Molecular Rearrangement: Phenyl-Ethylallyl-Alcohols and Their Derivatives

131 Pages·12.44 MB·English

by  Waddan, Dhafir Y

Molecular Rearrangement* .
phenyl-ethylallyl Alcohols and their Derivatives
being a thesis, submitted to the University of London,
for the Degree of Doctor of Philosophy*
Dhafir*T*Waddan* B.Sc* (Alexandria*)
1951
ProQuest Number: 10803968
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The-researches, described in this thesis, were carried out
in the Research Laboratories of Battersea Polytechnic under
the direction of 23r.J.Kenyon. F.R.S* to whom the author is
indebted for his invaluable help and kindness throughout
the course of . the . work*
io Dr.M.P.Balf® and Dr.1.A.Rohan, also, the author expresses
his gratitude for their interest in, and many helpful
suggestions towards, the problems under investigation.
Introduction#— — -------------— ■— «i
fabler 1 -XT311-V . !
Specif ic rotatory powers of ^~Ph©nyl-eC~@thyl--—
allyl-aleohol^ its;di'broffiO-d@ri^atiTe; aad'the' :
related/ketone* - - ■ v
^Spedlfio rotatory powers of; k-Phenyl-r-ethyl— 12
allyl alcohol and its hydrogen phfchalie ester*
A short history of asymmetric synthesis™— ----— — — 13 ..
The addition of bromine to ^Phenyl-oUethylallyl— 2?
alcohol*
Th© anionotropic rearrangement and substitution of— *-46
.©C«Phenyl-ar«ethylal'ly 1 alcohol and its deriYatiires#
Comparison of the mobility of the anions of o(-Phenyl— 66
allyl alcohol, <x,-pheny 1-^-methylally1 alcohol and
©c-Phenyl-r-ethylallyl alcohol and .their derivatives#
SSSSISSSSii*
Preparation and optical resolution of (*)«*^.phenyl— -68
c<«ethylallyl alcohol*
The addition of Bromine to <r*-Pheny 1 - thylally 1— — 74-77
alcohol*
The addition of Bromine to (j)-y«Ph@nyl~^-ethylally 1— 78
acetate*
Oxidation of etbylr-y* -dibromo-^-phenyl@thyl— ------- -79-83
earbinols*
Preparation and optical resolution of (*)-<<-phenyl— — 84
r-ethylallyl alcohol*
Bearrangement reactions of o(-phenyl-/"-ethylally 1— 92
hydrogen phthalate* .
Bearrangement 'reaotions,,of ^phenyl-r-ethylallyl-^— -4499
,;:alOOhol#-:':.°-: V - V • ;: ^ ■
Bearrangement of o<-phenyl-y^ethyl&liyl acetate— — 105
Conver si on of (4} -phenyl v inyl carbinol 10— — — 106
einnamyl alcohol* •'
Baeemisation of (4) -*^pheny!-«<-©thylallyl aleohol— -— 107
, iifacidic-' medium*"- v - ; . -
■SHAPES I-■■■■■/ ■ .''"v ; : -
Showing the rate of "'rac emisat ion of some substituted-110
allyl aleohols.and their kinetie order*' "
Bibliography# — -------- — ----— -— — ----------— —
I
-I2S22H2S25*: ■
A study has been made of the addition of bromine to,
and the rearrangement of# r'~phenyl-<*-ethylallyl alcohol and
c* -phenyl-vcethylallyl alcohol. Partridge (1) had previously
made a somewhat similar study on the corresponding methyl,
derivative but in this thesis the stereochemistry of the
bromine addition has been given much closer attention and
it has been shown that addition of bromine to optically active
x'-phenyl-ouethylallyl alcohol results in an asymmetric
synthesis in which both carbon atoms of the double bond ©.re
affected* The product of this addition has been shown to
be a mixture of two diastereoisomeric:dibromo-alcohols which
can be separated by crystallisation. Destruction of the
original centre of;asymmetry, by oxidation, results in the
formation of an optically active dibromo-ketone.
c<-phenyl-y-ethylallyl alcohol and its derivatives were
found to undergo:isomeric change in solution# and in one case
