CS240373B1 - Method of s-triazines' physico-chemically stable mixture production - Google Patents

Description

(54) Process for producing a physicochemically stable mixture of s-triazines

I

The present invention relates to a process for the preparation of a physicochemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazine with 2,4-bis-alkylamino-6-methyltto-s-triazine by reacting a mixture of cyanuric chloride with 2,4-dichloro -6-methylthio-s-triazine in a non-polar organic solvent with the same amount of alkylamine of formula I

R ⁴ NH 2 (I) and with the same amount of alkylamine of the formula II

R ² NH 2 (II) wherein

^{R 1 (II)} and R @ ² are as defined in the description., Each in the presence of sodium hydroxide as a hydrogen chloride binding agent and, after removal of non-polar solvent, the physico-chemical cost was obtained by crystallisation from 20 to 25% strength aqueous solution of an aliphatic ketone . The radicals R ⁴ and R ² may be the same or different.

The invention relates to a process for the preparation of a physically-chemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazine with 2,4-bis-alkylamino-6-methylthio-s-triazine.

Mixtures of 2,4-bis-alkylamino-6-chloro-s-triazines with 2,4-bis-alkylamino-6-methylthio-s-triazines are known to be ingredients of many important herbicidal formulations. The most known are mixtures of 2-ethylamino-4-chloro-6-tert-butylamino-s-triazine (terbutylazine) with 2-ethylamino-4-methylthio-6-tert-butylamino-s-triazine (terbutyrene), 2-ethylamino 4-Chloro-6-isopropylamino-s-triazine (atrazine) with 2-ethylamino-4-isopropylamino-6-methylthio-s-triazine (ametrynine, etc.).

Treatment of 2,4-bis-alkylamino-6-chloro-s-triazines

The 2,4-bis-alkylamino-6-methylthio-s-triazines present a technical problem since the preparations obtained by physically mixing the two active substances and modifying the mixture thus obtained have an inadequate storage stability of the physical properties.

Z Čs. pat. No. 194,660, it is known that a physicochemically stable mixture of these compounds can be obtained, for example, by quenching both components and slowly cooling and seeding the cooling melt, or crystallizing the mixture just below the melting point. This method is disadvantageous because it requires the isolation of both components in a pure state, a melting component, long crystallization times (cooling at 0.01 to 0.2 ° C / min) and a solid block of the intramolecular compound to be crushed and ground. Another method for preparing a stable intramolecular compound is to crystallize both components from anhydrous solvents such as nitriles, amides, alcohols or ketones, or mixtures thereof with hydrocarbons. However, this crystallization yields very low yields (60% in the case of methanol, 40% in the case of hexane: acetone 1: 1).

Z čs. of the author's certificate no. 226,627, it is known that 1 mole of 2,4-dichloro-6-methylthio-s-triazine (MDTJ reacts with 1 mole of amine in the presence of 1 mole aqueous sodium hydroxide solution practically adiabatically. To replace chlorine in 2-alkylamino-4-chlorine 6-methylthio-s-triazines with another alkylamino group it is necessary to raise the temperature of the reaction mixture to 60-70 ° C for 2 to 5 hours, even in acetone (U.S. Pat. No. 145,197J).

It is further known that cyanuric chloride reacts with alkylamine in the presence of sodium hydroxide in a biphasic aqueous, o-organic medium practically under adiabatic conditions (U.S. Pat. 156,446). It is also known that chlorine in 2,4-bis-alkylamino-6-chloro-s-triazines is difficult to exchange nucleophilically.

Most of the lack of preparation of a physicochemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazines with 2,4-bis-alkylamino-6-methylthio-s-triazines in a weight ratio of 1: 9 to 9: 1 eliminates the production method of the invention.

The present invention consists in reacting a mixture of cyanuric chloride with 2,4-dichloro-6-methylthio-s-triazine in a non-polar organic solvent with an equal amount of alkylamine of the formula I

R ⁴ NH 2 (I) wherein

R ¹ represents an alkyl group having 1 to 5 carbon atoms and an equal amount of an alkylamine of the formula II

R ² NH 2 (II) wherein

R ² is C 1 -C 5 alkyl in the presence of sodium hydroxide as the hydrogen chloride-binding agent and, after removal of the non-polar solvent, the physicochemically stable mixture is obtained by crystallization from a 20 to 50% aqueous solution of an aliphatic ketone. If R ¹ -R ² , the amount of alkylamine is twice the amount of the mixture of cyanuric chloride and 2,4-dichloro-6-methylthio-s-triazine.

The physicochemically stable mixture obtained can be treated by grinding, mixing with fillers such as kaolin, silica, dispersants, emulsifiers and the like for wettable dusts which can be stored for up to two years at a temperature of -5 to +30 ° C without changing their physico-chemical properties.

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

EXAMPLE

9.9 g of 2,4-dichloro-6-methylthio-s-triazine (0.05 mol) were dissolved in 500 cm ^{3 of} toluene and

83.8 g of cyanuric chloride (0.45 mol). To the solution, 51.9 g of a 70.4% aqueous t-butylamine solution (0.50 mol) and 136.8 g of a 14.62% aqueous sodium hydroxide solution (0.50 mol) were added with stirring, the temperature of the reaction mixture did not exceed 50 ° C. After stirring for 15 minutes, 50.8 g of a 44.4% aqueous solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous solution of sodium hydroxide (0.503 mol) were added to the reaction mixture. The reaction mixture was stirred at reflux for 1 hour. Thereafter, toluene was distilled off with scientific steam, 125 cm ^{3 of} acetone were added to the residue, and the reaction mixture was cooled to 20 ° C with stirring. The precipitated crystalline product was filtered off, washed with

250 ml of water and dried to constant weight.

