CN1685818A

CN1685818A - Simplified production technology of bisultap

Info

Publication number: CN1685818A
Application number: CN 200510057026
Authority: CN
Inventors: 段儒华
Original assignee: Individual
Current assignee: Individual
Priority date: 2005-04-21
Filing date: 2005-04-21
Publication date: 2005-10-26
Anticipated expiration: 2025-04-21
Also published as: CN100410239C

Abstract

A simplified process for preparing the bisultap from dimethylamino acrylate includes such steps as chloridizing addition and direct sulfonating. Its advantages are high output rate, low cost and high purity.

Description

Simplified process for producing dimehypo

One, the technical field

The present invention belongs to agricultural pesticide, and is especially the production process of carbon and sulfur containing organic thiosulfonate compound.

Second, background Art

The insecticidal bis (N, N-dimethylamino-1, 3-sodium dithiosulfonate propane) is a high-efficiency and low-toxicity bionic agricultural insecticide, and the prior art adopts dimethylamino propylene hydrochloride as a starting raw material, adopts three process steps of chlorination addition, low-temperature neutralization and sulfonation to produce the insecticidal bis (N, N-dimethylamino-1, 3-sodium dithiosulfonate). For example, a Chinese patent application with publication No. CN1273240A, 11/15/2000, discloses dissolving dimethylaminopropylene hydrochloride in an organic solvent, introducing dry chlorine gas under anhydrous conditions to complete chlorination addition reaction, adding water, heating to remove all solvents, and obtaining a solution with a content of 45-55 wt% (weight percentage, the same applies hereinafter)Dimethylamino dichloropropane hydrochloride with the meta-acidity of less than 1%; then adding alkali to neutralize under the condition of low temperature to prepare neutral dimethylamino dichloropropane; finally, adding the sodium bicarbonate according to the molar ratio of 1: 1, putting the sodium bicarbonate into water to dissolve the sodium bicarbonate, and sulfonating the mixture for 3 to 4 hours at the temperature of between 10 and 100 ℃ to obtain the bisultap product. The above prior art has the following disadvantages: 1) the anhydrous condition of the chlorination addition reaction system is difficult to ensure by adopting the method of adding water and raising the temperature to remove the solvent, and once a trace amount of water enters the addition system, the method inevitably occurs Further, HClO causes oxidation of dimethylaminopropene hydrochloride, resulting in a decrease in yield; meanwhile, the generated HCl is carried into the dimethylamino dichloropropane hydrochloride by water, so that the acid value is difficult to control below 1 percent. 2) The addition of alkali at low temperature for neutralization increases energy consumption and production cost. 3) The finally obtained bisultap product can only be aqueous solution with the content of about 30 percent, which is not beneficial to the processing of subsequent products and has low yield.

Third, the invention

The invention aims to overcome the defects in the prior art, and provides a simplified production process which is different from the prior process, so that the energy consumption and the production cost in the process are reduced, and a high-content bisultap product is obtained.

The purpose of the invention is realized by adopting the following technical scheme.

A simplified process for producing dimehypo uses dimethylamino propylene hydrochloride as a starting raw material, and is characterized by comprising two steps of chlorination addition and direct sulfonation:

mono) chlorination addition

Dissolving dimethylamino propylene hydrochloride in halogenated alkane organic solvent, introducing dry chlorine under the anhydrous condition of 30-100 ℃ to perform addition reaction to generate dimethylamino dichloropropane hydrochloride, wherein the chemical reaction equation is as follows:

stopping introducing chlorine when the reaction temperature begins to drop; then, the halogenated alkane organic solvent with the amount of 1/3-1/2 is evaporated, cooled to room temperature, crystallized and separated to prepare the solid dimethylamino dichloropropane hydrochloride with the purity of 98 percent and the acid value of less than 0.5 percent. The solid can be directly used as an intermediate for preparing the bisultap.

Di) direct sulfonation

Directly mixing the high-purity low-acid-value solid dimethylamino dichloropropane hydrochloride and sodium thiosulfate prepared in the previous step according to a molar ratio of 1: 1.8-2.4, dissolving the mixture in a polar solvent, selecting a acid beating agent as a catalyst, and carrying out constant-temperature sulfonation reaction for 2-3 hours at the temperature of 30-100 ℃ under a stirring state to generate the N, N-dimethylamino-1, 3-sodium dithiosulfonate propane (dimehypo), wherein the chemical reaction equation is as follows:

when the residual amount of the sodium thiosulfate in the reaction system is less than 4 percent and the residual amount of the dimethylamino dichloropropane hydrochloride is less than 0.3 percent, the temperature is reduced to room temperature, and the bisultap original drug with the content of 35 to 45 percent is obtained.

