5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate | 370558-07-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate
• 英文别名: 1-Acetoxy-3,3-dimethyl-5-vinylcyclohexa-1,5-diene；1-Acetoxy-3,3-dimethyl-5-vinyl-cyclohexa-1,5-diene；(5-ethenyl-3,3-dimethylcyclohexa-1,5-dien-1-yl) acetate
• CAS: 370558-07-9
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: HSXIIFQCFJAOIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-羟基对萘醌 、 5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate 以 甲苯 为溶剂， 反应 60.0h， 以68%的产率得到11-hydroxy-3,3-dimethyl-7,12-dioxo-3,4,6,6a,7,12,12a,12b-octahydro-benz[a]anthracen-1-yl acetate
  参考文献：
  名称：

  11-Hydroxy-3,3-dimethyl-7,12-dioxo-3,4,6,6a,7,12,12a,12b-octahydrobenz[a]anthracen-1-yl acetate

  摘要：

  The Diels-Alder reaction between 5-hydroxy-1,4-naphthoquinone and 5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate by endo addition gives the title compound, C22H22O5, in 68% yield. This racemic diastereoisomer has the opposite regiochemistry to ochromycinone analogues produced previously and may allow access to a new type of anticancer-active saquayamycin analogue.

  DOI：

  10.1107/s0108270103013374
• 作为产物：
  描述：

  5,5-Dimethyl-3-vinylcyclohex-2-en-1-one 、 乙酸酐 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 以75%的产率得到5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate
  参考文献：
  名称：

  A regio- and stereo-selective synthesis of 2-hydroxy-3-methylochromycinone in three steps from 2-bromo-5-acetoxy-1,4-naphthoquinone and 1-acetoxy-3,3-dimethyl-5-vinylcyclohexa-1,5-diene†

  摘要：

  2-Hydroxy-3-methylochromycinone 4 采用三阶段策略合成。通过 2-溴-5-乙酰氧基-1,4-萘醌和 1-乙酰氧基-3,3-二甲基-5-乙烯基环己-1,5-二烯之间的 Diels-Alder 反应，得到了 1-乙酰氧基-12a-溴-3,3-二甲基-7,12-二氧代-3,4,6,6a,7,12-八氢苯并[a]蒽-8-基的单一外消旋非对映异构体、12a,12b-八氢苯并[a]蒽-8-基乙酸酯 5，收率为 63%，环氧化可得到双环氧化物 8-乙酰氧基-12a-溴-3,3-二甲基-7,8-二氧代-3,4,4a,5,6,6a,7,12,12a,12b-十氢-1aH-苯并[6,7]氧代[2′,3′：10,10a]菲并[3,4-b]氧杂卓-12-基乙酸酯 6，收率为 82%。双环氧化物 6 可直接转化为 2-羟基-3-甲基罗红霉素酮 4，收率为 45%，或通过两种中间体之一[如 2,5-二羟基-3,3-二甲基-1,7,12-三氧代-1,2,3,4,5,6,7,12-八氢苯并[a]蒽-8-基乙酸酯 8]转化，收率为 80-85%。中间体 8 在 µM 浓度下对肺癌、乳腺癌和中枢神经系统癌症具有中等抗癌活性，而目标化合物 4 在 10-4 M 浓度下才具有活性。

  DOI：

  10.1039/b101756j

文献信息

• 11-Hydroxy-3,3-dimethyl-7,12-dioxo-3,4,6,6a,7,12,12a,12b-octahydrobenz[<i>a</i>]anthracen-1-yl acetate
  作者：Tomas Rozek、John H. Bowie、Brian W. Skelton、Allan H. White

  DOI：10.1107/s0108270103013374

  日期：2003.8.15

  The Diels-Alder reaction between 5-hydroxy-1,4-naphthoquinone and 5,5-dimethyl-3-vinyl-1,2-cyclohexadienyl acetate by endo addition gives the title compound, C22H22O5, in 68% yield. This racemic diastereoisomer has the opposite regiochemistry to ochromycinone analogues produced previously and may allow access to a new type of anticancer-active saquayamycin analogue.
• A regio- and stereo-selective synthesis of 2-hydroxy-3-methylochromycinone in three steps from 2-bromo-5-acetoxy-1,4-naphthoquinone and 1-acetoxy-3,3-dimethyl-5-vinylcyclohexa-1,5-diene†
  作者：Tomas Rozek、John H. Bowie、Simon M. Pyke、Brian W. Skelton、Allan H. White

  DOI：10.1039/b101756j

  日期：——

  2-Hydroxy-3-methylochromycinone 4 has been synthesised using a three stage strategy. The Diels–Alder reaction between 2-bromo-5-acetoxy-1,4-naphthoquinone and 1-acetoxy-3,3-dimethyl-5-vinylcyclohexa-1,5-diene gives a single racemic diastereoisomer of 1-acetoxy-12a-bromo-3,3-dimethyl-7,12-dioxo-3,4,6,6a,7,12,12a,12b-octahydrobenzo[a]anthracen-8-yl acetate 5 in 63% yield, which may be epoxidised to give the bis-epoxide 8-acetoxy-12a-bromo-3,3-dimethyl-7,8-dioxo-3,4,4a,5,6,6a,7,12,12a,12b-decahydro-1aH-benzo[6,7]oxireno[2′,3′:10,10a]phenanthro[3,4-b]oxiren-12-yl acetate 6 in 82% yield. The bis-epoxide 6 may be converted directly into 2-hydroxy-3-methylochromycinone 4 in 45% yield, or via one of two intermediates [e.g. 2,5-dihydroxy-3,3-dimethyl-1,7,12-trioxo-1,2,3,4,5,6,7,12-octahydrobenzo[a]anthracen-8-yl acetate 8] in 80–85% yield. The intermediate 8 shows moderate anticancer activity at µM concentrations against lung, breast and central nervous system cancers, while the target compound 4 is only active at 10−4 M.

  2-Hydroxy-3-methylochromycinone 4 采用三阶段策略合成。通过 2-溴-5-乙酰氧基-1,4-萘醌和 1-乙酰氧基-3,3-二甲基-5-乙烯基环己-1,5-二烯之间的 Diels-Alder 反应，得到了 1-乙酰氧基-12a-溴-3,3-二甲基-7,12-二氧代-3,4,6,6a,7,12-八氢苯并[a]蒽-8-基的单一外消旋非对映异构体、12a,12b-八氢苯并[a]蒽-8-基乙酸酯 5，收率为 63%，环氧化可得到双环氧化物 8-乙酰氧基-12a-溴-3,3-二甲基-7,8-二氧代-3,4,4a,5,6,6a,7,12,12a,12b-十氢-1aH-苯并[6,7]氧代[2′,3′：10,10a]菲并[3,4-b]氧杂卓-12-基乙酸酯 6，收率为 82%。双环氧化物 6 可直接转化为 2-羟基-3-甲基罗红霉素酮 4，收率为 45%，或通过两种中间体之一[如 2,5-二羟基-3,3-二甲基-1,7,12-三氧代-1,2,3,4,5,6,7,12-八氢苯并[a]蒽-8-基乙酸酯 8]转化，收率为 80-85%。中间体 8 在 µM 浓度下对肺癌、乳腺癌和中枢神经系统癌症具有中等抗癌活性，而目标化合物 4 在 10-4 M 浓度下才具有活性。