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    • 专利摘要:
    There is provided a process, preferably continuous and in a given case successive, substitution of one or two chlorine atoms of cyanuric chloride by one or two amines, which may be the same or different, in the presence of an acid acceptor and in the presence of an organic solvent, particularly for the production of 2-alkylamino-4,6-dichloro and preferably for the production of 2,4-di(alkylamino)-6-chloro-s-triazines wherein there is added 1.00 to 1.05 mole, preferably 1.00 to 1.03 mole of a first amine to a 4.5 to 50 weight % suspension or solution of cyanuric chloride in a mixture of 65 to 85 weight % of xylene, toluene, ethylbenzene, benzene and/or an aliphatic or cycloaliphatic hydrocarbon with 5 to 10 carbon atoms (toluene being preferred) and 35 to 15 weight % of a ketone with 3 to 8 carbon atoms, preferably acetone, while maintaining the temperature between about 0 and about 20 DEG C, preferably about 10 to 18 DEG C., continuously so regulating the pH value of the reaction mixture obtained in accordance with the reaction time by addition of alkali and in a given case, water so that this corresponds to a point within the area bounded by lines ABCD of FIG. 1, which runs through the area beginning with the reaction time t,(step 1)= 0 until reaching a position in the area bounded by the lines BCEF and after reaching a pH of 7.0, preferably 7.2 maintains a temperature of about 10 DEG to about 60 DEG C., preferably about 25 DEG to 40 DEG C., after addition of 0.96 to 1.05, preferably 0.98 to 1.02 equivalents of alkali per mole of cyanuric chloride, adding at least an equimolar amount, preferably 1.00 to 1.02 mole of the second amine per mole of cyanuric chloride and continuously so adjusting the pH value of the reaction mixture obtained depending on the reaction time by addition of alkali that this corresponds to a point within the area which is defined by lines GHIJ in FIG. 3 which passes through the band beginning with the reaction time t(step 2)= 0 of the second reaction step until reaching a position in the area bounded by the lines HIKL and thereby maintaining a temperature of 40 to 70 DEG C., preferably 45 DEG to 55 DEG C. and thereafter working up the product in known manner wherein t1 is a time of 4 to 10 hours, preferably about 7 hours and t2 is a time of 2 to 8 hours, preferably about 6 hours and wherein the B C corresponds to the equation, pH = -(12.6/t1)+ 14.35 and the line H I corresponds to the equation pH = -(24,857/t2)+ 23.9285. There are also disclosed novel, purified mono and bis alkylamino-cyanoalkylalkylamino - s - triazines.
    公开号:SU725556A1
    申请号:SU2323877
    申请日:1976-02-10
    公开日:1980-03-30
    发明作者:Хашке Хайнц；Шрайер Герд；Шварце Вернер；Зухсланд Хельмут
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    I
    The invention relates to an improved method for the sequential replacement of chlorine atoms of cyanuric chloride with amines to form 2-alkylamino-4,6-dichloro- or 2,4-bis-dialkylamino-6-chloro-c "l-triazines", which are used as herbicides. and raw materials for their synthesis.
    A known method for producing 2,4-di- (alkylamine) -6-chloro-syl of lg-triazines by successively replacing chlorine in cyanure chloride with two identical or different amines in an organic solvent, such as toluene, benzene, carbon tetrachloride, in the presence of an acid acceptor , such as alkali, added periodically 1.
    The disadvantages of this known method are the insufficiently high yield of the target product (no more than 95%) and its contamination with large amounts of by-products.
     There is a known method of successively replacing chlorine in cyanure chloride with two identical or different amines in acetone or a mixture of acetone and water at ~ 20 ° C while adjusting the pH by periodically adding alkali 2.
    The disadvantages of this method are the insufficiently high yield of the target product and their contamination by side products. Thus, the yield of 2-isopropylamino-4-ethylamino-6-chloro-sijlg-triazine is 97.5%; in the case of the synthesis of cyanoalkylamino derivatives, the yield is not higher than 93%.
    Also known is the closest in its effect to the proposed method of successively replacing chlorine atoms of cyanuric chloride with an amine or two identical or different amines in ketones that are limitedly biased with water, for example, methyl ethyl ketone, at a temperature of about 20 ° C and adjusting the pH by periodically adding alkali 3
    The yield of 2,4-dialkylamino-6-chloro-c "lgl-triazines at different amines reaches 97.5% at a frequency of 99.6%.
    The disadvantages of this method are the insufficiently high yields and contamination of the target products with side products.
    The purpose of the invention is to increase the yield of the target product and increase its purity.
    The goal is achieved by the method of sequential replacement of chlorine atoms.
    cyanure chloride amine or two identical or different amines in a mixture of 65-85 weight. % xylene, ethylbenzene, benzene and / or aliphatic and / or cycloaliphatic hydrocarbon with 5-TO carbon atoms and 35-15 weight. % ketone with 3-8 carbon atoms and the pH of the reaction mixture in the first stage of the injection are maintained continuously by adding alkali so that it corresponds to a point inside the region bounded by the ABCD lines (Fig. 1) and the pH of the reaction mixture the region starting from the reaction time t до to values in the region bounded by the BCEF lines, and upon reaching a pH of 7.0-7.2 the temperature of the reaction mixture rises to 10-60 ° C; in the second stage, the pH of the reaction mixture is added by adding alkali so about In order that it corresponds to a point inside the region that is bounded by the GHIJ lines (Fig. 2), at a temperature of 40-70 ° C and the pH of the reaction mixture passes the region starting from the reaction time of the second stage, t O, to the values in the area limited by mi HIKL with ulo-, VII that i 4-10 h and tj 2-8 h, and the line BC. Corresponds to the pH equation - (12,64i) t + 14.35 and the HI line corresponds to the pH equation - (24,857 t g) t + + 23.9285.
    The proposed method is preferably carried out as follows. The process in the first stage begins at 10–18 ° C and 1.00–1.02 mol of the first amine is added to 1 mol of cyanuric chloride and at 25: –40 ° C at the end of the first stage and the temperature increases when the pH reaches 7.2. up to 25-40 ° C and .0.98-1.02 equiv. per 1 mole of cyanurate chloride is added. alkalis, in the second stage, 1, .2 mol of the second amine is added to 1 mol of chlorine cytur used, while the temperature is increased to 45-55 ° C and the above pH of the reaction mixture is adjusted by the alkali, 7 4 , t and 6 h.
    The method is preferably carried out in such a way that, after adding the first one, the reaction mixture is kept under the following conditions at a temperature of 10-18 ° C by adding alkali and keeping the water under known conditions.
    pH Reaction time, min
    1a) 3.5-5.03-43
    16) 4.5-6.250-56
    1 c) 5.5-7.017-189
    1g) 7.0-8.0.30-493
    and a temperature of 10-50 ° C, where stages 1a and 16, 16 and 1b can be either in one, and after adding the second amine, the reaction mixture at 40-70 ° C by adding alkali is maintained under the conditions:
    pH Reaction time, min 2a) 6.5-8.02-60 26) 7.25-9.0О-Я2
    2c) 8.0-10.00-172
    2g) 10.0-11.2515-408
    moreover, stages 2a and 26, 26 and 2c can be combined into one.
