ethyl 2,6,6-trimethylcyclohex-2-ene-1-carboxylate | 96849-99-9

• 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: ethyl 2,6,6-trimethylcyclohex-2-ene-1-carboxylate
• 英文别名: ethyl α-cyclogeraniate；(+/-)-2.6.6-trimethyl-cyclohexene-(5)-carboxylic acid-(1)-ethyl ester；2,6,6-trimethyl-cyclohex-2-enecarboxylic acid ethyl ester；2,6,6-Trimethyl-cyclohex-2-encarbonsaeure-aethylester；(+/-)-2.6.6-Trimethyl-cyclohexen-(5)-carbonsaeure-(1)-aethylester；α-Cyclogeraniumsaeureaethylester；Ethyl 2,6,6-trimethyl-2-cyclohexene-1-carboxylate
• CAS: 96849-99-9
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: UMXBKVFQEPMZTB-UHFFFAOYSA-N

物化性质

• 沸点：
  110-140 °C(Press: 12 Torr)
• 密度：
  0.933±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  ethyl 2,6,6-trimethylcyclohex-2-ene-1-carboxylate 在 氢氧化钾 、 五氯化磷 作用下， 生成 (+/-)-2.2.6-trimethyl-cyclohexene-(5)-carboxylic acid-(1)-amide
  参考文献：
  名称：

  Bouveault, Bulletin de la Societe Chimique de France, 1910, vol. <4> 7, p. 354

  摘要：

  DOI：
• 作为产物：
  描述：

  4-甲基-3戊烯-2-酮 在 三乙基硅烷 、 三氟化硼乙醚 、 zinc(II) chloride 作用下， 以 正庚烷 、 甲苯 为溶剂， 反应 62.0h， 生成 ethyl 2,6,6-trimethylcyclohex-2-ene-1-carboxylate
  参考文献：
  名称：

  A new synthetic route to (.+-.)-Strigol

  摘要：

  DOI：

  10.1021/jo00386a016

文献信息

• Lipase-mediated resolution of the hydroxy-cyclogeraniol isomers: application to the synthesis of the enantiomers of karahana lactone, karahana ether, crocusatin C and γ-cyclogeraniol
  作者：Stefano Serra、Francesco G. Gatti、Claudio Fuganti

  DOI：10.1016/j.tetasy.2009.05.013

  日期：2009.6

  study on the lipase PS-mediated resolution of different hydroxy-geraniol isomers is reported. A number of α-, β- and γ-isomers bearing a 2-, 3- or 4-hydroxy functional group were synthesised regioselectively and then submitted to the lipase-mediated kinetic acetylation. The latter experiments showed that the 2-hydroxy isomers 4, 5 and 14 (α, γ and β, respectively) as well as cis-3-hydroxy α-cyclogeraniol

  报道了对脂肪酶PS介导的不同羟基香叶醇异构体拆分的综合研究。选择性地合成许多带有2-，3-或4-羟基官能团的α-，β-和γ-异构体，然后进行脂肪酶介导的动力学乙酰化。后者实验表明，2-羟基异构体4，5和14（α，γ分别和β），以及顺式-3-羟基α-cyclogeraniol 7和顺式-4-羟基γ-cyclogeraniol 10可以很容易地通过此过程解决。这些化合物主要部分的对映体纯度通过重结晶而提高，所得对映体二醇被用作合成天然萜类化合物卡拉汉内酯，卡拉汉醚和番红花素C的组成部分，并用于制备合成中间体γ-环香叶醇。二醇的对映异构体的绝对构型7，10，14和19通过用已知化合物的化学相关性来确定40，41，39和41分别。
• Process for preparing seed germinating stimulants
  申请人：The United States of America as represented by the Secretary of

  公开号：US04723038A1

  公开（公告）日：1988-02-02

  Processes for preparing compounds which exhibit seed germinating activity are disclosed. An ester of acetoacetic acid is condensed with a ketone to produce a substituted cyclohexenone which is reacted with a thiol to get a dithioketal which is then desulfurized to produce an ester of a substituted cyclohex-2-ene-1-carboxylic acid which exhibits seed germinating activity. The same compound can be produced by a different process which reacts the substituted cyclohexenone with a reducing agent. An exemplary reducing agent would be an organosilane and a Lewis acid.

