3,5-dimethyl-2,3-epoxycyclohexanone | 5110-56-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 3,5-dimethyl-2,3-epoxycyclohexanone
• 英文别名: 4,6-dimethyl-7-oxabicyclo[4.1.0]heptan-2-one
• CAS: 5110-56-5
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: ILGKZCPUVQJRIY-UHFFFAOYSA-N

物化性质

• 沸点：
  65 °C(Press: 2 Torr)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,5-dimethyl-2,3-epoxycyclohexanone 在 对甲苯磺酰肼 作用下， 生成 4-甲基-6-庚炔-2-酮
  参考文献：
  名称：

  New approaches to the synthesis of alkyl-substituted enol lactone systems, inhibitors of the serine protease elastase

  摘要：

  We have synthesized a series of alkyl-substituted enol lactones designed to act as mechanism-based inhibitors of human neutrophil elastase (HLE). General methods were developed for the preparation of alpha- and beta-alkyl-substituted 5-hexynoic acids by the bromoform reaction on the corresponding alkynoic methyl ketone, prepared by an Eschenmoser-Tanabe fragmentation sequence from a suitably substituted cyclohexenone. By this method, beta-methyl- and beta,beta-dimethyl-5-hexynoic acids were synthesized from commercially available isophorone and 3,5-dimethyl-2-cyclohexen-1-one, respectively. Alpha-Substituted 5-hexynoic acids were prepared from 3-ethoxy-2-cyclohexen-1-one, using a novel ZnCl2-mediated alkylation that we developed; this method gives high yields of alpha'-alkylation products, even with secondary halides. The most efficient method for the preparation of alpha-substituted 5-hexynoic acids involved a four-reaction sequence-alkylation of the alpha-substituted ester with 1,4-dibromobutane, elimination, bromination and bisdehydrobromination-that proceeded in high overall yield. Protio enol lactonizations were performed with mercury(II) catalysis in CH2Cl2 or CH2Cl2-H2O. Stereo-selective Z-bromo enol lactonization was carried out by Br+-induced lactonization in the presence of Ag+. E-Bromo enol lactonization with N-bromosuccinimide in CH2Cl2 in the presence of a small amount of water gave better yields and shorter reaction times than the traditional anhydrous conditions. In studies of the inhibitory activity of these lactones toward several proteases (reported in full elsewhere), we found that the alpha-alkyl-substituted protio and bromo enol lactones 1-3 were very good inhibitors of HLE, with k(a)/K(i) values ranging from 14 500 to 37 500 M-1 s-1; the beta-alkyl-substituted enol lactones 5-8 showed only moderate inhibition of HLE.

  DOI：

  10.1021/jo00059a049
• 作为产物：
  描述：

  3,5-二甲基-2-环己烯-1-酮 在 sodium hydroxide 、 双氧水 作用下， 以 乙醇 为溶剂， 生成 3,5-dimethyl-2,3-epoxycyclohexanone
  参考文献：
  名称：

  烷基化的iridolactone类似物的合成

  摘要：

  双环δ-内酯是在双环连接处带有烷基的铱-内酯类似物，是通过分子内的Horner-Wadsworth-Emmons反应从α-烷基-α-羟甲基环戊酮获得的。

  DOI：

  10.1016/s0040-4039(03)01320-0

文献信息

• The reaction of trialkylstannylmethyllithium with α,β-epoxy ketones and α-chloro ketones
  作者：Tadashi Sato、Toshihiro Kikuchi、Hiroshi Tsujita、Atsushi Kaetsu、Norio Sootome、Ken-ichiro Nishida、Kazutaka Tachibana、Eigoro Murayama

  DOI：10.1016/s0040-4020(01)86394-8

  日期：1991.1

  The reactions of trialkylstannylmethyllithium with α,β-epoxy ketones afforded mainly cyclopropanols, while α-chloro ketones afforded allyl alcohols and/or cyclopropanols, in varying amounts depending upon the molar ratio of the reagent to the substrate.

  三烷基锡烷基甲基锂与α，β-环氧酮的反应主要产生环丙醇，而α-氯酮的生成烯丙醇和/或环丙醇的量取决于试剂与底物的摩尔比而变化。
• Sustainable Epoxidation of Electron-Poor Olefins with Hydrogen Peroxide in Ionic Liquids and Recovery of the Products with Supercritical CO2
  作者：Olga Bortolini、Sandro Campestrini、Valeria Conte、Giancarlo Fantin、Marco Fogagnolo、Silvia Maietti

  DOI：10.1002/ejoc.200300442

  日期：2003.12

  An efficient procedure is described for the epoxidation of electron-deficient olefins, in particular Vitamin K-3 and analogues, with aqueous basic solutions of hydrogen peroxide in different ambient temperature ionic liquids (ILs) [bmim(+)][X-] [bmim(+)] = 1-butyl-3-methylimidazolium; [X-] = [BF4-], [CF3SO3-], [PF6-] [N(CF3SO2)(2)(-)]}. Various factors affecting epoxide yield (in the range 80-99%)

  描述了在不同环境温度的离子液体 (IL) [bmim(+)][X-] 中使用过氧化氢碱性水溶液环氧化缺电子烯烃，特别是维生素 K-3 和类似物的有效程序[bmim(+)] = 1-丁基-3-甲基咪唑鎓；[X-] = [BF4-], [CF3SO3-], [PF6-] [N(CF3SO2)(2)(-)]}。已经检查了影响环氧化物产率（80-99%）、反应速率和再现性的各种因素。用超临界 CO2 从反应介质中几乎定量地提取环氧化物。然后回收离子液体并在随后的循环中重新使用。(C) Wiley-VCH Verlag GmbH & Co.KGaA, 69451 Weinheim, Germany, 2003。
• Electrosynthesis of hydrogen peroxide in room temperature ionic liquids and in situ epoxidation of alkenes
  作者：Michael Chi-Yung Tang、Kwok-Yin Wong、Tak Hang Chan

  DOI：10.1039/b416837b

  日期：——

  Hydrogen peroxide can be electrosynthesized from oxygen in [bmim][BF4]–water and used in situ for the epoxidation of alkenes.

  过氧化氢可以从氧气在[bmim][BF4]–水体系中电合成，并在现场用于烯烃的环氧化反应。
• Cerium(III) chloride mediated regioselective synthesis of cyclic α-chloro-α,β-enones and α-chloro-β-hydroxy ketones
  作者：Antonio Garrido Montalban、Lars-Oliver Wittenberg、Alexander McKillop

  DOI：10.1016/s0040-4039(99)01129-6

  日期：1999.8

  Reaction of cyclic α,β-epoxy ketones with Ce(III) chloride under hydrous or anhydrous conditions yields the corresponding cyclic α-chloro-α,β-enones or cyclic α-chloro-β-hydroxy ketones, respectively.

  在含水或无水条件下，环状α，β-环氧酮与氯化铈（Ⅲ）的反应分别产生相应的环状α-氯-α，β-烯酮或环状α-氯-β-羟基酮。
• Preparation of optically pure 2,3-epoxycyclohexanones
  作者：Koichi Tanaka、Fumio Toda

  DOI：10.1039/c39830001513

  日期：——

  One hundred per cent optically pure methyl-substituted 2,3-epoxycyclohexanones [(2)–(4)] were obtained using a complexation method with optically active 1,6-di(o-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol (1).

  使用具有光学活性的1,6-二（邻氯苯基）-1,6-二苯基六-2的络合方法获得了100％的光学纯的甲基取代的2,3-环氧环己酮[（2-（4）] ，4-二炔-1,6-二醇（1）。