May, 1938
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COMMUNICATIONS T O T H E EDITOR LACTONE FORMATION IN THE SULFONATION OF HEAT TREATED ROSIN
The hydroxytetrahydroabietic acid of L. Ruzicka, H. Waldmann, Paul J. Meier and H. Hosli Sir: [Helv. Chin?.Acia, 16, 139-181 (1933)], obtained Some time ago Ruzicka and Meyer [ Helv. Chim. by saponification of the corresponding lactone, Acta, 5, 333 (1922)] described the formation of melted a t 162-163'. Ruzicka and co-workers a lactone obtained on treating dihydroabietic mention that the hydroxy acid is easily transacid with strong mineral acids. Apparently we formed into the lactone, which observation fully have been able to obtain a similar, if not identical, agrees with the properties of the hydroxytetralactone by sulfonation of heat treated rosin or hydroabietic acid obtained by us. We have observed that the hydroxytetrahydroabietic acid heat treated abietic acid. when treated with acetyl chloride in the usual Fifty grams by weight of partially refined manner, yielded the lactone quantitatively which pseudopimaric acid [Brennan, Cairncross, Hasselnow melted a t 131-131.5 (corr.); it did not lower strom and Hull, U. S. Patent 2,072,6281 melting the melting point when mixed with the lactone point 167-169' (corr.), (CZ)~'D 46.3', and 250 isolated from the original sulfonation product. g. of sulfuric acid, sp. gr. 1.84, were mixed at This investigation is being continued. Further -5 to 5', and stirred for about twenty mininformation will be published a t a later date. utes. The brownish precipitate was collected, INC. TORSTEN HASSELSTROM washed with cold water until the washing clouded G. &. A. LABORATORIES, GEORGIA E.A. BRENNAN when mixed with the original liquor, and the SAVANNAH, JOHN D. MCPHERSON washed precipitate then extracted three times RECEIVED APRIL8, 1938 with boiling water, leaving a brownish insoluble, semi-solid rosin. The aqueous extracts on cooling VITAMIN B d deposited crystalline sulfonic acid in a yield of 25.5 g. After repeated crystallizafion from gla- Sir: cial acetic acid, it melted with decomposition a t We have reported the isolation of vitamin B-6 about 222-223' (uncorr.). as its hydrochloride, m.p. 204-206' (dec.) elseThe brownish insoluble semi-solid rosin where [Proc. Exp. Biol. & Med., 38, 64-65] amounted to 30 g. When an acetone solution of (1938). Elementary analysis of the substance this by-product was allowed to stand, it deposited gives the empirical formula CsH12N03C1. Calcd. 4 g. of a saturated lactone, a crystalline, white solid for C8H12N03C1: C, 46.70; H, 5.88; N, 6.81; which, after recrystallization, melted a t 130-131 ' C1, 17.25. Found: C, 46.89, 46.79; H, 6.12, (corr.). Calcd. for C20H3202: C, 78.9; H, 10.5. 6.10; N, 6.81, 6.94; C1, 17.03, 17.13. DeterFound: C, 79.36, H, 10.51; C, 78.9, H, 10.79; C, minations of 0-CH3, N-CH3 and water of 79.52, H, 10.73; C, 79.08, H, 10.53. The melting crystallization were negative. It is optically point of Ruzicka and Meyer's lactone was 130-131 '. inactive. The base itself, m.p. 160') was isolated The above lactone was saponified with 10% from the hydrochloride. Anal. Calcd. for CsHI1alcoholic potassium hydroxide solution for thirty- NO3: C, 56.80; H, 6.56. Found: C, 56.54, six hours. After evaporating the alcohol, the 56.84; H, 6.35, 6.15. Both the base and the potassium salt of the hydroxy acid was dissolved hydrochloride readily sublime and final purificain a large quantity of water and the hydroxy acid tion of the vitamin can be effected in this way. liberated with dilute acetic acid. The precipi- With ferric chloride the vitamin gives a reddishtated acid was purified through crystallization brown coloration. The pure substance is stable first from methanol-acetone, then from methanol to concentrated hydrochloric acid a t elevated and finally from hexane. The acid, fine white temperatures. It is not affected by heating with needles, melted a t 161-162' (uncorr.), 165' (corr.) alkalies, nitrous acid, ethyl nitrate or Fehling's (dec.). Calcd. for CzoHWOa:C, 74.5, H, 10.6. solution. Found: C, 74.73; H, 10.77. Since electrometric titration studies of the
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COMMUNICATIONS TO THE EDITOR
hydrochloride show that there is but one break in the titration curve when all the chloride ion has been neutralized, the formula for the vitamin is C&1NOa.HCl. The absorption spectrum studies of the vitamin hydrochloride in acid, alkaline and neutral solutions indicate that we are dealing with a compound with tautomeric properties. Vitamin B-6 shows pronounced and welldefined absorption in the spectral region from 2300 to 3300 8. In dilute hydrochloric acid (pH 2) there is a single band with maximum absorption at 2925 A. The hydrochloride dissolved in water (PH 4.5) shows that the band a t 2925 A. diminished in intensity along with a new band with maximum absorption a t 3275 8. At PH 6.75 the band at 3275 if. has increased markedly while that a t 2925 8. has disappeared and simultaneously a new band a t 2560 A. has appeared. At PH 10.2 the two bands which were present a t PH 6.75 have increased in intensity and shifted toward the shorter wave lengths.
