p-cyanophenyl tris(p-chlorophenyl) orthocarbonate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: p-cyanophenyl tris(p-chlorophenyl) orthocarbonate
• 英文别名: 4-[Tris(4-chlorophenoxy)methoxy]benzonitrile；4-[tris(4-chlorophenoxy)methoxy]benzonitrile
• 化学式: C₂₆H₁₆Cl₃NO₄
• 分子量: 512.776
• InChiKey: RPQPREFVCNVALI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  60.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  p-cyanophenyl tris(p-chlorophenyl) orthocarbonate 在 sodium-DIPSO 、 水 作用下， 以 乙腈 为溶剂， 生成 双(4-氯苯基)碳酸酯 、 4-羟基苯甲腈 、 对氯苯酚
  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：

  二硫化碳 、 4-羟基苯甲腈 、 对氯苯酚 在 sodium hydride 、 copper(l) chloride 作用下， 生成 p-cyanophenyl tris(p-chlorophenyl) orthocarbonate
  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

文献信息

• Hydrolysis of Aryl Orthocarbonates by General Acid Catalyzed and Spontaneous Processes. Characterization of the Water Reaction of (ArO)3COAr' and (ArO)3CN3
  作者：Pramod Kandanarachchi、Michael L. Sinnott

  DOI：10.1021/ja00092a009

  日期：1994.6

  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.