(E)-N-(prop-1-enyl)-o-toluamide | 139583-85-0

• 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: (E)-N-(prop-1-enyl)-o-toluamide
• 英文别名: (E)-N-propenyl-o-toluamide；2-methyl-N-[(E)-prop-1-enyl]benzamide
• CAS: 139583-85-0
• 化学式: C₁₁H₁₃NO
• 分子量: 175.23
• InChiKey: CNPRHPQOVVZEJV-FPYGCLRLSA-N

物化性质

• 沸点：
  350.6±25.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N-丙-2-烯基苯甲酰胺 在 仲丁基锂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.33h， 生成 (E)-N-(prop-1-enyl)-o-toluamide
  参考文献：
  名称：

  Heteroatom-directed metalation. Lithiation of N-propenylbenzamides and N-propenyl-o-toluamides. Novel routes to ortho-substituted primary benzamide derivatives and N-unsubstituted isoquinolin-1(2H)-ones

  摘要：

  Reaction of N-propenylbenzamides 4 and 9, obtained by LDA-induced isomerization of the corresponding N-allylbenzamides 1, 8, and 14, with 2 equiv of sec-butyllithium or tert-butyllithium at low temperature regiospecifically generates the highly reactive N,ortho-dilithiated species (e.g., 5 and 17). These dilithio species react avidly with a wide spectrum of electrophilic reagents, including alkyl halides, giving adducts which on hydrolysis with warm 50% aqueous acetic acid are converted into ortho-substituted primary benzamides in excellent yields. Ortho-lithiation of N-propenylbenzamides is thus formally equivalent to ortho-lithiation of primary benzamides themselves. The utility of this important, previously unknown, synthetic operation is enhanced by the well-known facility with which the primary amide moiety can be transformed into other useful functional groups, as exemplified by the synthesis of 2-methoxy-6-methylbenzoic acid (12) and 2-methoxy-6-methylbenzonitrile (13) from N-propenyl-2-methoxybenzamide (9), N-Propenyl-o-toluamide (7) undergoes regiospecific dilithiation on nitrogen and on the methyl group under conditions analogous to those used for the N-propenylbenzamides. These dilithio species react with DMF or "Weinreb type" amides to give condensation products which cyclize to N-propenylisoquinolin-1(2H)-ones under midly acidic conditions. Removal of the N-propenyl moiety under more strongly acidic conditions provides N-unsubstituted isoquinolin-1(2H)-ones with high overall efficiency. This process is exemplified by the synthesis of isoquinolin-1(2H)-one (23) and its 3-n-butyl congener 26 from N-propenyl-2-methylbenzamide (7).

  DOI：

  10.1021/jo00035a030

文献信息

• Easy access to enamides: a mild nickel-catalysed alkene isomerization of allylamides
  作者：Lu Wang、Chao Liu、Ruopeng Bai、Yani Pan、Aiwen Lei

  DOI：10.1039/c3cc43875a

  日期：——

  The first Ni-catalysed alkene isomerization of allylamides for the synthesis of enamides was demonstrated. Various substituted N-allylamides were found to be suitable substrates for this isomerization. Isotopic labelling experiments showed that it is an intramolecular hydrogen transfer process.

  首次证明了烯丙基酰胺在镍催化下的烯烃异构化反应可用于合成烯酰胺。研究发现，各种取代的 N-烯丙基酰胺是这种异构化反应的合适底物。同位素标记实验表明，这是一个分子内氢转移过程。
• [EN] PROCESS FOR MAKING SPIROLACTONE COMPOUNDS<br/>[FR] PROCEDE DE PRODUCTION DE COMPOSES SPIROLACTONES
  申请人：MERCK & CO INC

  公开号：WO2004104009A1

  公开（公告）日：2004-12-02

  This invention relates to a process for making spirolactone compounds of general formula I, having an improved IA/IB ratio, according to the following shceme.

  本发明涉及一种制备具有改进的IA/IB比例的一般式I的螺内酯化合物的过程，其过程如下所示。
• Process for Making Spirolactone Compounds
  申请人：Volante P Ralph

  公开号：US20060014950A1

  公开（公告）日：2006-01-19

  This invention relates to a process for making spirolactone compounds analogous to formula I.

