4-(methylthio)trifluoroacetophenone oxime | 253585-96-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-(methylthio)trifluoroacetophenone oxime
• 英文别名: 2,2,2-trifluoro-1-(4-methylsulfanylphenyl)ethanone oxime；2,2,2-Trifluoro-1-(4-methylthiophenyl)-ethanone oxime；N-[2,2,2-trifluoro-1-(4-methylsulfanylphenyl)ethylidene]hydroxylamine
• CAS: 253585-96-5
• 化学式: C₉H₈F₃NOS
• 分子量: 235.23
• InChiKey: SBRHCHJCSMZWOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  57.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-(methylthio)trifluoroacetophenone oxime 在 吡啶 、 氨 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 3-(trifluoromethyl)-3-(4-(methylsulfonyl)phenyl)diaziridine
  参考文献：
  名称：

  The invention of radical reactions. 30. Diazirines as carbon radical traps. Mechanistic aspects and synthetic applications of a novel and efficient amination process

  摘要：

  A number of diazirines were synthesized for the purpose of exploring the addition of a carbon radical to the nitrogen-nitrogen double bond. Carbon radicals, generated from the photolysis of the O-acyl derivatives of N-hydroxy-2-thiopyridone or via radical exchange from the corresponding organotellurides, were shown to add smoothly to the diazirines leading to imines 34. When 3-(trifluoromethyl)-3-phenyldiazirine (13) is used as the trap, the thus formed imines can be easily hydrolyzed to amines. A mechanism that involves dimerization of the diaziridinyl radicals 32 to produce tetraazo intermediates 33 is suggested in accord with variable temperature NMR data for the reaction. Proof for this mechanistic scheme was furthermore obtained by isolation and X-ray structure determination of 33d. The first X-ray structure of a 3-(trifluoromethyl)-3-aryldiazirine is also reported.

  DOI：

  10.1021/ja00071a017
• 作为产物：
  描述：

  2,2,2-三氟-1-[4-(甲硫基)苯基]乙酮 在 盐酸羟胺 作用下， 以 吡啶 、 乙醇 为溶剂， 反应 3.0h， 以98%的产率得到4-(methylthio)trifluoroacetophenone oxime
  参考文献：
  名称：

  A Simple and Efficient Preparation of 3-Aryl-3-Trifluoromethyl-3H-Diazirinyl Sulfoxides and Sulfones

  摘要：

  3- 芳基-3-三氟甲基-3H-噻嗪基硫醚和砜的所有外向异构体都是通过五个步骤从相应的溴代苯甲醚中制备出来的，总收率极高。其中的关键步骤是同时氧化硫化物和二氮丙啶，根据反应条件的不同，生成二氮丙啶亚砜或砜。

  DOI：

  10.1055/s-1995-3956

文献信息

• O-acyloxime photoinitiators
  申请人：Ciba Specialty Chemicals Corporation

  公开号：US06596445B1

  公开（公告）日：2003-07-22

  Oximeester compounds of the formulae I, II, III and IV wherein R1 is phenyl, C1-C20alkyl or C2-C20alkyl optionally interrupted by —O—, C2-C20alkanoyl or benzoyl, or R1 is C2-C12alkoxycarbonyl or phenoxycarbonyl; R1′ is C2-C12alkoxycarbonyl, or R1′ is phenoxycarbonyl, or R1′ is —CONR10R11 or CN; R2 is C2-C12alkanoyl, C4-C6alkenoyl, benzoyl, C2-C6alkoxycarbonyl or phenoxycarbonyl; R3, R4, R5, R6 and R7 are hydrogen, halogen, C1-C12alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, C2-C12alkanoyl, C2-C12alkoxycarbonyl, phenoxycarbonyl or a group OR8, SR9, SOR9, SO2R9 or NR10R11; R4′, R5′ and R6′ are hydrogen, halogen, C1-C12alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, C2-C12-alkanoyl, C2-C12alkoxycarbonyl, phenoxycarbonyl, or are a group OR8, SR9, SOR9, SO2R9, NR10R11; provided that at least one of R3, R4, R5, R6, R7, R′4, R′5 and R′6 is OR8, SR9 or NR10R11; R8, R9, R10 and R11 are for example hydrogen, C1-C12alkyl, phenyl; are suitable as initiators for the photopolymerization of radically polymerizable compounds.

  化合物I、II、III和IV的肟酸酯，其中R1为苯基，C1-C20烷基或C2-C20烷基（可选地被—O—中断），C2-C20酰基或苯甲酰基，或R1为C2-C12烷氧羰基或苯氧羰基；R1'为C2-C12烷氧羰基，或R1'为苯氧羰基，或R1'为—CONR10R11或CN；R2为C2-C12酰基，C4-C6烯酰基，苯甲酰基，C2-C6烷氧羰基或苯氧羰基；R3、R4、R5、R6和R7为氢、卤素、C1-C12烷基、环戊基、环己基、苯基、苄基、苯甲酰基、C2-C12酰基、C2-C12烷氧羰基、苯氧羰基或OR8、SR9、SOR9、SO2R9或NR10R11基团；R4'、R5'和R6'为氢、卤素、C1-C12烷基、环戊基、环己基、苯基、苄基、苯甲酰基、C2-C12酰基、C2-C12烷氧羰基、苯氧羰基，或为OR8、SR9、SOR9、SO2R9、NR10R11基团；但至少有R3、R4、R5、R6、R7、R'4、R'5和R'6中的一个为OR8、SR9或NR10R11；R8、R9、R10和R11例如为氢、C1-C12烷基、苯基；适用于自由基聚合反应的光引发剂。
• Oxime derivatives and the use thereof as latent acids
  申请人：Ciba Specialty Chemicals Corporation

