CN112812059A - Preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide - Google Patents
Preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide Download PDFInfo
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- CN112812059A CN112812059A CN201911126218.0A CN201911126218A CN112812059A CN 112812059 A CN112812059 A CN 112812059A CN 201911126218 A CN201911126218 A CN 201911126218A CN 112812059 A CN112812059 A CN 112812059A
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- dimethylnicotinamide
- aminosulfonyl
- chloro
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- chlorosulfonyl
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- WYFKZPLSYVJLRB-UHFFFAOYSA-N n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S(N)(=O)=O WYFKZPLSYVJLRB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- QNZRJGJNLOMEGJ-UHFFFAOYSA-N 2-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1Cl QNZRJGJNLOMEGJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- BCZIPIDWLIDQGG-UHFFFAOYSA-N 3-(dimethylcarbamoyl)pyridine-2-sulfonyl chloride Chemical compound CN(C)C(=O)C1=CC=CN=C1S(Cl)(=O)=O BCZIPIDWLIDQGG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 21
- HYVMZYDJQLKOGW-UHFFFAOYSA-N n,n-dimethyl-2-sulfanylidene-1h-pyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S HYVMZYDJQLKOGW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- -1 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide Chemical compound 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- BHDXEAKWMYRYIX-UHFFFAOYSA-N C(=O)N.C(=O)N.C(#N)C(C)=CC=CN(C)C Chemical compound C(=O)N.C(=O)N.C(#N)C(C)=CC=CN(C)C BHDXEAKWMYRYIX-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 description 7
- IBRSSZOHCGUTHI-UHFFFAOYSA-N 2-chloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Cl IBRSSZOHCGUTHI-UHFFFAOYSA-N 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 3
- WSBYZKJRXJLIOH-UHFFFAOYSA-N 5-cyano-2-(dimethylamino)hepta-2,4-dienediamide Chemical compound C(#N)C(CC(=O)N)=CC=C(C(=O)N)N(C)C WSBYZKJRXJLIOH-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- QHOBMYLEKRESAA-UHFFFAOYSA-N [NH4+].N1=C(C=CC=C1)S(=O)[O-] Chemical compound [NH4+].N1=C(C=CC=C1)S(=O)[O-] QHOBMYLEKRESAA-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- PTYNSKRKVPMPAX-UHFFFAOYSA-N pyridine-2-sulfinic acid Chemical compound OS(=O)C1=CC=CC=N1 PTYNSKRKVPMPAX-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide, which comprises the following steps: synthesis of 2-chloro-N, N-dimethylnicotinamide takes 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas as raw materials, and the 2-chloro-N, N-dimethylnicotinamide is synthesized by reaction at the temperature of 0-100 ℃. Further, the preparation method provided by the invention also comprises the step of sequentially synthesizing 2-mercapto-N, N-dimethylnicotinamide, 2-chlorosulfonyl-N, N-dimethylnicotinamide and 2-aminosulfonyl-N, N-dimethylnicotinamide by taking 2-chloro-N, N-dimethylnicotinamide as a raw material. The preparation method of the 2-aminosulfonyl-N, N-dimethylnicotinamide provided by the invention provides a new preparation method by taking 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide as a starting material, and has the advantages of short synthetic route, high yield and low cost.
Description
Technical Field
The invention relates to the field of pesticide synthesis, and particularly relates to a preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide.
Background
2-aminosulfonyl-N, N-dimethylnicotinamide is used as an important intermediate of sulfonylurea herbicides, and the current industrial production method mainly adopts 2-chloronicotinic acid as a starting material and adopts a pyridine sulfinate amination method for synthesis. There are reports of the addition of SOCl using 2-chloronicotinic acid2Reacting, adding dimethylamine solution to prepare 2-chloro-N, N-dimethyl nicotinamide, reacting with sodium sulfide and sulfur to prepare polysulfide to obtain 2-mercapto-N, N-dimethyl nicotinamide, reacting with sodium hydroxide, oxidizing with hydrogen peroxide, ammoniating with ammonia gas to generate ammonium pyridine sulfinate, and oxidizing with sodium hypochlorite to obtain the product. In the method, 2-chloro-N, N-dimethyl nicotinamide can be synthesized by the intermediate 2-chloronicotinic acid through two-step reactionThe method has the advantages of long line, high cost and low yield; thereby also leading the cost of other intermediates synthesized by taking the 2-chloronicotinic acid as the raw material to be higher.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, so as to overcome the above problems.
Therefore, the invention provides a preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide, which comprises the following steps:
synthesis of 2-chloro-N, N-dimethylnicotinamide takes 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas as raw materials, and the 2-chloro-N, N-dimethylnicotinamide is synthesized by reaction at the temperature of 0-100 ℃.
