2‐(methylsulfanyl)‐1‐[4‐(trifluoromethyl)phenyl]ethanone | 136067-94-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2‐(methylsulfanyl)‐1‐[4‐(trifluoromethyl)phenyl]ethanone
• 英文别名: p-trifluoromethyl-α-methylthioacetophenone；2-(methylthio)-4'-(trifluoromethyl)acetophenone；2-methylthio-4'-(trifluoromethyl)acetophenone；2-(Methylsulfanyl)-1-[4-(trifluoromethyl)phenyl]ethan-1-one；2-methylsulfanyl-1-[4-(trifluoromethyl)phenyl]ethanone
• CAS: 136067-94-2
• 化学式: C₁₀H₉F₃OS
• mdl: MFCD16617821
• 分子量: 234.242
• InChiKey: JZJVYPCVACCIFG-UHFFFAOYSA-N

物化性质

• 沸点：
  293.1±40.0 °C(Predicted)
• 密度：
  1.266±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2‐(methylsulfanyl)‐1‐[4‐(trifluoromethyl)phenyl]ethanone 在 1-氟-2,4,6-三甲基吡啶三氟甲烷磺酸盐 、 zinc dibromide 作用下， 以 1,1,2-三氯乙烷 为溶剂， 反应 2.0h， 以60.1%的产率得到2,2-Difluoro-2-(methylthio)-1-[4-(trifluoromethyl)phenyl]-1-ethanone
  参考文献：
  名称：

  .ALPHA.,.ALPHA.-gem-Difluorination of .ALPHA.-(Alkylthio)acetophenone Derivatives with N-Fluoropyridinium Salts.

  摘要：

  用 N-氟吡啶鎓盐对 2'，4'-二氟-α-(甲硫基)苯乙酮 (1a) 进行α，α-锗二氟化反应，可得到 2'，4'，α，α-四氟-α-(甲硫基)苯乙酮 (3a)。加入氯化锌、溴化锌或无水氯化铁（III）可加速该反应，并获得比不加入添加剂时更高的产率。在溴化锌存在下使用 FP-T300 进行的宝石二氟化反应适用于其他 α-（烷硫基）苯乙酮衍生物 (1)。

  DOI：

  10.1248/cpb.48.1097
• 作为产物：
  描述：

  2-溴-4'-(三氟甲基)苯乙酮 以97.7的产率得到2‐(methylsulfanyl)‐1‐[4‐(trifluoromethyl)phenyl]ethanone
  参考文献：
  名称：

  Triazole derivatives and a composition for treating mycoses

  摘要：

  本发明公开了一种三唑衍生物。该化合物具有一般式##STR1##其中R.sup.1和R.sup.2代表氢原子或较低的烷基，或R.sup.1和R.sup.2共同形成较低的亚烷基，R.sup.3代表较低的烷基，n表示0至2的整数，但不得同时两个R.sup.1和R.sup.2都是氢原子。这些三唑衍生物及其盐对治疗或预防深部真菌病，例如真菌性脑膜炎，呼吸器官真菌感染疾病，真菌血症和尿路真菌病非常有效。

  公开号：

  US05147886A1

文献信息

• New Antifungal 1,2,4-Triazoles with Difluoro(substituted sulfonyl)methyl Moiety.
  作者：Hiromichi ETO、Yasushi KANEKO、Sunao TAKEDA、Minoru TOKIZAWA、Susumu SATO、Kouiti YOSHIDA、Setsuo NAMIKI、Masaki OGAWA、Kazuki MAEBASHI、Kazuya ISHIDA、Masaru MATSUMOTO、Takemitsu ASAOKA

  DOI：10.1248/cpb.49.173

  日期：——

  New 1, 2, 4-triazoles (2) having a difluoro(substituted sulfonyl)methyl moiety were designed and synthesized via α, α-difluoro-α-(substituted thio)acetophenones (3). Compounds (2) showed potent antifungal activities against C. albicans, C. krusei, A. flavus and A. fumigatus in vitro and against C. albicans in vivo for oral and i.v. administrations. Especially, (−)-2a, (−)-2b and (−)-2d showed potent antifungal activities.

