(2hem1cal. reactions and biological...
TRANSCRIPT
Chemical reactions and biological effectof sterculic acid and analogous fatty acids
Item Type text; Dissertation-Reproduction (electronic)
Authors Masson, James C., 1934-
Publisher The University of Arizona.
Rights Copyright © is held by the author. Digital access to this materialis made possible by the University Libraries, University of Arizona.Further transmission, reproduction or presentation (such aspublic display or performance) of protected items is prohibitedexcept with permission of the author.
Download date 06/07/2018 23:00:29
Link to Item http://hdl.handle.net/10150/565578
(2HEM1CAL. R EAC TIO N S A N D BIOLO GICAL E F F E C T
O F s t e r c u l i c a c i d
AND ANALOG OUS F A T T Y 'A C ID S
. > y
T am es C a r te r M as so n
A D is s e r ta t io n S u b m itted to th e F a c u lty o f th e
D E P A R T M E N T O F A G R IC U L T U R A L BIOCHEM ISTRY
In P a r t ia l F u lf i l lm e n t o f th e R e q u ir e m e n ts
F o r th e D e g r e e o f
D O C TO R O F PH ILO SO PH Y
In th e G raduate C o lle g e
U N IV ER SITY O F A R IZ O N A
A V;'.,;: 1 9 # , ... _ :■ , ■ .. Y
ST A T E M E N T BY A UTH O R
T h is d is s e r ta t io n has b een su b m itte d in p a r t ia l fu lf i l lm e n t o f r e q u ir e m e n ts fo r an a d v a n ced d e g r e e at th e U n iv e r s ity o f A r iz o n a and is d e p o s ite d in the U n iv e r s ity L ib r a r y to be m a d e a v a ila b le to b o r r o w e r s un der r u le s o f the L ib r a r y .
B r ie f q u ota tion s fro m th is d is s e r ta t io n a r e a llo w a b le w ithout s p e c ia l p e r m is s io n , p r o v id e d that a c c u r a te a ck n o w led g m en t o f so u r c e is m a d e . R e q u e sts fo r p e r m is s io n fo r ex ten d ed q u ota tion fro m or rep ro d u ctio n o f th is m a n u sc r ip t in w h o le o r in p a rt m a y be gran ted by the h ea d o f th e m a jo r d ep a rtm en t o r th e D ean o f the G radu ate C o lle g e w hen in th e ir ju d gm en t th e p r o p o se d u s e o f the m a te r ia l i s in the in t e r e s t s o f s c h o la r s h ip . In a l l o th er in s ta n c e s , h o w e v e r , p e r m is s io n m u st be o b ta in ed fro m the au th o r .
SIG NED:
tj6 . V\A
A P P R O V A L BY THESIS D IR EC TO R
T h is th e s is h a s b een ap p ro v ed on th e date show n b elow :
D r . A . R . K e m m e r e r P r o f e s s o r o f A g r ic u ltu r a l B io c h e m is tr y
i i
AC K ^dW liBD GMENTS
T he au th or w is h e s to e x p r e s s h is th an ks to D r , A . R , K ern raerer
fo r S u g g e stin g and d ir e c t in g th e p r o je c t , to- D r , H„ W. K ir c h e r and D r «
A . J. D en tschn aan fp r th e ir h e lp in th e c o u r s e o f th e p r o b le m , to M r.
B . W.» H eyw ang fo r c o o p e r a t in g in th e fe e d in g e x p e r im e n ts , and to th e
N a tio n a l C o tto n se e d P r o d u c ts A s s o c ia t io n w h o se g r a n t - in -a id p r o v id e d
m u ch o f th e eq u ip m en t and s u p p lie s u se d in th is p r o je c t .
T he au th or w ou id a ls o l ik e to a ck n o w led g e th e g e n e r o u s g ift p f
s t e r c u lia fo e t id a S eed fro m M r. F , R . A m o s , D ir e c to r o f F o r e s t r y ,
M a n ila , P h il ip p in e s .
TABLE OF CGNTENTS
' : . ' : " A , ''': , ; ' : . / ; ; P a g e
; . P A R T I
STU D IES O F F A T T Y ACIDS PR O D U O IN G P IN K EGG D ISG O L - : :ORATIO N - ' ■■■, ■ : ' V. : •; '
INTRODUCTION" « o a » •• <• ••■>»»•<■•»•>«•••• » o » j • o«o 1
, E X P E R IM E N T A L . . ■ . , . . . „ . . » . . .« ; . . . . . . « . . . . . . « . . 5
o o q o d o o ad o .oS te r c u lic A c id F e e d in g ;E x p e r im e n t s . . . . .A ttem p ted I so la t io n o f th e F a tty A c id fro m C o tto n s e e d O il R e sp o n s ib le fo r th e H alphen R e a c t io n . . . . . . . , 9H y d ro g en a tio n o f R e fin e d C o tto n se e d O il. . 14
D B c W i O N An d C G N C L R S iO N |.v . . . . . . > . . , . . . „ . . , . A: i s
S te r c u lic A c id F e e d in g E x p e r im e n ts . . . „ „ . . . . . . „ . . . . 18A ttem p te d I so la t io n o f th e F a tty A c id fro m C o tto n -
; ’ s e e d O il R e s p o n s ib le fo r th e H alphen R e a c t io n . . . . . . . . 19■' H ydrogenation: o f C o tto n se e d O i l . . . . . . . . . . ...» .«» 22
p a r t i i -
A ST UDY O F T H E PO L Y M E R IZ A T IO N AND ISO M ER IZATIO N R EA C TIO N S O F S T ERC U LIC ACID ( A '
,IN T ' UXS/T IO N . * O © ■ ». » . . ». 6; . . . . » ,. 0 ® . . . »' @ . . . . . O ® "o a". ' .9 » O 6 0 .2 3
E X P E R IM E N T A L .. . . .. . . . . . . .... . . . @ . . . . » . . . 27
N o te s on I n fr a r e d and U ltr a v io le t S p ectra .. . . . * . . . » . « » 27■ Iso la t io n o f S te r c u lic Held®,. . . . » . . . . . . . . » . © . . . . a a . » . . 28
P o ly m e r iz a t io n . . . . . a . . . . . © .. . . * . . . . . . @ . 30,H y d r o ly s is o f th.e. P o ly m e r . . . . . . 0 . . . . . . . . . . . . . . . . . . 31
3233
o o o d- o- o e e o d d - o e d o a « o, a e a '<> ® o a e o p & a o o o ® o ©
e- 'q > - a .0 '« & ®; o p d #» e ©• "a" e^'e d."
IV
T;A.BjLE: OF CONTENTS (cont'd)
3ir O C G d u 3T G o o ©; a © © »© © © © ©■ © o ■© & © ©■ @ © o e, © © q © ©, © » © 3-5
36o q a b o a © © © o a © a o a a © o © a e o © q © ©, © » o
o © a © q © o e © o © b © « © o © q
D B C U SS^ ^ © a© ©q©©© ©©q©©©©© ©a a © o © 3^
P o ly m e r lz a t ip n o f S te r c u lic Acid© © © © © © © © © © © © © © © © © ©© v * 38Is o m e r iz a t io n o f M eth y l S te rculate© ,© © © ©» e © © © © © © © © © © © 52
S U l V i ^ / X j A f l . \ © q © e, © © © o e a © q o © q p 6 q © a o © q a a e » a o ©> a e o © o & © © o o o e © o d o e 5 6
: -■ ■'■■■■ ; v ' ; ' v : v ' V . '■ ' ' . to © ©. ©- o p © a q e q o o o © o o e o a o . © © © o © o. © © e e e o ©■ o o s
LIST QF' FIG UR ES
F ig u r e ' - , . P a g e
1. Gas C h r o m a to g ra p h ic S e p a r a tio n o f P r e c ip ita t e X E '.. e'fc'tiyl -i—s ter,a @ ® p. @ o @ @ o © © © o © © © © © © ©■ © © © © „ © © @ @ © p © ©. 1 S'
2 , P r e ssu r e : H y d ro g en a tio n R e a c t o r . , » »« » »» , = 0 « « o « » .<, » ’ 15
3. Gas C h r o m a to g ra p h ic S e p a r a tio n o f D ep b ly m er ize .d. j&xiid s etl^^rl E^atera© . . . . . . . . . . . . . . . . . . . . . . a , . ; . . 3^
4 , In fr a red S p ectra . o f S te r c u lic A c id , S te r c u lic A c id a fte r l /2 H our Pc^ jF tuerizatidn at R S°C . $ jS te r c u lie
, A c id a fte r 19 H ou rs P o ly m e r iz a t io n at 9 8 ? C . . . . . . . . ' 39
5. M e c h a n ism II fo r th e P o ly m e r iz a t io n o f S te r c u licA c id . . . . . . . .. . o', o e- o . . . @ . . . o o . . O n o . o o . . .
h. G h au ge'in E q u iv a le n t W eight P u r in g th e P o iy m e r i -n ation o f "Ste r c u lic 3 .cl d. . , . . . . . . . . . @. . . . . . . . . . . . . . . © 13
7. C hange in R q fr a c tiv e Index D u r in g the P o ly m e r iz a -t io n o f S te r c u lic ,,^-c.id.. . . . . . . . . . . . . . . . . . . . . . .... . . 43
8. In fr a red S p e c tr a o f G as C h ro m a to g ra p h F r a c t io nB, M eth y l 9 - and ;1 0 « K e tp ;s te a r a te .. . . . . . . . . . . . . . . . 45
9. in fr a r e d S p e c tr a o f G as C h ro m a to g ra p h F r a c t io n G , Gas C hro in atograp h . F r a c t io n C (a fter H y d r d -
" g en a tio n o f th e P o ly m e r ) , M eth y l 9~ and 10 ~ H y d ro x y “s t e a r a t e . . . . « . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 {
10. In fr a r e d S p e c tr a o f D e p o ly m e r iz e d A c id s 3 GasC h ro m a to g ra p h F r a c t io n A, G as C h ro m a to g ra p h F r a c t io n A (a fte r H y d ro g en a tio n o f th e P o l y m e r ) . . . . 48
11. In fr a red S p e c tr a o f M e th y l S te r c u la te , G as: ; C h r o m a to g r a p h .is o m e r iz a t io n P r o d u c t o f M e th y l ■ >"
S t e r c u l a t e . . . . . . . . . . . . . . . . . . . . . . . . . . * ©.. . . . . . . . . . . 49
1 vi . . ■■ . ,
' LIST OF FIGURES (coat'd)
'FigttregV' ■ ' ' . - '■ .
13. Mtringic YiSGbSity of SterculiG Acid Polymer. .
14. . C hange in U ltr a v io le t ,A b so r p t io n S p ectru m D u r in gI s o m e r iz a t io n o f M eth y l S te r c u la te at 1 9 8 °C .
' : ■ V ;. ' LIST O F T A B L E S ,
T a b le . : ' - ■ P ; ' ,
T i . ■ F r a c t io n o f E g g s D is c o lo r e d in E x p e r im e n t l l l j th e F e e d in g o f V a r io u s L e v e ls o f S te r c u lia fo e t id a .Oil
PART I
STU D IES O F F A T T Y ACIDS PR O D U C IN G
P IN K EGG DISC O LO RATIO N
IN TR O D UCTIO N
P in k d is c o lo r a t io n o f c o ld s to r a g e e g g s w&s f i r s t r e p o r te d by
TW m p.W n (42) in 191.8„ T he e.ggs w e r e n o r m a l w hen f r e s h ly la id , but
b e c a m e d is c o lo r e d a f te r s e v e r a l m o n th s o f c o ld S to r a g e , T he d is c o lo r - ;
a tion w a s ch ar .a .cter ized by p ink w h ite s , en larged , w a tery $ s a lm o n - .
'co lo red y o lk s , and in c r e a s e d f r a g il i t y o f th e y it e l l in m e m b r a n e , J S h er-
w ood (4.0) in 1928 , a ttr ib n ted i t to th e p r e s eric e o f co tto n s e e d p ro d u cts
in th e d ie t o f th e la y in g h e n g .
S c h a ib le , B a n d im e r , and D a v id so n (33 , 34, 35, 36 , 37) sh o w ed
th at th e pirik c o lo r found in the w h ite w a s Caris ed b y a co m b in a tio n o f
co n a lb u m in , a p r o te in c o n s titu e n t o f th e w h ite , w ith f e r r o u s ibri, an
e g g y o lk co m p o n en t. N o r m a lly , the v it e l l in m e m b r a n e su rro u n d in g
th e y o lk o f th e eg g i s im p e r m e a b le and no io n tr a n sp b r t ta k e s p la c e
a c r o s s i t . In th e p r o c e s s le a d in g to- p in k d is c o lo r a t io n , h o w e v e r , th e
m e m b r a n e b e c o m e s p e r m e a b le , e y e n to la r g e p r b te in m o le c u le s (12 ,
3 7 ). T h u s , s o m e co m p o n en t o f th e c o t to n se e d o il o r m e.a l m u s t be
r e s p o n s ib le fo r th e .in c r e a s e in y i t e l l in m e m b r a n e p e r m e a b il l fy le a d in g
to p ink d is c o lo r a t io n .
L o r e n t and A lm q u is t ' (22) sh o w ed th at th e e th e r - s o lu b le lip id
fr a c t io n fro m th e y o lk s o f th e d is c o lo r e d e g g s g a v e a p o s i t iv e H alph en
t e s t . T he H alphen t e s t i s an e m p ir ic a r c o lo r r e a c t io n u s e d to id e n tify
th e p r e s e n c e o f c o t to n s e e d o i l in o th er fa ts o r o i l s (3A ). It i s m a d e by
h e a tin g .a .S am p le o f th e o i l in a so lu t io n o f su lfu r in c a rb o n d isu lf id e
and is o a m y l a lc o h o l. A r e d c o lo r in d ic a te s a p o s it iv e t e s t . N o o th er
-oomra e r c ia i p lan t o i l s ‘•y ie ld ' a p b s i t iv e : t e S f . . ; H pw eye,r, P a v o lin i an d
P a v o U n i (29) r e p o r te d th at o i l s e x tr a c te d fr o m s e e d s o f th e fo llo w in g
p la n ts gave th e H alphen r e a c t io n : 11 A lth a ea o f f ic in a lis : ,', A . r o s e a ,
M alya r o tu n d ifo lia , M . p a r v if lo r a . H ib isc u s r o s e u s , H. sa b d a r if fa ,
A b e lm a s ch u s m o s c h a tu s , G o ssy p iu m s.pp. , M ai ope S p p ., C e ib a sp p .
A d a n so n ia S p p . , T i l ia cQ rdata , T . p la ty p h illa , T . to m e n to s G ly p h a ea
g r e w io id e s , C o la y e r a , S te r c u lia tr a g a c a n th a , and F a r m ia n a p la ta n i-
'fo lia . h .S te r c u lia fo e t id a o i l i s a l s o know n to g iv e th e H a lp h en t e s t (10 ).
