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COMMUNICATIONS TO THE EDITOR
Vol. 57
comparing favorably with nicotine for use against lapping and complication of the spectrum. With continued progress toward the final state, the aphids. INSECTICIDE DIVISION C. R. SMITH overlapping disappears, the sharply defined bands BUREAU OF ENTOMOLOGY AND PLANTQUARANTINE of C6De only remaining. U. S.DEPA.RTMENT OF AGRICULTURE In four successive equilibrations with 5 cc. of D. C. WASHINGTON, RECEIVED APRIL20, 1935 benzene using an initial 10 cc. of 95% DzO and then successively 10, 20 and 20 cc. of 100% D20 a product containing 55, 85, 97 and >99% of the THE PREPAWTION AND PROPERTIES OF hydrogen as deuterium has been prepared. The BENZENEd6 sir: deuterium contents have been estirmted from the We have developed a technique for the ex- absorption spectra. For example, in the 97y0 change reaction between deuterium oxide and product, the bands corresponding to C6D5H and benzene, discovered by Horiuti and Polanyi C6D6were the only ones visible, the former with [Nature, 134, 377 (1934); Trans. Faraday Soc., about one-fifth the intensity of the latter. Den30, 1164 (1934) J which permits the ready produc- sities of the carefully purified and redistilled samtion of benzene-ds. Two cylindrical Pyrex ves- ples at the first two stages were, 523'0,dZ540.9146; sels of about 50-cc. capacity are connected by a 85%, d254 0.9349; and the final product had a Pyrex U-tube containing an active nickel catalyst density of 0.9417. After four separate processes supported on kieselguhr. The catalyst tube is of purification we received approximately 3.5 cc. heated externally by a closely fitting electric fur- of final product. Measurements are being made nace, and the catalyst reduced (in our case with of the Raman spectra, infra-red and ultraviolet deuterium) at 420'. After the system is thor- absorptions and other physical properties. We oughly evacuated and sealed a sample of 5 cc. of are continuing our study of the variables in the benzene and 10-20 cc. of heavy water is intro- preparation and also extending the procedure to duced in vacuo through a special breakable seal. other compounds. LABORATORY P. I. BOWMAN By means of an electric furnace, which closely FRICKCHEMICAL PRINCETON UNIVERSITY W. S.BENEDICT* fits either cylinder, the water is btought to ebulli- PRINCETON, H. S.TAYLOR N. J. tion and, carrying with it a proportion of benzene RECEIVED APRIL22, 1936 vapor, is driven over the catalyst, heated to 200°, (*) National Research Fellow. where some exchange occurs, the product condensing in the second cylinder appropriately THE HYDROLYSIS OF ERGOTININE AND ERGOCLAVINE cooled. By reversing the procedure the benzenewater mixture can then be passed once more sir: Following our preliminary communications through the catalyst. Frequent repetition of the process ultimately establishes an equilibrium [J. Biol. Chew., 104, 547 (1934); THISJOURNAL, partition of deuterium between water and ben- 57,383 (1935); Science, 81,256 (1935)l regarding zene. By replacing the hydrogen-diluted deu- the cleavage of ergotinine by alkali to lysergic terium oxide with fresh pure deuterium oxide and acid, isobutyrylformic acid, ammonia and a polycontinuing the passage over the catalyst, further peptide which on further hydrolysis with acid conversion toward benzene-de can be obtained. yielded proline and phenylalanine, we have made We traced the progress of the exchange by at- a logical extension of the investigations to the taching to the reaction system via a quartz-Pyrex study of the cleavage of ergotinine by acid. Heatseal a cylindrical quartz absorption cell 30 mm. ing with hydrochloric acid resulted in the dethick. Benzene vapor a t room temperatures struction of the lysergic acid portion of the molegives a series of sharply defined ultraviolet ab- cule with the formation of obscure amorphous masorption bands. Each of the substituted ben- terial. On the other hand, I-phenylalanine, zenes, CsH6D, CaH4D2,etc., shows similar bands, [CY]~OD -28O (c = 0.39 in HzO), was obtained displaced toward the ultraviolet by frequency as such while proline was isolated as the methyl differences varying for each band but roughly ester (Anal. C, 55.70; H, S.Sl), [(Y]*~D4-33" constant for each additional D atom. As ex- (c = 0.65 in CHsOH), which was further characchange occurs forming an equilibrium among the terized by the gold salt (AnaE. C, 15.70; H, 2.62; 13 benzenes this results in a considerable over- Au, 41.83).
