UA30599C2 - A method for preparation of potassium (1,1-dioxothiolane-3-yl) dithiocarbamate - Google Patents

Abstract

(1,1-dioxothiolane-3-yl) of potassium dithiocarbamate is prepared in an interaction of (1,1-dioxothiolane-3-yl) of potassium hydroxide with hydrogen sulphide in a solution of ethyl alcohol by a simultaneous dosing of amine and potassium hydroxide solution in ethyl alcohol in a solution of hydrogen sulphide in ethyl alcohol, separation of a residue, rinse of a product in 3 stages and drying, where a mixture of 85-90 % amine and 10-15 % of ethyl alcohol is taken for dosing, and a pure alcohol is substituted by a principal (aldehyde-ether) fraction of ethyl alcohol and by an ethyl alcohol, regenerated from the waste products obtained during this process, and the rinse of the product is carried out in 3 stages on the filter drying it each time in the vacuum. The resulted dried product contains 99.3-99.5 % (1,1-dioxothiolane-3-yl) of potassium dithiocarbamate, the rest is water, with an output of 87.1-87.8 %, amine is not crystallized in the measurer, pipelines and accessories, improving dosing conditions, reducing the costs of energy and price of raw material.

Description

Description of the invention

The invention relates to the chemistry of heterocyclic sulfur compounds, in particular to the production of (1,1-dioxothiolan-3-yl)2 potassium dithiocarbamate, which is a highly effective fungicide for agriculture.

Known /1/ method of obtaining (1,1-dioxothiolan-Z-yl) potassium dithiocarbamate (DTDTK) by the interaction of (1,1-dioxothiolan-Z-yl) amine (ZAS) and potassium hydroxide with carbon disulfide in a solution of ethyl alcohol at a temperature of 2 - 7"С by supplying amine (Amin is the abbreviated name of the starting material of the production of DTDTK, which includes 85 - 9095 (1,1-dioxothiolan-3-yl)uamine and impurities obtained as a result of its production.) with 70 speed 0.045 - 0 .05 mol/min ZAS per kg of carbon disulfide in a mixture containing 30 - 4595 mass of ethyl alcohol and 50 - 7090 of carbon disulfide with simultaneous feeding after 1 - 7 minutes at the same rate of 25 - 2795 (mass) of a solution of potassium hydroxide in ethyl alcohol alcohol to the molar ratio of loaded carbon disulfides: amine (1.05...1.10) 1.0, with further treatment of the reaction mass with a solution of potassium hydroxide to pH 7U.5 - 8.5. The precipitate is separated, washed with ethyl alcohol and dried. Yield DTDTK is 75 - 8090.

Disadvantages of method e: 1) low yield of the product and the presence of unidentified impurities in it; 2) crystallization of part of the reaction products (up to 7 - 1595 of the total mass of the obtained DTDTK) on the inner surfaces of the reactor in the form of a solid layer that impairs heat transfer and requires additional operations to remove it; 3) the need to use a low-temperature coolant (-5...-575).

The closest technical essence to the proposed method is the method /2/ of obtaining DTDTK by the interaction of (1,1-dioxothiolan-3-yl)amine and potassium hydroxide with carbon disulfide in an ethyl alcohol solution at -3570 with simultaneous dosing of a potassium hydroxide solution in ethyl alcohol and amine in the molar ratio of potassium hydroxide to ZAS (1.2...1.33 : 1.0 in a solution of carbon disulfide in ethyl alcohol up to 25 seconds, setting the molar ratio of loaded ZAS and carbon disulfide (0.08...0, 13) : (1.10...1.20). Then Ge) the feed rate of potassium hydroxide is reduced until the ratio of it to the fed ZAS is established (0.95...1.053 : 1.00. Reagents are fed until the the molar ratio of the loaded ZAS and carbon disulfide is 1.00: (1.10...1.20). The temperature of the reaction mixture after the supply of 70 - 8095 of the starting amine is raised to 37 - 40"C and maintained after the completion of the supply of the starting reagents for 70 - 10 minutes Me.

