CS235153B1 - 2-(substituted)-4,5-dichlor-3-oxo-2h-pyridazines - Google Patents

Description

The invention relates to 2- (substituted) -4,5-dichloro-3-oxo-2H-pyridazines as well as a process for their preparation. Said compounds can be used as starting products for the synthesis of pesticidally active substances, such as e.g. for the preparation of 2-substituted-4-alkoxy (alkylthio) -5-chloro-3-oxo-2H-pyridazines, 2-substituted-4-chloro-5-alkoxy (alkylthio) -3-oxo-2H-pyridazines.

2-dialkylaminoethyl (-4,5-dichloro-3-oxo-2H-pyridazines, 2-rhodonomethyl-4,5-dichloro-3-oxo-2H-pyridazines as well as 2-hydroxymethyl (chloromethyl) -4 are known from the literature. 5-dichloro-3-oxo-2H-pyridazines as starting materials for the synthesis of numerous compounds [Monatsheffte fur Chemie 99, 15-04 (1968)].

2- (substituted) -4,5-dichloro-3-oxo-2H-pyridazines in general have now been found

wherein R is C 1 -C 4 alkyl, phenyl optionally substituted with 1 to 3 substituents selected from the group consisting of methyl, halogen, nitro, trifluoromethyl, and X is oxygen or sulfur.

At the same time, a process for the preparation of compounds of the formula I by reacting 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine of formula II,

Cl xy ⁰ with alcohol, alkylthiol, phenol or thiophenol, all; vzórca III

MX-R (III) wherein R, X are as defined above and M is hydrogen, sodium or potassium in an organic solvent such as methanol, ethanol, acetone, butyl acetate, benzene, toluene and the like. at a temperature of from -15 ° C to -60 ° C. In the case where M is hydrogen, the reaction is also carried out in the presence of a target. amines such as pyridine, trimethylamine, triethylamine, N, N-dimethylaniline and the like.

The following examples illustrate but do not limit the scope of the invention.

Example 1

2-methoxymethyl-4,5-dichloro-3-oxo-2-H-pyridazin

To 0.2 mol of 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine in 200 ml of methanol at 0-5 ° C was added successively 0.21 mol of sodium methylate in 80 ml of methanol. Then the reaction mixture was stirred at room temperature for 30 min. and another 30 min. at 50 ° C. After cooling, the precipitated sodium chloride was removed by filtration, and methanol was distilled off under reduced pressure. The distillation residue was dissolved in 200 ml of toluene, washed with 200 ml of water, dried, toluene was distilled off under reduced pressure and the residue was purified by crystallization. A white crystalline substance with m.p. t. 115 DEG -117 DEG C. in 70.1% yield, having the following composition:

Analysis for C & HeCl2N2Oa (MW 209.0):

calculated:

13.40% N, 33.92% Cl Found:

13.29% N, 34.17% Cl IC in CCU:

v (C = O), 1688 cm ^-1 v (C = N), 1612 cm ^-1

UV in CH3OH:

max max (nm) (log ε) 216.0 (4.53)

297.4 (3.80)

Example 2

2-etoxometyl-4,5-dichloro-3-oxo-2H-pyridazin

To 0.2 mole of 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine in 200 ml of ethyl alcohol was added, with stirring, 0.21 mole of sodium ethylate and 100 ml of ethyl alcohol at 5-10 ° C. The further procedure was the same as in Example 1. A white crystalline substance with m.p. t. 101-102 ° C, in 90.5% yield, having the following composition:

Analysis for C7H8Cl2N2O2 (m, h, 223.0)

calculated:

12.56% N, 31.79% Cl Found:

N, 12.88. Cl, 31.99

IC in CC14:

v (C = C), 1686 cm ^-1 v (C = C), 1609 cm ^-1 in CHCl 3:

v (C = C), 1674 cm ^-1 v (C = N), 1611 cm ^-1

UV in CH 2 OH:

