CN101391969A - Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide - Google Patents
Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide Download PDFInfo
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- CN101391969A CN101391969A CNA2008102020131A CN200810202013A CN101391969A CN 101391969 A CN101391969 A CN 101391969A CN A2008102020131 A CNA2008102020131 A CN A2008102020131A CN 200810202013 A CN200810202013 A CN 200810202013A CN 101391969 A CN101391969 A CN 101391969A
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Abstract
The invention discloses a method for preparing N-methyl-2-(2, 4-dichlorophenoxy) acetamide, which comprises the steps: a. 4-chlorophenol, a solvent N, N-dimethylformamide and anhydrous potassium carbonate taken as an acid-binding agent are added into a vessel for reaction; b. 2-(4-chlorophenoxy) methyl acetate and ethanol are added into the vessel for reaction; and c. N-methyl-2-(4-chlorophenoxy) acetamide and the solvent methanoic acid are added into the vessel and dropped with the mixed solution of sulfuric chloride and methanoic acid for reaction, and then the N-methyl-2-(2, 4-dichlorophenoxy) acetamide is obtained after drying. The invention selects initial raw materials with comparatively low toxicity, has high product yield and low cost, and can be used for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of benzene oxanamide compounds, more particularly relating to benzene oxanamide compound chloride on a kind of phenyl ring is the preparation method of N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide.
Background technology
2,4-dichlorophenoxy carboxylic acid cpd and derivative thereof be inhale in a kind of, plant-growth regulator efficiently, can promote the intravital biosynthesizing of plant, prevent fruit drop, improve the fruit rate of doing, enhancement fruit growth speed, promote ripen in advance, also have herbicide effect simultaneously.At Synthetic 2, when 4-dichlorophenoxy carboxylic acid cpd and derivative thereof, in the past, how be that raw material and halogen carboxylic acid, haloid ether, haloamide etc. react in alkaline aqueous solution and obtain with the 2,4 dichloro phenol, therefore, raw material halogenide facile hydrolysis; In addition, 2,4 dichloro phenol is expensive, and toxicity is bigger, has therefore hindered the development of its suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is that 4-chlorophenol less with toxicity, not facile hydrolysis is a starting raw material, by reacting with haloid ether, separate through ammonia and to obtain intermediate N methyl-2-(4-chlorophenoxy) ethanamide, obtain purpose product N-methyl-2-(2 through chlorination again, the 4-dichlorophenoxy) ethanamide, this method product yield height, cost is low, and industrial production foreground is arranged.
Technical solution of the present invention: the method for the N-methyl-2-of a kind of preparation structural formula (I) (2,4 dichloro benzene oxygen base) ethanamide comprises the following steps:
(I)
A. in container, add 4-chlorophenol solvent N, dinethylformamide and as the Anhydrous potassium carbonate of acid binding agent, be heated with stirring to 50～90 ℃, slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dripping end, at 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrate is sloughed partial solvent N, behind the dinethylformamide, pour in the water, treat that solid fully separates out, suction filtration obtains 2-(4-chlorophenoxy) methyl acetate with crude product through the ethanol/water recrystallization;
B. in container, add 2-(4-chlorophenoxy) methyl acetate, ethanol, be heated with stirring to 30～70 ℃, drip the ethanolic soln of methylamine, the dropping time is 0.5～1h, drip to finish the back at 30～70 ℃ of insulation reaction 2～6h, reaction solution is sloughed partial solvent ethanol after, pour in the water, treat that solid fully separates out, suction filtration obtains N-methyl-2-(4-chlorophenoxy) ethanamide with crude product with the ethanol/water recrystallization;
C. add N-methyl-2-(4-chlorophenoxy) ethanamide in container, solvent formic acid is heated with stirring to 30～60 ℃, drip the mixing solutions of sulfuryl chloride and formic acid, the dropping time is 0.5～2h, after dropping finishes, at 30～60 ℃ of insulation reaction 3～8h, after reaction solution sloughed partial solvent acetate, pour in the water, treat that solid fully separates out, suction filtration, and extremely neutral with 5% sodium carbonate solution washing, get N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide after the drying.
