CN106380427B - A kind of synthetic method of N cyclopropyl [[(2 methoxybenzoyl base) amino] sulfonyl] benzamide - Google Patents
A kind of synthetic method of N cyclopropyl [[(2 methoxybenzoyl base) amino] sulfonyl] benzamide Download PDFInfo
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- CN106380427B CN106380427B CN201610763679.9A CN201610763679A CN106380427B CN 106380427 B CN106380427 B CN 106380427B CN 201610763679 A CN201610763679 A CN 201610763679A CN 106380427 B CN106380427 B CN 106380427B
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- 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
- C07C303/40—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 reactions not involving the formation of sulfonamide groups
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- 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
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Abstract
The present invention relates to a kind of synthetic method of N cyclopropyl [[(2 methoxybenzoyl base) amino] sulfonyl] benzamide; this method is used as raw material using P―Carboxybenzenesulfonamide; catalyst is used as using acid, prepares N cyclopropyl [[(2 methoxybenzoyl base) amino] sulfonyl] benzamide.The present invention reduces the dosage of chlorination reagent 40% from effective catalyst, greatly reduce the discharge of sour gas sulfur dioxide and hydrogen chloride, meet energy-conservation, consumption reduction, the technological requirement of environmental protection at present, and product yield is high, purity is high, with cost advantage, quality-advantage, this synthesis technique has very big development space in the industrial production.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulphonyl
Base] benzamide synthetic method.
Background technology
N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide, English name
Cyprosulfamide, molecular formula：C18H18N2O5S, molecular weight 374.41, structural formula is as follows：
N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide is that Beyer Co., Ltd was sent out in 1997
A kind of existing acylsulfamoylbenzamides compound.As a kind of safener of herbicide, since two thousand eight, every year with two
The growth rate of digit increases, and it is effectively prevented and kill off more than 65 kinds of grassy weed and broad leaved weed, such as wild broomcorn millet, lady's-grass, Amaranthus retroflexus,
Green bristlegrass, eleusine indica, lamb's-quarters, barnyard grass and piemarker etc..
United States Patent (USP) (WO9916744) describes acylsulfamoylbenzamides derivative and its is used to remove as safener
The purposes of weeds is controlled in careless agent, the safe Herbicidal mixture has ideal agronomy performance and has potential business
Value.Chinese patent CN100413848 reported its synthetic method, but uses chloroform as reaction dissolvent poor selectivity,
Purity is low, and chlorination reagent dosage is bigger, complex process, reaction time length, can also produce sour gas sulfur dioxide and chlorination
Hydrogen, etching apparatus, pollution air, is unfavorable for popularization and application.Reaction temperature is higher, and its is expensive, not environmentally, uneconomical.
For these reasons, a kind of N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl is developed
The green syt new method of amine is imperative.
The content of the invention
To overcome the defect of prior art, the purpose of the present invention is just to provide a kind of economical synthesis N- cyclopropyl-[[(2-
Methoxybenzoyl base) amino] sulfonyl] and benzamide method, can effectively solve under low expense, using it is selective it is high,
The strong catalyst of repeatability is referred to as economical synthesis N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl]
Benzamide, its process route is simple, the reaction time is short, its thionyl chloride decrement 40%, and greatly reduces sour gas dioxy
Change the discharge of sulphur and hydrogen chloride.
The present invention is used as catalyst using P―Carboxybenzenesulfonamide as raw material, using acid, prepares N- cyclopropyl-[[(2- first
Epoxide benzoyl) amino] sulfonyl] benzamide, synthetic route is：
Comprise the following steps that：
(1) o-methoxybenzoic acid, P―Carboxybenzenesulfonamide, catalyst are put into toluene solvant, heating band water is to clear
It is bright；
(2) after system is limpid, 40-50 DEG C is cooled to, thionyl chloride is added dropwise, is warming up to backflow, is incubated 1-5 hours, reaction
Desolvation after end；
(3) material after above-mentioned desolvation is added into dichloromethane, cyclopropylamine is added drop-wise to sodium hydrate aqueous solution pair
Dichloromethane solution in, -0 DEG C of controlling reaction temperature -10 DEG C carry out react 5-10 hours, filter to obtain filter cake, filter cake is N-
Cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide.
For selection toluene as reaction dissolvent, not only boiling point is high, and can be with water, this reaction O-methoxy in step (1)
Benzoic acid, P―Carboxybenzenesulfonamide select toluene temperature rising reflux band water, water byproduct are taken out of, promoted under catalysts conditions
Balance is moved rearwards, so as to improve reaction efficiency.Reaction time is 1-1.5h.P―Carboxybenzenesulfonamide and o-methoxybenzoic acid
Mol ratio is 1:During 1.1-1.2, preferable reaction effect can be obtained.
