I. THE REDUCING ACTION OF T-BUTYL GRIGNARD REAGENT II. THE DEHYDRATION OF 2,2-DIMETHYL-4-ETHYL-3-HEXANOL III. FRIEDEL-CRAFTS REACTION ON NEOPENTYL ALCOHOL AND BENZENE

125 Pages·2016·6.72 MB·English

by  CLAPPER

DOCTORAL DISSERTATION SERIES
Studies dj LTfitTfefacing Action tift-Buiyl
TITLE
Grignard mgent.__ //. The iDehydmiioh ofIbHmSyl-
t-Tlhyl-S-Hexaml. III. Triedel Gafts Reaction on HapmlyI
Alcohol anA Benzene
Thomas Wayne Clapp
AUTHOR tn DATE Aug. ! $ 4 -X
Tetmsiflvdnid S tdle College
UNIVERSITY,
DEGREE PUBLICATION NO.
w n
1
\ M u UUNNIIVERSITY MICROFILMS
A R B O R M I C H I G A N
A NN
THE PENNSYLVANIA STATE COLLEGE
The Graduate School
Department of Chemistry
STUDIES OF:
I® THE REDUCING ACTION OF Jj-BUTYL GRIGNARD REAGENT
II® THE DEHYDRATION OF 2, 2-DIT£ETHYI^4-ETim^3-HEXAN0L
III® FRIEDEL-CRAFTS REACTION ON NEOPENTYL ALCOHOL AND
BENZENE
A Hies is
THOMAS WAYNE CLAPPER
Submitted in partial fulfillment of the requirements
for the degree of
DOCTOR OF PHILOSOPHY
August, 1942
Approved;-^/ k 1942 Approvedi~— .V" 1942
By.
Research Professor of Head of Department of
Organic Chemis try Chemia try
Tlie author wishes to express his gratitude t©
Dean Frank C® Whitmore, director of this research, for
his Interest, ©neouragement, and suggestions, and to
Dr© R® V® McGrow for assistance©
TABLE OF CONTENTS
X o THE REDUCING ACTION OF t-BUTYL GRIGNARD REAGENT
Pap.Q
INTRODUCTION————-—— -------_ _ _ ----------------—, 1
HISTORICAL--------—_ _ _ _ _ -----—-----—------ —---------------------- 2
DISCUSSION -----—_ _ ------------ —-----—— 5
DESCRIPTION OF APPARATUS —----_ _ _ _ _ _ _ —.
EXPERIMENTAL 7
A. PREPARATION OF STARTING MATERIAIS
1® Preparation of _t-butyl chloride— 9
2® Preparation of Jj-buty Irnagne3ium
chloride... _ _ ------------------_ _ _ _ _ —— 9
3© Preparation of phenylacetyl chloride— 10
4© Preparation of diphenylacatyl chloride 11
B© REACTIONS
1© Treatment of Jb-butylmagneaiurn chloride
with phenylace tyl chloride—————— > 12
2« Treatment of j;»butyXmagnesinra. chloride
with diphenyl acetyl chloride ———~ 20
SUMMARY ___—— ----------------------------------------------------- 26
BIBLIOGRAPHY. _ _ _ _______ -_____ _ _ _ _ 27
I I . THE DEHYDRATION OF 2,2-DBffiTHYL-4-ETHYI^3-HEXAN0L
28
INTR ODUC TI ON- —————— ---------------_ _ _
HIS TORICAL -----------------~ ——— SO
DISCUSSION— _ _ _ _ — 37
Page
45
DESCRIPTION OP APPARATUS ---------- —
EXPERIMENTAL—------— ----------— ----— ------------------ 45
A® DEHYDRATION OP 2, 2-DI0^THYL-4-ETHYTj-3-
HEXANOL -----— — 46
B® TREATMENT OP jb-BUTYL GRIGNARD REAGENT WITH
DIE THYLACE TALDEHYDE — —— —— — ---- 49
C* SECOND DEHYDRATION OP THE SUBSTITUTED
TTRY ATyTOT, —— _ — 57
D. OZONOLYSIS OP THE MATERIAL WITH HIGH INDEX
OF REFRACTION FROM THE DEHYDRATION--------------- 62
E® OZONOLYSIS OF THE MATERIAL WITH LOW INDEX
OF REFRACTION PROM THE DEHYDRATION------—— 68
SUMMARY—— -----—— 73
BIBLIOGRAPHY—————r——------ 74
III. FRIEDEL-CRAFTS REACTION ON NEOPENTYL ALCOHOL AND BENZENE
INTR ODUG T ION 7 6
HISTORICAL—---------—-——-----—--'-—---—— r/r/
DISCUSSION--™-—— — — 80
EXPERIMENTAL — — ------------------------------------------_ _ 07
A® PREPARATION OP STARTING MATERIALS
1® Preparation of benzy imagnesium chloride 37
2© Preparation of neopentylbenzene _ 37
3® Preparation of t-butylmagne3lum chloride 93
4® Preparation of neopentyl alcohol! _________ 92
Page
B* REACTIOHS
1» Reaction of neopentyl alcohol with
benzene in the presence of aluminum
chloride-——- . ———— —-— 95
a© Experiment # 1-—— ----------——— 95
b® Experiment # 2---— ~—————«—— 98
c® Experiment # 3 ——-——— 100
d® Experiment # 4- •■■■ ICS
o © Experiment # 5—————«--——------;—— 103
