CN105949092A - Preparing method for methyl sulfamide - Google Patents
Preparing method for methyl sulfamide Download PDFInfo
- Publication number
- CN105949092A CN105949092A CN201610448521.2A CN201610448521A CN105949092A CN 105949092 A CN105949092 A CN 105949092A CN 201610448521 A CN201610448521 A CN 201610448521A CN 105949092 A CN105949092 A CN 105949092A
- Authority
- CN
- China
- Prior art keywords
- methylsulfonamides
- temperature
- ammonia
- preparation
- reactor
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title abstract description 8
- NOXPGSDFQWSNSW-UHFFFAOYSA-N (sulfamoylamino)methane Chemical compound CNS(N)(=O)=O NOXPGSDFQWSNSW-UHFFFAOYSA-N 0.000 title abstract 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical class CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 claims description 36
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- BGZZWXTVIYUUEY-UHFFFAOYSA-N fomesafen Chemical compound C1=C([N+]([O-])=O)C(C(=O)NS(=O)(=O)C)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 BGZZWXTVIYUUEY-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparing method for methyl sulfamide. Methylsufonyl chloride is used as a raw material, and the preparing method includes the following steps that 1, raw materials are mixed; 2, reaction is carried out; 3, heating and filtering are carried out; 4, the steps 2 and 3 are repeated, and reaction is stopped when introducing amount of ammonia gas is equal to discharging amount in the step 2; 5, concentrating and drying are carried out. The preparing method for methyl sulfamide is simple and easy to implement, ammonia gas and methylsufonyl chloride are subjected to an ammoniation reaction, on one hand, raw material cost is reduced, and the price of the finished methyl sulfamide product is substantially reduced; on the other hand, the reaction process is stable, safe and high in operability; the obtained product is high in purity and large in yield, and enterprise benefits can be substantially increased.
Description
Technical field
The present invention relates to pharmaceutical intermediate preparing technical field, particularly relate to the preparation method of a kind of methylsulfonamides.
Background technology
Methylsulfonamides is a kind of important fine chemical product intermediate. it is widely used as the synthesis material of medicine, pesticide, is one of indispensable important source material in the synthesis of new and effective Soybean herbicides fomesafen.
The preparation method of existing methylsufonyl chloride mostly uses Methyl disulfide method, methyl isothiourea method and uv irradiation method etc., the shortcoming such as have that reaction is complicated, dangerous big and yield is low, and industrialized production benefit is poor.
Summary of the invention
The technical problem that present invention mainly solves is to provide the preparation method of a kind of methylsulfonamides, it is possible to solve in place of existing methylsulfonamides prepares above shortcomings.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provides the preparation method of a kind of methylsulfonamides, with methylsufonyl chloride as raw material, comprises the steps:
(1) raw material mixing: add methylsulfonamides and organic solvent by certain mass ratio in the reactor of band agitating function, circulating cooling and circulating-heating function, be stirred to dissolve；
(2) reaction: be circulated the reactor in step (1) and be cooled to uniform temperature, then limit stirring stirring limit is passed through ammonia with constant rate of speed in reactor；
(3) heating and filtering: stop being passed through ammonia, and reacted reactor in step (2) is circulated is heated to uniform temperature, after constant temperature stirs a period of time, heat filtering takes filtrate；
(4) step (2) and (3) is repeated, until the intake of ammonia is equal to output, stopped reaction in step (2)；
(5) concentrate drying: be evaporated last filtrate in step (4) concentrating, carry out reduced vacuum after concentrate is cooled to room temperature and be dried, obtain described methylsulfonamides.
In a preferred embodiment of the present invention, in described step (1), the mass ratio of described methylsulfonamides and organic solvent is 1:3～5；Described reactor uses frozen water and hot water to be circulated cooling and circulating-heating respectively.
In a preferred embodiment of the present invention, described organic solvent is anhydrous acetonitrile or absolute ether.
In a preferred embodiment of the present invention, in described step (2), described circulating cooling temperature is 0～5 DEG C；The speed that is passed through of described ammonia is 0.5～2L/min, and intake is 1～2 times of the methylsulfonamides quality added in described step (1).
In a preferred embodiment of the present invention, in described step (3), described heating-up temperature is 55～65 DEG C；Described constant temperature mixing time is 5～15min.
In a preferred embodiment of the present invention, in described step (5), described evaporation and concentration temperature is 70～80 DEG C, and the condition of described drying under reduced pressure is pressure 0.01MPa, temperature 60～65 DEG C.
