RU2135480C1 - Method of synthesis of n-(heterocyclylaminocarbonyl)-aryl- -sulfoneamide alkaline salts as water-soluble granules - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: invention describes a method of synthesis of N-(heterocyclylaminocarbonyl)-arylsulfoneamides alkaline salts of the formula (I) where R₁ - Cl, COOCH₃; R₂ is CH₄,OCH₃; R₃ is CH₃; X is N, CH; M is Na, K as water-soluble granules that is carried out by interaction of equimolar amounts of the corresponding N-(heterocyclylaminocarbonyl)- -arylsulfoneamide (IV) and alkaline metal hydroxide followed by obtained salt granulation. Method is characterized in that salt producing, its crystallization and granulation is carried out in the single unit in fluidized layer by continuous feeding the dispersed an aqueous solution of alkaline metal hydroxide at concentration 35%, not less, and preferably 40-44% on layer of solid particles consisting of compounds (IV) and (I) and with addition of surface-active substance moving at the rate 3-11 m/s. Process is carried out at 20-40 C and at moisture 14%, not above, and preferably at 8-12%. EFFECT: high quality of the end product. 4 ex

Description

где R₁ - Cl, COOCH₃; R₂ - CH₃, OCH₃, R₃ - CH₃; X - N, CH, M - Na, K, более конкретно к способу получения натриевых и калиевых солей хлорсульфурона II и сульфометуронметила III.The invention relates to a method for producing sodium and potassium salts of N-heterocyclylaminocarbonyl / arylsulfonamides of the general formula

where R ₁ is Cl, COOCH ₃ ; R ₂ is CH ₃ , OCH ₃ , R ₃ is CH ₃ ; X - N, CH, M - Na, K, and more particularly to a method for producing sodium and potassium salts of chlorosulfuron II and sulfomethuronomethyl III.

Соединения II и III используются в качестве гербицидов в посевах сельскохозяйственных культур, в посадках различных древесных пород против однолетних и многолетних трав, а также для сплошного уничтожения растительности на полотне железных дорог, аэродромов и др. /патенты СССР N 1435141, N 1836014; патент США N 4721520 /1988/; Н.Н.Мельников и др. Справочник "Пестициды и регуляторы роста растений", Москва, "Химия", 1995, стр. 145, 189/.

Compounds II and III are used as herbicides in crops of crops, in the plantings of various tree species against annual and perennial grasses, as well as for the complete destruction of vegetation on the canvas of railways, airfields, etc. / USSR patents N 1435141, N 1836014; U.S. Patent No. 4,721,520 / 1988 /; NN Melnikov et al. Handbook "Pesticides and Plant Growth Regulators", Moscow, "Chemistry", 1995, p. 145, 189 /.

где R₁, R₂, R₃, X, M имеют вышеуказанные значения /патент США N 4127405 и патент ЕПВ N 559044/.These compounds are usually prepared by reacting the corresponding N- / heterocyclylaminocarbonyl / arylsulfonamides with aqueous alkali solutions, taken in equivalent amounts, by reaction

where R ₁ , R ₂ , R ₃ , X, M have the above meanings / US patent N 4127405 and EPO patent N 559044 /.

 Under laboratory conditions, it is relatively easy to obtain a small amount of salt of satisfactory quality from this reaction. Sulfonylureas IV are poorly soluble in water, so the reaction is usually carried out in a water-alcohol medium.

 In industrial conditions, reactor-type apparatuses are used. The resulting salt is crystallized, filtered and dried, then a formulation is prepared from it, which is also a multi-stage process. In general, the process is associated with the consumption of a large amount of solvent, the need for its regeneration, the creation of capture systems and ensure explosion safety.

 The resulting salt quickly coalesces, which creates problems with its further use for the preparation of the formulation. The experiments showed the unsuitability of this method of producing salts of I under experimental industrial conditions.

 In accordance with the present invention, the problems were solved by carrying out the process of obtaining salts of formula I, and at the same time their crystallization and granulation in the fluidized bed, as well as by determining the technological parameters, the combination of which allows the process to be obtained and products that meet the requirements of the consumer, and suitable for use for the purpose indicated above.

 A known process for producing a granular formulation of N- / heterocyclylaminocarbonyl / arylsulfonamide in a fluidized bed by supplying water to a moving bed of material from a pre-ground mixture of ingredients including an active substance, a surfactant and an inert carrier / cm. US Pat. U.S. Patent No. 4,127,405, p. 23 /.

 A feature of the proposed process is that upon contact of the dispersed alkali solution and solid sulfonylurea IV, it occurs over a period of time, determined mainly by the crystallization rate. The chemical reaction of salt formation, its crystallization and the formation of granules.

To carry out the process according to the proposed method, a dispersed alkali solution of a concentration of at least 35%, preferably 40 to 44%, is continuously fed to a layer of solid particles consisting of sulfonylurea IV and salt I with the addition of a surfactant and moving at a speed of 3-11 m / sec, which is created by a rotating device. The temperature should be maintained in the range of 20 - 40 ^o C, and humidity not higher than 14%, preferably 8-12%.

