N-methyl-N-phenyl-2-methylbenzenesulfonamide | 54437-71-7

• 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: N-methyl-N-phenyl-2-methylbenzenesulfonamide
• 英文别名: N-methyl-N-phenyl-o-toluenesulfonamide；N,2-dimethyl-N-phenylbenzenesulfonamide
• CAS: 54437-71-7
• 化学式: C₁₄H₁₅NO₂S
• mdl: MFCD20037346
• 分子量: 261.345
• InChiKey: KOABIVJKIPDBRU-UHFFFAOYSA-N

物化性质

• 沸点：
  397.2±35.0 °C(Predicted)
• 密度：
  1.224±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-methyl-N-phenyl-2-methylbenzenesulfonamide 在 水 、 三氟乙酸 作用下， 生成 2-甲基苯磺酸
  参考文献：
  名称：

  Wagenaar, Anno; Kirby, Anthony J.; Engberts, Jan B. F. N., Recueil des Travaux Chimiques des Pays-Bas, 1985, vol. 104, # 7-8, p. 203 - 205

  摘要：

  DOI：
• 作为产物：
  描述：

  α,α-diphenyl-o-(N-methyl-N-phenylsulfamyl)benzyl alcohol 在 2,2,6,6-tetramethylpiperidinyl-lithium 、 锂1-丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 3.17h， 生成 N-methyl-N-phenyl-2-methylbenzenesulfonamide
  参考文献：
  名称：

  Intermediacy of o-Sulfonylium Arenide Ylides in the Reactions of Arenesulfonyl Derivatives with Strong Bases:  Insight into the Puzzling Rearrangement of N-Arylarenesulfonamides into 2-Aminodiaryl Sulfones¹

  摘要：

  Benzenesulfonyl derivatives, PhSO(2)E, such as benzenesulfonyl fluoride, phenyl benzenesulfonate, and N-methyl-N-phenylbenzenesulfonamide, have been found to undergo ortho-lithiation with lithium 2,2,6,6-tetramethylpiperidide (LTMP) in THF at -78 degrees C. The resulting lithio derivatives undergo 1,3-elimination of LiE to form the transient o-sulfonylium benzenide. The latter ylide, which may be stabilized by its carbenoid character and its complexation with LiE, can be trapped by benzophenone acting as a 1,3-dipolarophile to form the adduct, 3,3-diphenyl-1,2-benzoxathiole 1,1-dioxide. The alternative formation of the latter cyclic sulfonate by reaction of the initially formed o-lithio derivative with benzophenone and by subsequent cyclization was shown not to occur. If not trapped with benzophenone, such an ylide decomposes partly into SO2 and benzyne and then undergoes self-condensation to yield poly(phenylene-o,o'-biphenylene sulfones), o-Sulfonylium benzenide also can be captured by lithium alkoxides, either present adventitously or intentionally added, to generate the corresponding alkyl benzenesulfonate. However, such alkoxides, unaided by LTMP, are themselves unable to extract an ortho-proton from benzenesulfonyl fluoride or from N-methyl-N-phenylbenzenesulfonamide to yield the corresponding o-lithio derivative. With benzenesulfonyl fluoride the lithium alkoxide can also form the sulfonate ester by direct substitution at the sulfonyl group. The Closson-Hellwinkel rearrangement of N-methyl-N-phenylbenzenesulfonamide into o-(methylamino)diphenyl sulfone by RLi or LTMP is reinterpreted as proceeding by way of the 2-lithio- or 2,6-dilithiobenzenesulfonyl derivative which eliminates lithium N-methylanilide to form the o-sulfonylium benzenide or its 6-lithio derivative. Attack of the latter ylide, acting as an electrophile, upon the ortho-position of the presumably complexed LiNMePh then consummates the rearrangement.

  DOI：

  10.1021/jo950727j

文献信息

• [EN] CRTH2 MODULATORS<br/>[FR] MODULATEURS DE CRTH2
  申请人：IRONWOOD PHARMACEUTICALS INC

  公开号：WO2010039982A1

  公开（公告）日：2010-04-08

  Modulators of CRTH2, particularly antagonists of CRTH2, that are useful for treating various disorders, including asthma and respiratory disorders are disclosed. The compounds fall within a genus described by formula I.

  CRTH2的调节剂，特别是CRTH2的拮抗剂，可用于治疗包括哮喘和呼吸道疾病在内的各种疾病。这些化合物属于由式I描述的一类。
• <i>N</i>-ALKYLATION OF<i>N</i>-MONOSUBSTITUTED SULFONAMTOES IN IONIC LIQUIDS
  作者：Yi Hu、Zhen-Chu Chen、Zhang-Goo Le、Qin-Guo Zheng

  DOI：10.1080/00304940409458677

  日期：2004.8

  N-dimethylformamide,2.7." and xylene." This method involves harsh reaction conditions, long reaction times and low yields in organic solvents. This reaction also can be accomplished via phase-transfer catalysts process? but involves the use of organic solvents. Recently, the N-alkylation of N-monosubstituted sulfonamides via the Mitsunobu reaction has been reported? However, these conditions require the use