The invention has the beneficial effects as follows: the preparation method of a kind of methylsulfonamides of the present invention is simple, easily realizes, it carries out aminating reaction by ammonia and methylsufonyl chloride, on the one hand reduces cost of material, the price of finished product methylsulfonamides is greatly reduced；On the other hand course of reaction is stable, and safety is workable；The purity of products obtained therefrom is high, and productivity is big, can increase substantially the performance of enterprises.
Detailed description of the invention
Below presently preferred embodiments of the present invention is described in detail, so that advantages and features of the invention can be easier to be readily appreciated by one skilled in the art, thus protection scope of the present invention is made apparent clear and definite defining.
The embodiment of the present invention includes:
Embodiment 1
The preparation method of a kind of methylsulfonamides, with methylsufonyl chloride as raw material, comprises the steps:
(1) raw material mixing: the mass ratio pressing 1:3 in the reactor of band agitating function, circulating cooling and circulating-heating function adds methylsulfonamides and anhydrous acetonitrile, and stirring makes methylsulfonamides be dissolved completely in anhydrous acetonitrile；Wherein, reactor uses frozen water and hot water to be circulated cooling and circulating-heating respectively, to realize cooling and heating function；
(2) reaction: the reactor in step (1) is passed through circulating cooling frozen water, temperature in the kettle is made to be cooled to 0～5 DEG C, in reactor, ammonia it is passed through the most while stirring with the constant rate of speed of 0.5～1L/min, and 1～1.5 times that the intake controlling ammonia is the methylsulfonamides quality added in described step (1), during being passed through of ammonia, methylsulfonamides and ammonia react generation methylsulfonamides, and part ammonia produces ammonium chloride simultaneously；
(3) heating and filtering: stop being passed through ammonia and circulating cooling frozen water, and reacted reactor is passed through circulating hot water in step (2), makes temperature in the kettle be heated to 55 DEG C, constant temperature stirring 15min, making ammonium chloride all separate out, then heat filtering takes filtrate, and filtering residue reclaims；
(4) step (2) and (3) is repeated, until the intake of ammonia is equal to output, stopped reaction in step (2)；In repeating step, the intake of each ammonia is last 60%；
(5) concentrate drying: filtrate last in step (4) (is the most no longer reacted the filtrate of ammonia, now methylsufonyl chloride has reacted complete) it is evaporated concentrating at 70 DEG C, all volatilize to solvent, then concentrate is cooled to after room temperature at 0.01MPa, carry out reduced vacuum under conditions of 60 DEG C to be dried, obtain described methylsulfonamides.
Embodiment 2
The preparation method of a kind of methylsulfonamides, with methylsufonyl chloride as raw material, comprises the steps:
(1) raw material mixing: the mass ratio pressing 1:5 in the reactor of band agitating function, circulating cooling and circulating-heating function adds methylsulfonamides and anhydrous propanone, and stirring makes methylsulfonamides be dissolved completely in anhydrous acetonitrile；Wherein, reactor uses frozen water and hot water to be circulated cooling and circulating-heating respectively, to realize cooling and heating function；
(2) reaction: the reactor in step (1) is passed through circulating cooling frozen water, temperature in the kettle is made to be cooled to 0～5 DEG C, in reactor, ammonia it is passed through the most while stirring with the constant rate of speed of 1～2L/min, and 1.5～2 times that the intake controlling ammonia is the methylsulfonamides quality added in described step (1), during being passed through of ammonia, methylsulfonamides and ammonia react generation methylsulfonamides, and part ammonia produces ammonium chloride simultaneously；
(3) heating and filtering: stop being passed through ammonia and circulating cooling frozen water, and reacted reactor is passed through circulating hot water in step (2), makes temperature in the kettle be heated to 65 DEG C, constant temperature stirring 5min, making ammonium chloride all separate out, then heat filtering takes filtrate, and filtering residue reclaims；
(4) step (2) and (3) is repeated, until the intake of ammonia is equal to output, stopped reaction in step (2)；In repeating step, the intake of each ammonia is last 80%；
(5) concentrate drying: filtrate last in step (4) (is the most no longer reacted the filtrate of ammonia, now methylsufonyl chloride has reacted complete) it is evaporated concentrating at 80 DEG C, all volatilize to solvent, then concentrate is cooled to after room temperature at 0.01MPa, carry out reduced vacuum under conditions of 65 DEG C to be dried, obtain described methylsulfonamides.
The final products index that above-described embodiment obtains is as follows:
Purity>99.7%, ammonium chloride<0.01%；< 0.05%, appearance white crystallizes moisture.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalent structure utilizing description of the invention content to be made or equivalence flow process conversion; or directly or indirectly it is used in other relevant technical fields, the most in like manner it is included in the scope of patent protection of the present invention.
