I. A STUDY OF THE ACTION OF GRIGNARD REAGENTS WITH CARBONYL COMPOUNDS ANDA PROPOSED MECHANISM FOR THE REACTION II. DEHYDRATION OF TERTIARY ALCOHOLS III. SYNTHESIS OF NEW ALIPHATIC HYDROCARBONS IV. MISCELLANEOUS

195 Pages·2016·8.1 MB·English

by  GEORGE

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Diehard \)tehL George 1343
a u th o r date
State Co/h
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UNIVERSITY
9
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DEGREE PUBLICATION NO.
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|! UNIVERSITY MICROFILMS
E M
M ANN ARBOR - M I C HI GA N
The Pennsylvania State College
The Gr adua t e 8choo 1
Department of Chemistry
I. A Study of the Action of Grigna,rd Reagents
with Carbonyl Compounds and a Proposed
Mechanism for the Reaction
II. Dehydration of Tertiary Alcohols
III. Synthesis of New Aliphatic Hydrocarbons
IV. Miscellaneous
A Thesis
by
Richard Stanley George
Submitted in partial fulfillment
of the requirements
for the degree of
Doctor of Philosophy
August 19^-3
Approved:
J uly 19^3 Research Professor of Organic
Chemistry
July 3 a, 19^3 Head of Department of Chemistry
ACKNOWLEDGEMENT
The author is deeply indebted to Dr. Frank C. Whitmore
who suggested and directed this research. Thanks are
due to Dr. George H. Fleming for his help and advice on
semi-micro fractionations and on the determinations of
physical properties, to Dr. T. S. Oakwood who prepared
some of the tertiary alcohols used in the dehydration
study, to R. E. Meyer and N. C. Cook who did the hydro­
genations necessary for this work and to E, R, Weidlein, Jr.
who has taken over the investigation of sterically hin­
dered carbonyl compounds and will thus finish some of'
the studies started in this work. Thanks are also due
to 'The Pennsylvania State College and the Abbott Laboratorie
for fellowships which made these studies possible.
TABLE OP CONTENTS
Part 1
Page
I. Introduction 1
p
II. Historical
III. Discussion 12
IV. Experimental 32
1. Description of Fra.ctj.onating Columns 32
2. Preparation of Starting Materials 32
(a) Alkyl Halides 32
(b) Dllsopropyl Ketone 33
(c) Pinaco'lone 33
(a) G-rignard Reagents 37
3« Refractive Index of Diisopropylcarbinol-
DiIsopropyl Ketone Mixtures 37
k. Refractive Index of Diisopropylcarbinol-
R-Diisopropylc&rbinol Mixtures 3g
5. Tbe Action of Methylmagneslum Bromide with
D hi sopropyl Ketone 39
6 . The Action of Ethylmagnesium Bromide with
Dilsopropyl Ketone bo
7* The Action of n-propylmagneslum Bromide
with Dilsopropyl Ketone b2
S. The Action of Isopropylmagnesium Bromide
with Dilsopropyl ketone il4
9 . The Action of n-Butylmagnesium Bromide
with Dilsopropyl Ketone
10. The Action of Isobutylmagnesium Bromide
with Dilsopropyl Ketone 4-g
11. The Action of t-Butylmagnesium Chloride
with Dilsopropyl Ketone 53
12. The Action of jt-Amylmagneslum Chloride
with Dilsopropyl Ketone 55
13. The Action of Neopentylmagnesium Chloride
with Diisopropyl Ketone 56
1^-. The Action of Laurylraagnesium Bromide
with Diisopropyl Ketone 60
15. The Action of n-Fropylmagnesium Bromide
with Pinacolone 6*J-
V. Summary 66
VI. Bibliography 67
Part 2
I. Introduction 70
II. Historical ?2
III. Discussion
IV. Experimental 69
1. Determination of Physical Properties 69
2. Preparation and Properties of Starting
Materials
3. Method for Identification and Estimation
of DehydrationP roducts 92
4. Preparation of Compounds Necessary for
Identification of Ozonolysis Products 92
(a.) Synthesis of n-Fropyl Isopropyl
Ketone 93
(b) Synthesis of Isopropyl n-Butyl Ketone 95
Page
(c) Synthesis of Isopropyl Isobutyl
Ketone 9&
(&) Synthesis of Isopropyl n-Amyl
Ketone 96
(e) Synthesis of Isopropyl Isoamyl
Ketone 97
(f) Synthesis of 3> 3"rDime'4hyl-2-hexanone 9&
5. Physical Properties of Intermediate Second­
ary Alcohols 99
6. Dehydration of Methyldlisopropylcarbinol 99
7. Dehydration of Ethyldilsopropylcarbinol 101
g. Dehydration of n-Propyldiisopropyl-
cerbiriol 102
9 . Dehydration of n-Butyldiisopropylcarbinol 104
10. Dehydration of Isobutyldiisopropyl-
carbinol 106
11. Dehydration of n-Amyldiisopropylcarbinol 109
12. Dehydration of Isoamyldiisooropylcarbinol 111
13. Dehydration of NeopentyldiIsopropyl­
carbinol ll4
14. Dehydration of Methyl-n-propyl-t-butyl-
carbinol 116
¥. Summary 125 ’
VI. Bibliography 126
Part 3
Page
I. Introduction 12S
II. Discussion 131
III. Experimental 135
1. Starting Materials 135
