methyl 3-cyano-4-hydroxy-2-methylbenzoate | 131236-59-4

• 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 3-cyano-4-hydroxy-2-methylbenzoate
• 英文别名: methyl 3-cyano-4-hydroxy-2-methylbenzene-1-carboxylate
• CAS: 131236-59-4
• 化学式: C₁₀H₉NO₃
• 分子量: 191.186
• InChiKey: ZGKBKBIXKFVQSN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  70.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 3-cyano-4-hydroxy-2-methylbenzoate 在 palladium on activated charcoal sodium tetrahydroborate 、 氢气 、 potassium carbonate 、 cobalt(II) chloride 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 47.33h， 生成 4-羟基-2,3-二甲基苯甲酸甲酯
  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：

  5-Cyano-6-methyl-4-oxo-bicyclo[3.1.0]hex-2-ene-6-carboxylic acid methyl ester 以 苯 为溶剂， 生成 methyl 3-cyano-4-hydroxy-2-methylbenzoate
  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

• Isoxazoles as Latent Siloxybutadienes: An Easy Entry to Polyfunctionalized Benzene Systems via Diels-Alder Reaction with Acetylenes
  作者：Francisco J. Pulido、Asunción Barbero

  DOI：10.1055/s-2004-815929

  日期：——

  Base-induced or reductive cleavage of isoxazole rings followed by silylation of the resulting open-chain products affords bis(siloxy)butadienes in high yields. Their synthetic usefulness in the construction of multifunctionalized aromatic systems, via Diels-Alder reactions, is shown. The ability of bis(siloxy)butadienes to undergo deprotonation and reaction with electrophiles is also studied.

  异恶唑环的碱诱导或还原裂解，然后对所得开链产物进行甲硅烷基化，以高产率提供双（甲硅烷氧基）丁二烯。显示了它们在通过 Diels-Alder 反应构建多功能芳烃系统中的合成用途。还研究了双（甲硅烷氧基）丁二烯进行去质子化和与亲电试剂反应的能力。
• 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：——
• Photochemical and acid-catalyzed dienone-phenol rearrangements. The effect of substituents on the regioselectivity of 1,4-sigmatropic rearrangements of the type A intermediate
  作者：Arthur G. Schultz、Steven A. Hardinger

  DOI：10.1021/jo00003a037

  日期：1991.2

  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.