5,5-Dimethyl-3-(phenylthio)cyclohexanone | 77670-23-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5,5-Dimethyl-3-(phenylthio)cyclohexanone
• 英文别名: 3,3-Dimethyl-5-(phenylsulfanyl)cyclohexan-1-one；3,3-dimethyl-5-phenylsulfanylcyclohexan-1-one
• CAS: 77670-23-6
• 化学式: C₁₄H₁₈OS
• 分子量: 234.362
• InChiKey: HFEMNVGWVVXPDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-Dimethyl-3-(phenylthio)cyclohexanone 、 3,5-二硝基苯甲酸 生成 (3,3-dimethyl-5-phenylsulfanylcyclohexyl) 3,5-dinitrobenzoate
  参考文献：
  名称：

  MATOBA, KATSUHIDE;TOKIZAWA, MINORU;MORITA, TAKASHI;YAMAZAKI, TAKAO, CHEM. AND PHARM. BULL., 1984, 33, N 1, 368-372

  摘要：

  DOI：
• 作为产物：
  描述：

  5,5-二甲基-3-溴环己-2-烯酮 在 sodium hydroxide 、 lithium aluminium tetrahydride 、 硫酸 、 三氟乙酸 作用下， 以 四氯化碳 、 乙醚 、 乙醇 、 丙酮 为溶剂， 反应 3.5h， 生成 5,5-Dimethyl-3-(phenylthio)cyclohexanone
  参考文献：
  名称：

  Matoba, Katsuhide; Tokizawa, Minoru; Morita, Takashi, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 368 - 372

  摘要：

  DOI：

文献信息

• Catalysis of the Addition of Benzenethiol to 2-Cyclohexen-1-ones by Uranyl-Salophen Complexes: A Catalytic Metallocleft with High Substrate Specificity
  作者：Valeria van Axel Castelli、Antonella Dalla Cort、Luigi Mandolini、David N. Reinhoudt、Luca Schiaffino

  DOI：10.1002/(sici)1521-3765(20000403)6:7<1193::aid-chem1193>3.3.co;2-6

  日期：2000.4.3

  The base induced addition of benzenethiol to 2-cyclohexen-1-one and its 4,4-, 5,5- and 6,6-dimethyl derivatives is catalysed by a salophen-uranyl based metallocleft 2 in chloroform solution with high turnover efficiency and low product inhibition. Analysis of rate data coupled with equilibrium measurements for complexation of the catalyst with the enone reactants and addition products shows that the

  碱诱导的苯硫酚向2-cyclohexen-1-one及其4,4-，5,5-和6,6-二甲基衍生物的加成反应是由基于Salophen-uranyl的metallocleft 2在氯仿溶液中催化的，具有较高的转换效率和低产物抑制。速率数据分析以及用于催化剂与烯酮反应物和加成产物络合的平衡测量结果表明，催化机理涉及单底物酶促工艺的三个主要步骤，即底物结合和识别，结合底物的转化，并释放出反应产物。与参考的塞洛芬-呋喃基1不同，由于识别了它们的形状和大小，因此使催化剂2具有结构化的结合位点，该结合位点负责所研究的烯酮中高度的底物特异性。
• Photocatalytic C(sp³)–H thiolation by a double S_H2 strategy using thiosulfonates
  作者：Nobukazu Taniguchi、Mamoru Hyodo、Lin-Wei Pan、Ilhyong Ryu

  DOI：10.1039/d3cc05149h

  日期：——

  Site-selective C(sp3)–H thiolation using thiosulfonates has been achieved using the decatungstate anion as a photocatalyst. Using the protocol, a variety of thiolated compounds were synthesized in good yields. The transformation consists of a cascade of double SH2 reactions, HAT and ArS group transfer, and PCET (proton-coupled electron transfer) of the leaving arylsulfonyl radical to arylsulfinic acid

  使用十钨酸盐阴离子作为光催化剂，实现了使用硫代磺酸盐的位点选择性 C(sp 3 )–H 硫醇化。使用该方案，以良好的产率合成了多种硫醇化化合物。该转化由一系列双 S H 2 反应、HAT 和 ArS 基团转移以及离开芳基磺酰基到芳基亚磺酸的 PCET（质子耦合电子转移）组成，从而使催化剂 W 10 O 32 4−成为恢复了。
• A Kinetic Study of the Conjugate Addition of Benzenethiol to Cyclic Enones Catalyzed by a Nonsymmetrical Uranyl−Salophen Complex
  作者：Valeria van Axel Castelli、Antonella Dalla Cort、Luigi Mandolini、Valentina Pinto、Luca Schiaffino

  DOI：10.1021/jo070357m

  日期：2007.7.1

  The Et3N-assisted addition of benzenethiol to enones in chloroform is catalyzed with high turnover efficiency by the phenyl-substituted uranyl-salophen compound 3. Catalytic data show a close adherence to a quatermolecular mechanism involving reaction of a base-activated thiol with a reversibly formed complex of enone and metal catalyst, with a complication of product inhibition due to the formation of a product-catalyst complex. The role of the binding energy made available by interactions with the aromatic sidearm of the catalyst is discussed in terms of catalyst-substrate and catalyst-transition state complementarity.