2-氯-3,4-二甲氧基苯甲腈 | 119413-61-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-氯-3,4-二甲氧基苯甲腈
• 中文别名: 2-氯-3,4-二甲氧基苄腈
• 英文名称: 2-chloro-3,4-dimethoxybenzonitrile
• CAS: 119413-61-5
• 化学式: C₉H₈ClNO₂
• 分子量: 197.621
• InChiKey: DVVLTABTKVOGCS-UHFFFAOYSA-N

物化性质

• 熔点：
  101 °C
• 稳定性/保质期：
  如果按照规格使用和储存，则不会分解，未有已知危险反应。请避免与氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  42.2
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险等级：
  6.1
• 危险类别码：
  R36/37/38
• 危险品运输编号：
  3276
• 海关编码：
  2926909090
• 包装等级：
  III
• 危险类别：
  6.1
• 安全说明：
  S26,S36/37/39

反应信息

• 作为反应物：
  描述：

  2,6-二甲基苯基溴化镁 、 2-氯-3,4-二甲氧基苯甲腈 在 zinc(II) chloride 、 二(三叔丁基膦)钯 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 为溶剂， 反应 18.33h， 以77%的产率得到2,3-dimethoxy-6-cyano-2',6'-dimethylbiphenyl
  参考文献：
  名称：

  钯催化的芳基和氯乙烯交叉偶联的第一种通用方法：使用市售 Pd(P(t-Bu)3)2 作为催化剂

  摘要：

  使用单一协议，市售的 Pd(P(t-Bu)(3))(2) 可以影响范围广泛的芳基和氯乙烯与芳基和烷基锌试剂的 Negishi 交叉偶联。该过程耐受硝基，并有效地生成空间位阻联芳基。此外，可以实现高周转数（> 3000）。

  DOI：

  10.1021/ja003954y
• 作为产物：
  描述：

  2-氯-3,4-二甲氧基苯甲醛 在 叠氮基三甲基硅烷 、 氯化锆(IV) 作用下， 以 乙腈 为溶剂， 反应 0.33h， 以85%的产率得到2-氯-3,4-二甲氧基苯甲腈
  参考文献：
  名称：

  Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles

  摘要：

  The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.

  DOI：

  10.1021/acs.joc.5b01305

文献信息

• Facile Synthesis of Substituted 4-Alkoxy-2-oxazolines and Exploration of the Reaction Mechanism
  作者：Bo Li、Jiye Shi、Weiliang Zhu、Jianming Zhu、Xiaolong Li、Guimin Wang、Zhijian Xu、Shikai Tian、Adrian Hall、Jingshan Shen

  DOI：10.1055/s-0035-1561386

  日期：——

  4-alkoxy-2-oxazolines. The proposed reaction mechanism has been validated by quantum chemistry calculations, key intermediate synthesis, and NMR spectra. Substituted 4-alkoxy-2-oxazolines have been synthesized via the reaction of nitriles with beta-hydroxyacetals promoted by trifluoromethanesulfonic acid. The reaction is proposed to be initiated by the protonation of the acetals to produce carbocations that are then

  摘要 通过腈与由三氟甲磺酸促进的β-羟基缩醛的反应合成了取代的4-烷氧基-2-恶唑啉。提议该反应通过缩醛的质子化来引发，以产生碳阳离子，然后该碳阳离子被腈的氮原子攻击，随后进行分子内环化反应以形成4-烷氧基-2-恶唑啉。所提出的反应机理已通过量子化学计算，关键中间体合成和NMR光谱进行了验证。 通过腈与由三氟甲磺酸促进的β-羟基缩醛的反应合成了取代的4-烷氧基-2-恶唑啉。提议该反应通过缩醛的质子化来引发，以产生碳阳离子，然后该碳阳离子被腈的氮原子攻击，随后进行分子内环化反应以形成4-烷氧基-2-恶唑啉。所提出的反应机理已通过量子化学计算，关键中间体合成和NMR光谱进行了验证。
• Palladium-Catalyzed Difluoromethylation of Aryl Chlorides and Triflates and Its Applications in the Preparation of Difluoromethylated Derivatives of Drug/Agrochemical Molecules
  作者：Changhui Lu、Hao Lu、Jiang Wu、Hong C. Shen、Taishan Hu、Yucheng Gu、Qilong Shen