After the completion of the reaction of point water, thionyl chloride is added into reaction system, thionyl chloride and P―Carboxybenzenesulfonamide rub
You are than being 1:1.1-1.6.Thionyl chloride temperature is added dropwise can not be too high, because pressure can be played, the more raised pressure of temperature is about big, has certain
It is dangerous；Dropping temperature is less than 40 DEG C, and temperature is too low, and reactivity is low, has a large amount of unreacted thionyl chlorides in system, after
Temperature of continuing rising, easy slug, and it is unfavorable for follow-up temperature reaction.It is added dropwise, is warming up to backflow, be incubated 3-5 hours, during insulation
Between determined according to reaction result, insulation starts to sample after 3 hours, once o-methoxybenzoic acid, to carboxyl this sulfonamide raw material
Remaining ＜ 0.5%, is post-processed immediately, if continuing insulation backflow material can decompose, insulation is less than 3 hours, and reaction is endless,
Influence yield, content.Reaction terminates rear desolvation.
Because dichloromethane preferably can dissolve the product of o-methoxybenzoic acid, P―Carboxybenzenesulfonamide, therefore,
Using dichloromethane as solvent in step (3).
Because the product of o-methoxybenzoic acid and P―Carboxybenzenesulfonamide reaction generation is a kind of acyl chlorides, double dropwise additions are not only
It is promoted to react generation N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide with cyclopropylamine, and
Avoid its hydrolysis.- 0 DEG C of controlling reaction temperature -10 DEG C.Reaction temperature is less than -10 DEG C, and whether the reaction or not.Temperature is higher than 0 DEG C,
Hydrolysis impurity can increase to 2%, influence yield, product content.Carry out reacting 5-10 hours, filter obtained filter cake.Step (3)
In, with the molar ratio computing of pure material, the mol ratio of sodium hydroxide and P―Carboxybenzenesulfonamide is 1:During 1.1-1.8, it is ensured that
Reaction is preferably carried out.In addition, sodium hydrate aqueous solution mass fraction is 15%-30%, the effect for tiing up acid was both played, had been avoided again
Product hydrolyzes under conditions of alkalescence is too strong.Sodium hydrate aqueous solution mass fraction preferably 30%.
In the present invention, the mol ratio of cyclopropylamine and P―Carboxybenzenesulfonamide is 1:2-7.
Catalyst of the present invention is p-methyl benzenesulfonic acid or benzene sulfonic acid or p-nitrophenyl sulfonic acid or its mixture.Due to neighbour
Methoxy benzoic acid, P―Carboxybenzenesulfonamide are in catalyst (p-methyl benzenesulfonic acid or benzene sulfonic acid or p-nitrophenyl sulfonic acid), toluene body
System's heating band water reacts, and promotes o-methoxybenzoic acid that intermolecular dehydration occurs first with P―Carboxybenzenesulfonamide, generates sulphur
Uride, o-methoxybenzoic acid is inherently avoided first to be prepared into o-methoxy benzoyl chloride and to carboxyl with thionyl chloride reaction
Benzsulfamide is condensed, so as to save the dosage of thionyl chloride.The dosage of the catalyst is P―Carboxybenzenesulfonamide quality
0.5%-15%.
The present invention reduces the dosage of chlorination reagent 40% from effective catalyst, greatly reduces sour gas sulfur dioxide
With the discharge of hydrogen chloride, meet energy-conservation, consumption reduction, the technological requirement of environmental protection at present, and product yield is high, purity is high, have into
This advantage, quality-advantage, this synthesis technique have very big development space in the industrial production.
Brief description of the drawings
Fig. 1 is N- cyclopropyl of the present invention-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide nuclear magnetic spectrogram.
Embodiment
Technical scheme is elaborated below in conjunction with specific embodiment, but protection domain is not limited by this.
Embodiment 1
203.22g P―Carboxybenzenesulfonamides (1mol), 167.33g o-methoxybenzoic acids are added in four-hole bottle
(1.1mol), 1.1g p-methyl benzenesulfonic acid stir 0.5 hour in 600g toluene solvants, and temperature rising reflux reacts 4 hours to limpid；
40 DEG C are cooled to, 180g thionyl chlorides are added dropwise into bottle, after being added dropwise, are incubated 3 hours.Solvent is sloughed, is added
650g dichloromethane infiltrates to obtain the dichloromethane solution of 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride.
Dichloromethane (70g), 74.8g cyclopropylamines (1.3mol), -8 DEG C of temperature control, stirring are added in other four-hole bottle
Under, the dichloromethane solution and 200g sodium hydroxides of 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride are water-soluble
Liquid (mass fraction 30%) is double into system to be added dropwise.In the insulation 9 hours of -4 DEG C of temperature after being added dropwise, -2 DEG C of suction filtrations obtain white
Crystal, content 98.3%, total recovery 93%.
