Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2003-05-14
2004-04-06
Lambkin, Deborah C. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S442000
Reexamination Certificate
active
06717013
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel perfluoroalkylated aniline derivative, which is a useful intermediate, to an industrially advantageous novel process for producing the aniline derivative and to a novel aniline derivative, which is also a useful intermediate, derived from the said derivative.
Perfluoroalkylated aniline derivatives are useful as intermediates or raw materials for the synthesis of agricultural chemicals, pharmaceuticals, surface active agents, rubber materials, mold release agents, water and oil repellents, optical materials, gas separation membrane materials, resist materials, antifouling paints, weatherproofing paints, paper-converting agents, textile-treating agents, heat resistant resins, etc. (cf, for example, “Saisentan Gijutsu (Advanced Technologies) in Halogen Chemicals”, published by CMC); for use in agricultural chemicals, in particular, they are useful compounds as raw materials for the agricultural and horticultural insecticides disclosed in EP 919542. With regard to perfluoroalkylanilines, however, virtually no simple and useful process for the production thereof has hitherto been reported.
The present invention provides a novel process for producing perfluoroalkylated, paticularly secondary perfluoroalkylated aniline derivatives and novel, useful intermediates which can be produced by the process.
2. Related Art Statement
Known processes for producing perfluoroalkylated aniline derivatives include, for example, [A] a method which comprises introducing a perfluoroalkyl group by replacing the halogen atom of a halogenated nitrobenzene and then reducing the nitro group into the amino group and a method which comprises introducing a perfluoroalkyl group by replacing the halogen atom of a halogenated aniline. The following processes have been reported with regard to producing perfluoroalkylated aniline derivatives according to either of the above-mentioned methods.
(a) Processes wherein the reaction is conducted by using a perfluoroalkyl halide as the perfluoroalkylating agent in the presence of metallic copper are described, for example, in (1) Tetrahedron, 1969, 25, 5921, (2) Offenlegungsschrift 26 06 982, (3) J. Chem. Soc. Japan, 1972, 1876, (4) J. Chem. Soc. Perkin Trans. 1, 1980, 661, and (5) Bull. Chem. Soc. Jpn., 1992, 65, 2141. These processes, however, are industrially disadvantageous in that previous introduction of a halogen to an appropriate position of a nitrobenzene or an aniline is necessary, excess of copper is required, and further the reaction temperature is unfavorably high.
(b) Processes wherein the reaction is conducted by using a perfluoroalkylcarboxylic acid metal salt as the perfluoroalkylating agent in the presence of copper iodide are described, for example, in (1) J. Chem. Soc. Perkin Trans, 1, 1988, 921 and (2) Synth. Commun., 1988, 18, 965. These processes are also industrially disadvantageous in that they require a nitrobenzene having a halogen atom introduced to its appropriate position, it needs a large amount of copper iodide, and the reaction temperature is unfavorably high.
(c) A process wherein the reaction is conducted by using a perfluoroalkyltrialkylsilane as the perfluoroalkylating agent in the presence of potassium fluoride and copper iodide is described, for example, in (1) Tetrahedron Lett., 1991, 32, 91. This process also is industrially unsuitable in that it requires a nitrobenzene having a halogen atom introduced to its appropriate position, the perfluoroalkylating agent is expensive and the use of stoichiometric amounts of potassium fluoride and copper iodide is necessary.
(d) Processes wherein a perfluoroalkene is made to react on a fluoronitrobenzene in the presence of fluorine anions are described, for example, in (1) J. Chem. Soc. (c), 1968, 2221, (2) J. Org. Synth Chem. Japan, 1969, 27, 993, (3) J. Chem. Soc. Japan, 1976, 198 and (4) Tetrahedron, 1995, 51, 13167. These processes are not suitable for general use because the substrates which can be used are restricted to those compounds which have been strongly activated by an electron attractive groups, e.g., perfluoronitrobenzenes and dinitrofluorobenzenes and hence the compounds which can be prepared by these processes are greatly restricted in their structure.
