(RS)-3-chloro-2,2-dimethyl-4-oxochroman-3-sulfenyl chloride | 154385-09-8

• 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: (RS)-3-chloro-2,2-dimethyl-4-oxochroman-3-sulfenyl chloride
• 英文别名: 3-chloro-3-chlorosulfenyl-2,2-dimethylchroman-4-one；3-Chloro-2,2-dimethyl-4-oxo-3-chromanesulfenyl chloride；(3-chloro-2,2-dimethyl-4-oxochromen-3-yl) thiohypochlorite
• CAS: 154385-09-8
• 化学式: C₁₁H₁₀Cl₂O₂S
• 分子量: 277.171
• InChiKey: JRBADPGQBXJVPB-UHFFFAOYSA-N

物化性质

• 熔点：
  84-85 °C
• 沸点：
  378.9±42.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (RS)-3-chloro-2,2-dimethyl-4-oxochroman-3-sulfenyl chloride 在 吗啉 作用下， 以 四氯化碳 、 乙醚 为溶剂， 生成 2,2,5',5''-tetramethylspiro<1,3,4>oxadithiin>-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：

  2,2-二甲基-苯并二氢吡喃-4-酮 在 氯化亚砜 作用下， 反应 14.0h， 以88%的产率得到(RS)-3-chloro-2,2-dimethyl-4-oxochroman-3-sulfenyl chloride
  参考文献：
  名称：

  衍生自thiochroman-4-ones的亚磺酰胺的环收缩

  摘要：

  噻苯并吡喃-4-酮和苯并吡喃-4-酮与过量的亚硫酰氯反应生成α-氯亚磺酰氯（2），当用仲胺处理时，形成亚磺酰胺（3）。水解时，（3）发生环收缩，得到苯并[ b ]噻吩-3-酮（4）。

  DOI：

  10.1016/s0040-4020(01)80797-3

文献信息

• [4 + 2]-Cycloaddition Reactions Involving α-Oxo Thioketone Intermediates
  作者：Mohamed I. Hegab、Abd El-Galil A. Amr、Farouk M. E. Abdel-Megeid

  DOI：10.1515/znb-2002-0813

  日期：2002.8.1

  α-Chloro β-oxo sulfenyl chlorides 2 were reduced by iodide ions to the corresponding α-oxo thioketones 3 which dimerized in situ in a hetero-[4 + 2] cycloaddition to give the 1,3,4- oxadithiin derivatives 4. The α-oxo thioketones 3, in situ, cyclized also with 2,3-dimethyl-1,3- butadiene to give the corresponding adducts 5 and only in case of the oxo thioketone intermediate 3d two products 4d and 5d were obtained. Also, The α-oxo thioketones 3a,c, underwent in situ, cycloaddition with furan to give the corresponding adducts 6a,c together with the corresponding thioketone dimers 4a,c. When this reaction was carried out in the presence of diethyl acetylenedicarboxylate or chalcone derivative 8, only the oxo thioketone dimers 4a-d were obtained.

  α-氯β-氧基磺酰氯化物2被碘离子还原为相应的α-氧基硫酮3，在异[4 + 2]环加成中原位二聚形成1,3,4-氧硫代噻吩衍生物4。α-氧基硫酮3也在原位与2,3-二甲基-1,3-丁二烯发生环化反应，形成相应的加合物5，仅在氧基硫酮中间体3d的情况下得到两种产物4d和5d。此外，α-氧基硫酮3a、c在原位与呋喃发生环加成反应，形成相应的加合物6a、c以及相应的硫酮二聚体4a、c。当在乙酸二乙酯乙炔二羧酸酯或查尔康衍生物8存在的情况下进行此反应时，仅得到氧基硫酮二聚体4a-d。
• Ring contraction of sulfenamides derived from thiochroman-4-ones
  作者：Christopher D. Gabbutt、John D. Hepworth、B.Mark Heron、Magan Kanjia

  DOI：10.1016/s0040-4020(01)80797-3

  日期：1994.1

  chroman-4-ones react with an excess of thionyl chloride to give the α-chlorosulfenyl chlorides (2) which form sulfenamides (3) when treated with secondary amines. On hydrolysis, (3) undergo a ring contraction to give benzo[b]thiophen-3-ones (4).

  噻苯并吡喃-4-酮和苯并吡喃-4-酮与过量的亚硫酰氯反应生成α-氯亚磺酰氯（2），当用仲胺处理时，形成亚磺酰胺（3）。水解时，（3）发生环收缩，得到苯并[ b ]噻吩-3-酮（4）。
• A new reaction of α-chloro-α-chlorosulfenyl ketones: facile syntheses of 3,3-dichloro- and 3-chloro-chroman-4-ones and thiochroman-4-ones
  作者：Christopher D. Gabbutt、John D. Hepworth、B. Mark Heron

  DOI：10.1016/s0040-4020(01)90434-x

  日期：1994.4
• Gabbutt Christopher D., Hepworth John D., Heron B. Mark, Kanjia Magan, Tetrahedron, 50 (1994) N 3, S 827-834
  作者：Gabbutt Christopher D., Hepworth John D., Heron B. Mark, Kanjia Magan

  DOI：——

  日期：——
• 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.