Molar ratio of material N-methyl-2-(4-chlorophenoxy) ethanamide: sulfuryl chloride=1:1～2 among the step c, the quality of solvent formic acid are 3～8 times of N-methyl-2-(4-chlorophenoxy) ethanamide quality.
Beneficial effect of the present invention: in this reaction, overcome the halid hydrolysis of raw material in the past, selected the relatively low starting raw material of toxicity for use.In chlorination reaction, there is hydrogenchloride to generate, hydrogenchloride can generate hydrochloride with N-methyl-2-(4-chlorophenoxy) ethanamide, as use chlorinated solvent benzene commonly used, toluene, tetracol phenixin etc., N-methyl-2-(4-chlorophenoxy) acetamide hydrochloride can be separated out in these solvents, the process of influence reaction, even hinder reaction.Among the present invention, be solvent, make N-methyl-2-(4-chlorophenoxy) acetamide hydrochloride can be dissolved in formic acid well, thereby improved degree of purity of production and yield with formic acid.For this reason, the inventor is starting raw material and haloid ether reaction with the 4-chlorophenol, and after ammonolysis reaction obtains intermediate N methyl-2-(4-chlorophenoxy) ethanamide, obtain purpose product N-methyl-2-(2 through chlorination again, the 4-dichlorophenoxy) ethanamide, this method product yield height, cost is low, and the future of suitability for industrialized production is arranged.
Embodiment
Below by specific embodiment the present invention is described in further detail: the method for the N-methyl-2-of a kind of preparation structural formula (I) (2,4 dichloro benzene oxygen base) ethanamide comprises the following steps:
A. in container, add 4-chlorophenol, solvent N, dinethylformamide and as the Anhydrous potassium carbonate of acid binding agent, be heated with stirring to 50～90 ℃, slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dripping end, at 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrate is sloughed partial solvent N, behind the dinethylformamide, pour in the water, treat that solid fully separates out, suction filtration obtains 2-(4-chlorophenoxy) methyl acetate with crude product through the ethanol/water recrystallization;
B. in container, add 2-(4-chlorophenoxy) methyl acetate, ethanol, be heated with stirring to 30～70 ℃, drip the ethanolic soln of methylamine, the dropping time is 0.5～1h, drip to finish the back at 30～70 ℃ of insulation reaction 2～6h, reaction solution is sloughed partial solvent ethanol after, pour in the water, treat that solid fully separates out, suction filtration obtains N-methyl-2-(4-chlorophenoxy) ethanamide with crude product with the ethanol/water recrystallization;
C. add N-methyl-2-(4-chlorophenoxy) ethanamide in container, solvent formic acid is heated with stirring to 30～60 ℃, drip the mixing solutions of sulfuryl chloride and formic acid, the dropping time is 0.5～2h, after dropping finishes, at 30～60 ℃ of insulation reaction 3～8h, after reaction solution sloughed partial solvent acetate, pour in the water, treat that solid fully separates out, suction filtration, and extremely neutral with 5% sodium carbonate solution washing, get N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide after the drying.Molar ratio of material N-methyl-2-(4-chlorophenoxy) ethanamide: sulfuryl chloride=1:1～2 among the step c, the quality of solvent formic acid are 3～8 times of N-methyl-2-(4-chlorophenoxy) ethanamide quality.
Embodiment 1
The adding of 10g (0.05mol) N-methyl-2-(4-chlorophenoxy) ethanamide is had in the 250mL four-hole boiling flask of agitator, thermometer, prolong and dropping funnel, add 60mL formic acid, be heated to 40 ℃.Under agitation drip the mixed solution of 9.5g (0.07mol) sulfuryl chloride and 20mL formic acid, then, in 40 ℃ of insulation 5h.Reaction finishes, slough partial solvent after, pour raffinate in 300mL water elutriation, behind suction filtration, washing and the recrystallization, obtain white solid N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide 10g, its yield is greater than 85%, fusing point: 106.5 ℃～106.8 ℃.IR(KBr)，v/cm
-1：3317(N-H)，1664(C＝O)，1249cm
-1(-O-)，
1HNMR(CDCl
3)：7.40(m，1H，-C
6H
5)，7.20(m，2H，-C
6H
5)，6.60(q，1H，-NH-)，4.45(2H，-CH
2-)，2.80(d，3H，-CH
3)。Ultimate analysis C
9H
9NO
2Cl
2, measured value (calculated value)/%:W (C)=46.12 (46.18), W (H)=3.84 (3.87), W (N)=5.92 (5.98).
