There are disclosed halogeno-4-methylpyrazoles represented by the formula (I): ##STR1## wherein R represents an alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group; X represents a hydrogen atom or a halogen atom; and Y represents a halogen atom, and a process for preparing the same which comprises reacting 1-substituted-4-methylpyrazoles of the formula (II): ##STR2## wherein R has the same meaning as defined above, with a halogen.

BACKGROUND OF THE INVENTION 
This invention relates to halogeno-4-methylpyrazoles useful as 
intermediates for pharmaceuticals and agricultural chemicals, etc. and 
processes for producing the same, more particularly to 
5-halogeno-1-substituted-4-methylpyrazoles and 
3,5-dihalogeno-1-substituted-4-methylpyrazoles and processes for producing 
these. 
Chemical Abstract vol. 71, 112859i discloses that no 
halogeno-methylpyrazole is formed, but a trimer is formed by bromination 
of 4-methylpyrazole. 
Journal of Agricultural Food Chemistry (J. Agrc. Food. Chem.), vol. 25, No. 
4, p. 884 (1977) discloses a process for preparing 
4-methyl-3,5-dibromopyrazole which comprises permitting butyl lithium to 
act on 3,4,5-tribromopyrazole, followed by substitution with methyl 
iodide. 
However, this process cannot be said to be an industrial production 
process, because synthesis of 3,4,5-tribromopyrazole is complicated, and 
moreover the synthesis steps are lengthy, and yet expensive butyl lithium 
is used. 
Chemical Abstract Vol. 66, 94950x discloses a process for preparing 
3-bromo-1,4-dimethylpyrazole which comprises brominating 
1,4-dimethyl-5-hydroxycarbonylpyrazole, followed by decarboxylation. 
However, this process cannot be said to be an industrial production 
process, because 1,4-dimethyl-5-carboxypyrazole is expensive, and the 
synthesis steps are complicated. 
SUMMARY OF THE INVENTION 
The present inventors have investigated intensively about processes for 
obtaining halogeno-4-methylpyrazoles with good yield, and consequently 
accomplished the present invention. 
More specifically, the present invention concerns 
halogeno-4-methylpyrazoles represented by the formula (I): 
##STR3## 
(wherein R represents an alkyl group having 1 to 4 carbon atoms, a 
substituted or unsubstituted phenyl group or a substituted or 
unsubstituted pyridyl group, X represents a hydrogen atom or a halogen 
atom and Y represents a halogen atom) and a process for preparing 
halogeno-4-methylpyrazoles represented by the formula (I), which comprises 
reacting 1-substituted-4-methylpyrazoles of the formula (II): 
##STR4## 
(wherein R represents an alkyl group having 1 to 4 carbon atoms, a 
substituted or unsubstituted phenyl group or a substituted or 
unsubstituted pyridyl group) with a halogen. 
In the halogeno-4-methylpyrazoles of the above formula (I) and the 
1-substituted-4-methylpyrazoles of the formula (II), the alkyl group of R 
having 1 to 4 carbon atoms may include a methyl group, an ethyl group, a 
n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a 
t-butyl groups. 
Examples of the substituted or unsubstituted phenyl group may include a 
phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 
4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 
4-ethylphenyl group, a 2-n-propylphenyl group, a 2-i-propylphenyl group, a 
3-n-propylphenyl group, a 3-i-propylphenyl group, a 4-n-propylphenyl 
group, a 4-i-propylphenyl group, a 2-t-butylphenyl group, a 
4-n-butylphenyl group, a 4-i-butylphenyl group, a 4-t-butylphenyl group, a 
2,4-dimethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-diethylphenyl 
group, a 2,6-diethylphenyl group, a 2-methoxyphenyl group, a 
3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 
3-ethoxyphenyl group, a 4-ethoxyphenyl group, a 2-n-propoxyphenyl group, a 
2-i-propoxyphenyl group, a 3-n-propoxyphenyl group, a 4-n-propoxyphenyl 
group, a 4-i-propoxyphenyl group, a 2-n-butoxyphenyl group, a 
4-n-butoxyphenyl group, a 4-i-butoxyphenyl group, a 4-t-butoxyphenyl 
group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl 
group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl 
group, a 2,4-dichlorophenyl group, a 2,4-difluorophenyl group, a 
2,6-dichlorophenyl group, a 2,6-difluorophenyl group, a 2-nitrophenyl 
group, a 3-nitrophenyl group, a 4-nitrophenyl group, a 
2-difluoromethoxyphenyl group, a 3-difluoromethoxyphenyl group, a 
4-difluoromethoxyphenyl group, and the like, and examples of the 
substituted or unsubstituted pyridyl group may include a 2-pyridyl group, 
a 3-methyl-2-pyridyl group, a 4-methyl-2-pyridyl group, a 
5-methyl-2-pyridyl group, a 6-methyl-2-pyridyl group, a 3-chloro-2-pyridyl 
group, a 4-chloro-2-pyridyl group, a 5-chloro-2-pyridyl group, a 
6-chloro-2-pyridyl group, a 3,5-dichloro-2-pyridyl group, a 
3-trifluoromethyl-2-pyridyl group, a 5-trifluoromethyl-2-pyridyl group, a 
3-pyridyl group, a 2-methyl-3-pyridyl group, a 4-methyl-3-pyridyl group, a 
5-methyl-3-pyridyl group, a 6-methyl-3-pyridyl group, a 2-chloro- 
3-pyridyl group, a 5-chloro-3-pyridyl group, a 6-chloro-3-pyridyl group, a 
4-pyridyl group, a 2-methyl-4-pyridyl group, a 3-methyl-4-pyridyl group, a 
2-chloro-4-pyridyl group, a 3-chloro-4-pyridyl group and the like. 
