CS217685B1 - New o-/2-chlorethyl/-o-isobutyl-o-/1-methyl-5-metoxy-6-oxo 1h-pyridazin-4-yl/thiopheosphate and method of making the same - Google Patents

Abstract

New O- (2-chloroethyl) O-isobutyl O- (1-methyl- -5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate formula II, Cl-CH 2 Cl 2 í-o4h9o organic diluent such as methyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene, at temperature 40-110 ° C. Process for preparing the compound of formula II by reaction O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-one) -oxo-1H-pyridazin-4-yl) chlorothiophosphate of the formula Process for preparing the compound of formula II by reaction O- (2-chloroethyl) O-isobutylchlorothiophosphate of Formula III C1-CHoCH5C) 2 2 P-Cl i-c4H9o ^ 's with 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol salt formula IV with isobutyl alcohol or with alkaline butylate at 0 to 60 ° C. Process for preparing compounds of formula II by reaction O-isobutyl-O- (1-methyl-5-methoxy-6-oxo- H-pyridazin-4-yl) chlorothiophosphate of formula VI '4 9 M = alkali metal, especially sodium, potassium, on tetraethylammonium, in a water environment -CHs 2-chloroethanol at 0 to 60 ° C.

Description

The present invention provides novel O- (2-chloroethyl) O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate as well as a process for its preparation. The compound of the invention may be used as a pesticide.

Numerous pyridazin-4-yl esters of organophosphoric acids of formula I are known from the literature as pesticides,

wherein R ¹ and R ² are the same or different alkyls, alkoxy, alkylamido, dimethylamido, R ³ is halogen, alkoxy, alkylthio, R ⁴ is alkyl, cycloalkyl, aryl (Pestic, Sci. 10, 227-238 (1979); Sci., 7, 107-114 (1976); Collection 44, 1761-1771 (1979); Collection 43, 2415-2426 (1978).

The novel O- (2-chloroethyl) O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate of formula II has now been found.

C1-CH ₂ CH ₂ O-c ₄ h ₉ 0 ^x

At the same time, a process for the preparation of a compound of formula II by reaction of O- (2-chloroethyl) O-isobutylchlorothiophosphate of formula III was found.

G1 ₉ CH-CH ^ _o 0 ⁴ - C ₄ H ₉ ic N of a salt of l-methyl-5-methoxy-6-oxo-pyridazin-4-ol of formula IV,

wherein M is an alkali metal, in particular sodium, potassium, further tetraethylammonium, in a suitable organic diluent such as methyl ethyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene and the like, at a temperature of 40-110 ° C. It has also been found that the compound of formula II can be prepared by reacting O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula V

C1CH ₂ CH ₂ O

with isobutyl alcohol using an alkali carbonate, a tertiary amine such as triethylamine, pyridine and the like, or directly with an alkali butylate in an organic diluent such as e.g. dioxane, acetic acid nitrile, methyl ethyl ketone, toluene and the like, at 0 to 60 ° C.

The compound of formula II can also be prepared by reacting O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of the formula

VI iG ₄ H ₉ O

with 2-chloroethanol using an alkali, tertiary amine carbonate such as triethylamine, pyridine and the like in an organic diluent such as dioxane, acetic nitrile, acetone, methyl ethyl ketone, butyl acetate, toluene and the like at 0 to 60 C.

The following examples illustrate but do not limit the novel O- (2-chloroethyl) O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophostate and the preparation thereof.

Example 1

To 0.11 mole of 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol potassium salt in 100 mL of methyl ethyl ketone was added 0.1 mole of O-isobutyl O- (2-chloroethyl) chlorothiophosphate with stirring. The reaction mixture was stirred at 80 ° C for 4 hours, then cooled, the precipitated potassium chloride was collected by filtration. Methyl ethyl ketone was distilled off from the filtrate under reduced pressure. The distillation residue was dissolved in 100 ml of toluene, which was washed with 50 ml of 5% aqueous sodium carbonate solution and still with water. After drying, toluene was distilled off from the toluene solution under reduced pressure. The distillation residue was purified by column chromatography on SiO 2 using toluene or toluene with addition of acetone.

