N-trifluoromethylsulfonyl-(4-fluorophenyl)-carboximidoyl chloride | 343337-74-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-trifluoromethylsulfonyl-(4-fluorophenyl)-carboximidoyl chloride
• 英文别名: 4-fluoro-N-(trifluoromethylsulfonyl)benzimidoyl chloride；4-fluoro-N-(trifluoromethylsulfonyl)benzenecarboximidoyl chloride
• CAS: 343337-74-6
• 化学式: C₈H₄ClF₄NO₂S
• 分子量: 289.638
• InChiKey: ZWLCVADFIOHTKH-UHFFFAOYSA-N

物化性质

• 沸点：
  284.7±50.0 °C(Predicted)
• 密度：
  1.57±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  54.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N-trifluoromethylsulfonyl-(4-fluorophenyl)-carboximidoyl chloride 在 sodium azide 作用下， 以 乙二醇二甲醚 为溶剂， 生成
  参考文献：
  名称：

  Aza Curtius 重排

  摘要：

  关于 N-（三氟甲基磺酰基）羧亚氨基酰氯（羰基氧原子被更强的吸电子 =NSO2CF3 基团取代的酰基氯的类似物）与叠氮化钠在甘醇二甲醚或乙腈中在 -5 至 +10 °C 下的相互作用，二氮被定量消除，并以高产率形成碳二亚胺 RN=C=NSO2CF3。换句话说，发生 aza Curtius 重排。碳二亚胺与水、醇和仲胺反应生成相应的脲、异脲和胍衍生物。具有除 SO2RF 以外的取代基的亚氨酰氯不参与 aza Curtius 反应。

  DOI：

  10.1002/1099-0690(200104)2001:7<1225::aid-ejoc1225>3.0.co;2-6
• 作为产物：
  描述：

  4-fluoro-N-((trifluoromethyl)sulfonyl)benzamide 在 五氯化磷 、 三氯氧磷 作用下， 反应 2.0h， 以95%的产率得到N-trifluoromethylsulfonyl-(4-fluorophenyl)-carboximidoyl chloride
  参考文献：
  名称：

  Aza Curtius 重排

  摘要：

  关于 N-（三氟甲基磺酰基）羧亚氨基酰氯（羰基氧原子被更强的吸电子 =NSO2CF3 基团取代的酰基氯的类似物）与叠氮化钠在甘醇二甲醚或乙腈中在 -5 至 +10 °C 下的相互作用，二氮被定量消除，并以高产率形成碳二亚胺 RN=C=NSO2CF3。换句话说，发生 aza Curtius 重排。碳二亚胺与水、醇和仲胺反应生成相应的脲、异脲和胍衍生物。具有除 SO2RF 以外的取代基的亚氨酰氯不参与 aza Curtius 反应。

  DOI：

  10.1002/1099-0690(200104)2001:7<1225::aid-ejoc1225>3.0.co;2-6

文献信息

• Trifluoromethanesulfonylimides of arenehydroxamic acids and their aza Lossen rearrangement
  作者：Lev M. Yagupolskii、Svetlana V. Shelyazhenko、Irina I. Maletina、Liubov V. Sokolenko、Alexander N. Chernega、Eduard B. Rusanov、Ivan F. Tsymbal

  DOI：10.1016/j.jfluchem.2007.01.002

  日期：2007.5

  Trifluoromethanesulfonylimides of arenehydroxamic acids ArC(NSO2CF3)NHOH (1), analogues of arenehydroxamic acids, in which sp2 hybridized oxygen atom is replaced by the much stronger electron-withdrawing group NSO2CF3, have been synthesized, and the abilities of these compounds to undergo transformations similar to the Lossen rearrangement have been studied.

  合成了芳烃异羟肟酸的三氟甲磺酰亚胺ArC（NSO 2 CF 3）NHOH（1），其中芳烃异羟肟酸的类似物，其中sp 2杂化的氧原子被更强的吸电子基团NSO 2 CF 3取代，并且其能力已经研究了这些化合物中的哪些经历类似于Lossen重排的转化。
• The immense acidifying effect of the supersubstituent NSO₂CF₃on the acidity of amides and amidines of benzoic acids in acetonitrile
  作者：Lev M. Yagupolskii、Vitalij N. Petrik、Natalia V. Kondratenko、Lilli Sooväli、Ivari Kaljurand、Ivo Leito、Ilmar A. Koppel

  DOI：10.1039/b204172c

  日期：——

  The pKa values of acidic dissociation of the conjugate acids of derivatives of benzoate anions, where one or two oxygen atoms are replaced by an NSO2CF3 group, N-aroyltrifluoromethanesulfonamides 1a–f and previously unreported N,N′-bis(trifluoromethylsulfonyl)benzamidines 4a–f, were measured in acetonitrile. In the case of the parent compound, the incorporation of the first NSO2CF3 group instead of the oxygen atom leads to a sharp (by 9.6 pKa units) increase in the acidity, whereas the replacement of the second oxygen atom results in a further huge increase in the acidity by 4.9 powers of ten. It was found that the sensitivity of the reaction series under consideration towards substituent effects (in the benzene ring) decreases in the following order: benzoic acids > benzamides (1a–f) > benzamidines (4a–f). The results of this work carry potentially important implications for the design of new types of superacids and catalytic materials.

