The Reactions of Some Triarylsilanes with Methyllithium and Phenylisopropylpotassium and the Reaction of Nitrogen Tetroxide and Dimethylaniline

124 Pages·5.126 MB·English

by  Riel, Frank J

PURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
by Frank J. Riel___________________
ENTITLED THE REACTIONS OF 5CME TRIARYLSILANES WITH IJETHYLLITHIUM
AND PHENYLIS0PRQPYLP0TA3SIÜM and THE REACTION OP NITROGEN TETRQXIDE
AND DIMBTHYIAHUNE
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
Professor in Charge of Thesis
Head of School or Department
TO THE LIBRARIAN:--
«-
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
FBOPBSSOB ES CHARGE
GRAD* SCHOOL FORM 9

THE REACTIONS OF SOME TRIARYLSILANES
WITH METHYILITHH3M AND PHENYUSOPROPYLPOTASSIUM
AND
THE REACTION OF NITROGEN TETRQXIDE AND DIMETHYLANILINE
A Thesis
Submitted to the Faculty
of
Purdue University
by
Frank J. Riel
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
January, 1950
ProQuest Number: 27714203
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AGKNOWIJBDtaaENT
The writer wishes to thank Dr. R, A. Benkeser for
his advice and assistance during the progress of this research.
TABLE OF CONTENTS
Page
ABSTRACT
Part 1. The Reactions of Soane Triarylsilanes with
fitethyllithium and Phenylisopropylpotassium......... . 1
Part 2. The Reaction of Nitrogen Tetroxide with
Dimethylaailine........... xiv
LITERATURE SURVEY OF THE ORGANIC COMPOUNDS OF T I N ....... 1
Introduction . . . . . . . . . . . . . . . 1
Aliphatic Tin Compounds
Derivatives of RSn^H . . . . . . . . . . . . . . . . . 1
Derivatives of RSnHg . . . . . . . . . . . . ....... 2
Derivatives of RSiSg (Sn^ )nSnH^................... 3
Derivatives of RSnHgOH 5
Derivatives of RSnH(0H)2 ......... 6
Derivatives of RSn(QH)^................ 7
Isocyclic Tin Compounds
Derivatives of RSn^H ................. 10
Derivatives of RSnH^........................ 12
Derivatives of RS11H2 (Sn^ )nSziH^ . . . . . . . . . . . . 16
Derivatives of RSn%(0H) . . . . . . . . . . . . . . . 17
Derivatives of RSnH(0H)2 • • • • ......... 20
Bibliography...................• • • • . .......... 23
PART I. THE REACTIONS OF SOME TRIARYLSILANES WITH
METHYLLITHIUM AND PHENYLISOPROPYLPOTASSIUM........... 24
Introduction . . . . . . ................... • • • • . 24
Page
Experimental . . . . . . . . . . . . . . . . 27
Discussion.................... 47
Summary •• . . . . . . . . . . . . . . . 5°
Bibliography ............ 51
PART II. THE REACTION OF NITROGEN TETRQXIDE WITH
DIMETHYLANILINE.................. 52
Introduction......... . . . . . . . . . . . . . . . . . 52
Experimental . ..................... 54
Discussion . . . . . . . . . . . . . . . 86
Summary •• . . . . . . . . . . . . . . . . . 91
Bibliography • • • • .............. 92
VITA...............................................
use OF TABLES
Table Page
1« Physical constants and yields of some triarylsilanes
and triarylaethylsilanes..................... ii, 25
II» Summary of products obtained from reaction of
nitrogen tetroxide and dimethylaniline • • • • • • • • xvii
(Contribution from the Department of Chemistry, Purdue University)
PART I
THE REACTIONS OF SOME TRIARYLSILANES
WITH MBTHYLLITKEUM AND PHENYLISQPRQPYLPOTASSIÜM (1)
(1) Contains material from Mr. F. J. Riel's doctoral thesis,
By Frank J. Riel and Robert A. Benkeser
AN ABSTRACT
In attempts to prepare a compound containing a silicon-
metal bond Gilman and Massie (2) and Meals (3) have investigated
(2) Gilman and Massie, J. Am. Chem. Soc.. 68. 1128 (1946).
(3) Meals, R. N«. ibid.. i860 (1946).
the reaction of n-butyllithium, n-propyllithium, phenyllithium,
and methyllithium on triethyl- and triphenylsilane. In every
case the silane was converted to the corresponding tetrasubstituted
compound, while lithium hydride was reported as the other biproduct.
This indicates that the silicon hydrogen bond was broken with
the elimination of a hydride ion.
ii
It nas thought that if three electron attracting groups
were attached to the silicon the acidity of the hydrogen atom
might be increased to the point where a hydride ion would no
longer be eliminated.
With this idea in mind a aeries of compound of the type
^ ^■~^.j$jHwaa prepared where B represents ,
£-Cl-, and 2-GF3-. Both electron attracting and repelling groups
were ineluded for comparison.
Treatment of each of the para-substituted compounds with
methylli thium gave the expected triarylmethylsilane* Tri-o-tolyl-
silane failed to react under the conditions employed. The results
are summarized in Table I.
Table I
£ » « — “ O ™ .
R m,p, m,p. % yield
o-GE^ 88-89° — a
B-CH^ 82.5-83.5 91-93° 61
&-CH3O 75.5-76 133-134.5 47
Ê-C1 80-81 83-85 58
2-GF3 82-83 106-1G7.5 64
a About 70% of unreacted tri-o-tolylsilane was recovered.
It is of interest that tri-e-tolylsilane failed to react
even though Oilman and Smart (4) report that phenyllithium reacts