CN103012258A - Production technology of 2-sulfamide-N,N-dimethylnicotinamide - Google Patents
Production technology of 2-sulfamide-N,N-dimethylnicotinamide Download PDFInfo
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- CN103012258A CN103012258A CN2012105270120A CN201210527012A CN103012258A CN 103012258 A CN103012258 A CN 103012258A CN 2012105270120 A CN2012105270120 A CN 2012105270120A CN 201210527012 A CN201210527012 A CN 201210527012A CN 103012258 A CN103012258 A CN 103012258A
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- dimethyl nicotinamide
- ammonia
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Abstract
The invention relates to a production technology of 2-sulfamide-N,N-dimethylnicotinamide, and belongs to the field of chemical production. The production technology takes isothiourea hydrochloride to substitute thiol compound as a substrate for an oxychlorination reaction to avoid stink in the production process and generation of thioether byproducts and improve the yield of the product. Chloropyridine and thiourea form isothiourea hydrochloride; and the dosage of thiourea is not a lot to avoid a lot of H2S gas and S generated in the thiolation process, so as to reduce the emission of the three wastes (wastewater, waste gases and residues).
Description
Technical field
The present invention relates to chemical production field, be specifically related to a kind of 2-sulphonyl ammonia-N, the production technique of N-dimethyl nicotinamide.
Background technology
2-sulphonyl ammonia-N, N-dimethyl nicotinamide are the key intermediates of synthetic herbicide nicosulfuron.Nicosulfuron is a kind of high efficiency corn weedicide by the exploitation of Japanese Ishihara Sangyo Kaisha, Ltd., it is a kind of systemic herbicide, can in plant materials, be conducted subsequently by plant stem-leaf and root absorption, cause sensitive plant cessation of growth cessation, cauline leaf chlorisis, withered gradually.
The 2-sulphonyl ammonia-N that has reported, the synthetic method of N-dimethyl nicotinamide has: (1) US 4789393 is take the 2-hydroxyl-3-cyanogen pyridine as raw material, through SOCl
2Chlorination generates 2-chloro-nicotinonitrile, generates 2-phenyl methylthio group-nicotinonitrile with the benzyl sulfhydrate condensation again, again through hydrolysis, SOCl
2Chlorination, the synthetic 2-phenyl methylthio group-N of dimethylamine amination, the N-dimethyl nicotinamide is finally by Cl
2Oxychlorination, the ammonification synthesising target compound.Benzyl sulfhydrate is expensive, and cost is high.(2) EP 0388994 is take 2-sulfydryl-3-chloropyridine as raw material, through Cl
2Oxychlorination, 3-chloropyridine sulphonamide is synthesized in ammonification.Again with the synthetic nicotinonitrile sulphonamide of KCN reaction, finally by hydrolysis, SOCl
2Chlorination, dimethylamine amination synthesising target compound.There is potential safety hazard in the KCN severe toxicity.(3) JP 1016765A, US 5128474A are with 2-chloro-N, and the N-dimethyl nicotinamide is raw material, through NaS
2Or NaS
xSulfhydrylation synthesizes 2-sulfydryl-N, and the N-dimethyl nicotinamide passes through Cl at last
2Oxychlorination, the ammonification synthesising target compound.The mercaptolation foul smelling, and easily generate thio-ether type compounds, yield is lower.
