 87 Alkyl Bromination of jc-Tolylt rimet hyls ilane ............... 87 Alkyl Chlorination of jd-TolyItrimethylsilane .............. 88 Alkyl Chlorination of j>-Tolyltriphenylsilane....... 88 Alkyl Bromination of jD-Tolyltriphenylsilane ............... 89 Oxidation of Tolyltr imet hyls ilanes ....... 90 o-Ethylphenyltrimethylsilane.......................... . 91 o-Trimethylsilylbenzyl Methyl Ether..................... 92 jg-Trimethylsilylbenzyl Methyl Ether...... 93 Page Cleavage Comparisons for the Ortho Oxygen Effect ....*♦•.•• 95 Phenyldimethylmethoxysilane . ......... 99 m-Tolylt rime t hylsilane .... 99 jg-Methoxyphenyltrimethylsilane............... 99 jg-Dimet hylaminophenylt rimet hyls ilane ........ 100 Reaction of ^-Dimethylaminophenyltrimethylsilane with Acetic Acid ».............. 100 Reaction of the Aminophenyltriethylsilanes with Bromine ... 101 SUMMARY ................... 102 BIBLIOGRAPHY.................................................104 SUGGESTED PROBLEMS FOR FURTHER STUDY................... 106 VITA............... .................. .................... LIST OF TABLES Page 1* Properties of Nitrosilanes Prepared ...... 35 2. Properties of Aminosilanes Prepared............ *..... 42 3. Properties of Acetaminosilanes Prepared ..... 43 4. Nitration of Aniline with Metal Nitrates ....... 55 5. Déterminât i on of Para Isomer Ratio for Nit ro phenyls ilanes .... 74 6. Results of Rate Studies with Bromine Cleavages .... 97
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