    According to the proposed method, the mixture is preferably maintained under the conditions:
    pH Reaction time, min
    1 a) 4.25-4.75
    9-21 16) 5.0-5.5
    3-18 51-93 1c) 5.75-6.25
    at a temperature from 15 to 35 ° C 135-330 1 g) 7.25-7.9 10-30 2a) 6.75-7.25 0-36 26) 7.5-8.0 2c) 8.25-8.75 9-66
    at a temperature
    2 g) 10.25-10.75 45-55 ° С135-306
    With continuous implementation of the method, which is advantageous due to the volume and time yields achieved in this case, it is advisable to use solutions or suspensions of the chemical flux at the end of the concentrate, which is determined by the content of ketone in the organic medium used in the following way.
    The amount of cyanuric chloride is 0.2 times the amount of ketone in the solvent mixture plus 1.5, but not more than K, and
    K is 15, preferably 5.
    The solvent mixture used is from the group of aliphatic hydrocarbons: pentane, hexane, heptane, octane, nonane, decane and / or their isomers, and also tsclolohexane and / or, from the group of aromatic hydrocarbons: benzene, toluene, ethylbenzene or xylenes and one or more ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, ethyl n-amyl ketone, ethyl iso-amyl ketone, or cyclohexanone.
    When synthesizing cyanoalkylaminochlorotriazines, it is especially advantageous to use as a solvent mixtures of 70 wt. % toluene and 30 wt. % ketone, which corresponds to the cyanoalkylamine used, i.e., would give it when interacting with hydrocyanic acid and ammonia.
    Preferably, before or immediately after the start of the addition of the acid acceptor, when adding the first amine, for example, cyanoalkylamine, 0.5 to 25 wt. % of water in relation to the amount of solvent used, i.e. establish the formal composition of the system hydrocarbon (ketone): water-99.5-80 weight. / about a mixture of hydrocarbons - ketone and 0,5-: 20 weight. % water . It is especially advantageous to add enough water to the reaction mixture before the addition of the acid acceptor in the first stage of the reaction; to form a formal mixture of solvents hydrocarbon (ketone): water of composition 99.5-98.0 weight. / about a mixture of hydrocarbons - ketone and 0.5-2 weight. % of water, i.e., taking into account aqueous alkali, to the formal composition of the mixture of hydrocarbons (ketone) water: 95-80 weight. %; preferably 88-
    84 weight. ° / o, a mixture of hydrocarbons (ketone) and 5-20 wt. ° / o, preferably 12-16 wt.%, -, water; water is added only when a pH of at least 4.5, preferably at least 5.0, is reached in the reaction mixture: not dependent on the specified addition of water before or at the beginning of the acid acceptor dosage for the method according to the invention using an acidic agent, it is possible to use aqueous solutions of inorganic bases, i.e. oxides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals; It is preferable to use hydroxides, especially alkali metal hydroxides. They are used preferably in the form of aqueous solutions that contain an acceptor in concentrations of 10-50 wt. %, especially 20-40 weight. %, preferably 20-30 wt.%.
    In carrying out the process of the invention, cyanur chloride is dissolved in or suspended in a mixture of solvents and then solutions or suspensions are sequentially introduced into the reaction with the same or different amines, first to obtain 2-alkylamino-4, b-dichloro-s-triazines and then to 2,4-di- (alkyl-mino) -6-chloro-syzh-triazines. Since the interaction takes place in two separate stages
    In other words, the proposed method is also advantageous for obtaining 2-alkylamino-4,6-dichlorosym-triazino B.
    Suitable amines for the proposed method are 1-cyanoalkylamines- {G), such Kai a-aminoisobutyronitrile (1-cyano-1-methylethylamine- (1)), 1-cyano-T-methylpropylamine, 1-cyano-1,2- dimethylpropylamine, cycloxylate ano-1-aminocyclohexane, as well as simple alkylamines such as methylamine, dimethylamine, ethylamine, n- or isopropylamine, cyclo-35 lopropylamine, ethylenimine or diethylamine. If cyanur chloride is to be converted to 2-alkylamine 6-4,6-dichloro-c ".l g-triazines or to 2,4-di (alkylamino) -6-chloro-c" l "l -triazines with various alkylamine substituents mi in 4- or 6-position, then among these amines G-cyanoalkylamines are preferred. Particularly preferred in all cases is α-aminoisobutyronitrile for introducing the first amino substituent into this triazine topic. As amines for the second stage of the synthesis, simple primary and secondary alkylamines, such as methylamine, dim.ethylamine, α-ethylamine, n- or iso- or cyclopropylamine, ethylene amine or diethylamine, are used. Ethylamine and cyclopropylamine are preferred, 50% ethylamine is particularly preferred.
    According to the method of the invention, Amen is added in molar amounts, relative to extracted cyanuric chloride; a slight excess of amine, maximum 5%, before-. respectfully a maximum of 3% is permitted for the first stage of the reaction, especially if cyanoalkylamine is used. Such an excess is also allowed in the second transformation step, regardless of the type used. Less than molar amounts of amine per mole of cyanuric chloride used, always lead to a decrease in the yield and purity of the product.
    In this case, amines can be used both in pure form and in the form of solutions, in inert solvents, preferably those that must be present in the reaction as components of the hydrocarbon-ketone system, or in the case when it is not about cyanoalkylamine - also in water.
    Cyanoalkylamines can be used in the form of their equilibrium mixture of keton cyanohydrin and ammonia dissolved in stoichiometric (P1 excess ketone.
    The addition of amines or solutions of amines should be done in such a way that, due to the heat of reaction or solvation resulting from this, the temperature of the reaction mixture does not rise above the temperature limits specified for the proposed method. Therefore, the addition of the amine must be carried out correspondingly slower and / or with appropriate cooling. However, the heat of reaction or solvation with the addition of an amine can be used fully or partially directly to establish the appropriate reaction temperature. In particular, this is possible at the beginning of the second stage of the synthesis in the synthesis of 2,4-di- (alkylamino) -6-hlop-cujJI-tryazinov, i.e. with the addition of a second amine.
    The method according to the invention achieves yields of over 99% of theory with a product purity of more than 98 or 99%. Obtained directly by this method after the usual processing products contain less than 0.7 weight. / about unreacted cyanure chloride and / or its hydrolysis products.
    As reaction products according to the method of the invention, depending on the selected initial concentration of cyanuric chloride and depending on the type, i.e. the solubility obtained by the aminochlorotriazine, two- or three-phase mixtures are obtained, the third phase being a solid.
