CN107540566A - A kind of preparation method of propyzamide - Google Patents
A kind of preparation method of propyzamide Download PDFInfo
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- CN107540566A CN107540566A CN201710753845.1A CN201710753845A CN107540566A CN 107540566 A CN107540566 A CN 107540566A CN 201710753845 A CN201710753845 A CN 201710753845A CN 107540566 A CN107540566 A CN 107540566A
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Abstract
The present invention provides a kind of preparation method of propyzamide, including condensation step：In 200~400 parts of the sodium hydroxide solution that 100~500 parts of 100~105 parts of 3 amino, 3 methyl butyne, 2~5 parts of triethylamine and solvent are put into 10%~32% ω in terms of mass parts, after stirring, it is added dropwise 3,5 100~105 parts of dichlorobenzoyl chlorides, temperature control is at 12~15 DEG C, after completion of dropwise addition, 1~5 hour is incubated.The preparation method of the propyzamide has the advantages of product purity is high.
Description
Technical field
The present invention relates to a kind of production method of acetamide-group herbicides, specifically, is related to a kind of life of propyzamide
Production method.
Background technology
Propyzamide also known as pentyl xanthate, chemical name are 3,5- bis- chloro- N- (1,1- alkynyl dimethyl) benzoyls
Amine, it is a kind of widely used herbicide, is usually used in the control of broad leaved weed.The propyzamide supplied on domestic market
Purity have 95%~99%, wherein accounting for the overwhelming majority with the propyzamide of 95%~97% purity, and meet international market
It is required that the propyzamide of purity >=98% account for a few part.
Liu Jie -- the study on the synthesis of herbicide pentyl xanthate, CDMD, 2005,
The fifth phase-disclose using concentrated hydrochloric acid as chlorinating agent and 3- hydroxy-3-methyl butine, in the presence of the concentrated sulfuric acid and catalyst
Synthesize the chloro- 3- methyl butynes of 3-；The reaction under silver nitrate catalysis of the chloro- 3- methyl butynes of 3- and liquefied ammonia obtains 3- amino -3- methyl
Butine；Last 3- amino -3- methyl butynes and 3,5- dichlorobenzoyl chloride, react by acid binding agent of NaOH, finally recrystallize
To 98% propyzamide.Three steps synthesize the chemical equation being related to：
Finally obtained propyzamide purity reaches 98% to the technical scheme, but it is to relate to recrystallize using solvent one
And the processing of solvent, second, the yield of product declines.
In order to solve the above problems, the propyzamide of high-purity is obtained, we are seeking a kind of preferable technology always
Solution.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, so as to provide the alkynes of a kind of not only purity height but also high income
Benzoyl grass amine preparation method.
A kind of preparation method of propyzamide, including condensation step：By 3- amino -3- methyl butynes in terms of mass parts
100~500 parts of 100~105 parts, 2~5 parts of triethylamine and solvent sodium hydroxide solutions for putting into 10%~32% mass fraction
In 200~400 parts, after stirring, 100~105 parts of 3,5- dichlorobenzoyl chlorides are added dropwise, temperature control is at 12~15 DEG C, drop
After adding end, 1~5 hour is incubated.
Based on above-mentioned, it also includes chloro step, by 100 parts of 3- hydroxy-3-methyls butine and 98% ω in terms of mass parts
100~120 parts of sulfuric acid is added drop-wise to comprising 100~150 parts of concentrated hydrochloric acids, 5~9 parts of zinc chloride and 5~7 parts of Macrogol 600s respectively
Mixed liquor in, reaction temperature during dropwise addition is 25~35 DEG C, and 2~3 hours are incubated after completion of dropwise addition.
Based on above-mentioned, reaction temperature when the 98% ω sulfuric acid is added dropwise is 30~35 DEG C.
Based on above-mentioned, it also includes amination steps, by the chloro- 3- methyl butynes of 100 parts of 3- and 50~100 parts in terms of mass parts
Liquefied ammonia reacts under the catalytic action of 0.05~5 part of silver nitrate, keep reaction temperature be 20~38 DEG C, reaction pressure be 0.5~
1.0MPa。
Based on above-mentioned, the reaction temperature of the chloro- 3- methyl butynes of liquefied ammonia and 3- is 25~29 DEG C.
