α,α-diphenyl-o-(N-methyl-N-phenylsulfamyl)benzyl alcohol | 174741-00-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: α,α-diphenyl-o-(N-methyl-N-phenylsulfamyl)benzyl alcohol
• 英文别名: 2-(α-hydroxy-benzhydryl)-benzenesulfonic acid-(N-methyl-anilide)；2-(α-Hydroxy-benzhydryl)-benzolsulfonsaeure-(N-methyl-anilid)；2-[hydroxy(diphenyl)methyl]-N-methyl-N-phenylbenzenesulfonamide
• CAS: 174741-00-5
• 化学式: C₂₆H₂₃NO₃S
• 分子量: 429.54
• InChiKey: UTHLFJHQDLUPBP-UHFFFAOYSA-N

物化性质

• 沸点：
  611.1±57.0 °C(Predicted)
• 密度：
  1.271±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  α,α-diphenyl-o-(N-methyl-N-phenylsulfamyl)benzyl alcohol 在 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以28%的产率得到N-甲基-N-苯基苯磺酰胺
  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
• 作为产物：
  描述：

  1,1-二氧代-2-苯基-1,2-苯并噻唑-3-酮 在 乙醚 作用下， 生成 α,α-diphenyl-o-(N-methyl-N-phenylsulfamyl)benzyl alcohol
  参考文献：
  名称：

  245.与苯并氧杂蒽的反应

  摘要：

  DOI：

  10.1039/jr9520001343

文献信息

• 245. Reactions with benzoxanthones
  作者：Ahmed Mustafa、Mustafa Kamal Hilmy

  DOI：10.1039/jr9520001343

  日期：——
• Intermediacy of <i>o</i>-Sulfonylium Arenide Ylides in the Reactions of Arenesulfonyl Derivatives with Strong Bases:  Insight into the Puzzling Rearrangement of <i>N</i>-Arylarenesulfonamides into 2-Aminodiaryl Sulfones¹
  作者：John J. Eisch、Yun Qian、Chingchen S. Chiu

  DOI：10.1021/jo950727j

  日期：1996.1.1

  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.