29.2 g of a colorless liquid were obtained with _D 2 ° = 1.5248 Analysis for C ₁₂ H ₂ OClN ₂ O _g PS (MW = 370.62)

N: 8.36% P 8.64% N 7.57% N Find: 8.42% P 8.78% N 7.88% N

The structure of the compound was confirmed by spectral methods:

IR in chloroform

1 H NMR in CDC1 _3:

k: v _(c , _{= 0} ) 1662 cm ^-1 s (c. _{= N} , 1622 cm ^-1 In P = p> θθ3 ^{cm-1 1675} cm " CH 7.91 p (ppm) -ch ₂ -o- 4.59 p (ppm) CH ₃ -O- 4.34 ó (ppm) -CH-C 4.15 δ (ppm) CH ₃ -N 3.88 δ (ppm) CH 2.31 ó (ppm) · CH, CH 1.17 p (ppm)

v _{(c = 0} ) ib »2 cm ¹¹ V (cn> 1622 cm ¹⁾

UV spectrum in methanol: J max;

214.3 nm (loge: 4.37) and 280.0 nm (loge: 3.70).

Molecular ion was confirmed in the mass spectrum: 370 ⁺ .

¹³ C NMR in CDCl 3: C = O 158.8 δ (ppm) P-O-C-C < 144.8 δ (ppm) CH ₃ —O — c = c < 138.6 δ (ppm) H — C = N — —CH ₂ —O — P—> CH — CH ₂ —O — P— ch ₃ -oci — ch ₂ - ch ₃ n-> ch— ch ₃ - 133.7 δ (ppm) 75.7 δ (ppm) 68.5 δ (ppm) 59.9 δ (ppm) 42.7 0 '(ppm) 39.8 δ (ppm) 28.5 <5 ppm 18.5 δ (ppm)

Example 2

To 0.22 mole of the 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol tetraethylammonium salt in 300 ml dioxane was added 0.2 mole of O- (2-chloroethyl) O-isobutylchlorothiophosphate with stirring. The reaction mixture was stirred at 60 ° C for 4 hours. After cooling, the precipitated tetraethylammonium chloride precipitated. Dioxane was distilled off from the filtrate under reduced pressure. The distillation residue was dissolved in 100 ml of toluene, which was washed with 50 ml of 5% aqueous sodium carbonate solution and then with water. After drying, toluene was distilled from the toluene solution under reduced pressure. The distillation residue was purified by column chromatography on SiO ₂ using toluene or toluene with little acetone addition.

Yield: 60.3 g (81.3% yield) of the compound identical to Example 1.

Ppíklsó 3

To 0.04 mol of O- (2-chloroethyl) -O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate in 80 ml of toluene was added 0.044 mol of potassium isobutyrate in stirring. 40 ml of toluene, at a temperature of 10 to 15 ° C. Stirring was then continued at 20 ° C for 6 h. The precipitated potassium chloride was dissolved in water, the toluene layer was washed once more with 100 ml of water, the toluene was distilled off under reduced pressure, and the residue was then purified by column chromatography. This gave 11.6 g of a colorless liquid, n _D ²⁰ = 1.5250, identical to the compound of Example 1.

Example 4

To 0.04 mole of O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate dissolved in 80 mL of toluene and 0.004 mole of triethylbenzylammonium chloride catalyst was added with stirring 0.1 mole ethylene chlorohydrin and 0.05 mole triethylamine in 40 ml toluene at 20 ° C. Stirring was continued at the same temperature for 5 h. The reaction mixture was washed with water, 5% hydrochloric acid, and after drying, toluene was distilled off under reduced pressure. The residue was purified by column chromatography. 10.9 g of a colorless liquid n _D ²⁰ - 1.5251, identical to the compound of Example 1, were obtained.

Claims (4)

OBJECT OF THE INVENTION New O- (2-chloroethyl) 0-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate of formula II. C 1 -CH ₂ CH ₂ t-C ₄ H ₉ of 2 2 \ p _{C 1} _ t-C ₄ H ₉ with the Sol' l-methyl-5-methoxy-6-oxo-pyridazin-4-ol of formula IV, Wherein M is an alkali metal, in particular sodium, potassium, and tetraethylammonium, in a suitable organic diluent such as methyl ethyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene at a temperature of 40 to 110 ° C. 2. A process for the preparation of a compound according to claim 1, which comprises reacting O- (2-chloroethyl) O-isobutylchlorothiophosphate of formula III. Cl-CH _o CH _o 0 3. A process for the preparation of a compound according to claim 1, which comprises reacting O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula V C1CH ₂ CH ₂ O with isobutyl alcohol using an alkali, tertiary amine carbonate such as triethylamine, pyridine, or directly with an alkali butylate in an organic diluent such as dioxane, acetonitrile, methyl ethyl ketone, toluene at 0 to 60 ° C . 4. A process for the preparation of compounds according to claim 1, which comprises reacting O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of the formula c ₄ h _{9 with} 2-chloroethanol using an alkali, tertiary amine carbonate such as triethylamine, pyridine in an organic diluent such as dioxane, acetic nitrile, acetone, methyl ethyl ketone, butyl acetate, toluene at 0 to 60 ° C .