4-[(2-nitrophenyl)sulfanyl]morpholine | 7257-62-7

• 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: 4-[(2-nitrophenyl)sulfanyl]morpholine
• 英文别名: N-(o-nitrophenylthio)morpholine；Morpholine, 4-[(2-nitrophenyl)thio]-；4-(2-nitrophenyl)sulfanylmorpholine
• CAS: 7257-62-7
• 化学式: C₁₀H₁₂N₂O₃S
• 分子量: 240.283
• InChiKey: OPGVYCMZBAGJPD-UHFFFAOYSA-N

物化性质

• 熔点：
  89-91 °C
• 沸点：
  385.7±52.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)
• 溶解度：
  32.2 [ug/mL]

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  83.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-[(2-nitrophenyl)sulfanyl]morpholine 在 sodium perchlorate 作用下， 以 乙腈 为溶剂， 以10.8%的产率得到双(2-硝基苯基)二硫化物
  参考文献：
  名称：

  Studies on sulfenamides. VIII. Anodic oxidation of 2-nitrobenzenesulfenamides derived from secondary cyclic amines.

  摘要：

  通过在玻璃碳阳极上对甲醇中的 N-（2-硝基苯硫基）胺（吗啉（1）、哌啶（2）、吡咯烷（3）、硫代吗啉（四氢-4H-1，4-噻嗪）（4））进行受控电位电解（CPE），生成了 2-硝基苯硫酸甲酯（5）。电解 1 得到的黄色粉末与三乙胺反应生成 2，4-双（邻硝基苯硫基）-5，6-二氢-1，4-恶嗪（7）。在乙腈中对 1-4 进行 CPE 反应，得到 2，2'-二硝基二苯二硫醚（6）。这些结果表明，1-4 在乙腈中阳极氧化的第一步是 EC 过程（先发生电子转移过程，然后发生化学反应），而在甲醇中则是 ECE 过程（先发生电子转移过程，然后发生化学反应，最后发生电子转移过程）。烯胺被认为是 1-4 在甲醇中阳极氧化的中间产物之一。

  DOI：

  10.1248/cpb.31.4530
• 作为产物：
  描述：

  在 三氟甲磺酸 甲醇 作用下， 以 乙腈 为溶剂， 生成 4-[(2-nitrophenyl)sulfanyl]morpholine
  参考文献：
  名称：

  Mechanism of nucleophilic substitution reactions of o-nitrobenzenesulfenamides: evidence for a substitution proceeding through a sulfuranide intermediate

  摘要：

  o-Nitrobenzenesulfenamides (1) undergo acid-catalyzed methanolysis (eq 2) in acetonitrile-methanol, affording methyl o-nitrobenzenesulfenate (2). They also undergo acid-catalyzed reaction with a thiol, giving an alkyl o-nitrophenyl disulfide (eq 3). In MeCN-8.2 M MeOH the thiolysis reaction exhibits a simple first-order dependence on both [R'SH] and [H+] for acid concentrations in the range 0.001-0.012 M. In marked contrast the rate of the methanolysis reaction is only slightly dependent on [H+] for the same range of acid concentrations. It is also markedly dependent on [MeOH], being seven times faster in MeCN-8.2 M MeOH than in MeCN-3.0 M MeOH. Measurement of the equilibrium constant for protonation of 1 to 1-H+ in MeCN-8.2 M MeOH shows that under the conditions used for the kinetic studies of eqs 2 and 3 the extent of protonation of 1 to 1-H+ is always small (<6%). Consideration of this fact, and the markedly different kinetic behavior of the two substitution reactions, leads to the following interpretation: (a) for the thiolysis the rate-determining step is the reaction of the thiol with 1-H+; (b) for the methanolysis, on the other hand, the mechanism is that shown in eq 9, where a sulfuranide species 4 is the key intermediate on the reaction coordinate. The lack of dependence of the rate on [H+] is because acid-catalyzed reversion of 4 to 1-H+ and methanol (Step k-6) is faster than the cleavage of 4 (step k7) to give 2 and R2NH. The methanolysis of 1 therefore represents another substitution at dicoordinate sulfur (similar to ref 10) where the kinetics require a mechanism with a hypervalent sulfur species as an intermediate on the reaction coordinate.