    When processing these products, these phase properties are governed. For example, when preparing 2- (1-cyano-1-methylethylamino) -4-ethylamino-6-chloro of f-triazines, if it comes out of approximately 10% solutions of cyanuric chloride in a mixture of toluene / acetone, at a temperature lower than 40 ° C, clear two-phase solutions are formed which can be easily divided into a lower aqueous acetone containing sodium chloride phase and an upper toluene acetone containing the desired product. Preferably, by treating it therefrom, the product can be obtained by evaporation of the solvent, for example, by distillation or after partial evaporation by spray drying or roller drying.
    A further expedient method is to precipitate the product from the "upper phase by partially evaporating the solvent by concentrating, for example, up to about 50% solids and thus separating the main part using conventional methods of separating the solid, such as centrifugation or filtration, while the mother liquor is returned for concentration. The solvent-free product obtained in this way can then be extinguished: with an electromusher, a fluidized bed dryer, an essence using a tray dryer, or simply in a drying cabinet. Similarly, these methods can also be used: for three-phase reaction mixtures formed by the proposed method, with separation of the solid product before and / or after concentration after separation of the predominant aqueous phase.
    However, it is also possible to precipitate a portion of the product by strongly diluting the reaction mixture with water, separating the precipitated solid and only then process the remaining organic phase by evaporation of the solvent. With this method of processing, there is a danger of decreasing the yield by a certain plant. the product's ability to be in (ketone-containing) water, which plays a significant negative role in the usual previously known methods, in which the desired product must also be washed in order to achieve sufficient product purity.
    2,4-Di-alkylamino-6-chloro-c "l {f-triazines, which can be obtained by the proposed method, correspond to the general formula
     ,,
    VA
    where Ri and Ri are the same or different and denote OH, ORs-, SRs-, CN-groups or halogen atoms substituted under known conditions, linear or branched alkyl with 1-4 carbon atoms, alkenyl, cycloalkyl or methylcyclopropyl, preferably unsubstituted ethyl - or cyclopropyl groups and where RS is an alkyl group with 1-4 carbon atoms and preferably Ri or RI means a hydrogen atom; Rj and R4 can have meanings like R and Ra, however, preferably Rs means a hydrogen atom and R4 is rpynny, B of which Re and R / are the same or different and denote a linear or branched alkyl or alkenyl group with 1-8 carbon atoms which may also be closed to a 5-7 membered ring or cycloalkyl, preferably methyl, methylcyclopropyl or cyclopropyl residue, in particular methyl residue, and also Re or R7 may be a hydrogen atom.
    Preferably, such compounds are prepared in which Ri-R4 means methyl, ethyl, isopropyl and cyclopropyl residue.
    Example 1. A 2-liter, two-liter flask equipped with a mechanical blender, reflux condenser, thermometer, glass electrode (single-strand measuring circuit from Schott and Gen., Jena type N., zero point 7, platinum diaphragm; calibrated with water buffer solutions: pH 7 (phosphate) and pH 9 (boric acid - sodium hydroxide solution (CS), a dropping funnel and a cooling bath, put a 10% solution
    5 92.2 g (0.5 mol) of cyanur chloride in 829.8 g of a mixture containing 70 toluene and 30 wt. ° / o acetone (650.9 g of toluene and 278.9 g of acetone). With stirring, the solution is cooled to, then 44.6 g of 98 / o is added dropwise over the course of 20 minutes.
     (0.52 mol) a-aminoisobutyronitrile. After that, 15 ml of water is added and a 25% aqueous solution of sodium hydroxide is added dropwise. Additive caustic soda is carried out continuously and in this way
    S to maintain the following pH dependency - time:
    At the beginning of the addition of caustic soda pH 3.5;
    26 minutes after the start of the addition of caustic soda pH 5.5;
     After 51 minutes from the start of the addition of caustic soda, 140 ml of water was added and the pH was adjusted to 6.5 by adding caustic soda.
    77 minutes after the start of the addition
    J caustic soda pH 7.0;
    103 min - pH 7.5; 129 minutes the temperature of the reaction mixture rises to S5 ° C and the pH is set to 7.5 by dosage of caustic soda; After 154 min. PH, 7;
    about 180 min. pH 7.7.
    Overall, 79 g of 25 /% caustic soda solution is added. Then, over the next 20 minutes, 57.1 g of a 50% aqueous solution of cyclopropylamine is added dropwise and the reaction mixture is then heated to 50 °. Upon reaching this temperature (after 15 minutes) an additional amount of 25% sodium hydroxide is added, and again continuously, on the next course of the pH – time dependence; at the beginning of the second addition of caustic soda pH 8.5. 17 minutes after the start of the second addition of caustic soda pH 9.5; after 34 minutes - pH 10.5; after 51 minutes the pH is 10.5; after 69 minutes - pH 10.5; after 86 minutes - pH 10.5; after 103 min - pH 10.5; after
    120 min - pH 10.5;
    A total of 81 g of caustic soda (25 ° / o) was added with a second addition of caustic soda. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase is discarded, the organic phase, together with the parts crystallized out of it, is evaporated to dryness in vacuo and then the residue is dried in vacuum at 60 ° C to constant weight. Obtain 120.1 g of the product, which according to the analysis contains 99.8% of 2- (1-cyano-1-methylethylamino) -4-cyclopropylamino-6-chlorosyl-triazine and which corresponds to 99.6% of the theoretical yield. Example 2. In a continuously operating equipment to the current of a 10% aqueous solution of cyanuric chloride in a mixture of 65 wt. % toluene and 35 wt. % acetone was continuously added to 1.02 mol of a-amino-isobutyronitrile per 1 mol of cyanurum chloride. The mixture is maintained at a temperature of + 10 ° C with cooling and immediately after the preparation of this mixture, i.e., after all the x-aminoisobutyronitrile has been added, it is fed to a cascade of reactors. The volume of the cascade consisting of 4 reactors is measured in such a way that the average residence time in it is 20, then 10, then 70, and finally, 175 minutes. The temperatures of the reaction mixture in individual reactors are maintained at 10.10, 10, respectively. Sp.C. In addition, in the first reactor of the cascade, they were continuously introduced in 6s, and at such a rate that 27 g of 1 h of water were introduced at a speed of 1 mol / h of triazine. In addition, by continuously supplying a 25% sodium hydroxide solution and a pH of 4.6 in the first cascade of the reactor (measured with a glass electrode as described in Example 1). Water and a 25% sodium hydroxide solution are also added to the product in the second stage of the reactor, namely water is added per 1 mole of the triazine to be consumed at a rate of 240 g / h; caustic soda is added so that pH 5.0 is constantly maintained. In the third and even-hearth reactors by supplying a 25% aqueous solution of caustic soda and in such a way that the pH of the third stage of the reactor is maintained at 6.0 and in the fourth cascade of the reactor - pH 7.8. The reaction mixture leaving the fourth cascade reactor, in the mixing nozzle, is shifted with 50% aqueous ethylamine and with a speed ratio of 1 mol / h of ethylamine to 1 mol / h of consumable triazine. The reaction mixture, using the heat of displacement of both components and lightly heated, is brought to a temperature of 50 ° C, immediately introduced into the second cascade of reactors, again consisting of four reactors. In the first reactor of this second cascade, a pH of 7.1 is maintained by the continuous addition of a 25% sodium hydroxide solution, in the second reactor of this second cascade by