  新型的1, 2, 4-三氮唑衍生物（2），其结构中含有一个二氟（取代磺酰基）甲基，通过α, α-二氟-α-（取代硫基）苯乙酮（3）的设计与合成得以实现。化合物（2）在体外展现出对白色念珠菌、克鲁斯念珠菌、黄曲霉和烟曲霉的强效抗真菌活性，并且在体内对于口服和静脉注射途径的白色念珠菌也表现出显著的抗真菌作用。特别是（−）-2a、（−）-2b和（−）-2d显示出强大的抗真菌活性。
• Rhodium-Catalyzed Methylthio Transfer Reaction between Ketone α-Positions: Reversible Single-Bond Metathesis of C−S and C−H Bonds
  作者：Mieko Arisawa、Katsunori Suwa、Masahiko Yamaguchi

  DOI：10.1021/ol802619e

  日期：2009.2.5

  ophenone giving α-phenylthio-α-methylthio ketones. The methylthio transfer reaction between the ketone α-positions was reversible and at equilibrium, and the methylthio group was transferred in preference to the phenylthio group. The reaction of tertiary alkyl methylthiomethyl ketones proceeded in high yields; the reaction of diastereomeric 4-(tert-butyl)-2-phenylthiocyclohexanones gave an axial 2-methylthiolated

  在催化量的RhH（PPh 3）4和1,2-双（二苯基正膦）乙烷（dppe）存在下，将α-苯硫酮与对氰基-α-甲基硫代苯乙酮进行甲硫醇化，得到α-苯硫基-α-甲硫基酮。酮α-位之间的甲硫基转移反应是可逆的，并且处于平衡状态，甲硫基优先于苯硫基转移。叔烷基甲硫基甲基酮的反应产率高。非对映异构体4-（叔丁基）-2-苯基硫代环己酮的反应得到轴向的2-甲基硫醇化产物。
• Substituted α-Sulfur Methyl Carbanions: Effective Homologating Agents for the Chemoselective Preparation of β-Oxo Thioethers from Weinreb Amides
  作者：Raffaele Senatore、Laura Ielo、Ernst Urban、Wolfgang Holzer、Vittorio Pace

  DOI：10.1002/ejoc.201800095

  日期：2018.6.7

  generation of α‐thiomethyllithium reagents via reductive lithiation or deprotonation followed by reaction with variously functionalized Weinreb amides represents an excellent method to access β‐oxo thioethers. The procedure is adaptable to alkyl‐ or aryl‐ thiomethyllithium conjugates. It has the advantages of conceptual simplicity and versatility of the addition of organometallics to Weinreb amides with the

  通过还原锂化或去质子化，然后与各种功能化的Weinreb酰胺反应，可以正确生成α-硫代甲基锂试剂，这是获得β-氧代硫醚的绝佳方法。该程序适用于烷基或芳基硫代甲基锂共轭物。它具有概念简单性和向Weinreb酰胺中添加有机金属化合物的多功能性，并有可能完全保留起始材料中包含的光学信息。
• Process for preparing diketone compounds and precursors thereto
  申请人：——

  公开号：US20010014761A1

  公开（公告）日：2001-08-16

  A process for preparing compounds of the formula: 1 wherein R 2 is lower alkyl; or phenyl optionally substituted by from one to five groups, the same or different, which are lower alkyl, lower haloalkyl, halogen or —SR 4 ; R 3 is halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, —S-alkyl, cycloalkyl having from 3 to 7 carbon atoms in the ring, alkenyl or alkynyl having from 3 to 7 carbon atoms, or —(CR 5 R 6 )—SR 2 wherein q is one or two; R 4 is lower alkyl; R 5 and R 6 independently represent hydrogen, lower alkyl or lower haloalkyl; and n is zero or an integer from one to three; intermediate compounds of the formula: 2 and processes for preparing them.

  一种制备公式为1的化合物的方法：其中R2为低碳基；或苯基，可选地被从一个到五个相同或不同的基团取代，所述基团为低碳基，低卤代烷基，卤素或-SR4；R3为卤素，低碳基，低卤代烷基，低烷氧基，低卤代烷氧基，-S-烷基，环烷基，环中含有3到7个碳原子，烯基或炔基，具有3到7个碳原子，或-(CR5R6)-SR2，其中q为1或2；R4为低碳基；R5和R6分别表示氢，低碳基或低卤代烷基；n为0或1至3的整数；公式2的中间体化合物及其制备方法。
• Rh/DuanPhos-Catalyzed Asymmetric Hydrogenation of β-Acetylamino Vinylsulfides: An Approach to Chiral β-Acetylamino Sulfides
  作者：Wenchao Gao、Hui Lv、Xumu Zhang

  DOI：10.1021/acs.orglett.7b01115

  日期：2017.6.2

  Rh/DuanPhos-catalyzed asymmetric hydrogenation of challenging beta-acetylamino vinylsulfides has been developed; affording chiral beta-acetylamino, sulfides with high yield's and excellent ee's (up to, 99% ee). This novel methodology provides an efficient and' concise, synthetic route, to chiral beta-acetylamino sulfides. The potential utility of this protocol in the synthesis of Apremilast has also been disclosed.