N-methoxycyclohexanecarboxamide | 84127-18-4

• 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: N-methoxycyclohexanecarboxamide
• CAS: 84127-18-4
• 化学式: C₈H₁₅NO₂
• 分子量: 157.213
• InChiKey: FBEWUCGAHVJCLI-UHFFFAOYSA-N

物化性质

• 密度：
  1.028±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-methoxycyclohexanecarboxamide 在 titanium(III) chloride 、 air 作用下， 生成 环己甲酰胺
  参考文献：
  名称：

  O-Methylarenehydroxamates as ortho-lithiation directing groups. Titanium(III)-mediated conversion of O-methyl hydroxamates to primary amides

  摘要：

  Reaction of O-methyl benzohydroxamates 2a-c with sec-butyllithium in the presence of TMEDA at -40-degrees-C regiospecifically generates the highly reactive N,ortho-dilithiated species (e.g. 3). These dilithio species react avidly with a wide spectrum of electrophilic reagents, including alkyl halides, giving adducts which on reduction with TiCl3 are converted into ortho-substituted primary benzamides in excellent yields. Ortho lithiation of O-methyl benzohydroxamates is thus formally equivalent to ortho lithiation of primary benzamides themselves. The utility of these synthetic operations is enhanced by the well-known facility with which the primary amide moiety can be transformed into other useful functional groups. The conversion of 0-methyl hydroxamates to primary amides is shown to be general, as exemplified by transformation of 14a-f to 15a-f.O-Methyl 2-methylbenzohydroxamate (4a) undergoes regiospecific dilithiation on nitrogen and on the methyl group when treated with sec-butyllithium at -70-degrees-C. These dilithio species react with DMF or ''Weinreb-type'' amides to give condensation products which cyclize to N-methoxyisoquinolin-1(2H)-ones under mildly acidic conditions. Removal of the N-methoxy moiety under conditions analogous to those used for O-methyl benzohydroxamate provides N-unsubstituted isoquinolin-1(2H)-ones with high overall efficiency. This process is exemplified by the synthesis of isoquinolin-1(2H)-one 9a, its 3-n-butyl congener 9b, and the tricyclic isoquinolin-1 (2H)-ones 20a and 20b from O-methyl 2-methylbenzohydroxamate (4a).

  DOI：

  10.1021/jo00066a014
• 作为产物：
  描述：

  (E)-1-环己基-N-羟基甲亚胺 在 sodium methylate 、 sodium 、 氯 、 碳酸氢钠 作用下， 以 甲醇 为溶剂， 生成 N-methoxycyclohexanecarboxamide
  参考文献：
  名称：

  Novel oxime-phosphate compounds

  摘要：

  已经发现了新型的无环和杂环羟肟磷酸酯化合物，具有杀虫、杀螨和杀线虫的活性。

  公开号：

  US04339444A1

文献信息

• Intermolecular Electrochemical C(<i>sp</i> ³ )-H/N-H Cross-coupling of Xanthenes with <i>N</i> -alkoxyamides: Radical Pathway Mediated by Ferrocene as a Redox Catalyst
  作者：Meng-Ying Lin、Kun Xu、Yang-Ye Jiang、Yong-Guo Liu、Bao-Guo Sun、Cheng-Chu Zeng

  DOI：10.1002/adsc.201701536

  日期：2018.4.17

  with xanthenes is reported. The protocol is carried out in an undivided cell under constant current conditions employing simple, cheap and readily available ferrocene (Fc) as a redox catalyst. Cyclic voltammetry and control experiments disclosed that the dehydrogenative cross‐coupling reaction may proceed via an amidyl radical.

  报道了N-烷氧基酰胺与黄嘌呤的有效分子间脱氢交叉偶联。该方案是在恒定电流条件下，使用简单，廉价且容易获得的二茂铁（Fc）作为氧化还原催化剂，在未分裂的电池中进行的。循环伏安法和对照实验表明，脱氢交叉偶联反应可能通过酰胺基进行。
• Rh(III)-Catalyzed C–H Amidation of Arenes with <i>N</i>-Methoxyamide as an Amidating Reagent
  作者：Guodong Ju、Guobao Li、Guanwen Qian、Jingyu Zhang、Yingsheng Zhao