    725556
    10 additions of a 25% sodium hydroxide solution maintain a pH of 7.6, in the third reactor of this second cascade also maintain a pH of 7.8 in the fourth (last) reactor of this second cascade by adding a 25% aqueous solution of sodium hydroxide. 10.4 (again, by continuously adding 25% sodium hydroxide solution). The volumes of the individual cascade reactors are sized in such a way that they correspond to the average residence time of the continuous current of the product — 20, then 10, 35, 175 minutes. All reactors of the first and also of the second cascade are equipped with a well-functioning stirring system, so that the stratification of the reaction mixtures contained in them is impossible, and homogeneous suspensions Or solutions from the reactor come to the nearest / e. The reaction mixture leaving the last (4th) reactor of the second cascade is fed to an automatic phase separator, in which the upper phase is continuously separated through a density regulator and fed to an apparatus for evaporation of the solvent. From the latter, 98.5% 2- (1-cyano-1-methylethylamino) -4-ethylamino-6-chloro-syzh and triazine is obtained by continuous separation with a yield of 99% of theory (in terms of cyanuric chloride introduced at the beginning of the reaction). 2- (1; Cyano-1-methylethylamino) -4,6-dichloro-sylzh-triazine and 2,4-diethylamino-6-chloro-cml-triazine are not detected in the product by thin layer chromatography. The wastewater leaving the phase separator, after the distillation contains acetone contained in it, contains practically common salt along with traces of cyanuric acid. Example 3. In a device similar to Example 1, a 10% solution of 92.2 g (0.5 mol) of cyanuric chloride and 829.8 g of a mixture consisting of 70 wt. % Α-xylene and 30% acetone (650.9 g α-xylene and 278.9 g acetone). The reactor is cooled to 10 ° C with stirring, then 44.6 g of a 98% solution (0.52 mol) (x-aminoisobutyronitrile) are added dropwise over 20 minutes (x-aminoisobutyronitrile is added. 15 ml of water are added and the addition is started dropwise a 25% aqueous solution of caustic soda. Addition of caustic soda occurs continuously, namely in such a way that the following mode of pH change over time is maintained. By the time the caustic soda is added, the pH is 3.3. 26 minutes after the start of the addition of caustic sodium pH 5.5. After 51 min after the start of the addition of sodium hydroxide, about Regular 140 ml of water and set the pH to 6.5 by changing the rate of addition of caustic soda. 77 minutes after the start of the addition of caustic soda pH 7.0, 103 minutes after the start of the addition of caustic soda pH 7.5. The start of the addition of caustic soda is increased to 35 ° C and the pH is adjusted to pH 7.6 by varying the rate of addition of caustic soda 154 minutes after the start of the addition of caustic soda pH 7.7. 180 minutes after the start of the addition of caustic soda pH 7.7. A total of 79 g of a 25 ° / caustic soda solution was added. Thereafter, over the next 20 minutes, 57.1 g of a BO / O-HOH solution of cyclopropylamine in water is added dropwise, and then the reaction mixture is heated to 50 ° C. Upon reaching this temperature (after 15 minutes), 25 ° / s of caustic soda solution is continuously added again, observing the following mode of changing the pH values with time. By the beginning of the second stage of the addition of caustic soda pH 8.3; 7 minutes after the start of the second stage of the addition of caustic soda pH 9.5; after 34 minutes the pH is 10.5; after 51 minutes the pH is 10.5; after 69 minutes the pH is 10.5; after 86 minutes the pH is 10.5; after 103 minutes the pH is 10.5; after 120 minutes the pH is 10.5. In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase is discarded, the organic phase, together with the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 119.86 g of a product is obtained, containing the results of an analysis of 99.5% of 2- (1-cyano-1-methylethylamino) -4-cyclopropylamino-6-chloro-syl {. (Triazine), which corresponds to 99 , 5% of the theoretical yield of the pure product. Example 4. A 10% solution of 92.2 g (0.5 mol) of cyanuric chloride is placed in 829.8 g of a mixture consisting of 80% i-xylene and 20% methyl ethyl ketone ( 663.8 g of g-xylene and 166.0 g of methyl ethyl ketone.) The solution is cooled to 10 ° C while being transferred, then 44.6 g of a 98% solution (0.52 mol) are added dropwise within 20 minutes α-aminoisobutyronitrile. Then add 15 ml of water and start iribavlenie dropwise a 25% aqueous solution of caustic soda. Adding caustic soda occurs continuously, namely in such a way that the following mode changes in pH over time is maintained. By the time the caustic soda is added, pH 3.6; minutes after the start of the addition of sodium hydroxide, pH 5.5; after the following 51 minutes, the next 140 ml of water is added and the pH is adjusted to 6.5 by changing the speed of addition of sodium hydroxide; after 77 min. pH 7.0; after 103 minutes the pH is 7.5; after 129 minutes, the temperature of the reaction mixture is raised to 35 ° C and the pH is adjusted to 7.6 by varying the rate of addition of caustic soda; after 154 minutes the pH is 7.7; after 180 minutes the pH is 7.7. 79 g of a 25% solution are added in total. 7 6 Thereafter, over the next 20 minutes, 57.1 g of a 50% aqueous solution of cyclopropylamine is added dropwise and then the reaction mixture is heated to 50 ° C. When this temperature is reached (after 15 min), a 25% solution of sodium hydroxide solution is again started to be added continuously, observing the following mode of changing pH pH over time. . By the time the second stage of the addition of caustic soda is added, the pH is 8.4 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; after 34 minutes the pH is 10.5; after 51 minutes the pH is 10.5; after 69 minutes the pH is 10.5; after 86 minutes the pH is 10.5; after 103 minutes the pH is 10.5; after 120 minutes the pH is 10.5. In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone, and thereafter the phases are separated at 45 ° C. The aqueous phase is discarded; the organic phase, together with the crystallized part, is evaporated to dryness in vacuum, then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 119.61 g of a product consisting of 99.7% of 2- (1-cyano-1-methylethylamino) -4-cyclopropylMino-6-chloro-strength (.d-triazine, corresponding to 99.1% of the theoretical yield of the pure product. Example 5. In a device analogous to example 1, put a 10% solution of 92.2 g (0.5 mol) of cyanuric chloride in 829.8 g of a mixture consisting of 75 weight % cellosolve and 25% by weight acetone (622.4 g cellosolve and 207.5 g acetone). The solution is cooled to 10 ° C while being transported, then 44.6 g 98% - is added dropwise over the course of 20 minutes. solution (0.52 mol) of a-aminoisobutyronitrile After that, 15 ml of water are added and a 25% aqueous solution of sodium hydroxide is added dropwise. The sodium hydroxide is added continuously, in such a way that it is maintained after the next pH regime with time. soda pH 3.4; after 26 minutes from the start of the addition the pH is 5.5; after 51 minutes the next 140 ml of water is added and the pH is adjusted to 6.5 by changing the speed of the addition of sodium hydroxide; after 77 minutes the pH is 7.0; after 129 minutes, the temperature of the reaction mixture is raised to 35 ° C and the pH is adjusted to 7.6 by varying the rate of addition of caustic soda; after 154 minutes the pH is 7.7; after 180 minutes the pH is 7.7; A total of 79 g of a 25% sodium hydroxide solution was added. Thereafter, over the next 20 minutes, 57.1 g of a 50% aqueous solution of cyclopropylamine was added dropwise and then the reaction mixture was heated to 50 ° C. When this temperature is reached (after 15 minutes), a 25% solution of sodium hydroxide is continuously added again.