Wherein, in the synthesis process of the 2-chloro-N, N-dimethylnicotinamide, the cyano group in the 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas generate triple bond addition reaction, then elimination reaction is carried out, and one molecule of dimethylamine is eliminated to form a ring; the synthesis scheme of the reaction is shown as follows:
based on the above, the step of synthesizing 2-chloro-N, N-dimethylnicotinamide includes: dissolving 2-cyano-5-dimethylamino-2, 4-pentadiene diformamide in a solvent, introducing hydrochloric acid gas, reacting for 1-3 h at 0-100 ℃, and removing the solvent after the reaction is finished to obtain the pure 2-chloro-N, N-dimethylnicotinamide, wherein the solvent is dichloromethane, tetrahydrofuran, chloromethane or acetone.
The preparation method based on the 2-aminosulfonyl-N, N-dimethylnicotinamide further comprises the following steps:
synthesizing 2-mercapto-N, N-dimethylnicotinamide, adding 2-chloro-N, N-dimethylnicotinamide into a 10-40% by mass sodium hydroxide aqueous solution, then adding sodium hydrosulfide and sulfur powder, reacting for 1-3 h at 0-100 ℃, and filtering after the reaction is finished to obtain 2-mercapto-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chloro-N, N-dimethylnicotinamide to the sodium hydrosulfide to the sulfur powder is 1: 1-3: 3-6.
The preparation method based on the 2-aminosulfonyl-N, N-dimethylnicotinamide further comprises the following steps:
synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide, dissolving 2-mercapto-N, N-dimethylnicotinamide in an acetic acid aqueous solution with the mass fraction of 50-90%, introducing chlorine, reacting for 1-3 h at 0-100 ℃, and after the reaction is finished, purifying to obtain the 2-chlorosulfonyl-N, N-dimethylnicotinamide. The specific purification treatment method in this step may be a method of removing the solvent from the solution obtained after the reaction is completed by distillation under reduced pressure.
The preparation method based on the 2-aminosulfonyl-N, N-dimethylnicotinamide further comprises the following steps:
synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide, dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide in dichloroethane, adding ammonia water, reacting at 0-100 ℃ for 1-3 hours to obtain a product mixed solution after the reaction is finished, pouring the product mixed solution into water for extraction to obtain an organic layer, and removing dichloroethane in the organic layer to obtain the 2-aminosulfonyl-N, N-dimethylnicotinamide. In the step, after the reaction is finished, the product mixed solution is poured into water for extraction to remove water-soluble impurities in the product mixed solution, the product is dissolved in the organic layer, and a reduced pressure distillation mode and the like can be adopted to remove the solvent in the product mixed solution.
The invention also provides a preparation method of the 2-aminosulfonyl-N, N-dimethylnicotinamide, which comprises the following steps:
synthesizing 2-chloro-N, N-dimethylnicotinamide by taking 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas as raw materials and reacting at 0-100 ℃ to synthesize 2-chloro-N, N-dimethylnicotinamide;
synthesizing 2-sulfydryl-N, N-dimethyl nicotinamide by using 2-chlorine-N, N-dimethyl nicotinamide as a raw material to synthesize 2-sulfydryl-N, N-dimethyl nicotinamide;
synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide by using 2-mercapto-N, N-dimethylnicotinamide as a raw material to synthesize 2-chlorosulfonyl-N, N-dimethylnicotinamide;
synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 2-chlorosulfonyl-N, N-dimethylnicotinamide is synthesized by using 2-chlorosulfonyl-N, N-dimethylnicotinamide as a raw material.
Compared with the prior art, the preparation method of 2-aminosulfonyl-N, N-dimethylnicotinamide provided by the invention takes 2-cyano-5-dimethylamino-2, 4-pentadienediformamide as a starting material to synthesize 2-chloro-N, N-dimethylnicotinamide, and further sequentially synthesizes the intermediate 2-mercapto-N, N-dimethylnicotinamide, 2-chlorosulfonyl-N, N-dimethylnicotinamide and 2-aminosulfonyl-N, N-dimethylnicotinamide, avoids taking 2-chloronicotinic acid as a starting material, develops a new preparation method of the intermediate of 2-aminosulfonyl-N, N-dimethylnicotinamide, has shorter synthetic route and high yield of the intermediate, for example, the yield of the intermediate 2-chloro-N, N-dimethylnicotinamide can reach 98%. Therefore, the preparation method of the 2-aminosulfonyl-N, N-dimethylnicotinamide provided by the invention is simple and feasible, high in yield, low in cost and capable of realizing industrial production.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Example 1
This example provides a method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, specifically including the following steps:
synthesizing 2-chloro-N, N-dimethylnicotinamide 9.66 g of 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide is dissolved in 150 mL of dichloromethane, hydrochloric acid gas is introduced, and the reaction is carried out for 2 h at the temperature of 60 ℃; after the reaction was completed, the solvent was removed to obtain 8.77 g of 2-chloro-N, N-dimethylnicotinamide with a yield of 94%. The nuclear magnetic detection of the synthesized product of this step resulted in 1H NMR (400 MHz, CHCl)3) δ 8.44(m,1H), δ 7.63(m, 1H), δ 7.28(m,1H), δ 3.02(s, 6H); therefore, it can be judged that the synthesis product of 2-cyano-5-dimethylamino-2, 4-pentadienedicarboxamide and hydrochloric acid gas is 2-chloro-N, N-dimethylnicotinamide.