  本发明涉及一种类似于式 I 的螺内酯化合物的制造工艺。
• Process for making spirolactone compounds
  申请人：Volante P Ralph

  公开号：US20060241299A1

  公开（公告）日：2006-10-26

  This invention relates to a process for making spirolactone compounds of general formula I, having an improved IA/IB ratio, according to the following shceme.

  本发明涉及一种通式 I 的螺内酯化合物的制造工艺，其 IA/IB 比率有所提高，具体方法如下。
• [EN] SUBSTITUTED 1-ISOQUINOLONE DERIVATIVES AS ANGIOTENSIN II ANTAGONISTS
  申请人：SYNTEX (U.S.A.) INC.

  公开号：WO1993014086A1

  公开（公告）日：1993-07-22

  (EN) 1-Isoquinolone derivatives and related compounds according to formula (I) wherein, Y is selected from the group consisting of H, OH, lower alkoxy, and halo; X is selected from the group consisting of H, lower alkyl acid, lower alkyl ester, and lower alkyl; and R1 is selected from the group consisting of H, alkenyl, lower alkyl, lower cycloalkyl, unsubstituted or substituted 3-spiro-1H-indane of structure (II) wherein R2 is H, OH, lower alkyl, lower alkoxy or halo, and 3-spiro-cycloalkyl of structure (III) wherein n is an integer from zero to six, provided that when R1 is spiro- X is H, or a pharmaceutically acceptable salt thereof, with the proviso that when R1 is spiro-, X is H, and when R1 is H, alkenyl, lower alkyl or lower cycloalkyl substituted at the 3-position of the isoquinolone moiety and X is H or lower alkyl, the (2'-1H--tetrazol-5-yl)biphenyl-4'-ylmethyl group cannot be at the 2(N) position, are useful as angiotensin II receptor antagonists. Also disclosed are methods of synthesis, intermediates, pharmaceutical formulations and methods of treatment.(FR) Dérivés d'isoquinolone-1 et composés apparentés répondant à la formule (I) dans laquelle Y est choisi dans le groupe composé de H, OH, alcoxy inférieur et halo; X est choisi dans le groupe composé de H, acide d'alkyle inférieur, ester d'alkyle inférieur et alkyle inférieur; et R1 spiro-1H-indane substitué ou non substitué de la structure dans laquelle R2 représente H, OH, alkyle inférieur, alcoxy inférieur ou halo, et 3-spiro-cycloalkyle de la structure dans laquelle n représente un nombre entier compris entre zéro et six, à condition que, lorsque R1 représente spiro, X représente H, ou un sel pharmaceutiquement accepatble, à condition que, lorsque R1 représente spiro-, X représente H, et lorsque R1 représente H, alcényle, alkyle inférieur ou cycloalkyle inférieur substitué dans la position 3 de la fraction d'isoquinolone, et que X représente H ou alkyle inférieur, le groupe (2'-1H--tétrazol-5-yl)biphényl-4'-ylméthyle ne peut pas se trouver dans la position 2(N). Ces dérivés et composés sont utiles comme antagonistes du récepteur de l'angiotensine II. Des procédés de synthèse sont également décrits, ainsi que des intermédiaires, des formulations pharmaceutiques et des procédés de traitement.

  1-甲氧estionone衍生物及相关化合物，按照分子式(I)，其中，Y选自以下组：H、OH、低级醇和卤素；X选自以下组：H、低级烷酸、低级烷酯和低级烷基；而R1选自以下组：H、烯基、低级烷基、低级环烷基，或者未被取代或部分取代的3-环辛烷-1H-甲氧estionone的结构(II)，其中R2选自以下组：H、OH、低级烷基、低级烷氧基或卤素，或者3-环烷基环辛烷的结构(III)，其中n为零到六的整数。此外，当R1为环烷基时，X选自H或低级烷基，而当R1选自H、烯基、低级烷基或低级环烷基并被3位置于甲氧estionone的环状基团时，其(X)不能与(2'-1H--tétrazol--5-yl)二苯基-4'-甲氧基在2(N)位。这些衍生物和化合物对角蛋白收缩抑制剂具有一定的用途。该文还描述了合成方法、中间体、药剂 formulations和治疗的方法。