    13, observe the following mode of pH change over time: By the time the second stage of the addition of caustic soda is added, pH 8.6; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; after 51 minutes the pH is 10.5; after 69 minutes the pH is 10.5; after 86 minutes the pH is 10.5; after 103 minutes the pH is 10.5; after 120 minutes the pH is 10.5. In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase is discarded; the organic phase, together with the crystallized part, is evaporated to dryness in vacuum, and the residue is dried in vacuum at 60 ° C to constant weight. Thus, 119.61 g of a product is obtained, which according to the analysis contains 99.6% of 2- (1-cyano-1-methylethylamino) -4-cyclopropylamino-b-chloro-syl-triazine, which corresponds to 99, from the theoretical yield of the pure product . Example 6. In a device analogous to Example 1, a U / O solution of 92.2 g (0.5 mol) of cyanur chloride was placed in 829.8 g of a mixture consisting of 70 wt. % toluene and 30 wt. % acetone (650 g of toluene and 278.9 g of acetone). The solution is cooled to 10 ° C with stirring, then 43.8 g of freshly distilled 98% (the rest is water) a-aminoisobutyronitrile is added dropwise over the course of 20 minutes. After that, 15 ml of water is added and the addition of 25 / o BojiHoro sodium hydroxide solution is started dropwise. Addition of caustic soda occurs continuously, namely in such a way that the following regime of pH changes over time is maintained. By the time the sodium hydroxide is added, pH 3.5; after 26 minutes the pH is 5.5; after 51 minutes, the following 140 ml of water are added, and the pH: 6.5 pH by changing the speed of adding caustic soda; after 77 minutes the pH is 7.0; after 103 minutes the pH is 7.5; after 129 minutes, the temperature of the reaction mixture is raised to 30 ° C and adjusted to pH 7.6 by varying the rate of addition of caustic soda; after 154 minutes the pH is 7.7; after 180 minutes the pH is 7.7: A total of 79 g of 25% sodium hydroxide solution is added. Thereafter, over the next 20 minutes, 31.3 g of a 50 ° aqueous aqueous solution of methylamine was added dropwise, and then the reaction mixture was heated to 50 ° C. When this temperature is reached (after 15 minutes), a 25 ° / s solution of caustic soda is continuously added again, observing the following mode of changing the pH value over time. By the beginning of the second stage of addition of caustic soda pH 8.5; after 7 minutes
    725556
    14 after the start of the second stage of addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 51 minutes after the start of the second stage of adding caustic soda pH 10.5, 69 minutes after the start of the second stage of adding caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of the addition of caustic soda pH 10.5. In total, 81 g of a 25% -ijoro sodium hydroxide solution was added during the second stage of addition of caustic soda. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase is discarded, the organic phase, together with the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 113.22 g of product are obtained, according to the results of the analysis of 99.8% of 2- (1 cyano-1-methylethylamino) -4-methylamino-6-chloro-c "LJ-triazine, which corresponds to 99.7% of theoretical yield of pure product. Example 7. A 10% solution of 92.2 g (0.5 mol) of cyanuric chloride in 829.8 g of a mixture consisting of 70 wt. % toluene and 30 wt. % acetone (650.9 g of toluene and 278.9 g of acetone). The solution is cooled to 10 ° C with stirring, then 43.8 g of freshly distilled 98% -– is added dropwise over the course of 20 minutes. Go (the rest is water) a-amin6 isobutyronitrile. After that, 15 ml of water is added and a 25% aqueous solution of sodium hydroxide is added dropwise. Addition of caustic soda occurs continuously, namely in such a way that the following mode of pH change is maintained over time: by the time the caustic soda is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after starting the addition of caustic soda, add the following 140 ml of water and adjust the pH to 6.5 by varying the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; after 103 minutes the pH is 7.5; 129 minutes after the start of the addition of sodium hydroxide, the temperature of the reaction mixture is raised to 30 ° C and the pH is adjusted to 7.6 by changing the speed of the addition of sodium hydroxide; 154 minutes after the start of the addition of caustic soda pH 7.7; after 180 minutes the pH is 7.7. A total of 79 g of a 25% sodium hydroxide solution was added. Thereafter, over the next 20 minutes, 59.7 g of a mixture consisting of 50:50 weight is added dropwise. including Isopropylamine and water, and then the reaction mixture is heated to 50 ° C. When this temperature is reached (after 15 min), ШШ; it is not recommended to add 25 ° /-. Of sodium hydroxide solution continuously, observe the following mode of pH values changing over time: by the time the second turn of sodium hydroxide is added, pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of the addition of caustic soda pH 10.5. In total, 81 g of a 25 /% caustic soda solution was added during the second stage of addition of caustic soda. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase is discarded, the organic phase, together with the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuum to constant weight at 60 ° C. Thus, 126.98 g of product is obtained, containing, according to the results of the analysis, 99.8% of 2- (1-cyano-1-methylethylamine) -4-isopropylamino-6-chloro-c "l" Lg-triazine, which corresponds to 99.5% of the theoretical yield of the pure product. Example 8. In a device analogous to Example 1, a 10 / o-th solution of 92.2 (0.5 mol) of cyanur chloride in an 829.8 g mixture consisting of 70 wt. % toluene. and 30 wt. % acetone (650.9 g of toluene and 278.9 g of acetone). The solution is cooled to 10 ° C with stirring, then 43.8 g of freshly distilled 98% (the rest is water) a-aminoisobutyronitrile is added dropwise over the course of 20 minutes. After that, 15 ml of water are added and a 25% solution of sodium hydroxide is added dropwise. The addition of caustic jaTpa occurs continuously, in such a way that the following mode of pH change is maintained at the time when sodium hydroxide is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after starting the addition of caustic soda, add the following 140 ml of water and adjust: pH 6.5 by changing the rate of addition of caustic soda; 77 minutes after the start of the addition, the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda pH 7.5; 129 minutes after the start of the addition of caustic soda, the temperature of the reaction mixture is increased to 30 ° C and the pH is adjusted to 7.6 by changing the speed of the addition of caustic soda; 154 minutes after the start of the addition of caustic soda pH 7.7; 180 minutes after the start of the addition of caustic soda pH 7.7. A total of 79 g of a 25% sodium hydroxide solution is added. After this, over the next 20 minutes, 57.7 g of a mixture consisting of equal parts by weight of cyclopropylamine and water are added dropwise, and then the reaction mixture is heated to 50 ° C. Upon reaching this temperature (after 15 minutes), 25 ° / s of caustic soda solution is continuously added again, observing the following mode of changing the