O f th e s e s e e d o i l s , th e o i l o f C e ib a Spp. (Kapok s e e d o il) and th e
o i l o f M alva p a r v if lo r a h a v e b een r e p o r te d to c a u se p ink e g g d is c o lo r a
tio n (10 , 39 ). L o r e n z (23) r e p o r te d th a t th e co m p o n en t r e s p o n s ib le fo r
'Or c lo s e ly - associated w ith th e Halphen r e a c t io n c a u s e s p in k eg g d i s c o l
o r a tio n . - -
S te r c u lic a c id , C j ^Hj^ Q g, is fou n d a s the p r in c ip a l fa t ty a c id fn.
th e t r ig ly c e r id e s o f th e s e e d o il o f S te r c u lia fo e t id a , th e J ava o liv e t r e e .
Nunn (2.8,) f i r s t e o r r e c t ly id e n t if ie d i t a s - ( 2 ~ n -o c ty lc y c lo p r o p -1 -.enyl).:.'
o cta n p ic a c id (I). CH-,
(I) G H 3(C H a )7G =C (G H 2 )7G 0aH .
3
S h en storie , V ic k e r y , and -vMajcIarlane (24 , 39) ha.ve r e p o r te d th e
i s o la t io n o f a C^g fa tty a c id fro m M a ly a p a r v if lo r a w h ich sh o w s an in fr a
r e d s p e c t in m s im i la r to. th a t o f s t e r c u l ic a c id and g iv e s a p o s it iy e H a l-
p h en t e a c t io n . T h is a c id i s r e p o r te d to c a u s e p ink e g g d is c o lo r a t io n .
. Gunstone. (17) has r e p o r te d th at c o tto n s e e d o i l co n ta in s a c y c lo p r o p e n e
fa tty acid, but o f fe r s ho p o s it iv e e v id e n c e . P u r e s t e r c u l ic a c id w as found
by F a u r e (15) to g iv e a p o s it iv e H alph en r e a c t io n . W ork in th is la b o r a
to r y (25) h a s sh ow n th a t s t e r c u l ic a c id w i l i p ro d n ce p in k e g g .d is c o lo r a =
iion d ; .:'v\ : ' ... d ; i -V-'VVW ■ ; ~ r - :-d ,■
D u e to th e u n d e s ir a b le e c o n o m ic im p lic a t io n s .of p in k e g g d i s c o l - • •
o r a t io n , it w ou ld be d e s ir a b le i f a tr e a tm e n t c o u ld be d e v is e d fo r c o t to n -
- a e e d o i l and rn .eal to e l im in a te o r m o d ify c h e m ic a lly the' com p ou n d
r e s p o n s ib le , E v a n s (13) h as r e p o r te d th at ad d ition o f v ita m in A , c a r o
t e n e , or f e r r ic c h lo r id e to c o t to n s e e d o i l d id n o t lo w e r th e in c id e n c e o f ‘
pink d is c o lo r a t io n . H e found , h o w e v e r , th at h e a tin g th e o i l to 2 5 0 -2 9 0 '°0 „
fo r ;d h b u r S 'w a s 'e f fe c t iv e , - , : ' . ■ ■ :‘ V : '■ - d d
' W ork in th is la b o r a to r y (25) h a s sh ow n th at h y d r o g e n a tio n o f ■
s te r c u lic . a c id to d ih y d rO sterc u lic a c id r e n d e r s it IhcLctive, O ther r e a c
t io n s know n to e l im in a te th e H alph en r e a c t io n and, p r e s u m a b ly , pink
d is c o lo r a t io n , in c lu d e h a lo g e n a tio n (26) and p o ly m e r iz a t io n (15),
T h e p u r p o se o f th is in v e s t ig a t io n w a s to id e n tify th e s tr u c tu r e o f
th e fa tty a c id in •co tto n seed o i l r e s p o n s ib le fo r p ink e g g d is c o lo r a t io n ;
4
and to in v e s t ig a te p o s s ib le te c h n iq u e s fo r c h e m ic a l tr e a tm e n t o f cbttqn-
s e e d o il and m e a l to in a c t iv a te th is com p ou n d .
E X P E R IM E N T AI<
MtfeTgulic A c id F e e d in g E xp erim ela ts
. ' ' E i^etoiim dnt 1 ' . '
S ix in d iv id u a lly c a g e d W hite L eg h o rn la y in g h en s w e r e divided.
. in to 3 grou p s and fe.d ad lib itu m fo r 1.5 day’s T h e fe e d w a s th e u su a l
g d to p le te r a tio n m ix e d w ith e r w ith ou t S terc .u lia fo e tid S o i l in c o r n o i l
a s follocws': ■ ■ ; ■' ' ' . '
G roup I 1. 5% c o r n o i l /
G roup 11 1. 5% c o r n o i l and 0„ 09% S_» fo e tid a o i l (ca« 0 , 1 gram
So fo e t id a o i l p e r h en p e r day)
G roup III 1„ 5% c o r n o i l and 0» 09% h y d ro g en a ted S» fo e t id a o il
T he o i l w a sT iy d r o g e n a te d h t a iB a o S p h er ic p r e s s u r e an d ro o m t e m
p e r a tu r e in e th a n o l u s in g a p a lla d iu m on c a lc iu m c a rb o n a te c a ta ly s t (8 ), .
In fr a red s p e c tr a sh o w ed th e a b so r p tio n band at lOpS cm*- -*" had sh if te d
16 1020 c m “ ^s in d ic a tin g th e c o n v e r s io n o f a c y c lo p r o p e n e ring: to a ;
c y c lo p r o p a n e r in g (14 , 2 8 ) a
Eggs, w e r e c o l le c t e d be g in n in g w ith th e se c o n d d ay o f fe e d in g and
' s to r e d a t r e f r ig e r a to r tem p e ra tu r e . A t the end o f one m o n th o f 'S torage- '
th e e g g s w e r e ' op en ed - A ll e g g s fro m G roups I and III w e r e n o r m a l,
w h ile 7 o f 11 in Group II show ed, .d e fin ite p in k d is c o lo r a t io n 0
. ..E x p er im en t 2 ,
S te r c u lic a c id w a s p r e p a r e d fr o m S te r c u lia io e t id a o i l by u r e a
"nompl-ex "Eerm.atifin nceorhj-hS to th e m e th o d o f Nunn (28 ). E r o m 2 0
, g ra m s o f th e o il , 2 . 5 g ra m s o f ste .rcu lrc a c id wa.s e v e n tu a lly is o la te d ,
n D ^” " 1 =, 4632 ^.it. n ^ ° ® 1, 4643 (14)j « S ix in d iv id u a lly c a g e d W hite
L e g h o r n .la y in g h en s w e r e d iv id ed in to 3 grou p s a n d ,in a d d itio n to th e
b a sa l r a t io n 3w e r e fed d a ily by p ip e tte a s fo llo w s ■
Group I 1 m l . co r n o il
G roup II 1 m l . c o r n o i l and 0 . 1 0 g ram s t e r c u l ic a c id .
; G roup 111 1 'm l. c d r n o i l and Q. B2B grakn a t e r c u l ic a.c£d ■
A fte r f m o n th d f c o ld s to r a g e , e g g s fro m G roups II and. I l l sh o w ed
definite p ink .d isc o lo n a tio u , w h ile e g g s fr o m Group I w e r e n o r m a l.
- . E x p e r im e n t '3 ' r
In a th ir d e x p e r im e n t , 24 h e n s w e r e d iv id ed in to 6 grou p s o f 4
'bir.ds e a e h ..l :In; n d d it io u to: th e :bas:al r a t io n , the^ w en e f e d d a ily by , .
p ip e tte a s ' f o l lo w s : . .. . ■ ; -.
Group I 0. 0 1 3 0 4 g. S . fo e t id a o i l (eq u iv . to 0, 00848 g.
.s t e r c u lic ac id ) in 1 m l , c o r n o il
Group II G„ 0 0 5 9 4 g« Su fo e t id a o i l (equiv» to Oo 00386 g„
s t e r c u l ic a c id ) in 1 m l c o r n o i l .
G roup III G. 00330 g„ S , fo e t id a o i l (e ’qu iv , to 0o 00.214 g„
; s t e r c u l i c a c id ) in 1 m l , c o r n o il
Group I ¥ 0» 00127 go SL fo e t id a o i l (eq u iy , to 0<, 80083 g ,
s t e r c u l ic a c id ) in 1 m l . c o r n o i l ,'
G roup V 0, 00012 g. fo e t id a o i l (e'quiVo to 0. 00008 g„
S te r c u lic ,acid) in 1 m L c o r n o il
' - G roup ¥1 1 r n l , c o r n ,o i l ’ : : ■■■
The q u a n titie s o f S te r c u lic a c id w e r e c a lc u la te d on th e b a s is that
s t e r c u l ic a c id c o m p r is e s b 5 w e ig h t p e r c e n t of. th e o i l (47). , , i
T he h en s w e r e fed th e ab ove su p p le m e n ts fo r 12 days* T he e g g s
w e r e c o l le c t e d s ta r t in g w ith th e s e c o n d d a y :of fe e d in g and d iv id e d in to
5 lo ts to be o p en ed a t th e end o f 1, 2 , 3 , 4 , and 6 m o n th s s to r a g e .
T a b le . 1 l i s t s th e findings:.. •
a
; . : ; • ' > ■ . ' T a b le 1 ., ' ‘ ' ; ;
F r a c t io n e>f. E g g s D is c o lo r e d in . E x p e r im e n t III, th e F e e d in g o f V a r io u s L e v e ls o f S te r c u lia fo e t id a O il to L a y in g H e n s »
L en gth of , 1 S to r a g e ! G roups
(months:) ' . . I 1 II IV "f- v , YT:/ ‘' ' 'y / ' ■, ' i
■ 1 ' 0 / 2: » V ;': v,
t 0 / 27 ■ ■ :
- 6 0 /6 ! -
I :i< 0 / 2 /f I
0 /2' 7 ' •
0 /2f
■ I
' 0 7 2
r 2f
0 / 6 " 0 / 6 ':i; ' • " f
0 / 6 ' 0 / 6t
' 0 / 51 :
: :: '"S'; •v . 3;. r
2 / 6 ■ 1 / 4■ r
■ 0 / 6 ■/:. 1 ' t -
0 / 5 / 0 / 5F ; ■■ , ; . ■ ' ' - '’ 0 /6
4 ' 3 / 6 ' 2 / 5r ■ ■
' 1 /6 ' i . t
0 / 5 - ' 0 /6 t
% 0 / 6' * , ‘ .
6 '■' ■ ■ ■ ■ : f
6 / 6 : o / s7 ■ ' - -
:/ o /s *i ■ i
0 / 6 ( 0 / 6■■ :t-
Q/6 :! -
9
A ttem p ted I so la t io n o f th e -Fatty A cid, in C o tto n se e d O il R e s p o n s ib le fo r the H alphen R e a c tio n ' , .
T h r e e a tte m p ts w e r e m a d e to i s o la t e th e fa tty a c id w h ich g iv e s
r i s e to th e H alphen r e a c t io n fro m c o tto n s e e d o il , jS e p e o f thera whS" .
co ija p le te ly .su ccesa fu lo A s m a l l s c a le p r o c e d u r e i s d e s c r ih e d b e lo w ,
: C o m m e r c ia l cru d e c o t to n se e d o il w a s found to be u n s a t is fa c to r y . •
fo r is o la t io n p r o c e d u r e s due to it s -d a r k brow n c o lo r w h ic h s ta y e d i n th e
fa tty a c id fr a c t io n a f te r s a p o n if ic a t io n and m a d e H alphen rea c tio n , c o lo r
e s t im a t io n im p o s s ib le . C o tto n se e d w a s d e lin te d w ith t e c h n ic a l s u lfu r ic
a c id , w a sh e d w ith w a te r and d r ie d . It w asb th en ground in a co ffee , g r in d e r
and e x tr a c te d s e y e r a l t im e s w ith p e tr o le u m e th e r at r o o m .te m p e r a tu r e .
T he p e tr o le u m e th e r w a s th en d is t i l le d o ff and the o i l (250 g ra m s) sa p o n «
i f ie d /w ith 700 m l, o f 10%,a lc o h o l ic p o ta s s iu m h y d ro x id e for- 24.hd;urS at '
ro o m te m p e r a tu r e . A fte r d ilu tio n w ith w a te r , th e u n sa p o n iiia b le m a tte r
w a s r e m o v e d b y e x tr a c tio n w ith e th y l e th e r . T he a q u eou s so lu t io n w a s
th en a c id if ie d w ith h y d r o c h lo r ic a c id and r e - ex t r a c t ed "with e th y l e th e r .
T he e th e r waS ey a p b ra ted and th e fa tty a c id s fr a c t io n a te d by u r e a c o m
p le x fo r m a tio n (38 ), T he m ix e d fa tty a c id s w e r e ad d ed to a .b o ilin g iso ln '-
f io n o f 700 m l , m e th a n o l s a tu r a te d w ith u r e a (233 g r a m s ) . A fter C oolin g ,
th e p recip ita te;w h:S f i l t e r e d . It "was th en d ls s o ly e d - in a .m in im u m am ount
o f b o ilin g m e th a n o l, c o o le d , and f i l t e r e d . T he 2 f i l t r a t e s (c a , 16.00 m l , )
w e r e co m b in ed and. s a tu r a te d w lt h h r e a (190 g r a m s ) at th e b o ilin g p o in t.
c o o le d , and f i l t e r e d . T h e p r e c ip ita te w a s r e c r y s t a i l i z e d a s b e fo r e and;
the f i l t r a t e s co m b in ed , .d ilu ted w ith w a te r , and e x tr a c te d w ith eth y l
e th e r . T he e th e r e x tr a c t w a s d r ie d o y e r c a lc iu m s u lfa te and th e e th er
e v a p o r a te d . T he fa tty a c id s fro m th e 2 p r e c ip ita te s n o te d a b o v e w e r e •
is o la t e d by a d d itio n o f a c id if ie d w a te r to th e u r e a c o m p le x e s and
e x tr a c t io n w ith e th y l e th e r . T h e e th e r e x tr a c ts w e r e d r ie d o v e r c a l
c iu m su lfa te and the e th e r eva .p orated . . T he fa tty a c id s o f th e f ir s t p r e ~ ,
e ip ita te w e ig h e d 45 g r a m s , had an io d in e n u m b er (H an u s) (3D) o f 7. 9
and gdye a n e g a t iy e H alph eh r e a c t io n '(3.A ). T h e fa tty a c id s o f the se c o n d '
p r e c ip ita te w e ig h e d 57 g ra m s and h ad an io d in e n u m b er o f 3d. 7; th e
H alphen r e a c t io n W as Only s l i g h t ly p o s i t iv e . T he fa tty a c id s re m a in in g
in th e f i l t r a te ga v e a s tr o n g ly p o s it iv e H alphen r e a c t io n .
