(difluoromethyl)(imino)(phenyl)-λ⁶-sulfanone | 1333375-53-3

• 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: (difluoromethyl)(imino)(phenyl)-λ⁶-sulfanone
• 英文别名: (Difluoromethyl)(imino)phenyl-lambda6-sulfanone；difluoromethyl-imino-oxo-phenyl-λ6-sulfane
• CAS: 1333375-53-3
• 化学式: C₇H₇F₂NOS
• 分子量: 191.201
• InChiKey: OVTMRPQANBHQPY-UHFFFAOYSA-N

物化性质

• 沸点：
  229.1±50.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  49.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (difluoromethyl)(imino)(phenyl)-λ⁶-sulfanone 在 三氯异氰尿酸 作用下， 以 乙腈 为溶剂， 反应 0.33h， 以89%的产率得到(chloroimino)(difluoromethyl)(phenyl)-λ⁶-sulfanone
  参考文献：
  名称：

  用N-氯S-氟烷基亚砜亚胺进行光氧化还原引发的烯烃的1,2-双官能化

  摘要：

  我们在这里描述了烯烃衍生物与N-氯S-氟代烷基亚砜亚胺的光氧化还原引发的1,2-双官能化，产生了新型的氟代烷基亚砜亚胺骨架。建议该反应通过原子转移自由基加成（ATRA）机理进行，该机理涉及生成氟化的以氮为中心的磺酰亚胺基。

  DOI：

  10.1002/adsc.201801207
• 作为产物：
  描述：

  difluoromethyl phenyl sulfoxide 在 sodium azide 、 发烟硫酸 作用下， 以 二氯甲烷 为溶剂， 以99%的产率得到(difluoromethyl)(imino)(phenyl)-λ⁶-sulfanone
  参考文献：
  名称：

  N,N-Dimethyl-S-difluoromethyl-S-phenylsulfoximinium tetrafluoroborate: A versatile electrophilic difluoromethylating reagent

  摘要：

  Over the past decade, sulfur-based fluoromethyl containing compounds have been exhaustively investigated as versatile fluoroalkylating reagents by our research laboratory as well as many others. Lately, we have designed a novel electrophilic difluoromethylating protocol employing in situ prepared N,N-dimethyl-S-difluoromethyl-S-phenylsulfoximinium salt. The present reagent provides excellent reactivity toward a broad spectrum of nucleophilic species (N-, P-, S-, and O-nucleophiles) to yield the corresponding difluoromethylated products with high efficacy under mild conditions. Additional studies have been performed to elucidate the mechanistic fundamentals of the reactions. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2011.04.023

文献信息

• Nucleophilic Difluoromethylation of Epoxides with PhSO(NTBS)CF₂H by a Preorganization Strategy
  作者：Xiao Shen、Qinghe Liu、Tao Luo、Jinbo Hu

  DOI：10.1002/chem.201402506

  日期：2014.5.26

  synthesis of β‐monofluoromethyl alcohols by nucleophilic monofluoromethylation of epoxides, the synthesis of β‐difluoromethyl alcohols by nucleophilic difluoromethylation of epoxides still remains a challenge. Herein, studies on tackling this problem with PhSO(NTBS)CF2H (2; TBS=tert‐butyldimethylsilyl) are reported. The preorganization of 2 and epoxides with BF3⋅Et2O was found to be crucial for the

  与通过环氧化物的亲核单氟甲基化轻松合成β-单氟甲基醇不同，通过环氧化物的亲核二氟甲基化合成β-二氟甲基醇仍然是一个挑战。在此，已报道了用PhSO（NTBS）CF 2 H（2； TBS =叔丁基二甲基甲硅烷基）解决此问题的研究。的preorganization 2个环氧化物与BF 3 ⋅的Et 2发现O对于反应至关重要。该反应显示出优异的区域选择性并且具有广泛的底物范围。开环产物容易转化为β-二氟甲基，γ-二氟甲基和β-二氟亚甲基醇，证明了该反应的合成效用。
• Synthesis of α-Difluoromethyl Aryl Ketones through a Photoredox Difluoromethylation of Enol Silanes
  作者：Elias Selmi-Higashi、Jinlei Zhang、Xacobe C. Cambeiro、Stellios Arseniyadis

  DOI：10.1021/acs.orglett.1c01177

  日期：2021.6.4

  We report here an efficient and highly straightforward access to α-difluoromethylated ketones through a visible light-mediated difluoromethylation of readily available enol silanes. The method, which takes advantage of the polyvalence of Hu’s reagent, N-tosyl-S-difluoromethyl-S-phenylsulfoximine, used here as a CHF2 radical precursor under catalytic photoredox conditions, is practical, scalable, and