in the homogeneous state, with '-considerable ease yielding the
corresponding v -phenyl-<<-.ethylallyl derivative; where
optically compounds were used these changes were accompanied
by considerable racemisation.>
y'-Phenyl-<-ethylallyl alcohol was prepared by the reaction
between cinnamaldehyde ©nd ethyl magnesium chloride and was -
a |
-H
**.
resolved into;its 'Optical antipodes by fractional crystallisation
from,ethyl acetate# of the einehonidine salt of the hydrogen
phthalic ester' which gave the (|) form* : .Decomposition of
the motherliquor of the former and addition of brucine gave
an alkuloidal salt which# on fractional crystallisation, from
methyl: acetate, yielded the (-} form.- >
\ Hydrolyses of these esters with strong solutions of
sodium hydroxide yielded the optically pure alcohol but
hydrolyses with dilute alkalineosolutions resulted in
racemisation*
c* -Phenyl-y^ethylallyl alcohol was synthesised in a.
number of steps commencing with the oxidation of n-amyl alcohol
to n-valeraldehyde which: was! converted to <^-bromo-n~valerald@hyde
diethyl acet&l by the action of bromine followed by addition
of alcohol* Removal of hydrogen bromide, with potassium *
hydroxide, yielded A-u~penten.al diethyl acetal which -was
: hydrolysed to the corresponding pentenal. Reaction of the
latter with phenyl magnesium bromide yielded c*-phenyl-h«ethyl~
■allyl alcohol. .The alcohol was resolved into its optical
, antipodes, via the. hydrogen phthalic; ester , which it was
necessary, to. prepare with .considerable, care; to avoid
isomerisation to the r-phenyl~^-ethyl8,llyl derivative.
U5C ■
It was also necessary .to^freshly, prepared hydrogen phthalic
ester ,for the preparation of the alkaloidal ;salf ; since,;,
isomerisation occurred in.the,homogeneous•state* v
: ■ Recrystallisation of. the quinidine S8.it-from roe tone h;
yielded , the ' (*r)-hydrogen .phthalic ester . which could,not be
crystallised without isomerisation* The optically active
alcohol was obtained by hydrolyses of the hydrogen phthalic
ester with sodium in absolute alcohol. ^
TABLE JL. "
Specific Roi&t o ry JPowers of ^inGhonicline'
allyl Hjdgogen^phthalate^ ,* /,■
(c,2*58j 1,2 in chloroform solution^),
l^y*
I-S2.3/'V-55.9 i -6 2.5 r 49.3 • -75.9 i -88.1 s-10S.l
- JABLB u
Specific Rotatory Powers of Bruein® salt of {-)-»'-Phenyl-°<—Ethyl.
ailZl_SZ5E2i®2_25S!}2lS™i ’
(c,2.385 1,2 in :chloroform solution,) . ' ■.■■■■'. ■"'■
5893 5780 ; | ;,8 ; 54SI ' s : '5086 's ' 4800___8 4358^;-
,*:! : ! .{,■■: ■ . t': ■■ . : -4 : J' : .
s -32.1 -35.4 s , -40.5 : : -50.8:j -61.7 s -88.1
f f ’i ’ *
.
• •. * , • l! ' * • * • *
s
TABLE^lll
Ipecifie Rototory ;Power0|of. (*}-<r-;phenyl-°<-Sthylallyl Hydrogen
Phthalate.
CSp si*46it♦53• 4 s*63.1 s*8Q*5 s*36.4 s*106.7:*127.1
* ■ ■ ■ ' .5 .■■"•'■ ■ ■ '* : 5 5 5 *
AoOH :2.27:426.1 :-»27.2 :+32,l :+39,8 :*S3.5
; S : i i t * . * j . . .. *
CgHjK :1.61:417.0 :*17.9 :+19.8 :*24.4 :427.8 :*38.2
I ■ ■ | ■ I ' S 2 .
CC14 :2.l6Ull.5 :4l2.2 Ul4.3 1.1717 1421.0 1.30.4
■ ': . ■■ ■. % '■ : : : :
CHC1, :2.38;♦9,4 :.10.1 :.12.2 :.13.4 :.16.4 :.26.2
: 4 : •■ «* . ♦♦ '■ «* *•
p.^ s 2.32: *7.3/; :+3.0 **iiU. 5*i3#o s*14.0 s.20.6
C6H6
« ♦ * • »
# * •
•.
Ms GO # s2.02:-S. 2 :-6.9 5-9.1 5-9.9 5-11.1 1-13.1
*• • : •» *• * 5 > • **
. • •
Et20 7: ■ s2*G0;- ■"7.8 :-8.0 s 5-9,0 5-9.8 5-11.9 5-13.9
: • *
'• 0 . * 9
3 4
■
ItOH ■■■■ *13*85 -4.4 :-4. 5 s-5.0 1-5.5; —6 .1- ; 5-7.2
s : ♦ : * ^- .*_■■■ ' * .. . a« ■
. •
C#* g. per 100c• c# of solution*