Aug., 1937
COMMUNICATIONS TO THE EDITOR
a small concentration for the cryptozoon formations. The overlying shale, however, does not differ appreciably from that normally present in rocks of this type.
1579
POLAR GROUP ORIENTATION IN LINEAR POLYMERIC MOLECULES. THE OMEGAHYDROXYDECANOIC ACIDS
Sir :
From dielectric constant-frequency data obtained with dilute solutions the average times Per cent. Per cent. of relaxation and molecular weights of zein, Source total K Abundance ratio K41 gliadin, lignin, hemoglobin, etc., have been deMineral Water termined. In these cases the molecular weight 13.85 * 0 . 1 6.76 Geyser 3.40 values so obtained agree with figures which have 13.85 * . 1 6.76 Coesa 3.73 13.85 * .1 6.76 Hathorn 6.03 been obtained by the application of the classical diffusion, sedimentation and osmotic pressure Cryptozoon methods, and the identity of the electrical and Undailatum Small 13.95 * 0 . 1 6.69 molecular kinetic units is established. Prollferum 13.95 * .1 6.69 Trenton limestone Trace 14.00 * .1 6.67 However, there is a class of high molecular Shale overlying ? 14.20 * .03 6 . 5 8 weight polymeric substances which a t least in dilute solutions did not give a measurable disThe abundance ratio for the isotopes of lithium persion of dielectric constant in a frequency inin the Saratoga mineral waters and cryptozoon terval where an effect of this kind would be was Li7/Li6 = 11.8 * 0.1. In comparison the expected if electrical and kinetic or chemical abundance ratio for the majority of other lithium units are assumed to be equivalent, but the data sources tested ranged between 11.6 and 11.8. do show a definite and constant orientation The lithium isotope ratio in Saratoga water, contribution of the solute molecules to the ditherefore, does not differ appreciably from electric constant of the solution over a connormal. The amount of rubidium present was siderable range of frequency. so small that an accurate abundance ratio could The w-hydroxydecanoic acid polymers are typinot be obtained, although the results showed cal of substances of this class. Their dielectric that the ratio did not differ appreciably from behavior in dilute solution can be explained if normal, which is RbS5/Rbs7= 2.6. it is assumed that in the long molecules there The results just described are of interest in are polar groups a t regularly recurring intervals t h a t they represent the only inorganic source which can orient in the applied field. Since so far discovered in which the K41 content is there are nine C-C bonds between each pair of appreciably higher than normal. It is significant polar ester groups, free rotation of the latter that the lithium isotope ratio does not deviate seems probable. In this event the mean square correspondingly. It would appear, in consesum of n group moments is approximately equal quence, that the process which concentrated to the sum of the squares of the several individual K4’ does not concentrate Li7; this precludes moments ; thus most physical mechanisms [Brewer, J . Chem. p 2 = P& P (n ~ - ~ 1) ~h~~ ~ Phys., 4, 350 (1936)l for the isotope effect since they would be expected to result in larger devia- In this equation, p is the average dipole moment tions for lithium than for potassium. The of the polymeric molecules. Since, in Debye 1.7; pc00H 1.4; pcooc 1.8, simplest interpretation for these results is, units, OH (n - 1) therefore, that the salt deposits from which the this equation reduces to pz = 4.85 water arises are of marine plant origin rather 3.24. We give in tabular form below electric than that any isotope effect is occurring a t the moment data for six polymeric w-hydroxydecanoic present time which would result in an abnormal acids. The observed moments have been calculated from dielectric constant, density and abundance ratio for potassium. refractive index data for dilute benzene solutions BUREAUOF CHEMISTRY AND SOILS A. KEITHBREWER U. S. DEPARTMENT OF AGRICULTURE obtained in this Laboratory. Dielectric constant WASHINGTON, D. C. measurements were made a t wave lengths X = NEWYORKSTATE RESEARCH OSKARBAUDISCH 79 m. and X = 180 m. FOR HYDROTHERAPY INSTITUTE It appears that the individual polar ester SARATOGA SPRINGS, N. Y. RECEIVED JUNE 14, 1937 groups spaced in regular fashion along the length TABLEI
+
+
+
1580
COMMUNICATIONS TO THE EUrroK
TABLEI POLARITY UF 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. BRIDGMAKa 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 trimethylRECEIVED JULY 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 ERNEST M. 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 con-