pH values with time. By the beginning of the second stage of the addition of caustic soda pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of the addition of caustic soda pH 10.5. In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at. The aqueous phase is discarded, the organic phase, together with the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 126.10 g of product is obtained. the one containing, according to the results of the analysis, 99.8% of 2- (1-cyano-1-methylethylamino) -4-cyclopropylamino-6-chloro-sil {.l-triazine, which corresponds to 99.6% of the theoretical yield of the pure product. Example 9. In a device analogous to Example 1, a 10% solution of 92.2 g (0.5 mol) of cyanuric chloride was placed in 829.8 g of a mixture consisting of 70 wt. % toluene and 30 wt. % acetone (650.9 g of toluene and 278.8 g of acetone). The solution is cooled to 0 ° C with stirring, then 29.7 g of isopropylamine is added dropwise over 20 days. After that, 15 ml of water is added and a 25% aqueous solution of sodium hydroxide is added dropwise. Addition of caustic soda occurs continuously, namely in such a way that the following mode of pH change is maintained over time: by the time the caustic soda is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after the start of the addition of caustic soda, the following 140 ml of water was added and the pH was adjusted to 6.5 by changing the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda 7.5; 129 minutes after the start of the addition of sodium hydroxide, the temperature of the reaction mixture is raised to 20 ° C and the pH is adjusted to 7.6 by changing the speed of the addition of sodium hydroxide; 154 minutes after the start of the addition of caustic soda pH 7.7; 180 minutes after the start of the addition of caustic soda pH 7.7.
    A total of 79 g of a 25% sodium hydroxide solution was added: After this, 45.5 g of a 50% aqueous solution of ethylamine was added dropwise over the next 20 minutes and then the reaction mixture was heated to 50 ° C. When this temperature is reached (after 15 minutes), a 25% sodium hydroxide solution is started to be added continuously, observing the following changes in pH in time:
    by the beginning of the second stage of the addition of caustic soda pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5, 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of the addition of caustic soda pH 10.5.
    In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added.
    The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase together with the precipitated product is carefully separated, the separating funnel is washed with acetone from traces of precipitate and the resulting suspension in a mixture of acetone and toluene after adding about 50 ml of toluene is washed with water (without entrainment of the solid phase) until chlorine ions are left in the washing water. The resulting (mostly) toluene suspension of the triazine, together with the other organic phase, and the crystallized portion is evaporated to dryness in vacuo, and then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 107 g of a product is obtained, which according to the results of analysis contains 99.8% of 2-isopropylamino-4-ethyl-b-chloro-cslc-triazine (“atrazine), which corresponds to 99.0% of the theoretical yield of the pure product.
    Example 10. In a device similar to example 1, put the Schwee. An o / solution of 92.2 g (0.5 mol) of cyanuric chloride in 829.8 g of a mixture consisting of 70 wt. % toluene and 30% acetone (650.9 g of toluene and 278.9 g of acetone).
    The solution is cooled to 10 ° C with stirring, then 29.9 g of isopropylamine is added dropwise over the course of 20 minutes. After that, 15 ml of water is added and a 25% aqueous solution of sodium hydroxide is added dropwise. Addition of caustic soda occurs continuously, namely in such a way that the following regime of pH changes over time is maintained:
    by the time the sodium hydroxide is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after starting the addition of caustic soda, add the following 140 ml of water and adjust the pH to 6.5 by varying the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda pH 7.5; 129 minutes after the start of the addition of sodium hydroxide, the temperature of the reaction mixture is raised to 30 ° C and the pH is adjusted to 7.6 by changing the speed of the addition of sodium hydroxide; after 154 minutes after the addition of caustic soda pH 7.7; 180 minutes after the start of the addition of caustic soda pH 7.7.
    A total of 79 g of a 25% sodium hydroxide solution was added. Thereafter, over the next 20 minutes, 30.1 g of isopropylamine is added dropwise, and then the reaction mixture is heated to 50 ° C. Upon reaching this temperature (after 15 minutes), a 25% solution of sodium hydroxide is continuously started to be added again, observing the following mode of change:
    by the beginning of the second stage of the addition of caustic soda pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second order of addition of caustic soda, pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second addition of caustic soda pH 10.5.
    In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added.
    The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase together with the precipitated product is carefully separated, the separating funnel is washed with acetone from traces of sediment and the suspension obtained in a mixture of acetone and toluene after adding about 500 ml of toluene is washed with water (without entrainment of solids) until the hlbr ions are washed out. The mainly obtained toluene suspension of triazine together with another organic phase and crystallized
    part is evaporated in a vacuum to dryness, and the residue is dried in vacuum at 60 ° C to constant weight. Thus, 114.7 g of a product is obtained, containing, according to the results of analysis, 99.8% of 2,4-bis-isopropylamino-6-chloro-symm-1 griazine (propazine), which corresponds to 99.7% of the theoretical
    5th
    1ShShSh Estrgo g1rb1ukta:., - ..
     Example 11. In a device analogous to Example 1, a U / o solution of 92.2 g (0.5 mol) of cyanuric chloride was placed in 829.8 g mixture, consisting of. 70 weight. % toluene and 30 wt. % acetone (650.9 g of toluene and 278.9 g of acetone).
    The solution is cooled to 20 ° C with stirring, then, over the course of 20 minutes, it is added -: dropwise 46 g of 50 / o-nogov 6diggb ethylamine solution. After that, 15 ml of water is added and the addition of 25% aqueous sodium hydroxide solution is started drop by drop. Addition of caustic soda occurs continuously, 9 in such a way that the following regime of pH change over time is maintained.
    By the time the sodium hydroxide is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after starting the addition of caustic soda, add the following 140 ml of water and adjust the pH to 6.5 by varying the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda pH 7.5; 129 minutes after the start of the addition of sodium hydroxide, the temperature of the reaction mixture is raised to 30 ° C and the pH is adjusted to 7.6 by changing the speed of the addition of sodium hydroxide; at J54 min after the start of the addition of caustic soda pH 7.7; 180 minutes after the start of the addition of caustic soda pH 7.7.
