4'-hydroxy-2-isopropenyl-4,5-(methylenedioxy)diphenylmethane | 148517-63-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 4'-hydroxy-2-isopropenyl-4,5-(methylenedioxy)diphenylmethane
• 英文别名: 4-[(6-prop-1-en-2-yl-1,3-benzodioxol-5-yl)methyl]phenol
• CAS: 148517-63-9
• 化学式: C₁₇H₁₆O₃
• 分子量: 268.312
• InChiKey: VIXCIRASDYXVTN-UHFFFAOYSA-N

物化性质

• 沸点：
  424.9±14.0 °C(predicted)
• 密度：
  1.196±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  甲醇 、 4'-hydroxy-2-isopropenyl-4,5-(methylenedioxy)diphenylmethane 在 碘苯二乙酸 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以41%的产率得到7,8-dihydro-8'-methoxy-8'-methylspiro<2,5-cyclohexadiene-1,6'(5'H)-naphtho<2,3-d>-1,3-dioxol>-4-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：

  Phenol, 4-[[6-(1-methylethenyl)-1,3-benzodioxol-5-yl]methyl]-, acetate 在 氢氧化钾 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 4.0h， 以84%的产率得到4'-hydroxy-2-isopropenyl-4,5-(methylenedioxy)diphenylmethane
  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