Embodiment 2
The adding of 10g (0.05mol) N-methyl-2-(4-chlorophenoxy) ethanamide is had in the 250mL four-hole boiling flask of agitator, thermometer, prolong and dropping funnel, add 60mL formic acid, be heated to 60 ℃.Under agitation drip the mixed solution of 9.5g (0.07mol) sulfuryl chloride and 20mL formic acid, then, in 60 ℃ of insulation 5h.Reaction finishes, slough partial solvent after, pour raffinate in 300mL water elutriation, behind suction filtration, washing and the recrystallization, obtain white solid N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide 6.5g, its yield is 56%.
Embodiment 3
The adding of 10g (0.05mol) N-methyl-2-(4-chlorophenoxy) ethanamide is had in the 250mL four-hole boiling flask of agitator, thermometer, prolong and dropping funnel, add 60mL formic acid, be heated to 30 ℃.Under agitation drip the mixed solution of 8.2g (0.06mol) sulfuryl chloride and 20mL formic acid, then, in 30 ℃ of insulation 5h.Reaction finishes, slough partial solvent after, pour raffinate in 300mL water elutriation, behind suction filtration, washing and the recrystallization, obtain white solid N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide 5.8g, its yield is 49.5%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. a method for preparing N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide of structural formula (I) comprises the following steps:
A. in container, add 4-chlorophenol, solvent N, dinethylformamide and as the Anhydrous potassium carbonate of acid binding agent, be heated with stirring to 50～90 ℃, slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dripping end, at 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrate is sloughed partial solvent N, behind the dinethylformamide, pour in the water, treat that solid fully separates out, suction filtration obtains 2-(4-chlorophenoxy) methyl acetate with crude product through the ethanol/water recrystallization;
B. in container, add 2-(4-chlorophenoxy) methyl acetate, ethanol, be heated with stirring to 30～70 ℃, drip the ethanolic soln of methylamine, the dropping time is 0.5～1h, drip to finish the back at 30～70 ℃ of insulation reaction 2～6h, reaction solution is sloughed partial solvent ethanol after, pour in the water, treat that solid fully separates out, suction filtration obtains N-methyl-2-(4-chlorophenoxy) ethanamide with crude product with the ethanol/water recrystallization;
C. add N-methyl-2-(4-chlorophenoxy) ethanamide in container, solvent formic acid is heated with stirring to 30～60 ℃, drip the mixing solutions of sulfuryl chloride and formic acid, the dropping time is 0.5～2h, after dropping finishes, at 30～60 ℃ of insulation reaction 3～8h, after reaction solution sloughed partial solvent acetate, pour in the water, treat that solid fully separates out, suction filtration, and extremely neutral with 5% sodium carbonate solution washing, get N-methyl-2-(2,4 dichloro benzene oxygen base) ethanamide after the drying.
2. the described N-methyl-2-(2 of claim 1, the 4-dichlorophenoxy) preparation method of ethanamide, it is characterized in that: molar ratio of material N-methyl-2-(4-chlorophenoxy) ethanamide: sulfuryl chloride=1:1～2 among the step c, the quality of solvent formic acid are 3～8 times of N-methyl-2-(4-chlorophenoxy) ethanamide quality.
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| CN101391969B CN101391969B (en) | 2012-05-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167453A (en) * | 2016-08-04 | 2016-11-30 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acid methyl ester |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
-
2008
- 2008-10-30 CN CN2008102020131A patent/CN101391969B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167453A (en) * | 2016-08-04 | 2016-11-30 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorphenoxyacetic acid methyl ester |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
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| CN101391969B (en) | 2012-05-09 |
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