 Only if all of the above conditions are met, the maximum contact surface of the solid and liquid phases is provided, which is necessary for the complete chemical reaction and optimal heat transfer, and phenomena such as channel formation, aggregation, and mainly the possibility of decomposition of thermally unstable target products are excluded.

 The proposed method has a simple technological design, the process of salt formation, its crystallization and granulation is carried out in one device. At the same time, due to the lack of dust particles and explosive products, additional dust removal and explosion suppression systems are not required.

 The proposed method provides a very high quality of the resulting preparations both in the content of the active substance, and in the particle size distribution and the shape of the granules. The products have a good presentation, are easy to use, do not cake during storage.

 The resulting water-soluble granules can be used for the preparation of solutions, as well as directly by embedding in the soil or treating plants.

 The following are examples of the method.

 Example 1. Obtaining potassium salt of chlorosulfuron.

In a device with a capacity of 7 liters with a jacket into which water is supplied, and a mixing device for the sublayer of particles of chlorosulfuron and retur from its potassium salt and sodium lignosulfonate moving at a speed of 10-11 m / s, a 43% solution of potassium hydroxide in dispersed the state in the amount of 0.6 kg / h, the humidity of the reaction mass is 8%, temperature 20 - 30 ^o C.

Salt crystallization time 10 minutes. At the end of the process, the granules are dried by supplying hot water to the jacket. The potassium salt of chlorosulfuron is obtained with a quantitative yield in the form of round-shaped granules. The active substance content is 92%, the surfactant is 4%. Granulometric composition: less than 0.2 mm - 5%
0.2 - 1.5 mm - 80%
more than 1.5 mm - 15%.

 Example 2. Obtaining the sodium salt of chlorosulfuron.

In a device with a capacity of 7 liters with a jacket into which water is supplied, a 40% solution of sodium hydroxide in a dispersed state is supplied in a quantity of 0 to a sublayer of particles of chlorosulfuron, a retur of its sodium salt and sodium alkylbenzenesulfonate, moving at a speed of 3-6 m / s 5 kg / hour. The humidity of the reaction mass is 10%, a temperature of 30 - 40 ^o C.

 The crystallization time of salt is 12 minutes. The granulate obtained is dried by supplying hot water to the jacket. Sodium salt of chlorosulfuron is obtained with a quantitative yield in the form of round-shaped granules of the following composition: less than 0.2 mm - 7%; 0.2 - 2 mm - 75%; more than 2 mm - 18%.

 The active substance content of 94%, surfactant 2%.

 Example 3. Obtaining a potassium salt of sulfometuronmethyl.

In a device with a capacity of 7 liters with a jacket into which water is supplied and a mixing device on the sublayer of sulfometuronomethyl, retur of its potassium salt and surfactant / sulfite-yeast mash, SBD /, moving at a speed of 9-11 m / sec., Are fed 43% solution of potassium hydroxide in a dispersed state in an amount of 0.4 kg / h, a temperature of 20 - 30 ^o C, humidity 12%. Salt crystallization time 20 minutes. The granulate is dried by supplying hot water to the shirt. The yield is quantitative, the active substance content in granules is 92%, surfactant is 5%, composition: less than 0.2 mm - 2%, 0.2 - 2 mm - 80%, more than 2 mm - 18%. Productivity was 1 kg / hour.

 Example 4. Obtaining the sodium salt of sulfometuronomethyl.

In a device with a capacity of 7 liters with a jacket into which water is supplied, and a mixing device on the sublayer of sulfomethuronomethyl, retur of its sodium salt and surfactants / sodium alkylbenzenesulfonate /, moving at a speed of 6-9 m / sec., A 35% sodium hydroxide solution is supplied in a dispersed state in an amount of 0.5 kg / h, a temperature of 20 - 30 ^o C, humidity 8%. Salt crystallization time 20 min. The granulate is dried by supplying hot water to the shirt.

 The product is obtained in quantitative yield in the form of rounded granules of the following composition: less than 0.2 mm - 16%, 0.2 - 2 mm - 75%, more than 2 mm - 9%. The content of the active substance is 93%, surfactant is 4%.

Claims (1)

The method of producing alkaline salts of N- (heterocyclylaminocarbonyl) arylsulfonamides of the formula I

where R ₁ is СI, СООСН ₃ ;
R ₂ is CH ₃ , OCH ₃ ;
R ₃ is CH ₃ ;
X is N, CH;
M - Na, K,
in the form of water-soluble granules by the interaction of equimolar amounts of the corresponding N- (heterocyclylaminocarbonyl) arylsulfonamide of the formula IV
and alkali metal hydroxide and granulation of the obtained salt, characterized in that the preparation of salt, its crystallization and granulation is carried out in one apparatus in a fluidized bed by continuously supplying a dispersed aqueous solution of alkali metal hydroxide with a concentration of at least 35%, preferably 40 to 44%, per layer solid particles, consisting of compounds IV and I with the addition of a surfactant moving at a speed of 3 to 11 m / s, and the process is carried out at 20 to 40 ^o C and a moisture content of not more than 14%, preferably 8 to 12%.