CN115417813A - Preparation method of smoke sulfamide - Google Patents
Preparation method of smoke sulfamide Download PDFInfo
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- CN115417813A CN115417813A CN202211137823.XA CN202211137823A CN115417813A CN 115417813 A CN115417813 A CN 115417813A CN 202211137823 A CN202211137823 A CN 202211137823A CN 115417813 A CN115417813 A CN 115417813A
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- smoke
- formamide
- dimethyl pyridine
- sulfamide
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- 239000000779 smoke Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 66
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229960001238 methylnicotinate Drugs 0.000 claims abstract description 28
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 18
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 18
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000007069 methylation reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 11
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- 150000003456 sulfonamides Chemical class 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011218 binary composite Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- 239000012022 methylating agents Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims 1
- -1 dimethyl Bromide Chemical compound 0.000 claims 1
- 239000012374 esterification agent Substances 0.000 claims 1
- IBRSSZOHCGUTHI-UHFFFAOYSA-N 2-chloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Cl IBRSSZOHCGUTHI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007858 starting material Substances 0.000 abstract description 4
- 239000005586 Nicosulfuron Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 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 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material 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 relates to the field of fine chemistry, in particular to a preparation method of smoke sulfamide, which takes nicotinic acid as a raw material to carry out esterification reaction to obtain methyl nicotinate; methyl nicotinate is subjected to a methylation reaction to obtain 3-N, N-dimethyl pyridine formamide; carrying out oxidation reaction on the 3-N, N-dimethyl pyridine formamide to obtain 3-N, N-dimethyl pyridine formamide nitric oxide; carrying out sulfonation and ammoniation reactions on the 3-N, N-dimethyl pyridine formamide nitrogen oxide to obtain smoke sulfamide; the invention uses nicotinic acid as the starting material to replace 2-chloronicotinic acid, the cost of the main raw material is greatly reduced, and the nicotinic acid is esterified, methylaminated, oxidized, sulfonated and aminated, the conditions are simple, the production operation difficulty is low, and the total yield is high.
Description
Technical Field
The invention relates to the field of fine chemistry, and particularly relates to a preparation method of smoke sulfamide.
Background
Nicosulfuron, 2-aminosulfonyl-N, N-dimethylnicotinamide are key intermediates for the synthesis of nicosulfuron. In the prior art, 2-chloronicotinic acid is mainly used as a starting material, and the 2-chloronicotinic acid is subjected to the steps of acyl chlorination, methylamination, sulfhydrylation, chlorination, ammoniation and the like to prepare the smoke sulfamide. The method for preparing the smoke sulfamide has long preparation route, high cost and harsh production conditions. Other methods for preparing the smoke sulfamide mostly use 2-chloronicotinic acid as a raw material, are slightly changed on the basis, and are not obvious in cost, yield and the like due to convenient optimization.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of the smoke sulfamide, which uses nicotinic acid as a starting material to replace 2-chloronicotinic acid, has low cost, high yield and mild reaction conditions, and comprises the following steps:
a preparation method of smoke sulfamide comprises the following steps: taking nicotinic acid as a raw material, and carrying out esterification reaction to obtain methyl nicotinate; methyl nicotinate is subjected to a methylation reaction to obtain 3-N, N-dimethyl pyridine formamide; carrying out oxidation reaction on the 3-N, N-dimethyl pyridine formamide to obtain 3-N, N-dimethyl pyridine formamide nitric oxide; and 3-N, N-dimethyl pyridine formamide nitrogen oxide is subjected to sulfonation and ammoniation reaction to obtain the smoke sulfamide.
The reaction route is as follows:
further, methanol is adopted as an esterifying agent in the esterification reaction process.
The nicotinic acid is added to the methanol, which acts both as an esterifying agent and as a solvent.
Furthermore, p-toluenesulfonic acid is added as a catalyst in the esterification reaction process.
The molar ratio of the toluenesulfonic acid to the nicotinic acid is 1: (0.001-0.003).
Further, dimethylamine is adopted as a methylating agent in the process of the methylating reaction.
Furthermore, one or two of formamide and DBU are added as catalysts in the process of the methylamine reaction.
The molar ratio of one or two of formamide and DBU to the nicotinic acid is 1: (0.003-0.006).