The reaction mixture is treated with potassium hydroxide until the pH is 8.5 - 9.5. The precipitation of DTDTK that fell, Ge"! filtered, washed on the filter with an equal amount of ethyl alcohol and dried. The output of DIDTK is 85 - 90905. o

The disadvantages of the method are the instability of the DTDTK yield when the process is implemented in factory conditions, which is caused by its dependence on the accuracy of the dosing of components, which is difficult to maintain stable with the help of dosing pumps due to high viscosities (2.07 - 10 m/s at 202) of amine and, especially, about its crystallization temperature (1572). During dosing, amine crystallizes in the meter, pipelines, pump, and fittings, disrupting the operation of the dosing pump and the ratio of reactants during the reaction. At the same time, the adhesion of reaction products to the walls increases, decreases to 70 - 7195 output of DTDTK to (1,1-thioxothiolan-3-yl) amine, " and the heat exchange conditions deteriorate, the productivity of the installation decreases, and the working conditions deteriorate. A decrease in the viscosity and crystallization of the amine by heating it in the gauge and pipelines can cause its decomposition and lead to an increase in energy costs for heating the amine and, especially, for cooling the reaction mixture (the process takes place with absorption of a large amount of heat (87.5 kJ/mol). The disadvantages are also the presence of unidentified impurities in the obtained DTDTK up to 5595, high costs for raw materials (ethyl alcohol).

The invention is based on the task of developing a method of obtaining (1,1-dioxothiolan-3-yl) dithiocarbamate with 15 potassium, which would allow to improve the conditions of the process on factory equipment, eliminate amine crystallization in pipelines, gauges, fittings, stabilize and increase the yield of DTDTK , to increase (а) its content in the product, to get rid of unidentified impurities in it, to increase the productivity of the installation, and to reduce the costs of raw materials and energy costs.

The task is performed by using instead of amine a mixture that includes 85 - 9095 amine (se) 50 and 10 - 1595 ethyl alcohol, due to the more complete removal of the liquid phase in which the impurities are dissolved, from the sediment with a vacuum after each stage of washing, using of the main (aldehyde-ether) fraction of ethyl alcohol and regenerated alcohol instead of pure ethyl alcohol.

The product obtained in this way due to better washing contains 99.3 - 99.5 (1,1-dioxothiolan-3-yl) potassium dithiocarbamate. Reducing the viscosity of the flow, which includes the amine, and lowering its crystallization temperature to -8...-10"C made it possible to improve the operation of the dosing pumps and obtain the output of DTDTK in factory conditions

GF) more than 8790, get rid of energy costs for heating pipelines, pump, meter, reduce costs of 7 raw materials due to the use of a cheaper (10 times) main fraction of ethyl alcohol and ethyl alcohol regenerated from waste after separation and washing. In order to obtain (1,1-dioxothiolan-3-yl) potassium dithiocarbamate, the following reagents are used: because bis (1,1-dioxothiolan-3-yl) amine no more than 4.0 accommodates up to 2 95 aldehydes, ketones, higher alcohols, carboxylic acids; (AEF)

Before use, potassium hydroxide is dissolved from the purified main fraction of ethyl alcohol (AEF) or in

RES to obtain 23.395 solution.

The essence of the proposed invention is explained by examples. Experiments are carried out in the laboratory in the conditions of the sector of experimental installations of the Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine and the experimental and production sector of the Ukrainian Research Institute of Synthetic Fiber.

Example 1.

19Okg of amine containing 9095 (1,1-dioxothiolan-3-yl) amine and 1Okg of pre-prepared AEF are loaded into a reactor with a stirrer with a volume of 0.250m3, mixed for 10 minutes and 200kg of a mixture containing 9595 (wt. ) of amine and 590 AEF. Similarly, a mixture containing 1095, 1595, 2090 AEF, as well as 1090 regenerated alcohol is obtained. Measure the viscosity of the obtained mixture samples and the temperature of the beginning of crystallization.

Example 2.

