GEM-DITHIOLS
GEM-DITHIOLS
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DOI：
10.1021/ja01136a004
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发表时间：
1952-01-01
影响因子：
15
通讯作者：
MCKUSICK, BC
中科院分区：
文献类型：
--
作者：
CAIRNS, TL;EVANS, GL;MCKUSICK, BC
本文首次合成并分离出了偕二硫代二硫代二硫当醛或酮与硫化氢在压力下加热时，它们与多硫化物沿着形成。偕二硫醇的结构是通过双酰化为R2 C（SCOR '）2、双烷基化为R2 C（SR'）2、还原为R2 CHSH、水解为母体醛或酮而确定的。还描述了偕二硫醇的其它性质。偕-二硫醇是通式R2 C（SH）2的化合物。似乎在此之前没有这个类的成员被隔离。Baumann用硫化氢处理中性甲醛水溶液，通过醚萃取油的甲基化和氧化得到CH 2（SO2 CH 3）2，它是甲二硫醇的衍生物，但他没有分离出甲二硫醇本身。Mitchell、Ott和Reid 3用锌和乙酸还原二硫化碳，并分离出重金属盐，这些重金属盐被认为是CH 2（SCSSH）2（缩合产物甲二硫醇）的衍生物。Farlow和Signaigo [4]认为偕二硫醇可能是醛和酮在压力下被氢和硫或硫化氢催化转化为硫醇的中间体，但没有分离出任何纯态的中间体。Kelber和Schwarz 5在氢氧化钾的作用下将芳基甲基酮与二硫化碳缩合，得到α-酮基硫代酸，其在几个反应中表现为硫醇的偕二硫醇，ArCOCH= C（SH）2。
gem-Dithiois, R2C (SH) 2, havebeen prepared and isolated as chemical entities for the first time. They are formed, along with polysulfides, when aldehydes or ketones are heated with hydrogen sulfide under pressure. The structures of the gem-dithiols were established by diacylation to R2C (SCOR') 2l dialkylation to R2C (SR') 2, reduction to R2CHSH, and hydrolysis to the parent aldehyde or ketone. Other properties of the gem-dithiols are also described. gem-Dithiols are compounds of the general formula R2C (SH) 2. It appears that no member of this class has been isolated before now. Baumann2 treated neutral, aqueous formaldehyde with hy-drogen sulfide and by methylation and oxidation of an ether-extractable oil obtained CH2 (S02CH3) 2, a derivative of methanedithiol, but he did not iso-late methanedithiol itself. Mitchell, Ott and Reid3 reduced carbon disulfide with zinc and acetic acid and isolated heavy-metal salts believed to be derivatives of CH2 (SCSSH) 2, the condensation product methanedithiol. Farlow and Signaigo4 suggested that gem-di thiols might be intermediates in the catalytic conversion of aldehydes and ketones to mercaptans by hydrogen and either sulfur or hy-drogen sulfide under pressure, but did not isolate any such intermediate in a pure state. Kelber and Schwarz5 condensed aryl methyl ketones with carbon disulfide under the influence of potassium hydroxide and obtained ß-ketocarbodithioic acids, which in several reactions behaved as the enthiolic gem-dithiols, ArCOCH= C (SH) 2.