The DBU is 1, 8-diazabicycloundecen-7-ene.
Furthermore, hydrogen peroxide is used as an oxidant in the oxidation reaction process.
The molar ratio of the hydrogen peroxide to the nicotinic acid is 1: (1.2-2), the concentration of the added hydrogen peroxide is 30%.
Furthermore, a binary composite catalyst is added in the oxidation reaction process.
The molar ratio of the binary composite catalyst to the nicotinic acid is 1: (0.02-0.1), wherein the binary catalyst consists of molybdenum oxide and titanium dioxide, and the content of the molybdenum oxide in the binary composite catalyst is 1%.
Furthermore, chlorosulfonic acid is used as a sulfonating agent and ammonia gas is used as an ammoniating agent in the sulfonation and ammoniation reaction processes.
The molar ratio of the 3-N, N-dimethyl pyridine formamide nitrogen oxide to chlorosulfonic acid is 1: (1.05-1.15).
Further, during the sulfonation and amination reaction, dichloromethane is used as a solvent.
Further, the method comprises the following steps:
(1) Preparation of methyl nicotinate:
mixing nicotinic acid and methanol, adding p-toluenesulfonic acid as a catalyst, heating under the condition of continuous stirring to perform reflux reaction, and then distilling and recovering the methanol to obtain a methyl nicotinate solution;
heating to reflux reaction, stopping heating and maintaining, reflux reaction for 3-5 hr, and distilling at 60-70 deg.c to recover methanol;
(2) Preparation of 3-N, N-dimethylpyridine formamide:
cooling the methyl nicotinate solution to room temperature, adding one or two of formamide and DBU (dimethyl-N-butyl-N) serving as a catalyst into the methyl nicotinate solution, introducing dimethylamine gas into the methyl nicotinate solution to react, and preserving the temperature to react when the pH of the solution is 8-9 to obtain a 3-N, N-dimethyl-pyridine formamide solution;
preserving the temperature at room temperature and carrying out reaction;
(3) Preparation of 3-N, N-dimethyl pyridine formamide nitroxide:
adding a molybdenum-loaded titanium dioxide catalyst into a 3-N, N-dimethyl pyridine formamide solution, heating, adding hydrogen peroxide for heat preservation reaction, then cooling to be less than or equal to 0 ℃, centrifuging, and drying to obtain 3-N, N-dimethyl pyridine formamide nitric oxide;
after adding a molybdenum-loaded titanium dioxide catalyst, raising the temperature to 35-55 ℃, slowly dripping 30% hydrogen peroxide into the solution within 0.4-0.6 hour, and reacting for 0.5-1.5 hours under heat preservation;
(4) Preparation of smoke sulfamide:
mixing 3-N, N-dimethyl pyridine formamide nitrogen oxide with dichloromethane, adding chlorosulfonic acid, preserving heat for reaction, then cooling, adding water to quench excessive chlorosulfonic acid, standing for layering, separating and removing a water layer, introducing ammonia gas into an organic layer for reaction, preserving heat for reaction when the pH value of a system is 8-9, then washing with water, centrifuging, and drying to obtain a finished product of the smoke sulfonamide;
after the chlorosulfonic acid is dripped, the temperature is kept at 35-55 ℃ for 1-2 hours for reaction, then ammonia gas is introduced when the temperature is reduced to-5 ℃, and the temperature is kept for 1-2 hours when the pH value of the system is 8-9.
The invention can bring the following beneficial effects:
1. the invention uses nicotinic acid as the starting material to replace 2-chloronicotinic acid, so that the cost of the main raw material is greatly reduced, and the nicotinic acid is subjected to esterification, methylamination, oxidation, sulfonation and ammoniation, the conditions are simple, the production operation difficulty is low, and the total yield is high.
2. The preparation method of the smoke sulfamide is simple, generates few byproducts, reduces the environmental protection treatment pressure and reduces the environmental pollution risk.
3. The reaction material used in the invention can be recycled, so that the waste of raw materials is avoided, and the production cost is reduced.