  DOI：10.1021/acs.joc.7b02989

  日期：2018.1.19

  A palladium-catalyzed difluoromethylation of a series of aryl chlorides and triflates under mild conditions was described. A variety of common functional groups were tolerated. In addition, by using this protocol, several drug molecules containing an aryl chloride unit were successfully difluoromethylated, thus enabling medicinal chemists to rapidly access novel drug derivatives with potentially improved

  描述了在温和条件下钯催化的一系列芳基氯和三氟甲磺酸二氟甲基化反应。可以耐受各种常见的功能基团。此外，通过使用该协议，几个包含芳基氯单元的药物分子成功地被二氟甲基化，从而使药物化学家能够通过后期功能化快速访问具有潜在改善特性的新型药物衍生物。
• Catalysts for Suzuki−Miyaura Coupling Processes:  Scope and Studies of the Effect of Ligand Structure
  作者：Timothy E. Barder、Shawn D. Walker、Joseph R. Martinelli、Stephen L. Buchwald

  DOI：10.1021/ja042491j

  日期：2005.4.1

  catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, for reactions of aryl chlorides at room temperature. Additionally, structural studies of various 1.Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki-Miyaura coupling processes. Moreover, a comparison of the reactions with 1 and with 2-(2',4',6'-t

  芳基和杂芳基卤化物与芳基-、杂芳基-和乙烯基硼酸的 Suzuki-Miyaura 偶联反应使用 2-(2',6'-二甲氧基联苯) 二环己基膦 SPhos (1) 以非常好的收率进行。这种配体为这些过程提供了前所未有的活性，允许在低催化剂水平下进行反应，制备极受阻的联芳基化合物，并且通常在室温下进行芳基氯的反应。此外，还介绍了各种 1.Pd 配合物的结构研究以及有助于阐明 1 对 Suzuki-Miyaura 偶联过程的功效的计算数据。此外，与 1 和 2-(2',4',6' -三异丙基联苯）二苯基膦（2）在确定配体体积和给电子能力在源自此类配体的催化剂的高活性中的相对重要性方面提供了信息。此外，当芳基溴变得太受阻时，一个有趣的 CH 键官能化-交叉偶联序列会介入以提供高产率的产物。
• The First General Method for Palladium-Catalyzed Negishi Cross-Coupling of Aryl and Vinyl Chlorides:  Use of Commercially Available Pd(P(<i>t</i>-Bu)₃)₂ as a Catalyst
  作者：Chaoyang Dai、Gregory C. Fu

  DOI：10.1021/ja003954y

  日期：2001.3.1

  With a single protocol, commercially available Pd(P(t-Bu)(3))(2) can effect the Negishi cross-coupling of a wide range of aryl and vinyl chlorides with aryl- and alkylzinc reagents. The process tolerates nitro groups, and it efficiently generates sterically hindered biaryls. In addition, a high turnover number (>3000) can be achieved.

  使用单一协议，市售的 Pd(P(t-Bu)(3))(2) 可以影响范围广泛的芳基和氯乙烯与芳基和烷基锌试剂的 Negishi 交叉偶联。该过程耐受硝基，并有效地生成空间位阻联芳基。此外，可以实现高周转数（> 3000）。
• Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
  作者：Phongprapan Nimnual、Jumreang Tummatorn、Charnsak Thongsornkleeb、Somsak Ruchirawat

  DOI：10.1021/acs.joc.5b01305

  日期：2015.9.4

  The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.