T he fa tty a c id s fro m th e f i l t r a t e s w e r e th en su b j e c te d to lo w tern -
■ p e r a tu r e c r y s t a l l iz a t io n . B row n and K olb (7) d is c u s s lo w te m p e r a tu r e
c r y s ta l l iz a t io n p ro ced u res: and l i s t th e s o lu b i l i t ie s o f th e co m m o n fa tty
a c id s in a fY a r ie ty p f aQlyeEtS: a t low '::tenrperatures. M eth a n o l w a s c h o se n
a s a s o lv e n t b e c a u s e d if fe r e n c e s in s o lu b il i ty am on g th e fa tty a c id s a r e
g r e a te r in it than- in Other c o m m o n ly u s e d •Solyents . T h e fa tty a c id s
w e r e d ilu ted 1:10 by w e ig h t w ith m e th a n o l, .cooled to th e d e s ir e d t e m
p e r a tu r e , a llo w e d to e q u ilib r a te fo r 3 h o u rs and f l i t e r e d by S u e tio n . '
P r e c ip ita t e s w e r e r e d ilu te d w ith m e th a n o l ;to m a k e t h e ir v o lu m e s eq u a l
to th at b e fo r e th e c r y s ta l l iz a t io n . T he fo llo w in g c h a r t show S th e c o u r s e
11
T o ta l U n sa tu ra ted F a tty A cid s (ca . 12 5 g. )
- 5 0 °
p r e c ip ita te A
- 5 0 °
f i l t r a te A
p r e c ip ita te B
-4 0
c o m b in e w ith f i l t r a te A
r e c o n c e n tr a te d
-50 '
I------------p r e c ip ita te Z
- 60 °
p r e c ip ita te C
- 4 0 °
f i l tr a te C (ca . 50 g. )
f i l t r a te Z
- 60 °
r | p r e c ip ita te Y f il t r a te Y p r e c ip - f i l t r a tec o m b in e w ith ( 1 1 . 0 g. ) (4. 5 g. ) i t a te X Xf il tr a te C (7. 5 g. ) (23 . 7 g. )
rp r e c ip ita te D (1 5 .4 g. )
T he c o u r s e o f th e fr a c tio n a tio n w a s fo llo w e d by m e a n s o f the H a l-
p en r e a c t io n . In o r d e r to m in im iz e l o s s o f the f r a c t io n s , a m ic r o p r o
c e d u r e w a s e m p lo y e d . By p ip e tte , 0. 2 m l . o f the fa tty a c id fr a c tio n
w a s t r a n s fe r r e d in to a s m a ll t e s t tube and 1. 0 m l. o f a so lu tio n o f 1%
su lfu r in ca rb o n d is u lf id e , 1. 0 m l . o f i s o a m y l a lc o h o l and a s m a ll b o i l
in g ch ip w e r e added . T he t e s t tu b es w e r e p la c e d in a sa tu r a te d so d iu m
c h lo r id e so lu tio n and h e a te d on a hot p la te u n til th e ca rb o n d isu lf id e w as
d r iv e n o ff. T he te m p e r a tu r e w as th en r a is e d to the b o ilin g po in t of the
s a lt s o lu t io n and m a in ta in e d fo r about 1 h o u r . The c o lo r s o f th e s o lu
t io n s w e r e co m p a r e d v is u a lly .
12
:'v ' r n V-
> / ; ;;i>recip:£ta,te' iD "w xtb-'d^lar; / .. ■' % : " ;;■ ■ .. • :: ::.;v ■ ;
: ■■'■' p r e c ip ita te X - red ;■■ r ; ' ; \ ' ! ' ' ' : ' ' ,■
/.f iltr a te :X « lap:pp |br\./' ■ : ■ : . ■.
' - p r e c ip S M e T - P iig h tly r e d . ; . N,-1 '' ; ' ■ . 1 -//'
. . \ f i l t r a te Y » s l l g i t l y r e d '■ f :
- P r e c ip ita t e X (7= 3 gram s)., w h ich sh o w ed the h ig h e s t concenfcra- >
^ ■....................................... .................... ‘ . . . ' : - Ytio n o f fh e H alphen r e a c t io n p ro d u c in g a c id , v^as e s t e r i f ie d with, d ia z o -
m e th a n e a s p r e v io u s ly d e s c r ib e d (26). U n e s te r if ie d a c id s w e r e r e m o v e d
;. by e x tr a c t io n o f th e e th y l e th e r so lu tio n w ith sodium , b ic a r b o n a te . T he
e th e r w a s e v a p o r a te d u n d er v a cu u m , y ie ld in g 5. 4 g r a m s o f m e th y l
e s t e r s . : t \ ' ; . : ' f" f. VV: : ■ Y '; ' - : f Yv;-
H yd rogen ation . o f 0 .2 8 9 g ra m s le a . 1 m M ) o f th e m eth y l, e s t e r s o f
p r e c ip ita te X in e th a n o l o v e r a p a lla d iu m on c a lc iu m c a r b o n a te c a ta ly s t
(50 m g . ) r e s u lte d in an uptake o f 43 m l . h y d ro g en (40 m l . c p r r e c te d tb
S . T . P . ) ( l . :7 9 r ^ '-' 'y ' ■ - ; "- V ;- ' . Y " .
T he e s t e r s w e r e a n a ly s e d by v a p o r p h a se ch r o m a to g r a p h y u s in g
a iO -fo d t .HAG^4 2 1 0 °C . w ith a S o w r a te o f 105 m l. o f
h e liu m p e r m in u te . T he r e s u lt s a r e sh ow n in F ig u r e 1. T he c o m p o s ite
e f f lu e h t fr o m s e v e r a l sam p les; o f th e u n h y d ro g en a ted p r e c ip ita te X w a s /
c o l le c t e d and a H alp h en r e a c t io n ru n . It w a s n e g a t iv e .
1 A
r\3
0 4 8 12 16 20 24 281 I----------------------- 1------------------1______________ 1____________ I_____________ I____________L_
TIME (m in u tes)
F igu re 1. Gas C hrom atographic S eparation o f P r e c ip ita te X F atty A cid M ethyl E s te r s .1. P r e c ip ita te X M ethyl E s te r s .2 . P r e c ip ita te X M ethyl E ste r s a fter H ydrogenation3. S tan d ard s:
A. M ethyl P alm it& te; B. M ethyl S tearate; C. M ethyl Ole ate;D. M ethyl L in o lea te ; E. M ethyl L in olenate.
14-
In o th er r u n s c o n s id e r a b ly m o r e fr a c tio n a tio n by lo w te m p e r a tu r e '
c r y s ta l l iz a t io n w a s a ttem ptedg but s u b s ta n t ia lly id e n t ic a l r e s u lt s w e r e
o b ta in ed . T he fr a c t io n r ic h e s t in th e H alph en r e a c t io n p r o d u c in g 'c o m
p on en t sh o w ed , on y a p o r p h a se ch ro m a to g ra p h y o f th e m e th y l e s t e r s ,
p e a k s w ith th e sa m e r e te n tio n tim es, a s d id p r e c ip ita te X .
H y d ro g en a tio n o f H e fin ed C ottons e e d O il
, T h e p r o c e d u r e u s e d fo r the h yd ro .genation w as s im i la r to that ;
d e s c r ib e d by E ld ib and A lb r ig h t (1 1 ), T he o p e r a tin g v a r ia b le s u s e d
w e r e c h o se n b e c a u se th e ab ove a u th o r s 1 p a p e r sh o w e d th em to be e f f e c -
t iy e in p rod u cin g , a r e a c t io n o f m o d e r a te v e lo c ity , A 300 m l , c a p a c ity .
S tir r e d a u td c ia y e w a s u s e d tti c a r r y out th e h y d ro g en a tio n . It w a s
f it te d fo r c a ta ly s t a n d h y d ro g en in tr o d u c tio n and s a m p le w ith d ra w a l a s
sh o w n in- F ig u r e 2 . , . - ,
One hu nd red m l , o f r e f in e d c d tto n se e d o il- (ca . f ! l g r a m s) w a s -
p la c e d in: th e a n to c la y e and th e s y s t e m e v a c u a te d . W h ile e v a cu a ted , th e
te m p e r a t i ir e w a s b rou gh t up t o 12Si£ 1 . and th e e ie c t r ic s t ir r e r (750
rpm ) s ta r te d . A th e r m o c o u p le w ir e in th e a u to c la y e w a s c o n n e c te d to
a B row n r e c o r d e r ^ w h ich both r e c o r d e d and, th rou gh a m e r c u r y s w itc h
1 M od el A B E -3 0 0 A u to c la v e E n g in e e r s , E r ie , P a .
W e sso n o i l , ' 1 ■ ■ ■
3 M in n ea p o lis -H o n ey w e lT jG o . ,P h ila d e lp h ia , P a .
D
Hydrogentank
VACUUM
F igu re 2. P r e s s u r e H ydrogenation R eactor .A. R eactor Inlet V alveB. A ddition Funnel V alveC. L ine V alveD. Sam pling V alveE. 3 -w ay V alve to Vacuum and H ydrogen.
16
and a r e la y , c o n tr o lle d th e te m p e ra tu r e 0 H ydro gen w a s th en a d m itted
to th e s y s te m a t 30 pounds p r e s s n f Ce V a lv e A (a ll l e t t e r s r e f e r to the
d e s ig n a tio n iti F ig u r e 2) w a s th en c lo s e d , th e tu b in g e v a c u a te d and th en
v a lv e G c lo sed e A su sp e n s io n o f Q. 4 g r a m s R u fer t f la k e n ic k e l c a ta
ly s t (25, 57% n ic k e l) in 2o 2 m lo hbt c o t to n s e e d o i l w a s p la c e d in the ,
fu n nel a b ove v a lv e B and th en v a lv e B was; op en ed to su ck th e s u sp e n s io n
in and th en c lo s e d 0 V a lv e G w a s th en op en ed and th e h y d ro g en p r e s s u r e
in c r e a s e d to 40 p o u n d s. V a lv e A w as th en op en ed to in tr o d u c e the ca t a - =
ly s t to th e sy ste m o T h is w a s c o n s id e r e d th e s ta r t o f th e r e a c t io n , A
sample" w a s im m e d ia te ly w ith d raw n by c a r e fu l op en in g o f v a lv e D , T he
f ir s t m l , w a s d is c a r d e d and th en a c a , 2 m l , s a m p le c o l le c t e d in a s m a ll
t e s t tu b e , S a m p le s w e r e c o l le c t e d a t in te r v a ls th rou gh ou t th e c o u r s e o f
th e r e a c t io n . T h ey ‘w e r e c e n tr ifu g e d to b r in g down th e su sp e n d e d cata-»
■ i y u : ■ ■■ ' : . . ■
H alphen r e a c t io n s (1:5 d ilu tio n ) and H anus io d in e n u m b er d e t e r
m in a tio n s (3B) w e r e run on e a c h s a m p le , t a b l e 2 l i s t s th e r e s h it s .
-1 . ■ ' _ 1 • ■ . _P r o v id e d th ro n g h th e c o u r te s y o f th e H arsh aw C h e m ic a l C o . ,
C l evelctnd, O h io .
t able 2 ,
C hange in Iod in e N u m b er and H alp h en R e a c tio n
. , t i m e , (m in , )
. { ... .
' •' t ■Iddine
n o . !■ ;•. .-H alphen
"reactio ii "
*i.i 112, 0
t■ , .'.Vf.: '
0 i■ ■ T ■
109, 8 tt
w ea k
10 ! f V 1 ■ "
: i o 2 , t f.f
2 0 ,: f' , .1, .
9 9 .1 • • 5. ; r ' ;
: " w ■ ■ ■ ' -
30 i . i :
92: 5 ' < i:, r
1 .: 9 0 .0 ; : '-m; f '
* 1
60. i' i
7 4 .1 1- ' . f •'
# ■'V ■v 6% 0
112 ■ .1" i v'.:
5 6 .4 ■ '.T
3 0 0 - ' i'X . I
: 35 . ;5 ■
B e fo r e add-itipn o f c a ta ly s t .
DISCUSSION AND CONCLUSIONS
S te r c u lic A c id F e e d in g E x p er im en tg
T h e se e x p e r im e n ts sh ow th at s t e r c u l ic a c id , e ith e r p u re or a s
S te r c u lta fo e tid a o il , w h en in c lu d ed in th e d ie t o f la y in g h e n s , i s r e s p o n -
s ib le fo r th e a lte r a t io n in p e r m e a b il i ty o f th e v i t e l l ih m e m b r a 11© w hiph .
. le a d s , to pin|c e g g d is c o lo r a t io n . T he m e c h a n is m by w h ic h th is ch an ge
: in p e r m e a b il ity o c c u r s i s unknow n.
H y d ro g en a tio n Of S te r c u lia fo e t id a o i l r e d u c e s s t e r c u l ic a c id to '
d ih y d r o s te r e u lic a c id and r e n d e r s it in a c t iv e in p ro d u c in g p ink e g g
d is c o lo r a t io n . T he - e x a c t am dhnt o f s t e r c u l ic A cid n e c e a s a r y to p rod u c e
th e p ink d is c o lo r a t io n h as not been , e s ta b lis h e d . U nd ou b ted ly , th is
w ould v a r y so m e w h a t w ith th e in d iv id u a l h en . S c h a ib le , B a n d im er , and
D avid s on. (33) o b s e r v e d that p r o n e n e s s to la y e g g s w h ich w i l l b e c o m e ,
d is c o lo r e d i s ah in d iv id u a l .c h a r a c te r is t ic . D ata fr o m e x p e r im e n t 2 ,
sh ow th at both 0 .1 and 0. 025 g ra m s t e r c u l ic a c id p e r h e n .p e r day r e p
r e s e n t h igh le v e ls o f the; a c id , s in c e both p ro d u ced th e d is c o lo r a t io n a f te r .
S torage fo r 1 m o n th . T he lo w e r l im it o f s t e r c u l ic a c id w h ich w i l l p r o -
v educe p ink e g g d is c o lo r a t io n a p p ea rs -to be in the ra n g e o f 0 . 0020 to
0. 0037 g ram p e r h en p e r day, as sh ow n in e x p e r im e n t 3 (T ab le 1 ). ■
19
;A ttem p ted I so la t lo ii o f |h.e F a tty A c id in G o tto n seed O il R e s p o n s ib le ,
fo r th e H alphen R ea ctip ti
'Iso la tio n fr o m e o tto n se e d o i l o f th e H alphen r e a c tio n -p r o d u c in g
fa tty a c id by m e a n s o f u r e a c o m p le x fo r m a tio n and lo w te m p e r a tu r e .
c r y s ta l l iz a t io n w a s a tte m p te d . A fter: a s e r i e s o f fr a c tio n a tio n s* th e
fr a c t io n g iv in g th e m o s t in ten s e H alphen r e a c t io n w a s e s t e r l f ie d and
su b je c te d to? vajior p h a se c h r o m a to g r a p h y . T he chrom atogr'am . (F ig u r e
1) sh o w ed 2 p e a k s . One c o r r e sp o n d e d , in r e te n tio n t im e , to m e th y l
o le a te , th e o th e r to m e th y l l in o le a te . N e ith e r fr a c t io n upon e m e r g e n c e
gave a p o s it iv e H alphen r e a c t io n . H a ter w o r k , u s in g m e th y l s t e r c u la t e ,
Show ed th at gas ch r o m a to g r a p h y c a u s e d is o m e r iz a t io n and co n seq u en t
l o s s p f th e H alphen r e a c t io n . It is l ik e ly th at th e fa tty a c id e s te r , c o n
ta in in g th e c y c lo p ro p eu e r in g u n d erw en t i s o m e r iz a t io n d u rin g gas c h r o
m atograp h y^ I s o m e r iz a t io n w ould, p r o d u c e a com pbUnd h a v in g 2 double
b o n d s, w h ich in a p o la r co lu m n w ou ld p r o b a b ly h ave th e s a m e r e te n t io n 1
tihae a s 'm e th y l l ln o le a te . ... ? . - i/?;.