Specific examples of the halogeno-4-methylpyrazoles of the formula (I) may 
include 5-chloro-1,4-dimethylpyrazole, 5-bromo-1,4-dimethylpyrazole, 
5-chloro-1-phenyl-4-methylpyrazole, 5-bromo-1-phenyl-4-methylpyrazole, 
5-chloro-1-(2-pyridyl)-4-methylpyrazole, 
5-chloro-1-(3-pyridyl)-4-methylpyrazole, 
5-chloro-1-(4-pyridyl)-4-methylpyrazole, 
3,5-dichloro-1,4-dimethylpyrazole, 3,5-dibromo-1,4-dimethylpyrazole, 
3,5-dichloro-1-phenyl-4-methylpyrazole, 
3,5-dibromo-1-phenyl-4-methylpyrazole, 
3,5-dichloro-1-(2-pyridyl)-4-methylpyrazole, 
3,5-dichloro-1-(3-pyridyl)-4-methylpyrazole, 
3,5-dichloro-1-(4-pyridyl)-4-methylpyrazole, 
3,5-dibromo-1-(2-pyridyl)-4-methylpyrazole, 
3,5-dibromo-1-(3-pyridyl)-4-methylpyrazole, 
3,5-dibromo-1-(4-pyridyl)-4-methylpyrazole, and the like. 
Specific examples of the 1-substituted-4-methylpyrazoles of the formula 
(II) may include 1,4-dimethylpyrazole, 1-ethyl-4-methylpyrazole, 
1-n-propyl-4-methylpyrazole, 1-i-propyl-4-methylpyrazole, 
1-n-butyl-4-methylpyrazole, 1-i-butyl-4-methylpyrazole, 
1-t-butyl-4-methylpyrazole, 1-phenyl-4-methylpyrazole, 
1-(2-pyridyl)-4-methylpyrazole, 1-(3-pyridyl)-4-methylpyrazole, 
1-(4-pyridyl)-4-methylpyrazole and the like (In the above, n means normal, 
i means iso and t means tertiary, respectively). 
The 1-substituted-4-methylpyrazoles represented by the formula (II) can be 
produced with good yield by the reaction between 
2,3-dichloro-2-methylpropanal and a substituted hydrazine (see Japanese 
Provisional Patent Publication No. 270345/1988). 
In the halogeno-4-methylpyrazoles of the above formula (I), as the halogen 
atom of X and Y, a chlorine atom and a bromine atom may be employed. 
In the following, the reaction conditions of the 
1-substituted-4-methylpyrazoles of the formula (II) and halogen are to be 
described in detail. 
As the reaction temperature, a range generally of -10.degree. to 
100.degree. C. is employed. 
As the reaction time, a range generally of 5 minutes to 15 hours is 
employed. 
The present invention can be practiced with no solvent, but a solvent can 
be also used. 
As the solvent, there may be included halogenated aliphatic hydrocarbons 
such as methylene chloride, chloroform, carbon tetrachloride, 
dichloroethane, tetrachloroethane, etc., halo-substituted aromatic 
hydrocarbons such as chlorobenzene, dichlorobenzene, etc. 
The above solvents can be also used as a mixture of two or more kinds. 
As the solvent, one or more solvents selected from halogenated aliphatic 
hydrocarbon solvents such as dichloroethane, etc., halo-substituted 
aromatic hydrocarbons such as o-dichlorobenzene, etc. are particularly 
preferred. 