  披露了制备具有种子萌发活性化合物的过程。乙酰乙酸酯与酮缩合，产生取代环己烯酮，然后与硫醇反应得到二硫醚醛，再去硫化产生一种展现种子萌发活性的取代环己-2-烯-1-羧酸酯。同样的化合物也可以通过另一种方法制备，即将取代环己烯酮与还原剂反应。一个示范性的还原剂可以是有机硅烷和路易斯酸。
• Synthese und Cyclisation der 3,7-Dimethyl-octadien-(2,7)-säure-(1) und über eine neue Herstellungsart der 5-Methyl-hexen-(5)-säure-(1)
  作者：H. Kappeler、D. Stauffacher、A. Eschenmoser、H. Schinz

  DOI：10.1002/hlca.19540370403

  日期：——

  A. 3,7-Dimethyl-octadien-(2,7)-säure-(1) (Limonenform der Geraniumsäure) wurde ausgehend von 5-Methyl-hexen-(5)-säure-(1) über 6-Methyl-hepten-(6)-on-(2) nach der Acetylenäthermethode hergestellt.

  A.3,7-二甲基辛二烯-（2,7）-säure-（1）（天竺葵（Limonenform derGeraniumsäure））由5甲基-己烯-（5）-säure-（1）über6-甲基-庚烯-（6）-（2）上的乙酰丙酮法赫氏酯。
• Préparation de quelques composés apparentés á l'acide allo-cyclogéranique
  作者：Ch. A. Vodoz、H. Schinz

  DOI：10.1002/hlca.19500330529

  日期：——

  A. L'allo-cyclogéraniol et l'allo-cyclocitral sont décrits.

  A. L'allo-cyclogéraniol等。
• Enantioselective enzymatic resolution of racemic alcohols by lipases in green organic solvents
  作者：Abderahmane Belafriekh、Francesco Secundo、Stefano Serra、Zeineddine Djeghaba

  DOI：10.1016/j.tetasy.2017.02.004

  日期：2017.3

  The effects of two eco-friendly solvents, 2-methyltetrahydrofuran (MeTHF) and cyclopentyl methyl ether (CPME), on the enzyme activity and enantioselectivity of Novozym 435, Candida rugosa lipase (CRL), Porcine pancreas lipase (PPL), Lipase AK, Lipase PS, and Lipozyme, a series of commercial lipases, in the enantioselective transesterfications of racemic menthol, racemic sulcatol and racemic alpha-cyclogeraniol were studied. Vinyl acetate was chosen as the acyl donor and the reactions were carried out at water activity 0.06. The activity of lipases in CPME was similar to that observed in other largely employed organic solvents [toluene and tert-butyl methyl ether (MTBE)], and was slightly lower in MeTHF. However, for most of the lipases tested, the enantioselectivity was higher in the eco-friendly solvents. Lipase AK exhibited a high enantioselectivity (E = 232) for the resolution of racemic menthol but the reaction rate was low. Lipase formulation (the enzyme was frozen and lyophilized in potassium phosphate buffer without and with 5% (w/v) of sucrose, D-mannitol, or methoxy poly(ethylene glycol)) was tested with this lipase in order to improve its activity, which increased up to 4.5 times, compared to the untreated enzyme. CALB was found to be a useful biocatalyst for the resolution of racemic sulcatol, where high activity and enantioselectivity were obtained (E >= 1000). For the resolution of the racemic primary alcohol alpha-cyclogeraniol, most of the lipases tested were active but not enantioselective, except lipase PS which displayed a moderate enantioselectivity (E = 19). The effect of the presence of a low percentage of two ionic liquids (ILs) 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFS1]) (5% (v/v)) and 1-Butyl-3-methylimidazoliumtetrafluoroborate ([BMIM][BF4]) (1% (v/v)) in the medium was also investigated. Only in the case of CRL the ILs slightly increased the enantioselectivity from E = 91 to E = 103 and E = 120 for [BMIM][TES1] and [BMIM][BF4], respectively. However, in all cases ILs caused a decrease of enzyme activity. (C) 2017 Elsevier Ltd. All rights reserved.