1-trideuteriomethyl-1,2-dihydrobenzocyclobuten-1-ol | 247574-61-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-trideuteriomethyl-1,2-dihydrobenzocyclobuten-1-ol
• 英文别名: 7-(Trideuteriomethyl)bicyclo[4.2.0]octa-1,3,5-trien-7-ol
• CAS: 247574-61-4
• 化学式: C₉H₁₀O
• 分子量: 137.154
• InChiKey: IUEURZITPVNHKP-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-苯基马来酰亚胺 、 1-trideuteriomethyl-1,2-dihydrobenzocyclobuten-1-ol 以 氘代苯 为溶剂， 反应 5.5h， 生成 (3aS,4S,9aS)-4-hydroxy-2-phenyl-4-(trideuteriomethyl)-9,9a-dihydro-3aH-benzo[f]isoindole-1,3-dione
  参考文献：
  名称：

  Mechanistic Study on Thermal Isomerization of 1-Methylbenzocyclobutenol to 2-Methylacetophenone

  摘要：

  Heating 1-trideuteriomethylbenzocyclobutenol 7 in benzene-d(6) at 160 degrees C gave 2-monodeuteriomethyl- and 2-methylacetophenone 9 and 10 in a ratio of 96:4. Thermolysis of 7 in nonpolar solvents (hexane, toluene, mesitylene) gave similar results. On the contrary, heating 7 in polar solvents (ethanol, acetonitrile, chloroform) or in benzene-d(6) in the presence of proton source (PhCO2H) gave 10 as the major product. However, heating a mixture of 7 and N-phenylmaleimide at 160 degrees C in benzene-d(6) or acetonitrile-d(3) gave adduct 12 of N-phenylmaleimide and the dienol generated by ring opening of 7 almost quantitatively. These results indicate that 1-methylbenzo cyclobutenol undergoes selective thermal opening to the E-dienol. The resulting E-dienol isomerizes to 2-methylacetophenone by 1,5-sigmatropic shift of hydrogen from the methyl group in nonpolar solvent. In polar solvent, the E-dienol isomerizes to 2-methylacetophenone by both intra- and intermolecular processes. The k(H)/k(D) value for isomerization was 1.13. Since this relatively low value is a secondary kinetic effect, overall reaction is governed by the ring opening step. The selective opening to the E-dienol was supported by calculation.

  DOI：

  10.1021/jo990705n
• 作为产物：
  描述：

  苯并环丁烯酮 、 氘代碘甲烷 在 magnesium 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 1-trideuteriomethyl-1,2-dihydrobenzocyclobuten-1-ol
  参考文献：
  名称：

  Mechanistic Study on Thermal Isomerization of 1-Methylbenzocyclobutenol to 2-Methylacetophenone

  摘要：

  Heating 1-trideuteriomethylbenzocyclobutenol 7 in benzene-d(6) at 160 degrees C gave 2-monodeuteriomethyl- and 2-methylacetophenone 9 and 10 in a ratio of 96:4. Thermolysis of 7 in nonpolar solvents (hexane, toluene, mesitylene) gave similar results. On the contrary, heating 7 in polar solvents (ethanol, acetonitrile, chloroform) or in benzene-d(6) in the presence of proton source (PhCO2H) gave 10 as the major product. However, heating a mixture of 7 and N-phenylmaleimide at 160 degrees C in benzene-d(6) or acetonitrile-d(3) gave adduct 12 of N-phenylmaleimide and the dienol generated by ring opening of 7 almost quantitatively. These results indicate that 1-methylbenzo cyclobutenol undergoes selective thermal opening to the E-dienol. The resulting E-dienol isomerizes to 2-methylacetophenone by 1,5-sigmatropic shift of hydrogen from the methyl group in nonpolar solvent. In polar solvent, the E-dienol isomerizes to 2-methylacetophenone by both intra- and intermolecular processes. The k(H)/k(D) value for isomerization was 1.13. Since this relatively low value is a secondary kinetic effect, overall reaction is governed by the ring opening step. The selective opening to the E-dienol was supported by calculation.

  DOI：

  10.1021/jo990705n

文献信息

• Mechanistic Study on Thermal Isomerization of 1-Methylbenzocyclobutenol to 2-Methylacetophenone
  作者：Katsumi Iida、Kaori Komada、Masaichi Saito、Michikazu Yoshioka

  DOI：10.1021/jo990705n

  日期：1999.10.1

  Heating 1-trideuteriomethylbenzocyclobutenol 7 in benzene-d(6) at 160 degrees C gave 2-monodeuteriomethyl- and 2-methylacetophenone 9 and 10 in a ratio of 96:4. Thermolysis of 7 in nonpolar solvents (hexane, toluene, mesitylene) gave similar results. On the contrary, heating 7 in polar solvents (ethanol, acetonitrile, chloroform) or in benzene-d(6) in the presence of proton source (PhCO2H) gave 10 as the major product. However, heating a mixture of 7 and N-phenylmaleimide at 160 degrees C in benzene-d(6) or acetonitrile-d(3) gave adduct 12 of N-phenylmaleimide and the dienol generated by ring opening of 7 almost quantitatively. These results indicate that 1-methylbenzo cyclobutenol undergoes selective thermal opening to the E-dienol. The resulting E-dienol isomerizes to 2-methylacetophenone by 1,5-sigmatropic shift of hydrogen from the methyl group in nonpolar solvent. In polar solvent, the E-dienol isomerizes to 2-methylacetophenone by both intra- and intermolecular processes. The k(H)/k(D) value for isomerization was 1.13. Since this relatively low value is a secondary kinetic effect, overall reaction is governed by the ring opening step. The selective opening to the E-dienol was supported by calculation.