Process for producing 3-phenyluracil compounds

Details Process for producing 3-phenyluracil compounds Process for producing 3-phenyluracil compounds

2000-11-13

2002-01-15

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...

C544S314000, C544S310000, C544S311000, C544S312000, C544S105000, C544S052000

Reexamination Certificate

active

06339155

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for producing 3-phenyluracil compounds.
BACKGROUND ARTS
It is described in U.S. Pat. No. 4,859,229, WO91/00278 and so on that the 3-phenyluracil compounds represented by the formula:
wherein R represents haloalkyl group and Q represents a substituted phenyl group,
and derivatives thereof have excellent herbicidal activity.
Some processes for producing 3-phenyluracil compounds are known. The processes given by the schemes 1 to 3 are known, with regard to the processes using the amide compound represented by the formula below:
wherein R
100
represents optionally substituted alkyl group and Q
100
represents optionally substituted phenyl group, as a starting material.
The process of Compound [1-a] to Compound [1-b] is carried out in an acidic condition using p-toluenesulfonic acid and the process of Compound [1-b] to Compound [1-c] is carried out in a basic condition using metal alkoxide.
The process of Compound [2-a] to Compound [2-b] is carried out in a condition using phosgene/pyridine/4-dimethylaminopyridine and the process of Compound [2-b] to Compound [2-c] is carried out in a condition using aqueous ammonia.
The process of Compound [3-a] to Compound [3-b] is carried out in a basic condition using anhydrous sodium acetate and the process of Compound [3-b] to Compound [3-c] is carried out in a condition using phosgene/pyridine/4-dimethylaminopyridine.
However, the intermediate compounds are required to be isolated, as every process shown by the schemes 1 to 3 is a 2-step reaction which is difficult to carry out the steps subsequently. Therefore, it is not sufficient process as an ecomonical one.
Under these circumstances, an economical process for producing the 3-phenyluracil compounds represented by the formula [V] that has a simple operation and high yield is desired to be developed.
SUMMARY OF THE INVENTION
The present invention provides a process for producing the 3-phenyluracil compounds represented by the formula [V]:
wherein R
1
represents C1-C5 perfluoroalkyl group and Q represents an aromatic group,
which comprises making the amide compound represented by the formula [II]:
wherein R
1
and Q have the same meanings defined above, or its hydrate react with a cyanate salt in the presence of a protonic acid at 55° C. to 150° C.
The present invention provides an economical process for producing the 3-phenyluracil compounds because they can be produced in one-pot and in high yield.
DETAILED DESCRIPTION OF THE INVENTION
The process of the present invention is explained in detail. Typical process of the present invention is performed by adding a cyanate salt gradually into a mixture of an amide compound of the formula [II] or its hydrate and a protonic acid at 55° C. to 150° C. and allowing them to react.
The cyanate salt in the present invention means both of cyanate salts of a narrow meaning and isocyanate salts. Such cyanate salts of the narrow meaning are exemplified by alkali metal salts of cyanic acid (e.g., sodium cyanate, potassium cyanate). Examples of the isocyanate salt include silver isocyanate.
Examples of the protonic acid include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid and trichloroacetic acid; aromatic carboxylic acids such as benzoic acid and 4-nitrobenzoic acid; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; inorganic mineral acids such as hydrochloric acid and sulfuric acid; and boronic acids such as phenylboronic acid.
The amount of the cyanate salt to be used in the present process is usually 1 mol to 10 mols, preferably 1 mol to 2 mols based on 1 mol of the amide compound given by the formula [II]. The amount of the protonic acid to be used in the present process is usually 1.1 mol to a large excess based on 1 mol of the amide compound given by the formula [II].
It is possible to utilize a solvent in the present process and the solvent that is inert in the present reaction condition can be used. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane and cyclohexane; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene and m-dichlorobenzene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; ethers such as diethyl ether, tert-butyl methyl ether, diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran; alcohols such as methanol, ethanol, propanol and 2-propanol; amides such as N,N-dimethyformamide and N,N-dimethylacetamide; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; nitro compounds such as nitromethane, nitroethane and 2-nitropropane; aliphatic nitrites such as acetonitrile; and mixtures thereof.
The present reaction is usually carried out in 30 minutes to 100 hours. It is preferable that the reaction mixture is kept under 50° C. at first and then aged at 55C to 150° C. after disappearance of most of the amide compound represented by the formula [II]. Thereafter, the reaction mixture is subjected to usual work-up procedures such as methods (a), (b), (c) and (d) to give the 3-phenyluracil compound represented by the formula [V].
(a) To concentrate the reaction mixture directly, wash with water and/or an organic solvent, and dry it.
(b) To pour the reaction mixture into water, neutralize with diluted acid such as diluted hydrochloric acid and diluted sulfuric acid, extract with an organic solvent, dry and concentrate it.
(c) To pour the reaction mixture into water, collect precipitated crystals by filtration and dry them.
(d) To cool the reaction mixture, collect precipitated crystals by filtration, wash with water and/or an organic solvent, and dry them.
The 3-phenyluracil compounds represented by the formula [V] can be purified by usual procedures such as recrystallization, column chromatography and so on.
The amide compounds represented by the formula [II] utilized in the present process can be prepared according to the known methods in U.S. Pat. No. 5,360,713, WO95/32952, WO98/27057 and WO98/27067, or prepared according to the preparation method described below: The production process by allowing an aniline compound given by the formula [III]:
H
2
N-Q  [III]
wherein Q has the same meaning defined above, to react with an acetate ester compound given by the formula [IV]:
wherein R
1
has the same meaning defined above and R
40
represents methyl group or ethyl group, in a solvent or without solvent.
The reaction temperature in said process is usually in the range of room temperature to 150° C., or room temperature to boiling point of a solvent utilized. Further, by-produced alcohol (methanol or ethanol) may be distilled away from the reaction mixture or a small amount of an acid or a base may be added for the purpose of speeding up the reaction.
The amount of the acetate ester compound, which is provided to the reaction, given by the formula [IV] is usually at the rate of 1 mol to 5 mols based on 1 mol of the aniline compound given by the formula [III].
Examples of the acid used for speeding up the reaction include protonic acids such as p-toluenesulfonic acid and methanesulfonic acid, and the amount of the used acid is at the rate of 0.05 mol to 1 mol based on 1 mol of the aniline compound given by the formula [1II]. Examples of the base include tertiary amines such as triethylamine, tributylamine and N,N-dimethylaniline; pyridines such as pyridine and picoline; and inorganic bases such as potassium carbonate and sodium hydride, and the amount of the used base is at the rate of 0.05 m

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