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n L N Frequency in crn.-l. Fig. 1.-Spruce native lignin: curve A, 3% solution in dioxane, 0.127 mm. cell; curve B, 10-15% dispersion in Nujol, smear on salt plate; curve C, film from dioxane-EtOH on salt plate (1900 ~ r n . - ~ 2 6 0crn.-l 0 section essentially transparent).
sample, recrystallized twice from acetone-isooctane, was obtained as colorless glistening platelets, m. p. 78-79'. Anal. Calcd. for CsH90N: C, 73.43; H, 6.16; THEINSTITUTE OF PAPERCHEMISTRY APPLETON,WISCONSIN EDWARD J. JONES N, 9.52; mol. wt., 147.2. Found: C, 73.20; H, RECEIVED APRIL3, 1948 6.23; N, 9.58; mol. wt., 139 (Rast). A suspension of the lactam (0.5 g.) in 5 ml. of N sodium hydroxide was warmed with shaking t o A NOVEL SYNTHESIS OF A @-LACTAM 70-80'. After ten to twelve minutes the solution Sir: became completely clear. From the cooled acidiIn the course of an investigation of amino acid derivatives, a unique synthesis of the /3-lactam of fied solution crystalline N-phenyl-palanine (0.25 N-phenyl-&alanine was discovered. The re- g., m. p. 59-60') was recovered by ether extraction, action between an isocyanate and diazomethane evaporative distillation, and crystallization from does not seem to have been studied previously, carbon disulfide-ligroin. No depression in meltWe have found that in the case of phenyl iso- ing point was observed for a mixture with authencyanate two methylene units are added in a re- tic N-phenyl-P-alanine (m. p. 58-59'), prepared action analogous to the formation of cyclobuta- from aniline and P-iodopropionic acid by the method of Bischoff and M i n k 2 none from ketene and diazomethane.' This appears to be the simplest P-lactam re0 ported; other known representatives of this class // of compounds have a t least two substituents on CBH~NCO 2CHtNz +CeHbN-C 2Nz I 1 the ring.3 It is of interest to note the ease of CHz-CHs hydrolysis in the present case as compared to more To a solution of 2.38 g. (0.02 mole) of freshly highly substituted p-lactams or normal amides. distilled phenyl isocyanate in 25 ml. of anhydrous The reaction between diazomethane and other isoether was added 109 ml. of a 0.46 M cold ethereal cyanates and isothiocyanates has been investisolution of diazomethane (0.05 mole) dried over gated and will be reported shortly, sodium. Within about two minutes a vigorous reWe are indebted to Dr. John D. Roberts for action commenced with evolution of nitrogen and valuable suggestions and to Swift and Company the simultaneous deposition of an amorphous for support of a fellowship for one of us (P.T.T. 1. orange precipitate. After twenty hours at 0-5' DEPARTMENT OF CHEMISTRY JOHNC. SHEEHAN the solution was separated from insoluble ma- MASSACHUSETTS INSTITUTE OF TECHNOLOGY terial (0.9 g.), and concentrated under reduced CAMBRIDGE 39, MASSACHUSETTS PATRICK T. Izzo pressure to a brown, viscous oil (1.8 g.). EvapoRECEIVED APRIL15, 1948 rative distillation a t 80-120' and 1 mm. gave 0.59 (2) C . A. Bischoff and N. Mintz, Ber., 16, 2351 (1892). g. (20%) of the colorless crystalline p-lactam of (3) H. Staudinger and S.Jelagin, ibid., 44, 373 (1911) ; Staudinger, N-phenyl-P-alanine, m. p. 74-76'. An analytical ibid., 60, 1038 (1917); H.Breckpot, Bull. SOC. chim. Bclg., a i , 424 pounds, of lignin derivatives, and of lignin from other sources and as the result of industrial processing is in progress.
+
(1) P. Lipp and R. Kbter, Be?., 64, 2823 (1931).
+
(1923);
E.Gilman and M. Speeter, TRIEJOURNAL, M,2255 (1943).
