2-(2'-chloro-6'-methylbenzoyl)-3-methyl-1,2-dihydroisoquinaldonitrile | 1394818-03-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(2'-chloro-6'-methylbenzoyl)-3-methyl-1,2-dihydroisoquinaldonitrile
• CAS: 1394818-03-1
• 化学式: C₁₉H₁₅ClN₂O
• 分子量: 322.794
• InChiKey: XETOOTUTDSBQMS-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  2-(2'-chloro-6'-methylbenzoyl)-3-methyl-1,2-dihydroisoquinaldonitrile 在 二硫化碳 、 sodium hydride 、 重水 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 生成
  参考文献：
  名称：

  The stereochemistry of isoquinoline Reissert compounds: a unique platform for observation of steric and electronic interactions

  摘要：

  Isoquinoline Reissert compounds (2-acyl-1,2-dihydroisoquinaldonitriles) with either 3-H (1) or 3-CH3 (2) substituents and various N-acyl groups have been examined in detail by H-1 and C-13 NMR spectroscopy and X-ray crystallography. In all cases the trans amide conformation, with reference to the carbonyl oxygen and the 3-position of the isoquinoline ring, predominates in solution. In the solid state the nitrite moieties are pseudo-axial and the amides exist almost exclusively in the trans form, except for the case of 2-isobutyryl-3-methyl-1,2-dihydroisoquinaldonitrile (2c), which exists exclusively as the cis amide form in the solid state. In N-aroyl 3-CH3 compounds with two ortho-aroyl substituents both amide isomerism and hindered aryl/carbonyl rotation are observed by H-1 NMR spectroscopy. In other N-aroyl derivatives only hindered aryl/carbonyl rotations are observed by NMR and in N-alkanoyl compounds amide isomerism is observable only at very low temperatures. X-ray crystallography reveals the two rotamers in the solid state in four cases of ortho-substituted benzoyl compounds; with one exception, the rotamer with the larger ortho-aroyl substituent syn to the pseudo-axial cyano group is favored. Unusual solubility and reactivity patterns observed with these compounds are rationalized in terms of the interplay between steric and electronic factors. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.06.008

文献信息

• Stereochemistry of alkylated isoquinoline Reissert compounds
  作者：Harry W. Gibson、Michael A.G. Berg、Terry L. Price、Zhenbin Niu、Minjae Lee、Mason A. Rouser、Carla Slebodnick

  DOI：10.1016/j.tet.2014.06.027

  日期：2014.9

  A series of alkylated isoquinoline Reissert compounds (2-acyl-1-alkyl-1,2-dihydroisoquinoline-1-nitriles) with either 3-H (3) or 3-CH3 (4) substituents was examined by 1H, 13C, and 19F NMR spectroscopies and X-ray crystallography. In all cases the trans-amide conformation, with reference to the carbonyl oxygen and the 3-position of the isoquinoline ring, exists exclusively in the solid state, and predominates

  用1 H，13检查了具有3-H（3）或3-CH 3（4）取代基的一系列烷基化的异喹啉Reissert化合物（2-酰基-1-烷基-1,2-二氢异喹啉-1-腈）C，19 F NMR光谱学和X射线晶体学。在所有情况下，相对于羰基氧和异喹啉环的3-位，反式-酰胺构型仅以固态存在，并主要存在于溶液中。如所预期的，在所有情况下，1-烷基（异丙基，异丁基，苄基）几乎是伪轴向或轴向的。在N-芳酰基化合物中，较大的邻-芳酰基取代基为顺式X射线晶体学研究显示，在11例病例中，有9例中的1烷基部分是“ 1-烷基”。在溶液NMR结果显示有关的Ar / CO键即旋转对映异构通常是在室温下快速，但在-50℃下缓慢且通常有利于顺式异构体。4的3-甲基质子与N-芳酰基部分的CH⋯π相互作用似乎会影响阻转异构现象。