methyl 6-amino-hexane-1-carbamate

• 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: methyl 6-amino-hexane-1-carbamate
• 英文别名: methyl 6-aminohexane-1-carbamate；MHC；(6-amino-hexyl)-carbamic acid methyl ester；(6-Amino-hexyl)-carbamidsaeure-methylester；Methyl (6-aminohexyl)carbamate；methyl N-(6-aminohexyl)carbamate
• 化学式: C₈H₁₈N₂O₂
• 分子量: 174.243
• InChiKey: PPNOBJDLQVQFIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  64.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  甲醇 、 (6-氨基己基)氨基甲酸 在 cerium(IV) oxide 作用下， 139.84 ℃ 、1.0 MPa 条件下， 以53 %的产率得到methyl 6-amino-hexane-1-carbamate
  参考文献：
  名称：

  CeO2 催化剂上烷基氨基甲酸与醇的直接酯化反应

  摘要：

  CO 2 -捕获的胺的转化：在CeO 2催化剂上用甲醇证明了苄基氨基甲酸的直接酯化，这很容易通过苄胺吸收CO 2产生。在最佳条件下合成了目标产物，收率64%。 CeO 2催化剂可重复使用，广泛适用于各种基材。

  DOI：

  10.1002/cssc.202301436

文献信息

• Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by<i>in situ</i>Generated Hydroxide Ion: A Mechanistic Consideration
  作者：Dae Won Kim、Eun Soo Huh、Sang Do Park、Ly Vinh Nguyen、Mai Dao Nguyen、Hoon Sik Kim、Minserk Cheong、Dinh Quan Nguyen

  DOI：10.1002/adsc.200900699

  日期：2010.2.15

  The methoxycarbonylation reactions of aliphatic diamines with dimethyl carbonate are accelerated greatly in the presence of water. Theoretical investigations on the mechanistic aspects of the methoxycarbonylation of 1,6-hexanediamine strongly suggest that the hydroxide ion, generated in situ from the interaction of 1,6-hexanediamine with water, is an active catalytic species and plays a pivotal role

  在水的存在下，脂肪族二胺与碳酸二甲酯的甲氧基羰基化反应大大加快。对1,6-己二胺甲氧基羰基化机理的理论研究有力地表明，由1,6-己二胺与水的相互作用原位产生的氢氧根离子是一种活性的催化物质，在速率上起关键作用。 -确定从氨基提取氢的步骤。
• Effective synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and dimethyl carbonate using 3-amino-1,2,4-triazole potassium as a solid base catalyst at ambient temperature
  作者：Peixue Wang、Yuqing Fei、Qinghe Li、Youquan Deng

  DOI：10.1039/c6gc02509a

  日期：——

  A newly basic catalyst 3-Amino-1,2,4-triazole potassium (KATriz) was prepared, characterized and employed for synthesis of dimethylhexane 1,6-dicarbamate (MHDC) by methoxycarbonylation of 1,6-hexanediamine (HDA) and dimethyl carbonate (DMC). Results showed that...

  制备了新型碱性催化剂3-氨基-1,2,4-三唑钾（KATriz），表征并用于通过1,6-己二胺（HDA）和二甲基的甲氧基羰基化合成二甲基己烷1,6-二氨基甲酸酯（MHDC）碳酸盐（DMC）。结果表明...
• CH3COONa as an effective catalyst for methoxycarbonylation of 1,6-hexanediamine by dimethyl carbonate to dimethylhexane-1,6-dicarbamate
  作者：Da-Lei Sun、Shun-Ji Xie、Jian-Ru Deng、Cai-Juan Huang、Eli Ruckenstein、Zi-Sheng Chao

  DOI：10.1039/b915023b

  日期：——

  Methoxycarbonylation of 1,6-hexanediamine (HDA) by dimethyl carbonate (DMC) was carried out, using, for the first time, CH3COONa as catalyst. The effects of the solvent, reaction temperature, reaction time, and catalyst amount, were investigated. A yield as high as 99.0% of dimethylhexane-1,6-dicarbamate 2 has been obtained at a temperature of 348 K and a reaction time of 6 h. Mechanistic studies revealed that N-substituted acetamide, as the active intermediate product, and NaOH were first formed via the reaction between HDA and CH3COONa. A further reaction between the N-substituted acetamide and DMC generated carbamates and methyl acetate, via a hexatomic ring intermediate. The CH3COONa catalyst was finally recovered through the reaction between NaOH and methyl acetate, which thus completed the catalytic cycle.

  首次使用 CH3COONa 作为催化剂，对 1,6-hexanediamine (HDA) 与碳酸二甲酯 (DMC) 进行了甲氧基羰基化反应。研究了溶剂、反应温度、反应时间和催化剂用量的影响。机理研究表明，作为活性中间产物的 N-取代乙酰胺和 NaOH 首先通过 HDA 和 CH3COONa 反应生成。N-取代乙酰胺和 DMC 之间的进一步反应通过六原子环中间体生成氨基甲酸酯和乙酸甲酯。CH3COONa 催化剂最终通过 NaOH 和醋酸甲酯之间的反应回收，从而完成了催化循环。
• Methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to dimethylhexane-1,6-dicarbamate over Zn/SiO₂ catalyst
  作者：Lina Zhang、Hongguang Li、Feng Li、Yanfeng Pu、Ning Zhao、Fukui Xiao

  DOI：10.1039/c6ra08492c

  日期：——

  The activated Zn(OAc)₂ in Zn/SiO₂ catalysts facilitates the activation of DMC which leads to better catalytic performance.

  在Zn/SiO2催化剂中激活的Zn(OAc)2促进了DMC的激活，从而导致更好的催化性能。
• Sc(OTf)3-catalyzed carbomethoxylation of aliphatic amines with dimethyl carbonate (DMC): DMC activation by η1η1-O(CO) coordination to Sc(III) and its relevance to catalysis
  作者：M DISTASO、E QUARANTA

  DOI：10.1016/j.jcat.2007.11.004

  日期：2008.1.25

  The role of metal center in the Sc(OTf)(3)-catalyzed carbomethoxylation of aliphatic amines with DMC has been investigated. We have shown that the catalytic formation of carbamate ester is promoted by coordination of DMC to scandium(III) ion through the carbonyl oxygen atom. The ability of DMC to coordinate to Sc(III) has been proved by IR and NMR spectroscopy and fully demonstrated also by the isolation, for the first time, of a DMC-metal complex characterized as (eta(1)-O(C=O)-DMC)Sc(OTf)(3). A relationship has been shown between the coordination mode of DNIC to Sc(III) and the reactivity of coordinated organic carbonate: coordination of DMC to Sc(III) activates both carbonyl group and O-CH3 moieties of the carbonic acid diester and enhances not only the carbomethoxylating but also the methylating activity of the ambident electrophile (DMC), as documented by the different selectivity exhibited by the catalyst in the aminolysis reaction of DMC with benzylamine and aniline, respectively. (c) 2007 Elsevier Inc. All rights reserved.