bis(phenylthio)malononitrile | 30866-18-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: bis(phenylthio)malononitrile
• 英文别名: Bis(phenylthio)malonitril；2,2-Bis(phenylsulfanyl)propanedinitrile
• CAS: 30866-18-3
• 化学式: C₁₅H₁₀N₂S₂
• 分子量: 282.39
• InChiKey: SKGBRCGHCMYENA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  98.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-苯硫基-吡咯啉-2,5-二酮 、 丙二腈 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 bis(phenylthio)malononitrile
  参考文献：
  名称：

  活性亚甲基化合物与磺胺的磺酰化

  摘要：

  衍生自仲烷基胺的次磺酰胺与活性亚甲基化合物的等摩尔反应以良好的产率提供单次磺酰化的化合物。2 mol 衍生自酰亚胺的次磺酰胺与 1 mol 活性亚甲基化合物在碱存在下反应，得到二亚磺酰化化合物。发现α-单-亚磺酰化酮是通过烯胺与衍生自酰亚胺的次磺酰胺反应制备的。α-gem-Di-sulfenylated 酮是通过 α-mono-sulfenylated 酮与衍生自酰亚胺的亚磺酰胺在碱存在下反应制备的。还研究了N-苯基硫代苯甲脒盐酸盐的制备和反应。

  DOI：

  10.1246/bcsj.45.866

文献信息

• Pyrolysis of (2-Phenylethyl)phenylsulfonium Ylides.
  作者：Toshiaki Yoshimura、Atsushi Motoyama、Akiko Morishige、Eiichi Tsukurimichi、Choichiro Shimasaki、Kiyoshi Hasegawa

  DOI：10.1246/bcsj.66.174

  日期：——

  In order to obtain information concerning the reaction mechanism of the pyrolysis of sulfonium ylides bearing a substituted phenyl group on the 2-position in the S-ethyl group of ethylphenylsulfonium ylide, (2-phenylethyl)phenylsulfonium bis(methoxycarbonyl)methylide (1) and dicyanomethylide (2) were subjected to pyrolysis in benzene. The reaction rates of 1 and 2 at 140 °C were 6.0- and 3.2-times faster than those of ethylphenylsulfonium bis(methoxycarbonyl)methylide and dicyanomethylide, respectively. The activation parameters for 1 were ΔH‡ = 125 kJ mol−1 and ΔS‡ = −3.8 J K−1 mol−1, while those for 2 were ΔH‡ = 124 kJ mol−1 and ΔS‡ = −2.5 J K−1 mol−1. Substituent effects on the β-phenyl groups in 1 and 2 afforded positive Hammett ρ-values: ρ = 0.49 (γ = 0.997) and ρ = 0.26 (γ = 0.993), respectively.From the obtained results, it was suggested that the pyrolysis proceeds through essentially a concerted intramolecular cis-elimination inclined toward a slightly carbanion-like type from an E1-like type by introducing a phenyl substituent at the 2-position of the ethyl group in the ethylphenylsulfonium ylide.

  为了获取有关乙基苯基亚磺酸乙酯中乙基的2-位上带有取代苯基的磺酸亚磺酸分解反应机理的信息，将（2-苯乙基）苯基亚磺酸双（甲氧基羰基）甲亚基（1）和双氰基甲亚基（2）在苯中进行分解。在140°C时，1和2的反应速率分别比乙基苯基亚磺酸双（甲氧基羰基）甲亚基和双氰基甲亚基快6.0倍和3.2倍。1的活化参数为ΔH‡ = 125 kJ mol−1，ΔS‡ = -3.8 J K−1 mol−1，而2的活化参数为ΔH‡ = 124 kJ mol−1，ΔS‡ = -2.5 J K−1 mol−1。1和2中β-苯基的取代效应提供了正的Hammett ρ值：ρ = 0.49（γ = 0.997）和ρ = 0.26（γ = 0.993）。从得到的结果可以看出，通过在乙基苯基亚磺酸乙的乙基的2-位引入苯基取代基，基本上是通过倾向于稍微类似于碳负离子的顺式消除过程，从而类似于E1型反应。
• Vulcanizable rubber compositions inhibited from premature vulcanization by methylene thioethers, and novel methylene thioethers
  申请人：MONSANTO COMPANY