    A total of 79 g of 25 /% caustic soda solution was added. After this, 47 g of a 50% aqueous ethylamine solution is added dropwise over the next 20 minutes and then the reaction mixture is heated to 50 ° C. Upon reaching this temperature (after 15 minutes), a 25% solution of caustic soda is added again continuously, observing the following mode of pH value changes over time; ..
    by the beginning of the second stage of the addition of caustic soda pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second addition phase, the pH is 10.5; 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of addition of caustic soda pH
    10.5 ....;;,;;. ::.: ,,. ; .. d, ..; , -,,
    In total, during the second stage of addition of caustic soda, 81 g of a 25% solution of caustic soda was added.
    The resulting reaction mixture was diluted with 20 ml of acetone and this was carried out. phase separation at 45 ° C. The aqueous phase together with the precipitated product is carefully separated, the separating funnel is washed with acetone from traces of precipitate and the resulting suspension in a mixture of acetone and toluene after adding about 500 ml more, the toluene is washed with water (without: entrainment of the solid phase) until chlorine ions are not in the washing water. The resulting (mainly) toluene suspension of triazine, together with the other organic phase and the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuum at 60 ° C to constant weight. Thus, 100.9 g of the Product are obtained, containing, according to the results of the analysis, 99.8% of 2.4-b "c-ethylamino-6-chloro-cmll-triazine, which corresponds to 99.9% of the theoretical yield of the pure product.
    Example 12. In a device similar to Example 1, a 10% solution of 92.2 g (0.5 mol) of cyanurum in 829.8 g of a mixture consisting of 70 wt. % toluene and 30 wt. % acetone (650.9-g toluene and 278.9 g acetone).
    The solution is cooled to 0 ° C with stirring, then 57.5 g of a mixture consisting of equal parts by weight of cyclopropylamine and water is added dropwise over the course of 20 minutes. After this, 15 ml of water are added and the solution is dropped. m 25% aqueous solution of caustic soda. Addition of caustic soda occurs continuously, namely in such a way that the following regime of pH change over time is maintained: - -. - -:. .
    by the time you start adding caustic. pH 3.5. 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after the start of the addition of caustic soda at .. g., the next 140 ml of water is added and the pH is adjusted to 5.5 by changing the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda pH 7.5; 129 minutes after the start of the addition of sodium hydroxide, the temperature of the reaction mixture is raised to 10 ° C and the pH is adjusted to 7.6 by varying the rate of addition of dilute sodium; 154 minutes after the start of the addition of caustic soda pH 7.7; 180 minutes after the start of the addition of caustic soda pH 7.7.
    权利要求:
    Claims (3)
    [1]
    A total of 79 g of a 25% sodium hydroxide solution was added. Thereafter, over the next 20 minutes, 45.5 g of a 55-50% ethylamine aqueous solution is added dropwise and then the reaction mixture is heated to 50 ° C. Upon reaching this temperature (after 15 minutes), I begin to continuously add 25% sodium hydroxide solution, observing the following mode of pH change over time: by the time the second stage of sodium hydroxide is added, pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 51 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after: the beginning of the second stage of the addition of caustic soda pH 10.5; after 103 min. after the start of the second stage of addition of caustic soda pH 10.5; 120 minutes after the start of the second addition of caustic soda, pH 10.5. , In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase together with the precipitated product is carefully separated, divide; the funnel is washed with acetone from traces of sediment and the resulting suspension in a mixture of acetone and toluene after adding about 500 ml of toluene, washed with water (without entrainment of solids) until there are no ions in the washing water chlorine. The resulting mainly toluene suspension of triazine, together with the other organic phase and the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuo at 60 ° C to constant weight. Thus, 106.5 g of a product is obtained, which according to the results of analysis contains 99.8% of 2-cyclopropylamino-4-ethylamino-6-chloro-c "l-triazine, which corresponds to 99.5% of the theoretical yield of the pure product. Example 13. In a device analogous to example 1, a 10% solution of 92.2 g (0.5 mol) of cyanuric chloride and 829.8 g of a mixture consisting of 70 wt. % toluene and 30 wt. % acetone (650.9 g of toluene and 278.9 g of acetone). The solution is cooled to 0 ° C, with stirring, then 57.2 g of a mixture consisting of equal parts by weight of allylamine and water are added in -caps for 20 minutes. After that, 15 ml of water is added and a 25% aqueous solution of sodium hydroxide is added dropwise. Addition of caustic soda occurs continuously, namely in such a way that the following mode of pH change is maintained over time: by the time the caustic soda is added, pH 3.5; 26 minutes after the start of the addition of caustic soda pH 5.5; 51 minutes after the start of the addition of caustic soda, add the following 140 ml of water and adjust the pH to 6.5 by varying the rate of addition of caustic soda; 77 minutes after the start of the addition of caustic soda pH 7.0; 103 minutes after the start of the addition of caustic soda pH 7.5; after 129 Ain, after starting the addition of caustic soda, the temperature of the reaction mixture is increased to 10 ° C and the pH is adjusted to 7.6 by changing the rate of addition of caustic soda; 154 minutes after the start of the addition of caustic soda pH 7.7; after 180 minutes after the start of the addition of caustic soda pH 7.7. A total of 79 g of a 25% sodium hydroxide solution was added. After that, over the next 20 minutes, 59.5 g of a mixture of isopropylamine and water are added dropwise with their weight ratio of 1: 1 and then the reaction mixture is heated to 50 ° C. When this temperature is reached (after 15 minutes), a 25% sodium hydroxide solution is again started to be added continuously, observing the following mode of changing the pH value over time. By the beginning of the second stage of the addition of caustic soda pH 8.5; 17 minutes after the start of the second stage of the addition of caustic soda pH 9.5; 34 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 5 Gmin after the start of the second stage of the addition of caustic soda pH 10.5; 69 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 86 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 103 minutes after the start of the second stage of the addition of caustic soda pH 10.5; 120 minutes after the start of the second stage of the addition of caustic soda pH 10.5. In total, during the second stage of addition of caustic soda, 81 g of 25% aqueous solution of caustic soda was added. The resulting reaction mixture is diluted with 200 ml of acetone and then the phases are separated at 45 ° C. The aqueous phase together with the precipitated product is carefully separated, the separating funnel is washed with acetone from traces of precipitate and the resulting suspension in a mixture of acetone and toluene after adding about 500 ml of toluene is washed with water (without entrainment of solids) until chlorine ions are absent in the washing water. The resulting (mainly) toluene suspension of triazine, together with the other organic phase and the crystallized portion, is evaporated to dryness in vacuo, and then the residue is dried in vacuo at 60 ° C to constant n. weight. Thus, 113.0 g of a product is obtained, which according to the results of the analysis contains 99.8% of 2-allylamino-4-isopropyl-amino-6-x-Lor-c "yl-triazine", which corresponds to 99.1% of the theoretical yield of the pure product. The invention of the method of sequential replacement of chlorine atoms of cyanuric chloride with an amine or two identical or different
    amines in organic solvents (when adjusting the pH by adding alkali), in order to increase the yield of the target product and increase its purity, the process is carried out in a mixture of 65-85 wt.% xylene, ethylbenzene, benzene and / or aliphatic and / or cycloaliphatic hydrocarbon with 5–10 carbon atoms and 35–15 w / v ketone with 3–8 carbon atoms and the pH of the reaction mixture in the first aminating step, depending on the reaction time, are maintained continuously by adding alkali so that it matched the point inside the region bounded by the AVSD lines (Fig. 1) and the pH of the reaction mixture passed through the region starting from the reaction time t до to values in the region bounded by the BCEF lines and upon reaching pH 7.0-7.2 the temperature of the reaction mixture increases up to 10-60 ° C, in the second stage, the pH of the reaction mixture is added by adding alkali in such a way that it corresponds to a point inside the region that is limited to the GHIJ lines (Fig. 2) at 40-70 ° C and the pH of the reaction mixture passes the region starting with the reaction time of the second stage t до to values the area bounded by the HIKL lines under conditions that ti 4-104nta 2-8 h and the BC line corresponds to the pH equation - (12.6 t,) t 4 14.35 and the HI line corresponds to the pH equation - (24.857 t g) t + -4- 23.9285.
