CN101735145B - Preparation method of smoke sulfamide - Google Patents
Preparation method of smoke sulfamide Download PDFInfo
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- CN101735145B CN101735145B CN2009102343236A CN200910234323A CN101735145B CN 101735145 B CN101735145 B CN 101735145B CN 2009102343236 A CN2009102343236 A CN 2009102343236A CN 200910234323 A CN200910234323 A CN 200910234323A CN 101735145 B CN101735145 B CN 101735145B
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Abstract
The invention relates to a preparation method of smoke sulfamide, which is characterized by comprising the following steps of: oxygenizing 2-sulfydryl-N, N-dimethyl smoke nicotinamide into disulphide by adopting an oxidant; introducing chlorine to reach with the disulphide to prepare a compound III in the presence or absence of a phase transfer catalyst; and introducing ammonia to reach with the compound III for reaction to prepare the smoke sulfamide. The invention firstly oxygenizes the 2-sulfydryl-N, N-dimethyl smoke nicotinamide (I) into the disulphide (II) and then carries out oxychlorination, thereby preventing the side reaction of de-sulfhydryl and achieving high yield coefficient.
Description
Technical field
The invention belongs to the fine chemistry field, be specifically related to a kind of preparation method of aminosulfonyl-N, N-dimethylnicotinamide.
Background technology
Nicosulfuron is a kind of sulfonylurea herbicide, is one of one type of weedicide that activity is the highest up to now, consumption is minimum.Nicosulfuron synthetic key is midbody synthesizing with regard to aminosulfonyl-N, N-dimethylnicotinamide.About aminosulfonyl-N, N-dimethylnicotinamide synthetic the lot of documents introduction is arranged, introduce in the documents such as US4789393, US4844728, US4946494,2-chlorine N; Chlorine in the N-dimethyl nicotinamide replaces with benzylthio-or sulfydryl; Oxychlorination system SULPHURYL CHLORIDE in sour water then, wherein the benzylthio-substituting group will be used expensive benzyl sulfhydrate, and benzylthio-substituting group oxychlorination yield is not high; And following side reaction can take place during oxychlorination in the sulfydryl substituting group in sour water, and yield is not high yet.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming, a kind of preparation method of midbody aminosulfonyl-N, N-dimethylnicotinamide of nicosulfuron is provided.
The object of the invention can reach through following measure:
A kind of preparation method of aminosulfonyl-N, N-dimethylnicotinamide comprises the steps:
(a) adopt oxygenant with 2-sulfydryl-N, the N-dimethyl nicotinamide is oxidized to disulphide;
(b) disulphide feeding chlorine under phase-transfer catalyst existence or non-existent condition carries out the prepared in reaction compound III;
(c) compound III feeds ammonia gas react and makes aminosulfonyl-N, N-dimethylnicotinamide;
Oxygenant is H among the step a
2O
2, NH
2Cl or MnO
2, oxygenant is 0.2～1: 1 with I amount of substance ratio.Adopt H
2O
2Can suitably add concentrated hydrochloric acid during as oxygenant to strengthen the oxidisability of ydrogen peroxide 50.
The temperature of reaction of step a is 0～50 ℃.
Solvent is aromatic hydrocarbons, alkane, halohydrocarbon, water, alcohol or ether among the step a; Wherein aromatic hydrocarbons is preferably benzene, toluene or YLENE; Alkane is preferably normal hexane, hexanaphthene or heptane; Halohydrocarbon is preferably methylene dichloride, ethylene dichloride or chlorobenzene, and alcohol is preferably methyl alcohol, ethanol or Virahol, and ether is preferably ether, THF or dioxane.
Solvent among the step b is a water, or the mixed solvent of water and water-insoluble organic solvent, and organic solvent wherein is with step a.If use mixed solvent, water and volume of organic solvent ratio are 1: 0.5～2.
Temperature of reaction is-10～30 ℃ among the step b.
Phase-transfer catalyst among the step b is tetraethylammonium bromide, chlorination phenyltrimethyammonium or methyl chloride tributyl ammonium, and phase-transfer catalyst is 0～0.015: 1 with the ratio of the amount of substance of I.
Temperature of reaction is-10～30 ℃ among the step c.
Because there are side reaction in compound I and III, so the present invention is first, and N-dimethyl nicotinamide (I) is oxidized to dichloride (II), and then oxychlorination 2-sulfydryl-N, the side reaction of having avoided taking off sulfydryl, and yield is high.
Embodiment
Embodiment 1: the preparation of disulphide (II) preparation
18.2g 0.1mol2-sulfydryl-N; N-dimethyl nicotinamide, 50g water, 30ml concentrated hydrochloric acid join in the flask, stir, and maintain the temperature at 20～30 ℃ in 10min dropping 6.8g 0.06mol 30% ydrogen peroxide 50 stirring reaction; Control among the HPLC to raw material reaction intact, disulphide (II) suspension-s.
Embodiment 2: the preparation of disulphide (II) preparation
18.2g 0.1mol2-sulfydryl-N; N-dimethyl nicotinamide, 50g ether join in the flask, stir, and maintain the temperature at 20～30 ℃ and in 15min, drip the diethyl ether solution that contains 3.1g 0.06mol chloramines; Refluxing and stirring reaction again; Control among the HPLC to raw material reaction intact, disulphide (II) diethyl ether solution, take off ether and get disulphide II.