  公开号：EP0029719A1

  公开（公告）日：1981-06-03

  Sulfur-vulcanizable rubber compositions containing sulfur-vulcanizing agent and organic vulcanization accelerating agent are inhibited from premature vulcanization by activated methylene di (thioethers) ofthe formula in which R is alkyl of 1-20 carbon atoms, cycloalkyl of 5-12 carbon atoms, benzyl, a-methylbenzyl, phenyl, or substituted phenyl wherein the substituents are lower alkyl, lower alkoxy, or halo, R is R or anilino or substituted anilino wherein the substituents are lower alkyl, lower alkoxy or halo, and R2 is phenyl or substituted phenyl as above; in which R is the same as above and X is o-phenylene or straight or branched alkylene of 2-4 chain carbon atoms; in which R is the same as above, R3 is lower alkyl or lower alkoxy, and R4 is carboalkoxy of 1-5 carbon atoms orSR in which R is the same as above and R, is carboalkoxy of 1-5 carbon atoms, substituted carbamoyl of the formula in which R6 is hydrogen or R, R, is R or carboalkoxy of 1-5 carbon atoms, or R6 and R7 together is alkylene or oxydialkylene of 4-8 carbon atoms which along with the nitrogen atom forms a heterocycle. Methylene di (thioethers) having the above formulae are novel compounds. There may also be used in the vulcanizable compositions methylene di (thioethers) in which R5 is cyano; and, provided the organic accelerating agent is 2-mercaptobenzothiazole, methylene di (thioethers) in which R4 is lower alkyl or R3 is carbamoyl.

  含有硫磺硫化剂和有机硫化促进剂的可硫化橡胶组合物通过活化的亚甲基二（硫醚）来抑制过早硫化，其式为 其中 R 为 1-20 个碳原子的烷基、5-12 个碳原子的环烷基、苄基、a-甲基苄基、苯基或取代苯基（其中取代基为低级烷基、低级烷氧基或卤基），R 为 R 或苯胺基或取代苯胺基（其中取代基为低级烷基、低级烷氧基或卤基），R2 为苯基或取代苯基，如上所示； 其中 R 同上，X 为邻苯基或 2-4 链碳原子的直链或支链亚烷基； 其中 R 同上，R3 为低级烷基或低级烷氧基，R4 为 1-5 个碳原子的羧基烷氧基或 SR 其中 R 同上，R 是 1-5 个碳原子的羧基烷氧基，式中的取代氨基甲酰基 其中 R6 是氢或 R，R, 是 R 或 1-5 个碳原子的羧基烷氧基，或 R6 和 R7 合在一起是 4-8 个碳原子的亚烷基或氧基二烷基，与氮原子一起形成杂环。 具有上述分子式的亚甲基二（硫醚）是新型化合物。 在可硫化组合物中还可使用 R5 为氰基的亚甲基二硫代硫醚；以及 R4 为低级烷基或 R3 为氨基甲酰基的亚甲基二硫代硫醚（如果有机促进剂为 2-巯基苯并噻唑）。
• US4271050A
  申请人：——

  公开号：US4271050A

  公开（公告）日：1981-06-02
• US4342705A
  申请人：——

  公开号：US4342705A

  公开（公告）日：1982-08-03
• Sulfenylation of Active Methylene Compounds with Sulfenamides
  作者：Takanobu Kumamoto、Susumu Kobayashi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.45.866

  日期：1972.3

  secondary alkylamines with active methylene compounds afforded mono-sulfenylated compounds in good yields. The reactions of 2 mol of sulfenamides derived from imides with 1 mol of active methylene compounds in the presence of a base gave di-sulfenylated compounds. It was found that α-mono-sulfenylated ketones were prepared by the reactions of enamines with sulfenamides derived from imides. α-gem-Di-sulfenylated

  衍生自仲烷基胺的次磺酰胺与活性亚甲基化合物的等摩尔反应以良好的产率提供单次磺酰化的化合物。2 mol 衍生自酰亚胺的次磺酰胺与 1 mol 活性亚甲基化合物在碱存在下反应，得到二亚磺酰化化合物。发现α-单-亚磺酰化酮是通过烯胺与衍生自酰亚胺的次磺酰胺反应制备的。α-gem-Di-sulfenylated 酮是通过 α-mono-sulfenylated 酮与衍生自酰亚胺的亚磺酰胺在碱存在下反应制备的。还研究了N-苯基硫代苯甲脒盐酸盐的制备和反应。