4. According to the invention, titanium dioxide loaded by molybdenum is used as a catalyst to catalyze hydrogen peroxide to oxidize so as to prepare the 3-N, N-dimethyl pyridine formamide nitric oxide, the reaction condition is mild, and the equipment is prevented from being corroded by an acidic environment to cause equipment damage.
Detailed Description
The present invention will be further described with reference to the following examples. The present disclosure is not limited to these examples.
Example 1
(1) Preparation of methyl nicotinate:
taking 61.5g of nicotinic acid and 200ml of methanol as raw materials, adding the raw materials into a 500ml three-necked bottle, adding 0.086g of p-toluenesulfonic acid as a catalyst, slowly heating under the condition of continuous stirring, carrying out reflux reaction for 4 hours, and then distilling and recovering the methanol at 65 ℃ to obtain a methyl nicotinate solution;
(2) Preparation of 3-N, N-dimethylpyridine formamide:
slowly cooling the methyl nicotinate solution to room temperature, adding 0.068g of formamide serving as a catalyst into the methyl nicotinate solution, introducing dimethylamine gas for reaction, and carrying out heat preservation reaction for 0.5 hour at room temperature when the pH of the solution is 8-9 to obtain a 3-N, N-dimethyl pyridine formamide solution;
(3) Preparation of 3-N, N-dimethyl pyridine formamide nitroxide:
adding 6.15g of molybdenum-loaded titanium dioxide catalyst into a 3-N, N-dimethyl pyridine formamide solution, heating to 50 ℃, slowly dropwise adding 68g of hydrogen peroxide into the solution within 0.5 hour, keeping the concentration of the used hydrogen peroxide at 30%, carrying out heat preservation reaction for 1 hour, then cooling to 0 ℃, centrifuging and drying to obtain 77.4g of 3-N, N-dimethyl pyridine formamide nitrogen oxide with the content of 97.5% and the yield of 91.4%;
(4) Preparation of smoke sulfamide:
adding 33.2g of the 3-N, N-dimethyl pyridine formamide nitrogen oxide into a 500ml three-necked bottle, adding 250ml of dichloromethane, mixing the 3-N, N-dimethyl pyridine formamide nitrogen oxide with dichloromethane, dropwise adding 26.8g of chlorosulfonic acid at room temperature, preserving heat at 55 ℃ for 2 hours after dropwise adding, reacting, cooling to 0 ℃, adding water to quench excessive sulfonating reagent, standing for layering, separating and removing a water layer, introducing ammonia gas into an organic layer at 0 ℃ for reacting, preserving heat at 0 ℃ for 1 hour when the pH value of the system is 8-9, washing with water, centrifuging, and drying to obtain 47.6g of the smoke sulfonamide, wherein the content is 98.0%, and the yield is 95.3%.
Example 2
(1) Preparation of methyl nicotinate:
taking 61.5g of nicotinic acid and 200ml of methanol as raw materials, adding the raw materials into a 500ml three-neck flask, adding 0.086g of p-toluenesulfonic acid as a catalyst, slowly heating under the condition of continuous stirring, carrying out reflux reaction for 4 hours, and then distilling and recovering the methanol at 65 ℃ to obtain a methyl nicotinate solution;
(2) Preparation of 3-N, N-dimethylpyridine formamide:
slowly cooling the methyl nicotinate solution to room temperature, adding 0.068g of formamide serving as a catalyst into the methyl nicotinate solution, introducing dimethylamine gas into the methyl nicotinate solution to react, and preserving the temperature at room temperature for 0.5 hour when the pH of the solution is 8-9 to obtain a 3-N, N-dimethylpyridine formamide solution;
(3) Preparation of 3-N, N-dimethyl pyridine formamide nitroxide:
adding 1.23g of molybdenum-loaded titanium dioxide catalyst into a 3-N, N-dimethyl pyridine formamide solution, heating to 35 ℃, slowly dropwise adding 68g of hydrogen peroxide into the solution within 0.5 hour, keeping the concentration of the used hydrogen peroxide at 30%, reacting for 1 hour, then cooling to below 0 ℃, centrifuging, and drying to obtain 67.9g of 3-N, N-dimethyl pyridine formamide nitrogen oxide with the content of 97.0% and the yield of 90.7%;
(4) Preparation of smoke sulfamide:
adding 33.2g of the 3-N, N-dimethyl pyridine formamide nitrogen oxide into a 500ml three-necked bottle, adding 250ml of dichloromethane, mixing the 3-N, N-dimethyl pyridine formamide nitrogen oxide with dichloromethane, dropwise adding 24.5g of chlorosulfonic acid at room temperature, keeping the temperature at 50 ℃ for 2 hours after dropwise adding, reacting, cooling to-5 ℃, adding water to quench excessive sulfonating agent, standing for layering, separating and removing a water layer, introducing ammonia gas into an organic layer at-5 ℃ for reacting, keeping the temperature at-5 ℃ for 1 hour when the pH value of the system is 8-9, washing with water, centrifuging, and drying to obtain 47.4g of the smoke sulfonamide, wherein the content is 97.8%, and the yield is 94.8%.