  DOI：10.1021/acs.orglett.9b02625

  日期：2019.9.20

  The Rh(III)-catalyzed amidation of C(sp2)-H bonds has been reported by employing the N-methoxyamide as a novel amino source. An excellent level of functional group tolerance can be achieved when N-methoxyamide derivatives are used as the amidating reagents. Importantly, several known bioactive compounds such as Aminalon, Pregabalin, Gabapentin, and Probenecid can be transformed to effective amidating

  通过使用N-甲氧基酰胺作为新型氨基源，已经报道了Rh（III）催化的C（sp2）-H键的酰胺化反应。当使用N-甲氧基酰胺衍生物作为酰胺化试剂时，可以达到极好的官能团耐受性。重要的是，可以将几种已知的生物活性化合物（例如阿米那隆，普瑞巴林，加巴喷丁和丙磺舒）转化为有效的酰胺化试剂，以利于开发新的生物活性分子。
• Copper-Catalyzed Cross-Coupling of O-Alkyl Hydroxamates with Aryl Iodides
  作者：Martins Katkevics、Tatyana Kukosha、Nadezhda Trufilkina、Sergey Belyakov

  DOI：10.1055/s-0031-1290384

  日期：2012.8

  derivatives were prepared by copper-catalyzed cross-coupling of hydroxamates with aryl iodides. The reaction conditions are compatible with standard hydroxy-protecting groups on the hydroxylamine moiety and are applicable to a broad range of coupling partners. N-Aryl-O-alkylhydroxamic acid derivatives were prepared by copper-catalyzed cross-coupling of hydroxamates with aryl iodides. The reaction conditions

  摘要 N-芳基-O-烷基异羟肟酸衍生物是通过异羟肟酸酯与芳基碘化物的铜催化交叉偶联制备的。该反应条件与羟胺部分上的标准羟基保护基相容，并且适用于广泛的偶联伴侣。 N-芳基-O-烷基异羟肟酸衍生物是通过异羟肟酸酯与芳基碘化物的铜催化交叉偶联制备的。该反应条件与羟胺部分上的标准羟基保护基相容，并且适用于广泛的偶联伴侣。
• Electrodimerization of <i>N</i> -Alkoxyamides for Zinc(II) Catalyzed Phenolic Ester Synthesis under Mild Reaction Conditions
  作者：Kripa Subramanian、Subhash L. Yedage、Bhalchandra M. Bhanage

  DOI：10.1002/adsc.201701646

  日期：2018.7.4

  electrochemical On‐Off method for phenolic ester synthesis from N‐alkoxyamides has been reported. This one‐pot protocol begins with rapid and selective electrodimerization of the amide using n‐Bu4NI (TBAI) as an electrocatalyst. The reaction proceeds further in the absence of current via Zn catalyzed C−N bond activation of the amide dimer followed by its coupling with phenol to form the ester. The present

  已经报道了从N-烷氧基酰胺合成酚酯的电化学开-关方法。这种一锅法的协议开始于使用n- Bu 4 NI（TBAI）作为电催化剂对酰胺进行快速和选择性的电二聚。在不存在电流的情况下，该反应会进一步通过酰胺催化的二聚体的Zn催化C-N键活化而进行，然后将其与苯酚偶联形成酯。本方法学不含配体，在温和的反应条件下进行。这种转变结合了多种酚和酰胺底物，导致形成功能化的酯，从而突出了其多功能性。
• Copper‐Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of <i>N</i> ‐Methoxyamides
  作者：Shona Banjo、Eiko Nakasuji、Tatsuhiko Meguro、Takaaki Sato、Noritaka Chida

  DOI：10.1002/chem.201901145

  日期：2019.6.12

  A copper‐catalyzed electrophilic amidation of aryltrifluoroborates with use of N‐methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N‐methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed

  据报道，使用N-甲氧基酰胺进行了铜催化的芳基三氟硼酸酯的亲电酰胺化反应。该反应显示出源自两个明显特征的高官能团相容性：1）N-甲氧基酰胺的高稳定性，以及2）在LiCl存在下的非碱性温和条件。所开发的方法还可以用于合成广泛分布于天然产物中的烯酰胺。初步的机理研究表明，第一步是在LiCl的协助下对三氟硼酸芳基酯进行金属转移，生成的芳基铜中间体通过非S N 2氧化添加至N-甲氧基酰胺并随后进行还原消除而提供了苯胺。