  DOI：

  10.1021/jo00038a013

文献信息

• Iodosulfenylation of olefins with sulfenamides in the presence of metal iodides
  作者：N. V. Zyk、E. K. Beloglazkina、S. E. Sosonyuk、M. N. Bulanov、Yu. B. Chudinov

  DOI：10.1007/bf02495161

  日期：2000.9

  tin(iv), antimony(iii), or magnesium iodides were investigated. In the case of cage olefins, the reactions afford mixtures of 1,2-iodosulfides and diiodides, the ratio between which depends on the type of iodine-containing Lewis acid. lodosulfides were obtained in the highest yields in the reactions of cage olefins upon activation with zinc or tin(ii) iodides. In the case of olefins prone to the Wagner—Meerwein

  研究了在锌、锡 (ii)、锡 (iv)、锑 (iii) 或碘化镁存在下芳基次磺酰胺、芳基次磺酸盐、硫代双胺和二硫代双胺与烯烃的反应。在笼状烯烃的情况下，反应生成 1,2-碘硫化物和二碘化物的混合物，其比例取决于含碘路易斯酸的类型。在笼状烯烃与碘化锌或碘化锡（ii）活化后的反应中，以最高产率获得碘硫化物。在烯烃易于发生 Wagner-Meerwein 重排（双环 [2.2.1] 庚烷）或加成消除反应（莰烯）的情况下，会形成相应的产物。提出了反应机理。
• Reaction of sulfenamides withN,N-dimethylaniline in the presence of phosphorus(v) oxochloride
  作者：N. V. Zyk、E. K. Beloglazkina、M. A. Belova

  DOI：10.1007/bf02499090

  日期：1990.1

  Reaction of arylsulfenamides withN,N-dimethylaniline in the presence of POCl3 at room temperature affords unsymmetrical diaryl sulfide, onlypara-substitutedN,N-dimethylanilines being formed.

  芳基次磺酰胺与 N,N-二甲基苯胺在 POCl3 存在下在室温下反应得到不对称的二芳基硫化物，仅形成对位取代的 N,N-二甲基苯胺。
• A CONVENIENT METHOD FOR BROMOSULFENYLATION: REACTIONS OF SULFENAMIDES WITH OLEFINS IN THE PRESENCE OF POBr₃
  作者：Nikolai V. Zyk、Elena K. Beloglazkina、Rimma Gazzaeva、Vladimir S. Tyurin、Igor D. Titanyuk

  DOI：10.1080/10426509908044968

  日期：1999.12

  Abstract A general method for the one-pot transformation of alkenes into abromoalkyl-arylsulfdes has been proposed based on the sulfenylation reaction by means of sulfenamides in the presence of phosphorus oxibromide. The plausible reaction mechanism and the results of reactions with a number of model alkenes such as cyclohexene, I-heptene, norbornene and other from the bicyclo[2.2.1] heptane series

  摘要 基于亚磺酰胺在三溴化磷存在下的亚磺酰化反应，提出了一种将烯烃一锅法转化为溴代烷基芳基硫醚的通用方法。讨论了可能的反应机理和与许多模型烯烃反应的结果，如环己烯、I-庚烯、降冰片烯和其他双环 [2.2.1] 庚烷系列。
• Electrophilic addition to norbornene derivatives containing CF3 and NO2 groups
  作者：N. V. Zyk、E. K. Beloglazkina、S. E. Sosonyuk、M. N. Bulanov、R. L. Antipin

  DOI：10.1007/s11172-005-0432-z

  日期：2005.6

  of bicyclo[2.2.1]heptenes containing CF3 or NO2 group in position endo-5 were studied. The sulfenylation and selenenation were accomplished by arylsulfene- and arylselenenamides activated by POHal3 (Hal = Br, Cl), and iodination was performed by KICl2. The reactions are regiospecific and involve an exo-attack of the electrophilic fragment (arylthio or arylseleno group or iodine) on the C=C bond atom

  研究了在endo-5 位置含有CF3 或NO2 基团的双环[2.2.1] 庚烯的亲电亚磺酰化、硒化和卤化。亚磺酰化和硒化是通过 POHal3 (Hal = Br, Cl) 激活的芳基亚砜和芳基硒酰胺完成的，碘化是通过 KICl2 进行的。这些反应是区域特异性的，涉及亲电片段（芳硫基或芳基硒基或碘）对位于更靠近 或 基团的 C=C 键原子的外向攻击。
• Arylsulfenylation of heterocyclic compounds with arylsulfenamides in the presence of phosphorus(V) oxochloride
  作者：R. L. Antipin、A. N. Chernysheva、E. K. Beloglazkina、N. V. Zyk

  DOI：10.1007/s10593-010-0629-4

  日期：2010.12

  The electrophilic sulfenylation of a series of indoles and pyrroles with arylsulfenamides in the presence of phophorus(V) oxohalide has been studied. It has been shown that arylsulfenylation of indoles led to products with substitution at position 3, while in the case of pyrrole it occurred at position 2.

  研究了在存在卤化磷（V）的情况下，一系列的吲哚和吡咯与芳基亚磺酰胺的亲电子亚磺酰化反应。已经显示，吲哚的芳基亚磺酰基化导致产物在3位被取代，而在吡咯的情况下，它发生在2位。