Vol. 60
the transition state has been suggested for the concentration effect [private communication from Harold F. Walton, Princeton University]. DEPT.OF CHEW& CHEM.ENG. PAULM. LEININGBR TOWNESCIENTIFIC SCHOOL MARTINKILPATRICK UNIVERSITY OF PENNSYLVANIA PHILADELPHIA, PENNA. RECEIVED MARCH25, 1938
AROMATIC AMINES AS CATALYSTS FOR THE DEHYDROGENATION OF GLYCERALDEHYDE
Sir: Transformation of glyceraldehyde into pyruvic aldehyde (methyl glyoxal) by the catalytic action of aromatic amines in dilute acetic acid solution [Strain and Spoehr, J. Bwl. Chm., 89,527 (1930)l may be regarded as an intramolecular hydrogenation-dehydrogenation reaction. In the presence of amines and hydrogen acceptors (oxygen, methylene blue and indigo carmine) hydrogen is removed from the glyceraldehyde. This dehydrogenation yields a mixture of carbonyl compounds as is shown by the formation of phenylRESEARCH LABORATORY JOHNC. KERESZTESYhydrazine and 3-nitrobenzohydrazine derivatives and their chromatographic adsorption. ReacMERCK & Co., INC. JOSEPHR.STEVENS RAHWAY, N E WJERSEY tion of glyceraldehyde with oxygen in the presRECEIVED APRIL22, 1938 ence of amines is accompanied by the formation of peroxides and colored insoluble products. HYDROLYSIS OF SUCROSE Pyruvic aldehyde itself does not reduce methylene Sir : blue in the presence of amines, and dihydroxyIn the literature on the hydrolysis of sucrose by acetone exhibits only a slow reducing action. acids no mention seems to have been made of the Substances which might be expected to occur as following effect, which we have observed experi- dehydrogenation products of glyceraldehyde such as those produced by oxidation of dihydroxyacementally. The rate of inversion of 2% sucrose solutions by tone with cupric acetate [Evans and Waring, hydrochloric acid a t various concentrations has THISJOURNAL, 48, 2678 (1926)] exhibit very been measured carefully a t temperatures from strong reduction. Intermolecular oxidation and 0 to 35O, using the dilatometric method. It has reduction of glyceraldehyde and its intermediate been observed that the energy of activation varies transformation products may account for the both with temperature, as already has been shown, variations in the yields of pyruvic aldehyde preand with the concentration of hydrochloric acid, viously observed (Ref. 1, p. 532). These obserwhich has not, we believe, been noted previ- vations also indicate that aromatic amines may be regarded as catalysts (analogous to dehydroously. Choosing, for example, the temperature range genases) for the dehydrogenation of glyceraldefrom 0 to loo, we iind that the energy of activation hyde as well as for the molecular rearrangement varies from 24.2 kcal. at 4.842 molar hydrochloric of glyceraldehyde to pyruvic aldehyde. OF PLANT BIOLOGY HAROLD H. STRAIN acid to 26.2 kcal. at 1.1235 molar hydrochloric DIVISION CARNEGIE INSTITUTION OF WASHINGTON acid. STANFORD UNIVERSITY, CALIFORNIA A possible explanation based on the theory of RECEIVED FEBRUARY 21,1938
