Synthesis of Organosilicon Compounds

170 Pages·7.748 MB·English

by  Landesman, Herbert

PURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
Herbert l-andesman
entitled Synthesis of Organosilicon Compounds
COMPLIES 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
P rofessor in C harge of Thesis
Head of School or Department
___________19 57
TO THE LIBRARIAN:--
SF
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
A . lï-HsnÀ*4Ajh>
PBoressoB nr ohakgs
GRAD. SCHOOL FORM 9

SYNTHESIS OF ORGANOSILICON COMPOUNDS
A Thesis
Submitted to the Faculty
of
Purdue University
by
Herbert Landesman
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
June, 1951
ProQuest Number: 27714221
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 27714221
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 thanks Professor R. A, Benkeser for suggesting
the investigations herein reported and for the encouragement and
advice so freely given during the course of this work.
A grant from The Research Corporation is also gratefully
acknowledged.
TABLE OF CONTENTS
Page
ABSTRACTS
The Oxidation of Organosilanes with Selenium Dioxide ..... i
The Reaction of Triphenylbromo- and Trlphenylchloro-
silane with Lithium in Ethylamine ........ vii
Evidence for Resonance Involving Silicon in Arylsilyl
Anions: A New Preparation of Arylsilylpotassium
Compounds ....... xiii
Nitration of the Tolyltriethylsilanes ..........xxiii
SURVEY OFCEEANOTIN COMPOUNDS, 1928-1950 ................. 1
Derivatives of Stannane ....... 1
Alkylhalostannanes ...... 1
Alkylstannanes ....... 11
Distannanes ...... 15
Arylstann&nes ........ 16
Alkyl-arylstannes ...... 19
Arylhalostannanes ...... 22
Alkyl-arylhalostannanes ...... 27
Organostannanes Containing Oxygen .............. 28
Organostannanes Containing Sulfur and Phosphorous......... 30
BIBLIOGRAPHY........................................... 32
THE OXIDATION OF ORGANOSILANES WITH SELENIUM DIOXIDE........ 36
Introduction ....... 36
Discussion.......... 37
Experimental............ 41
Attempted Acylation of 2-Trimethylsilylthiophene
with^Super Filtrol" ...... 41
Page
2-Chloro-5-Trimethylsilylthiophene and 2,5-Bia-
( trimethylsilyl) -thiophene......................... 42
Attempt to Prepare 2-Acetyl-5-Trimethylsilylthiophene
from 2-Chloro-5-trimethylsilylthiophene.......... 42
Reaction of 2-Trimethylsilyl-5-thienyllithium and
Acetonitrile...... ....................... ....... 43
2-Trimethylsilyl-5-thiophenecarboxylic Acid.......... 43
(5-Trimetbylsilyl-2-thienyl)-glyoxal Monohydràte ....... 44
2-(5-Trimethylsilyl-2-thienyl)quinoxaline .............. 45
5-Trimethylsilyl-2-furylglyoxal Monohydrate ......... 46
2-(5-Trimethylsilyl-2-furyl)-quinoxaline .......... 46
SUMMARY............................................ 47
BIBLIOGRAPHY........................................ 48
THE REACTION OF TRIPHENYLBROMOSILANE AND LITHIUM INE THYLAMINE .. 49
Introduction.................. ...... ........ 49
Discussion..... ................. ................... 50
Summary .... .............. ........ ........ 58
Experimental ............. ......................... 59
Triphenyls ilane ............................. 59
Triphenylb romos ilane................... .......... 59
Triphenylchlorosilane ... .................... 60
Ethylamine........... ........ 60
Lithium ................................... . 60
Liquid Ammonia .. ..... 61
Bromobenzene ................. 6l
Reaction of Triphenylbromosilane with Lithium in
Ethylamine .................................... 6l
Concentration of Ether Solutions of the Compound from
the Kraus-Eatough Reaction and Triphenyl-N-ethylamino-
