methyl 4-chlorobenzylcarbamate

• 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: methyl 4-chlorobenzylcarbamate
• 英文别名: methyl N-(4-chlorobenzyl)carbamate；methyl N-[(4-chlorophenyl)methyl]carbamate
• 化学式: C₉H₁₀ClNO₂
• mdl: MFCD03384668
• 分子量: 199.637
• InChiKey: CONFXLQNTBOPII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.222
• 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：

  methyl 4-chlorobenzylcarbamate 在 C₂₅H₁₉BrMnN₂O₂P 、 potassium tert-butylate 、 氢气 作用下， 以 甲苯 为溶剂， 130.0 ℃ 、2.0 MPa 条件下， 反应 48.0h， 以89%的产率得到甲醇
  参考文献：
  名称：

  氨基甲酸酯和尿素衍生物的锰催化加氢

  摘要：

  我们报告了氨基甲酸酯和尿素衍生物的氢化，这两种最具挑战性的羰基化合物被氢化，首次由地球丰富的金属络合物催化。这些 CO2 衍生化合物的氢化反应在锰钳络合物的催化下产生甲醇以及胺和醇，这使得该方法成为将 CO2 转化为甲醇的可持续两步路线，包括碱-金属催化剂。此外，氢化在温和压力（20巴）下进行。我们的观察结果支持涉及 Mn-H 络合物的氢化机制。基于信息丰富的机械实验提出了一个合理的催化循环。

  DOI：

  10.1021/jacs.9b05591
• 作为产物：
  描述：

  对氯苯乙腈 在 盐酸 、 Oxone 、 碘苯 作用下， 以 甲醇 、 水 为溶剂， 反应 9.0h， 生成 methyl 4-chlorobenzylcarbamate
  参考文献：
  名称：

  使用氧酮作为终氧化剂，高价碘催化甲酰胺的霍夫曼重排

  摘要：

  使用碘酮作为氧化剂，可将甲酰胺的霍夫曼重排成氨基甲酸酯可被碘苯有效地催化。该反应涉及在甲醇水溶液中在1,1,1,3,3,3-六氟异丙醇（HFIP）存在下由催化量的PhI和Oxone原位生成的高价碘物质。在这些条件下，各种羧酰胺的霍夫曼重排以高收率提供了相应的氨基甲酸酯。

  DOI：

  10.1021/jo302375m

文献信息

• Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile
  作者：Hyuck-Keun Oh

  DOI：10.5012/bkcs.2011.32.5.1539

  日期：2011.5.20

  The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0. The () values are in the range 0.62-0.80 with a negative cross-interaction constant, = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles () are large, = 1.29-1.75, suggesting that the N-H(D) bond is partially

  在 -45.0 的乙腈中研究了 O-甲基 S-芳基硫代碳酸酯与苄胺的氨解作用。() 值在 0.62-0.80 范围内，负交叉交互常数 = -0.42，这被解释为表示协调机制。涉及氘化苄胺亲核试剂的动力学同位素效应 () 很大，= 1.29-1.75，表明 NH(D) 键在过渡态通过形成氢键四中心环状结构而部分断裂。MeO 基团提供的强大推动力增强了协同机制，这增强了假定的两性离子四面体中间体中苄胺和烯硫醇盐的离核性。
• Practical Metal-Free C(sp³)H Functionalization: Construction of Structurally Diverse α-Substituted<i>N</i>-Benzyl and<i>N</i>-Allyl Carbamates
  作者：Zhiyu Xie、Lei Liu、Wenfang Chen、Hongbo Zheng、Qingqing Xu、Huiqing Yuan、Hongxiang Lou

  DOI：10.1002/anie.201310193

  日期：2014.4.7

  is a practical and universal CH functionalization of readily removable N‐benzyl and N‐allyl carbamates, with a wide range of nucleophiles at ambient temperature promoted by Ph3CClO4. The metal‐free reaction has an excellent functional‐group tolerance, and displays a broad scope with respect to both N‐carbamates and nucleophile partners (a variety of organoboranes and CH compounds). The synthetic utility