λ max nm (log ε) 215.9 (4.52) 296.4 (4.33)

Example 3

2-ethylthiomethyl-4,5-dichloro-3-oxo-2H-pyridazin

To 0.206 mol of 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine in 150 ml of acetonitrile was added 0.206 mol of ethyl mercaptide sodium suspended in 100 ml of benzene with stirring at 0-5 ° C. After the addition, stirring was continued for 1 h. at 20 ° C and 30 min. at 55 ° C. The precipitated sodium chloride was removed by filtration, and acetonitrile and benzene were distilled off under reduced pressure. The further procedure is the same as in Example 1. A white crystalline substance with m.p. t. 94 DEG-96 DEG C. in 81% yield, as follows:

C7H8Cl2N2OS (m, d, 239.1):

calculated:

N, 11.71; Cl, 29.65; S, 13.41%

found:

N, 12.01; Cl, 29.73; S, 13.50

IC spectra in CCl4: v (C = O), 1684 cm ^-1 v (C = N), 1589 cm ^-1

UK spectra in CH3OH:

A _max (nm) (log ε) 213.4 (4.25)

305.0 (4.09)

Example 4

2 R (4'-di'Chlóirf0nyltiometyl) -4,5-dichloro-3-oxo-2H-pyridazin

To 0.2 mol of 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine in 150 ml of acetonitrile was added 0.2 mol of sodium 4-chlorothiophenolate sodium gradually with stirring at 4-10 ° C. Stirring was continued for 1 h. at room temperature and 30 min. at 40 ° C. The further procedure was the same as in Example 1. A viscous viscous liquid was obtained in 75% yield, having the following composition:

C11H7Cl2N2OS (m, d, 321.6):

calculated:

N, 8.71; Cl, 33.11; S, 9.97

found:

N 8.91, Cl 33.40, S 10.11. Example 5

2‘- (2‘, 4‘, 5‘-trichlorophenoxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine

To 0.15 mol of 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine in 100 ml of methyl ethyl ketone with stirring was added 0.15 mol of 2,4,5-trichlorophenol sodium in 50 ml of methyl ethyl ketone, at a temperature of Deň: 18 ° C. Stirring was continued for 30 min. at room temperature and 1 h. at 75 ° C. The further procedure was the same as in Example 1. A white crystalline substance (from methanol) with m.p. t. 152-154 ° C, having the following composition:

C11H5Cl5N2O2 (m, h 374.41):

calculated:

N, 7.48; Cl, 47.30

found:

N, 7.52; Cl, 47.23

The following substances were prepared in the same manner:

2- (4‘-bromophenoxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine, mp 161-163 ° C,

2- (4‘-fluorophenoxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine, mp 91-93 ° C,

2- (m-tolyloxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine, m.p. t. 70 - 72 ° C,

2- (4‘-nitrophenoxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine, mp 184-187 ° C,

2- (4‘-Trifluoromethylphenoxymethyl) -4,5-dichloro-3-oxo-2H-pyridazine, mp 61-63 ° C.

Claims (2)

SUBJECT 2- (substituted) -4,5-dichloro-3-oxo-2H-pyridazines of formula I YNALEZH wherein R is C 1 -C 4 alkyl, phenyl optionally substituted with 1 to 3 substituents selected from the group consisting of methyl, halogen, nitro, trifluoromethyl, and X is oxygen or sulfur. 2. A process for the preparation of the compounds according to claim 1, which comprises reacting 2-chloromethyl-4,5-dichloro-3-oxo-2H-pyridazine of the formula II with an alcohol, an alkylthiol, a phenol or a thiophenol of the formula III. MX-R (III) wherein R, X are as defined above and M is hydrogen, sodium or potassium, when M is hydrogen using a tertiary amine, in an organic solvent such as methanol, ethyl alcohol, acetone, butyl acetate , benzene, thien at -15 to +60 ° C.