Example 3
(1) Preparation of methyl nicotinate:
taking 61.5g of nicotinic acid and 200ml of methanol as raw materials, adding the raw materials into a 500ml three-necked bottle, adding 0.086g of p-toluenesulfonic acid as a catalyst, slowly heating under the condition of continuous stirring, carrying out reflux reaction for 4 hours, and then distilling and recovering the methanol at 65 ℃ to obtain a methyl nicotinate solution;
(2) Preparation of 3-N, N-dimethylpyridine formamide:
slowly cooling the methyl nicotinate solution to room temperature, adding 0.228g of DBU (dimethyl dithiocarbamate) serving as a catalyst into the methyl nicotinate solution, introducing dimethylamine gas for reaction, and carrying out heat preservation reaction for 0.5 hour at room temperature when the pH of the solution is 8-9 to obtain a 3-N, N-dimethyl picolinamide solution;
(3) Preparation of 3-N, N-dimethyl pyridine formamide nitroxide:
adding 1.23g of molybdenum-loaded titanium dioxide catalyst into a 3-N, N-dimethyl pyridine formamide solution, heating to 55 ℃, slowly dripping 113.3g of hydrogen peroxide into the solution within 0.5 hour, keeping the concentration of the used hydrogen peroxide at 30%, reacting for 1 hour, then cooling to below 0 ℃, centrifuging, and drying to obtain 77.2g of 3-N, N-dimethyl pyridine formamide nitrogen oxide with the content of 97.6% and the yield of 91.3%;
(4) Preparation of smoke sulfamide:
adding 33.2g of the 3-N, N-dimethyl pyridine formamide nitrogen oxide into a 500ml three-necked bottle, adding 250ml of dichloromethane, mixing the 3-N, N-dimethyl pyridine formamide nitrogen oxide with the dichloromethane, dropwise adding 26.8g of chlorosulfonic acid at room temperature, preserving the temperature for 2 hours at 35 ℃ after dropwise adding, reacting, cooling to 5 ℃, adding water to quench excessive sulfonating reagent, standing for layering, separating and removing a water layer, introducing ammonia gas into an organic layer at 5 ℃ for reacting, preserving the temperature for 1 hour at 5 ℃ when the pH value of the system is 8-9, washing with water, centrifuging, and drying to obtain 47.5g of the smoke sulfonamide, wherein the content is 98.2%, and the yield is 95.4%.
All the embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A preparation method of smoke sulfamide is characterized by comprising the following steps: taking nicotinic acid as a raw material, and carrying out esterification reaction to obtain methyl nicotinate; methyl nicotinate is subjected to a methylation reaction to obtain 3-N, N-dimethyl pyridine formamide; carrying out oxidation reaction on the 3-N, N-dimethyl pyridine formamide to obtain 3-N, N-dimethyl pyridine formamide nitric oxide; and (3) carrying out sulfonation and ammoniation reactions on the 3-N, N-dimethyl pyridine formamide nitrogen oxide to obtain the smoke sulfamide.
2. The method for preparing smoke sulfamide according to claim 1, wherein methanol is used as esterification agent during the esterification reaction.
3. The method for preparing smoke sulfamide according to claim 2, wherein p-toluenesulfonic acid is further added as a catalyst during the esterification reaction.
4. The method for producing a smoke sulfonamide according to claim 1, wherein dimethylamine is used as a methylating agent in the process of the methylamination reaction.