Summary of the invention
For the deficiency that exists in the aforesaid method, the object of the present invention is to provide a kind of 2-sulphonyl ammonia--N, the production technique of N-dimethyl nicotinamide, the present invention can implement by the following technical programs:
(1) with 2-chloro-N, N-dimethyl nicotinamide, thiocarbamide add in the enamel reaction still through charging opening respectively, add quantitative rare HCl by header tank through under meter; Open steam valve, be warming up to 80 ~ 100
oC, reaction 1-2h;
(2) acetic acid, is passed into chilled brine and is cooled to-5 ~-15 in volume pump is squeezed into reactor in the step (1) by the acetic acid storage tank in the chuck
oC; Liquid chlorine blasts above-mentioned reaction mass by the liquid chlorine storage tank through chlorine liquid carburetor, gas meter, and reaction 1-2h separates out white solid; N
2Bubbling is removed the Cl of dissolving
2, centrifugation gets 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide, and filtrate is removed wastewater treatment equipment;
(3) 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide is added in the enamel reaction still by charging opening, CH
2Cl
2Squeezed in the reactor through volume pump by storage tank, pass into chilled brine in the cover and be cooled to 0 ~ 10
oC.Liquefied ammonia blasts above-mentioned reaction mass by liquid ammonia storage tank through liquid ammonia vaporization device, gas meter, treats system pH〉9 o'clock stopped reaction.Centrifugation ammonium chloride, the filtrate decompression distillation, solvent is put into relay tank and is applied mechanically, and but crystallization of still liquid cooling, centrifugation get 2-sulphonyl ammonia--N, N-dimethyl nicotinamide.
The described molar ratio n of step (1) (2-chloro-N, N-dimethyl nicotinamide) wherein: n (thiocarbamide) is 1.1 ~ 1.4; Described rare HCl consumption m (HCl): m (2-chloro-N, N-dimethyl nicotinamide) is 4 ~ 6; The concentration of described dilute hydrochloric acid is 2 ~ 10wt%.
Wherein the described acetic acid consumption of step (2) is with 2-chloro-N, and N-dimethyl nicotinamide quality is counted 5 ~ 20wt%.
The described CH of step (3) wherein
2Cl
2Consumption m (CH
2Cl
2): m (2-chloro-N, N-dimethyl nicotinamide) is 4 ~ 6.
Beneficial effect of the present invention
(1) the present invention replaces sulfhydryl compound as the substrate of oxi-chlorination with the isothiuronium salts hydrochlorate, avoids stench in the production process and the generation of thioether class by product, has improved the yield of product.
(2) chloro-pyridine and thiocarbamide form the isothiuronium salts hydrochlorate, and thiocarbamide need not be greatly excessive, avoids in the sulfhydrylation process a large amount of H of generation
2S gas and simple substance S have reduced the quantity discharged of the three wastes.
Description of drawings
Accompanying drawing 1 is process flow sheet of the present invention.
Specific embodiment
Embodiment 1
1, with 50kg2-chloro-N, N-dimethyl nicotinamide and 23kg thiocarbamide join in the 500L enamel reaction still through charging opening respectively, add 200kg 2wt%HCl by header tank through under meter.Open steam valve, be warming up to 80
oC, stirring reaction 1h.
2, with 2.5kg acetic acid by the acetic acid storage tank in volume pump is squeezed into reactor in the step 1, pass into chilled brine in the chuck and be cooled to-5
oC.Cl
2By the liquid chlorine storage tank, blast above-mentioned reaction mass through chlorine liquid carburetor, gas meter, reaction 1h.Use N
2Bubbling is removed the Cl of dissolving
2, then centrifugation gets 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide, and filtrate is gone in the wastewater treatment equipment.
3, with the 2-SULPHURYL CHLORIDE-N that obtains in the step 2, the N-dimethyl nicotinamide is joined in the 500L enamel reaction still by charging opening, 200kgCH
2Cl
2To be squeezed in the reactor through volume pump by storage tank, and pass into chilled brine in the cover and be cooled to 10
oC.Liquefied ammonia blasts above-mentioned reaction mass by liquid ammonia storage tank through liquid ammonia vaporization device, gas meter, treats system pH〉9 o'clock stopped reaction.Centrifugation ammonium chloride, the filtrate decompression distillation, solvent is put into relay tank and is applied mechanically, and but crystallization of still liquid cooling, centrifugation get 2-sulphonyl ammonia-N, N-dimethyl nicotinamide 47.8kg, yield 77%, purity 99.5% (HPLC).
