cis-2-Mercapto-3,4-dimethyl-2,3-dihydrothiophene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢噻吩类
• 英文名称: cis-2-Mercapto-3,4-dimethyl-2,3-dihydrothiophene
• 英文别名: 5-[5-(Methylsulfanyl)-2-thienyl]-1,3-oxazole；(2S,3R)-3,4-dimethyl-2,3-dihydrothiophene-2-thiol
• 化学式: C₆H₁₀S₂
• 分子量: 146.277
• InChiKey: VNWDIRWAEAIXKU-RITPCOANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-2-Mercapto-3,4-dimethyl-2,3-dihydrothiophene 、 乙酰氯 生成 S-[(2S,3R)-3,4-dimethyl-2,3-dihydrothiophen-2-yl] ethanethioate
  参考文献：
  名称：

  BLOCK, ERIC;SHU, HAI ZHAO, TETRAHEDRON LETT., 31,(1990) N5, C. 4999-5002

  摘要：

  DOI：
• 作为产物：
  描述：

  (E,E)-di-1-propenyl disulfide 生成 cis-2-Mercapto-3,4-dimethyl-2,3-dihydrothiophene
  参考文献：
  名称：

  BLOCK, ERIC;SHU, HAI ZHAO, TETRAHEDRON LETT., 31,(1990) N5, C. 4999-5002

  摘要：

  DOI：

文献信息

• Onion essential oil chemistry. Cis-and trans-2-mercapto-3,4-dimethyl 2,3-dihydrothiophene from pyrolysis of bis(1-propenyl) disulfide
  作者：Eric Block、Hai Zhao Shu

  DOI：10.1016/s0040-4039(00)97788-8

  日期：1990.1
• <i>Allium</i> Chemistry:  Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide <i>S</i>-Oxides from Cut Onion and Garlic¹
  作者：Eric Block、Thomas Bayer、Sriram Naganathan、Shu-Hai Zhao

  DOI：10.1021/ja953444h

  日期：1996.1.1

  Reduction (LiAlH4) of propyl 1-propynyl sulfide (8) to (E)-1-propenyl propyl sulfide ((E)-10), C-S cleavage (Li/NH3) to lithium (E)-1-propenethiolate (Li(E)-11), and reaction with MeSO(2)Cl gives (E,E)-bis(1-propenyl) disulfide ((E,E)-2); i-Bu(2)AlH reduction of 8 to (Z)-10 and reaction with Li/NH3 and then MeSO(2)Cl gives (Z,Z)-2 via Li (Z)-11. Reaction of MeSO(2)SR (R = Me (12a), n-Pr (12b), CH2CH=CH2 (12c), CH=CHMe (12d)) with K (E)-11 gives (E,Z)-2 from (Z)-12d; Li (E,Z)-11 gives alkyl (E)- and (Z)-1-propenyl disulfides (MeCH=CHSSR, R = Me (3a), n-Pr (3b), CH2=CHCH2 (3c)) from 12a-c, respectively. Oxidation at -60 degrees C of (E,E)-, (Z,Z)-, and (E,Z)-2 gives (E)-1-propenesulfinothioic acid S-(E)-1-propenyl ester ((E,E)-13, (E,E)-MeCH=CHS(O)SCH=CHMe) from (E,E)-2, (Z,Z)-13 from (Z,Z)-2, and ca. 2:1 (E,Z)-13)/(Z,E)-13 from (E,Z)-2. Warming (Z,Z)-13 gives (+/-)-(1 alpha,2 alpha,3 beta,4 alpha,5 beta)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1a), endo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14a), and exo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2. 1]heptane (14b). Warming (E,E)-13 gives 14a and 14b; (E,Z)-13/(Z,E)-13 gives (1 alpha,2 alpha,3 alpha,4 alpha,5 beta)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1b), exo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14c), and endo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14d). Oxidation of 3a-c gives MeCH=CHSS(O)R (4) and MeCH=CHS(O)SR (5). At -60 degrees C, m-CPBA (2 equiv) converts (E,E)-2 into (Z,Z)-d,l-2,3-dimethyl-1,4-butanedithial 1,4-dioxide (26) while (Z,Z)-2 gives meso- and d,l-26. With NaIO4, 4/5 (R = Me) gives (E)- or (Z)-12a and MeCH=CHSO(2)SMe (6a); with m-CPBA (Z)-MeS(O)CHMeCH=S+-O- (25a) forms. At 85 degrees C 2 gives 1:1 cis- and trans-2-mercapto-3,4-dimethyl-2,3-dihydrothiophene (29).
• BLOCK, ERIC;SHU, HAI ZHAO, TETRAHEDRON LETT., 31,(1990) N5, C. 4999-5002
  作者：BLOCK, ERIC、SHU, HAI ZHAO

  DOI：——

  日期：——