5. The method for preparing the smoke sulfamide according to claim 4, wherein one or two of formamide and DBU are added as catalysts in the methylamine reaction process.
6. The method for preparing smoke sulfamide according to claim 1, wherein hydrogen peroxide is used as an oxidant in the oxidation reaction process.
7. The method for preparing smoke sulfamide according to claim 6, wherein a binary composite catalyst is further added during the oxidation reaction.
8. The method for preparing nicotineamide according to claim 1, wherein chlorosulfonic acid is used as a sulfonating agent and ammonia gas is used as an ammoniating agent during the sulfonation and ammoniation reaction.
9. The method for preparing smoke sulfonamide according to claim 8, wherein dichloromethane is used as a solvent during the sulfonation and amination reaction.
10. The process for the preparation of smoke sulfonamides according to any of claims 1 to 9, comprising the steps of:
(1) Preparation of methyl nicotinate:
mixing nicotinic acid and methanol, adding p-toluenesulfonic acid as a catalyst, heating under the condition of continuous stirring to perform reflux reaction, and then distilling and recovering the methanol to obtain a methyl nicotinate solution;
(2) Preparation of 3-N, N-dimethylpyridine formamide:
cooling the methyl nicotinate solution to room temperature, adding one or two of formamide and DBU (dimethyl Bromide) serving as a catalyst into the methyl nicotinate solution, introducing dimethylamine gas for reaction, and carrying out heat preservation reaction when the pH of the solution is 8-9 to obtain a 3-N, N-dimethyl pyridine formamide solution;
(3) Preparation of 3-N, N-dimethyl pyridine formamide nitroxide:
adding a molybdenum-loaded titanium dioxide catalyst into a 3-N, N-dimethyl pyridine formamide solution, heating, adding hydrogen peroxide for heat preservation reaction, then cooling to below 0 ℃, centrifuging, and drying to obtain 3-N, N-dimethyl pyridine formamide nitric oxide;
(4) Preparation of smoke sulfamide:
mixing 3-N, N-dimethyl pyridine formamide nitrogen oxide with dichloromethane, adding chlorosulfonic acid, preserving heat for reaction, then cooling, adding water to quench excessive chlorosulfonic acid, standing for layering, separating and removing a water layer, introducing ammonia gas into an organic layer for reaction, preserving heat for reaction when the pH value of a system is 8-9, then washing with water, centrifuging, and drying to obtain a finished product of the smoke sulfonamide.
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| CN202211137823.XA CN115417813A (en) | 2022-09-19 | 2022-09-19 | Preparation method of smoke sulfamide |
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| CN202211137823.XA Pending CN115417813A (en) | 2022-09-19 | 2022-09-19 | Preparation method of smoke sulfamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784977A (en) * | 2023-02-06 | 2023-03-14 | 淄博新农基作物科学有限公司 | Synthesis process of 2-chloro-3-trifluoromethylpyridine |
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| US4786734A (en) * | 1986-11-28 | 1988-11-22 | E. I. Du Pont De Nemours And Company | Herbicidal pyridine sulfonamides |
| US20120095238A1 (en) * | 2009-06-30 | 2012-04-19 | Clariant Finance (Bvi) Limited | Continuous Method For Producing Amides Of Aromatic Carboxylic Acids |
| CN112479994A (en) * | 2020-12-18 | 2021-03-12 | 淄博新农基作物科学有限公司 | Preparation method of smoke sulfamide |
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| US4786734A (en) * | 1986-11-28 | 1988-11-22 | E. I. Du Pont De Nemours And Company | Herbicidal pyridine sulfonamides |
| US20120095238A1 (en) * | 2009-06-30 | 2012-04-19 | Clariant Finance (Bvi) Limited | Continuous Method For Producing Amides Of Aromatic Carboxylic Acids |
| CN112479994A (en) * | 2020-12-18 | 2021-03-12 | 淄博新农基作物科学有限公司 | Preparation method of smoke sulfamide |
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| 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, vol. 28, no. 9, pages 47 - 48 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784977A (en) * | 2023-02-06 | 2023-03-14 | 淄博新农基作物科学有限公司 | Synthesis process of 2-chloro-3-trifluoromethylpyridine |
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