GaS c h ro m a to g ra p h y o f th e s a m e fr a c t io n a fte r m ild h y d ro g en a tio n
Show ed (F ig u r e 1) th at th e p eak c o r r e sp o n d in g to m e th y l l in o le a te w a s .
e lim in a te d , but th a t 2 p e a k s rem adned , C o rresp o n d in g in r e te n tio n t im e S
to m e th y l s t e a r a t e a n d m e th y l o le a te . H yd rogehation . o f th e m e th y l e s te r s ; ,
w o u ld red u c e th e c y c lo p rop en e group to a c y c lo p rop an e d e r iv a t iv e . S u eh
a com p ou n d w o u ld h ave th e " eq u iv a len t of'1 1 double bond and p ro b a b ly
the g a m e r e te n t io n t im e a s m e th y l o le a te . O ther i s o la t io n p r o c e d u r e s
e m p lo y in g .m o r e e x te n s iv e lo w te m p e r a tu r e . c r y s t a l l i ’za tio n gave .S im ila r
resn ltS o G as c h r o m a to g r a p h ic a n a ly s is sh o w ed , in e a c h c a s e , that the'
fr a c t io n •giving th e m o s t in te n s e H a lp h en t e s t had p e a k s c o r r e sp o n d in g
to m e th y l o le a te and m e th y l l in o le a te . In one c a s e , a p ea k c o r r e s p o n d -
in g to m e th y l p a lm ito le a te w a s a ls o o b ta in ed , , .
U n fo r tn n a te ly , d u rin g th e .t im e th a t th e s e is o la t io n p r o c e d u r e s
w e r e b e in g ru n , n o in fr a r e d s p e c tr o p h o to m e te r w a s a y a ila b le to follow'
th e p r o g r e s s o f th e .se p a r a tio n and ch e c k fo r the p r e s e n c e o f a c y c lo -
p ro p en e r in g a b so r p tio n , A fr a c t io n fr o m one- o f th e is o la t io n p r o c e
d u res g iv in g a s tr o n g H alph en r e a c t io n w a s S to r e d fo r a p p r o x im a te ly
4 m o n th s in a d ry ic e stor.ag.e c h e s t . M o st o f th is t im e t h e sa m p le w a s
at d r y i c e t e m p e r a tu r e . H o w ev er , bn s e v e r a l o c c a s io n s it w a s a llo w e d
to; w a r m up to ro o m te m p e r a tu r e . The: in fr a r e d sp e c tr u m o f th is produG t
sh o w ed a w ea k a b so r p tio n at 1009 c m ” , a r e g io n c h a r a c te r is t ic o f th e
c y c lo p r p p e n e r in g (TO), a r a th e r s tr o n g band at 1743: c m , c h a r a c te r
i s t ic Of e s t e r s , and a fr e e c a r b o x y l band a t 1710 cm™ . T h e e s t e r
• ab S brption in d ic a te s th at e x te n s iv e p o ly m e r iz a t io n o c c u r r e d in v o lv in g . ‘
th e fa tty a c id co n ta in in g the c y c lo p r b p e n e r in g . T h e m e c h a n is m o f th is
p o ly m e r iz a t io n in s t e r c u l ic a c id i s d is c u s s e d in S e c t io n l l .
A lthough th e is o la t io n fr o m c o t to n s e e d o il o f th e fa tty a c id c a u s in g
th e H alph en e r e a c t io n w a s not s u c c e s s f u l , th e fo l io w in g in f o r m a ti on w a s ,
ob ta in ed . In s o lu b il i ty at lo w t e m p e r a tu r e s , e a s e o f fo r m in g u r e a c o m
p le x e s and r e te n tio n t im e in th e gas chrom atograp h .,' th e a c id .,in Q uestion
i s y e r y S im ila r to l in o le ic a c id . R ep ea ted 1 ow te m p e r a tu r e c r y s t a l l i z a
t io n s .w ould not s e p a r a te th e twb> s.© .long a s l in o le ic a c id w a s th e .m ain I,
C O iistituent. In S te r c u lia fo e t id a oil> w h e r e s t e r c u l ic a c id i s t h e m a jo r ■
co m p o n en t with: a S m a ll am ou n t o f l in d le ic a c id p r e s e n t , th e y a r e s e p a r - '
a ted e a s i ly by lo w te m p e r a tu r e c r y s t a l l i s a t io n . jS tercu llc a c id p r e c ip i -
ta t e s a t - 5 0 o G. and le a v e s th e l in o le ic a c id in so lu t io n . H o w ev er , in' . ■
c o tto n se e d o i l , th e la r g e a m ou n ts o f l in o le ic a c id s o lu b i l iz e d the H a l-
p h en r e a c t io n " p rod u cin g .a c id , and it w o u ld not p r e c ip ita te a t - 50°G .
and n s u a l ly n o t at - 6 0 °G . . . . . . _ ' < . .. . ; :
A lth ou gh it S e e m e d d e s ir a b le to S tart w ith a la r g e qu antity o f
c o tto n se e d o i l in o r d e r to e f fe c t th e is o la t io h , s t im e difficTaltieS w ere ,
e x p e r ie n c e d w ith la r g e v o lu m e s , . H ow te m p e r a tu r e c r y s t a l l i s a t io n '
~ sep ara tion s w e r e .p o o r e r w h e n la r g e . b a tc h e s w e r e ru n ,.■■■_ T h is w a s p r o b -
a b iy due to two. f a c t o r s :- .equilibrium , b e tw een th e p r e c ip ita te and th e s o l
u tion w a s r e a c h e d m o r e s lo w ly ; and, b e c a u s e the c r y s ta l l iz a t io n s co u ld :
not be c a r r ie d out in D ew a r f la s k s , it w a s 'e x t r e m e ly d if f ic u lt to m a in
ta in th e te m p e r a tu r e c o n sta n t d u r in g th e c r y s t a l l is a t io n . E v en w ith ,
s t ir r in g , a te m p e ra tu r e d if fe r e n t ia l e x is t e d .b etw een th e top and b o tto m
o f th e c r y s t a l l is a t io n v e s s e l , ' ' : ;
T he la b i l i t y 'o f th e H alphen r e a c t!o n -p r o d u e in g fa tty a c id added
to th e d if f ic u lt ie s o f s e p a r a t io n , s in c e p r o c e d u r e s had to be a v o id ed
w h ich w ou ld r e s u lt in c o n c e n tr a tio n or h ea tin g o f th e a c id s fo r any but
sh o r t p e r io d s o f t im e . T h e au th or b e l ie v e s th a t th e b e s t p o s s ib i l i t y
fo r is o la t io n o f th e a c id m ig h t be co lu m n efarom a to g ra p b y o f th e ;iaci<$ss '
a fte r th e in it ia l cru d e s e p a r a t io n s u s in g u r e a c o m p le x e s and lo w t e m
p e r a tu r e c r y s t a l l i s a t io n s . . ■
H y d ro g en a tio n o f R e fin e d G ottons e e d O il '
U nder th e h y d ro g en a tio n c o n d itio n s em p lo y ed (1 2 6 0 C» , p o u h d s
h yd rogen p r e s s u r e , 0 . 10% n ic k e l c a ta ly s t , 750 rpm s t i r r e r sp e e d ) , the
com p ou n d in c o t to n s e e d o i l g iv in g r i s e to th e H alphen , r e a c t io n w as
h y d ro g en a ted a lm o s t in s ta n ta n e o u s ly w ith o u t a p p r e c ia b le ch an ge in th e
io d in e n u m b e r . T h is i s to be e x p e c te d w h e n e v e r h y d ro g en a tio n c o n d i
t io n s a r e m ild enough to p e r m it s e le c t iv ity * T he c y c lo p r o p e n e r in g i s
e x tr e m e ly r e a c t iy e b e c a u s e o f i t s lts t r a in e d !'' c o n fig u r a tio n and w il l p r e
fe r e n t ia l ly r e a c t to r e l ie v e th is s t r a in , , T h e c y c lo p r o p a n e r in g fo r m e d ,
'■ 'w hile-alsd istrained ,- i s m u c h leSU Sd^and, h e n c e , m o r e s t a b le «
S h ort p e r io d h y d ro g en a tio n w ou ld be u s e fu l to m o d ify r e f in e d
c o tto n s e e d o i l fo r u s e in e x p e r im e n ta l d ie ts w ith ou t a p p r e c ia b ly ch a n g
in g its^content' -df d le id h n d y H n o ie iC 'd c id s ,' . :lt-w d u id ‘b e ;le s:S ;u sefU l,in :
tr e a t in g cru d e c o t to n s e e d o il , s in c e th e cru d e p ro d u ct c o n ta in s c o n s id
e r a b le fo r e ig n m a te r ia l w h ich co u ld p o is o n the c a ta ly s t .
H to ii (2 § |, in l f 5 2 , ItoSt iB p la ted stexcT lli^ a c id , a fa tty a c id
c o n stitu e n t o f the t r ig ly c e r id e s o f S te x c u lia fo e tid a o i l . H e co n c lu d ed ,
on the b a s is o f i t s d eg ra d a tio n p r o d u c ts , th at i t s s tr u c tu r e w a s
. ^ - ( Z - n - o c t y lc y c lo p .r o p - l - e n y l ) o c ta n o ic a c id (I), ’ :
' i t v ■; ^ 2 ^^: ;.i. (I) C H g-iC H ^) 7 - .C = G -(G H 2 ) ?™C 0 2 H •' : ^
H is s tr u c tu r a l d e te r m in a tio n w a s b a se d on th e fo llo w in g f a c t s :
s t e r c u i ic a c id tm d e r g o e s a 2=«step h y d ro g en a tio n , u lt im a te ly co n su m in g
2 m o le s o f h y d ro g en p e r m o le o f ac id ; d ih y d r o s te r c u lic a c id , the p r o d
u ct fo r m e d upon co n su m p tio n o f 1 m o l e o f h y d ro g en , h as an in fr a r e d .
a b so r p tio n p ea k at 1015 c m ”'*', c h a r a c te r is t ic o f c y c lo p r o p a n e s ; upon
o z o n o ly s is o f s t e r c u i ic a c id and red u c tio n o f th e o z o n id e , a ^ -d ik e -
to n e , 9, 1 1 -d ik e to n o n a d e c a n o ic a c id , i s fo r m e d , and d ir e c t oxidation, o f
s t e r c u i ic a c id w ith p o ta s s iu m p erm a n g a n a te p rod u ces, a z e la ic and
'p e la r g o h ic a c id s ? -v i . ', - k:/'
I fa r m a , N ath , and A g g a rw a l, h o w e y e r , h a v e p u b lish e d n u m e r o u s
p a p e r s (43 , 44 , 4 5 , 46) in su p p o rt o f th e ir p o s tu la te d s tr u c tu r e o f
S te r c u iic a c id as 0 ~ { Z -n -h e x y lc y c lo p r o p y l)” 9 :1 0 -d e c e n o ic a c id (II).
■x;: ; :?.-v v ' 'I' : ' ' . ;^
' (II) CH3 -(G H 2 )5 - C H -C H - GH2= C H - (CH2 C 0 2H : .
■ ;1 ' T h e ir ar.guraents' a r e b a sed m a in ly upon in fr a r e d s tu d ie s p f s t e r - %
; c u lic a c id a n d s o m e :■ m odal: "c y c lo p r o p a n e !r and !'oyClppr©pane:“ a c id s »
T h e y a ls o r e p o r t is o la t io n o f k ep ta n p ic a c id an d m e th y l-n -h e x y l k e to n e
■ fr o m th e p erm an gan a .te oxidation, o f s t e r c u l ic a c id . . ' , 1
W ork in o th er la b o r a to r ie s h a s r e s u lt e d in a la r g e am ount o f
e v id e n c e in fa v o r o f N unn 's a s s ig n m e n t o f s t r u c t u r e . $ e y e r a l la b o r a
t o r ie s h a y e r e p o r te d (43 5 , 6 , 2 1 , 27) sy n th e s is , pf 9, ,11 -d ik e to n o n a d e c a n o ic
.acid and it s id e n tity w ith th e a c id r e p o r te d by N unn. H ofm ann et a l . (18)
h a y e r e p o r te d th e s y n th e s is o f D L .-c is -9 , 1 0 -m e th y le n e o c ta d e c a n o ic •
a c id and by m ik e d m e lt in g p o in t and x - r a y d if fr a c t io n d ata h a v e e s ta b
lis h e d it s c o m p le te id e n t ity w ith d ih yd ro s t e r c u l ic a c id . T he p o s it io n o f
.th e .cy c lo p ro p a n e t in g h a s been.: th e r e fo r e f ir m ly e s ta b lis h e d and th e ,
s tr u c tu r e p r o p o s e d by Y a rm a et a l . i s not c o r r e c t . R in eh a r t and o th e r s
: (3 l)j S tu d y in g th e n u c le a r m a g n e f ic res.onan c e s p e c tr u m o f S te r c u lic
,acid:found th a t th e r e was^.no abso.rptldn^ y in y i h y d r o
gen . If th e d ou b le bond w e r e in any p o s it io n o th er th an th at p o s tu la te d
by N unn (I), th e r e w o u ld be a v in y l h y d r o g e n . T h e r e fo r e , N unil's p la c e
m en t o f th e d b u b le bond 1 s c o r r e c t and th e stru ctu re :-o f s t e r c u l i c a c i d i ’
i s a s h e p o s tu la te d (I). _ - d'v'. , .'-d:':'.,,
S te r c u l ic a c id and i t s e S t6 r:.s a r e la b i le . T h e a c id U n d erg o es a •
"hpbntdnedtts- p o ly m e r is a t io n r e a c t io n p lo w ly a t room tem b n ^ n tu re and :
' q u ite r a p id ly at e le v a te d te m p e r a tu r e s (28 ). Nunn (28) p o s tu la te d th at
th e p o ly m e r iz a t io n p ro b a b ly o c c u r r e d by a d d itio n o f th e c a r b o x y l group
o f one m o le c u le a c r o s s th e double bond o f the c y c lo p r o p a n e r in g in '
a n o th er mqiEen pvtechanisna I ), - ; , : " ‘Vv-
(M ec h a n ism 1) . ' y,/-' / .. ' ' j v : . r ' ,
CH3-.(CH2) -r G ™ C -(C H 2 )7-.C 02H — ^ CH3(CH2 )7 -.GH -C-(CH2 )7- C 0 2H""I/:'::'' / '■ : : ■ ■.; & : , . . '■
. ' V ;
. ; r m ; ■ ■. : r :
F a u re and S m ith (15), on th e b a s is o f in fr a r e d s p e c tr a , r e p o r te d
th at th e dou b le bond r e m a in e d in ta c t and th at th e c y c lo p r o p e n e r in g iyas
ru p tu red a t one o f th e s in g le , bonds by th e c a r b o x y l group fro m a n o th er
m o le c u le (M ec h a n ism II).
(M echan ism : II) ■ ' . • V
. • . ■ ^ \ P 3 :: ■GHg^ (CH2 )7~C=C~(CH2 ) 7« C 0 2H —> GH^(GH2 )7-C “ C - (GH2 )7«G 02 H '
. - ■ ; ' - ' ■' ' " ' ' . - ■' - " '■ I .
y y- y. ; :" R : : ■ y f ~ ° ' y ,
; . , R :
' ■ ; * ■■ V ...... -.V v , . GH2rQ-G-R-^ .