Embodiment 2
1, with 50kg2-chloro-N, N-dimethyl nicotinamide and 29kg thiocarbamide join in the 500L enamel reaction still through charging opening respectively, add 300kg 10wt%HCl by header tank through under meter.Open steam valve, be warming up to 100
oC, stirring reaction 2h.
2, with 10kg acetic acid by the acetic acid storage tank in volume pump is squeezed into reactor in the step 1, pass into chilled brine in the chuck and be cooled to-10
oC.Cl
2By the liquid chlorine storage tank, blast above-mentioned reaction mass through chlorine liquid carburetor, gas meter, reaction 2h.Use N
2Bubbling is removed the Cl of dissolving
2, then centrifugation gets 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide, and filtrate is gone in the wastewater treatment equipment.
3, with the 2-SULPHURYL CHLORIDE-N that obtains in the step 2, the N-dimethyl nicotinamide is joined in the 500L enamel reaction still by charging opening, 300kgCH
2Cl
2To be squeezed in the reactor through volume pump by storage tank, and pass into chilled brine in the cover and be cooled to 0
oC.Liquefied ammonia blasts above-mentioned reaction mass by liquid ammonia storage tank through liquid ammonia vaporization device, gas meter, treats system pH〉9 o'clock stopped reaction.Centrifugation ammonium chloride, the filtrate decompression distillation, solvent is put into relay tank and is applied mechanically, and but crystallization of still liquid cooling, centrifugation get 2-sulphonyl ammonia-N, N-dimethyl nicotinamide 52.8kg, yield 85%, purity 98.9 % (HPLC).
Embodiment 3
1, with 50kg2-chloro-N, N-dimethyl nicotinamide and 25kg thiocarbamide join in the 500L enamel reaction still through charging opening respectively, add 225g 5wt%HCl by header tank through under meter.Open steam valve, be warming up to 90
oC, stirring reaction 1.5h.
2, with 6kg acetic acid by the acetic acid storage tank in volume pump is squeezed into reactor in the step 1, pass into chilled brine in the chuck and be cooled to-15
oC.Cl
2By the liquid chlorine storage tank, blast above-mentioned reaction mass through chlorine liquid carburetor, gas meter, reaction 1.4h.Use N
2Bubbling is removed the Cl of dissolving
2, then centrifugation gets 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide, and filtrate is gone in the wastewater treatment equipment.
3, with the 2-SULPHURYL CHLORIDE-N that obtains in the step 2, the N-dimethyl nicotinamide is joined in the 500L enamel reaction still by charging opening, 250kgCH
2Cl
2To be squeezed in the reactor through volume pump by storage tank, and pass into chilled brine in the cover and be cooled to 6
oC.Liquefied ammonia blasts above-mentioned reaction mass by liquid ammonia storage tank through liquid ammonia vaporization device, gas meter, treats system pH〉9 o'clock stopped reaction.Centrifugation ammonium chloride, the filtrate decompression distillation, solvent is put into relay tank and is applied mechanically, and but crystallization of still liquid cooling, centrifugation get 2-sulphonyl ammonia-N, N-dimethyl nicotinamide 49.1kg, yield 79%, purity 99.1% (HPLC).
Claims (4)
1. 2-sulphonyl ammonia-N, the production technique of N-dimethyl nicotinamide is characterized in that carrying out according to following step:
(1) with 2-chloro-N, N-dimethyl nicotinamide, thiocarbamide add in the enamel reaction still through charging opening respectively, add quantitative rare HCl by header tank through under meter; Open steam valve, be warming up to 80 ~ 100
oC, reaction 1-2h;
(2) acetic acid, is passed into chilled brine and is cooled to-5 ~-15 in volume pump is squeezed into reactor in the step (1) by the acetic acid storage tank in the chuck
oC; Liquid chlorine blasts above-mentioned reaction mass by the liquid chlorine storage tank through chlorine liquid carburetor, gas meter, and reaction 1-2h separates out white solid; N
2Bubbling is removed the Cl of dissolving
2, centrifugation gets 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide, and filtrate is removed wastewater treatment equipment;
(3) 2-SULPHURYL CHLORIDE-N, the N-dimethyl nicotinamide is added in the enamel reaction still by charging opening, CH
2Cl
2Squeezed in the reactor through volume pump by storage tank, pass into chilled brine in the cover and be cooled to 0 ~ 10
oC; Liquefied ammonia blasts above-mentioned reaction mass by liquid ammonia storage tank through liquid ammonia vaporization device, gas meter, treats system pH〉9 o'clock stopped reaction; Centrifugation ammonium chloride, the filtrate decompression distillation, solvent is put into relay tank and is applied mechanically, and but crystallization of still liquid cooling, centrifugation get 2-sulphonyl ammonia--N, N-dimethyl nicotinamide.
