(9ci)-2-甲基-1-环己烯-1-羰酰氯 | 74517-10-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 中文名称: (9ci)-2-甲基-1-环己烯-1-羰酰氯
• 英文名称: 2-Methyl-1-cyclohex-1-ene carboxylic acid chloride
• 英文别名: 2-Methylcyclohex-1-ene-1-carbonyl chloride；2-methylcyclohexene-1-carbonyl chloride
• CAS: 74517-10-5
• 化学式: C₈H₁₁ClO
• 分子量: 158.628
• InChiKey: OITXLFPWWSAEPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (9ci)-2-甲基-1-环己烯-1-羰酰氯 在 copper(l) iodide 、 copper(I) bromide dimethylsulfide complex 、 N,N-二异丙基乙胺 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 生成 benzyl 3-hydroxy-1,7a-dimethyl-2-oxo-2,4,5,6,7,7a-hexahydro-1H-indene-1-carboxylate
  参考文献：
  名称：

  阴离子加速不对称纳扎罗夫环化：获得邻位全碳四元立构中心

  摘要：

  我们开发了一种催化不对称纳扎罗夫环化，可高产率形成两个连续的全碳四元立构中心，并具有出色的不对称诱导水平。该方法不需要在作为简单二酮酯的起始材料中存在催化剂识别元素。起始材料的几何纯E或Z异构体可产生具有高对映选择性的非对映异构纯产物，因为进行环化的物质是构型稳定的烯醇铑。

  DOI：

  10.1039/d3ob00735a
• 作为产物：
  描述：

  Ethyl 2-methyl-1-cyclohex-1-ene carboxylate 在 草酰氯 、 lithium hydroxide monohydrate 、 水 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 (9ci)-2-甲基-1-环己烯-1-羰酰氯
  参考文献：
  名称：

  催化对映选择性Nazarov环化：邻域全碳原子四元立体中心的构建。

  摘要：

  邻位全碳原子四元立体中心的非对映选择性不对称合成是有机合成中一个具有挑战性的问题，对此仅描述了很少的解决方案。现在报道了完全取代的二烯酮的催化不对称纳扎罗夫环化，其提供具有高光学纯度并且作为单一非对映异构体的具有邻位季铵立体中心的环戊烯酮衍生物。

  DOI：

  10.1002/anie.201403587

文献信息

• Diastereospecific Nazarov Cyclization of Fully Substituted Dienones: Generation of Vicinal All-Carbon-Atom Quaternary Stereocenters
  作者：Anais Jolit、Saleta Vazquez-Rodriguez、Glenn P. A. Yap、Marcus A. Tius

  DOI：10.1002/anie.201305218

  日期：2013.10.11

  vacancy: Fully substituted dienones that are highly polarized by a vinylogous carbonate group were found to undergo a remarkably rapid and diastereospecific Nazarov cyclization that led to cyclopentenones with vicinal all‐carbon‐atom quaternary centers (see example; SEM=2‐(trimethylsilyl)ethoxymethyl, Tf=trifluoromethanesulfonyl).

  无空位：发现被乙烯基碳酸酯基团高度极化的完全取代的二烯酮经历了非常快速和非对映特异性的 Nazarov 环化，导致环戊烯酮具有邻位全碳原子四元中心（参见示例；SEM=2-（三甲基甲硅烷基）乙氧基甲基，Tf=三氟甲磺酰基）。
• 1-Cycloalkenyltetrazolinones
  申请人：NIHON BAYER AGROCHEM K.K.

  公开号：EP0728750A1

  公开（公告）日：1996-08-28

  1-Cycloalkenyltetrazolinone derivatives of the following formulae (I) and (II): wherein R1represents cycloalkenyl which may optionally be substituted by halogen or C1-4 alkyl, or bicycloalkenyl which may optionally be substituted by halogen or C1-4 alkyl, and R2 and R3each independently represents alkyl, cycloalkyl, phenyl, substituted phenyl (said substituent being selected from nitro, cyano, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio), alkenyl or alkynyl, or R2 and R3may optionally form, together with N-atom to which they are bonded, a 5- or 6-membered heterocyclic ring, said heterocyclic ring may optionally be benzo-condensed and/or be substituted by C1-4 alkyl. The compounds of formula (I) exhibit an excellent herbicidal activity and the compounds of formula (II) are useful as intermediate compounds in the production process of the compounds of the formula (I).

  下式(I)和(II)的 1-环烯基四唑啉酮衍生物： 其中 R1 代表可任选被卤素或 C1-4 烷基取代的环烯基，或可任选被卤素或 C1-4 烷基取代的双环烯基，以及 R2 和 R3 各自独立地代表烷基、环烷基、苯基、取代苯基（所述取代基选自硝基、氰基、卤素、烷基、卤代烷基、烷氧基、卤代烷氧基和烷硫基）、烯基或炔基、 或 R2 和 R3 可选择与它们所结合的 N 原子一起形成一个 5 或 6 元杂环，所述杂环可选择为苯并缩合和/或被 C1-4 烷基取代。 式（I）化合物具有优异的除草活性，式（II）化合物可作为式（I）化合物生产过程中的中间化合物。
• Influence of the nature of chiral auxiliaries on the diastereoselective hydrogenation of ortho-substituted benzoic acid derivatives
  作者：Michèle Besson、Pierre Gallezot、Samuel Neto、Catherine Pinel

  DOI：10.1016/s0957-4166(00)00112-9

  日期：2000.5

  The diastereoselective hydrogenation of o-toluic acid or o-methoxy benzoic acid covalently bound to different chiral auxiliaries was performed on Rh and Ru supported catalysts. The cis-isomers were formed predominantly, with a diastereoselectivity largely influenced by the structure of the chiral inductor and the steric hindrance brought for the preferential adsorption of one face of the aromatic substrate. The effect of the functional group on the proline auxiliary (alcohol or ester groups susceptible to modify the anchoring of the aromatic substrate) was weak. Hydrogenolysis occurred rather extensively with the methoxy benzoic acid and constituted the most important hydrogenation pathway on Rh/C. The presence of the C=O group in the pyroglutamic acid methyl ester is a determining factor for obtaining good diastereoselectivity. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Asymmetric Synthesis of 2-Methyl Cyclohexane Carboxylic Acids by Heterogeneous Catalysis: Mechanistic Aspects
  作者：Michèle Besson、Françoise Delbecq、Pierre Gallezot、Samuel Neto、Catherine Pinel

  DOI：10.1002/(sici)1521-3765(20000317)6:6<949::aid-chem949>3.0.co;2-h

  日期：2000.3.17

  The catalytic hydrogenation of (S)-alkyl-N-(2-methylbenzoyl)pyroglutamates was studied over supported rhodium and ruthenium catalysts at room temperature and a pressure of 5 MPa. The reaction was diastereoselective with the predominant formation of (1S,2R)-2-methylcyclohexane carboxylic acid with a diastereomeric excess (de) of up to 96%. The most stable conformation was determined by means of a combination of modelling calculations, NMR spectroscopy and X-ray structural determination. In this conformation, the carbonyl group of the pyroglutamate auxiliary shields one face of the aromatic ring. The observed selectivity may thus be explained by a preferential adsorption at the unshielded face which avoids steric repulsion by the C=O group to result in a cis hydrogenation. The addition of an amine, the nature of the support (alumina or active carbon) or of the metal (Rh or Ru) were shown to give additional stabilisation of the adsorption at the unshielded face to increase the diastereoisomeric excess.
• US5654257A
  申请人：——

  公开号：US5654257A

  公开（公告）日：1997-08-05