acetyl (RS)-3-chloro-4-oxospiro-3-yl disulfide | 219829-57-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: acetyl (RS)-3-chloro-4-oxospiro-3-yl disulfide
• 英文别名: S-(3-chloro-4-oxospiro[chromene-2,1'-cyclopentane]-3-yl)sulfanyl ethanethioate
• CAS: 219829-57-9
• 化学式: C₁₅H₁₅ClO₃S₂
• 分子量: 342.867
• InChiKey: PMMCPJJPZIUSAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  94
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  acetyl (RS)-3-chloro-4-oxospiro-3-yl disulfide 在 吗啉 作用下， 以 乙醚 、 氯仿 为溶剂， 以12%的产率得到dispirohexathiepan>-4'-one
  参考文献：
  名称：

  Cycloadditions with 2,2-Dialkyl-3-thioxochroman-4-one S-Sulfides Including an Unprecedented [3 + 5] Cycloaddition

  摘要：

  We report the facile generation of the chroman-4-one-derived thiosulfines 10 under mild conditions by our well-established nucleophilic "unzipping" of the corresponding acetyl alpha-chloroalkyl disulfides 9 which in turn can be prepared from the corresponding alpha-chloro sulfenyl chlorides 8. Spontaneous partial loss of sulfur from 10, most probably by the disproportionation of 10 to 11 and 12, generates the expectedly reactive beta-oxo thioketones 11 which partly dimerize in a precedented Diels-Alder fashion, to give the 1,3,4-oxadithiins 13, and partly cycloadd to 10 to form the 1,2,4-trithiolanes 14 in a well-precedented fashion. Dimerization of 10 can occur in two competing ways: the precedented nonconcerted [3 + 3] cycloaddition (to give 1,2,4,5-tetrathianes 15) and the unprecedented concerted [3 + 5] addition to give 1,3,4,5,6-oxatetrathiocins 16. In the latter interaction one molecule of 10 behaves as a 1,5-dipole and a second molecule as a 1,3-dipole. In one case (10d) extensive sulfur scrambling takes place with formation of the 1,2,3,4,5,6-hexathiepane 17d. It is remarkable how sensitive the reactions of 10 are to minor variations of the simple alkyl substituents in the 2-position. In addition to the usual spectroscopic characterization all isolated key compounds were subjected to X-ray single-crystal structure determinations.

  DOI：

  10.1021/jo981534+
• 作为产物：
  描述：

  螺[2H-1-苯并吡喃-2,1-环戊并n]-4(3h)-酮 在 氯化亚砜 作用下， 以 四氯化碳 为溶剂， 生成 acetyl (RS)-3-chloro-4-oxospiro-3-yl disulfide
  参考文献：
  名称：

  Cycloadditions with 2,2-Dialkyl-3-thioxochroman-4-one S-Sulfides Including an Unprecedented [3 + 5] Cycloaddition

  摘要：

  We report the facile generation of the chroman-4-one-derived thiosulfines 10 under mild conditions by our well-established nucleophilic "unzipping" of the corresponding acetyl alpha-chloroalkyl disulfides 9 which in turn can be prepared from the corresponding alpha-chloro sulfenyl chlorides 8. Spontaneous partial loss of sulfur from 10, most probably by the disproportionation of 10 to 11 and 12, generates the expectedly reactive beta-oxo thioketones 11 which partly dimerize in a precedented Diels-Alder fashion, to give the 1,3,4-oxadithiins 13, and partly cycloadd to 10 to form the 1,2,4-trithiolanes 14 in a well-precedented fashion. Dimerization of 10 can occur in two competing ways: the precedented nonconcerted [3 + 3] cycloaddition (to give 1,2,4,5-tetrathianes 15) and the unprecedented concerted [3 + 5] addition to give 1,3,4,5,6-oxatetrathiocins 16. In the latter interaction one molecule of 10 behaves as a 1,5-dipole and a second molecule as a 1,3-dipole. In one case (10d) extensive sulfur scrambling takes place with formation of the 1,2,3,4,5,6-hexathiepane 17d. It is remarkable how sensitive the reactions of 10 are to minor variations of the simple alkyl substituents in the 2-position. In addition to the usual spectroscopic characterization all isolated key compounds were subjected to X-ray single-crystal structure determinations.

  DOI：

  10.1021/jo981534+

文献信息

• Cycloadditions with 2,2-Dialkyl-3-thioxochroman-4-one <i>S</i>-Sulfides Including an Unprecedented [3 + 5] Cycloaddition
  作者：Farag A. G. El-Essawy、Salah M. Yassin、Ibrahim A. El-Sakka、Ahmed F. Khattab、Inger Søtofte、Jørgen Øgaard Madsen、Alexander Senning

  DOI：10.1021/jo981534+

  日期：1998.12.1

  We report the facile generation of the chroman-4-one-derived thiosulfines 10 under mild conditions by our well-established nucleophilic "unzipping" of the corresponding acetyl alpha-chloroalkyl disulfides 9 which in turn can be prepared from the corresponding alpha-chloro sulfenyl chlorides 8. Spontaneous partial loss of sulfur from 10, most probably by the disproportionation of 10 to 11 and 12, generates the expectedly reactive beta-oxo thioketones 11 which partly dimerize in a precedented Diels-Alder fashion, to give the 1,3,4-oxadithiins 13, and partly cycloadd to 10 to form the 1,2,4-trithiolanes 14 in a well-precedented fashion. Dimerization of 10 can occur in two competing ways: the precedented nonconcerted [3 + 3] cycloaddition (to give 1,2,4,5-tetrathianes 15) and the unprecedented concerted [3 + 5] addition to give 1,3,4,5,6-oxatetrathiocins 16. In the latter interaction one molecule of 10 behaves as a 1,5-dipole and a second molecule as a 1,3-dipole. In one case (10d) extensive sulfur scrambling takes place with formation of the 1,2,3,4,5,6-hexathiepane 17d. It is remarkable how sensitive the reactions of 10 are to minor variations of the simple alkyl substituents in the 2-position. In addition to the usual spectroscopic characterization all isolated key compounds were subjected to X-ray single-crystal structure determinations.