silane .................. ............... . 61
Page
Hydrolysis of Triphenyl-N-ethylaminosilane and of the
Material from the Kraus-Eatough Reaction .... . 62
Reaction of the Compound from the Kraus-Eatough Reaction
with Lithium in Ethylamine .................. 62
Reaction of Triphenylchlorosilane with Lithium in
Ethylamine .................. 0. 63
Triphenyl-N-ethylaminosilane ..... .............. 63
Triphenylchlorosilane and Pure Ethylamine ..... . 64
Triphenyl-N-ethylaminosilane and Lithium (2 Equivalents)
in Ethylamine under Nitrogen ............ 64
Reaction of Triphenyl-N-ethylaminosilane and Two
Equivalents of Lithium under Nitrogen 65
Distillation of the Residue in the Kraus-Eatough
Reaction in a Closed Vacuum System .............. 66
Residue from the Kraus-Eatough Reaction .......... 66
Reaction of Triphenylsilylpotassium with Ethylamine ... 6?
Bibliography ......................... ........ 68
EVIDENCE FOR RESONANCE INVOLVING SILICON IN ARYLSILYL ANIONS:
A NEW PREPARATION OF ARYLSILYLPOTASSIUM COMPOUNDS...........». 69
Introduction ..... ............. 69
Discussion .... .......... ................. . 74
Experimental .......................... 90
Sodium-Potassium Alloy......................... . 90
Triphenyl-N-Ethylaminosilane .............. 90
Reactions of the Mixture from Triphenyl-N-ethyl­
aminosilane and Alloy
Carbon Dioxide......................... 90
Acetone ..... .......................... 90
Page
Hydrogen Chloride 91
Oxygen................ 91
Triphenylchlorosilane 92
Moist Ether ..... 92
Chlorobenzene ..... 92
o-Bromoanisole ........ 93
Gas Measurements .... 93
Triphenyl-N,N-diethylaminosilane ......... 95
Triphenyl-N,N-diethylaminosilane and Alloy...... 96
Reactions of the Mixture from Triphenyl-N-ethylamino-
silane and Alloy
Triphenylchloromethane .................... 96
Mercury...................................... 97
Sulfur....................................... 97
Iodine........ 97
Attempts to Isolate the Product of Reaction of Triphenyl-
N-ethylaminosilane and Alloy .... 97
Triphenylethylsilane......... 98
Triphenylethylsilane and Alloy......... 98
Triphenylcyclohexylsilane............... 99
Triphenylcyclohexylsilane and Alloy.......... 99
Triphenylsilane ..... 99
Tetraphenylsilane .......................... 100
1,1, l-Trimethyl-2 , 2,2-t riphenyldisilane.............. 100
Trixenylsilane ....... ......100
-Bis (trixenylsilyl) cumene...... 101
Page
<xf,jD-Bis(trixenylsilyl)cumene and Alloy ...... . 101
Tetraxenylsilane ........ 102
Tris ( -naphtlqrl) silane..... .................. 102
Tris( af-naphthyl)silane and Alloy................ 103
Triethylsilane.......... « 104
Triethylsilane and Alloy............ ............ 104
Phenyldimethylchlorosilane................. . 105
Phenyldimethylsilane..................... 105
Phenyldimethyls ilane and Alloy......... . 105
Tribenzylsilane .... ......... . 10?
Tribenzylsilane and Alloy ... . 107
Diphenyls ilane ... ......... . »........ 108
Diphenyls ilane and Alloy ... .......... . 108
Phenylsilane................................. 109
Phenylsilane and Alloy ..................... 109
Summary ....................... ............. 110
Bibliography.................. .................... Ill
NITRATION OF THE TOLYLTRIETHYLSILANES..................... 112
Introduction................................ ...... 112
Discussion ..... ....................... . 113
Experimental .................... 116
o-Tolyltriethylsilane .... ......... . . . 116
m-folyltriethylsilane............. ............. 117
JhTelyltriethylsilane ........................... 117
2-Methyl-5-nitrophenyltriethylsilane •••........... 117