: ' : | ' ; ‘ '. ' ... CH3(CH2 )7«C=CH-(GH2 )7 -.GG2 H
V a rm a et a l . (46 ) rej e c t both m e c h a n is m s b e c a u s e th e y c o n f lic t
w ith th e ir p o s tu la te d s tr u c tu r e o f s t e r c u l ic a c id , but do n o t ad van ce ah
a lte r n a te m ech a n ism o
26
R e a c tio n s s im i la r to m e c h a n is m 1 have b een r e p o r te d in th e l i t e r
ature^ F o r m ic a c id w il l add a c r o s s th e d ouble bond o f o le ic a c id to
fo rm an e s t e r in th e p r e s e n c e o f an a c id c a ta ly s t (19)* N o r e a c t io n s
s im ila r fo m e c h a n is m II have b een rep ortedo
T he p u r p o se o f th e p r e s e n t in v estig a tio n . w as to e lu c id a te th e
s tr u c tu r e o f the p o ly m e r th a t fo r m s w h en s t e r c u l ic a c id i s h e a te d »
E X P ER IM ENT A t;
; N o te s @n In frafed : and U ltr a v io le t Spectra.
A ll in fr a r e d s p e c tr a i l lu s tr a te d w e r e d e te r m in e d u s in g a B eck m an
M od el IR -4 double b ea m r e c o r d in g in fr a r e d s p e c tr o p h o to m e te r w ith
s,odium c h lo r id e p r i s m s . M ic r o so d iu m c h lp r id e c e l l s o f 0 ,1 m m ,
th ic k n e s s and 20 j&l, c a p a c ity w e r e u se d . A ll s p e c tr a sh o w n w e r e run
in Carbon te tr a c h lo r id e s o lu t io n a g a in s t a ca rb o n te tra ch lo ;r id e s o lv e n t
blank . E x a c t c o n c e n tr a t io n s w e r e not d e te r m in e d a s o n ly q u a lita tive ' '
r e s u lt s w e r e S ou gh t, T he n u m b e rs p r in te d in the c e n te r o f th e s p e c tr a
r e f e r to p e r c e n t .tr a n s m is s io n , ■,
■ D ue to sc a n n in g sp e e d and p e r io d c h o s e n , th e s p e c t r a show n in
F ig u r e s 4 and 11 a p p ea r to ■have th e w a v e le n g th v a lu e s b e lo w 2000 c m “i
d is p la c e d by about 10 e m “ , T he a b so r p tio n m a x im u m fo r the c y c lo -
'p ro p en e r in g i s r e p o r te d (14) a s 1009 cm " 1; w e fin d 1020 c m " 1,
T he d ia l s e t t in g s fo r th e s p e c tr a w e r e a s fo llo w s : s l i t w id th
0, 75 m m . at 1000 c m s l i t p r o g r a m - s e le c t , c h a r t s c a le 0 « 100%
tr a n s m itta n c e , sca n n in g sp eed ' 100 cm"-*- p e r m in u te b e lo w 2000 cm"*-,
ahd 400 c m . p e r m in u te ab ove 2000 cm " * , auto in , ga in 10, 350 , and
p e r io d 2 d r 8y. d ep en d in g on the r e s o lu t io n r e q u ir e d , -
\ ' ' - ' v _ ; : ; 28
T h e u ltr a v io le t sp eG tra sh b w h in. F ig u r e 12 w e r e d e te r m in e d u s in g
a B eck m a n M od el P U s p e c tr o p h o to m e te r j a l l o th e r s w e r e d e te r m in e d on
a.-C ary M o d el 11 d ou b le b ea m r e c o r d in g s p e c tr o p h o to m e te r „ F o r th e
. s p e c tr a ta k en oh t h e .G ary, th e d ia l -settingsf w e r e a s fo llo w s : s l i t c o n t r o l '
10, ch a r t ran ge Q-,2. 4 , sca n n in g sp e e d 1 ,pe:r s e c o n d i ; : v " ' - v :
I so la t io n o f S te r c u lic A c id ,
' T he is o la t io n p r o c e d u r e is e s s e n t ia l ly th at o f Nunh (28). yhblO ' -
S te r c u lia fo e t id a s e e d s (1663 g r a m s ) w e r e ground in a h o u se h o ld m e a t .
g r in d er and e x tr a c te d at ro o m te m p e r a tu r e w ith p e tr o le u m e th er (ca .
'20 l i t e r s ) w ith in te r m it te n t a g ita tio n fo r 5 h o u r s . T he s o iv e n t w as, th en
d eca n ted and th e p r o c e s s r e p e a te d . T he p e tr o le u m e th e r w a s e v a p o r - :
at ed u n d er r e d u e e d p r e s s u r e in a , la r g e c a p a c ity s te a m ev a p o r a to r (Ac e
G la ss C o. # 6 7 1 1 ). T he y ie ld w a s 566 g r a m s o f o i l . A 10% so lu tio n o f
p b tassiu tia h y d ro x id e in eth a n o l. (3. m o le s ) w a s ad d ed to th e o i l , s t ir r e d ,
■ and le f t at ro o m te m p e r a tu r e fo r 2 d a y s „ T he so lu t io n w a s th en d ilu te d ;x
w ith w a te r , and th e u n sa p o n ifia h le fr a c t io n w a s e x tr a c te d w ith e th y l
e th e r . T he’ atjUeous s o lu t io n o f so a p s w a s th en a c id if ie d w ith h yd ro«
ch lo r ic - a c id , and th e f r e e fa t ty a c id s w e r e e x tr a c te d w ith e th y l e th e r .
T he e th e r e x tr a c t w a s . d r ie d ahd e v a p o r a te d u n d er r e due e d p r e SSur e ,
y ie ld in g 424. g r a m s :o f f r e e fa tty a c id s .; : - :::v"
The: fa tty a c id s w ere , a d d e d to (a s o lu t lp n o f g r a m s n r e a in . . ;
1500 m l . m eth a n b i at th e b o ilin g p o in t . T’h e m ix t u r e w a s s t i r r e d and .
th en a llo w e d to c o o l to r o o m te m p e r a tu r e . T he p r e c ip ita te w as f i l t e r e d / "
•s lu r r ie d With a s m a ll v o lu m e o f m e th a n o l sa tu r a te d w ith u r e a , and a g a in
f i l t e r e d . T he p r e c ip ita te (650 g r a m s) c o n s is t e d o f th e u r e a c o m p le x e s
o f th e sa tu r a te d a c id s ,(180 g ra m s j . It w a s d is c a r d e d . A t th is p o in t an •
a c c id e n t r e s u lte d in th e lo s s o f .a p p ro x im a te ly h a lf th e f i l t r a t e , R eco v ~ ,
: e r y o f 127 g r a m s df fa tty a c id s ■'w&s m a d e . T h e s e fa tty a c id s w e r e :/
added to a s o lu t io n o f 127 g ra m s o f u r e a d is s o lv e d in 390 m l . o f b o ilin g
m e th a n o l. T he s o lu t io n w a s then, co o led ,, f i l t e r e d , and w a s h e d . T h e
f i l t r a te (650 m l . ) w a s h e a te d w ith 113 g ra m s o f u r e a , c o o le d , f i l t e r e d ,
and w a sh e d . T he f in a l f i l t r a te w as d ilu te d w ith w a te r and e x tr a c te d i
W ith e th y l e th e r . T he e th e r e x tr a c t w a s d r ie d f ir s t o v e r so d iu m su lfa te
and th en m agn esiu m - s u lfa te . T he e th e r w a s th en e v a p o r a te d at r e d u c e d
p r e s s u r e , y ie ld in g 46 g ra m s o f fa t ty a c id s . T h e fa tty a c id s w e r e d ilu te d
With .200 m l . a c e to n e (ACS grad e) and c o o le d to “ 5 0 °C , in a d ry i c e -
aceton e: bath fo r 4 hours,;' T h e 'p r e c ip ita te w a s f i l t e r e d u s in g a s in te r e d
g la S s f i l t e r s t ic k and' w a sh e d w ith a c e to n e p r e c o o le d to - 7 8 0 C«,
A fte r 2 r e c r y s ta l l iz a t io n s a l l a c e to n e w as r e m o v e d fro m the p ro -: '
duct u # ln g o i l pum p y a c d u n i. T h e ,eq u ly a len t w p fgh t w a s 29:3 (th e o r e t ic :
c a l .294, 5), m e lt in g p o in t 17 . 8 -1 8 . 0o C , and. n^ 5 1. 4 6 5 0 . I ’a u re and
S m ith (14) r ep o r te d ra . p . 18, 2^ C . and n ^ 0 1 . 4 6 4 3 , ,
30
A s m a ll p y r e x r e a c t io n v e s s e l w ith a n itr o g e n b iib b ler apd a p o r t
for w ith d ra w in g s a m p le s w a s co n stru cted ,, It wras s e a le d in s id e a D ew a r
f la s k eq u ip p ed w ith a n ic h r o m e h e a t in g - c o i l and a r e f lu x c o n d e n se r . T h e
■ tem perature w a s m a in ta in e d at 98 C„ d u rin g the p o ly m e r iz a t io n h y
h o ilin g w a te r in ;the D ew a r f la s k . . ■
T w en ty m l . o f s t e r c u l ic a c id (c a . 18 g r a m s) w a s p ip e tte d in to th e
•rea c tio n v e s s e l . S a m p le s w e r e r e m o v e d at in te r v a ls fo r d e te r m in a tio n
of e q u iv a le n t w e ig h t and r e fr a c t iv e in d e x , h i a d d itio n , la r g e r sa m p le s .
W ere r e m o v e d a fte r 30 m in u te s and 1.00 m in u te s fo r d e te r m in a tio n o f
in fr a r e d s p e c tr a and unsaturati-on . ' ' ■
E q u iv a le n t w eights: w e r e d e te r m in e d h y w e ig h in g a d r o p o f th e
p ro d u ct on a ta r e d g la s s c o v e r s l ip , d is s o lv in g i t in a c id - f r e e e th an o l
and t itr a t in g w ith 0. 0 108 N b a r iu m h y d ro x id e to th e p h en o l r e d en d
p o in t. A s th e p o ly m e r iz a t io n p r o c e e d e d ; th e p ro d u ct b e c a m e qu ite
in s o lu b le id e th a n o l an d th e tr u e e q u iv a le n c e p o in t w a s d if f ic u lt to ’
o b s e r v e due to thd fa d in g en d -p o in t . '
' I te fr a c t iv e in d ic e s w e r e d e te r m in e d at 2 5 ° C . w ith an Abbe r e f r a c -
to m e te r . F ig u r e s 6 and 7 sh o w th e ch a n g e in eq u iv a le n t w e ig h t and: •
r e fr a c t iv e - in d e x with, tim e.- , : - 'e .-.I ■ ,, v. ; ■: : . ; ;
T he u n sa tu r a tio n e q u iv a le n t w a s d e te r m in e d w ith th e b r o m in e -
sod iu m b ro m id e 'rea g en t d e s c r ib e d b y B y rn e and Joh n son , (9 ). V a lu es
found w e r e a s fo llo w s :
V . ' e q u iy a le n t w e ig h t . \',v \ . ■ ;: v ' ^ .• ■ ' ■ - ; p e r b ro m in e ;v- ■
n reth y l o le a te ' .299 , ( th e o r e t ic a l 2 96o 5 )
s t e r c u l ic ai:ci.d ' ^ 227 . ( th e o r e t ic a l 147 fo r 2 : ' y . ' Br^. p h r 'm o le c u le )
30r-mirtote p o ly m e r iia a tio a 496
'iOO mimdre p o lym eris^ a tioa 1130
19 h o u r p o ly tn er iK a tio n ' 2100 . • ,
•The in tr in s ic v i s c o s i t y o f the, p o ly m e r w as .d e te rm in ed in a 4 c c .
O stw a ld v is corn et ex in c h lo r o fo r m so lu tion ,, In tr in s ic v i s c o s i t y i s ,
d e fin e d (49) as [l^j s .sp' w h e r e ^ and ‘ i s \V' c . '^Pr_ - r e ■ re ,
th e t im e r e q u ir e d fo r th e so lu t io n o f c o n c e n tr a tio n c (g r a m s p e r 100
g ra m s so lv e n t) to pass th ro u g h th e y is c o m e t e r c a p il la r y .d iy id ed by th e
t im e r e q u ir e d fo r th e p u re so lv e n t to p a s s th rou gh . T he r e s u l t s a r e
sh o w n in F ig u r e 13. . T he in tr in s ic v i s c o s i t y found (0. 105) i s c h a r a c
t e r i s t i c o f lo w m o le c u la r w e ig h t p o ly m e r s .
T he in fr a r e d s p e c tr a o f s t e r c u l ic a c id , th e r e a c t io n m ix tu r e a fte r
30 m in u te s at 9 8 ° G. and th e f in a l r e a c t io n m ix tu r e a f te r 19 h o u rs at
98°G . a r c sh ow n in F ig u r e 4 , • ,
H y d ro iy S is o f th e P o ly m e r ;' ' .
T h e sa p o n if ic a t io n e q u iv a le n t w a s d e te r m in e d by r e flu x in g 8, 175
g ra m s o f th e p o ly m e r w ith 7 5 m l . a lc o h o lic p o ta s s iu m h y d ro x id e fo r 2
h o u rs .. A b lank w as run s im u lta n e o u s ly . T he e x c e s s b a s e w a s th e n
t i t r a te d w ith Z. 25 N h y d r o c h lo r ic a c id . T he sa p o n if ic a t io n eq u iv a len t
w as 296= 5 ( th e o r e t ic a l 2 9 4 , 5). A fte r a d d itio n o f e x c e s s h y d r o c h lo r ic
a c id , th e d e p o ly h ie r ia e d a c id s w e r e e x tr a c te d wdth e th y l .e th er , d r ie d
o v e r so d iu m s u lfa te and m a g n e s iu m s u lfa te and th en th e e th e r w a s
e v a p o r a te d u n d er v a c u u m .; T he r e s u lt in g a c id (s ) had. a n eq u iv a le n t
w eig h t o f 3 1 6 -3 1 8 ( th e o r e t ic a l 312 . 5 fo r a d d itio n o f T h ey w e r e
so lu b le in h e x a n e , c a rb o n te tr a c h lo r id e , e th a n o l, and d e c o lo r iz e d a
S d lu iib n . o f b ro m in e in ca rb o n t e tr a c h lo r id e .
A ttem p ts to h y d r o g e n a te th e p o ly m e r in b en zen e u s in g a p a lla d iu m
on c a lc iu m ca r b o n a te c a ta ly s t (8) at a tm o s p h e r ic p r e s s u r e and room
.te m p e ra tu re w e r e u n s u c c e s s fu l . , T h e d e p o ly m e r iz e d a c id s in e th an o l
W ould n ot h y d ro g en a te u n d er S im ila r c o n d it io n s . A 1. 3 g ra m sa m p le b f
th e d e p o ly m e r iz e d a c id s w a s h y d r o g e n a te d in a P a r r a p p a ra tu s in
a b so lu te edhanol u h in g a p la tin u m , c a ta ly s t i l ) in id e f 50 pounds p r e s s u r e
at ro o m te m p e r a tu r e fo r 24 h o u r s . T h e p ro d u ct s t i l l d e c o lo r iz e d b r b - :
m in e in c a r b o n t e tr a c h lo r id e , but c r y s t a l s fo r m e d in th e f la s k a fte r
S e v e r a l d ays s ta n d in g . S im ila r tr e a tm e n t o f the p o ly m e r ( in e th an o l
and e th e r d r in g la c ia l a c e t ic a c id ) d id n o t e f f e c t h y d r o g e n a tio n .