Embodiment 2
101.1g P―Carboxybenzenesulfonamides (0.5mol contents 99%200.19), 86g O-methoxies are added in four-hole bottle
Benzoic acid (0.56mol 152.12), 1g benzene sulfonic acids stir 1 hour in 250g toluene solvants, and temperature rising reflux reacts 6 hours extremely
It is limpid；
45 DEG C are cooled to, 78.1g thionyl chlorides (1.3eq 118.98) are added dropwise into bottle, and after being added dropwise, insulation 4 is small
When.Solvent is sloughed, 300g dichloromethane is added and infiltrates to obtain 4- [[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The dichloromethane solution of chlorine.
Dichloromethane (40g), 30.2g cyclopropylamines (1.05eq), -5 DEG C of temperature control, stirring are added in other four-hole bottle
Under, the dichloromethane solution and 120g sodium hydroxides of 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride are water-soluble
Liquid (mass fraction 30%) is double into system to be added dropwise.In the insulation 6 hours of -7 DEG C of temperature after being added dropwise, -2 DEG C of suction filtrations obtain white
Crystal, content 98.1%, total recovery 92.9%.
Embodiment 3
2235g P―Carboxybenzenesulfonamides (11mol, content 99%), 1506g o-methoxybenzoic acids are added in four-hole bottle
(content 99%, 10mol), 335g p-nitrophenyls sulfonic acid stir 1 hour in 4500g toluene solvants, and temperature rising reflux reacts 3 hours
It is extremely limpid；
50 DEG C are cooled to, 1562g thionyl chlorides are added dropwise into bottle, after being added dropwise, are incubated 5 hours.Solvent is sloughed, is added
The dichloromethane that 3000g dichloromethane infiltrates to obtain 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride is molten
Liquid.
Add dichloromethane (4000g), 806g cyclopropylamines in other four-hole bottle, -6 DEG C of temperature control, under stirring, 4-
The dichloromethane solution of [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride and 1860g sodium hydrate aqueous solutions
(mass fraction 30%) is double into system to be added dropwise.After being added dropwise white crystalline substance is obtained in the insulation 5 hours of -5 DEG C of temperature, -3 DEG C of suction filtrations
Body, content 98.9%, total recovery 93.9%.
Embodiment 4
1067g P―Carboxybenzenesulfonamides (5.25mol, content 99%), 768.3g O-methoxy benzene are added in four-hole bottle
Formic acid (content 99%, 5mol), 20g p-nitrophenyl sulfonic acid, 25g p-methyl benzenesulfonic acids, 0.5 are stirred in 3000g toluene solvants
Hour, temperature rising reflux reacts 4 hours to limpid；
50 DEG C are cooled to, 661g thionyl chlorides are added dropwise into bottle, after being added dropwise, are incubated 1 hour.Solvent is sloughed, is added
The dichloromethane that 1000g dichloromethane infiltrates to obtain 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride is molten
Liquid.
Add dichloromethane (1000g), 345g cyclopropylamines in other four-hole bottle, -4 DEG C of temperature control, under stirring, 4-
The dichloromethane solution of [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride and 800g sodium hydrate aqueous solution (matter
Measure fraction 30%) double dropwise additions into system.In the insulation 10 hours of 0 DEG C of temperature after being added dropwise, -4 DEG C of suction filtrations obtain white crystal,
Content 99.0%, total recovery 92.3%.
Embodiment 5
439.0g P―Carboxybenzenesulfonamides (2.16mol, content 99%), 307.3g O-methoxy benzene are added in four-hole bottle
Formic acid (content 99%, 2mol), 4g benzene sulfonic acids, 4g p-methyl benzenesulfonic acids, stir 0.5 hour, heat up in 800g toluene solvants
Back flow reaction 3.5 hours is to limpid；
40 DEG C are cooled to, 276.4g thionyl chlorides are added dropwise into bottle, after being added dropwise, are incubated 2.5 hours.Slough solvent,
600g dichloromethane is added to infiltrate to obtain the dichloromethane of 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride
Solution.
Add dichloromethane (600g), 144g cyclopropylamines in other four-hole bottle, -5 DEG C of temperature control, under stirring, 4-
The dichloromethane solution of [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride and 333g sodium hydrate aqueous solution (matter
Measure fraction 30%) double dropwise additions into system.After being added dropwise white crystalline substance is obtained in the insulation 10 hours of -10 DEG C of temperature, -4 DEG C of suction filtrations
Body, content 98.8%, total recovery 92.1%.
