CS240362B1 - Process for preparing a mixture of 2-alkylthio-4,6-diamino-s-triazines with 2,4-diamino-6-chloro, -s-triazines - Google Patents

Abstract

The invention relates to a method for producing a mixture of 2- - / -alkylthio-4,6-diamino-s-triazines with 2,4-diamino-6-chloro-s-triazines in a solvent, diluent or mixture thereof, whereby 2-alkylamino-4,6-dichloro- -s-triazine is first reacted with sodium salt of alkanethiol and then with alkylamine and sodium hydroxide. - The reaction with sodium salt of alkanethiol is carried out at a temperature of 10 to 70 °C, the reaction with alkylamine at the reflux temperature of the reaction mixture. '< The above compounds are effective as herbicides.

Description

The present invention relates to a process for the preparation of a mixture of 2-alkylthio-4,6-diamino-s-triazines with 2,4-diamino-6-chloro-s-triazines of formulas I and II

S-R

X 'νηΛΛNHR ^:

R NH

Cl

NHR '(II) wherein

R ^{@ 1} and R @ ³ represent the same aromatic alkyl radical having 1 to 5 carbon atoms,

R ² represents a lower alkyl radical having 1 to 5 carbon atoms. In the above formulas I and II, alkyl radicals are primarily to be understood as meaning alkyl radicals such as methyl, ethyl, η-propyl, i-propyl, tert-butyl, η-butyl, n- pentyl- etc. Preferably, R ¹ is tert-butyl, R ³ is ethyl and R ² is methyl, or when R ¹ and R ³ are isopropyl and R ² is meityl.

It is known that some of these mixtures, such as a mixture of 30% terbutylazine (2-Tetylamino-4-chloro-6-tert-butylamino-s-triazine) with 70% terbutryne (2-ethylamino-4-methylthio-6) tert-butylamino-s-triazine) have been widely used for the production of herbicidal preparations and have been prepared hitherto by mixing and treatment of the individual active ingredients.

. It is further known that one chlorine atom in the N-monosubstituted 2-amino-4,6-dichloro-s-triazines is very readily nucleophilically replaceable by an alkylamino group (U.S. Pat. No. 156,446), respectively. alkylthio (U.S. Pat. No. 145,197). In 2-alkylamino-4-alkylthio-6-chloro-s-triazines, the chlorine atom is nucleophilically exchangeable for an alkylamino group as opposed to 2,4-bis-alkylamino-6-chloro-s-triazines in which the chlorine atom is relatively difficult to replace with an alkylamino group.

It has now been found to be advantageous to prepare mixtures of 2-alkylthio-4,6-diamino-s-triazines with 2,4-diamino-6-chloro-s-triazines from 2-alkylamino-4,6-dichloro-s-triazines in a solvent or diluent medium or a mixture thereof according to the method of the invention.

SUMMARY OF THE INVENTION Each mole is prepared in a manner known per se by the prepared 2-alkylamino-4,6-dichloro-s-triazine of formula III

in which

R ¹ is as defined above, is treated first with 0.01 to 0.99 mol of the sodium salt of mercaptans of the formula IV /

R ² . S — Na (IV) in which

R ² is as defined above, and then with 1 mole of an alkyl amine of formula V R * ^3rd NHz (V) in which

R ³ is as defined above, of about the moles of sodium hydroxide.

It is also possible to react 2-alkylamino-4,6-dichloro-s-triazine with a selected molar ratio of alkanethiol in the presence of hydrogen chloride-binding agents and the corresponding polar amounts of alkylamine and sodium hydroxide.

Hocisa states (US Pat. No. 145,197) that it is advantageous to introduce an alkylthio group into the 2-alkylamino-4,6-dichloro-s-triazines molecule at 0-5 ° C, in the process of the present invention, that the reaction can be carried out at temperatures of 10 to 70 ° C, preferably 25 to 40 ° C. The reactivity of the chlorine atom in 2-alkylamino-4-alkylthio-6-chloro-s-triazines and the first chlorine in 2-alkylamino-2,4-dichloro-s-triazines is so close that a second portion of amine and sodium hydroxide can be introduced into the reaction mixture practically adiabatically and to react, the reaction mixture is kept under reflux for 2 to 5 hours.

