p-cyanophenyl tris(m-methylphenyl) 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(m-methylphenyl) orthocarbonate
• 英文别名: 4-[Tris(3-methylphenoxy)methoxy]benzonitrile；4-[tris(3-methylphenoxy)methoxy]benzonitrile
• 化学式: C₂₉H₂₅NO₄
• 分子量: 451.522
• InChiKey: NISVFTHCLIAQQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 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(m-methylphenyl) orthocarbonate 在 溶剂黄146 作用下， 以 乙腈 为溶剂， 生成 二间甲苯基碳酸酯 、 4-羟基苯甲腈 、 间甲酚
  参考文献：
  名称：

  Hydrolysis of Orthocarbonates. Evidence for Charge Imbalance in the Transition State for the General Acid Catalyzed Process

  摘要：

  Catalytic constants have been measured for the hydrolysis of a range of aryl orthocarbonates, in which both the leaving group and trioxocarbenium ion moiety have been systematically varied, by neutral carboxylic acids (trichloroacetic, difluoroacetic, dichloroacetic, malonic, chloroacetic, and acetic) at 70.0 degrees C in 60% water-40% acetonitrile, I = 1.0 M (KCI). Curvature cannot be detected in Bronsted plots involving carboxylic acids only, but inclusion of the point for H3O+ suggests downward curvature (i.e. p(x) greater than or equal to 0). beta(lg), Plots are curved downward (i.e. p(y') = -partial derivative beta(lg)/partial derivative pK(lg) > 0). Substitutent effects in the tris(aryloxy)carbenium ion fragment were quantitated by use of the experimental aqueous pK(a) values of the phenol (pK(rc)), rather than Hammett sigma values, since this gave better correlations for the spontaneous reactions (Kandanarachchi, P.; Sinnott, M. L. J. Am. Chem. Sec., preceding paper in this issue). Cross coefficients are large and not constant: p(xy') (measured as partial derivative alpha/partial derivative pK(lg) rather than partial derivative beta(lg)/partial derivative pK(HA)) varies from 0.26 for (PhOC+ to 0.16 for (pMeOC(6)H(4)OC+. Likewise, p(xy) (measured as -partial derivative alpha/partial derivative pK(rc) rather than -partial derivative beta(rc)/partial derivative partial derivative pK(HA)) experiences large changes with the leaving group pK. Data to estimate p(yy') (beta(rc)/partial derivative K-lg) are more limited, but it too changes with the pK(a) of the catalyzing acid. These data indicate that a two-dimensional More O'Ferrall-Jencks diagram, with one axis representing both C-O cleavage and the ability of substituents in the tris(aryloxy)carbenium ion moiety to sense positive charge development, is inadequate to represent this reaction: separate axes are required for carbon-oxygen bond cleavage and development of carbon-oxygen double-bond character.

  DOI：

  10.1021/ja00092a010
• 作为产物：
  描述：

  二硫化碳 、 4-羟基苯甲腈 、 间甲酚 在 sodium hydride 、 copper(l) chloride 作用下， 生成 p-cyanophenyl tris(m-methylphenyl) 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 Orthocarbonates. Evidence for Charge Imbalance in the Transition State for the General Acid Catalyzed Process
  作者：Pramod Kandanarachchi、Michael L. Sinnott

  DOI：10.1021/ja00092a010

  日期：1994.6

  Catalytic constants have been measured for the hydrolysis of a range of aryl orthocarbonates, in which both the leaving group and trioxocarbenium ion moiety have been systematically varied, by neutral carboxylic acids (trichloroacetic, difluoroacetic, dichloroacetic, malonic, chloroacetic, and acetic) at 70.0 degrees C in 60% water-40% acetonitrile, I = 1.0 M (KCI). Curvature cannot be detected in Bronsted plots involving carboxylic acids only, but inclusion of the point for H3O+ suggests downward curvature (i.e. p(x) greater than or equal to 0). beta(lg), Plots are curved downward (i.e. p(y') = -partial derivative beta(lg)/partial derivative pK(lg) > 0). Substitutent effects in the tris(aryloxy)carbenium ion fragment were quantitated by use of the experimental aqueous pK(a) values of the phenol (pK(rc)), rather than Hammett sigma values, since this gave better correlations for the spontaneous reactions (Kandanarachchi, P.; Sinnott, M. L. J. Am. Chem. Sec., preceding paper in this issue). Cross coefficients are large and not constant: p(xy') (measured as partial derivative alpha/partial derivative pK(lg) rather than partial derivative beta(lg)/partial derivative pK(HA)) varies from 0.26 for (PhOC+ to 0.16 for (pMeOC(6)H(4)OC+. Likewise, p(xy) (measured as -partial derivative alpha/partial derivative pK(rc) rather than -partial derivative beta(rc)/partial derivative partial derivative pK(HA)) experiences large changes with the leaving group pK. Data to estimate p(yy') (beta(rc)/partial derivative K-lg) are more limited, but it too changes with the pK(a) of the catalyzing acid. These data indicate that a two-dimensional More O'Ferrall-Jencks diagram, with one axis representing both C-O cleavage and the ability of substituents in the tris(aryloxy)carbenium ion moiety to sense positive charge development, is inadequate to represent this reaction: separate axes are required for carbon-oxygen bond cleavage and development of carbon-oxygen double-bond character.
• 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.