6604
Vol.
so
TABLE IV CONDITIONS FOR COCONDENSATION REACTIONS WITH COPPER-BRONZE h-0.
1 2 3 4 5 G r
i
8
10 11 12
7-Phthalonitrileg. mole
-Tetranitrileg.
mole
0.946 1.421 1.800 1.890 1.988 2.080 2.364 2,710 1.Y88
0.0074 .0111 .0141 .0148 .0155 ,0163 ,0185 .0222 .0155
...
... ,
2.000 2.000 2,000 2.000 2.000 2.000 2.000 2.000 2.000 2.000 3.000
0,0074 ,0074 ,0074 .0074 ,0074 .00T4 ,0074 ,0074 .0074 .0074 .0111
...
.. . .
--Copper-bronze3. g. a t o m s
Dinitrile/ tetranitrile
Reacn. time, hr.
0,0049 .0062 ,0072 ,0074 ,0076 .0079 .008G .0099 ,0076 .0037 ,0056
1.00/1.00 1.50/‘1. O O 1.90/1 .00 2 . O O / l .OO 2.10/1 .[JO 2.20/1.00 2.50/1.0!1 3.00/1 .OO 2.10/1 .00
3 3 3 3 3 3 3
0.311 ,394 ,457 .470 ,482 ,502 ,546 ,629 ,482 ,236 .356
2
11.26 3 11.25
.... ,. . . ... ..
Product,
I’ield,
1.9
47 50 61
s 1.5
0 9
1.1
2.4 2.9
13.4 2.0 3.7 2.5 1.6 2.5
ro
--
03
65 55 5:; 69 56 71 75
TABLE V COXDITIONS FOR COCONDENSATION WITH SODIC‘M AhlYLATE No.
-Phthdlonitrilefi. mole
--Tetranitrile6.
mole
-Sodium6.
g. a t o m s
Dinitrile/ tetranitrile
Yield,
%
70 b
(g./100 ml.)
13 2.10/1.00 50 0.28 (0.27) 1.988 0.0155 2.000 0.0074 0.697 0,6303 14 2.00/1.00 65 .10 ( .13) 1.890 .0144 2.000 ,0296 ,0074 ,680 15 1.90/1 .00 55 .07 ( .44) 1.813 ,0141 2.000 ,0289 ,0074 ,664 ”Viscosities in pyridine a t 25”. Viscosity of monomeric metal-free phthalocyauiiic is 0.10 (0.25 g./100 ml.). Cocondensation of Phthalonitrile and 3,3’,4,4’-Tetracyanodiphenyl Ether with Sodium Amy1ate.-To a solution of sodium arnylate in 32 ml. of amyl alcohol was added an intimate mixture of phthalonitrile and 3,3’,4,4’-tetracyanodiphenyl ether. After refluxing for 40 minutes, 50 ml. of methanol was added, and the mixture allowed t o stand for two hours a t room temperature. The product was collected on a buchner funnel, washed with hot methanol until the
[CONTRJUUTION FROM
TIIE
wasliings were colorlcs am1 then citr,tcted for tliree days with acetone in a Soxlilet extractor. Reaction conditioiis and viscosities appear in Table V. Heat stabilities in air were determined by placing about 10 mg. of sample in a fusion tube, and placing the tube in an oven a t the desired temperature. The tube then was weighed periodically t o check weight loss. CRUANA, ILL.
ROCKEFELLER INSTITUTE]
Isolation and Structure of the CIa Unsaturated Fatty Acids in Menhaden Body Oil1 B Y LITILLY
STOFFEL AND E. H. AHRENS,
JIi.
RECEIVED JUNE2, 1958
A itiixturc of Ci6uusaturdted fatty acids was isolated from mcrihadeii body oil by fractional crystallizatiotl, folloued by high vacuum fractional distillation. Countercurrent distribution yielded pure tetraem, triene, diene aud iiionoene fractions. The structures of these acids were determined by oxidative and reductive ozonolysis with identification of the fragments by reversed phase, paper and gas-liquid chromatographic analysis. These several acids were identified : n-hexaileca-6,9,12,15-tetraenoicacid, n-hexadeca-4,7,10,13-tetraenoicacid, n-hexadeca-6,9,12-trienoicacid! n-hexadeca-7,10,13trienoic acid, n-hexadeca-6,g-dienoic acid, n-hexadeca-9,12-dienoic acid, n-hexadeca-9-monoenoic acid and n-hexadeca-8nionoenoic acid. Gas-liquid chromatographic characteristics of these acids arc described.
I n recent years a number of polyenoic fatty acids with chain lengths CIS,Caoand C2z have been isolated from natural sources in the laboratories of Klenk,2-8 Riemen~chneider~and Lundberg. lo Structural studies of these acids suggest certain common pathways in their biosynthesis, for in widely diverse systems (triglycerides and phosphatides of liver and brain in marine and mammalian (1) Aided in parts b y grants from t h e U. S.Public H e a l t h Service (11-2539)a n d t h e Nutritional Foundation. ( 2 ) E. Klenk a n d W. Bongard, 2. physiol. Chetn., 291, 104 (1952). (3) E. Klenk a n d W.Bongard, ibid., 290, 181 (1952). (4) E. Klenk a n d W . Montag, A n n . , 604,4 (1957). (5) E. Klenk a n d D. Eberhagen, Z. physiol. Cheni.. SOT, 41 (1957). (6) E.Klenk a n d F. Lindlar, i b i d . , 299, 74 (1955). (7) E. Klenk a n d H. J. Tomuschat, ibid., SOS, 165 (1957). (8) E . Klenk a n d H. Brockerboff, i b i d . , 807, 272 (1957). (9) S. F. H e r b , R. W. Riemerischrteider a n d G. Donaliken, J. A m . (lit Chrin. Soc.. 28, 6.5 (1927). ( I O ) T i . (; 1 1 . i ~ n n 1 ~ m : i t~i dl L1‘ 0 , l , u m I l ~ ~: ~b ri d~, ,3 0 , I,’M (IKj3)
species) the polyenoic acids have two characteristics in common : (1) the double bonds are arranged in the divinyl-methane rhythm, often called methylene-interrupted or “skipped” double bonds, and ( 2 ) each of these acids belongs either to the linoleic or to the linolenic acid family, Le., with the double bond farthest from the carboxyl group six or three carbons from the terminal methyl group, respectively. Studies of the Cle uiisaturated acids have been much less comprehensive. Smith and Brown” in 1945 were the first to note the presence of a Ci6 tetraene as a component in menhaden oil and in 1958 Mangold and Schlenk12 confirmed the presence in menhaden oil of C16 mono-, di-, tri- and tetraenes. A CI6tetraene also was noted by Paschke (11) F 4 Smith i n d J U l31own, Otl and s < J O f i , 22, 280 (1945). ( 1 2) I1 R 3Iai1.,