2. Hydrogenation of Olefins 135
3. Purification of the Saturated Hydrocarbons 135
Determination of Physical Properties 136
5. 2,2,3-Trlmethylhexane 136
(a) Hydrogenation of Olefins 136
(To) Rehydrogenation 137
(c) Refractionation of Nonane I3S
(d) Physical Properties of 2,2,3“
Trlmethylhexane l4l
6. 2-Methyl-3“Isopropylhexane l4l
(a) Hydrogenation of Olefins l4l
(b) Refractionation of Decane 14-2
(c) Physical Properties of 2-Methyl~3-
i sopropylhexane 143
7. 2“Methyl“3“isopropylheptane 144
(a) Hydrogenation of Olefins 144
(b) Refractionation 144
(c) Physical Properties of 2-Methyl-3-
isopropylheptane l46
S. 2,6“Dimethyl-3-isopropylheptane 147
(a) Hydrogenation of Olefins 147
Page
(b) Refractionation l4g
(c) Physical Properties of 2,6-Dimethyl-
3-isopropylheptane 150
IV. Bibliography 151
Part 4
I. Introduction 152
II. Discussion 15^
III. Experimental 165
1. Purification of Methyl-t-butylneopentyl-
Chloride 165
2. Purification of Dineopentylacetyl
Chloride 166
3. Preparation of Me thy1-t-bu t ylne op e n t yl -
acetaldehyde 16b
K. Preparation of Isopropyl Me thy l-_t-butyl-
neopentylcarbinyl Ketone 16B
E. Preparation of Ethyl Dineopentylcarblnyl
Ketone 170
6 . Addition of Acetyl Chloride to the Bromo­
ms, gne slum Enolate of Ethyl Dineopentyl-
ctC etyl Ketone ■ 172
7. Attempt to Cleave 1-Acetyl-1-dineopentyl-
acetyl-ethane with Methylmagneslum
Bromide 176
6 . Preparation of 3 > 5 > rimethyl-3-t-
butylhexahol-2 179
9. Oxidation of 3,5, E-Trimethyl-3-t-
butylhexanol-2 ISO
10. Attempts to Isolate the Coordination' Com­
plex from t-Butylmagneslum Chloride and
Me thy1-jfc-b ut y1neope nty1ac e t aid ehy d e 162
IV. Bibliography 186
PART I
a study of the action of g-rig-nard reagents with carbonyl
COMPOUNDS AND A PROPOSED MECHANISM FOR THE REACTION
INTRODUCTION
In the preparation of a series of tertiary alcohols for
dehydration studies the action of several Grlgnard reagents
with dilsopropyl ketone was investigated* With increasing com­
plexity of the alkyl group of the Grignard reagent the yield
of addition product, the tertiary alcohol, was markedly
decreased. When branched Grignard reagents, such as the
1
isopropyl reagent, were used no tertiary alcohol could be found
Mpst of the Grignard reagents gave the reduction product and
the enollzation product, but in no case could any condensation
product be found. The close relationship between the structure
of the Grignard reagents and the yields of reaction products
soon became apparent.
While the relation of the structure of the carbonyl
compound to the products of the Grignard reaction has received
adequate attention by workers in this field, the influence of
the Grignard reagent on The reaction products has been somewhat
neglected. Thus, the above series of reactions was run with
the study of this influence as a primary objective. In several
cases the experiments were planned to give optimum conditions
for throvring some light on the mechanism of the addition,
reduction and enolization reactions.
HISTORICAL
2
The Grignard reaction, first reported in 1900 , is one
of the most important reactions in organic chemistry. Count­
less studies have been made on this reaction and recorded in
the literature. However, because of the failure of many invest!
gators to recognize the possibility of obtaining a mixture of
several reaction products, and because adequate fractionating
equipment for a complete investigation of these products has
only recently become available, much of this work is of question
able value. Thus, in the only recorded investigations of the
enolization of carbonyl compounds by different G-rignard reagents
3, 4- 9
done by G-rignard and coworkers , reduction was mistaken for
enolization in many of their experiments. The failure to
distinguish between enolization and reduction products from
Grignard reactions has resulted in an erroneous observation
regarding the enolization of ketones by Grignard reagents
which seems to be generally accepted today. This observation
may be stated as follows: '‘Enolization of ketones by Grignard
reagents is primarily a function of hindrance in the ketone
and branching of the chain In the reagent Is of relatively
6
minor importance in this reaction" .
The studies on the reduction of carbonyl compounds by
1, 7, S, 9, 10
e-rignard reagents nave been more numerous, and
they have contributed substantially to the chemistry of the