2. a kind of 2-sulphonyl ammonia-N according to claim 1, the production technique of N-dimethyl nicotinamide, it is characterized in that wherein the described molar ratio n of step (1) (2-chloro-N, N-dimethyl nicotinamide): n (thiocarbamide) is 1.1 ~ 1.4; Described rare HCl consumption m (HCl): m (2-chloro-N, N-dimethyl nicotinamide) is 4 ~ 6; The concentration of described dilute hydrochloric acid is 2 ~ 10wt%.
3. a kind of 2-sulphonyl ammonia-N according to claim 1, the production technique of N-dimethyl nicotinamide is characterized in that wherein the described acetic acid consumption of step (2) is with 2-chloro-N, N-dimethyl nicotinamide quality is counted 5 ~ 20wt%.
4. a kind of 2-sulphonyl ammonia-N according to claim 1, the production technique of N-dimethyl nicotinamide is characterized in that the wherein described CH of step (3)
2Cl
2Consumption m (CH
2Cl
2): m (2-chloro-N, N-dimethyl nicotinamide) is 4 ~ 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105270120A CN103012258A (en) | 2012-12-10 | 2012-12-10 | Production technology of 2-sulfamide-N,N-dimethylnicotinamide |
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|---|---|---|---|
| CN2012105270120A CN103012258A (en) | 2012-12-10 | 2012-12-10 | Production technology of 2-sulfamide-N,N-dimethylnicotinamide |
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| CN103012258A true CN103012258A (en) | 2013-04-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279015A (en) * | 2016-08-10 | 2017-01-04 | 安徽省化工研究院 | A kind of 2 amino-sulfonyl N, the preparation method of N dimethyl nicotinamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789393A (en) * | 1986-03-07 | 1988-12-06 | E. I. Du Pont De Nemours And Company | Herbicidal pyridine sulfonamides |
| CN101817782A (en) * | 2010-04-15 | 2010-09-01 | 山东京博控股发展有限公司 | Method for synthesizing 2-aminosulfonyl-N,N-dimethylnicotinamide |
-
2012
- 2012-12-10 CN CN2012105270120A patent/CN103012258A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789393A (en) * | 1986-03-07 | 1988-12-06 | E. I. Du Pont De Nemours And Company | Herbicidal pyridine sulfonamides |
| CN101817782A (en) * | 2010-04-15 | 2010-09-01 | 山东京博控股发展有限公司 | Method for synthesizing 2-aminosulfonyl-N,N-dimethylnicotinamide |
Non-Patent Citations (2)
| Title |
|---|
| 孙健等: "《烟嘧磺隆中间体2-氨基磺酰基-N,N-二甲基烟酰胺的合成研究》", 《化学与生物工程》 * |
| 杨荣国等: "《N,N-二甲基-2-胺基磺酰基-吡啶酰胺的合成研究》", 《科技信息》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279015A (en) * | 2016-08-10 | 2017-01-04 | 安徽省化工研究院 | A kind of 2 amino-sulfonyl N, the preparation method of N dimethyl nicotinamide |
| CN106279015B (en) * | 2016-08-10 | 2019-06-11 | 安徽省化工研究院 | A kind of preparation method of 2- amino-sulfonyl-N, N- dimethyl nicotinamide |
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Application publication date: 20130403 |