Embodiment 6
11380g P―Carboxybenzenesulfonamides (56mol, content 99%), 8604.7g O-methoxy benzene are added in four-hole bottle
Formic acid (content 99%, 56mol), 300g benzene sulfonic acids, 300g p-methyl benzenesulfonic acids, 300 p-nitrophenyl sulfonic acid are in 80000g toluene
Stirred 1 hour in solvent, temperature rising reflux reacts 3 hours to limpid；
45 DEG C are cooled to, 7211g thionyl chlorides are added dropwise into bottle, after being added dropwise, are incubated 2 hours.Solvent is sloughed, is added
The dichloromethane that 60000g dichloromethane infiltrates to obtain 4- [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride is molten
Liquid.
Add dichloromethane (60000g), 3742g cyclopropylamines in other four-hole bottle, -5 DEG C of temperature control, under stirring, 4-
The dichloromethane solution of [[(2- methoxybenzoyls base) amino] sulfonyl] chlorobenzoyl chloride and 8667g sodium hydrate aqueous solutions
(mass fraction 30%) is double into system to be added dropwise.After being added dropwise white crystalline substance is obtained in the insulation 8 hours of -4 DEG C of temperature, -4 DEG C of suction filtrations
Body, content 98.9%, total recovery 93.0%.
The above described is only a preferred embodiment of the present invention, any form is not done to technical scheme
Limitation.Any simple modification, equivalent change and modification that every technical spirit according to the present invention is made to above case study on implementation,
Each fall within protection scope of the present invention.
Claims (6)
1. a kind of synthetic method of N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide, its feature
It is, using P―Carboxybenzenesulfonamide as raw material, catalyst is used as using acid, prepares N- cyclopropyl-[[(2- methoxybenzoyls
Base) amino] sulfonyl] benzamide, comprise the following steps that：
(1) o-methoxybenzoic acid, P―Carboxybenzenesulfonamide, catalyst are put into toluene solvant, heating band water is to limpid；
(2) after system is limpid, 40-50 DEG C is cooled to, thionyl chloride is added dropwise, drop finishes, and is incubated 1-5 hours, and reaction removes after terminating
Solvent；
(3) material after above-mentioned desolvation is added into dichloromethane, the two of cyclopropylamine is added drop-wise to sodium hydrate aqueous solution pair
In chloromethanes solution, it is added dropwise, -0 DEG C of controlling reaction temperature -10 DEG C carries out reacting 5-10 hours, filters to obtain filter cake, filter cake is
For N- cyclopropyl-[[(2- methoxybenzoyls base) amino] sulfonyl] benzamide；
Described catalyst is p-methyl benzenesulfonic acid or benzene sulfonic acid or p-nitrophenyl sulfonic acid or its mixture；
The dosage of the catalyst is the 0.5%-15% of P―Carboxybenzenesulfonamide quality.
A kind of 2. N- cyclopropyl according to claim 1-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The synthetic method of amine, it is characterised in that P―Carboxybenzenesulfonamide is 1 with o-methoxybenzoic acid mol ratio:0.9-1.2.
A kind of 3. N- cyclopropyl according to claim 1-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The synthetic method of amine, it is characterised in that the mol ratio of thionyl chloride and P―Carboxybenzenesulfonamide is 1.1-1.6:1.
A kind of 4. N- cyclopropyl according to claim 1-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The synthetic method of amine, it is characterised in that with the molar ratio computing of pure material, the mol ratio of sodium hydroxide and P―Carboxybenzenesulfonamide is
1.1-1.8：1.
A kind of 5. N- cyclopropyl according to claim 1-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The synthetic method of amine, it is characterised in that with the molar ratio computing of pure material, sodium hydrate aqueous solution mass fraction is 15%-30%.
A kind of 6. N- cyclopropyl according to claim 1-[[(2- methoxybenzoyls base) amino] sulfonyl] benzoyl
The synthetic method of amine, it is characterised in that the mol ratio of cyclopropylamine and P―Carboxybenzenesulfonamide is 1.05-1.3:1.
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| CN113372245B (en) * | 2021-06-17 | 2023-01-13 | 仪征市海帆化工有限公司 | Synthetic method of N-benzoyl-O, O-p-toluenesulfonyl-diethanolamine |
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| CN105636942A (en) * | 2013-10-10 | 2016-06-01 | 拜耳作物科学股份公司 | Process for preparing 4-[[(benzoyl)amino]sulphonyl]benzoyl chlorides and preparation of acylsulphamoylbenzamides |
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| CN105636942A (en) * | 2013-10-10 | 2016-06-01 | 拜耳作物科学股份公司 | Process for preparing 4-[[(benzoyl)amino]sulphonyl]benzoyl chlorides and preparation of acylsulphamoylbenzamides |
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| Title |
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| Design of novel CSA analogues as porential safeners and fungicides;Yang Zheng等;《Bioorganic ＆ Medicinal Chemistry Letters》;20150215;第25卷(第4期);791-794页 * |
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