Embodiment 3: the preparation of disulphide (II) preparation
18.2g 0.1mol2-sulfydryl-N, N-dimethyl nicotinamide, 2.6g 0.03mol Manganse Dioxide, 50g toluene join in the flask, and stirring and refluxing reaction is controlled to raw material reaction intactly among the HPLC, filter, piptonychia benzene gets disulphide (II) 17.6g, yield 95.8%.
Embodiment 4: the preparation of aminosulfonyl-N, N-dimethylnicotinamide (V)
With gained disulphide suspension-s among the embodiment 1, cool to-5～0 ℃, begin logical chlorine, keep temperature-5～0 ℃, control among the HPLC to reaction end, add dichloromethane extraction, the dichloromethane solution of SULPHURYL CHLORIDE.Then, logical ammonia under 0～5 ℃ of condition, to pH=8～9, restir reaction 1h, precipitation gets aminosulfonyl-N, N-dimethylnicotinamide, yield 94.3% (with 2-sulfydryl-N, N-dimethyl nicotinamide meter).
Embodiment 5: the preparation of aminosulfonyl-N, N-dimethylnicotinamide (V)
With gained disulphide in embodiment 2 or 3, add 50ml water and 50ml methylene dichloride, add 0.165g 0.0007mol methyl chloride tributyl ammonium again; Cool to-5～0 ℃, logical chlorine keeps temperature-5～0 ℃; Control among the HPLC to reaction end; Separatory, water dichloromethane extraction, combined dichloromethane get the dichloromethane solution of SULPHURYL CHLORIDE mutually.Then, logical ammonia under 0～5 ℃ of condition, to pH=8～9, restir reaction 1h, precipitation gets aminosulfonyl-N, N-dimethylnicotinamide, yield 95.1% (with 2-sulfydryl-N, N-dimethyl nicotinamide meter).
Claims (8)
1. the preparation method of an aminosulfonyl-N, N-dimethylnicotinamide is characterized in that comprising the steps:
(a) in the presence of solvent, adopt oxygenant with 2-sulfydryl-N, the N-dimethyl nicotinamide is oxidized to disulphide;
(b) disulphide feeding chlorine under phase-transfer catalyst existence or non-existent condition carries out the prepared in reaction compound III; Wherein the solvent in this reaction is a water, or the mixed solvent of water and water-insoluble organic solvent;
(c) compound III feeds ammonia gas react and makes aminosulfonyl-N, N-dimethylnicotinamide;
2. method according to claim 1 is characterized in that oxygenant is H among the step a
2O
2, NH
2Cl or MnO
2
3. method according to claim 1, the temperature of reaction that it is characterized in that step a is 0～50 ℃.
4. method according to claim 1 is characterized in that solvent is aromatic hydrocarbons, alkane, halohydrocarbon, water, alcohol or ether among the step a.
5. method according to claim 1 is characterized in that described water-insoluble organic solvent is methylene dichloride, toluene or ethylene dichloride.
6. method according to claim 1 is characterized in that temperature of reaction is-10～30 ℃ among the step b.
7. method according to claim 1 is characterized in that the phase-transfer catalyst among the step b is tetraethylammonium bromide, chlorination phenyltrimethyammonium or methyl chloride tributyl ammonium.
8. method according to claim 1 is characterized in that temperature of reaction is-10～30 ℃ among the step c.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102343236A CN101735145B (en) | 2009-11-24 | 2009-11-24 | Preparation method of smoke sulfamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102343236A CN101735145B (en) | 2009-11-24 | 2009-11-24 | Preparation method of smoke sulfamide |
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|---|---|
| CN101735145A CN101735145A (en) | 2010-06-16 |
| CN101735145B true CN101735145B (en) | 2012-01-18 |
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| CN2009102343236A Active CN101735145B (en) | 2009-11-24 | 2009-11-24 | Preparation method of smoke sulfamide |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928134B (en) * | 2017-03-06 | 2019-07-16 | 山东理工大学 | A kind of preparation facilities and synthetic method of nicosulfuron intermediate |
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 |
| EP0353944A2 (en) * | 1988-08-04 | 1990-02-07 | Ishihara Sangyo Kaisha, Ltd. | Aminocarbonyl-substituted pyridinesulfinic acid or salts thereof |
-
2009
- 2009-11-24 CN CN2009102343236A patent/CN101735145B/en active Active
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 |
| EP0353944A2 (en) * | 1988-08-04 | 1990-02-07 | Ishihara Sangyo Kaisha, Ltd. | Aminocarbonyl-substituted pyridinesulfinic acid or salts thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP特平开5-294936A 1993.11.09 |
| 王耀良.磺酰胺的制备.《化工中间体》.2004,第1卷(第6期),第44-46页. * |
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| CN101735145A (en) | 2010-06-16 |
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Owner name: NANJING HUAZHOU PHARMACEUTICAL CO., LTD. Free format text: FORMER OWNER: NANJING FIRST PESTICIDE GROUP CO., LTD. Effective date: 20110921 |
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Effective date of registration: 20110921 Address after: Dongfeng Road, Xi Zhen Gaochun County of Nanjing City, Jiangsu province 211308, No. 9 Applicant after: Nanjing Huazhou Pharmaceutical Co., Ltd. Address before: 211300 Pagoda Road 269, Gaochun County, Jiangsu, Nanjing Applicant before: Nanjing First Pesticide Group Co., Ltd. |
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