The experiment is carried out in laboratory conditions. 63 g of carbon disulfide and 37 g of ethyl alcohol are loaded into a reactor with a volume of 0.5 l, located in a bath with cold water. A mixture of amine (9095) and AEF (10905) is fed into the resulting mixture at a temperature of 207 and constant mixing at a rate of 0.05Omol/min. (1,1-dioxothiolan-Z-yl) amine per 1 kg of carbon disulfide and 2595 potassium hydroxide solution in AEF at a rate of 0.0 bOmol/min. per kg of carbon disulfide (that is, at a molar ratio to ZAS of 1.2 : 1.0). The temperature of the reaction mixture is maintained at the level of 25 - 307 by supplying cold water to the bath. After reaching a molar ratio of 0.10 : 1.15 between the ZAS and carbon disulfide fed into the reactor, the rate of supply of the potassium hydroxide solution is set to 0.05Omol/min. per kg of carbon disulfide (molar ratio to ZAS, serving 1.00 : 1.00). After reaching a molar ratio of 0.75 : 1.15 of the supplied ZAS and carbon disulfide, the temperature of the reaction mixture is raised to 40"C and (o) the process is carried out until the ratio of the supplied ZAS and carbon disulfide is 1.0 : 1.15. Dosing of reagents is stopped, the reaction mixture is mixed at 40"C for another 90 minutes, then a solution of potassium hydroxide is added to it until the pH of the medium is 9.0. The reaction mixture is fed to a filter where the sediment (DGDTC) is separated, which is washed three times with Fü zr by AEF and dried on the filter with the help of a vacuum. The sediment is unloaded from the filter, spread on clean paper and dried to a constant mass. The obtained product is analyzed. (22)

The method of determining DTDT is based on the decomposition of diluted with sulfuric acid (1,1-dioxothiolan-3-yl) and potassium dithiocarbamate to the salt (1,1-dioxothiolan-3-yl) amine and the subsequent determination of its concentration by titration with sodium hydroxide /3/. The method for determining water is based on drying the product in a vacuum to a constant (2 ov Mass. | | | | | s

A total of 165.1 g of a white crystalline product is obtained, containing (mass fractions in 9b): (1,1-dioxothiolan-3-yl) potassium dithiocarbamate 99.8 water 0.2

The yield of DTDTK in the calculation of ZAS is 92,965. no) with Example 3. "» The experiment (according to the prototype) is carried out in laboratory conditions similar to that described in example 1 with " the difference that instead of the mixture of amine with AEF, amine is taken instead of AEF for the reaction and washes use pure ethyl alcohol. Washing is carried out in 3 steps without drying the sediment in a vacuum. The results are shown in the table. o Example 4. o The experiment is carried out on factory equipment in the conditions of experimental production. 30.9 kg of carbon disulfide and 1 bkg of AEF (Zamas. 90) are loaded into a 200-liter stirred reactor. A mixture of amine (95965) with

Te) 20 AEF (595) at a rate of 0.05Omol/min (1,1-dioxothiolan-Z-yl)amine per kg of carbon disulfide and 2595 (wt.) potassium hydroxide solution in AEF at a rate of 0.0bOmol/min per kg of carbon disulfide (that is, with a molar ratio to amine of 1.2: 1.0). The temperature of the reaction mixture, which rises rapidly due to the heat released as a result of the reaction, is maintained at the level of 25 - 30"C by supplying cold water to the cooling jacket of the reactor.

After reaching a molar ratio of 0.10 : 1.15 fed into the ZAS reactor and carbon disulfide, the speed 22 of supplying the potassium hydroxide solution is set to 0.05 Omol/min per 1 kg of carbon disulfide (molar ratio to

F! ZAS serving 1.00 : 1.00). After reaching a molar ratio of 0.75: 1.16 of the supplied ZAS and carbon disulfide, the temperature of the reaction mixture is raised to 40"C and the process is continued until the ratio of the supplied ZAS and carbon disulfide (1: 1.15) is reached for another 90 minutes, then the solution is fed into the reactor of potassium hydroxide until the pH of the medium reaches 9.0. The reaction suspension is fed to a filter where the sediment is separated (DTDTK), which is washed three times at 60, removing the liquid phase each time with the help of a vacuum (dried). The wet sediment is shaken onto pallets covered with porous material, for example, paper and dried to a constant weight.The resulting powdery product is analyzed.