P a r r: In s tr u m en t G o . , M o lin e , I l l in o is „
S m a ll anaounts (cac, 100 mg„ ) o f th e d e p o ly m e r iz e d a c id s and th e
h yd ro gen at e d, dep o ly m e r iz e d a c id s w e r e e s t e r if le d w ith d ia zo m e th an e
a s p r e v io u s ly d e s c r ib e d (26)« T he m e th y l e s t e r s w e r e a n a ly z e d by
m e a n s o f gas ch ro m a to g ra p h y ^ A W ilk in s gas'•ch rom atograp h^ w ith a
5-fO ot C r a ig p o ly e s t e r co lu m n w a s u sed , fo r th e s e p a r a t io n . T h e O per
a tin g co n d itio n s w e r e .as. ib l l o w s : te m p e r a tu r e 2 1 0 2 2 o Go , h e liu m p r e s -
s u r e 26 p o u n d s, f lo w ra te 200 m l , p e r m in u te . T h e re 'su lts a r e sh o w n
in T’ig u r e 3 . On e m e r g e n c e th e com p ou n d s w e r e c o l le c t e d on co tto n
p lu g s in g la s s tu b e s « T h e y w e r e e lu te d w ith ca rb o n te tr a c h lo r id e and ,
th e ir in frared ; s p e c t r a w e r e d e te r m in e d (F ig u r e s 8 , 9 , T O), F r a c t io n s
A and B (F ig u r e 3) o f th e d e p o ly m e r iS e d a c id s d id not d e c o lo r iz e b r o
m in e in ca rb o n t e t r a c h lo r id e , w h ile f r a c t io n C d id . N on e o f th e f r a c
t io n s fr o m th e h y d ro g en a ted dep Olym e r i z e d a c id s d e c o lo r iz e d b ro m in e
in ca rb o h t e tr a c h lo r id e .
P r e p a r a t io n o f M o d el C om pounds
Tw o m o d e l com p ou n d s w e r e p r e p a r e d fo r c o m p a r is o n w ith th e
d e p o ly m e r iz e d a c id s . A m ix tu r e o f th e 9 - and 10 - i s o m e r s of h y d r o x y -
s t e a r ic a c id w a s p r e p a r e d a c c o r d in g to th e m eth o d Of K night et a l . (1 9 ).
A fter r e c r y s ta l l iz a t io n fro m h e x a n e , th e m .p , w a s ? 3 -7 4 ° C . J^lit, 7 2 -
7 3 °C , (19)J . A s a m p le w a s c o n v e r te d to th e m e th y l e s t e r u s in g
:‘W ilk in s In stru m en t and R e s e a r c h , .The, > W alnut G r o v e } C a lif .
D E
A_A_________ ___0 8 16 24 32 40 48 56 64 1------------------------------ 1------------------------------ 1------------------------------ 1____________________I___________________ I____________________ I__________ I___________________ L _
TIME (m inutes)F igu re 3. Gas C hrom atographic S eparation o f D ep o ly m erized A cid s M ethyl E s te r s .
1. D ep o ly m er ized A cid s.2. D ep o ly m erized A cids a fter H ydrogenation.3. C om posite C hrom atogram
D. M ethyl D ih y d ro stercu la te .E. M ethyl S tercu la te .F. M ethyl 9 & 10 -K e to ste a ra te .G. M ethyl 9 & 10 -H y d ro x y stea ra te . UJ
d iazom eth an e« A m ix tu r e o f th e 9“ and 1 0 - i s o m e r s o f k e to a te a r ic
a c id w a s p r ep a r e d fro m th e c o r r e sp o n d ih g h yd r oxy c om pound b y c h r o m ic
o x id e o x id a tio n a c c o r d in g to th e m eth o d o f R o ss e t a l, (3 2 ). A fte r
r e c r y s ta i l iz a t io n fr o m a c e to n e -p e tr o le 'u m e th e r th e m . p . w a s 61 - 6 3 , 9 C .
i t , 8;2 °C . fo r 9 “k e t o s t e a r ic 3 7 2 -7 3 ° C . f o r 10 -k e to s t e a r ic (32 )1 „ A
sa m p le o f t h i s a c id w a s c o n v e r te d to th e m e th y l e s t e r by re flu x in g in ,
m e th a n c d w ith a d ro p o f s ia lfiir ic a c id . : , ■
T h e se tw o com p ou n d s w e r e ch ro m a to g r a p h e d u n d er th e s a m e con "
-d ition s a s th e e s t e r s o f th e d e p o ly m e r iz e d a c id s . T h e r e s u l t s a r e sh o w n
in F ig u r e 3 . ■ ■ /''k':.:, \ ; . , , / ( /■ , t .. 1 ^
(bcidatlon P r o c e d u r e -
F r a c t io n C (F ig u r e 3) (57 m g„ ) fro m s e v e r a l s u c c e s s iv e gas c h r o
m a to g ra p h runs 'of th e e ster s of th e d e p o ly m e r iz e d a c id s w a s c o l le c te d
on a co tto n p lu g . It w a s e lu te d w ith s'o m l . o f 40% te r t -b u ta n o l and o x i
d iz e d w ith a p e r m a n g a n a te -p e r io d a te r e a g e n t a c c o r d in g to th e p r o c e d u r e •
o f v o n R ud lo ff (4 8 ). Into a 500 m l . g la s s S top p ered e r le n m e y e r w e r e
'put: 60 m l . o f s to c k o x id an t so lu tio n (.20 .86 g ra m s so d iu m m e ta p e r io -
d ate and 250 m l . 0 . 01 M p o ta s s iu m .p erm a n g a n a te p e r l i t e r ) , 30 m l.
w a te r c o n ta in in g 75-m .g. p o ta s s iu m c a r b o n a te and 180 m l . te r t" b u ta n o l.
T o th is so lu t io n w a s a d d e d t h e 30 m l . o f 40% t e r t “b u ta n o l co n ta in in g 57
m g . o f fr a c t io n C . T h e so lu tio n w a s p la c e d on a sh a k e r a t room ■
' V ; v ; . _ ; 3 6
te m p e r a tu r e and sh a k en fo r 4 h o u r s . A 65 m g . s a m p le o f m e th y l o le a te
w a s tr e a te d s im i la r ly . A fte r 4 h o u rs th e o x id a tio h w a s s to p p ed by
a d d itio n o f e x c e s s so d iu m b is u lf i t e . .A p p ro x im a te ly 2 g r a m s o f p ot a s - .
s lu m h y d ro x id e p e l l e t s w a s ad d ed and th e so lu t io n s w e r e h e a te d on a
r o ta r y e v a p o r a to r u n til a l l th e liq u id w a s e v a p o r a te d . T he r e s id u e s
w e re th en a c id if ie d w ith s u lfu r ic a c id and e x tr a c te d s e v e r a l t im e s w ith
e th y l e th e r . T h e e t h e f e x tr a c ts w e r e t r e a t e d w it h d ia z o m e th a n e to
e s t e r i f y th e a c id s , and th e e th e r w a s e v a p o r a te d . G as ch ro m a td g ra p h y
u s in g th e 5 -fo o t A p iezo n co lu m n sh o w ed d im e th y la z e le a te (show n to be
id e n t ic a l w ith a u th en tic d im e th y la z e le a te by In fr a r e d S p ec tra ) p r e s e n t
in both p r o d u c ts , but on ly a s m a ll a m o u n t o f m e th y l p e la r g o n a te fro m -'
fr a c t io n G and none fr o m th e m e th y l o lea te* In sn ffid ie n t p o ta s s iu m
h y d ro x id e d u rin g th e h e a tin g p r o c e s s w a s th e p ro b a b le c a u s e o f th is
l o s s . . A n oth er sa m p le o f m e th y l o le a te o x id is e d s im i la r ly but e v a p o r -
ated w ith c a . 5 g r a m s p o ta s s iu m h y d ro x id e p r e s e n t sh o w ed p e a k s c o r
r e sp o n d in g to both d im e th y la z e le a te and m e th y l p e la r g o n a te .
I so m e r iz a t io n o f M eth y l S te r c u la te . '
: ' G aS 'G hrom atdgraphic ' >•
: A s a m p le o f m e t h y l s t e r c u la te , p r e p a r e d f r o m s t e r c u l i c a c id by
a c tio n , o f d ia zo m eth an e (26), w as c o l le c t e d a fte r gas 'ch ro m a to g ra p h y
u s in g th e 5“fo o t C r a ig P o ly e s t e r C o lu m n a t 21G0 C.„ T h e in fr a r e d and
' u ltr a v io le t S p ec tra o f th is com pound c o m p a r e d to th e o r ig in a l m e th y l
'S tercu la te a r e sh ow n in F ig u r e s 11, 12, and 14. .
A ;sa m p le o f m e th y l s t e r c u la te ( IvZ g r a m s ) w a s p la c e d in a 10 m l .
2 -n e c k e d f la s k eq u ip p ed with: an a ir c o n d e n se r and a n it r o g e n bubbler»
It w‘3 s p la c e d in an o i l bath p r e h e a te d to 100£.2 C. S a m p le s w e r e w ith
draw n at v a r io u s t im e s , and th e u lt r a v io le t s p e c tr a w e r e d e te r m in e d .
A fte r 2 h o u r s h e a t in g , no ch an ge in th e s p e c tr u m w a s n o te d . T he
s a m p le w a s .then t r a n s f e r r e d to a n o th er o i l h a th at 1 98°C„ ' T he ch an ge
in. th e u lt r a v io le t sp e c tr u m w ith t im e is sh o w n in F ig u r e 14, A fter 16
h o u rs ‘h e a t in g , an a tte m p t w a s m a d e to d i s t i l l th e p r o d u c t u n d er va cu u m
No m a te r ia l w o u ld d i s t i l l b e lo w 2 3 5 ° C» w ith a vacu u m e s t im a te d a t 0 . 1
m m . A p a le y e llo w o i l d is t i l le d b e tw een 235™ 250°C. T he u ltr a v io le t
a b so r p tio n sp e c tr u m d if fe r e d S o m ew h a t fr o m th a t o f th e m a t e r ia l p r io r
to th e d is t i l la t io n . Its r e te n t io n t im e in.-the gas chrG m atpgraph; a t
2 1 0 o C , , 200 m l . /m in . h e liu m flo w , w a s 19 m in u te s c o m p a r e d to 13 .
fo r m e th y l s t e r c u la te . T he in fr a r e d s p e c tr u m sh o w e d th e com pound to
DISCUSSION A ND CONCLUSIONS
P o ly m e r iz a t io n o f S ter .cu llc A c id : : ,
T he p o ljn m erixa tion o f s t e r c u l ic a c id c a r r ie d out at 9 8 0C» in an
in e r t a tm p sp h e r e p ro d u ced a v i s c o u s s lo w m o le c u la r w e ig h t p o ly m e r .
Infra.red s p e c tr a (F ig u r e 4) sh o w ed th a t d u r in g th e c o n r s e o f th e p o ly -
m e r iz a t io n th e c y c lo p ro p en e r in g a b sd fp t io n n e a r 1 0 2 0 c m ” d isa p p e a r e d
a lo n g w ith a band at 1880 ass'ign ed . by F a u r e and' S m ith (14) to th e
c y c lo p r p p e n e r in g S tr e tc h in g v ib r a t io n . A d is t in c t band at 1 655 c m ” ,
in a r e g io n c h a r a c t e r is t ic df dou b le bonds (20 A ), a p p ea red ; th e p r in c i
p a l c a r b o x y l group a b so r p tio n s h if te d fr o m 1720 to 1745 c m ” > in d ic a
t iv e o f th e ch a n g e o f a c a r b o x y lic c a c id to ■an e s t e r (20 H ), a lth ou gh a
"weaker /abadrp'tidn^'rerttained n e a r 1720 crn” 0 T he b ro a d en in g o f th e
C-=—H s tr e tc h in g v ib r a tio n a b so r p tio n n e a r 3000 c m “ ^, c h a r a c te r is t ic
,o f c a r b o x y ll ic a c id d im e r s (20 F ) , a ls o d isa p p e a r e d a s th e p o ly m e r iz a
tio n p r o g r e s s e d . N o band r e m a in e d i n th e 9« 5 to 10. Qjjl ran ge (1053 to
1000 c m ” -*-) a s s ig n e d by S la b e y (41) to c y c lo p r o p a n e r ih g v ib r a tio n s ;
th e r e fo r e , it i s u n lik e ly th a t th e p o ly m e r is a t io n p r o g r e s s e d by th e
m e c h a n is m (1) s u g g e s te d by Nunn (28). On tb e o th e r h an d , th e appear-* ;•
a n ce . o f a band in the. c a r b o n -c a r b o n d o u b le bond r e g io n a s .fir s t r e p o r te d
39W A V E L E N G TH IN M IC R O N S
90-
-10-
30-
20-
3 0
2 0 —
10-
1800 1700 1600W A V E N U M B E R IN CM'*
1200 9001500 1400 1300 "1100" 10002500 19003000 200000
F ig u r e 4. In fra red S p e c tr a . Top: S te r c u lic A cid ; M idd le: S te r c u lic A c id a fte r 1 /2 H our P o ly m e r iz a t io n at 9 8 °C . ; B o tto m : S te r c u lic A cid a fte r 19 H ou rs P o ly m e r iz a t io n at 9 8 °C .
. by F an re a n d S m ith (14) lends; su p p o rt to th e ir m e c h a n is m (II) „ F ig u r e
5 sh o w s in d e ta il a ty p ic a l p o ly m e r w h ich m e ch an iS m (II) w ou ld p ro d u ce
and it s e x p e c te d h y dr o ly s is p ro due t s „ F r o m the in fr a r e d s p e c tr a and
th e e ^ iv r a le n t W eight, d e te r m in a t io n s , i t appearB c e r ta in th a t th e p o ly
m e r iz a t io n in v o lv e s an e s t e r i f ic a t io n r e a c t io n , '
A s th e p o ly m e r iz a t io n p r o g r e s s e d , th e ap p aren t am ou n t o f u n s a t
u r a tio n , a s d e te r m in e d by a so d iu m b r o m id e -b r o m in e r e a g e n t , d e c r e a s e d
(9)o A lthbugh th is s e e m s to fa v o r th e m e c h a n is m s u g g e s te d by N unn,
both c h a in -b r a n c h in g h n d S u b stitu tio n o f e le c tr o n e g a t iv e grou p s on a
e a r b o n -c a r b o n double bond In h ib it b r o m in a t io n by th is r e a g e n t (9 )«,
zfC her^efore,: if. th e p o ly m e r iz a t io n p r o g r e s s e d a c c o r d in g to m e c h a n is m (II),
S im ila r r e s u lt s m ig h t be e x p e c te d . F a ilu r e o f th e p o ly m e r to h y d r o g e n - ;
a te m a y be e x p la in e d on a s im i la r b a s is . D ue to th e s i z e a n d b r a n c h in g
o f th e p o ly m e r , c o n ta c t w ith th e h y d ro g en at th e s u r fa c e o f the c a ta ly s t
w o u ld be d if f ic u lt . O th er h ig h ly b ra n ch ed o ie f in ic com p ou n d s a r e know n
to r e q u ir e 100 * a tm o s p h e r e s p r e s s u r e and h ig h t e m p e r a tu r e to e f fe c t
h y d r o g e n a tio n (2 ).