f© Experiment # 8 ------————- 104
g® Experiment # 7 111
SUmAKT- _— i 117
BIBLIOGRAPHY— 118
1
I„ THE REDUCING ACTION OP t-BUTYL GRIGNARD REAGENT
INTRODUCTION
Greenwood, Vtfhitmore, and Crooks (1) investigated
tiie reaction of trim© thy lace tyl chloride with _t- butyl-
magnesium chloride which gave neopentyl alcohol, and
di-Js-l^tylcarbinol® They also studied the reducing action
of Jfc-bu.tylmagne3ium chloride on butyryl and Isobutyryl
chloride and found that primary and secondary alcohols were
the only products© Their work indicated that J;-butyl Grig-
nard reagent reduced substituted acid chlorides to primary
alcohols® Tertiary acid chlorides were reduced more reasily
than secondary acid chlorides, which in turn were reduced
more readily than primary acid chlorides® Since the n 8 the
reduction of aliphatic acid chlorides by Grignard reagents,
mainly _t~butyl Grignard reagent, has been extensively
studied in this laboratory (2)®
Tie author, in extending the study of the reducing
action of Grignard reagent to benzoyl chloride (3), Isolated
benzaldehyde, and jb-butylphenylcarbinol« The investigation
of th© reducing action of Grignard reagents on aromatic sub­
stituted acetyl chloride was then undertaken®
2
HISTORICAL
Hie reducing action of the Grignard reagent waa
observed by Grignard (4) in his first communication® He
Isolated benzyl alcohol as a product of Hi© reaction of
benzaldehyde with isoamyl Grignard reagent® More recently
Whitmore and co-workers (X) found that J>>bu tylmagne slum
chloride acted as a reducing agent on substituted acid
chlorides® Since then, an extensive study of th© reducing
action of the Grignard reagent has been carried on in this
laboratory, mainly by Whitaker, Zeck, Popkin, and Wheeler®
Wheeler (5) obtained carbon monoxide, isobutane,
iaobutene, ethyl acetate, pinacclone, mesityl oxide, pina-
colyl acetate, and hexam©thy 1©than© from the reaction of
j;~bu tylmagne slum chloride with acetyl chloride® PinacolyX
acetate, the reduction product, was obtained In a yield of
8©2 per cent©
Greenwood, Whitmore, and Crooks (1) investigated
th© reduction of :n»butyryl chloride by J>*bu.tylmagnesium
chloride« They obtained a 9 per cent yield of X«butanoX,
and a 71 per cent yield of Jj-butyX^n-propyXcarblnol© They
also obtained a 94 per cent yield of di-J>-butyXcarblnoX
from the reduction of trim©thylac©tyl chloride with Jb-butyl­
magne slum chloride®
Hi© present author (5) found that the reaction
of benzoyl chloride wi th Jb-bu.tylmagne3Ium. chloride yielded
34@3 per cent of jb°butyXph©nyXcarbin©l as the reduction
product®
Whitmore and Heyd (6) found that the reduction
of Wbutylaee tyl chloride by j>*bu tylmagne slum chloride gave
only a trace of neopentylearbinolg and 71 per cent of
n© opentyl-b-butylcarbinol®
An examination of the acid chlorides reduced in
this laboratory indicated that alpha substitution had a
marked effect on th© reducing action of th© Grignard
reagent©
Recently Whitmore and co-workera (7) have ad­
vanced the following mechanism for the reaction of the
Grignard reagent®
RCOR»
RCOCX -> RCHO — RCHGHR*
RCHgOH
An excellent summary was given of the general
reactions by which a Grignard reagent reduces an acid
chloride to an aldehyde and then reacts with the latter
4
to give an ordinary addition reaction or further reduces
it to a primary alcohol surveyed in relation to (a) meeh,-
aniem^ (Tb) miscellaneous factors including presence of
free magnesium^ th© halogen present^, Hi© concentration
of Hi© Grignard solution and the order o f adding the r©a~
gentsg and (c) influence of structure of th© acid chloride
and of til© Grignard reagent©