methyl 4-(((benzyloxy)carbonyl)oxy)-3-cyano-2-methylbenzene-1-carboxylate | 131236-61-8

• 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: methyl 4-(((benzyloxy)carbonyl)oxy)-3-cyano-2-methylbenzene-1-carboxylate
• 英文别名: methyl 3-cyano-2-methyl-4-phenylmethoxycarbonyloxybenzoate
• CAS: 131236-61-8
• 化学式: C₁₈H₁₅NO₅
• 分子量: 325.321
• InChiKey: CUDSSOVFWNSBIZ-UHFFFAOYSA-N

物化性质

• 熔点：
  79.0-79.5 °C(Solv: hexane (110-54-3); carbon tetrachloride (56-23-5))
• 沸点：
  503.1±50.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.37
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  85.62
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl 4-(((benzyloxy)carbonyl)oxy)-3-cyano-2-methylbenzene-1-carboxylate 在 sodium tetrahydroborate 、 cobalt(II) chloride 作用下， 以 甲醇 为溶剂， 反应 0.33h， 以39%的产率得到methyl 3-(aminomethyl)-4-(((benzyloxy)carbonyl)oxy)-2-methylbenzene-1-carboxylate
  参考文献：
  名称：

  Photochemical and acid-catalyzed dienone-phenol rearrangements. The effect of substituents on the regioselectivity of 1,4-sigmatropic rearrangements of the type A intermediate

  摘要：

  Birch reduction of isophthalic acid and 3-cyanobenzoic acid followed by (1) methylation of the resulting enolate with methyl iodide and (2) esterification with diazomethane provided 2-carbomethoxy- and 2-cyano-6-methyl-6-carbomethoxy-1,4-cyclohexadienes 9 and 25. Type A photorearrangements of a series of 2-carbomethoxy-, 2-cyano-, 2-methoxy-, and 2-methyl-4-carbomethoxy-4-methyl-2,5-cyclohexadien-1-ones 11, 26, 45a, and 45b gave 4-carbomethoxy-3-methyl-2-substituted-phenols 12, 28, 46, and 31. It has been demonstrated that the regioselectivity of type A photorearrangement of C(2) substituted 2,5-cyclohexadien-1-ones is governed by electronic rather than steric effects to give the intermediate C(1) rather than C(3) substituted bicyclo [3.1.0(1,5)]hex-3-en-2-ones. Regioselectivities of the acid-catalyzed dienone-phenol rearrangements of C(2) substituted 2,5-cyclohexadienones 11, 45a, and 45b appear to be dependent upon the relative stabilities of carbocations resulting from migration of the C(4) carbomethoxy group.

  DOI：

  10.1021/jo00003a037
• 作为产物：
  描述：

  methyl 1-methyl-3-cyano-4-oxo-2,5-cyclohexadiene-1-carboxylate 在 potassium carbonate 作用下， 以 二氯甲烷 、 水 、 苯 为溶剂， 反应 43.0h， 生成 methyl 4-(((benzyloxy)carbonyl)oxy)-3-cyano-2-methylbenzene-1-carboxylate
  参考文献：
  名称：

  Photochemical and acid-catalyzed dienone-phenol rearrangements. The effect of substituents on the regioselectivity of 1,4-sigmatropic rearrangements of the type A intermediate

  摘要：

  Birch reduction of isophthalic acid and 3-cyanobenzoic acid followed by (1) methylation of the resulting enolate with methyl iodide and (2) esterification with diazomethane provided 2-carbomethoxy- and 2-cyano-6-methyl-6-carbomethoxy-1,4-cyclohexadienes 9 and 25. Type A photorearrangements of a series of 2-carbomethoxy-, 2-cyano-, 2-methoxy-, and 2-methyl-4-carbomethoxy-4-methyl-2,5-cyclohexadien-1-ones 11, 26, 45a, and 45b gave 4-carbomethoxy-3-methyl-2-substituted-phenols 12, 28, 46, and 31. It has been demonstrated that the regioselectivity of type A photorearrangement of C(2) substituted 2,5-cyclohexadien-1-ones is governed by electronic rather than steric effects to give the intermediate C(1) rather than C(3) substituted bicyclo [3.1.0(1,5)]hex-3-en-2-ones. Regioselectivities of the acid-catalyzed dienone-phenol rearrangements of C(2) substituted 2,5-cyclohexadienones 11, 45a, and 45b appear to be dependent upon the relative stabilities of carbocations resulting from migration of the C(4) carbomethoxy group.

  DOI：

  10.1021/jo00003a037

文献信息

• SCHULTZ, ARTHUR G.;HARDINGER, STEVEN A., J. ORG. CHEM., 56,(1991) N, C. 1105-1111
  作者：SCHULTZ, ARTHUR G.、HARDINGER, STEVEN A.

  DOI：——

  日期：——