3-bromotetrahydrothiapyran 1,1-dioxide | 38690-81-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: 3-bromotetrahydrothiapyran 1,1-dioxide
• 英文别名: 3-bromotetrahydro-2H-thiopyran 1,1-dioxide；3-bromo-1λ⁶-thiane-1,1-dione；3-Brom-thiacyclohexan-1,1-dioxid；3-bromo-tetrahydro-thiopyran-1,1-dioxide；3-Brom-tetrahydro-thiopyran-1,1-dioxid；3-bromothiane 1,1-dioxide
• CAS: 38690-81-2
• 化学式: C₅H₉BrO₂S
• mdl: MFCD19607669
• 分子量: 213.095
• InChiKey: RFBOGDDBWJVTLD-UHFFFAOYSA-N

物化性质

• 熔点：
  87 °C
• 沸点：
  360.1±35.0 °C(Predicted)
• 密度：
  1.672±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-bromotetrahydrothiapyran 1,1-dioxide 在 双氧水 、 溶剂黄146 作用下， 以 仲丁醇 为溶剂， 反应 1.25h， 生成 3-(methylsulfonyl)tetrahydrothiapyran 1,1-dioxide
  参考文献：
  名称：

  α-磺酰基碳负离子形成的容易程度随不同β-取代基的取向而变化：负超共轭作为重要取代基效应的普遍性的实验证据

  摘要：

  继我们之前观察到的 β-烷氧基取代的 α-磺酰基碳负离子的形成速率取决于烷氧基的立体化学之后，我们发现当 β-取代基为 R2N、RS 或 R3N+ 时也有类似的行为。对于每个取代基，kN 的变化（由 kN = (kexch)X /(kexch) 模型定义）与 log kN = a + b cos2θ 形式的方程一致，其中 θ 是 HCCX 扭转角。我们建议 a 项描述极性（场加感应）效应，b 项描述取代基的负超共轭效应；我们展示了如何在这个框架内轻松适应 a 和 b 的变化。根据我们的结果讨论了先前在文献中假设的三烷基氨基的一些特征。 关键词：负超共轭，取代基效应，

  DOI：

  10.1139/v03-015
• 作为产物：
  描述：

  3,4-dihydro-2H-thiopyran 1,1-dioxide 、 氢溴酸 生成 3-bromotetrahydrothiapyran 1,1-dioxide
  参考文献：
  名称：

  Thiapyran Derivatives. III. The Preparation, Properties and Reactions of ▵²-Dihydrothiapyran 1,1-Dioxide

  摘要：

  DOI：

  10.1021/ja01126a068

文献信息

• Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Xiao-Feng Ren、Edward Turos、Charles H. Lake、Melvyn Rowen Churchill

  DOI：10.1021/jo00125a038

  日期：1995.10

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.
• [EN] TETRAHYDROQUINOLINE COMPOSITIONS AS BET BROMODOMAIN INHIBITORS<br/>[FR] COMPOSITIONS DE TÉTRAHYDROQUINOLINE UTILISÉES COMME INHIBITEURS DE PROTÉINES À BROMODOMAINE ET DOMAINE EXTRATERMINAL (BET)
  申请人：BAIR KENNETH W

  公开号：WO2015074064A3

  公开（公告）日：2015-07-09
• Regiochemical studies on halocyclization reactions of unsaturated sulfides
  作者：Ren Xiao-Feng、Edward Turos

  DOI：10.1016/0040-4039(93)85010-t

  日期：1993.3
• Thiapyran Derivatives. III. The Preparation, Properties and Reactions of ▵²-Dihydrothiapyran 1,1-Dioxide
  作者：Edward A. Fehnel

  DOI：10.1021/ja01126a068

  日期：1952.3
• Variation of the ease of α-sulfonyl carbanion formation with the orientation of different β-substituents: Experimental evidence for the generality of negative hyperconjugation as an important substituent effect
  作者：James F King、Manqing Li、Allan Zijun Cheng、Vinod Dave、Nicholas C Payne

  DOI：10.1139/v03-015

  日期：2003.6.1

  Following up on our previous observation that the rate of formation of a β-alkoxy-substituted α-sulfonyl carbanion depends on the stereochemistry of the alkoxy group, we have found similar behaviour when the β-substituent is R2N, RS, or R3N+. With each substituent, the variation of kN (defined by kN = (kexch)X /(kexch)model) is consistent with an equation of the form log kN = a + b cos2θ, where θ is

  继我们之前观察到的 β-烷氧基取代的 α-磺酰基碳负离子的形成速率取决于烷氧基的立体化学之后，我们发现当 β-取代基为 R2N、RS 或 R3N+ 时也有类似的行为。对于每个取代基，kN 的变化（由 kN = (kexch)X /(kexch) 模型定义）与 log kN = a + b cos2θ 形式的方程一致，其中 θ 是 HCCX 扭转角。我们建议 a 项描述极性（场加感应）效应，b 项描述取代基的负超共轭效应；我们展示了如何在这个框架内轻松适应 a 和 b 的变化。根据我们的结果讨论了先前在文献中假设的三烷基氨基的一些特征。 关键词：负超共轭，取代基效应，