OCHg), 2.55 (3 H, s, NCH3); mass spectrum m/e 341 (M+), 340 (M -1, base peak), 326 (M -15), 310 (M -31); uv Xm,°H 279 nm (log e 4.04), 304 (4.04). The spectral properties and mixture melting point of 18 were identical with those of authentic (± )-thaliporphine.Northaliporphine (17) from 12.-A suspension of the oxoaporphine 12 (40 mg) in tetrahydrofuran (10 ml) was added to a stirred suspension of zinc amalgam [prepared from 2% HgCh (15ml), zinc dust (1.5g), and 2 N HC1 (15 ml)].The reaction was completed and worked up as for the reduction of 15 to give a reddish residue. Purification by preparative tic [silica gel, CHCl3-MeOH (5:1) eluent] afforded 17 (21 mg, 52%) as colorless needles, mp 212-214°( from CHCl3-etherhexane), identical by spectral properties and mixture melting point with the sample prepared by reduction of 15.
ethylene glycol, 6.9 g of the mixture of 25 and 27, and 6.0 g of hydrazine hydrate, at 210" for 3 hr. The mixture was diluted with water, neutralized, and extracted three times with ether to give 1.7 g (about 30% yield) of an oil, bp 110-1 12" (2 mm). Gas chromatography on column A (see above) separated, with difficulty, (-)-2-methyl-2-ethylpentanoic acid (26) from its isomer 28, 3-methyI-3-ethylpentanoic acid. The ir spectrum of 26 was identical with that of authentic material, made after Prout.16 The mixture of 26 and 28 was used in the next step, in which 1.4 g of the mixture (0.01 mol) was treated with 3 ml of thionyl chloride at room temperature for 18 hr. After heating to reflux for 2 hr, the thionyl chloride was removed in uacuo, 0.5 g of activated sodium azide and 3 ml of xylene were added, the solution was heated to 80", and another 0.5 g of sodium azide was added. After 5 hr, the temperature was raised to 180". The filtrate was stirred for 12 hr with 4 ml of concentrated hydrochloric acid at about 80" and cooled, the aqueous layer separated, and the organic solution extracted once with hydrochloric acid. From the aqueous layers, the amine was liberated by Stereochemical Studies.Abstract: The four possible optically active stereoisomeric N-methyl-N-neopentyl-4-methylcyclohexylamine oxides were individually prepared. The stereomeric secondary amines, cis-and trans-N-neopentyl-4-methylcyclohexylamines (3 and 4), obtained by reductive amination procedures, were separated and converted to the corre-
Nuclear magnetic resonance spectra of a number of isomeric 4-substituted-1 -methylcyclohexanes are reported. These spectra substantiate the useful stereochemical generalization that the signals due to the ring protons of a diequatorial isomer appear as a significantly broader envelope than do those which arise from the ring protons of the corresponding nondiequatorial form.
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