111.5 g of product were obtained, which, according to analysis, contained 90.4% terbutylamine and 9.2% terbutryne.

Example 1 a d 2

The procedure was as in Example 1 except that 500 cm ^{3 of} toluene was added

46.8 g of cyanuric chloride (0.25 mol) and 49.5 grams of 2,4-dichloro-6-methylthio-s-triazine (0.25 mol). The toluene solution was stirred with stirring. 51.9 g of a 70.4% aqueous solution of t-butylamine (0.50 mol), 136.8 g of 14.62% aqueous solution were added. a solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous sodium hydroxide solution (0.503 mol). After distilling off toluene, adding acetone, cooling, isolating and drying, 114 g of a white to cream colored crystalline product were obtained containing 49.5% terbutylazine and 48.8% terbutryne.

Example 3

a)

67.3 g of 2,4-dichloro-6-methylthio-s-triazine (0.34 mol), 28.0 g of cyanuric chloride (0.15 mol) were dissolved in 500 cm @ ^{3 of} toluene and successively adiabatic in solution. 51.9 g of a 70.4% aqueous solution of tert-butylamine (0.50 mol), 136.8 g of 14.62% sodium hydroxide (0.50 mol) and after 15 min. stirring 50.8 grams of a 44.4% aqueous solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous solution of sodium hydroxide (0.503 mol). After stirring the reaction mixture for 1 hour at the boiling point, toluene was distilled off with steam, 150 ml of acetone were added to the residue, and after cooling, filtering, washing and drying, 119 g of a product containing 67.8% terbutryne and 30.9% terbutylazine were obtained.

b)

336.3 g were dissolved in 2500 cm ^{3 of} toluene

2,4-dichloro-6-methylthio-s-triazine (1.72 mol) and 139.7 g of cyanuric chloride (0.76 mol). 256.9 g of a 71.16% aqueous solution of t-butylamine (2.50 moles), 687.4 grams of a 14.62% aqueous sodium hydroxide solution (2.51 moles) were added adiabatically to the obtained solution. mol). The reaction mixture was then kept at reflux for 1 hour, the aqueous layer was separated and the solvent was distilled off with water vapor from the toluene solution. 1000 cm ^{3 of} acetone was added to the residue, the mixture was cooled at 29 ° C, the solid crystalline material was filtered off, washed with 500 cm ^{3 of} water and dried to constant weight. 560 g of a product containing 72.1% terbutryne and 27.3% terbutylazine were obtained.

Example 4

The procedure was as in Example 1 except that 88.23 g of 2,4-dichloro-6-methyltlo-s-triazine (0.45 mol) and 9.3 g of cyanuric chloride (0) were added to 500 cm ^{3 of} toluene. , 05 mole),

51.9 g of a 70.4% aqueous solution of t-butylamine (0.5 mol), 136.8 g of a 14.62% aqueous sodium hydroxide solution (0.5 mol). After distilling off toluene, addition of acetone and further conventional work-up, 120.0 g of product were obtained containing 11.4% terbutylazine and 88% terbutryne.

Example 5

49.02 g were dissolved in 500 cm ^{3 of} toluene

2,4-dichloro-6-methylthio-s-triazine (0.25 mol), 46.1 g of cyanuric chloride (0.25 mol) and 49.1 g of a 60.2% aqueous solution were added with stirring. isopropylamine (0.5 mol) and 133.4 g of a 15.0% aqueous sodium hydroxide solution (0.5 mol). After stirring for 30 minutes, 53.7 g of a 42.0% aqueous solution of ethylamine (0.5 mol) and 133.4 g of a 15.0% aqueous solution of sodium hydroxide (0.5 mol) were added to the reaction mixture. The reaction mixture was then stirred for an additional 1 hour at the boiling point of the reaction mixture. Thereafter, toluene was distilled off with water, 125 cm ^{3 of} acetone were added to the residue, the reaction mixture was cooled to 20 ° C with stirring, the precipitated crystalline product was filtered off, washed with 250 ml of water and dried to constant weight.

107.5 g of product were obtained which, according to analysis, contained 49.3% atrazine and 49.4% and 49.4% amethylene.

Claims (2)

SUBJECT Process for the preparation of a physico-chemical mixture of a 2,4-bis-alkylamino-6-chloro-s-triazine with 2,4-bis-alkylamino-6-methylthio-s-triazine, characterized in that a mixture of cyanuric chloride with 2,4,4-dichloro-6-methylthio-s-triazine in a non-polar organic solvent is reacted with an equal amount of alkylamine in general of formula I R ¹ NH ₂ (I) wherein R ¹ is an alkyl of 1 to 5 carbon atoms with the same amount of an alkylamine of formula II R 2 NH ₂ (II) wherein R ² is alkyl of 1 to 5 carbon atoms each in the presence of sodium hydroxide as a hydrogen chloride binding agent and On removal of the nonpolar solvent, the physical chemieky standing was obtained by crystallisation from 20 to 25% strength aqueous solution of an aliphatic a ketone, wherein the radicals R ¹ and R ² can be the same or different.