In the above-mentioned chlorination addition reaction, the haloalkane organic solvent used is preferably dichloroethane, dichloromethane, carbon tetrachloride or chloroform, optionally one of them; the separation is preferably performed by suction filtration, pressure filtration or centrifugation, optionally one of them.

In the above sulfonation, the polar solvent used is preferably water, methanol or ethanol, optionally one of them; the acid agent is preferably KOH or NH₄OH、NaCO₃NaOH or tetraethylammonium bromide, optionally one of them.

Compared with the prior art, the simplified process for producing the dimehypo does not adopt a method of adding water, raising the temperature and removing the reduced solvent in the chlorination addition process and using crystallization separation to remove the reduced solvent, can avoid the defect caused by bringing a small amount of water into a chlorination addition reaction system, can obtain a high-purity and low-acid-value dimehypo intermediate-dimethylamino dichloropropane hydrochloride, and has the yield increased by 5-8 percent; the low-temperature alkali addition neutralization process in the prior art is reduced, so that the energy consumption and the production cost in the process are reduced; the high-purity dimethylamino dichloropropane hydrochloride is directly sulfonated under the action of a selected polar solvent and a acid-beating agent, so that the reaction time is shortened by at least 1 hour, the high-content bisultap raw pesticide can be obtained, convenience is provided for processing subsequent products, and the sulfonation yield is improved by 6-9%. The simplified process for producing dimehypo of the present invention has significant progress and substantive features.

Fourth, detailed description of the invention

The simplified process for producing bisultap according to the invention is further illustrated below by the preparation examples. The first step is as follows: dissolving dimethylamino propylene hydrochloride in dichloroethane solvent, azeotropically removing possible water if necessary, introducing dry chlorine at 40 ℃ to perform chlorination addition reaction, and stopping introducing chlorine when the reaction temperature begins to drop; then the solvent with 1/3 percent in the reaction material flow is distilled off, and then the solid dimethylamino dichloropropane hydrochloride with the purity of 98 percent and the acid value of less than 0.5 percent is obtained by crystallization and suction filtration. The second step is that: directly mixing the high-purity low-acid-value solid dimethylamino dichloropropane hydrochloride and sodium thiosulfate prepared in the previous step according to a molar ratio of 1: 2.08, dissolving the mixture in a methanol solvent, selecting NaOH as a catalyst, carrying out sulfonation reaction for 2-3 hours at the temperature of 60 ℃ under a stirring state, cooling to room temperature when the residual quantity of the sodium thiosulfate in the reaction system is less than 4% and the residual quantity of the dimethylamino dichloropropane hydrochloride is less than 0.3%, and discharging to obtain the bisultap original medicine with the content of 35-40%.

Claims

1. A simplified process for producing dimehypo uses dimethylamino propylene hydrochloride as a starting raw material, and is characterized by comprising two steps of chlorination addition and direct sulfonation: 1) dissolving dimethylaminopropene hydrochloride in a halogenated alkane organic solvent, introducing dry chlorine gas at the temperature of 30-100 ℃ under the anhydrous condition to perform addition reaction to generate dimethylaminopropylene hydrochloride, and stopping introducing the chlorine gas when the reaction temperature begins to drop; then, distilling out the halogenated alkane organic solvent with 1/3-1/2 amount, cooling to room temperature, crystallizing and separating to obtain the high-purity low-acid value solid dimethylamino dichloropropane hydrochloride. 2) Directly mixing the high-purity low-acid-value solid dimethylamino dichloropropane hydrochloride and sodium thiosulfate according to the molar ratio of 1: 2.0-2.4, dissolving the mixture in a polar solvent, selecting a acid beating agent as a catalyst, carrying out constant-temperature sulfonation reaction for 2-3 hours at the temperature of 30-100 ℃ under a stirring state, and cooling to room temperature when the residual quantity of the sodium thiosulfate in the reaction system is less than 4% and the residual quantity of the dimethylamino dichloropropane hydrochloride is less than 0.3%, thereby obtaining the originalinsecticidal medicine.

2. A simplified process for the production of bisultap according to claim 1 wherein during the chlorination addition reaction said haloalkane organic solvent is dichloroethane, dichloromethane, carbon tetrachloride or chloroform, optionally one of them.

3. A simplified process for the production of bisultap according to claim 1, wherein during the chlorination addition reaction, said separation is suction filtration, pressure filtration or centrifugation, optionally one of them.

4. A simplified process for the production of bisultap according to claim 1, wherein during the sulfonation reaction, the polar solvent is water, methanol or ethanol, optionally.

5. A simplified process for the production of bisultap according to claim 1, wherein during the sulfonation reaction, the acid scavenger is KOH or NH₄OH、NaCO₃NaOH or tetraethylammonium bromide, optionally one of them.