CN100410239C - Simplified production technology of bisultap - Google Patents
Simplified production technology of bisultap Download PDFInfo
- Publication number
- CN100410239C CN100410239C CNB2005100570260A CN200510057026A CN100410239C CN 100410239 C CN100410239 C CN 100410239C CN B2005100570260 A CNB2005100570260 A CN B2005100570260A CN 200510057026 A CN200510057026 A CN 200510057026A CN 100410239 C CN100410239 C CN 100410239C
- Authority
- CN
- China
- Prior art keywords
- hydrochloride
- dimethylin
- disosultap
- dimehypo
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention belongs to an agricultural pesticide, and relates to a simplified technology for producing dimehypo. Dimethylamino propene hydrochloride is used as an initial raw material, and the present invention is characterized in that the agricultural pesticide is prepared through a chlorination addition process and a direct sulphonation process. When the simplified technology for producing dimehypo of the present invention is compared with the prior art, a water addition heating method is not used for eluting and decomposing a solvent in the chlorination addition process, but a crystallisation separation method is used for eluting and decomposing the solvent. The defect caused by that a small amount of water is carried in a chlorination addition reaction system can be avoided, and simultaneously, a dimehypo intermediate body, namely the dimethylamino propene hydrochloride, with high purity and low acid values can be obtained. The yield of the dimehypo intermediate body can also be increased by 5 to 8%. A low temperature alkali addition neutralization process of the prior art is eliminated so as to reduce energy consumption and production cost in technical processes. The dimethylamino propene hydrochloride with high purify is directly sulfonated under the action of an acid-binding agent in an adopted polar solvent, the reaction time is shortened by at least 1 hour, a dimehypo original agricultural chemical with high content can also be obtained, which provides convenience for the processing of subsequent products. Simultaneously, the sulfonation yield is also enhanced by 6 to 9%.
Description
One, technical field
The invention belongs to the what agricultural insecticide, the production technique of the thiosulfonates organic compound of particularly a kind of carbon containing and sulphur.
Two, background technology
Disosultap (N, N-dimethyl amido-1,3-dithio sodium sulfonate group propane) is a kind of bionical agricultural insecticide of efficient, low toxicity, prior art all is to do initial raw material with dimethylin propylene hydrochloride, adopt the chlorination addition, the low temperature neutralization, and then sulfonated three step process process is produced.For example, it is open that the Chinese invention patent that a publication number is arranged is CN1273240A applies on November 15th, 2000, it is that dimethylin propylene hydrochloride is dissolved in the organic solvent, under anhydrous condition, feed dry chlorine gas earlier and finish the chlorination addition reaction, add the water intensification again and remove whole solvents, obtain content between 45-55% (weight percentage, as follows), acidity is at the dimethylin propylene dichloride hydrochloride below 1%; Under cold condition, add the alkali neutralization then, make neutral dimethylin propylene dichloride; Add sodium thiosulfate and drop into by 1: 1 mol ratio at last and make it dissolving in the water, under 10-100 ℃ of temperature condition sulfonation reaction 3-4 hour, obtain the disosultap product.There is following defective in above-mentioned prior art: 1) adopt to add the water way that removes solvent that heats up and be difficult to guarantee the anhydrous condition of chlorination addition reaction system, add architectonical in case there is the water of trace to enter, H must take place
2O+Cl
2The reaction of → HClO+HCl, and then, yield is reduced by the oxidation that HClO causes dimethylin propylene hydrochloride; The HCl of Sheng Chenging can be brought in the dimethylin propylene dichloride hydrochloride by water again simultaneously, makes acid number be difficult to be controlled at below 1%.2) add the alkali neutralization at low temperatures, its energy consumption and production cost all will increase.3) the disosultap product that obtains at last can only be the aqueous solution of content about 30%, both be unfavorable for the processing of subsequent product, and yield is not high yet.
Three, summary of the invention
The objective of the invention is provides a kind of production technique that is different from existing technological process in order to overcome the above-mentioned defective that prior art exists, and technological process energy consumption and production cost are reduced, and obtains high-load disosultap product.
Realize purpose of the present invention by the following technical solutions.
A kind of production technique of disosultap is done initial raw material with dimethylin propylene hydrochloride, it is characterized in that being made up of chlorination addition and two step of Direct Sulfonation process:
One) chlorination addition
Earlier dimethylin propylene hydrochloride is dissolved in the halogenated alkane organic solvent, feeds exsiccant chlorine under the anhydrous condition of 30-100 ℃ of temperature, make it to take place addition reaction and generate dimethylin propylene dichloride hydrochloride, its chemical equation is as follows:
The question response temperature stops to feed chlorine when beginning to descend; Then, the halogenated alkane organic solvent of 1/3-1/2 amount is steamed, reduce to room temperature, pass through crystallization, separation again, make that purity reaches 98%, acid number is at the solid-state dimethylin propylene dichloride hydrochloride below 0.5%.This solids can be directly as the intermediate for preparing disosultap.
