Process for the preparation of benzonitrile compounds

Details Process for the preparation of benzonitrile compounds Process for the preparation of benzonitrile compounds

2000-03-28

2001-12-18

Ford, John M. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Nitrogen attached directly or indirectly to the purine ring...

Reexamination Certificate

active

06331628

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the preparation of benzonitrile compounds as described in U.S. Pat. No. 5,127,935 and JP-5-186436A, which are useful as herbicides and their intermediates.
2. Description of the Background
A process for the preparation of benzonitrile compounds is described in JP-9-48761A. Since the process includes the use of copper cyanide as a cyanizing agent, the industrial application thereof has the following problems. The treatment of a waste fluid is troublesome since the waste fluid contains copper which is one of the metals designated in Water Pollution Control Law. In addition, copper cyanide is expensive. Accordingly, the improvement of the above process has been demanded.
SUMMARY OF THE INVENTION
The present inventors concentrated on developing another process for the preparation of benzonitrile compounds useful as herbicides and their intermediates so as to solve the above problems. As the result, it was found that the benzonitrile compound can be obtained with a high yield by synthesizing it in the presence of a metallic catalyst even if potassium, sodium or zinc cyanide, which has a reactivity lower than that of copper cyanide, is used as a cyanizing agent. Thus, the present invention relates to the process for the preparation set forth below.
[1] A process for the preparation of benzonitrile compounds represented by the formula (1):
 wherein
X is hydrogen, fluorine or chlorine atom;
Z is nitro, amino, C
1
-C
4
alkylsulfonylamino, bis(C
1
-C
4
alkylsulfonyl)amino, (C
2
-C
5
alkoxycarbonyl)amino, (C
2
-C
5
alkylcarbonyl)amino, (optionally substituted benzoyl)amino, (C
2
-C
5
alkylcarbonyl)(C
1
-C
4
alkylsulfonyl)amino or (optionally substituted benzoyl)(C
1
-C
4
alkylsulfonyl)amino group; and
Q is hydrogen atom, or nitro, amino, (C
2
-C
5
alkoxycarbonyl)amino, 6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione-3-yl, 1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl or 1-amino-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl group, provided that if Z is nitro or amino group, then Q is (C
2
-C
5
alkoxycarbonyl)amino, 6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl, 1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl or 1-amino-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl group, characterized in that the process comprises reacting a halogenated benzene compound represented by the formula (1a):
wherein X, Z and Q are as defined above, and Y is fluorine, chlorine, bromine or iodine atom, provided that if X is fluorine atom, then Y is chlorine, bromine or iodine atom, and if X is chlorine atom, then Y is bromine or iodine atom,
 with one or more cyanides selected from potassium cyanide, sodium cyanide and zinc cyanide in the presence of a metallic catalyst.
[2] A process as described in the above item [1] wherein Z is C
1
-C
4
alkylsulfonylamino, bis(C
1
-C
4
alkylsulfonyl)amino, (C
2
-C
5
alkylcarbonyl)(C
1
-C
4
alkylsulfonyl)amino or (optionally substituted benzoyl)(C
1
-C
4
alkylsulfonyl)amino group.
[3] A process as described in the above item [1] wherein Z is C
1
-C
4
alkylsulfonylamino group.
[4] A process as described in the above item [1] wherein Q is 6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl, 1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl or 1-amino-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl group.
[5] A process as described in the above item [2] wherein Q is 6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl, 1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl or 1-amino-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl group.
[6] A process as described in the above item [3] wherein Q is 6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl, 1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl or 1-amino-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione-3-yl group.