The above reaction sequence can be carried out in a variety of solvents (water, acetone, ethyl methyl ketone, etc.), or mixtures thereof. Particular preference is given to the use of acetone, resp. of its aqueous solutions.

These examples illustrate but do not limit the scope of the invention.

EXAMPLE

To 93.1 g of 99% cyanuric chloride (0.5 mole) was added 250 mL of t-oluene and 50.65 grams of 72.2% t-butylamine (0.5 mole) was added with vigorous stirring. ) and 133 g of a 15.03% aqueous solution of sodium hydroxide (0.5 mol). The temperature of the reaction mixture increased from 18 ° C to 50 ° C. Then, the mixture was cooled to 20 ° C, the aqueous layer was separated, and toluene was distilled off in vacuo. To the crystalline 2,4-dichloro-6-tert-butylamino-s-triazine obtained was added 125 cm ^{3 of} water. The temperature of the reaction mixture was adjusted to 20-40 ° C and 119.2 g of a 20.15% aqueous solution of methanesol sodium (0.34 mol) was added to the mixture at this temperature over 1 hour. After stirring for half an hour, the reaction mixture was neutral, 56.7 g of a 41.78% aqueous solution of ethylamine (0.53 mol) and 143 g of a 15.03% aqueous solution of sodium hydroxide * (0.537) were added. mole), whereby the reaction mixture reached 49 ° C. The reaction mixture was then heated to reflux (69 ° C) with stirring for 2 hours. Upon cooling to 15 ^° C, a crystalline product precipitated which was aspirated, washed with 300 centimeters of cubic water and dried to a constant weight. 115 g of products were obtained which, according to gas chromatographic analysis, contained 32.8% tert-butylazine and 68.5% terhutyrene.

Example 1 a d 2

To 110.5 g of 2,4-dichloro-6-tert-butylamine-s-triazine (0.5 mol) in 250 cm @ ^{3 of} 50% aqueous acetone solution was added 90.0 g of 20.45 with stirring. % aqueous solution of sodium metantiol (0.263 mol) at 20-45 ° C. After achieving a neutral reaction, 56.3 g of a 40% aqueous solution of ethylamine (0.5 mol) and 133.4 g of a 15% aqueous sodium hydroxide solution (0.5 mol) were added to the mixture and heated to · Reflux at which it lasted 2.5 hours. After cooling to 20 [deg.] C., crystallization, suction and washing with 250 ml of water, after drying, 117.0 g of product were obtained which, according to gas chromatographic analysis, contained 51.6% terbutylazine and 47.9% terbutryin.

Příklad.3

K 110.5 g techn. 2,4-Dichloro-6-tert-butylamino-s-triazine (0.5 mole) in 250 cm @ ^{3 of a} 40% aqueous acetone solution was added with stirring to 18.0 g of dichloromethane ^. g of a 20.45% solution of sodium methanesole (0.053 mol) at 30-45 ° C. After a neutral reaction, 56.3 g of a 40% w / v aqueous solution of ethylamine (0.5 mol) and 133.4 g of a 15% aqueous sodium hydroxide solution (0.5 mole) were added to the mixture and heated. to reflux, which lasted for 2 hours. After further conventional work-up (as in Example 2), 114 g of a product was obtained which contained 88.4% terbutylazine and 10.8% terbutryne.

Example 4 110,5 g techn. 2,4-dichloro-6-tert-butylamino-s-triazine (0,5'mole) - 250 cm ^{3 of a} 55% aqueous acetone solution was added with stirring 162 g of a 20.45% aqueous sodium solution methanesol salt (0.473 mol) at 30 to 60 ° C. When the reaction was neutral, 56.3 g of a 40% aqueous ethylamine solution (0.5 mol) and 133.7 g of 15% sodium hydroxide solution (0.5 mol) were added and the mixture heated to reflux, which lasted 3 hours. Further conventional work-up (as in Example 2) yielded 121 g of a product which, according to gas chromatographic analysis, contained 11.1% terbutylazine and 90.3% terbutryne.

