三(间甲基苯氧基)甲基叠氮化物 | 156420-96-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 三(间甲基苯氧基)甲基叠氮化物
• 英文名称: tris(m-methylphenoxy)methyl azide
• 英文别名: 1-[azido-bis(3-methylphenoxy)methoxy]-3-methylbenzene
• CAS: 156420-96-1
• 化学式: C₂₂H₂₁N₃O₃
• 分子量: 375.427
• InChiKey: QKDCWWOEKYIYJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  28.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  76.45
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  三(间甲基苯氧基)甲基叠氮化物 在 sodium-DIPSO 、 水 作用下， 以 乙腈 为溶剂， 生成 二间甲苯基碳酸酯 、 间甲酚
  参考文献：
  名称：

  Hydrolysis of Aryl Orthocarbonates by General Acid Catalyzed and Spontaneous Processes. Characterization of the Water Reaction of (ArO)3COAr' and (ArO)3CN3

  摘要：

  Twenty-four aryl orthocarbonates of formula (Aro)(4)C, (ArO)(2)C(OAr')(2), or (ArO)(3)COAr' have been made by coupling of the copper phenoxides with carbon disulfide, and their hydrolyses have been examined in 60% water-40% acetonitrile (I = 1.00 M, KCl) at 70.0 degrees C. Their hydrolysis by general acid catalyzed and, in the case of (ArO)(3)COAr' when Ar'= p-nitrophenyl and p-cyanophenyl, spontaneous processes yields aryl carbonates. The initial, rate-determining event for both processes is the cleavage of the bond between the central carbon and the least basic phenoxy group: with mixed orthocarbonates of phenols differing in pK by <1 unit, parallel pathways are observed. The spontaneous reactions of (X-C6H4O)(3)C-O-p-C6H4NO2 and (X-C6H4O)(3)C-O-p-C6H4CN where the sigma value of X varies from -0.23 to 0.22 are 4-10 times slower than reactions of p-nitrophenyl tetrahydropyrans reported in the literature and give rise to nonlinear Hammett plots. However, plots against the pK(a) of X-C6H4OH are linear, and the derived beta(reaction center) values indicate substantial buildup of positive charge on the central carbon atom. A similar plot is obtained for the spontaneous reactions of five azides (XC(6)H(4)O)(3)CN3 for which common ion inhibition experiments have been performed. The derived selectivities (M(-1)) of the tris(aryloxy)carbenium ion intermediates between azide ion and water vary from 8.5 X 10(3) to 6.6 X 10(3) as the sigma value of X changes from -0.28 to 0.06. The lifetime of the tris(aryloxy)carbenium ion intermediates in water is therefore likely to be > 10(-6) s. The slow formation and slow hydrolysis of tris(aryloxy)carbenium ions suggests that (in the formation direction) development of conjugative stabilization lags behind carbon-oxygen bond cleavage and (in the hydrolysis direction) precedes carbon-oxygen bond formation. The stereochemistry of tetraaryl orthocarbonates immediately suggests reasons why this should be so.

  DOI：

  10.1021/ja00092a009
• 作为产物：
  描述：

  p-nitrophenyl tris(m-methylphenyl) orthocarbonate 在 sodium azide 、 15-冠醚-5 作用下， 以 乙腈 为溶剂， 反应 30.0h， 生成 三(间甲基苯氧基)甲基叠氮化物
  参考文献：
  名称：

  Hydrolysis of Aryl Orthocarbonates by General Acid Catalyzed and Spontaneous Processes. Characterization of the Water Reaction of (ArO)3COAr' and (ArO)3CN3

  摘要：

  Twenty-four aryl orthocarbonates of formula (Aro)(4)C, (ArO)(2)C(OAr')(2), or (ArO)(3)COAr' have been made by coupling of the copper phenoxides with carbon disulfide, and their hydrolyses have been examined in 60% water-40% acetonitrile (I = 1.00 M, KCl) at 70.0 degrees C. Their hydrolysis by general acid catalyzed and, in the case of (ArO)(3)COAr' when Ar'= p-nitrophenyl and p-cyanophenyl, spontaneous processes yields aryl carbonates. The initial, rate-determining event for both processes is the cleavage of the bond between the central carbon and the least basic phenoxy group: with mixed orthocarbonates of phenols differing in pK by <1 unit, parallel pathways are observed. The spontaneous reactions of (X-C6H4O)(3)C-O-p-C6H4NO2 and (X-C6H4O)(3)C-O-p-C6H4CN where the sigma value of X varies from -0.23 to 0.22 are 4-10 times slower than reactions of p-nitrophenyl tetrahydropyrans reported in the literature and give rise to nonlinear Hammett plots. However, plots against the pK(a) of X-C6H4OH are linear, and the derived beta(reaction center) values indicate substantial buildup of positive charge on the central carbon atom. A similar plot is obtained for the spontaneous reactions of five azides (XC(6)H(4)O)(3)CN3 for which common ion inhibition experiments have been performed. The derived selectivities (M(-1)) of the tris(aryloxy)carbenium ion intermediates between azide ion and water vary from 8.5 X 10(3) to 6.6 X 10(3) as the sigma value of X changes from -0.28 to 0.06. The lifetime of the tris(aryloxy)carbenium ion intermediates in water is therefore likely to be > 10(-6) s. The slow formation and slow hydrolysis of tris(aryloxy)carbenium ions suggests that (in the formation direction) development of conjugative stabilization lags behind carbon-oxygen bond cleavage and (in the hydrolysis direction) precedes carbon-oxygen bond formation. The stereochemistry of tetraaryl orthocarbonates immediately suggests reasons why this should be so.

  DOI：

  10.1021/ja00092a009