  我们在这里报告了通过可见光介导的现成烯醇硅烷的二氟甲基化来高效且高度直接地获得 α-二氟甲基化酮。的方法，它接受胡的试剂的多价的优点，Ñ甲苯磺酰小号-difluoromethyl-小号-phenylsulfoximine，这里用作CHF 2催化photoredox条件下自由基前体，是实用的，可扩展的，并且提供了相应的α-CHF 2酮的产率很好。
• Synthesis of <i>N</i> -Alkenyl and <i>N</i> -Alkynyl <i>S</i> -Perfluoroalkylated Sulfoximines by Copper Catalysis
  作者：Elsa Anselmi、Thanh Nghi Le、Sébastien Bouvet、Patrick Diter、Bruce Pégot、Emmanuel Magnier

  DOI：10.1002/ejoc.201600649

  日期：2016.9

  propose a simple catalytic system based on copper iodide for the reaction with bromoalkenes and bromoalkynes, and based on copper dichloride for the coupling with terminal alkynes. The fluorinated chain was varied from perfluorobutyl to monofluoromethyl. The reaction proceeds efficiently when the unsaturated system is substituted by an aryl or alkyl group. In particular, aliphatic terminal alkynes are efficient

  描述了将双键或三键引入 S-全氟烷基亚砜亚胺的氮原子。我们提出了一种基于碘化铜的简单催化体系，用于与溴代烯烃和溴代炔烃的反应，并基于二氯化铜用于与末端炔烃的偶联。氟化链从全氟丁基到单氟甲基不等。当不饱和体系被芳基或烷基取代时，反应有效进行。特别是，脂肪族末端炔烃是这种转化的有效底物。
• Tuning the Reactivity of Difluoromethyl Sulfoximines from Electrophilic to Nucleophilic: Stereoselective Nucleophilic Difluoromethylation of Aryl Ketones
  作者：Xiao Shen、Wei Zhang、Chuanfa Ni、Yucheng Gu、Jinbo Hu

  DOI：10.1021/ja308419a

  日期：2012.10.17

  A stereoselective synthesis of enantiomerically enriched difluoromethyl tertiary alcohols by tuning the reactivity of difluoromethyl sulfoximines from electrophilic to nucleophilic difluoromethylating agents is reported. The key feature of this chemistry is the diastereoselective addition of the difluoromethyl sulfoximine to the prochiral carbon of the ketone. The present method was used to prepare

  报道了通过调节二氟甲基亚砜亚胺的反应性从亲电子到亲核二氟甲基化试剂的立体选择性合成对映体富集的二氟甲基叔醇。这种化学的关键特征是二氟甲基亚砜亚胺与酮的前手性碳的非对映选择性加成。本方法用于制备对映体富集的二氟甲基仲醇和天然产物 gossonorol 和 boivinian B 的二氟化类似物，证明了该方法的效力。
• One‐Pot Synthesis of Aryl‐ and Alkyl <i>S</i> ‐Perfluoroalkylated <i>NH</i> ‐Sulfoximines from Sulfides
  作者：Slim Chaabouni、Jean‐François Lohier、Anne‐Laure Barthelemy、Thomas Glachet、Elsa Anselmi、Guillaume Dagousset、Patrick Diter、Bruce Pégot、Emmanuel Magnier、Vincent Reboul

  DOI：10.1002/chem.201805055

  日期：2018.11.16

  efficient one‐pot synthesis of S‐perfluoroalkylated NH‐sulfoximines from sulfides has been developed using phenyliodine diacetate (PIDA) and ammonium carbamate. Remarkable rate enhancement with trifluoroethanol was observed, presumably due to H‐bonding effects. These mild and metal‐free conditions are compatible with ‐CH2F, ‐CFCl2, ‐CF2H, ‐CF2Br, ‐C4F9, and ‐CF3 groups, in both the alkyl‐ and aryl series. Based

  使用二碘苯基碘二乙酸酯（PIDA）和氨基甲酸铵开发了一种通用的由硫化物有效地单锅合成S-全氟烷基化NH-亚磺酰亚胺的方法。观察到三氟乙醇显着提高了速率，这可能是由于氢键作用所致。这些温和且无金属的条件在烷基和芳基系列中均与-CH 2 F，-CFCl 2，-CF 2 H，-CF 2 Br，-C 4 F 9和-CF 3基团兼容。根据19 F NMR分析，λ 6，提出了-acetoxysulfanenitrile中间体。