EXAMPLE

To 103.5 g of 2,4-dihydro-6-isopropylamino-s-triazine (0.5 mol) in 250 cm ^{3 of a} 55% aqueous acetone solution was added 85.7 g of 20.45% aqueous aqueous solution with stirring. sodium methanesol solution (0.25 mol) at 25-35 ° C. After reaching a neutral reaction, 73.9 g of a 40% aqueous isopropylamine solution (0.5 mole) and 133.7 g of 15% sodium hydroxide (0.5 mole) were added to the mixture, and the zffies were heated to reflux at After the usual work-up (as in Example 2), 115.0 g of a product were obtained which, according to gas chromatographic analysis, contained 50.3 percent of propazine (2,4-bis-isopropylamino-6-methylthio). triazine).

EXAMPLE 6 To 103.5 g of 2,4-dichloro-6-isopropylamino-s-triazine (0.5 mol) in 250 cm @ ^{3 of a} 45% aqueous acetone solution was added 168, under stirring, at a temperature of 10 to 70 ° C. 20 g of a 20.0% aqueous solution of sodium methanesol (0.48 mol). After reaching a neutral reaction, 56.1 g of a 40% aqueous solution of ethylamine (0.5 mol) and 133.7 g of 15% sodium hydroxide solution (0.5 mol) were added to the mixture, and the mixture was heated to reflux. , which lasted 2.5 to 3 hours. After usual work-up (as in Example 2), 113.0 g of product was obtained which, according to gas chromatographic analysis, contained 94.2% amethylene (2-ethylamino-4-isopropylamino-6-methylthio-s-triazine) and 4.8% atrazine (2). -ethylamino-4-chloro-6-isopropylamino-s-triazine).

Example 7 \

To 93.1 g of 99% cyanuric chloride (0.5 moles) was added 250 ml of toluene and, with vigorous stirring, 64.60 grams of a 45% aqueous solution of isopro2483-2 pylamine (0.5 moles) and 133 ml. g of a 15.0.3% aqueous solution of sodium hydroxide (0.5 mol) The temperature of the reaction mixture was increased from 20 ° C to 50 ° C, after which the reaction mixture was cooled to 20 ° C, the aqueous layer was separated and the organic layer 125 cm ^{3 of} acetone and 125 cm ^{3 of} water were added to the thus obtained 2,4-dichloro-6-isopropylamino-s-triazine, and at 20-40 ° C were added within one hour. 147.2 g of a 20.0% aqueous solution of sodium etantiol (0.35 mol) was added. After stirring for half an hour the reaction mixture was neutralized, then 57.5 g of a 42% aqueous ethylamine solution (0%) were added. , 51 moles) and 137.8 g of a 15.1% aqueous sodium hydroxide solution (0.52 moles) and heated to reflux with stirring After cooling to 18 DEG C., a crystalline white product precipitated, which was washed with 300 cm @ ^{3 of} water and dried to constant weight. 110.5 g of product were obtained which contained 72.1% of 2-ethylamino-4-ethylthio-6-isopropylamino-diazriazine and 27.5% of 2-ethylamino-4-chloro-6-isopropylamino-s- triazines.

Example 8

To 103.5 g of 2,4-dichloro-6-isopropylamino-s-triazine (0.5 mol) in 250 cm ^{3 of a} 55% aqueous acetone solution were added 174.27 g of 18.4% aqueous solution with stirring. an aqueous solution of n-butanethiol carbonate (0.25 mol]? 8 at .25 to 35 ⁹ C. on reaching neutral) reaction, the reaction mixture was added 73.9 grams 40% aqueous solution of isopropylamine (0.5 mol and 133.7 g of a 15% aqueous sodium hydroxide solution (0.5 mol) and the mixture was heated to reflux at which it remained for 3 hours, after which the usual work-up (as in Example 2) yielded 123.2 g. g of product containing 44.3% of 2,4-diisopropylamino-6-chloro-s-triazine, and 54.9% 2-n-butylthio-4,6-diisopropylamino-s-triazine. ¹

Example 9

To 110.9 g 2,4-dichloro-6- (3-methoxypropyl) amino-s-triazine (0.5 mol). in 250 cm ^{3 of a} 55% aqueous acetone solution, 90.0 g of a 20.45% aqueous solution of methanesol sodium (0.263 mol) was added under stirring at a temperature of 20 to 45 ° C. After a neutral reaction, 73.9 grams of a 40% aqueous isopropylamine solution (0.5 mol) and 133.4 g of a 15% aqueous sodium hydroxide solution (0.5 mol) were added to the mixture and heated to reflux at which it was maintained for 3.5 hours. After usual work-up (as in Example 2), 125.4 g of product were obtained which, on gas chromatographic analysis, contained 45.1% 2-chloro-4-isopropylamino-6- (3-methoxypropyl jamino-s-trlazine) and 54.2% 2-isopropylamino-4- (3-methoxypropyl) amino-6-methylthio-s-triazine.