  在乙腈中测量了苯甲酸阴离子衍生物（其中一个或两个氧原子被一个 NSO2CF3 基团取代）、N-芳酰基三氟甲基磺酰胺 1a-f 和以前未报道过的 N,N′-双（三氟甲基磺酰基）苯甲脒 4a-f 的共轭酸的酸性解离 pKa 值。在母体化合物中，取代氧原子而加入第一个 NSO2CF3 基团会导致酸度急剧增加（增加 9.6 pKa 单位），而取代第二个氧原子则会导致酸度进一步大幅增加 4.9 的十次方。研究发现，所研究的反应系列对（苯环上的）取代基效应的敏感性按以下顺序递减：苯甲酸 > 苯甲酰胺（1a-f） > 苯甲酰胺（4a-f）。这项工作的结果对设计新型超酸和催化材料具有潜在的重要意义。
• N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement
  作者：Lev M. Yagupolskii、Irina I. Maletina、Liubov V. Sokolenko、Yurii G. Vlasenko、Sergey A. Buth

  DOI：10.1016/j.jfluchem.2008.03.001

  日期：2008.6

  The analogues of carboxamides in which the sp(2)-hybridized oxygen atom is replaced by more electron-withdrawing groups, =NSO(2)CF(3) and =NSO(2)C(4)F(9), have been synthesized. The resulting N-perfluoroalkylsulfonyl arenecarboxamidines ArC(=NSO(2)R(f))NH(2) (Rf = CF(3), C(4)F(9)) undergo an oxidative Hofmann-type rearrangement to the corresponding carbodiimides ArN=C=NSO(2)R(f) under the action of (diacyloxy-iodo)arenes. Rearrangement of related compounds ArC(=NSO(2)R)NH(2) (R = CH(3), Ph) containing fluorine-free substituents at the sulfonyl group also occurs in similar conditions. It was found that the reactivity of amidines rises with the increasing electron-withdrawing ability of the substituent R. (C) 2008 Elsevier B.V. All rights reserved.
• The aza Arndt–Eistert reaction based on N-trifluoromethylsulfonylarenecarboximidoyl chlorides
  作者：Lev M. Yagupolskii、Irina I. Maletina、Liubov V. Sokolenko、Yurii G. Vlasenko、Maria V. Drozdova、Vitaliy V. Polovinko

  DOI：10.1016/j.jfluchem.2009.10.019

  日期：2010.2

  The aza analogues of carboxylic acids chlorides containing the =NSO2CF3 and =NSO2CH3 groups instead of oxygen atom were used in the Arndt-Eistert reaction. It was found that N-trifluoromethylsulfonyl-(4-fluorophenyl)-carboximidoyl chloride 1 reacts with diazomethane vigorously even at -70 degrees C with formation of 1-trifluoromethylsulfonylamino-2-(4-fluorophenyl)-2,3-dimorpholine-4-yl-propane 3, 2-trifluoromethylsulfonylamino-2-(4-fluorobenzyl)-7-oxa-4-azonia-spiro[3.5]nonane 4, 2-trifluoromethylsulfonylamino-2-(4-fluorobenzyl)-1,3-dimorpholine-4-yl-propane 5 and 1-trifluoromethyisulfonylamino-2-(4-fluorobenzyl)-2,3-dimorpholine-4-yl-propane 6. Reaction of N-methylsulfonylbenzcarboximidoyl chloride 8 with diazomethane proceeds at -15 degrees C yielding 4-chloro-4-methylsulfonylaminomethyl-3-phenyl-4,5-dihydro-1H-pyrazoline 9. (C) 2009 Elsevier B.V. All rights reserved.
• The Aza Curtius Rearrangement
  作者：Lev M. Yagupolskii、Svetlana V. Shelyazhenko、Irina I. Maletina、Vitalij N. Petrik、Eduard B. Rusanov、Alexander N. Chernega

  DOI：10.1002/1099-0690(200104)2001:7<1225::aid-ejoc1225>3.0.co;2-6

  日期：2001.4

  carbodiimides RN=C=NSO2CF3 are formed in high yield. In other words, an aza Curtius rearrangement occurs. The carbodiimides react with water, alcohols, and secondary amines to give corresponding ureas, isoureas, and guanidine derivatives. Imidoyl chlorides with substituents other than SO2RF do not enter into the aza Curtius reaction.

  关于 N-（三氟甲基磺酰基）羧亚氨基酰氯（羰基氧原子被更强的吸电子 =NSO2CF3 基团取代的酰基氯的类似物）与叠氮化钠在甘醇二甲醚或乙腈中在 -5 至 +10 °C 下的相互作用，二氮被定量消除，并以高产率形成碳二亚胺 RN=C=NSO2CF3。换句话说，发生 aza Curtius 重排。碳二亚胺与水、醇和仲胺反应生成相应的脲、异脲和胍衍生物。具有除 SO2RF 以外的取代基的亚氨酰氯不参与 aza Curtius 反应。