Two) Direct Sulfonation
Directly use and go on foot the high purity that makes, low acid number solid-state dimethylin propylene dichloride hydrochloride and Sulfothiorine by 1: the 1.8-2.4 mixed in molar ratio also is dissolved in the polar solvent, select for use acid binding agent to make catalyzer, under 30-100 ℃ of temperature and whipped state, carried out the constant temperature sulfonation reaction 2-3 hour, generate N, N-dimethyl amido-1,3-dithio sodium sulfonate group propane (disosultap), its chemical equation is as follows:
The residual quantity of Sulfothiorine is less than 4% in the question response system, and the residual quantity of dimethylin propylene dichloride hydrochloride was reduced to room temperature and got final product discharging less than 0.3% o'clock, obtains content at the former medicine of the disosultap of 35-45%.
In above-mentioned chlorination addition reaction process, used halogenated alkane organic solvent is ethylene dichloride, methylene dichloride, tetracol phenixin or chloroform preferably, and is optional wherein a kind of; Suction filtration, press filtration or centrifugal are preferably adopted in said separation, and be optional wherein a kind of.
In above-mentioned sulfonation reaction process, used polar solvent is water, methyl alcohol or ethanol preferably, and is optional wherein a kind of; Used acid binding agent is KOH, NH preferably
4OH, Na
2CO
3, N
aOH or tetraethyl-amine bromide, optional wherein a kind of.
The production technique of disosultap of the present invention compared with prior art, in the chlorination addition process, do not adopt and add water and heat up to take off and fall solvent and take off with the method for Crystallization Separation and to fall solvent, can stop minor amount of water and bring the drawback that chlorination addition reaction system causes into, can obtain simultaneously the disosultap intermediate-dimethylin propylene dichloride hydrochloride of high purity, low acid number, its yield also will improve 5-8%; The low temperature that prior art has fallen in leather adds the alkali N-process, and technological process energy consumption and production cost are reduced; With highly purified dimethylin propylene dichloride hydrochloride, Direct Sulfonation under sour agent effect is fought in the polar solvent neutralization of selecting for use makes the reaction times shorten at least 1 hour, and can obtain the former medicine of high-load disosultap, for the processing of subsequent product provides convenience, sulphonation recovery has also improved 6-9% simultaneously.The production technique of disosultap of the present invention has obvious improvement and substantive distinguishing features.
Four, embodiment
Further specify the production technique of disosultap of the present invention below with the preparation example.The first step: earlier dimethylin propylene hydrochloride is dissolved in the ethylene dichloride solvent, carries out azeotropic in case of necessity and deviate from presumable moisture content, feed exsiccant chlorine under 40 ℃ of temperature, make it to take place the chlorination addition reaction, the question response temperature stops logical chlorine when beginning to descend; Solvent with 1/3 amount in the reactant flow steams then, and again by crystallization, suction filtration, acquisition purity reaches 98%, acid number is at the solid-state dimethylin propylene dichloride hydrochloride below 0.5%.Second step: directly use high purity, low acid number solid-state dimethylin propylene dichloride hydrochloride and Sulfothiorine that the step makes by 1: 2.08 mixed in molar ratio and be dissolved in the methanol solvate, select for use NaOH to make catalyzer, under 60 ℃ of temperature and whipped state, carried out sulfonation reaction 2-3 hour, the residual quantity of Sulfothiorine is less than 4% in the question response system, the residual quantity of dimethylin propylene dichloride hydrochloride was less than 0.3% o'clock, reduce to room temperature and get final product discharging, obtaining content is the former medicine of disosultap of 35-40%.
Claims (5)
1. the production technique of a disosultap, do initial raw material with dimethylin propylene hydrochloride, it is characterized in that forming: 1) earlier dimethylin propylene hydrochloride is dissolved in the halogenated alkane organic solvent by chlorination addition and two step of Direct Sulfonation process, under 30-100 ℃ of temperature and anhydrous condition, feed exsiccant chlorine, make it to take place addition reaction and generate dimethylin propylene dichloride hydrochloride, the question response temperature stops to feed chlorine when beginning to descend; Then, the halogenated alkane organic solvent that 1/3-1/2 is measured steams, and reduces to room temperature, passes through crystallization, separation again, makes high purity, the low solid-state dimethylin propylene dichloride of acid number hydrochloride; 2) directly use high purity, low acid number solid-state dimethylin propylene dichloride hydrochloride and Sulfothiorine that the step makes by 1: the 1.8-2.4 mixed in molar ratio also is dissolved in the polar solvent, select for use acid binding agent to make catalyzer, under 30-100 ℃ of temperature and whipped state, carried out the constant temperature sulfonation reaction 2-3 hour, the residual quantity of Sulfothiorine is less than 4% in the question response system, the residual quantity of dimethylin propylene dichloride hydrochloride was less than 0.3% o'clock, reduce to room temperature, obtain the former medicine of disosultap.
2. according to the production technique of the described a kind of disosultap of claim 1, it is characterized in that in chlorination addition reaction process, said halogenated alkane organic solvent is ethylene dichloride, methylene dichloride, tetracol phenixin or chloroform, optional wherein a kind of.
3. according to the production technique of the described a kind of disosultap of claim 1, it is characterized in that in chlorination addition reaction process that said separation is suction filtration, press filtration or centrifugal, optional wherein a kind of.
