Acetic acid 2'-(1-methoxy-ethyl)-3'-methyl-biphenyl-4-yl ester | 148517-74-2

• 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: Acetic acid 2'-(1-methoxy-ethyl)-3'-methyl-biphenyl-4-yl ester
• CAS: 148517-74-2
• 化学式: C₁₈H₂₀O₃
• 分子量: 284.355
• InChiKey: ZDSFUHZWNXSTBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.29
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  Acetic acid 2'-(1-methoxy-ethyl)-3'-methyl-biphenyl-4-yl ester 在 氢氧化钾 、 4 A molecular sieve 、 lithium perchlorate 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 6.5h， 生成 4-(2-biphenylyl)-6,6-dimethoxy-2,4-cyclohexadien-1-one
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017
• 作为产物：
  描述：

  2-氨基-6-甲基苯甲酸 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 正丁基锂 、 草酰氯 、 氢溴酸 、 铜 、 sodium hydride 、 溶剂黄146 、 copper(I) bromide 、 锌 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 74.5h， 生成 Acetic acid 2'-(1-methoxy-ethyl)-3'-methyl-biphenyl-4-yl ester
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017