THE CHEMICAL WORLD THIS WEEK strate concentration of 2 X 10~* Af. Higher a n d lower concentrations of the disulfate yield r e d u c e d rates of hydrolysis, an indication t h a t t h e substrate also functions as an inhibitor. At the o p t i m u m substrate concentration, the pH for maximum activity at 37° C . is 5.7. The inhibition of phenolphthalein disulfate appears t o depend at least in p a r t o n its two highly acidic polar groups, since, in common with certain aromatic disulfonic acids, it readily precipitates proteins from slightly acidicsolution at room t e m p e r a t u r e . Labeled T h i a m i n e . F o r t h e purpose of eventually studying t h e metabolism of thiamine l a b e l e d w i t h C1* in t h e pyrimidine ring, E d w a r d Cerwonka and E . V. Brown of F o i d h a m University have worked out a practical synthesis of t h e vitamin tagged in this m a n n e r . O t h e r workers have reported t h e preparation of thiamine labeled w i t h C 14 in the thiazole ring. By analogous reactions, thiamine has b e e n labeled with S35. In the present synthesis, the c o m p o u n d has b e e n prepared i n an over-all yield of about 2 % , starting with barium c a r b o n a t e l a b e l e d with C14. Aspirin. In pyridine solution, acetylsalicylic acid ( a s p i r i n ) is able to convert an a-acylamino acid to its azolactone, reported D a v i d Davidson a n d Leatrice Auerbach of Brooklyn College. This reaction is characteristic of acylic acid anhydrides such as acetic a n h y d r i d e . A possible explanation of this phenomenon may b e that acetylsalicylic acid, particularly in the presence of bases, e n t e r s into equilibrium with the isomeric salicylacetic anhydride. This hypothesis serves t o explain a number of unusual properties of acetylsalicylic acid. T h e s e are its pronounced acetylating action on amines, phenols, and alcohols; its d e h y d r a t i n g action o n oxalic acid; its conversion t o acetyldiplosal in pyridine solution; its polymerization at moderate temperatures ( 1 3 5 ° to 200° C . ) ; a n d the nondependence of its rate of hydrolysis on p H b e t w e e n 5 a n d 8 . Acid-Base T i t r a t i o n s . Recent applications of potentiometric titrations to nonaqueous systems arise from t h e fact that m a n y substances a r e too weakly acidic or basic to permit titration in w a t e r solution. A paper b y Sister Marian Jose Smith, Paul T. Bishop, a n d M . J. McGuinness, Jr., of F o r d h a m University described the potentiometric and conductimetrio titrations of a n u m b e r of basic substances in glacial acetic acid using perchloric acid as titrant. Among t h e substances titrated as bases w e r e glycine, Z-tyrosine, /3naphthylamine, b r u c i n e , potassium acid phthalate, and the hydrochlorides of glycine, methylamine, /S-naphthylamine, and hydroxylamine. In certain instances, ethyl alcohol w a s a d d e d to the glacial acetic acid to provide increased solvency without introducing interference. Potentiometric titrations of the hydrochlorides are possible only if mercuric acetate is present. Chlorohydrins. T h e separation and identification of the 9,10- and 10,9-chlorohydrins of methyl oleate were described
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by E. J u n g e r m a n n a n d P. E . Spoerri of Polytechtnic Institute of Brooklyn. P u r e methyl oleate w a s converted into t h e epoxide by r e a c t i n g it with peracetic acid. T h e resulting 9,10-methyl epoxystearate was allowed to react w i t h hydrogen chloride in anhydrous ethyl ether, a n d a mixt u r e of 9,10- and 10,9-chlorohydrins was obtained. T h i s m a t e r i a l was separated by low-temperature fractional crystallization into two fractions. For purposes of identification, the individual chlorohydrins were converted t o the corresponding ketostearie acids. Xhe lower m e l t i n g chlorohydrin was identified a s methyl 10-hydroxy-9-chlorostearate. Th.e higher m e l t i n g chlorohydrin was identified a s methyl 9-hydroxy-10chlorostearate. Bound Dyes. T h e physico-chemical properties of dyes in solution are considerably altered when they are b o u n d to high polymers, reported Malcolm Schrader and Gerald Oster of Polytechnic Institute of
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Brooklyn. T h e i r research was concerned with t h e altered reduction potentials of dyes w h e n attached t o high polymers. Potentiometric titrations of t h e free dye and of the b o u n d dye w e r e carried out u n d e r an atmosphere of purified nitrogen. T h e cationic dyes of the azine a n d triphenylm e t h a n e families were linked with poly.methacrylic acid. Anionic dyes of the fluorescein family were b o u n d to polyvinylpyrrolidone. T h e measurements w e r e made i n buffered solutions at p H 4.5. In m o s t cases of t h e cationic dyes, the reduction potential was lowered u p o n binding, indicating a greater resistance of the d y e to reduction in this state. T h e anionic dyes, however, showed the opposite behavior. Special and photochemical properties of the dyes were different in the b o u n d state, as compared to the free state. Attempts have been made to correlate these effects with the altered reduction potentials.