4. according to the production technique of the described a kind of disosultap of claim 1, it is characterized in that in the sulfonation reaction process that said polar solvent is water, methyl alcohol or ethanol, optional wherein a kind of.
5. according to the production technique of the described a kind of disosultap of claim 1, it is characterized in that in the sulfonation reaction process that said acid binding agent is KOH, NH
4OH, N
A2CO
3, N
aOH or tetraethyl-amine bromide, optional wherein a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100570260A CN100410239C (en) | 2005-04-21 | 2005-04-21 | Simplified production technology of bisultap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100570260A CN100410239C (en) | 2005-04-21 | 2005-04-21 | Simplified production technology of bisultap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685818A CN1685818A (en) | 2005-10-26 |
| CN100410239C true CN100410239C (en) | 2008-08-13 |
Family
ID=35303860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100570260A Expired - Fee Related CN100410239C (en) | 2005-04-21 | 2005-04-21 | Simplified production technology of bisultap |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100410239C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648898B (en) * | 2009-09-23 | 2012-03-14 | 江苏安邦电化有限公司 | Membrane concentration process of dimehypo mother liquor |
| CN102304076A (en) * | 2011-07-05 | 2012-01-04 | 江苏兄弟维生素有限公司 | Preparation method of sodium n-propyl thiosulfate |
| CN104119259A (en) * | 2014-07-11 | 2014-10-29 | 江苏兄弟维生素有限公司 | A synthetic process of sodium n-propyl thiosulfate |
| CN104774167A (en) * | 2014-11-27 | 2015-07-15 | 湖南昊华化工有限责任公司 | Cartap intermediate 1, 3-thiocyanide normal compound preparation method |
| CN104610120B (en) * | 2015-01-28 | 2017-02-22 | 湖南昊华化工有限责任公司 | Preparation method capable of increasing proportion of 1,3-bit normal compound in bisultap |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273240A (en) * | 1999-05-07 | 2000-11-15 | 湖南南天实业股份有限公司 | Sulfonating reaction process in production of bisultap |
-
2005
- 2005-04-21 CN CNB2005100570260A patent/CN100410239C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273240A (en) * | 1999-05-07 | 2000-11-15 | 湖南南天实业股份有限公司 | Sulfonating reaction process in production of bisultap |
Non-Patent Citations (4)
| Title |
|---|
| 改善氯化工艺提高磺化收率. 刘琴芳等.安徽化工，第5期. 2001 |
| 改善氯化工艺提高磺化收率. 刘琴芳等.安徽化工，第5期. 2001 * |
| 杀虫双磺化工艺优化. 曹爱年等.化工时刊，第10期. 2000 |
| 杀虫双磺化工艺优化. 曹爱年等.化工时刊，第10期. 2000 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1685818A (en) | 2005-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100410239C (en) | Simplified production technology of bisultap | |
| US7569736B2 (en) | Process for producing monopentaerythritol of high purity and monopentaerythritol produced by the process | |
| CN101648895A (en) | Preparing method of para methyl p-tolyl sulfone | |
| CN105218472B (en) | A kind of preparation method of triazinone | |
| CN103641748A (en) | Method for preparing methanesulfonic acid by recycling byproduct, namely hydrochloric acid | |
| CN109942539A (en) | A kind of preparation method of the fluoro- 1,3- propane sultone of 2- | |
| CN101735167B (en) | Preparation method of 6-nitrosaccharin | |
| CN108246277A (en) | One kind efficiently synthesizes trifluoroiodomethane method | |
| CN116751139A (en) | Preparation method of N- (9-fluorenylmethoxycarbonyl) -O-tert-butyl-L-tyrosine | |
| CN110498744B (en) | Preparation method of 1-ethyl-3-nitrobenzene | |
| CN111138252A (en) | Synthetic method of cyclobutanone | |
| CN103265443A (en) | Industrial production method of high-purity iminodiacetic acid | |
| CN111153821A (en) | Preparation method of D-p-hydroxyphenylglycine methyl ester | |
| CN101712480A (en) | Method for preparing anhydrous sodium carbonate | |
| CN111574416B (en) | Method for preparing tiamulin from isothiourea salt and pleuromutilin p-toluenesulfonate | |
| CN111393340B (en) | Green production method of bisphenol S | |
| CN110684019A (en) | Preparation method of ticagrelor intermediate oxide impurity | |
| CN106045942A (en) | Preparation method of pramoxine hydrochloride | |
| CN102718810B (en) | After-treatment method of benzylation reaction product | |
| CN112409196A (en) | Preparation process of aminomethylbenzoic acid based on Delbin reaction | |
| CN111072473A (en) | Preparation method of dimethyl adipate | |
| CN117624110B (en) | Synthetic method of fluoroethylene carbonate | |
| CN104817424B (en) | Method for separation of difluoromethane from tetrafluoroethylene product | |
| CN103059027A (en) | Method for preparing tebipenem pivoxil | |
| CN102964415A (en) | Method for synthesizing progesterone midbody 3beta-hydroxy-5-pregnene-20-ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080813 Termination date: 20100421 |