  N-单取代磺酰胺的 N-烷基化是 Gabriel 型仲胺合成中的关键步骤，随后通过 SN 键的已知还原程序裂解磺酰胺。* 此外，磺胺类药物本身构成一类重要的药学化合物。* 然而，这种转化的可用途径有些有限。这种反应通常需要强碱，如 Na。N w 4 NaOR？KOH6等和甲醇等有机溶剂的使用？乙醇？N,N-二甲基甲酰胺，2.7." 和二甲苯。" 该方法涉及苛刻的反应条件、较长的反应时间和在有机溶剂中的低收率。这个反应也可以通过相转移催化剂过程来完成？但涉及使用有机溶剂。最近，有报道称 N-单取代磺酰胺通过光信反应进行 N-烷基化？然而，这些条件需要使用昂贵的试剂、惰性气体、有机溶剂，反应时间长，有时收率低。因此，使用简便有效的方法对 N-单取代磺酰胺进行 N-烷基化仍然是有机合成中的一个挑战。
• METHOD FOR DEPROTECTING ARYL OR ALKYL SULFONAMIDES OF PRIMARY OR SECONDARY AMINES
  申请人：Lefenfeld Michael

  公开号：US20090306391A1

  公开（公告）日：2009-12-10

  The invention relates to a method for removing an alkyl sulfonyl or aryl sulfonyl protecting group from a primary or secondary amine by contacting an alkyl sulfonamide or an aryl sulfonamide with a Stage 0 or Stage I alkali metal-silica gel material in the presence of a solid proton source under conditions sufficient to form the corresponding amine. The invention also relates to a method for removing an alkyl sulfonyl or aryl sulfonyl protecting group from a primary or secondary amine by a) reacting an alkyl sulfonamide or an aryl sulfonamide with a Stage 0 or Stage I alkali metal-silica gel material, and b) subsequently reacting the reaction product from step a) with an electrophile or a proton source. Preferred Stage 0 or Stage I alkali metal-silica gel materials include Na, K 2 Na, and Na 2 K.

  该发明涉及一种从一级或二级胺中去除烷基磺酰基或芳基磺酰基保护基的方法，方法包括将烷基磺酰胺或芳基磺酰胺与一种固体质子源接触，在足以形成相应胺的条件下，与0级或I级碱金属-硅胶材料反应。该发明还涉及一种从一级或二级胺中去除烷基磺酰基或芳基磺酰基保护基的方法，包括a)将烷基磺酰胺或芳基磺酰胺与0级或I级碱金属-硅胶材料反应，b)随后将步骤a)中的反应产物与亲电试剂或质子源反应。首选的0级或I级碱金属-硅胶材料包括Na、K2Na和Na2K。
• US8263808B2
  申请人：——

  公开号：US8263808B2

  公开（公告）日：2012-09-11
• [EN] METHOD FOR DEPROTECTING ARYL OR ALKYL SULFONAMIDES OF PRIMARY OR SECONDARY AMINES<br/>[FR] procede de deprotection de SULFONAMIDES d'aryle ou d'alkyle d'amines primaires ou secondaires
  申请人：SIGNA CHEMISTRY LLC

  公开号：WO2007095276A2

  公开（公告）日：2007-08-23

  [EN] The invention relates to a method for removing an alkyl sulfonyl or aryl sulfonyl protecting group from a primary or secondary amine by contacting an alkyl sulfonamide or an aryl sulfonamide with a Stage 0 or Stage I alkali metal - silica gel material in the presence of a solid proton source under conditions sufficient to form the corresponding amine. The invention also relates to a method for removing an alkyl sulfonyl or aryl sulfonyl protecting group from a primary or secondary amine by a) reacting an alkyl sulfonamide or an aryl sulfonamide with a Stage 0 or Stage I alkali metal - silica gel material, and b) subsequently reacting the reaction product from step a) with an electrophile or a proton source. Preferred Stage 0 or Stage I alkali metal - silica gel materials include Na, K₂Na, and Na₂K.
  [FR] La présente invention concerne un procédé d'élimination d'un groupe protecteur alkylsulfonyle ou arylsulfonyle à partir d'une amine primaire ou secondaire en mettant en contact un sulfonamide d'alkyle ou un sulfonamide d'aryle avec un matériau à base de métal alcalin et de gel de silice au Stade 0 ou au Stade I en présence d'une source solide de protons dans des conditions suffisantes pour former l'amine correspondante. L'invention concerne également un procédé d'élimination d'un groupe protecteur alkylsulfonyle ou arylsulfonyle à partir d'une amine primaire ou secondaire a) en faisant réagir un sulfonamide d'alkyle ou un sulfonamide d'aryle avec un matériau à base de métal alcalin et de gel de silice au Stade 0 ou au Stade I, et b) en faisant par la suite réagir le produit réactionnel provenant de l'étape a) avec un électrophile ou une source de protons. Les matériaux préférés à base de métal alcalin et de gel de silice au Stade 0 ou au Stade I comprennent Na, K₂Na et Na₂K.