  描述了一种实用的和普遍Ç 易于除去h的官能ñ -苄基和Ñ -烯丙基氨基甲酸酯，在环境温度下的宽范围的亲核试剂通过pH促进3 CClO 4。无金属反应具有出色的官能团耐受性，并且在N-氨基甲酸酯和亲核试剂（各种有机硼烷和CH化合物）方面都具有广阔的应用范围。展示了目标以及面向多样性的综合中的综合效用。
• Urethanes synthesis from oxamic acids under electrochemical conditions
  作者：Ikechukwu Martin Ogbu、Jonathan Lusseau、Gülbin Kurtay、Frédéric Robert、Yannick Landais

  DOI：10.1039/d0cc05069e

  日期：——

  Urethane synthesis via oxidative decarboxylation of oxamic acids under mild electrochemical conditions is reported. This simple phosgene-free route to urethanes involves an in situ generation of isocyanates by anodic oxidation of oxamic acids in an alcoholic medium. The reaction is applicable to a wide range of oxamic acids, including chiral ones, and alcohols furnishing the desired urethanes in a

  报道了在温和的电化学条件下通过草酸的氧化脱羧合成氨基甲酸酯。这种简单的无光气的氨基甲酸酯途径涉及在酒精介质中通过草酸的阳极氧化原位生成异氰酸酯。该反应适用于广泛的草酰胺酸，包括手性酸，以及在不使用化学氧化剂的情况下，通过一锅法即可提供所需氨基甲酸酯的醇。
• Facile preparation of protected benzylic and heteroarylmethyl amines via room temperature Curtius rearrangement
  作者：Matthew L. Leathen、Emily A. Peterson

  DOI：10.1016/j.tetlet.2010.03.101

  日期：2010.5

  Curtius rearrangement of phenyl and heteroaryl acetic acids is described. We have developed a protocol for room temperature Curtius rearrangement in MeOH or CHCl3 that provides an improvement over standard conditions, avoiding the use of additives or heat. This room temperature optimization of the Curtius rearrangement prevents the formation of side products often observed with benzylic acids, allowing

  描述了用于形成酰基叠氮化物以及随后的苯基和杂芳基乙酸的Curtius重排的分步室温过程。我们已经开发出了在MeOH或CHCl 3中进行室温Curtius重排的规程，该规程比标准条件有所改进，避免了使用添加剂或加热。Curtius重排的这种室温优化可防止形成通常在苯甲酸中观察到的副产物，从而可以使用各种苯甲基和杂芳基甲基胺。
• Application of Ag/TFPG-DMB COF in carbamates synthesis via CO2 fixation reaction and one-pot reductive N-formylation of nitroarenes under sunlight
  作者：Arpita Hazra Chowdhury、Ipsita Hazra Chowdhury、Surajit Biswas、Sk. Manirul Islam

  DOI：10.1016/j.mcat.2020.111050

  日期：2020.9

  We have designed mesoporous AgNPs decorated COF (Ag/TFPG-DMB COF) nanomaterial which has been formed by an easy ex-situ synthetic method. The synthesized material is characterized by FTIR, PXRD, UV-vis, N-2 adsorption-desorption studies, TEM, FESEM and XPS. The material showed the generation of identical mesopore at 3.9 nm. It is observed that the material can perform as both thermally and photochemically active catalyst for carbamate synthesis and one-pot reduction and N-formylation of nitroarenes respectively. The catalytic activity of the Ag/ TFPG-DMB COF nanomaterial is checked for green synthesis of carbamates from different amines and alcohols under 1 atmospheric pressure of CO2 with excellent yield (upto 95 %) as well as with high TOF value (182 h(-1)) and high selectivity. Additionally, the Ag/ TFPG-DMB COF nanomaterial is also applied as a potentially active photocatalyst for one-pot nitroarene reduction along with N-formylation reaction under sunlight irradiation in green reaction conditions with exceptionally high yield of formylated products upto 99 % as well as with high TOF value (762 h(-1)). The catalyst efficiently reduced and formylated para-nitrophenol, a potential water pollutant, which elaborates its scope as an efficient catalyst for water purification also. The catalyst recyclability is also checked for five reaction cycles for both the reactions and the Ag/TFPGDMB COF material showed outstanding recycling ability without any noticeable leaching of active metal or catalyst degradation.