[7] A process as described in the above items [1] to [6] wherein palladium, nickel or platinum is used as the metallic catalyst.
[8] A process as described in the above items [1] to [6] wherein palladium is used as the metallic catalyst.
[9] A process as described in the above items [7] and [8] wherein a metal selected from zinc, iron, manganese, tin, copper, magnesium, chromium, titanium and aluminum or a halide of the metal is used as a co-catalyst.
[10] A process as described in the above items [7] and [8] wherein a halide of a metal selected from zinc, tin and copper is used as a co-catalyst.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of the present invention will be described in more detail. Scheme of the process of the present invention is as follows:
wherein X, Y, Z and Q are as defined above.
In the process of the present invention, examples of Z include nitro, amino, methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, i-propylsulfonylamino, n-butylsulfonylamino, i-butylsulfonylamino, s-butylsulfonylamino, tert-butylsulfonylamino, bis(methylsulfonyl)amino, bis(ethylsulfonyl)amino, bis(n-propylsulfonyl)amino, bis(i-propylsulfonyl)amino, bis(n-butylsulfonyl)amino, bis(i-butylsulfonyl)amino, bis(s-butylsulfononyl)amino, bis(tert-butylsulfonyl)amino, methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, i-propoxycarbonylamino, n-butoxycarbonylamino, i-butoxycarbonylamino, s-butoxycarbonylamino, tert-butoxycarbonylamino, acetylamino, propionylamino, n-butyrylamino, i-butyrylamino, benzoylamino, 2-bromobenzoylamino, 3-bromobenzoylamino, 4-bromobenzoylamino, 2-chlorobenzoylamino, 3-chlorobenzoylamino, 4-chlorobenzoylamino, 2-fluorobenzoylamino, 3-fluorobenzoylamino, 4-fluorobenzoylamino, 2-toluoylamino, 3-toluoylamino, 4-toluoylamino, 2-ethylbenzoylamino, 4-ethylbenzoylamino, 2-i-propylbenzoylamino, 4-i-propylbenzoylamino, 2-tert-butylbenzoylamino, 4-tert-butylbenzoylamino, 2-methoxybenzoylamino, 3-methoxybenzoylamino, 4-methoxybenzoylamino, 2-ethoxybenzoylamino, 3-ethoxybenzoylamino, 4-ethoxybenzoylamino, 2-i-propyloxybenzoylamino, 3-i-propyloxybenzoylamino, 4-i-propyloxybenzoylamino, 2-n-butoxybenzoylamino, 3-n-butoxybenzoylamino, 4-n-butoxybenzoylamino, acetyl(methylsulfonyl)amino, propionyl(methylsulfonyl)amino, n-butyryl(methylsulfonyl)amino, i-butyryl(methylsulfonyl)amino, acetyl(ethylsulfonyl)amino, propionyl(ethylsulfonyl)amino, n-butyryl(ethylsulfonyl)amino, i-butyryl(ethylsulfonyl)amino, acetyl(n-propylsulfonyl)amino, propionyl(n-propylsulfonyl)amino, n-butyryl(n-propylsulfonyl)amino, i-butyryl(n-propylsulfonyl)amino, benzoyl(methylsulfonyl)amino, 2-bromobenzoyl(methylsulfonyl)amino, 3-bromobenzoyl(methylsulfonyl)amino, 4-bromobenzoyl(methylsulfonyl)amino, 2-chlorobenzoyl(methylsulfonyl)amino, 3-chlorobenzoyl(methylsulfonyl)amino, 4-chlorobenzoyl(methylsulfonyl)amino, 2-fluorobenzoyl(methylsulfonyl)amino, 3-fluorobenzoyl-(methylsulfonyl)amino, 4-fluorobenzoyl(methylsulfonyl)amino, 2-toluoyl(methylsulfonyl)amino, 3-toluoyl(methylsulfonyl)amino, 4-toluoyl(methylsulfonyl)amino, 2-ethylbenzoyl(methylsulfonyl)amino, 4-ethylbenzoyl(methylsulfonyl)amino, 2-i-propylbenzoyl(methylsulfonyl)amino, 4-i-propylbenzoyl(methylsulfonyl)amino, 2-tert-butylbenzoyl(methylsulfonyl)amino, 4-tert-butylbenzoyl(methylsulfonyl)amino, 2-methoxybenzoyl(methylsulfonyl)amino, 3-methoxybenzoyl (methylsulfonyl)amino, 4-methoxybenzoyl(methylsulfonyl)amino, 2-ethoxybenzoyl(methylsulfonyl)amino, 3-ethoxybenzoyl(methylsulfonyl)amino, 4-ethoxybenzoyl(methylsulfonyl)amino, 2-i-propyloxybenzoyl(methylsulfonyl)amino, 3-i-propyloxybenzoyl(methylsulfonyl)amino, 4-i-propyloxybenzoyl(methylsulfonyl)amino, 2-n-butoxybenzoyl(methylsulfonyl)amino, 3-n-butoxybenzoyl(methylsulfonyl)amino, 4-n-butoxybenzoyl(methylsulfonyl)amino, benzoyl(ethylsulfonyl)amino, 2-bromobenzoyl(ethylsulfonyl)amino, 3-bromobenzoyl(ethylsulfonyl)amino, 4-bromobenzoyl(ethylsulfonyl)amino, 2-chlorobenzoyl(ethylsulfonyl)amino, 3-chlorobenzoyl(ethylsu

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