(+/-)-trans-2,6,6-trimethyl-2-cyclohexen-1,4-diol | 141037-63-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-trans-2,6,6-trimethyl-2-cyclohexen-1,4-diol
• 英文别名: (1S,4S)-2,6,6-trimethylcyclohex-2-ene-1,4-diol
• CAS: 141037-63-0
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: GVYFIMKMHDHRLF-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-trans-2,6,6-trimethyl-2-cyclohexen-1,4-diol 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 以29%的产率得到(+/-)-trans-2,6,6-trimethylcyclohexane-1,4-diol
  参考文献：
  名称：

  Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives

  摘要：

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.

  DOI：

  10.1016/0957-4166(95)00159-m
• 作为产物：
  描述：

  2,6,6-三甲基-2-环己烯-1,4-二酮 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以12%的产率得到(1S,4R)-2,6,6-trimethyl-2-cyclohexen-1,4-diol
  参考文献：
  名称：

  Lipase-catalyzed asymmetric synthesis of (R)- and (S)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone and their dihydro derivatives

  摘要：

  Racemic 4-hydroxy-2,6,6-trimethyl-2-cyclohexenon trans- and cis-2,6,6-trimethyl-2-cyclohexene-1,4-diols were prepared by reduction of 4-oxoisophorone with sodium borohydride-cerium chloride. Lipase (PS-30)-catalyzed kinetic resolution of (+/-)-cis-2,6,6-trimethyl-2-cyclohexene-1,4-diol with vinyl acetate led to (1R, 4S)-4-acetoxy-2,6, 6-trimethyl-2-cyclohexen-1-ol (81 %ee);and (1S, 4K)-1-acetoxy-2,6,6-trimethyl-2-cyclohexene-4-ol (92 %ee). Hydrolysis of the former monoacetate and recrytallization of the resulting material afforded enantiomerically pure (1R, 4S)-2,6,6-trimethyl-2-cyclohexene-1,4-diol. On the other hand, recrystallization of (1S, 4R) monoacetate itself provided an optically pure sample, which was then hydrolyzed to give (1S, 417)-2,6,6-trimethylcyclohexene-1,4-diol. Transformation of both diols into (S)- and (R)-4-tert-butyldimethylsilyloxy-2,6,6-trimethyl-2-cyclohexenone was conducted in two steps including silylation and oxidation. Catalytic hydrogenation of these (S)- and(R)-silyloxy enones dyer Raney nickel afforded the corresponding dihydro derivatives.

  DOI：

  10.1016/0957-4166(95)00159-m

文献信息

• A new rearrangement: conversion of a diepoxycyclohexane into a dihydropyrancarbaldehyde
  作者：Gerard P. Moss、Cheng Keat Ooi

  DOI：10.1039/c39920000342

  日期：——

  Treatment of 2,7,7-trimethyl-3,8-dioxatricyclo[3.2.1.02,4]octane 5 and derivatives with BF3 gave the corresponding 4,4,5-trimethyl-3,4-dihydro-2H-pyran-2-carbaldehyde 7 and traces only of 3,5,5-trimethyl-7-oxabicyclo[2.2.1]-heptan-2-one 8.

  用BF3处理2,7,7-三甲基-3,8-二氧杂三环[3.2.1.02,4]辛烷5及其衍生物，得到相应的4,4,5-三甲基-3,4-二氢-2H-吡喃-2-甲醛7和微量的3,5,5-三甲基-7-氧杂双环[2.2.1]-庚烷-2-酮8。