Synthesis of 2-mercapto-N, N-dimethylnicotinamide 8.77 g of 2-chloro-N, N-dimethylnicotinamide was added to a 20% aqueous solution of sodium hydroxide, 2.8 g of sodium hydrosulfide and 6.4g of sulfur powder were added to the reaction system, and the reaction was carried out at 80 ℃ for 3 hours, after the reaction was completed, 7.96 g of 2-mercapto-N, N-dimethylnicotinamide was obtained by filtration, with a yield of 90%.
Synthesis of 2-chlorosulfonyl-N, N-dimethylnicotinamide 7.96 g of 2-mercapto-N, N-dimethylnicotinamide was dissolved in 60% acetic acid aqueous solution, chlorine gas was introduced into the reaction system, reaction was carried out at 40 ℃ for 2 hours, and after the reaction was completed, the solvent was removed to obtain 10.07 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with a yield of 92%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 10.07 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent to obtain 8.82 g of 2-aminosulfonyl-N, N-dimethylnicotinamide with a yield of 95%.
Therefore, the route for sequentially synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide using 2-cyano-5-dimethylamino-2, 4-pentadienedicarboxamide as a starting material provided in this example is as follows:
example 2
This example provides a method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, specifically including the following steps:
synthesizing 2-chloro-N, N-dimethylnicotinamide 9.66 g of 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide is dissolved in 150 mL of dichloromethane, hydrochloric acid gas is introduced, and the reaction is carried out for 3 h at the temperature of 40 ℃; after the reaction was completed, the solvent was removed to obtain 9.05 g of 2-chloro-N, N-dimethylnicotinamide with a yield of 98%.
Synthesizing 2-mercapto-N, N-dimethylnicotinamide 9.05 g of 2-chloro-N, N-dimethylnicotinamide is added into a 20% sodium hydroxide aqueous solution, 3.2 g of sodium hydrosulfide and 7.8 g of sulfur powder are added into a reaction system, the reaction is carried out for 3 hours at the temperature of 80 ℃, and after the reaction is finished, the 2-mercapto-N, N-dimethylnicotinamide 8.22 g is obtained by filtration, with the yield of 92%.
Synthesis of 2-chlorosulfonyl-N, N-dimethylnicotinamide 8.22 g of 2-mercapto-N, N-dimethylnicotinamide was dissolved in 60% acetic acid aqueous solution, chlorine gas was introduced into the reaction system, and the reaction was carried out at 40 ℃ for 2 hours, after the reaction was completed, the solvent was removed to obtain 10.8 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with a yield of 90%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 10.08 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent, whereby 8.74 g of 2-aminosulfonyl-N, N-dimethylnicotinamide was obtained with a yield of 93%.
Example 3
This example provides a method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, specifically including the following steps:
synthesizing 2-chloro-N, N-dimethylnicotinamide 9.66 g of 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide is dissolved in 150 mL of dichloromethane, hydrochloric acid gas is introduced, and the reaction is carried out for 1h at the temperature of 80 ℃; after the reaction was completed, the solvent was removed to obtain 8.86 g of 2-chloro-N, N-dimethylnicotinamide with a yield of 95%.
Synthesis of 2-mercapto-N, N-dimethylnicotinamide 8.86 g of 2-chloro-N, N-dimethylnicotinamide was added to a 20% aqueous solution of sodium hydroxide, 2.8 g of sodium hydrosulfide and 7.8 g of sulfur powder were added to the reaction system, and the reaction was carried out at 80 ℃ for 3 hours, after the reaction was completed, filtration was carried out to obtain 7.87 g of 2-mercapto-N, N-dimethylnicotinamide, with a yield of 90%.
Synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide 7.87 g of 2-mercapto-N, N-dimethylnicotinamide is dissolved in 60% acetic acid aqueous solution, chlorine is introduced into the reaction system, the reaction is carried out for 2 h at 40 ℃, and after the reaction is finished, the solvent is removed to obtain 9.52 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide, with the yield of 89%.
Synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 9.52 g of 2-chlorosulfonyl-N, N-dimethylnicotinamide was dissolved in dichloroethane, ammonia water was added, the reaction was carried out at 60 ℃ for 3 hours, after the reaction was completed, the reaction mixture was poured into clear water, and the organic layer was taken to remove the solvent, whereby 8.08 g of 2-aminosulfonyl-N, N-dimethylnicotinamide was obtained with a yield of 92%.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (6)
1. A method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, comprising the steps of:
synthesis of 2-chloro-N, N-dimethylnicotinamide takes 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas as raw materials, and the 2-chloro-N, N-dimethylnicotinamide is synthesized by reaction at the temperature of 0-100 ℃.
2. The method of preparing 2-aminosulfonyl-N, N-dimethylnicotinamide of claim 1, wherein the step of synthesizing 2-chloro-N, N-dimethylnicotinamide comprises: dissolving 2-cyano-5-dimethylamino-2, 4-pentadiene diformamide in a solvent, introducing hydrochloric acid gas, reacting for 1-3 h at 0-100 ℃, and removing the solvent after the reaction is finished to obtain the pure 2-chloro-N, N-dimethylnicotinamide, wherein the solvent is dichloromethane, tetrahydrofuran, chloromethane or acetone.
3. The method of preparing 2-aminosulfonyl-N, N-dimethylnicotinamide of claim 1 or 2, characterized by further comprising the steps of:
synthesizing 2-mercapto-N, N-dimethylnicotinamide, adding 2-chloro-N, N-dimethylnicotinamide into a 10-40% by mass sodium hydroxide aqueous solution, then adding sodium hydrosulfide and sulfur powder, reacting for 1-3 h at 0-100 ℃, and filtering after the reaction is finished to obtain 2-mercapto-N, N-dimethylnicotinamide; wherein the molar ratio of the 2-chloro-N, N-dimethylnicotinamide to the sodium hydrosulfide to the sulfur powder is 1: 1-3: 3-6.
4. The method of preparing 2-aminosulfonyl-N, N-dimethylnicotinamide of claim 3, further comprising the step of:
synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide, dissolving 2-mercapto-N, N-dimethylnicotinamide in an acetic acid aqueous solution with the mass fraction of 50-90%, introducing chlorine, reacting for 1-3 h at 0-100 ℃, and after the reaction is finished, purifying to obtain the 2-chlorosulfonyl-N, N-dimethylnicotinamide.
5. The method of preparing 2-aminosulfonyl-N, N-dimethylnicotinamide of claim 4, further comprising the step of:
synthesizing 2-aminosulfonyl-N, N-dimethylnicotinamide, dissolving 2-chlorosulfonyl-N, N-dimethylnicotinamide in dichloroethane, adding ammonia water, reacting at 0-100 ℃ for 1-3 hours to obtain a product mixed solution after the reaction is finished, pouring the product mixed solution into water for extraction to obtain an organic layer, and removing dichloroethane in the organic layer to obtain the 2-aminosulfonyl-N, N-dimethylnicotinamide.
6. A method for preparing 2-aminosulfonyl-N, N-dimethylnicotinamide, comprising the steps of:
synthesizing 2-chloro-N, N-dimethylnicotinamide by taking 2-cyano-5-dimethylamino-2, 4-pentadiene dimethylamide and hydrochloric acid gas as raw materials and reacting at 0-100 ℃ to synthesize 2-chloro-N, N-dimethylnicotinamide;
synthesizing 2-sulfydryl-N, N-dimethyl nicotinamide by using 2-chlorine-N, N-dimethyl nicotinamide as a raw material to synthesize 2-sulfydryl-N, N-dimethyl nicotinamide;
synthesizing 2-chlorosulfonyl-N, N-dimethylnicotinamide by using 2-mercapto-N, N-dimethylnicotinamide as a raw material to synthesize 2-chlorosulfonyl-N, N-dimethylnicotinamide;
synthesis of 2-aminosulfonyl-N, N-dimethylnicotinamide 2-chlorosulfonyl-N, N-dimethylnicotinamide is synthesized by using 2-chlorosulfonyl-N, N-dimethylnicotinamide as a raw material.
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| CN113461667A (en) * | 2021-06-30 | 2021-10-01 | 淄博新农基作物科学有限公司 | Method for synthesizing nicosulfuron by hydrogen sulfide closed loop |
| CN114181140A (en) * | 2022-02-16 | 2022-03-15 | 安徽华星化工有限公司 | Method for preparing 2-mercapto-N, N-dimethylnicotinamide |
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