S in c e th e p o ly m e rization - w a s c a r r ie d Out h ea t r a th e r th au i n ‘S o lu
t io n , and S in c e t h e r e a r e m a n y r e a c ta n fs ae w e l l aS; p rpductsi d if fe r in g > ;
in d e g r e e o f .p o ly m eZ iza tiO n ,: no a b so lu te s ta te m e n t c a n h e m a d e c o n e e r n -:
in g th e k in e t ic s o f the r e a c t io n . H o w e v e r , • m a k in g th e a p p r o x im a tio n ■ •
th a t th e f r e e e a r b p x y i group and th e c y c lo p r o p e n e r in g h a v e the s am e
41F ig u r e 5.
M ec h a n ism II fo r the P o ly m e r iz a t io n o f S te r c u lic A c id .C ^ 2
c h 3( c h 2 ) 7c = = c ( c h 2 )7c o 2h
P o ly m e r iz a t io n
19 h o u r s , 9 8 °C .
C H ,\\
CH3 0 2 C (C H 2 ) 7C -C H = C H (C H 2 )6 CH3
C H 3 (CH2 ) 7C = C ( C H 2 ) 7 c o 2
C H ,I 3
CH2 - 0 2 C (C H 2 )7 C =rC (C H 2 )7 C H 3
(a) CH 3 (CH2 )7C = C H (C H 2 )7 C 0 2 -C H 2
0 2 C (C H 2 )7 -C = C H (C H 2 )7 CH3
9 H 3 |(b) CH 3 (CH2 ) 7C = C (CH2 ) 7C 0 2H
a lk a lin e h y d r o ly s is ,
a c id if ic a t io n
^ d ia zo m eth a n e e s t e r i f ic a t io n
CHoOH I L
C H 3 (CH2 )7 C = C H (C H 2 )7C 0 2 C H 3 (III)
+ c h 2 o h C H 3 (CH2 ) 7 C H = C (CH2 ) 7c 0 2 CH3 (IV)
+ C H .I 5
C H 3 (CH2 )7 C H -C (C H 2 )7C 0 2 CH3 (V)
0
c h 31 5
CH3 (CH2 ) 7 C—HC(CH2 ) 7C 0 2 CH3 (VI)
o
P 2CH3 (CH2 )7C C H = C H (C H 2 )6 C 0 2 C H 3 (VII)
r ^ c t i W y r e i ^ o f |h e S iise to w h ich th e y a r e a tta ch ed ,
a l l m o le c u le s p r e s e n t in th e m ix tu r e ca n be c o n s id e r e d r e a c ta n ts . E a ch
r e a c tan t h a s one fr e e c a r b oxy 1 group and. one c y c lo p ro p eh e r in g. ■ T h e r e -
fo r e , c a r b o x y l group t itr a t io n w i l l r a e a s u r e th e 'co h cen tra tio n * o f
r e a c ta n ts r e m a in in g at any tim e., s in c e e q u iv a le n t w e ig h t is p r o p o r tio n a l
to (c o n c e n tr a t io n )" ^» R e a c tio n s in s o lu t io n fo llo w in g s e c o n d o r d e r k in e
t ic s c h a r a c t e r is t ic a l ly g iv e a s tr a ig h t l in e w hen (c o n c e n tr a t io n )- is
p lo tte d v e r s u s t im e (16 ). T he data ob ta in ed fro m th e p o ly m e r iz a t io n
c a r r ie d out at 980 C» s h o w s (F ig u r e 6 ) th at th is s tr a ig h t l in e r e la t io n s h ip
h o ld s at l e a s t in th e e a r ly s ta g e s pi the p o ly m e r iz a t io n . N unn's data (28)
fo r th e p o ly m e r is a t io n a t 9 6 C . sh o w s a .s im ila r r e la t io n sh ip .(F igure 6 ).
T he k in e t ic s q f-th is r e a c t io n a r e th e r e fo r e a n a lo g o u s to th os e o f a
se c o n d o r d e r r e a c t io n in S o lu tio n , ; T h e d ev ia tid n fr o m s e c o n d o r d e r
k in e t ic s in th e la t e r s t a g e s Of th e p o ly m e r iz a t io n m a y be due to a. s e c
on d ary r e a c t io n ta k in g p la c e w h ich d e s tr o y s so m e o f th e r e a c ta n ts , o r
th a t th e la r g e p o ly m e r s fo r m e d a r e l e s s r e a c t iv e than th e lo w e r m o le c
u la r w e ig h t m o le c u le s d u e to s t e r ic fa c to r s or v i s c o s i t y o f t h e s o lu t io n . .
T h e e x is t e n c e o f a s e c o n d a r y r e a c t io n is l ik e ly b e c a u s e th e in fr a r e d
S p ectrU m of th e p o ly m e r (F ig u r e d) sh o w ed th e p r e s e n c e o f f r e e c a r b o x y l
groups., but h o c y e ld p r o p e n e r in g . ; _ .. . ;
JU kaline h y d r o ly s is o f a s a m p le o f th e p o ly m e r ga y e a s a p o n if ic a
t io n eq u iv a le n t o f 2 9 6 . 5> w h ich i s in a g r e e m e n t w ith th e m o le c u la r w e ig h t
2000 _ 43
1750
1500
£ 1250
Su 1000
g§ 750
gI 500s250
0 ____________ I____________I____________I____________I____________I50 100 150 200 250
TIME (m inutes)F igu re 6. Change in E quivalent W eight D uring the P o ly m er iz a tio n
o f S tercu lic A cid .4800
1 .4 7 5 0
1 .4 7 0 0o
N Q
p
1 .4 6 5 0200 250100 150500
TIM E (m inutes)F igu re 7. Change in R efra c tiv e Index D uring the P o ly m e r iz a tio n
of S tercu lic A cid .
© 98°c.
• 96°C . (Nunn)
44
o f th e s ta r t in g m a te r ia l , s t e r c u l ic a c id (ea lco 2.94. 5), T itr a tio n o f th e
a c id s p ro d u ced by h y d r o ly s is o f the p o ly m e r (h e r e a fte r r e f e r r e d to a s
th e d e p o ly m e r iz e d a c id s )$ h o w e v e r , c o n s is 'ta n tly ga v e equ ivalent: w e ig h t "
v a lu e s in th e ra n g e 3 1 6 -3 1 8 . T h is i s 1„ 7 % ab ove th e v a lu e 'w hich w ou ld
be e x p e c te d i f s te r c .u lic acid , had added th e e le m e n ts o f w a te r (c a lc .
3 1 2 . 5). T he d e p o ly m e r iz e d a c id s w e r e e s t e r i f ie d and th e e s te r S p a s s e d
th rou gh th e gas c h r o m a to g r a p h to y ie ld th r e e fr a c t io n s , c a l le d .A, B,.
and G (F ig u r e 3). H y d ro g en a tio n o f th e d e p o ly m e r iz e d a c id s fo llo w e d
by e s te r i f ic a t io n and gas c h ro m a to g ra p h y o f th e e s t e r s r e s u lte d in a
d e c r e a s e in th e r e te n t io n t im e s o f fr a c t io n G and a m a jo r p o r tio n o f A
but d id n ot a f fe c t B .
T he in fr a r e d "Spectrum as w e l l a s th e retention: t im e o f fr a c t io n B
w as id e n t ic a l b e fo r e a n d a fte r h y d r o g e n a tio n o f th e d e p o ly m e r ik e d a c id s .
Its In fr a r e d s p e c tr u m (F ig u r e 8 ) sh o w ed tw o sh a rp c a r b o n y l b an d s, one
at 1 740 c m ” '*' c h a r a c t e r is t ic o f e s t e r s , and th e o th er a t 1710 cm "^ a
r e g io n w h e r e a lip h a tic ketO nes a b s o r b (20 G). G O m parisbn o f t h i s s p e c ~
trU m to th e S p ec tru n x ' o f m e th y l 9 - and 10-k e to S te a r a te (F ig u r e 8 ) p r e
p a r e d a s a m o d e l com p ou n d , sh ow s, th at th e y a r e v e r y s im i la r . T h u s , .
fraction B appears t o he a keto-ester, probably a mixture of methyl
9 -* m e th y l-1 0 -k e to s te a r a te (VI, F ig u r e 5) and m e t h y l l 0 - m e t h y l- 9 -k e to ~
S te a r a te '(V, F ig u r e 5). ■ ' / ; ■ .vp .' ■ < : , '■
45
WAVELENGTH IN MICRONS
■ • ^ i l l i i1400 iS o 1205 ii<S5 R » • 5MOO 1900 1800 1700 1600 1500
WAVENUMBER IN CM '
F ig u r e 8 . In fr a red S p e c tr a . T op: G as C h ro m a to g ra p h F r a c t io n B; B o tto m : M eth y l 9 - and 10 -K e to s te a r a te .
, The in ir a r e d sp e c tr u m o f fr a c t io n C o f the m e th y l e s t e r s o f th e ; h
d e p d ty m e x ite d a c id s (F ig u r e 9) sh o w s an ahso.rption. in th e 3600 cm "-1-
r e g io n c h a r a c t e r is t ic o f a lc o h o ls (20 E) and a b so r p tio n s in th e 1640
and 900 cm " r e g io n s c h a r a c te r is t ic o f double bonds (20 B)„ A fte r . •
h ydrogenation:, th e in fra red ' sp e c tr u m (F ig u r e 9) sh o w ed th at th e d ou b le
bond p ea k s at 1640 and 900 c m ” -1- h a d .d isa p p e a r e d , but th e w ea k a b s o r p -
, tion . n e a r 36.00 c m ™-1 r e m a in e d , A m o d e l com p ou n d , m e th y l 9~ and 1 0 -
h y d ro x y ste a ra te :, show ed, a s .im iia r , a lth ou gh s tr o n g e r , a b so r p tio n ( F ig
u r e 9) n e a r 3600" c m - . - V,'
O xidation o f fr a c t io n C u s in g a p e r io d a te -p e r m a n g a n a te r e a g e n t
(48) r e s u lt e d in th e p r o d u ctio n of a z e la ic a c id and p e la r g o n ic a c id ,
llh e se : p r o d u c ts ar:e;cdhM s tr u c tu r e co n ta in in g a su b stitu te d
a l ly l a lc o h o l , S in ce th is r e a g e n t w ou ld o x id iz e th e a lc o h o l ca rb o n to
'Carbon d io x id e . i B a se d on th is in fo r m a tio n , fra c tio n . C i s p ro b a b ly a ' : ’
n a ix tu re o f m e th y l 1 0 -» m eth y lo lo lea te ( i l l . F ig u r e 5) and m e th y l 9 ~ m eth y l~
o io le a te (IlT, F ig u r e 5). .
T he in fr a r e d S p ec tru m (F ig u r e l d( and r e te h f io n t im e (F ig u r e 3)
-O f'fraction A o f th e d e p o ly m e r iz e d a c id s w e r e s im i la r to th e in fr a r e d ■ • v :
sp e c tr u m (F ig u r e 11) and r e te n t io n t im e (F ig u r e 3) o f ch rO m atograp h ed
m e th y l s t e r c u la te . T h is in d ic a te s th at fr a c t io n A c o n s is t e d p a r t ia l ly o f
m e th y l s t e r c u la te or an is o m e r iz a t io n p ro d u ct o f i t . T h e r e te n t io n t im e
of fr a c t io n , A in d ic a te s th e abSenc e o f a: S econ d o x y g e h a te d fu n ctio n a l
47WAVELENGTH IN MICRONS
- 1 0 - r
m
20-
1300 1200" "110014001800 1700 ' 1600 'W AVENUMBER IN CM '
1500:ooo2500mo
F ig u r e 9. In fr a red S p e c tr a . T op: G as C h ro m a to g ra p h F r a c t io n C;M id d le : G as C h ro m a to g ra p h F r a c t io n C (a fter H y d ro g en a tio n o f th e P o ly m e r ) ; B ottom : M eth y l 9 - and 1 0 -H y d r o x y s te a r a te .
48WAVELENGTH IN MICRONS
5 0-
50-
4D-
11001400 1300 120025003000WAVENUMBER IN CM '1
F ig u r e 10. In fr a red S p e c tr a . Top: D e p o ly m e r iz e d A c id s ; M id d le : G asC h ro m a to g ra p h F r a c t io n A; B otto m : G as C h ro m a to g ra p h F r a c t io n A (a fte r H y d ro g en a tio n o f th e P o ly m e r ) .
49
WAVELENGTH IN Ml'
m m m u m
1800 1700 i« 5o fsbd 1365 tabs i w iw TW AVENUMBER IN CM '
F ig u r e 11. In fr a red S p e c tr a . Top: M eth y l S te r c u la te ; B o tto m : G as C h ro m a to g ra p h I s o m e r iz a t io n P r o d u c t o f M eth y l S te r c u la te
AB
SOR
PT
ION
, A
RB
ITR
AR
Y
UN
ITS
5
4
3
2
1
0235 240 245230225
50
W AVELENGTH mj*
F igu re 12. U ltra v io le t A bsorp tion S p ectra of:A. Gas C hrom atograph Iso m e r iz a tio n P rod u ct of
M ethyl S tercu la te .B. D ep o ly m er ized fatty a c id s .
. 1 4 -
A 01. 0 1. 5 2 . 00. 50
C $ 7 100 c c .