Based on above-mentioned, the solvent is toluene or dichloromethane.
The present invention is compared with the prior art with prominent substantive distinguishing features and significantly progressive, specifically, of the invention
Catalyst of triethylamine is used in condensation step, the HCl of generation passed into alkali carries out neutralization using the acid effect of tiing up of triethylamine and subtract
Few side reaction so that propyzamide need not recrystallize and final purity is more than 98%；Furtherly, the present invention walks in chlorination
It is rapid by the use of as composite catalyst, improving the selectivity of chlorination reaction, improve final products in zinc chloride and Macrogol 600
Yield.It has the advantages of reaction product purity is high.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
200 parts of 100 parts of 3- amino -3- methyl butynes, 2 parts of triethylamine and dichloromethane are put into 32% in terms of mass parts
In 150 parts of the sodium hydroxide solution of mass fraction, after stirring, 100 parts of 3,5- dichlorobenzoyl chlorides, dropping temperature control is added dropwise
System is at 12~15 DEG C, after completion of dropwise addition, is incubated 3 hours, samples finished product content >=98%, insulation terminates.Centrifugation obtains wet product and consolidated
Body, obtained wet product are dried at 80 DEG C, then sampling analysis, content 99%.
Embodiment 2
100 parts of 100 parts of 3- hydroxy-3-methyls butine and 98% ω sulfuric acid are added dropwise simultaneously in terms of mass parts and include 105 parts
In the mixed liquor of concentrated hydrochloric acid, 5 parts of zinc chloride and 5 parts of Macrogol 600s, reaction temperature during dropwise addition is 25 DEG C, after completion of dropwise addition
Insulation 2 hours.It is chloride that insulation is sufficiently stirred again stratification upper strata after terminating, and lower floor is poly-doped impurity.Divide sub-cloud miscellaneous
Filter to obtain the chloro- 3- methyl butynes of chloride sterling 3- again after putting into the water suction of water absorbing agent anhydrous sodium chloride after matter.By obtained chlorine
Compound and liquefied ammonia carry out aminating reaction and 3- amino -3- methyl butynes are made, by 3- amino -3- methyl butynes and 3,5- dichloro-benzenes first
Acyl chlorides carries out condensation reaction according to the method in embodiment 1 and propyzamide, sampling analysis, content 98.3% is made.
Embodiment 3
120 parts of 100 parts of 3- hydroxy-3-methyls butine and 98% ω sulfuric acid are added dropwise simultaneously in terms of mass parts and include 130 parts
In the mixed liquor of concentrated hydrochloric acid, 7 parts of zinc chloride and 5 parts of Macrogol 600s, reaction temperature during dropwise addition is 33 DEG C, after completion of dropwise addition
Insulation 3 hours.It is chloride that insulation is sufficiently stirred again stratification upper strata after terminating, and lower floor is poly-doped impurity.Divide sub-cloud miscellaneous
After matter, the anhydrous sodium chloride water suction of input water absorbing agent, then filter to obtain the chloro- 3- methyl butynes of sterling 3-.
In terms of mass parts by the chloro- 3- methyl butynes of 100 parts of 3- and 70 liquefied ammonia under the catalytic action of 0.1 part of silver nitrate it is anti-
Should, it is 27 DEG C to keep reaction temperature, reaction pressure 0.5MPa.After reaction terminates, 6 hours are incubated.Insulation terminates to add 200 parts
Process water stirs 1 hour, and mixture is transferred into distillation still carries out air-distillation, when kettle temperature degree to be distilled is increased to 120 DEG C, distillation
Terminate, it is residual to put kettle.Cut merges by before, during and after goes to washing kettle together, adds appropriate supersaturated brine stirring to stand 2 hours, point
Layer, upper materials are 3- amino -3- methyl butynes.
