cis-8a-methyl-1,2,4a,7,8,8a-hexahydronaphtalene-2,7-dione | 22920-14-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-8a-methyl-1,2,4a,7,8,8a-hexahydronaphtalene-2,7-dione
• 英文别名: cis-6-Methylbicyclo<4.4.0>deca-4,7-diene-3,9-dione
• CAS: 22920-14-5
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: VWSDGLBSDDUBDU-DKTWLAJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.67
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  cis-8a-methyl-1,2,4a,7,8,8a-hexahydronaphtalene-2,7-dione 以 苯 为溶剂， 以74%的产率得到
  参考文献：
  名称：

  9-甲基-四环[5.3.0 4,9 .0 8,10 ]-癸烷-2,6-二酮的光化学合成

  摘要：

  在苯中辐射（λ> 340 nm）顺式-8a-甲基-1,2,4a，7,8,8a-六氢萘-2.7-二酮（1）通过分子内[2 + 2]-环加成得到标题化合物2。

  DOI：

  10.1002/hlca.19820650214
• 作为产物：
  描述：

  cis-1-Carbomethoxy-2-hydroxy-4a-methylbicyclo<4.4.0>-1-decen-7-one 在 lithium carbonate 、 lithium bromide 、 copper(ll) bromide 作用下， 以 氯仿 、 磷酸 、 溶剂黄146 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 cis-8a-methyl-1,2,4a,7,8,8a-hexahydronaphtalene-2,7-dione
  参考文献：
  名称：

  Intramolecular Ring-Opening Of Cyclopropanones by Enolate Anions

  摘要：

  Treatment of cis-4a-methyldecalin-2,7-dione with 2 equiv of bromine gave cis-3,6(dieq)-dibromo-4a-methyldecalin-2,7-dione (9). Dehydrobromination of 9 with LiBr/Li2CO3 in DMF gave cis-6-methylbicyclo[4,4.0]deca-4,7-diene-3,9-dione (3). However, dehydrobromination of 9 with DBU in THF gave 1-bromo-5-methyltricyclo[4.4.0.0(1,7)]decane-2,8-dione (11). Bromination of cis-1-carbomethoxy-2-hydroxgy-4a-methylbicyclo[4.4.0]-1-decen-7-one (7), with cupric bromide in CHCl3/EtOAc provided cis-6(eq)-bromo-1-carbomethoxy-2-hydroxy-4a-methylbicyclo[4.4.0]-1-decen-7-one (13), whereas bromination of 7 with 2 equiv of bromine in CHCl3 provided cis-6(eq)-bromo-8(eq)-bromo-1-carbomethoxy-2-hydroxy-4a-methylbicyclo [4.4.0]-1-decen-7-one (14). Dehydrobromination of 13 with LiBr/Li2CO3 in DMF resulted in the loss of HBr with the formation of the methyl cis-3,4,4a,7,8,8a-hexahydro-2-hydroxy-4a-methyl-7-oxo-1-naphthoate (16) However, dehydrobromination of 13 with DBU in THF gave 16 (17%), 7-carbomethoxy-5-methyltricyclo[4.4.0.0(1,7)]decane-2,8-dione (17) (41%), and 2-carbomethoxy-1-hydroxy-8-methyltetracyclo[4.4.0.0(1,6).0(2,4)]decan-5-one (18) (40%). Dehydrobromination of the dibromo keto ester 14 gave only the tetracyclic ketol ester 20. Bromination of keto ester 7 with NBS and triethylamine gave the two epimers of methyl cis-3,4,4a,5,6,7,8,8a-octahydro-1-bromo-4a-methyl-2,7-dioxo-1(2H)-naphthoate (15) Dehydrobromination of 15a/b nith a variety of bases did not give the tricyclic diketo ester 22 but instead resulted in reductive debromination to regenerate starting material 7. The formation of 17 and 18 from 13 and of 20 from 14 are interpreted as occurring by novel intramolecular nucleophilic ring-openings of cyclopropanone-Favorskii intermediates by enolate anions.

  DOI：

  10.1021/jo00108a016