Formation of carbamic acid in organic solvents and in supercritical carbon dioxide

被引：66
作者：
Dijkstra, Z. J.
Doornbos, A. R.
Weyten, H.
Ernsting, J. M.
Elsevier, C. J.
Keurentjes, J. T. F.
机构：
[1] Eindhoven Univ Technol, Dept Chem Engn & Chem, Proc Dev Grp, SPD, NL-5600 MB Eindhoven, Netherlands
[2] Vito, Flemish Inst Technol Res, B-2400 Mol, Belgium
[3] Univ Amsterdam, Fac Sci, Vant Hoff Inst Mol Sci, NL-1018 WV Amsterdam, Netherlands
来源：
JOURNAL OF SUPERCRITICAL FLUIDS | 2007年 / 41卷 / 01期
关键词：
NMR; supercritical CO(2); amine; carbamic acid;
D O I：
10.1016/j.supflu.2006.08.012
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The behavior of amines in various CO(2)-rich solvents is described. (1)H and (13)C NMR spectra in DMSO, chloroform, and benzene show that the amines are completely converted into carbamic acid by just bubbling atmospheric CO(2) through the solution. However, the chemical shifts of several protons and the carbonyl (13)C in the newly formed compounds strongly depend on the organic solvent used. FT-IR measurements confirm the observation that carbamic acid formation occurs. Changing the solvent to supercritical CO(2) shows a temperature- and pressure-dependent equilibrium between the amine and the carbamic acid; higher pressures shift the equilibrium towards the carbamic acid, whereas higher temperatures favor the free amine. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码：109 / 114
页数：6
相关论文
共 34 条
  • [1] Halogen-free process for the conversion of carbon dioxide to urethanes by homogeneous catalysis
    Abla, M
    Choi, JC
    Sakakura, T
    [J]. CHEMICAL COMMUNICATIONS, 2001, (21) : 2238 - 2239
  • [2] Isolation and structural determination of two derivatives of the elusive carbamic acid
    Aresta, M
    Ballivet-Tkatchenko, D
    Dell'Amico, DB
    Bonnet, MC
    Boschi, D
    Calderazzo, F
    Faure, RE
    Labella, L
    Marchetti, F
    [J]. CHEMICAL COMMUNICATIONS, 2000, (13) : 1099 - 1100
  • [3] A new high pressure sapphire nuclear magnetic resonance cell
    Bai, S
    Taylor, CM
    Mayne, CL
    Pugmire, RJ
    Grant, DM
    [J]. REVIEW OF SCIENTIFIC INSTRUMENTS, 1996, 67 (01) : 240 - 243
  • [4] Green chemical processing using CO2
    Beckman, EJ
    [J]. INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2003, 42 (08) : 1598 - 1602
  • [5] KINETICS OF CARBAMATE FORMATION AND BREAKDOWN
    CAPLOW, M
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (24) : 6795 - &
  • [6] Practical approaches to green solvents
    DeSimone, JM
    [J]. SCIENCE, 2002, 297 (5582) : 799 - 803
  • [7] MECHANISM OF CLEAVAGE OF CARBAMATE ANIONS
    EWING, SP
    LOCKSHON, D
    JENCKS, WP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (09) : 3072 - 3084
  • [8] Reaction monitoring of aliphatic amines in supercritical carbon dioxide by proton nuclear magnetic resonance spectroscopy and implications for supercritical fluid chromatography
    Fischer, H
    Gyllenhaal, O
    Vessman, J
    Albert, K
    [J]. ANALYTICAL CHEMISTRY, 2003, 75 (03) : 622 - 626
  • [9] Olefin metathesis in supercritical carbon dioxide
    Fürstner, A
    Ackermann, L
    Beck, K
    Hori, H
    Koch, D
    Langemann, K
    Liebl, M
    Six, C
    Leitner, W
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (37) : 9000 - 9006
  • [10] Gaemers S, 1999, MAGN RESON CHEM, V37, P25, DOI 10.1002/(SICI)1097-458X(199901)37:1<25::AID-MRC408>3.0.CO
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