150 parts of 105 parts of 3- amino -3- methyl butynes, 5 parts of triethylamine and toluene are put into 20% mass in terms of mass parts
In 300 parts of the sodium hydroxide solution of fraction, after stirring, 100 parts of 3,5- dichlorobenzoyl chlorides are added dropwise, dropping temperature control exists
13~15 DEG C, after completion of dropwise addition, 3 hours are incubated, middle control sampling finished product purity is more than 98%, stops insulation.Centrifugation obtains wet product,
Obtained wet product is dried at 80 DEG C, then sampling analysis, content 98.7%.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
The embodiment of the present invention can be modified or equivalent substitution is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical scheme, it all should cover among the claimed technical scheme scope of the present invention.
Claims (6)
1. a kind of preparation method of propyzamide, including condensation step：By 3- amino -3- methyl butynes 100 in terms of mass parts
The sodium hydroxide solution 200~400 that 100~500 parts of~105 parts, 2~5 parts of triethylamine and solvent put into 10%~32% ω
In part, after stirring, 100~105 parts of 3,5- dichlorobenzoyl chlorides are added dropwise, temperature control is at 12~15 DEG C, after completion of dropwise addition,
Insulation 1~5 hour.
2. the preparation method of propyzamide according to claim 1, it is characterised in that：It also includes chloro step, with
100~120 parts of 100 parts of 3- hydroxy-3-methyls butine and 98% ω sulfuric acid are added drop-wise to comprising 100~150 by mass parts meter respectively
In the mixed liquor of part concentrated hydrochloric acid, 5~9 parts of zinc chloride and 5~7 parts of Macrogol 600s, reaction temperature during dropwise addition is 25~35
DEG C, it is incubated 2~3 hours after completion of dropwise addition.
3. the preparation method of propyzamide according to claim 2, it is characterised in that：When the 98% ω sulfuric acid is added dropwise
Reaction temperature be 30~35 DEG C.
4. the preparation method of the propyzamide according to claim any one of 1-3, it is characterised in that：It also includes ammonification
Step, the chloro- 3- methyl butynes of 100 parts of 3- and 50~100 parts of liquefied ammonia are made in the catalysis of 0.05~5 part of silver nitrate in terms of mass parts
With lower reaction, it is 20~38 DEG C to keep reaction temperature, and reaction pressure is 0.5~1.0MPa.
5. the preparation method of propyzamide according to claim 4, it is characterised in that：The chloro- 3- first of liquefied ammonia and 3-
The reaction temperature of base butine is 25~29 DEG C.
6. the preparation method of propyzamide according to claim 5, it is characterised in that：The solvent is toluene or two
Chloromethanes.
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| BE830915A (en) * | 1974-07-04 | 1975-11-03 | PROCESSES FOR THE PREPARATION OF PROPARGYL AMINES AND PRODUCTS OBTAINED BY LEDIT PROCEDE | |
| JPH02225427A (en) * | 1989-02-28 | 1990-09-07 | Pola Chem Ind Inc | Bicyclo (8.3.0) trideca-9,13-diene-2,7-diyn derivative |
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| US3534098A (en) * | 1967-01-10 | 1970-10-13 | Rohm & Haas | 3,5-disubstituted benzamides |
| US3742051A (en) * | 1971-06-02 | 1973-06-26 | Rohm & Haas | 3,5-dichloro-n-(1,1,dimethyl-2-propynyl)benzimidoyl halides and derivatives |
| BE830915A (en) * | 1974-07-04 | 1975-11-03 | PROCESSES FOR THE PREPARATION OF PROPARGYL AMINES AND PRODUCTS OBTAINED BY LEDIT PROCEDE | |
| JPH02225427A (en) * | 1989-02-28 | 1990-09-07 | Pola Chem Ind Inc | Bicyclo (8.3.0) trideca-9,13-diene-2,7-diyn derivative |
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| WO2017140754A1 (en) * | 2016-02-17 | 2017-08-24 | Advanced Biodesign | Process for preparing aminothiol ester compounds and salts thereof |
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Application publication date: 20180105 |