3-hydroxy-4,7,7-trimethyl-1,8-nonadien-5-one | 133420-20-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-hydroxy-4,7,7-trimethyl-1,8-nonadien-5-one
• 英文别名: 7-hydroxy-3,3,6-trimethylnona-1,8-dien-5-one
• CAS: 133420-20-9；133420-57-2
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: FQROWMLKUSTBTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  14.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-hydroxy-4,7,7-trimethyl-1,8-nonadien-5-one 在 咪唑 、 lithium aluminium tetrahydride 、 三正丁胺 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 氯苯 为溶剂， 反应 65.83h， 生成 1-<(tert-butyldimethylsilyl)oxy>-2,3,3a,4,5,7a-hexahydro-3,3,7a-trimethyl-1H-indene
  参考文献：
  名称：

  The synthesis of 2,3,3a,4,5,7a-hexahydro-1H-inden-1-ols by intramolecular Diels-Alder reactions of 1,3,8-nonatrien-5-ols. Dependence of product stereochemistry on the substitution pattern

  摘要：

  A short and efficient synthesis of the title compounds is described, starting from readily available alpha,beta-unsaturated carbonyl compounds 5 and beta,gamma-unsaturated ketones 4. Their directed aldol condensation yields the unsaturated hydroxy ketones 6 which are dehydrated to the trienones 7. Although these fail to cyclize on heating, the intramolecular Diels-Alder reaction can be brought about after reduction or alkyllithium addition to the carbonyl group. Alkyl substitution in the positions 1,2,3,5, and 7 has little influence on the ease and yield of cyclization, whereas a methyl group at C-4 hinders it considerably. The title compounds are obtained as mixtures of usually all four stereoisomers, of which one predominates (greater-than-or-equal-to 50%) in most cases. O-Alkylation in 8b has little effect on the isomer distribution. The major isomer of the 6-bromo derivative forms a highly crystalline p-nitrobenzoate 27, which permits stereochemical assignment through X-ray crystallography; for most other products assignments can be made by comparison and further evaluation of their H-1 NMR spectra. The results are discussed in terms of a simple transition state model. The intramolecular Diels-Alder reaction fails when the length of the tethering chain is reduced by one, or when the diene unit becomes part of a furan ring. Trienones 7 are sensitive to autoxidation, of which some products are described.

  DOI：

  10.1021/jo00008a045
• 作为产物：
  描述：

  5,5-dimethyl-6-hepten-3-ol 在 sodium acetate 、 pyridinium chlorochromate 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 5.33h， 生成 3-hydroxy-4,7,7-trimethyl-1,8-nonadien-5-one
  参考文献：
  名称：

  The synthesis of 2,3,3a,4,5,7a-hexahydro-1H-inden-1-ols by intramolecular Diels-Alder reactions of 1,3,8-nonatrien-5-ols. Dependence of product stereochemistry on the substitution pattern

  摘要：

  A short and efficient synthesis of the title compounds is described, starting from readily available alpha,beta-unsaturated carbonyl compounds 5 and beta,gamma-unsaturated ketones 4. Their directed aldol condensation yields the unsaturated hydroxy ketones 6 which are dehydrated to the trienones 7. Although these fail to cyclize on heating, the intramolecular Diels-Alder reaction can be brought about after reduction or alkyllithium addition to the carbonyl group. Alkyl substitution in the positions 1,2,3,5, and 7 has little influence on the ease and yield of cyclization, whereas a methyl group at C-4 hinders it considerably. The title compounds are obtained as mixtures of usually all four stereoisomers, of which one predominates (greater-than-or-equal-to 50%) in most cases. O-Alkylation in 8b has little effect on the isomer distribution. The major isomer of the 6-bromo derivative forms a highly crystalline p-nitrobenzoate 27, which permits stereochemical assignment through X-ray crystallography; for most other products assignments can be made by comparison and further evaluation of their H-1 NMR spectra. The results are discussed in terms of a simple transition state model. The intramolecular Diels-Alder reaction fails when the length of the tethering chain is reduced by one, or when the diene unit becomes part of a furan ring. Trienones 7 are sensitive to autoxidation, of which some products are described.

  DOI：

  10.1021/jo00008a045

文献信息

• KOZIKOWSKI, ALAN P.;TUCKMANTEL, WERNER, J. ORG. CHEM., 56,(1991) N, C. 2826-2837
  作者：KOZIKOWSKI, ALAN P.、TUCKMANTEL, WERNER

  DOI：——

  日期：——
• The synthesis of 2,3,3a,4,5,7a-hexahydro-1H-inden-1-ols by intramolecular Diels-Alder reactions of 1,3,8-nonatrien-5-ols. Dependence of product stereochemistry on the substitution pattern
  作者：Alan P. Kozikowski、Werner Tuckmantel

  DOI：10.1021/jo00008a045

  日期：1991.4

  A short and efficient synthesis of the title compounds is described, starting from readily available alpha,beta-unsaturated carbonyl compounds 5 and beta,gamma-unsaturated ketones 4. Their directed aldol condensation yields the unsaturated hydroxy ketones 6 which are dehydrated to the trienones 7. Although these fail to cyclize on heating, the intramolecular Diels-Alder reaction can be brought about after reduction or alkyllithium addition to the carbonyl group. Alkyl substitution in the positions 1,2,3,5, and 7 has little influence on the ease and yield of cyclization, whereas a methyl group at C-4 hinders it considerably. The title compounds are obtained as mixtures of usually all four stereoisomers, of which one predominates (greater-than-or-equal-to 50%) in most cases. O-Alkylation in 8b has little effect on the isomer distribution. The major isomer of the 6-bromo derivative forms a highly crystalline p-nitrobenzoate 27, which permits stereochemical assignment through X-ray crystallography; for most other products assignments can be made by comparison and further evaluation of their H-1 NMR spectra. The results are discussed in terms of a simple transition state model. The intramolecular Diels-Alder reaction fails when the length of the tethering chain is reduced by one, or when the diene unit becomes part of a furan ring. Trienones 7 are sensitive to autoxidation, of which some products are described.