  公开号：US06261738B1

  公开（公告）日：2001-07-17

  Compounds of formula I, II and III, wherein wherein R1 is for example hydrogen, C1-C12alkyl, C3-C30cycloalkyl, C2-C12alkenyl, C4-C8cycloalkenyl, phenyl, which is unsubstituted or substituted, naphthyl, anthracyl or phenanthryl, unsubstituted or substituted, heteroaryl radical which is unsubstituted or substituted; wherein all radicals R1 with the exception of hydrogen can additionally be substituted by a group having a —O—C-bond or a —O—Si-bond which cleaves upon the action of an acid; R′1 is for example phenylene, naphthylene, diphenylene or oxydiphenylene, wherein these radicals are unsubstituted or substituted; R2 is halogen or C1-C10haloalkyl; R3 is for example C1-C18alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the groups are unsubstituted or substituted, or R3 is e.g. C2-C6haloalkanoyl, or halobenzoyl, R′3 is for example phenylenedisulfonyl, naphthylenedisulfonyl, diphenylenedisulfonyl, or oxydiphenylenedisulfonyl, wherein these radicals are unsubstituted or substituted, X is halogen; are especially suitable as phototsensitive acid-donors in chemically amplified resist formulations.

  式I、II和III的化合物，其中R1例如为氢、C1-C12烷基、C3-C30环烷基、C2-C12烯基、C4-C8环烯基、苯基，其未取代或取代，萘基、蒽基或菲基，其未取代或取代，杂环芳基基团，其未取代或取代；除氢外，所有R1基团均可进一步用具有—O—C键或—O—Si键的基团取代，该基团在酸作用下断裂；R′1例如为苯基、萘基、二苯基或氧二苯基，其中这些基团未取代或取代；R2为卤素或C1-C10卤代烷基；R3例如为C1-C18烷基磺酰基、苯基磺酰基、萘基磺酰基、蒽基磺酰基或菲基磺酰基，其中这些基团未取代或取代，或R3例如为C2-C6卤代酰基或卤代苯甲酰基，R′3例如为苯基二磺酰基、萘基二磺酰基、二苯基二磺酰基或氧二苯基二磺酰基，其中这些基团未取代或取代，X为卤素；特别适用于化学放大光刻胶配方中的光敏酸供体。
• The invention of radical reactions. 30. Diazirines as carbon radical traps. Mechanistic aspects and synthetic applications of a novel and efficient amination process
  作者：Derek H. R. Barton、Joseph C. Jaszberenyi、Emmanouil A. Theodorakis、J. H. Reibenspies

  DOI：10.1021/ja00071a017

  日期：1993.9

  A number of diazirines were synthesized for the purpose of exploring the addition of a carbon radical to the nitrogen-nitrogen double bond. Carbon radicals, generated from the photolysis of the O-acyl derivatives of N-hydroxy-2-thiopyridone or via radical exchange from the corresponding organotellurides, were shown to add smoothly to the diazirines leading to imines 34. When 3-(trifluoromethyl)-3-phenyldiazirine (13) is used as the trap, the thus formed imines can be easily hydrolyzed to amines. A mechanism that involves dimerization of the diaziridinyl radicals 32 to produce tetraazo intermediates 33 is suggested in accord with variable temperature NMR data for the reaction. Proof for this mechanistic scheme was furthermore obtained by isolation and X-ray structure determination of 33d. The first X-ray structure of a 3-(trifluoromethyl)-3-aryldiazirine is also reported.
• A Simple and Efficient Preparation of 3-Aryl-3-Trifluoromethyl-3H-Diazirinyl Sulfoxides and Sulfones
  作者：John B.C. Findlay、Colin W.G. Fishwick、Ian D. Kersey、Peter Ward

  DOI：10.1055/s-1995-3956

  日期：1995.5

  All regioisomers of 3-aryl-3-trifluoromethyl-3H-diazirinyl sulfoxides and sulfones have been prepared in five steps from the corresponding bromothioanisoles in excellent overall yields. The key step involves a simultaneous oxidation of sulfide and diaziridine moieties respectively, to yield either the diazirine sulphoxide or sulphone, depending on reaction conditions.

  3- 芳基-3-三氟甲基-3H-噻嗪基硫醚和砜的所有外向异构体都是通过五个步骤从相应的溴代苯甲醚中制备出来的，总收率极高。其中的关键步骤是同时氧化硫化物和二氮丙啶，根据反应条件的不同，生成二氮丙啶亚砜或砜。