March, 1934
COMMUNICATIONSTO
m. p. 130-131". The substance is easily soluble in hot water, alcohol and acetone, less soluble in chloroform, insoluble in cold water, benzene, ether and petroleum ether. Anal. After drying a t 100' in vacuo over HZSO,, calcd. for C1oHl8O2N:C, 67.00; H, 7.32; N, 7.82. Found: C, 66.78; H, 7.11; N, 7.72. e(@-Aminopheny1)-caproic Acid.-Ten grams of e-@nitropheny1)-caproic acid reduced in the same manner as the nitrophenylbutyric acid yielded 7.5 g. of crude e-@-
THE
EDITOR
745
nitropheny1)-caproic acid. It was recrystallized from 80 volumes of boiling water. Long narrow microscopic platelets, m. p. 108-109". The substance is soluble in hot water, alcohol and acetone, less soluble in chloroform and benzol, insoluble in cold water, ether and petroleum ether. Anal. After drying a t 100" in vacuo over HsSOI, calcd. for C12H1702N:C, 69.52; H, 8.27; N , 6.76. Found: C, 69.46; H, 8.36; N, 6.64. NEWYORK,N. 1 '. RECEIVED DECEMBER 30, 1933
COMMUNICATIONS T O T H E EDITOR compared to 0.00546 found under identical conditions in ordinary distilled water. With the Sir: production of 100% deuterium water (D20) in The compound formed by interaction of ben- this Laboratory, it became possible to deterzene, 2-furoic acid and aluminum chloride is mine the velocity coefficient of the mutarotation a-naphthoic acid and not 3-phenyl-2,3-dihydro-2- of a-d-glucose in this medium. A 0.8030-g. sample furoic acid [THISJOURNAL, 49, 565 (1927)l. of pure a-d-glucose was dissolved in 3.3210 g. The formation of a-naphthoic acid, probably of D2O of djO1.1055 and the rotation of the soluthrough an endoxy compound as a consequence of tion (di! 1.175) was read at certain intervals of 1,4-addition, may be general with related types. time in a 2-dm. semi-micro tube with sodium light Other catalysts and experimental conditions, with at 20'. The first reading (a0 38.50') was taken a miscellany of compounds, are being investigated. seven minutes after the addition of DzO. The reIn the reaction between 2-furfura1, isopropyl sults obtained are shown in Table I. chloride and aluminum chloride in carbon diTABLE I sulfide [ibid., 55, 4197 (1933)], the isopropyl Time, 1 ki + k2 = - log s o minutes a t am-(I group is introduced into a ,&position despite the 0 a o = 38.50 availability of an a-position. Bromination of the 15 37.05 0.00221 corresponding acid gives a 5-bromo-/3-isopropyl-250 34.09 ,00221 furoic acid identical with that obtained by the 90 31.29 ,00220 oxidation of the bromoaldehyde obtained from 120 29.50 ,00221 180 26.72 ,00220 5-bromo-2-furfura1,isopropyl chloride and alumi300 23.06 00222 num chloride. The same acid is obtained by 697 19.35 ,00222 hydrolysis of the ester resulting by interaction of a m = 18.83 Mean 0.00221 1440 ethyl 5-bromo-2-furoate1 isopropyl chloride and The velocity coefficient for a-d-glucose in aluminum chloride. ordinary distilled water is given by Hudson and DEPARTMENT OF CHEMISTRY HENRYGILMAN IOWA STATECOLLEGE M. MCCORKLE Dale [THIS JOURNAL, 39,320 (1917)l as kl kz = N. 0. CALLOWAY AMES,IOWA 0.00635 at 20°, and as kl kz = 0.00225 at 10". RECEIVED DECEMBER 26, 1933 A comparison of these values with the mean value for k1 kz in Table I shows that the velocity of THE MUTAROTATION OF U-&GLUCOSE IN the mutarotation of a-d-glucose in pure DzO a t DEUTERIUM WATER 20" is identical with that found in ordinary disSir: tilled water a t 10'. In this case, therefore, the In a previous communication [THIS JOURNAL, effect of the deuterium water on the velocity of 5 5 , 5056 (1933)] it has been reported that the the mutarotation is equivalent t o a drop of 10' mutarotation of a-d-glucose in 60% heavy water in the temperature. The specific rotation of the at 18" has a velocity coefficient of 0.00290 as equilibrium solution in D20 is [a]? 18.83' X
ANOMALOUS FRIEDEL-CRAFTS REACTIONS WITH FURANS
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