6-Hydroxy-5-methyl-6-phenyl-[1,4]oxathiepan-7-one | 192383-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-Hydroxy-5-methyl-6-phenyl-[1,4]oxathiepan-7-one
• 英文别名: 6-Hydroxy-5-methyl-6-phenyl-1,4-oxathiepan-7-one；6-hydroxy-5-methyl-6-phenyl-1,4-oxathiepan-7-one
• CAS: 192383-52-1
• 化学式: C₁₂H₁₄O₃S
• 分子量: 238.307
• InChiKey: WALIQWVAZLCJJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  71.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-Ethylsulfanylethyl 2-oxo-2-phenylacetate 以 苯 为溶剂， 以100%的产率得到6-Hydroxy-5-methyl-6-phenyl-[1,4]oxathiepan-7-one
  参考文献：
  名称：

  含硫化物的烷基苯乙醛酸酯的光化学反应

  摘要：

  乙硫基烷基苯乙醛酸酯（2）进行区域选择性光环化，以高收率产生多达13元的环噻唑（3）。在激发的羰基和碳a到远端的硫之间发生环化。在羰基和硫化物之间放置的亚甲基越多，3的收率越低分子间氢提取引起的还原二聚作用和分子内的Norrish II型光解作用具有竞争性。可以通过从硫原子到激发的羰基的光诱导电子转移，然后进行质子转移和随后的双自由基环化，使远程环化合理化。随着连接电子给体和受体的链变得更长和更柔韧，电子传输的速率常数增加。

  DOI：

  10.1016/s0040-4020(97)00420-1

文献信息

• Photochemical Reactions of Halo-/Aryl Sulfide-Substituted Alkyl Phenylglyoxylate, an Assessment of the Lifetime of the Intermediate 1,4-Biradical
  作者：Shengkui Hu、Douglas C. Neckers

  DOI：10.1021/jo971201x

  日期：1997.10.1

  Photochemical reactions of several halo/aryl sulfide-substituted alkyl phenylglyoxylates (1) were studied. For 2'-bromo-(Ib), 2'-iodo- (1c), 2'-(phenylthio)- (1d), and 2'-(phenylsulfinyl)- (1e) ethyl phenylglyoxylate, vinyl phenylglyoxylate (2), proposed to be the result of beta-elimination from the 1,4-biradical formed by triplet state gamma-hydrogen abstraction, is the dominant photoproduct. In the cases Ib and Id Norrish Type II products were also observed. Vinyl phenylglyoxylate (2) was not observed with 2'-chloroethyl (la), 3'-bromopropyl (If), and 3'-(phenylthio)propyl (1g) phenylglyoxylate. The lifetime of the 1,4-biradical intermediate is deduced from the competition between the beta-elimination of the monoradical and the normal biradical decay. The triplet lifetime and the photoreaction efficiency of 1 were not significantly affected by halogen-substitution.
• Photochemical reactions of sulfide-containing alkyl phenylglyoxylates
  作者：Shengkui Hu、Douglas C. Neckers

  DOI：10.1016/s0040-4020(97)00420-1

  日期：1997.5

  yields. Cyclization occurred between the excited carbonyl group and the carbon a to the sulfur on the remote side. The more methylenes placed between the carbonyl group and the sulfide, the lower the yield of 3 while intermolecular hydrogen abstraction induced reductive dimerization and intramolecular Norrish Type II photolysis become competitive. The remote cyclization can be rationalized by a photoinduced

  乙硫基烷基苯乙醛酸酯（2）进行区域选择性光环化，以高收率产生多达13元的环噻唑（3）。在激发的羰基和碳a到远端的硫之间发生环化。在羰基和硫化物之间放置的亚甲基越多，3的收率越低分子间氢提取引起的还原二聚作用和分子内的Norrish II型光解作用具有竞争性。可以通过从硫原子到激发的羰基的光诱导电子转移，然后进行质子转移和随后的双自由基环化，使远程环化合理化。随着连接电子给体和受体的链变得更长和更柔韧，电子传输的速率常数增加。