    [2]
    2. The method of claim 1, wherein the process in the first stage starts at 10-18 ° C and 1.00-1.02 mol of the first amine is added per 1 mol of cyanurum and at 25-40 ° C at the end of the first stage and upon reaching a pH of 7.2, the temperature rises to 25-40 ° C, and 0.98-1.02 eq. per 1 mole of cyanure chloride is added. alkalis, in the second stage, 1.00-1.02 mol of the second amine are added per 1 mol of the cyanuric chloride used, while the temperature rises to 45-55 ° C, with ti 7 h, ta - 6 h.
    [3]
    3. Method according to paragraphs. 1 and 2, characterized in that, after adding the first amine, the reaction mixture is kept under the following conditions at 10-18 ° C by adding alkali and dosing water under the known conditions
    pH Reaction time, min
    1 a) 3.5-5.03-43
    16) 4.5-6: 250-56
    1c) 5.5-7.0.17-189
    1g) 7.0-8.030-493
    and a temperature of 10-50 ° C, and stages 1a and 16, 16 and 1b can be combined into one, and after adding the second amine, the reaction mixture at 40-70 ° C by adding alkali is maintained under the conditions:
    pH Reaction time, min
    2a) 6.5-8.02-60
    26) 7.25-9.00-92
    2c) 8-10.0 and at the temperature О-172 2g) 10.0-11.2545-55 ° С15-408
    moreover, stages 2a and 26, 26 and 2c can be combined into one. 4. The method according to claims. , characterized in that the mixture is kept under conditions
    5 p H Reaction time, min
    1a) 4.25-4.75.9--21
    16) 5.0-5.5 3-18
    IB) 5.75-6.25 and at a temperature of 51-93 1 g) 7.25-7.90 15-35 ° С135-330
    2a) 6.75-7.2510-30
    26) 7.5-8.00-36
    2c) 8.25-8.75 and at a temperature of 9-66 2g) 10.25-10.7545-55 ° С135-306
    Sources of information taken into account in the examination 5 1. US Patent No. 3590040, cl. 260-249.5, pub. 1971.
    2. The patent of Germany No. 1670541, cl. 12 p 10/05, published 1974.
    3. Forward number 1695117,
    cl. 12 p 10/05, published 1974 (prototype).
    pH 7
    , {D
    f / j ZHh ft 1/7 L // 7 "/ 7 tf Vui.l
    i2 / e 3i2 / g ftz / e stij tz FIG. 2
    Reaction time
    Reaction time t
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    同族专利:
    公开号 | 公开日
    IL49013A|1980-02-29|
    BE838471A|1976-08-11|
    JPS51105085A|1976-09-17|
    ES444742A1|1977-08-16|
    IL49013D0|1976-04-30|
    BR7600819A|1976-09-14|
    IT1060487B|1982-08-20|
    NL7600865A|1976-08-16|
    FR2300764A1|1976-09-10|
    AT350578B|1979-06-11|
    ZA76831B|1977-01-26|
    CH626355A5|1981-11-13|
    DD124383A5|1977-02-16|
    MX4470E|1982-05-18|
    DE2505704A1|1976-08-26|
    SU725556A3|1980-03-30|
    AU1103776A|1977-08-18|
    GB1523362A|1978-08-31|
    CA1041508A|1978-10-31|
    ATA96376A|1978-11-15|
    DE2505704B2|1979-12-13|
    DE2505704C3|1980-08-21|
    RO76667A|1981-04-30|
    HU175456B|1980-08-28|
    FR2300764B1|1980-05-09|
    US4058662A|1977-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3244712A|1960-02-19|1966-04-05|Geigy Ag J R|Acylamino symmetrical triazines|
    CH476746A|1965-12-13|1969-08-15|Agripat Sa|Process for the preparation of chloro-diamino-s-triazines|
    US3505325A|1966-07-16|1970-04-07|Degussa|Cyanoalkylamino substituted triazines having plant growth regulating action|
    CH546247A|1968-12-27|1974-02-28|Agripat Sa|ADIABATIC PROCESS FOR THE PREPARATION OF N-MONOSUBSTITUTED 2,4-DICHLORO-6-AMINO-S-TRIAZINES.|
    US3766182A|1971-05-26|1973-10-16|Ciba Geigy Corp|S-triazine derivatives|
    US3821220A|1972-01-04|1974-06-28|Ciba Geigy Corp|Reducing hydrogen cyanide levels in the formation of cyanoalkylamino substituted triazines|
    US3947374A|1973-03-21|1976-03-30|American Cyanamid Company|Substituted halotriazines as peroxygen bleach activators|IT1027241B|1975-01-03|1978-11-20|Rumianca Spa|PROCEDURE FOR THE PRODUCTION OF CHLORINE AMINO S TRIAZINE|
    IT1081516B|1977-07-07|1985-05-21|Rumianca Spa|PROCEDURE FOR THE PRODUCTION OF CHLORINE-BIS-S-TRIAZINE|
    US4166909A|1978-01-23|1979-09-04|Shell Oil Company|Process for preparation of a substituted triazine|
    IT1099676B|1978-09-29|1985-09-28|Rumianca Spa|PROCEDURE FOR THE PREPARATION OF CHLORINE-BIS-S-TRIAZINE|
    DE2912267A1|1979-03-28|1980-10-09|Rumianca Spa|Continuous prepn. of herbicidal triazine - from cyanuric chloride and amine in two=stage tubular reactor|
    US4275204A|1979-09-07|1981-06-23|Rumianca S.P.A.|Preparation of chloro-bis-s-triazines|
    US4224444A|1979-10-01|1980-09-23|Rumianca S.P.A.|Process for the preparation of chloro-bis-s-triazines|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2505704A|DE2505704C3|1975-02-12|1975-02-12|Process for the preparation of optionally substituted 2-alkylamino-4,6-dichloro-s-triazines and 2,4-bis-alkylamino-6-chloro-s-triazines|
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