[B] The following have been reported as to the method of directly perfluoroalkylating an aniline.
(a) Processes wherein a perfluoroalkyl halide is made to react on an aniline in the presence of a reducing agent are described, for example, in (1) EP 298,803 (JP-A-1-100135), (2) EP 206,951 (JP-A-62-26241), (3) J. Chem. Soc. Perkin Trans., 1, 1990, 2293, (4) J. Chem. Soc., Chem. Commun., 1987, 1701 and (5) J. Heterocyclic Chem., 1994, 31, 1413. In these processes, the yield of the intended product is low to medium and the selectivity is very poor as to the position to be perfluoroalkylated, hence they cannot be expected to be useful in practice.
(b) A process wherein the perfluoroalkylated compound is irradiated with light in the presence of a reducing agent is disclosed, for example in JP-A-57-18638. This process also gives a low to medium yield of the product and a very poor selectivity, and hence presents a low practical usefulness.
(c) Processes wherein a perfluoroalkyl halide or a perfluoroalkylsulfonyl chloride is heated in the presence of a metal catalyst are described, for example, in (1) J. Fluorine Chem., 1983, 22, 541, (2) JP-A-57-142923, (3) WO 93/16969 (Jap. Nat. Publ. (Kohyo) 7-504414, U.S. Pat. No. 5,276,194), (4) JP-A-3-240739 and (5) EP-0, 114,359. Among these, the processes of (1) and (2) give a low to medium yield, show a low selectivity, require a large amount of copper, need a high temperature and long reaction time, and thus are industrially disadvantageous. The process of (3) has the disadvantages of requiring an expensive catalyst and high reaction temperature and showing substantially no selectivity. The processes of (4) and (5) cannot be expected to be useful in practice because they require an expensive catalyst, high temperature and long time and moreover no embodiment treating an aniline is described.
(d) Processes wherein the peroxide of a perfluoroalkylcarboxylic acid is used are described, for example, in (1) JP-A-3-109362, (2) JP-A-5-246933, and (3) Bull. Chem. Soc. Jpn., 1995, 68, 1042. These processes, however, are disadvantageous in that they require the use of a hazardous peroxide and the substrate to be used is restricted to phenylenediamines or quinones and hence they are not suited to general use.
(e) A process wherein a perfluoroalkylhalide is treated under a high temperature and an applied pressure is described in U.S. Pat. No. 3,281,426, but the process is industrially disadvantageous in that it require a high temperature and a special apparatus.
(f) Processes wherein a perfluoroalkylcarboxylic acid is treated with xenon difluoride are described, for example, in (1) J. Org. Chem., 1988, 53, 4582, and (2) JP-A-6-184065. These processes have the disadvantages in that they require a large amount of highly toxic reagent and both the yield and the selectivity are not sufficiently high.
SUMMARY OF THE INVENTION
An object of the present invention is, overcomming the above-mentioned various problems of the prior techniques, to provide a process for producing a perfluoroalkyl-substituted aniline which uses raw materials, reagents and catalysts which are inexpensive, easily available, safe and easy to handle, is based on reactions which are mild, simple and give a high yield and selectivity, does not produce a large amount of wastes and is economically highly efficient also in the aftertreatment. Another object of the present invention is to provide a novel perfluoroalkylated aniline derivative, particularly a secondary perfluoroalkylated aniline derivative, which can be used for versatile and valuable applications.
DETAILED DESCRIPTION OF THE INVENTION
The present inventions have made are extensive study to solve the above-mentioned problems and resultantly found a novel process for
Kohno Eiji
Onishi Masanobu
Tsubata Kenji
Yoshiura Akihiko
Lambkin Deborah C.
Manelli Denison & Selter
Nihon Nohyaku Co. Ltd.
White, Jr. Paul E.
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