Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1998-10-13
2000-11-07
Richter, Johann
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
560 11, 560 13, 560 17, 560 27, 560 29, 560115, 560132, 560137, C07C26904
Patent
active
061439177
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a process for producing an aryl carbamate from a diaryl carbonate with a high selectivity and with a high yield.
The aryl carbamates are compounds useful in a wide range uses, as for example, pharmaceuticals, agricultural chemicals and materials for the synthesis thereof, as various fine chemicals and materials for the synthesis thereof and as reagents for analysis.
BACKGROUND ART
As processes for producing carbamates, (1) a process of reacting an isocyanate with an alcohol, (2) a process of reacting a chloroformate ester with an amine in the presence of a base, (3) a process of reacting phosgene with an alcohol and an amine, and (4) a process of reacting urea with an alcohol, are generally known.
However, these conventional processes are disadvantageous in that in the process (1), the isocyanate is stimulative and is difficult to handle; in the process (2), the base must be used in an molar amount equal to or more than that of the reactive compounds; in the process (3), phosgene exhibits a high toxicity and a base must be used for the reaction; and in the process (4), the reaction must be carried out at a high temperature under a high pressure.
On the other hand, as processes for producing aryl carbamates from diaryl carbonates, (5) a process of reacting a diaryl carbonate with an aromatic amine compound in the presence of a heterocyclic monocyclic tertiary amine compound, such as 2-hydroxypyridine, as disclosed in Japanese Unexamined Patent Publication No. 52-136,147, J. Polym. Sci., Polym. Chem. Ed., 17(3), 835 (1979), and Inst. Prog. Urethan, 2, 61 (1980), (6) a process of reacting a diaryl carbonate with an aliphatic amine compound without the presence of a catalyst, as disclosed in U.S. Pat. No. 4,097,676), (7) a process of reacting bis(4-nitrophenyl)carbonate with an aliphatic amine compound and aniline in methylene chloride, as disclosed in Synthesis, 423 (1989), (8) a process of reacting bis(2,4-dinitrophenyl)carbonate with amino acid ester, as disclosed in Chem. Ber., 99, 1576 (1966), (9) a process of reacting an asymmetric bis(nitro-substituted aryl)carbonate with an aliphatic primary amine compound as disclosed in Synth. Commun., 26 (2), 331 (1996), (10) a process of reacting diphenyl carbonate with an aromatic amine compound in the presence of an organic phosphoric acid, trifluoro-methanesulfonic acid, trifluoroacetic acid, propionic acid or an aromatic amine-hydrochloric acid salt, as disclosed in Tetrahedron, 51, 8073 (1995), (11) a process of reacting a diaryl carbonate with a primary or secondary polyamine in the presence of a Lewis acid catalyst, as disclosed in Japanese Unexamined Patent Publication No. 47-11,562, and (12) a process of reacting a diaryl carbonate with an alkylpolyamine, as disclosed in Japanese Unexamined Patent Publication No. 1-230,550, are known.
These processes are, however, disadvantageous in the following problems. In the process (5), the catalyst, which is expensive, must be used in an molar amount equal to or more than the molar amount of the reactive materials, the reaction rate is slow and, when the reaction temperature is raised to increase the reaction rate, urea derivatives are produced, as by-products, in a large amount. In the process (6), when an aromatic amine compound or other amine compound having a high stereostructual volume is used, the reactivity of the amine compound with the diaryl carbonate is very low, and when the reaction temperature is raised to enhance the reactivity of the amine compound, urea derivatives are produced, as by-products, in a large amount. In the process (7), although when the aliphatic primary amine compound is used a relatively good result can be obtained, when the secondary amine compound, which has a high steric hindrance, is used, the reaction rate is slow and, especially, when an aromatic amine (aniline) is used, the reaction rate is very slow and the yield is unsatisfactory. In the process (8), the amino acid ester to be used as a starting material is limited to a pr
REFERENCES:
patent: 4097676 (1978-06-01), Romano
J. Polym. Sci., Polym. Chem. Ed. vol. 17 (3), pp. 835-841 (1979).
"Reaction of Diphenyl Carbonate With Amines . . . ,", Inst. Pry. Urethan, 2 pp. 61-65 (1980).
Synthesis, pp. 423-425 (Jun. 1989).
Chem. Ber., 99, pp. 1576-1579 (1966).
Synth. Commun., 26(2), pp. 331-349 (1996).
Tetrahedron, vol. 51, No. 29, pp. 8073-8088 (1995).
Harada Katsumasa
Kashiwagi Kohichi
Matsuura Tsunao
Sugise Ryoji
Davis Brian J.
Richter Johann
Ube Industries Ltd.
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