An amount of the solvent used may be generally in the range of 0.1 to 20 
parts by weight, preferably 1 to 10 parts by weight, based on 1 part by 
weight of the 1-substituted-4-methylpyrazoles of the formula (II). Also, 
the solvent may be used those which are commercially available, but if 
necessary, when the solvent is subjected to drying treatment with 
molecular sieves, etc., good results can be obtained. 
As the halogen, chlorine and bromine may be mentioned. The halogen can be 
used either in liquid or gaseous state. 
An amount of the halogen used may be generally in the range of 0.5 to 1.6 
moles, preferably 0.8 to 1.33 moles, per one mole of the 
1-substituted-4-methylpyrazoles of the formula (II), when producing 
5-halogeno-1-substituted-4-methylpyrazoles which is monohalogeno-material 
among the compounds represented by the formula (I). 
On the other hand, in the case of producing 
3,5-dihalogeno-1-substituted-4-methylpyrazoles which is dihalogeno 
material among the compounds represented by the formula (I), an amount of 
the halogen may be generally in the range of 1.4 to 3.0 moles, preferably 
1.8 to 2.5 moles, based on one mole of the 1-substituted-4-methylpyrazoles 
of the formula (II). 
As the reaction method between the 1-substituted-4-methylpyrazoles 
represented by the formula (II) and halogen, there may be employed the 
reaction in which the reaction is carried out by blowing with gaseous 
state or adding dropwise a halogen into 1-substituted-4-methylpyrazoles 
represented by the formula (II), or the method in which the 
1-substituted-4-methylpyrazoles represented by the formula (II) are added 
dropwise into halogen, etc. 
After completion of the reaction, the halogeno-4-methylpyrazoles 
represented by the formula (I) can be isolated by direct distillation, 
etc., but if necessary, it can be also obtained with good results by 
removing almost all the parts of remaining halogen and by-produced 
hydrohalogenic acid in the reaction mixture by such operation as reducing 
pressure or blowing of nitrogen as a pretreatment, subsequently treatment 
with an alkaline aqueous solution such as sodium hydroxide, potassium 
hydroxide, etc. completely, and then purification such as distillation, 
etc. 
As the halogenating agent, in addition to the above chlorine and bromine 
atoms, there may be also used, for example, sulfuryl chloride, sulfuryl 
bromide, N-chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochloride, 
etc. 
Also, the reaction can be carried out without using a deacidificating 
agent, but an organic base such as triethylamine, N,N-dimethylaniline, 
pyridine, etc. or an inorganic base such as sodium carbonate, potassium 
carbonate, sodium hydroxide, etc. may be used. 
The reaction can be carried out without using a catalyst, but as the 
catalyst, a Lewis acid such as BF.sub.3, AlCl.sub.3, FeCl.sub.3, 
SbCl.sub.5, SbCl.sub.5, etc., a metal halide such as CuCl, CuCl.sub.2, 
etc., a metal such as iron, copper, etc., or a halogen such as iodine, 
etc. may be added thereto. 
By the reaction of the 1-substituted-4-methylpyrazoles represented by the 
formula (II) and halogen, halogeno-4-methylpyrazoles represented by the 
formula (I) can be obtained easily at high yield. 
The 5-halogeno-1-substituted-4-pyrazoles which are monohalogeno-material 
among halogeno-4-methylpyrazoles represented by the formula (I) can be 
oxidized at the methyl group at the 4-position to produce 
5-halogeno-1-alkyl-4-alkoxycarbonylpyrazoles which are useful as the 
intermediate for herbicides (Japanese Provisional Patent Publication No. 
122488/1984). 
Also, the 3,5-dihalogeno-1-substituted-4-methylpyrazoles which are 
dihalogeno material among halogeno-4-methylpyrazoles represented by the 
formula (I) can be oxidized at the methyl group at the 4-position to 
produce 3,5-dihalogeno-4-alkoxycarbonylpyrazoles which are useful as the 
intermediate for herbicides (Japanese Provisional Patent Publication No. 
208977/1985).

The present invention is described in detail below by referring to 
examples, by which the present invention is not limited at all. 
EXAMPLE 1 
Into a mixture of 19.3 g (0.2 mole) of 1,4-dimethylpyrazole and 96 g of 
1,2-dichloroethane was blown 18.9 g (0.266 mole) of chlorine under 
stirring for one hour, while maintaining the reaction temperature at 
25.degree. to 35.degree. C. 
After completion of blowing, the temperature was returned to room 
temperature, and analyzed by liquid chromatography to find that 17.5 g of 
5-chloro-1,4-dimethylpyrazole was contained. 
