1-(phenylthio)cyclohexanecarbonitrile | 36638-55-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-(phenylthio)cyclohexanecarbonitrile
• 英文别名: 1-(Phenylsulfanyl)cyclohexanecarbonitrile；1-phenylsulfanylcyclohexane-1-carbonitrile
• CAS: 36638-55-8
• 化学式: C₁₃H₁₅NS
• 分子量: 217.335
• InChiKey: NCJBSHUYCYISTH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(phenylthio)cyclohexanecarbonitrile 在 sodium hydroxide 作用下， 生成 1-Phenylsulfanylcyclohexanecarboxylic acid
  参考文献：
  名称：

  Reactions of organic anions. XLII. Catalytic alkylation of S-phenylthioglycolonitrile in aqueous medium

  摘要：

  DOI：

  10.1016/s0040-4039(01)85311-9
• 作为产物：
  描述：

  1-(pyridin-2-ylthio)cyclohexanecarbonitrile 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 3.75h， 生成 1-(phenylthio)cyclohexanecarbonitrile
  参考文献：
  名称：

  Arylthio-Metal Exchange of α-Arylthioalkanenitriles

  摘要：

  The addition of BuLi, Bu3MgLi, Et2ZnBuLi, or Me2CuLi to alpha-arylthioalkanenitriles triggers an arylthio-metal exchange. NMR spectroscopic analyses implicate organometallic attack on sulfur forming a three-coordinate sulfidate as the key intermediate. Electrophilic trapping affords tertiary and quaternary nitriles in high yield. The method addresses the challenge of improving the functional group tolerance and preventing polyalkylations.

  DOI：

  10.1021/ol403020s

文献信息

• Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles
  作者：Xun Yang、Dinesh Nath、Michael R. Gau、Omar W. Steward、Fraser F. Fleming

  DOI：10.1002/anie.201704028

  日期：2017.6.12

  sulfone–metal exchange is described. Treating substituted 2‐pyridylsulfonylacetonitriles with either BuLi or Bu3MgLi generates metalated nitriles that efficiently intercept a variety of electrophiles to afford quaternary nitriles. The 2‐pyridylsulfone is critical for the sulfone–metal exchange because chelation anchors the organometallic proximal to the electrophilic, tetrasubstituted sulfone to override

  描述了第一次一般的砜-金属交换。用BuLi或Bu 3 MgLi处理取代的2-吡啶基磺酰基乙腈会生成金属化的腈，该腈可有效拦截各种亲电试剂，从而生成季腈。2-吡啶基砜对于砜与金属的交换至关重要，因为螯合将有机金属锚定在亲电子的四取代砜的近端，以克服复合物引起的去质子化。用温和的碱（K 2 CO 3或DBU）烷基化2-吡啶磺酰基乙腈，然后进行砜-金属交换和烷基化，通过三个烷基化作用快速组装季腈，其中只有一个需要有机金属试剂。
• Nitrile Alkylations through Sulfinyl-Metal Exchange
  作者：Dinesh Nath、Fraser F. Fleming

  DOI：10.1002/anie.201105630

  日期：2011.12.2

  Triple alkylation: Phenylsulfinyl‐ and phenylthioacetonitrile can function as trianion equivalents of acetonitrile by sequential alkylation and sulfinyl–metal exchange (see scheme; mCPBA=meta‐chloroperoxybenzoic acid). The metalated nitriles alkylate a range of electrophiles to obtain nitriles with quaternary centers. The sulfinyl–metal exchange proceeds under very mild conditions and has a high functional‐group

  三重烷基化：通过顺序烷基化和亚磺酰基-金属交换，苯亚磺酰基和苯硫基乙腈可以作为乙腈的三价阴离子（见方案；m CPBA =间-氯过氧苯甲酸）。金属化的腈使一系列亲电试剂烷基化以获得具有季中心的腈。亚磺酰基-金属的交换在非常温和的条件下进行，并且具有很高的官能团耐受性。
• Sulfinylnitriles: Sulfinyl-Metal Exchange-Alkylation Strategies
  作者：Dinesh Nath、Fraser F. Fleming

  DOI：10.1002/chem.201203174

  日期：2013.2.4

  organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl–metal exchange to afford N‐ or C‐metalated nitriles. Sulfinyl–magnesium exchange–alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α‐Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and

  添加有机锂，格氏试剂，或锌酸盐到sulfinylnitriles触发器一个浅显亚磺酰基-金属交换，得到N -或C -金属化的腈。亚磺酰基-镁交换-烷基化有效地建立了四级和三级中心，即使在具有高酸性次甲基质子的叔亚磺酰基腈的情况下也是如此。α-亚磺酰基烯腈提供适度的亲核性镁化腈，通过转化为相应的镁酸酯可以显着提高反应性。亚磺酰基-金属交换非常快，可与季，叔和乙烯基α-亚磺酰基腈有效地进行交换，并且在腈烷基化反应中表现出出色的官能团耐受性。
• A Convenient Method for the Transformation of Alkenyl Sulfides to 2-(Phenylthio)alkanenitriles, Homoallyl Sulfides, and Thioacetals
  作者：Takeshi Takeda、Yuichiro Kaneko、Hitoshi Nakagawa、Tooru Fujiwara

  DOI：10.1246/cl.1987.1963

  日期：1987.10.5

  2-(Phenylthio)alkanenitriles, homoallyl sulfides, and thioacetals were obtained in good yields by the reaction of alkenyl sulfides with the corresponding silyl nucleophiles via thionium ion intermediates.

  通过烯基硫醚与相应的甲硅烷基亲核试剂通过锍离子中间体反应，以良好的收率获得了2-(苯硫基)烷腈、高烯丙基硫醚和硫缩醛。
• α-(Benzotriazolyl)methyl phenyl thioethers: Convenient reagents for α-phenylthioalkylation of silylated nucleophiles
  作者：Alan R. Katritzky、Jie Chen、Sergei A. Belyakov

  DOI：10.1016/s0040-4039(96)01493-1

  日期：1996.9

  Stable, crystalline α-(benzotriazolyl)methyl phenyl thioethers (1), easily prepared from carbonyl compounds, thiophenol and benzotriazole, are convenient reagents for the phenylthiomethylation of trimethylsilyl cyanide, trimethylallylsilane, and trimethylsilyl enol ethers to afford the corresponding substituted thioethers and β-phenylthioalkylketones (3) in good yields.

  容易从羰基化合物，硫酚和苯并三唑制备的稳定的结晶性α-（苯并三唑基）甲基苯基硫醚（1）是方便的试剂，可用于三甲基甲硅烷基氰化物，三甲基烯丙基硅烷和三甲基甲硅烷基烯醇醚的苯硫甲基化，从而提供相应的取代的硫醚和β-苯硫基烷基酮（3）的收率很高。