2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene | 313478-12-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene
• CAS: 313478-12-5
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: HHWXVDVEEPKUNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.09
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yloxoyl radical 、 2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene 以 二氯甲烷 为溶剂， 反应 504000.0h， 以0.03%的产率得到(2SR,4aRS,8RS)-3,4,4a,5,6,7-hexahydro-4a-methyl-8H,8-(1'',1'',3'',3''-tetramethylisoindolin-2''-yloxyl)-spiro-(naphthalen-2',2'-dimethyl-2,2'-oxirane)
  参考文献：
  名称：

  Synthesis and Allergenic Potential of a 15-Hydroperoxyabietic Acid-like Model:  Trapping of Radical Intermediates

  摘要：

  To better understand the skin sensitization mechanism of 15-hydroperoxyabietic acid-like compounds, 2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene 7 was synthesized. The allergenic activity of this compound was tested on mice using the local lymph node assay, and further evaluated on guinea pigs using the Freund's complete adjuvant test. Using these methods, hydroperoxide 7 was found to be a strong sensitizer. Radical-trapping experiments were carried out on this compound in the presence of the spin-trapping agent, 1,1,3,3-tetramethylisoindolin-2-yloxyl 17, using light to induce radicals. The formation of carbon-centered radicals derived from compound 7 by intramolecular cyclization of an oxygen-centered radical was observed. The reaction of these intermediates with 17 gave various adducts in a very low yield, but a 1/1 mixture of diastereomers 18a and 18b (0.1% yield) was isolated and characterized, together with compound 19 (0.03% yield). The results suggest that carbon-centered reactive radicals are formed from allylic hydroperoxides and that this could be the possible mechanism involved in allergic contact dermatitis to abietic acid.

  DOI：

  10.1021/tx9901433
• 作为产物：
  描述：

  4A-甲基-4,4a,5,6,7,8-六氢-3H-萘-2-酮 在 18-冠醚-6 、 硫酸 、 potassium tert-butylate 、 双氧水 、 silica gel 、 lithium bromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二乙二醇二甲醚 、 甲苯 、 正戊烷 为溶剂， 反应 14.0h， 生成 2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene
  参考文献：
  名称：

  Synthesis and Allergenic Potential of a 15-Hydroperoxyabietic Acid-like Model:  Trapping of Radical Intermediates

  摘要：

  To better understand the skin sensitization mechanism of 15-hydroperoxyabietic acid-like compounds, 2-(1'-hydroperoxy-1'-methylethyl)-4a-methyl-3,4,4a,5,6,7-hexahydronaphthalene 7 was synthesized. The allergenic activity of this compound was tested on mice using the local lymph node assay, and further evaluated on guinea pigs using the Freund's complete adjuvant test. Using these methods, hydroperoxide 7 was found to be a strong sensitizer. Radical-trapping experiments were carried out on this compound in the presence of the spin-trapping agent, 1,1,3,3-tetramethylisoindolin-2-yloxyl 17, using light to induce radicals. The formation of carbon-centered radicals derived from compound 7 by intramolecular cyclization of an oxygen-centered radical was observed. The reaction of these intermediates with 17 gave various adducts in a very low yield, but a 1/1 mixture of diastereomers 18a and 18b (0.1% yield) was isolated and characterized, together with compound 19 (0.03% yield). The results suggest that carbon-centered reactive radicals are formed from allylic hydroperoxides and that this could be the possible mechanism involved in allergic contact dermatitis to abietic acid.

  DOI：

  10.1021/tx9901433