character (aliphatic and aromaticamines, alcohoxydes, phenoxides, thiolates) are compared with regard to nucleophilic substitutions on dimethyl carbonate (DMC), using different reaction conditions. Results are well in agreement with the Hard−Soft Acid−Base (HSAB) theory. Accordingly, the high selectivity of monomethylation of CH2 acidic compounds and primaryaromaticamines with DMC can be explained
Although molecular bromine (Br2) is a useful brominating reagent, it is not easy to handle. Herein, we describe the preparation of a novel air-stable bromine complex prepared from 1,3-dimethyl-2-imidazolidinone (DMI) and Br2, which was identified to be (DMI)2HBr3 by spectral and X-ray techniques. This complex was then used to brominate olefins, carbonyl compounds, and aromatics, as well as in the Hofmann
The synthesis of alkyl carbamates from primary aliphatic amines and dialkyl carbonates in supercritical carbon dioxide
作者:Maurizio Selva、Pietro Tundo、Alvise Perosa
DOI:10.1016/s0040-4039(01)02390-5
日期:2002.2
130°C and in the presence of compressed CO2, primary aliphatic amines [RNH2, R=C10H21, C8H17, cHex, 1-(C10H7)CH2] react with organic carbonates (R′OCO2R; R′=Me, Et) to give alkyl carbamates (RNHCO2R′, 1). Although CO2 promotes the reaction also at a low pressure, good yields (∼80%) of 1 are achievable only with supercritical carbondioxide (scCO2) at 90 bar, which inhibits the formation of N-methylated
在130°C且存在压缩CO 2的情况下,伯脂肪族胺[RNH 2,R = C 10 H 21,C 8 H 17,cHex,1-(C 10 H 7)CH 2 ]与有机碳酸酯( R′OCO 2 R; R′= Me,Et)得到氨基甲酸烷基酯(RNHCO 2 R′,1)。尽管CO 2在低压下也能促进反应,但仅在90 bar的超临界二氧化碳(scCO 2)的情况下,才能达到1的良好收率(〜80%),这会抑制N-甲基化副产物的形成。
METHOD FOR TREATMENT OF ISOCYANATE RESIDUE, AND METHOD FOR TREATMENT OF CARBONATE
申请人:Shimokawatoko Yoshiki
公开号:US20120271067A1
公开(公告)日:2012-10-25
A method for treating an isocyanate residue, which comprises carrying out a thermal decomposition reaction of a carbamate that is produced by the reaction among an amine, urea and/or an N-unsubstituted carbamic acid ester and an alcohol to produce a decomposition solution, separating an isocyanate and the alcohol from the decomposition solution to produce the isocyanate residue, and bringing the isocyanate residue into contact with high-pressure/high-temperature water to decompose the isocyanate residue into an amine; and a method for treating a carbonate, which comprises bringing the carbonate into contact with high-pressure/high-temperature water to decompose the carbonate into an alcohol.
Carbamate synthesis from amines and dialkyl carbonate over inexpensive and clean acidic catalyst—Sulfamic acid
作者:Bo Wang、Jing He、Run Cang Sun
DOI:10.1016/j.cclet.2010.03.012
日期:2010.7
Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate. High selectivity, cost-efficiency and simple product separation were the advantageous features obtained in this process. Sulfamic acid could be reused several times and keep its initial activity in the recycle runs. In addition, sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines. (C) 2010 Bo Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.