F igu re 13. In tr in sic V isc o s ity of S tercu lic A cid P o ly m er in C hloroform Solution .
group . T he u lt r a v io le t s p e c tr u m o f th e d e p o ly m e r iz e d a c id s (F ig u r e 12)
sh o w ed an a b so r p tio n m a x im u m at 231 rn^i, a r e g io n c h a r a c t e r is t ic o f
conlu-gated d ieiieis • (30), ■ M elth er a c id (2'^) n o r i t s m e th y l e s t e r
(F ig u r e 14) h a v e an a b so r p tio n m a x im u m in th is r e g io n . H o w e v e r ,
; m e t h y l Ate r e f la t e after- p a ss in g : th ro u g h th e gas c h ro m a to g ra p h atZlO P.G ,
o r h e a te d in ant in e r t a tm p sp h ere . sh o w ed su ch an a b sp fp tid n ( F ig u r e s ; 12
l 4 i« : T herefchre, i t i s l ik e ly th at a cco m p a n y in g th e p o ly m e r iz a t io n r e a c
t io n , a s im u lta n e o u s is o m e r iz a t io n o c c u r r e d to a s m a ll e x te n t , w h ich
m a y b a v e l im ite d th e d e g r e e o f p p iy m e r iz a t io h , ' -. . / . -
:i ■ ;: T he c h r o m a to g r a m o f th e m e th y l e-sfeaS d f th e d e p o ly r n e r iz e d a c id s
a f te r h y d f b g eh a fio n (F ig u r e 3) sh o w ed a n in c r e a s e in th e s i z e o f th e m a in
co m p o n en t o f fr a c t io n A r e la t iv e to fr a c t io n s B and C , - T h is m a y h a v e
b een due to. a p a r t ia l r e d u c tio n o f th e n lly lic a lc o h o l grpup o f fr a c t io n C
to th e 'c b r resp o n d in g h y d ro ca rb o n . T h is r e a c t io n i s know n to a c c o m p a n y
n o r m a l h y d r o g e n a tio n o f su c h com p ou n d s (2 ),
' F rd m the p rp d u ctio n o f th e s e h y d r o ly s is , p r o d u c ts , a s w e l l as th e
in fr a r e d 'sp ec tru m o f th e p o ly m e r i t s e l f , i t is a p p a ren t th a t m ech a n ism
IT f i r s f p r ppds ed: by F a u r e a n d S m it h (14) fo r th e p o ly m e r iz a t io n of. : . • .
s t e r c u l ic ac id i s c o r r e c t , B as ed on th e r e la t iv e a r e a s u n d er th e c u r v e s
o f th e gas eh ro m a to g r a p h e d m e th y l e s t e r s d f the: d e p o ly m e r iz e d a c id s ,
t h e 'a l ly i e s t e r |"(a), F ig u r e 5^ i s fa v o r e d o y e r th e en o l e s t e r jjb)»
:F ig u re .5ri in the: p o ly m e r ,! , V f i t . : ^ ;
I g o m e r iz a ilo n o f M eth y l S te r c iila te , ' ' : ■ ' . ’ ,, ' \
, D u r in g th e r e s e a r c h co r icern ed w ith th e is o la t io n p f th e H alphen
r e a c t io n p ro d u c in g fa tty a c id fro m c o tto n s e e d o il , it w a s n o ted th at
the m e th y l e s t e r s o f fraction s, g iv in g -strong H alphen t e s t s g a v e , a f te r
gas c h r o m a to g r a p h y , no H alphen r e a c t io n at a l l . T h is was- found to be
t r u e a ls o o f m e th y l S te r c u la te , T he in fr a r e d s p e c tr u m o f a :Sam ple o f
m e th y l s t e r c u la t e a f te r v a p o r p h a se c h r o m a to g r a p h y a t 210°C » b e a r s
l i t t le r e s em b la n c e to th at o f th e o r ig in a l com pound (F ig u r e 11) ; th e
c y c lo p r o p e n e r in g a b so r p tio n at 1 0 2 0 cm d is a p p e a r e d c o m p le te ly a s
Vrell a s th e p e a k a t 1880 cm"1 ,, also- a s s ig n e d to the c y c lo p r o p e n e r in g
,(14)„ :%evr p ea k s ap p eared , at '8'84, 964 , 1 6 0 0 , and 1640 p m ” 1« T he
a b so r p tio n at 160 0 cm"*l is c h a r a c te r is t ic o f %C = Gj" s tr e tc h in g v ib r a
t io n s in co n ju g a ted d ie n e s (20 G); thds e at 1640 and 884 c m ” 1 h a v e b e e n
, L ■ .a s s ig n e d to th e ^C =,C f s tr e tc h in g and =C -H b en d in g v ib r a tio n s o f a
. . : , R j ' ■ ' P V, : , ; .group (20 A , 20 D ). T he a b so r p tio n at 964 c m ” h a s b een :
' 2 • . ' " ' . V : ■' ' _ - ■ ; ' v
a s s ig n e d to the=C -H b en d in g •v ibratioh o f a ^C — C group (20 D ),
N o a p p r e c ia b le s tr e tc h in g v ib r a t io n w ou ld be e x p e c te d fro m '
th is group as i t is s y x n m e tr ic a l ly su b s t itu te d (26 A|<, T h e u ltr a v io le t
a b sb r p fio n s p e c tr u m (F ig u r e 1 2 ) sh o w ed a m a x im u m at 231 t y ; m a x im a
in th is r e g io n a r e c h a r a c t e r is t ic o f co n ju g a ted d ie n e s (30) = T h u s, on
th e b a s is o f s p e c tr a l e v id e n c e , th e i s o m e r iz a t io n p r o d u c t o f m e th y l
5000
%X , 1 8 0 *
4000
960
30 0 0 -
2000
20
1000
250240220 230210W AVELENGTH
F igu re 14. Change in U ltra v io le t A b sorp tion Sp ectrum D uring Iso m e r iz a tio n o f M ethyl S tercu la te at 198° C.
T im e (in m in u tes) o f I so m er iza tio n .
s t e r c u la te i s p ro b a b ly a m ix tu r e o f m e th y l 1 0 -m e th y le n e o c ta d e c - 8 »
en o a te (VII) and m e th y l 9 -m e th y le n e o c ta d e c - 1 Ou-enodtef (Vlll«)„
: : ' •( v i l ) CH3 -(C H 2) 7 -G -C H = = C H -(C H 2 )6 -G 0 2 C H 3
(VIII) C H 3 w.(GH2 ) 6 ™ C H = a C H - C - (CH2 )7 - C 0 2 C H 3
W hen .e a r r ie d out n e a t in an in e r t a tm o s p h e r e , no is o m e r iz a t io n
(as m e a s u r e d by th e ch a n g e in u lt r a v io le t sp e c tr a ) o c c u r r e d at 1 0 O°C.
in 2 h o u r s . H o w e v e r , at 1 9 8 °C , the r e a c t io n w a s e s s e n t ia l ly c o m p le te
in 180 m in u tes» T h e u ltr a v io le t s p e c tr u m o f th e m e th y l s t e r c u la te a fte r
180 m in u te s is o m e r iz a t io n at 1 9 8 % ° (F ig u r e 14) w a s v e r y s im i la r to
th at o f m e th y l .s te r c u la te a f te r g a s c h ro m a to g ra p h y at 2 1 0 OC,, (F ig u r e
1 2 )° h o n g e r .p e r io d s o f is o m e r iz a t io n r e s u ite d in th e p r o d u c tio n o f
se c o n d a r y p r o d u e ts „ A fte r 16 h o u r s th e u lt r a v io le t s p e c tr u m ch an ged
c o n s id e r a b ly , r e p la c in g th e r a th e r sh a rp p ea k at 2 3 l eap- w a s a b ro a d
m axim um , ex ten d in g fro m 230-240tep , ( f ig u r e 14)°
D ue to i t s c y c lo p r o p a n e r in g , s t e r c u l ic a c id is an e x tr e m e ly
r e a c t iv e com,pound° A lthough th e r in g i s in e r t to c e r ta in r e a g e n ts S u ch
a s lith iu m a lu m in u m h y d r id e (28 ), i t is V e r y r e a c t iv e in th e p r e s e n c e o f
f r e e c a r b o x y l grou p s* T he p o ly m e r is a t io n r e a c t io n b e tw een th e f r e e
c a r b o x y l group o f s t e r c u l i c a c id and th e e y e lop r op en e r in g o c c u r s s lo w ly
55
at ro o m te m p e r a tu r e (28) but v e r y r a p id ly a t e le v a te d t e m p e r a tu r e s ,
A c o m p e t it iv e r e a c t io n in v o lv in g th e is o m e r iz a t io n o f th e c y c lo p r o p e n e
. r in g to a co n ju g a ted d ien e o c c u r s o n ly v e r y s lo w ly a t 98°C„ } but v e r y
ra p id ly a t 200°Cb W hen th e c a r b o n y l group o f s t e r c u l ic a c id is t ie d up
a s th e m e th y l e s t e r , no p o ly m e r iz a t io n o c c u r s , but th e is o m e r iz a t io n
r e a c t ip n is n ot a f fe c te d . S te r c u lia fo e t id a o il h a s b een repd:rted to
i$hde:rgo a v io le n t e x p tb e ir n ic r e a c t io n w h en h ea ted to 2 5 0 o Go (28). At
"• th is t e m p e r a tu r e , th e is o m e r iz a t io n r e a c t io n m a y be a lm o s t in s ta n ta n
e o u s , w ith th e r e s u lt in g e v o lu tio n o f h e a t a cco m p a n y in g th e c o n v e r s io n
to th e th e rm o d y n a m ic a l ly m o r e s ta b le fo r m . : : ■ ; f
SiUMMARY-
1. S te r c u lic a c id w a s found to c a u s e p ink e g g d is c o id r a t io n w hen fed
to la y in g .h e n s , D ih y d r o s te r c u lic a c id w ou ld not do th is .
2 . M ild h y d ro g en a tio n o f r e f in e d c o t to n s e e d o i l w a s found to e l im in a te
th e H alphen r e a c t io n a lm o s t im m e d ia te ly .
3 . U s in g v a r io u s p h y s ic a l p r o c e d u r e s , th e H alphen r e a c t io n p ro d u c in g
fa t ty a c id in c o t to n s e e d o i l w a s g r e a t ly c o n c e n tr a te d but w a s not
is o la te d , ' .
4 . T he p o ly m e r is a t io n r e a c t io n o f s t e r c u l i c a c id w a s found to fo llo w
a m ech h riiS m w h e r e b y th e c a r b o x y l group o f one a c id op en ed th e ,
c y c lo p r p p e n e r in g o f a n o th er at th e s in g le bond and fo r m e d an e s t e r .
B oth a l ly l e s t e r and en o l e s t e r bonds w e r e fo r m e d , A r e la t iv e ly
lo w (ca 2 0 0 0 ) m o le e u la r w e ig h t p o ly m e r w a s fo r m e d ; th e r e a c t io n
p r e su m a b ly s te p p e d at th is p o in t b e c a u s e a se c o n d a r y r e a c t io n had
d e s tr o y e d one o f th e r e a c t a n t s , T h is s e c o n d a r y r e a c t io n w as found
to be th e is o m e r iz a t io n o f s t e r c u l i c a c id to a co n ju g a ted d ien o ic
a c i d , ' ; . ■ ■ ■ ■ ^ v :':' • ’ "
56
LITERATURE CITED
Td A d a m s , R , .and V, V o o r h e e s , O rgan ic S y n th e se s , C o ll.. V o l. I,2nd E d . , W iley , N . Y . ,pp . 6 1 -4 7 . <1941).
2 . A d k in s , H. and R . L . ..S h r in er . C a ta ly t ic H y d ro g en a tio n and H ydro-g e n o ly s is , in O rgan ic C h e m is tr y , V o l. I, 2nd E d. , (H.G ilm an,. E d l ) "Wiley, N .- Y. p p . 7 9 7 -9 . (1 943 ). V
3. A . Q. A . C . , O ff ic ia l M eth od s o f A n a ly s is ., 8th E d , , W a sh in g ton ,D . C . , A , p . 475; B , pp . 4 6 4 -5 . (1955).
4 . B ro o k e , D . G. and J. C . S m ith , S te r c u lic A c id . T he S y n th e s is o fS o m e R e la te d yS -D ik eton es and C y c lo p r o p a n e s . J. C hem .
' S o c . , 2 7 3 2 -2 7 3 5 .
» S tr u c tu r e o f S te r c u lic A c id . C h em . and Ind. (L o n d on), 103 . (1958 ).
6. , . . . S tr u c tu r e o f S te r c u lic A c id . C h em . and Ind. (L o n don), 1 5 0 8 -1 5 0 9 . (1957).
7. . Brown,' J. B . and D . K . E o lb , A p p lica tio n o f L ow T e m p e r a tu r eC r y s ta ll iz a t io n in th e S e p a r a tio n o f th e F a tty A c id s and T h e ir C o m p ou n d s, in P r o g r e s s in th e C h e m is tr y o f F a ts and O ther L ip id s , V o l. 3 , (R . T . H o lm an , W. D. L u n db erg and T . M alk in , E d s . ) A c a d e m ic P r e s s , pp . 5 7 -9 4 . (1955 ).
8 . B u sch , M . and H. S to v e , A b lo su n g von o r g a n is c h geb u n d en emH a lo g en m it t e l s K a ta ly t is c h e r R edtik tion . B e r . , 4 9 , 1063.(1 9 1 6 ). : ■ ' • ■ " ' '
9» B y rn e , R . E . , J r . and J. B . Joh n son , U n sa tu ra tio n D e te r m in a t io n by A c id -C a ta ly z e d B r o m ih a tio n , A nal. C h em . , 2 8 , 126-
: 129 . (1 9 5 6 ). ■' ' : ; v ;: :
10. D ijk s tr a , G. and H. J. D ufn , S tr u c tu r e o f S te r c u lic A c id and O ther A n a lo g o u s F a tty A c id s . N a tu r e , 176 , 71. (1 9 5 5 ). .
57
58
11 „ E ld ib , I« A«: and L , j t ib r ig h t . O p era tin g V a r ia S le s in H y d ro - - gen a tin g G otto ilseed . Oil» Ind„ Eng„ C h em , s _49$ 8 2 5 -8 3 1 =
(1957X, . : ' . r':, ;/ , / ■' v; ' ,
!2« .EvaiiSg R» J . , S , L , B a n d im e r , J e A , D a v id so n , and D« H„ B a u e r s P r o te in D is tr ib u t io n in F r e s h and S to r e d S h e ll E g g s fro m HeUs F ed C rude C o tto n se e d O il, do A g r , F o o d C h em , ,-7,
" ' / - ' 4 7 « 5 d o ' ' ^ l S 5 9 ) o \ " % ' : ' ' ■
1 3 , ; E v a n s , R„ J0 , P r iv a te C om m un ieation o
. 14, F a u r e , P» K, and J , C , S m ith , T he S tru c tu re o f S te r c u lic A c id ,. v J . C h em , S o c , , 1 8 1 8 -1 8 2 1 , (1 9 5 6 ), . ,h:.\ '
15 , F a u r e , P , K , , S te r c u lic A cid and Its H alphen R e a c t io n , N a tu re , . '. ' _178s 3 7 2 -3 7 3 , (1 956 ), u t'A , ‘ • .
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17. G u n ston e , F . D . , S b c ie ty of C h e m ic a l In d u stry . C h em . and Ind.(EOndon), .1 4 7 6 . (1 9 5 5 ), , ^
18. H ofm ann, K. , S . F . O ro ch en a , and C» W. Y oho. U n eq u iv o ca l S yn th e s e s o f D L i-c is - 9 , 1 0 -M e th y le n e o c ta d e c a n o ic A c id (D ih y - d r o s te r c u lic A cid ) and D L - c is -1 1 , 12 -M e th y le n e o c ta d e c a n o ic
: : ' ' A c id . J. A m . C h em . S o c v , T9» 3 6 0 8 . (1 9 5 7 ). : ;
1 9 . K night, H . B . $ R . E . K q o s , a n d D , S w ern , A d d itio n o f F o r m icA cid to: O le f in ic C o m p ou n d s, I. M o n o d le fin ic C o m p o u n d s ..J . A m . C h em . S o c . , 75 , 6 2 1 2 -6 2 1 5 , (1 9 5 3 ).
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59
23 . L o r e n z , F , W .. ,■ E gg D e te r io r a t io n D ue to In g e s t io n by H ens o f ,M a lv a c e o u s M a te r ia ls . P o u ltr y S c i. , 18, 2 9 5 -3 0 0 . (19 3 9 ).
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. V ’ A c id . S c ie n c e , 1 26 , 751 . (1957). ' " , \ . A
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: ; : ( i9 5 7 ) .; ; : ' . ' . p ;;
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61
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