Claims (6)
1. the preparation method of a methylsulfonamides, it is characterised in that with methylsufonyl chloride as raw material, comprise the steps:
(1) raw material mixing: add methylsulfonamides and organic solvent by certain mass ratio in the reactor of band agitating function, circulating cooling and circulating-heating function, be stirred to dissolve；
(2) reaction: be circulated the reactor in step (1) and be cooled to uniform temperature, then limit stirring stirring limit is passed through ammonia with constant rate of speed in reactor；
(3) heating and filtering: stop being passed through ammonia, and reacted reactor in step (2) is circulated is heated to uniform temperature, after constant temperature stirs a period of time, heat filtering takes filtrate；
(4) step (2) and (3) is repeated, until the intake of ammonia is equal to output, stopped reaction in step (2)；
(5) concentrate drying: be evaporated last filtrate in step (4) concentrating, carry out reduced vacuum after concentrate is cooled to room temperature and be dried, obtain described methylsulfonamides.
The preparation method of methylsulfonamides the most according to claim 1, it is characterised in that in described step (1), the mass ratio of described methylsulfonamides and organic solvent is 1:3～5；Described reactor uses frozen water and hot water to be circulated cooling and circulating-heating respectively.
The preparation method of methylsulfonamides the most according to claim 2, it is characterised in that described organic solvent is anhydrous acetonitrile or absolute ether.
The preparation method of methylsulfonamides the most according to claim 1, it is characterised in that in described step (2), described circulating cooling temperature is 0～5 DEG C；The speed that is passed through of described ammonia is 0.5～2L/min, and intake is 1～2 times of the methylsulfonamides quality added in described step (1).
The preparation method of methylsulfonamides the most according to claim 1, it is characterised in that in described step (3), described heating-up temperature is 55～65 DEG C；Described constant temperature mixing time is 5～15min.
The preparation method of methylsulfonamides the most according to claim 1, it is characterised in that in described step (5), described evaporation and concentration temperature is 70～80 DEG C, and the condition of described drying under reduced pressure is pressure 0.01MPa, temperature 60～65 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610448521.2A CN105949092A (en) | 2016-06-21 | 2016-06-21 | Preparing method for methyl sulfamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610448521.2A CN105949092A (en) | 2016-06-21 | 2016-06-21 | Preparing method for methyl sulfamide |
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| Publication Number | Publication Date |
|---|---|
| CN105949092A true CN105949092A (en) | 2016-09-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610448521.2A Pending CN105949092A (en) | 2016-06-21 | 2016-06-21 | Preparing method for methyl sulfamide |
Country Status (1)
| Country | Link |
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| CN (1) | CN105949092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995552A (en) * | 2020-08-19 | 2020-11-27 | 河北亚诺生物科技股份有限公司 | Method for preparing methylsulfonamide by water method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970339A (en) * | 1988-11-30 | 1990-11-13 | Atochem North America, Inc. | Preparation of alkanesulfonamides |
| US5159112A (en) * | 1987-01-23 | 1992-10-27 | Societe Nationale Elf Aquitaine (Production) | Process of the production of alkanesulfonamides |
| US5166431A (en) * | 1988-11-30 | 1992-11-24 | Elf Atochem North America, Inc. | Preparation of alkanesulfonamides |
| US5455377A (en) * | 1993-07-28 | 1995-10-03 | Oxon Italia S.P.A. | Process to prepare alkansulphonamides |
-
2016
- 2016-06-21 CN CN201610448521.2A patent/CN105949092A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5159112A (en) * | 1987-01-23 | 1992-10-27 | Societe Nationale Elf Aquitaine (Production) | Process of the production of alkanesulfonamides |
| US4970339A (en) * | 1988-11-30 | 1990-11-13 | Atochem North America, Inc. | Preparation of alkanesulfonamides |
| US5166431A (en) * | 1988-11-30 | 1992-11-24 | Elf Atochem North America, Inc. | Preparation of alkanesulfonamides |
| US5455377A (en) * | 1993-07-28 | 1995-10-03 | Oxon Italia S.P.A. | Process to prepare alkansulphonamides |
Non-Patent Citations (2)
| Title |
|---|
| 张树奎等: "高纯度甲基磺酰胺的合成", 《化学试剂》 * |
| 祈建新等: "甲基磺酞胺合成工艺改进", 《农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995552A (en) * | 2020-08-19 | 2020-11-27 | 河北亚诺生物科技股份有限公司 | Method for preparing methylsulfonamide by water method |
| CN111995552B (en) * | 2020-08-19 | 2022-04-01 | 河北亚诺生物科技股份有限公司 | Method for preparing methylsulfonamide by water method |
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Application publication date: 20160921 |