The yield of 5-chloro-1,4-dimethylpyrazole was 67%. 
The above reaction mixture was washed with 30 g of a 20% aqueous sodium 
hydroxide solution, and after evaporation of the solvent, distillation was 
carried out by use of Widmer to give 17 g of 5-chloro-1,4-dimethylpyrazole 
of a purity of 95% at a boiling point range of 100.degree. to 110.degree. 
C./120 mm Hg. 
.sup.1 H-NMR (CDCl.sub.3): .delta.1.97 (3H, s), 3.75 (3H, s), 7.3 (1H, s). 
EXAMPLE 2 
Into a mixture of 9.65 g (0.1 mole) of 1,4-dimethylpyrazole and 48 g of 
1,2-dichloroethane was blown 15.6 g (0.22 mole) of chlorine under stirring 
for one hour, while maintaining the reaction temperature at 5.degree. to 
15.degree. C. 
After completion of blowing, the temperature was returned to room 
temperature, and analyzed by liquid chromatography to find that 14.4 g of 
3,5-dichloro-1,4-dimethylpyrazole was contained. 
The yield of 3,5-dichloro-1,4-dimethylpyrazole was 87%. 
After evaporation of the solvent from the above reaction mixture, 
distillation was carried out to give 15.2 g of 
3,5-dichloro-1,4-dimethylpyrazole of a purity of 90% at a boiling point 
range of 98.degree. to 109.degree. C./120 mmHg. 
.sup.1 H-NMR (CDCl.sub.3): .delta.1.9 (3H, s), 3.7 (3H, s). 
EXAMPLE 3 
Into a mixture of 3.1 g (0.0323 mole) of 1,4-dimethylpyrazole and 7 g of 
carbon tetrachloride was blown 7 g (0.097 mole) of chlorine under stirring 
for one hour, while maintaining the reaction temperature at 80.degree. C. 
After completion of blowing, the reaction temperature was returned to room 
temperature, and after evaporation of the solvent, distillation was 
carried out to give 3.6 g of 3,5-dichloro-1,4-dimethylpyrazole of a purity 
of 95% at a boiling point range of 98.degree. to 109.degree. C./20 mmHg. 
The yield of 3,5-dichloro-1,4-dimethylpyrazole was found to be 64%. 
EXAMPLES 4 
Into a mixture of 9.65 g (0.1 mole) of 1,4-dimethylpyrazole, 0.5 g of iron 
powder and 60 g of 1,2-dichloroethane was added dropwise 48 g (0.3 mole) 
of bromine under stirring for one hour, while maintaining the reaction 
temperature at 10.degree. to 35.degree. C., and stirring was continued at 
80.degree. C. for 15 hours. 
After completion of the reaction, bromine was removed under reduced 
pressure and the reaction mixture was neutralized with a 10% sodium 
hydroxide. Subsequently, insolubles were removed by filtration, washed 
with water and after evaporation of the solvent, distillation was carried 
out to give 9.3 g of 3,5-dibromo-1,4-dimethylpyrazole of a purity of 98% 
at a boiling point range of 124.degree. to 128.degree. C./20 mmHg. 
The yield of 3,5-dibromo-1,4-dimethylpyrazole was found to be 36%. 
.sup.1 H-NMR (CDCl.sub.3): .delta.1.95 (3H, s), 3.8 (3H, s). 
EXAMPLE 5 
Into a mixture of 2.5 g (0.0164 mole) of 4-methyl-1-phenylpyrazole and 20 g 
of 1,2-dichloroethane was blown 1.0 g (0.0141 mole) of chlorine under 
stirring for 15 minutes, while maintaining the reaction temperature at 
20.degree. to 25.degree. C. 
The reaction mixture was analyzed by gas chromatography and 1.3 g of 
5-chloro-4-methyl-1-phenylpyrazole was found to be contained. The yield 
was 41%. 
GC-MS: M/e: 192 (M.sup.+), 157 (M.sup.+ -C1), 130, 89, 77. 
Into the above reaction mixture was further blown 3.0 g (0.0423 mole) of 
chlorine under stirring for 45 minutes, while maintaining the reaction 
temperature at 30.degree. to 35.degree. C. After evaporation of the 
solvent, the residue was recrystallized with n-hexane to give 1.1 g of 
3,5-dichloro-1-(4-chlorophenyl)-4-methylpyrazole having a melting point of 
90.degree. to 91.5.degree. C. 
The isolated yield of 3,5-dichloro-1-(4-chlorophenyl)-4-methylpyrazole was 
26%. 
.sup.1 H-NMR (CDCl.sub.3): .delta.2.09 (3H, s), 7.56 (4H, s).