4264
GEORGE W. CANNON, ARTHURA. SANTILLI AND POPKIN SHENIAN
The ultraviolet spectrum of the trans-acid showed absorption maxima a t 232 ( e 14,.200), 278 ( e 1700), 283 ( e 1650) and 288 mp ( e 1170) in 95y0 ethan01.~' ~L-cis-9,10-Methyleneoctadecanoic Acid (Dihydrosterculic Acid).-A mixture of 22.0 g. (0.30 mole of zinc) of zinccopper couple, 5.0 g. (0.02 mole) of iodine, 53.6 g. (0.20 mole) of methylene iodide, 29.6 g. (0.10 mole) of distilled methyl oleate (b.p. 128-132" (0.4 mm.), n 2 6 ~1.4506) and 100 ml. of anhydrous ether was stirred under reflux for 48 hours. The cool reaction mixture was filtered, and the filtrate was washed successively with 5% hydrochloric acid, water, and 57c sodium sulfite solution. After the solution had been dried over anh! drous magnesium sulfate, the ether was evaporated, and the residue was distilled t o give 7.95 g. of recovered methyl oleate, b.p. 132-134" (0.4 mm.), n Z 5 D 1.4506. The distillation residue (17 8 . ) was heated under reflux with 4.0 g. of potassium hydroxide in 75 ml. of ethanol for 4 hours. The hot solution was filtered, and the filtrate was diluted with 400 ml. of water. Acidification of the solution with concentrated hydrochloric acid, filtration and drying of the solid afforded 15 g. (51%)of crude DL-cZ'S9,lO-meth) leneoctadecdiioic acid, m.p. 31-35". T ~ v ocrys[ C O S T R I R U T I O N FROM
Vol. 81
tallizations from petroleum ether a t -30" raised the melting point to 34-37', Liquid-solid countercurrent distribution of the urea complex of the acid42 did not reveal the presence of any impurities and raised the melting point to 36-38" .'3 The infrared spectrum showed characteristic cyclopropane absorption a t 3.25 and 9.90 /* and was identical with the published spectrum of dihydrosterculic acid .43b The amide was prepared and melted a t 87-88" (lit.,l* 1n.p. 86.487.6').
Acknowledgment.-The authors acknowledge with pleasure the many helpful discussions with Dr. B. C. McKusick. (42) IT.S.Sumerwell. T H I S JOVRKAL, 79, 8-111 11957). (48) ($1) Dihydrusterculic acid has been reported t o have rn.p 38.8-39.5' I I Y J . R . S u n n , J . C h e m . Soc , 313 (1952). and (b) m.p. 39 7 40 5' h y K , Hofmann, 0. Jucker. IV R . Miller, A . C. Young, J r . , anti F. Taussig, THISJ O U R N A L , 76, 1799 (19.54). (c) Synthetic DL-CiS9,lO-methyleneoctadecanoicacid has been reported t o h a r e m p 38.1339 6 0 . 8 \vILMISGTON,
DEI..
GOESSMANSCHEMISTRY LABORATORY, L S I V E R S I T Y
O F hfASS.4CHUSETTSI
Conjugation in Cyclopropanes. Attempted Acylation, Alkylation, Cyanoethylation and Deuterium Exchange BY GEORGEiV. Casxon-, .'IRTIIUR A.SANTILLI AND POPKIS SHEYIXN I
