NOTES 1889TABLE I POLARIZATION AND DENSITIES OF BENZENE-ETHYLENE DICHLORIDE MIXTURES DielecMole tric frac. cond2'4 dle Devia-CZHICIZ stant Pi,z Pz obs. calcd. tion 0,000 0.8739 ,113 2 , 7 9 1 33.096 83.698 ,9086 0,9085 -0 . 0 0 0 1 .211 3 . 3 1 8 38.077 80.805 ,9397 ,9400 + .0003 ,342 3.879 41.980 71.468 ,9863 ,9844 -,0019 .446 4.707 46.912 72.081 1.0192 1.0214 + ,0022 ,605 5.914 51.406 67.568 1,0802 1.0810 + ,0008 .719 6 . 9 4 0 54.137 64.878 1.1247 1.1261 + ,0014 ,857 8.455 56.734 61.753 1.1846 1.1832 -,0014 1.000 10 365 58.959 58.959 1.2453 ethylene dichloride calculated from the measured densities. Figure 1 is a plot of PB versus mole fraction including the values of G~o s s .~ 94 90 86 82 78 k 74 'io 66 62 B 8 0.2 0.4 0.6 0.8 1.0 Mole fraction ethylene dichloride. solutions.Fig. 1.-Polarization of ethylene dichloride in benzene NORTHEASTERN UNIVERSITY BOSTON, MASS.RECEIVED JULY 2, 1948 ration from N-(3,4-diethoxyphenylacetyl)-/3-hydroxy -/3 -(3,4 -diethoxyphenyl) -ethylamine has been reported,2 the details are meager, and the preparation and characterization of the requisite intermediates are not recorded. We have prepared perparin from N-(3,4-di-ethylamine by ring closure to the dihydroisoquinoline, and dehydrogenation of the latter, the same series of steps that were employed by Kindler and Peschke for the preparation of p a p a~e r i n e .~ 6-(3,4-Diethoxyphenyl) -ethylamine, required for the preparation of the amide, was prepared by catalytic hydrogenation of 3,4-diethoxymandelonitrile.Experimental 3,4-Diethoxybenzaldehyde. L S i x hundred and sixty-four grams of ethyl vanillin (4 moles) was mixed with 400 cc. of diethyl sulfate (472 g., 3 moles), the pasty mixture was stirred in a stainless steel container while 680 cc. of sodium hydroxide solution was added in 30-40-cc. portions over a period of one hour. The temperature was about 40". The mixture was warmed to 80" when complete solution was obtained. The solution was held at 80-82" and rapidly stirred while 440 cc. of additional diethyl sulfate (520 g., 3.4 moles) was added in 20-30-cc. portions over a period of one hour. The solution was stirred for another half-hour a t SO", then 120 cc. of 30% sodium hydroxide was added and stirred an additional ten minutes. The solution was cooled to room temperature and extracted with ether, the ether extract was washed with 5% sodium hydroxide solution, then with water until free from alkali.The ether was distilled and the residue was dried in vacuo; yield 736 g. (95%) of a nearly water white sirup which was used without further purification in the experiments. A sample for analysis was distilled and practically all distilled a t 128-130" and 2 mm. pressure. Anal.Calcd. for C I~H~, O~: C, 68.03; H, 7.26. Found: C, 67.83; H, 7.46. 3,4-DiethoxymandeIonitrile.-This compound was madefrom 3,4-diethoxybenzaldehyde in nearly quantitative yields according to directions for 3,4-dimethoxymandelonitrile.6 p-(3,4-Dietho~yphenyl)-ethylamine.~-Sixty-six grams of the crude 3,4-diethoxymandelonitrile (0.3 mole) was dissolved...
a t room temperature, sulfur and ammonium chloride precipitated from the reaction mixture; evaporation of the solvent gave only a tarry residue. With phenacyl bromides, however, the reaction appeared to follow a different course. The ammonium ion was not produced and 2-phenacylthio-&arylthiazoles precipitated directly from the reaction mixtures as relatively pure hydrobromides. They were hydrolyzed to the free bases by washing with water. Experimental3Thiuram Disulfide.-Ammonium dithiocarbamate was prepared according to the general procedure of Miller,4 except that butyl or amyl alcohol was used instead of the ether-alcohol mixture. The crude product was oxidized directly by the method of Freund and Bachrach.6 Highest yields of the disulfide were obtained (60%) when small quantities of ammonium dithiocarbamate were used and the oxidation carried out rapidly. Reaction of Phenacyl Bromides with Thiuram Disul-fide.--In a typical experiment, a solution of 1.84 g. (0.01 mole) of thiuram disulfide and 3.98 g. (0.02 mole) of phenacyl bromide in 30 ml. of acetone was allowed to stand at room temperature, with occasional shaking, for seventytwo hours. Precipitation began within two hours. The copious precipitate was separated by filtration, washed on the filter with 10 ml. of cold acetone and finally with water until the washings gave a negative test for bromide. There was obtained 2.9 g. (93%) of 2-phenacylthio-4phenylthiazole, which crystallized from 95% ethanol in fine white needles, m. p. 118 . No change in melting point was observed when a mixed melting point was run \$ith ct sample prepared according to the method of Buchman.2 A n d .
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