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New Sources of 9-D-Hydroxy-cis-12-octadecenoic Acid: L Ander
New Sources of 9-D-Hydroxy-cis-12-octadecenoic Acid: L Ander
6, Pages: 450-453
.s'"
aqueous solutions of the soaps with ether. After en
acidification, the free hydroxy acids were
'~"
,...,
"":
,..., N
-
"- -
recovered by ether extraction. The acids were 0 0
esterified with diazomethane, and the resulting '"'""
esters were purified by preparative TLC. Overall 2
yields were near 80% in each instance (based on .5
" r-:<r. .d-.'"
N
GLC of the total esters). ~
~ "- t"- t"-
<t N
~
Characterization of Hydroxy Acids
'"'"
Hydroxy acid methyl esters from the 4 oils >,
r-:t"- -<i" Nc: :xi0
(H. antidysenterica, N. oleander, N. illdicum, ,...,
"
...E'"
N N
and S. hispidus) were indistinguishable by IR ::g
and NMR. The spectra were consistent with a 0 0
''"" :~=
"'0
C 1 8 methyl ester having 1 hydroxyl and 1 cis
double bond. GLC of the esters gave single CIl
0
r-: r-:
<t
>0
<r.
-
:xi
peaks, > 98%, for each and retention character- '"" 0 " N
were consistent with those expected for methyl free carboxylic acid, but also had bands at 1724
9-acetoxY-cis-12-octadecenoate. GLC and TLC cm- 1 and 1235 cm- l , characteristic of an
showed the product to be homogeneous. acetoxy derivative. Treatment with diazo-
methane gave the methyl ester which was iden-
Glyceride Characterization
tical with known methyl 9-acetoxY-cis-12-octa-
An unknown component was observed upon decenoate, as demonstrated by IR, NMR, GLC
TLC analysis of N. oleander oil, which had an and TLC.
Rf slightly lower than normal triglycerides. A portion of lipolysate of the unusual
GLC of the oil indicated that acetotriglycerides glyceride mixture was silylated, and GLC
and triterpene acetates were absent because no showed no monoglycerides with acetoxy func-
significant components with carbon numbers tional groups. Similar treatment of a lipolysate
less than C52 were observed. A significant peak of the original oil showed that 5% of the mono-
was eluted as Cs 6, however, even though only glycerides contained acyl groups with hydroxy
2% C20 esters were found in the ester analysis. or acetoxy functions, or both. A portion of the
The presence of glycerides containing an whole oil lipolysate was treated with diazo-
acetylated hydroxy acid constituent was indi- methane and subsequent GLC demonstrated
cated by a conspicuous 1235 cm- 1 (acetate) that 12% acetoxy and 2% hydroxy methyl
band in the IR; only weak hydroxyl absorption esters were present in the mixture. Thus,
was present. assuming no acyl migration during lipolysis, all
IR of the unusual component, isolated by the acetoxyacyl and a portion of the hydroxy-
preparative TLC, showed a strong 1235 cm- 1 acyl groups are esterified on the outer glycerol
(acetate) band and no hydroxyl. A sharp singlet carbons.
was present in the NMR spectrum at 7 8.1
(CC1 4 solution) characteristic of an acetoxy
DISCUSSION
group. A multiplet was evident at 75.3, due to
a single proton, and a similar multiplet was The hydroxy acids of H. antidysenterica, N.
noted in the NMR spectrum of methyl oleander, N. indicum and S. hispidus are clearly
9-acetoxy-12-octadecenoate. This signal was identical, and experimental data are consistent
assigned to the proton on a carbon bearing an with only one structure: 9-0-hydroxy-cis-12-
acetoxy group (C 9 ). A multiplet, equivalent to octadecenoic acid. The presence of this acid in
4 protons, was present at 7 5.9, indicative of S. hispidus oil was demonstrated previously
protons on the outer carbons of a glycerol (12). Assignment of the 0 configuration was
moiety. Except for the signals at 7 8.1 and 7 possible as these 4 esters and known methyl
5.3, the spectrum was otherwise consistent with 9-0 -hydroxy-cis-12-octadecenoate (11) all gave
that of a glyceride. This unusual component, plain negative ORD curves that were nearly
when analyzed by GLC, gave peaks having car- superimposable. Confirmation of this assign-
bon numbers of C S2 , C S4 and CS6 ' ment was obtained by hydrogenating the
After the unusual glyceride mixture was sub- Holarrhena ester; the product gave an ORD
jected to pancreatic lipase hydrolysis, a product curve essentially the same as that for known
was isolated that migrated between normal free methyl 9-D-hydroxyoctadecanoate (4,11).
acids and diglycerides on TLC. This product Gunstone (1) found that methyl 9-hydroxy-
had an IR band at 1705 cm- l , associated with l2-octadecenoate gives abnormally high iodine
[3]
9-HYDROXY-CIS-OCT ADECENOIC ACID
[4 ]