Society of C h e m i c a l Industry
Cream of Chemical Industry Serving Government Regulatory Bureaus Wilson stock sale m a y d e t e r t o p executives entering public life, Fleischmann says NEW YORK.-The chemical industry made a slow start "hut a tremendous finish in sending capable m e n t o Washington during the Truman Administration to serve with government regulatory bureaus, said Manly Fleischmann, former head of the Defense Production Administration, before the Society of Chemical 'Industry here on Feb. 18. In fact t h e Government finally secured " t h e c r e a m of t h e crop," the best in any industry, except possibly steel, h e said. Mr. Fleischmann described the case surrounding Charles Wilson, new Defense Secretary, w h o w a s forced to dispose of his securities, as ""most distressing" a n d a case surrounded b y unfortunate publicity a n d hard feelings. Hereafter t o p executives m a y hesitate to g o to Washington in government service, h e said. T h e speaker said t h a t h e would h a t e to see a weakening of bonds b e t w e e n Government and business, such as the Wilson case is apt to accomplish. H e predicted that Charles Wilson will find it difficult to improve over M i . Lovett, w h o m Mr. Wilson succeeds, since Lovett w a s one of the most capable administrators t h e Government has ever had. T h e m a i n theme of Mr. Fleischmann's talk w a s outlook for t h e nation's security, taking a. more pessimistic view t h a n many. He quoted from the writers, Joseph and Stewart Alsop to the effect that t h e modern atomic o r hydrogen bombs c a n destroy whole states and nations. Mr. Fleisch-
CHEMICAL
mann stated t h a t another world war would destroy civilization as we k n o w it. Moreover, history h a s shown that w h e n two outstanding powerful nations continue to arm potentially against each other and engage in a cold war, a shooting war eventually is set in motion, not intentionally, but through some accident. Such is very apt t o happen between the United States a n d Russia, he said. T h e only p r e ventative, h e suggested, would b e a powerful joining of nations into a force to enact international law and enforce it in the interest of p e a c e . Despite such present obstacles, it is the only major undertaking t o strive for, he said. The speaker bemoaned the "resurgence" of Russia after the e n d of World W a r II and said if w e now h a d t h e power we had at the end of this war we could h a v e pulled the t e e t h of the Russian b e a r . However, a m o n g t h e more favorable factors in our national security is that we are infinitely more powerful t h a n two and a half years ago, at the start of Korean hostilities. H a d Russia moved against our meager forces a t that, time, things would have g o n e sorely with us. Mr. Fleischmann q u o t e d Walter L i p p man, w h o explained recently that the reason that N A T O is so slow in cooperating militarily with friendly nations in. rearming is t h a t they distrust conventional means of making war. They have no faith in infantry, tanks, and planes in this atomic age.
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