Claims (1)

Of pylamine (0.5 mol) and 133 g of 15.0.3% non-aqueous sodium hydroxide solution (0.5 mol). The temperature of the reaction mixture increased from 20 ° C to 50 ° C. After the reaction mixture was cooled to 20 ° C, the aqueous layer was separated and the organic layer was de-toluene removed by distillation under vacuum of 1500 Pa. To the thus obtained N -dichloro-5-isopropylamino-s-triazide, 125 cm 3 of acetone and 125 cm 3 of water were added and at 20-40 ° C 147.2 g of 20.0% sodium hydroxide was added in the course of one hour. After stirring the reaction mixture for half an hour, a neutral reaction was obtained, then 57.5 g of a 42% aqueous solution of ethylamine (0.51 mol) and 137.8 g of 15.1% were added. aqueous sodium hydroxide solution (0.52 mol) and heated to reflux, which was stirred for 2 hours, after cooling to 18 ° C, a crystalline white product precipitated, washed with 300 cm 3 of water 110.5 g of product were obtained, which contained 72.1% of 2-ethylamino-4-ethylthio-6-isopropylamino-4-azinine and 27.5% of 2-ethylamino-4-chloro-6-isopropanol. EXAMPLE 8 To 103.5 g of 2,4-dichloro-6-isopropylamino-s-triazine (0.5 mol in 250 cm 3 of 55% non-aqueous acetone solution, 174 was added with stirring). 27 g 18 A 4% aqueous solution of potassium n-butanethiolate (0.25 mol); 8 at a temperature of 25 to 35 ° C. Upon neutral reaction, 73.9 g of 40% aqueous isopropylamine (0.5 mol) and 133.7 g of 15% aqueous sodium hydroxide solution were added to the reaction mixture. 0.5 mole) and the mixture was heated to reflux for 3 hours. After the usual treatment (as in Example 2), 123.2 g of product was obtained, which contained 44.3% of 2,4-diisopropylamino-6-chloro-s-triazine and 54.9% of 2-n-butylthio-4. 6-diisopropylamino-s-triazine. EXAMPLE 9 K 110 g of 2,4-dichloro-6- (3-methoxypropyl) amino-s-triazine (0.5 mol). in 250 cm @ 3 of a 55% aqueous acetone solution, 90.0 g of a 20.45% aqueous solution of sodium methantiol sodium salt (0.263 mol) was added under stirring at a temperature of 20 to 45 ° C. Upon neutral reaction, 73.9 g of a 40% aqueous solution of isopropylamine (0.5 mol) and 133.4 g of a 15% aqueous sodium hydroxide solution (0.5 mol) were added to the mixture and heated to reflux. for 3.5 hours. After the usual work-up (as in Example 2), 125.4 g of product were obtained, which contained 45.1% of 2-chloro-4-isopropylamino-6- (3-methoxypropyl) -amino-s-triazine according to gas-chromatographic analysis and 54.2% of 2'-isopropylamino-4- (3-methoxypropyl) amino-6-methylthio-s-triazine The method of preparing a mixture of 2-alkylthio-4,6-diaminoosines of Formulas I and II triazine with 2,4-diamino-6-chloro-s-tri- wherein R 1 and R 3 are the same or different alkyl of 1 to 5 carbon atoms, R 2 is a lower alkyl radical of 1 to 5 carbon atoms of 2-alkylamino-4-dichloro-s-triazine of formula III C 1 (lili / 240362 wherein R 1 is as defined above in the solvent medium and / or diluent, wherein each mole of 2-alkylamino-4,6-dichloro-s-triazine of formula III is reacted with at least 0, From about 1 to about 0.99 moles of the sodium salt of the alkanol of formula IV R 2 -S-Na (IV) 10 wherein R 2 is as defined above with 1 mole of an alkylamine of formula V R 3. sodium hydroxide.