A total of 75.6 bkg of a white crystalline product is obtained, containing (mass fractions in 95): 65 1,1-diocothiolayl-3-yl) potassium dithiocarbamate 99.3 water 0.7

The yield of DTDTK on amine is - 87.1905.

Examples 5-9

Experiments are carried out similarly to example 4, changing the composition of the mixture of ZAS with AEF or RES, obtained according to example 1. In example 9 (prototype), an amine without alcohol content is used, as a solvent for carbon disulfide and potassium hydroxide, RES is used, washing is carried out as in example 3. Results obtained are given in the table.

From the above results, it can be seen that the use in the process of obtaining (1,1-dioxothiolan-3-yl) potassium dithiocarbamate in factory conditions of a mixture of (1,1-dioxothiolan-3-yl) amine with alcohol, the main fraction (aldehyde-ether) of ethyl alcohol or regenerated from waste obtained after the DTDT production process and more complete removal under vacuum of the liquid phase after each washing step allows to increase the DTDT content in the product to 99.3 - 99.595, to obtain a stable product yield of 87.1 - 87.895, in 36 times to reduce the cost of ethyl alcohol, that is, to reduce the cost of raw materials by 3795, to improve the conditions of the process, to get rid of the need to heat and clean the meter, pipelines and fittings, to stabilize the operation of the dosing pumps, and, thus, to increase the productivity of the installation.

Viscosity |Temperature Output Mass Mass Mass Mass fate

Mass Mass Mass crystallization mixture |IDTDTK, 90% product share water share |unidentified share share share share (At 207С, mixture "C reaction, kgIDdDTDTK in impurity in the product, 90 t tk tina of the product, In the product, in yuu zv00t5vabolvvveya00200000000

Zeroyutt 000100001020700092o00vo0, ble 9t900002. 19, vv vva vm tv6veo11111 sch 00180910,0013zvy00076 vya tv62)0vabi000000003000 in vv 5014181 lm vtrotvo,yao6 in yu003000t5)000 vv, v?)tvv; web in v19, rva00t8, v; tvo)yao6 I prototiti bo! 3171111 2otyuim?o o tb2,v2b el oB 77720 F

INFORMATION SOURCES USED. F 1. A, p. Mo1408781 (USSR), cl. SO7D 333/48. - 1986 iv) 2. A.s. Mo1489145 (USSR), cl. SO7D 333/48. 3. Sulfocarbathion-K. Technical conditions of TU U 88.264.038-97. about co

Claims (1)

The formula of the invention The method of obtaining potassium (1,1-dioxothiolan-3-yl)u-dithiocarbamate by simultaneous dosing of a solution of 470 potassium hydroxide in ethyl alcohol and (1,1-dioxothiolan-3-yl)u-amine (ZAS) in molar ratios - c (1.2...1.3)3 : 1.0 in a solution of carbon disulfide in ethyl alcohol at a temperature of 25-35917 until the molar ratio of loaded ZAS and carbon disulfide is established (0.08...0.13 ) : (1.10...1.20), a further decrease in the rate of "supply of potassium hydroxide until the molar ratio of it to the supplied ZAS is established, (0.95...1.05) : 1.00, dosing of reagents before setting the molar ratio of loaded ZAS and carbon disulfide 1.00: (1.10...1.20), raising the temperature of the reaction mixture after feeding 70-80 95 amine to 37-40 9C and maintaining it after the end of dosing for 70- 100 minutes, treatment of the reaction mixture with potassium hydroxide until the pH is set to 8.5-9.5, separation of the (1,1-dioxothiolan-3Z-yl)-dithiocarbamate (DTDTK) precipitate on the filter and subsequent washing with with an equal amount of ethyl alcohol in three doses, which differs in that instead of pure amine, a mixture containing (wt. 95): se) amine 85-90 Fo ethyl alcohol 10-15 HF) washing of the obtained DTDTK is carried out in C methods, drying the sediment each time with a vacuum, and instead of pure ethyl alcohol in the process, the main (aldehyde-ether) fraction of ethyl alcohol and ethyl alcohol regenerated from waste obtained after the process are used. 60 Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2003, M 1, 15.01.2003. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. b5