1-Fluoro-1-<(methylthio)methyl>cyclohexane | 129110-65-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: 1-Fluoro-1-<(methylthio)methyl>cyclohexane
• 英文别名: 1-Fluoro-1-(methylthiomethyl)-cyclohexane；1-Fluoro-1-methylsulfanylmethyl-cyclohexane；1-fluoro-1-(methylsulfanylmethyl)cyclohexane
• CAS: 129110-65-2
• 化学式: C₈H₁₅FS
• 分子量: 162.272
• InChiKey: UKGKMMQCBCHBHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  dimethyl(methylthio)sulfonium tetrafluoroborate 、 亚甲基环己烷 在 triethylamine tris(hydrogen fluoride) 作用下， 生成 1-Fluoro-1-<(methylthio)methyl>cyclohexane
  参考文献：
  名称：

  Synthesis of fluoroalkyl methyl thioethers by formal addition of methanesulfenyl fluoride to alkenes

  摘要：

  The electrophilic anti-1,2-addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds by a one-pot reaction of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine trishydrofluoride with various types of alkenes is used for the synthesis of beta-fluoroalkyl methyl thioethers. This reaction is stereospecific: starting from cis-cycloalkenes (1) trans-1-fluoro-2-(methylthio)cycloalkanes (2) are formed, while trans-cyclododecene (3) gives the cis product 4 everytime in good yields. With unsymmetrical alkenes these reactions proceed regioselectively to produce Markovnikov-oriented fluoro thioethers. With 2,6-norbornadiene (26) exclusive exo attack on one double bond and subsequent transannular participation of the second pi-bond gives rise to two isomeric 3,5-disubstituted nortricyclanes, 28 and 29, while starting from the medium-sized cis,cis-1,5-cyclooctadiene (10) no transannular pi-participation is observed: the trans-1,2-addition product to one of the two double bonds in 11 is isolated. In contrast, in the reaction of the monoepoxide 30 of this diene in addition to the simple 1,2-adduct 31 a transannular oxygen participation occurs producing three oxa bicyclic compounds 32-34. The oxidation of 1-fluoro-2-(methylthio)cyclooctane (2a) by sodium periodate yields the expected mixture of two diastereomeric 1-fluoro-2-(methylsulfinyl)cyclooctanes (36) which on pyrolysis give 3-fluorocyclooctene (37).

  DOI：

  10.1021/jo00028a056

文献信息

• Synthesis of β-fluoroalkyl phenyl (or methyl) thioethers by sulfur-assisted halogen exchange with triethylamine tris-hydrofluoride
  作者：C. Saluzzo、G. Alvernhe、D. Anker、G. Haufe

  DOI：10.1016/s0022-1139(00)82399-4

  日期：1990.5

  The exchange of chlorine in β-chloroalkyl phenyl (or methyl) thioethers by fluorine, with anchimeric assistance of sulfur, is very easily realized with the almost neutral fluorinating reagent, Et3N.3HF. The ‘one-pot’ reactions of alkenes with sulfenyl chlorides and subsequently with Et3N.3HF lead to the corresponding β-fluoroalkyl thioethers in high yields.

  用几乎中性的氟化试剂Et 3 N.3HF可以很容易地实现在氟的β-氯烷基苯基（或甲基）硫醚中氯的交换，并辅以硫。烯烃与亚磺酰氯的“一锅法”反应，然后与Et 3 N.3HF的“一锅法”反应，可高产率地生成相应的β-氟代烷基硫醚。
• ALLGEMEINE HERSTELLUNG VON FLUORVERBINDUNGEN
  申请人：Solvay Fluor und Derivate GmbH

  公开号：EP1542943A1

  公开（公告）日：2005-06-22
• [DE] ALLGEMEINE HERSTELLUNG VON FLUORVERBINDUNGEN<br/>[EN] GENERAL SYNTHESIS OF FLUORINE COMPOUNDS<br/>[FR] PREPARATION GENERALE DE COMPOSES DE FLUOR
  申请人：SOLVAY FLUOR & DERIVATE

  公开号：WO2004014820A2

  公开（公告）日：2004-02-19
• Synthesis of fluoroalkyl methyl thioethers by formal addition of methanesulfenyl fluoride to alkenes
  作者：Gunter Haufe、Gerard Alvernhe、Daniel Anker、Andre Laurent、Christine Saluzzo

  DOI：10.1021/jo00028a056

  日期：1992.1

  The electrophilic anti-1,2-addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds by a one-pot reaction of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine trishydrofluoride with various types of alkenes is used for the synthesis of beta-fluoroalkyl methyl thioethers. This reaction is stereospecific: starting from cis-cycloalkenes (1) trans-1-fluoro-2-(methylthio)cycloalkanes (2) are formed, while trans-cyclododecene (3) gives the cis product 4 everytime in good yields. With unsymmetrical alkenes these reactions proceed regioselectively to produce Markovnikov-oriented fluoro thioethers. With 2,6-norbornadiene (26) exclusive exo attack on one double bond and subsequent transannular participation of the second pi-bond gives rise to two isomeric 3,5-disubstituted nortricyclanes, 28 and 29, while starting from the medium-sized cis,cis-1,5-cyclooctadiene (10) no transannular pi-participation is observed: the trans-1,2-addition product to one of the two double bonds in 11 is isolated. In contrast, in the reaction of the monoepoxide 30 of this diene in addition to the simple 1,2-adduct 31 a transannular oxygen participation occurs producing three oxa bicyclic compounds 32-34. The oxidation of 1-fluoro-2-(methylthio)cyclooctane (2a) by sodium periodate yields the expected mixture of two diastereomeric 1-fluoro-2-(methylsulfinyl)cyclooctanes (36) which on pyrolysis give 3-fluorocyclooctene (37).