Acta Chimica Sinica ›› 1962, Vol. 28 ›› Issue (1): 31-43. Previous Articles     Next Articles

维生素丁的研究Ⅳ.2-取代-顺-亚环己基乙酸类化合物的合成(三)2-羥甲基-顺-亚环己基乙酸及Mannich-Braun化合物

汪猷, 黄敬坚   

  1. 中国科学院有机化学研究所
  • 投稿日期:1960-12-15 发布日期:2013-06-03

STUDIES ON VITAMIN D Ⅳ. THE SYNTHESIS OF COMPOUNDS OF 2-SUBSTITUTED CISCYCLOHEXYLIDENE ACETIC ACID TYPE (3) 2-HYDROXYMETHYL-CIS-CYCLOHEXYLIDENE ACETIC ACID AND MANNICH-BRAUN COMPOUND

WANG YU, HUANG JING-JAIN   

  1. Institute of Organic Chemistry, Academia Sinica
  • Received:1960-12-15 Published:2013-06-03

The present paper deals with the preparation of 2-hydroxymethyl-cis-cyclohexylidene acetic acid (Ⅲ) and its lactone (Ⅱ) and also with the conformation of the modified structural formula Vc for the Mannich-Braun compound[3]. The mechanism of the formation of (Vc) has been briefly discussed. 2-Hydroxymethyl cyclohexylidene acetic acid lactone[Ⅱ, m.p. 62-62.5°, λmaxEtOH 222 mμ (ε 13,100)] was obtained together with the Mannich-Braun comppund (m.p. 150.5-151.0°) from 2-acetoxymethyl cyclohexanone (Ⅳ) by the Reformatsky reaction. Based upon new evidences from the UV- and IR-absorption spectra and from the results of periodic acid oxidation, the modified structure of the Mannich-Braun compound (Vc) has been confirmed. On saponification with diluted alkali followed by acidification, (Ⅱ) was converted into the 2-hydroxymethyl-cis-cyclohexylidene acetic acid[(Ⅲ), m.p. 109一110°, λmaxEtOH 220 mμ (ε 11,100), of which the structure is supported by the results from investigations on the UV- and IR-absorption spectra and on the cyclization by means of heat or acid. With diazomethane, (Ⅲ) gives methyl 2-hydroxymethyl-cis-cyclohexylidene acetate (ⅩⅠ). Acetylation of ⅩⅠ produces methyl 2-acetoxymethyl-cis-cyclohexylidene acetate[(ⅩⅡ), b. p. 106-108°/0.2 mm; nD16 1.4887,λmaxEtOH 221 mμ (ε 12,800)], which yields Ⅱ again on treatment with concentrated hydrochloric acid. With 3,5-dinitrobenzoyl chloride, (ⅩⅠ) forms methyl 2-(3',5'-dinitrobenzoxymethyl)-cis-cyclohexylidene acetate [(ⅩⅢ), m.p. 100.5-101°]. Partial hydrolysis of (ⅩⅢ) with concentrated sulphuric acid gives 2-(3',5'-dinitrobenzoxymethyl)-cis-cyclohexylidene acetic acid [(ⅩⅣ), m.p. 188-189°], which has been reconverted into (ⅩⅢ) by esterification with diazomethane.