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TABLEI WHYUROXYDECANOIC ACIDPOLYMERS
Vol. 59
mixture, assuming that this compouiid was the sole source of the precipitate. Upon allowing Mrlecular n (monomeric our product to stand for thirty-six hours a t room weight units) L ~ W I W I . X 10l8 M ~ , I , ~ , IX, I O L h temperature with excess ammoniacal silver nitrate 5.0 905 5 4.2 2,120 12 6.6 &7 in aqueous alcohol [Meyer, “Analyse und Kon4,140 24 9.1 10.2 stitutionsermittlung organischer Verbindungen,” 12.4 7,780 4fi 12.4 J. Springer, Berlin, 19.71, p. 6331, the amount of 9,070 53 I 8 .3 1*5.7 silver precipitated as the sulfide (determined 13,900 82 16.4 19.0 volumetrically after proper deduction for the of the molecule are rotating in the electrical amount present as silver thiocyanate) correfield and are the main source of the observed sponded to 62% t-butyl isothiocyanate in our orientation polarization. Consistent with this product. We have not yet accounted for the explanation, polarization per gram for these remaining 6% and the possibility exists that polymers is found to be independent of molecular isobutyl compounds may be present in small weight and dipole moment varies with the square amount. We have modified the directions of root of molecular weight. The dielectric be- Wheeler and Merriam for the preparation of havior suggests that these polymeric molecules t-butyl thiocyanate by keeping the reaction have the form of flexible chains. mixture a t O’, and found that the product boiled DEPARTMENT OF CHEMISTRY WILBURB. BRIDGMAK a t 53-54’ at 25 mm. and contained 42y0 t-butyl UNIVERSITY OF WISCONSIN J. W. WILLIAMS thiocyanate, determined as described above. MADISON,WISCONSIN In similar fashion we found that trimethylRECEIVEDJULY 9, 1937 ethylene, styrene, 2-pentene and camphene add thiocyanic acid. The latter compound recalls THE ADDITION OF THIOCYANIC ACID TO the work of Challenger, Smith and Paton [ J . OLEFINIC DOUBLE BONDS Chem. Soc., 123, 1055 (1923)l who observed Sir : that pinene reacts with thiocyanic acid to yield In pursuance of a general plan of research on “a substance, . , containing nitrogen and sulfur.” the reactions of olefinic double bonds being car- Since this substance was never further identified, ried out in this Laboratory, we were led by the we assume that these authors have abandoned absence of work on the addition of thiocyanic the investigation. acid to simple olefins to examine the behavior We propose to study the additioii of thioof this substance. We have succeeded in adding cyanic acid to olefinic double bonds both inthiocyanic acid to a number of olefins. tensively and extensively with emphasis 011 the An ether solution of thiocyanic acid prepared effect of peroxides and other catalysts on addition according to Klason [J. prukt. Chem., [2] 35, 407 and rearrangement. (1887)] with an equimolar amount of isobutylene GEORGEHERBERT JONES LABORATORYM. S. KHARASCH yielded after four hours a t room temperature UNIVERSITY OF CHICAGO ERNESTM. MAY CHICAGO, ILLINOIS FRANKR. MAYO an oil boiling a t 51-54’ a t 25 mm. JULY 19, 1937 RECEIVED Anal. Calcd. for CsH9NS: C, 52.17; H, 7.82. Found: C, 52.08; H, 7.81. This product we have characterized as a mix- ISOLATION OF ERYTHROIDINE, AN ALKALOID OF ture of t-butyl thiocyanate. and t-butyl isothio- CURARE ACTION, FROM ERYTHRINA AMERICANA MILL. cyanate through their derivatives, t-buty1-NS i r : acetyldithiocarbamate of m. p. 113’ [Wheeler I t was known long ago by Altamirano [Gaceta and Merriam, THIS JOURNAL, 24, 680 (1902)l and t-butylthiourea of m. p. (decomp.) 168’ Medica De Mexico, 23, 369 (ISSS)] that extracts [Rudneff, Ber., 12, 1023 (1879)], respectively. of the seeds of Erythrina americana Mill. produce When our product was treated in aqueous alcohol a strong curare action, i. e., a selective paralyzing with silver nitrate for two, five, or ten minutes, action on motor nerve endings of striated muscle. the amount of silver thiocyanate formed by both Thus, the use of such an extract was suggested volumetric and gravimetric determinations cor- as a substitute for curare, which has been used responded to 327, of t-butyl thiocyanate in our therapeutically against tetanus and other conPOLARITY
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