CN101391969B - Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide - Google Patents
Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide Download PDFInfo
- Publication number
- CN101391969B CN101391969B CN2008102020131A CN200810202013A CN101391969B CN 101391969 B CN101391969 B CN 101391969B CN 2008102020131 A CN2008102020131 A CN 2008102020131A CN 200810202013 A CN200810202013 A CN 200810202013A CN 101391969 B CN101391969 B CN 101391969B
- Authority
- CN
- China
- Prior art keywords
- methyl
- ethanamide
- chlorophenoxy
- solvent
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *c(ccc(Cl)c1)c1Cl Chemical compound *c(ccc(Cl)c1)c1Cl 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 verivate 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 verivate 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; Through reacting with haloid ether, separate through ammonia and 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 is high, and cost is low, and industrial production foreground is arranged.
Technical scheme 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:
A. in container, add 4-chlorophenol, solvent N, dinethylformamide and as the Anhydrous potassium carbonate of acid binding agent is heated with stirring to 50～90 ℃; Slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dropping finishes; At 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrating 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. in container, add N-methyl-2-(4-chlorophenoxy) ethanamide, solvent formic acid is heated with stirring to 30～60 ℃, drips the mixing solutions of sulfuryl chloride and formic acid; The dropping time is 0.5～2h, after drip finishing, at 30～60 ℃ of insulation reaction 3～8h, reaction solution sloughed partial solvent after; 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 among the step c: sulfuryl chloride=1: 1～2, 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 uses chlorinated solvent benzene commonly used, toluene, tetracol phenixin etc., and 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, obtains purpose product N-methyl-2-(2 through chlorination again; The 4-dichlorophenoxy) ethanamide; This method product yield is high, and cost is low, and the future of suitability for industrialized production is arranged.
Embodiment
Through specific embodiment the present invention is described in further detail below: 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 is heated with stirring to 50～90 ℃; Slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dropping finishes; At 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrating 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. in container, add N-methyl-2-(4-chlorophenoxy) ethanamide, solvent formic acid is heated with stirring to 30～60 ℃, drips the mixing solutions of sulfuryl chloride and formic acid; The dropping time is 0.5～2h, after drip finishing, at 30～60 ℃ of insulation reaction 3～8h, reaction solution sloughed partial solvent after; 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 among the step c: sulfuryl chloride=1: 1～2, 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 whisking appliance, TM, prolong and tap 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 whisking appliance, TM, prolong and tap 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 whisking appliance, TM, prolong and tap 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%.
The above content is merely 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 is heated with stirring to 50～90 ℃; Slowly drip methyl chloroacetate then, the dropping time is 0.5～1h, after dropping finishes; At 50～90 ℃ of insulation reaction 2～5h, then reacting liquid filtering is removed inorganic salt, filtrating 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. in container, add N-methyl-2-(4-chlorophenoxy) ethanamide, solvent formic acid is heated with stirring to 30～60 ℃, drips the mixing solutions of sulfuryl chloride and formic acid; The dropping time is 0.5～2h, after drip finishing, at 30～60 ℃ of insulation reaction 3～8h, reaction solution sloughed partial solvent after; 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 said 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 among the step c: sulfuryl chloride=1: 1～2, the quality of solvent formic acid are 3～8 times of N-methyl-2-(4-chlorophenoxy) ethanamide quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102020131A CN101391969B (en) | 2008-10-30 | 2008-10-30 | Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102020131A CN101391969B (en) | 2008-10-30 | 2008-10-30 | Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101391969A CN101391969A (en) | 2009-03-25 |
| CN101391969B true CN101391969B (en) | 2012-05-09 |
Family
ID=40492506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102020131A Expired - Fee Related CN101391969B (en) | 2008-10-30 | 2008-10-30 | Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101391969B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167453B (en) * | 2016-08-04 | 2019-06-21 | 山东省化工研究院 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid methyl esters |
| CN106242971B (en) * | 2016-08-04 | 2019-06-25 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and its new method for preparing 2,4-D ester |
| CN106278862B (en) * | 2016-08-04 | 2019-06-25 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorophenoxyacetic acid |
-
2008
- 2008-10-30 CN CN2008102020131A patent/CN101391969B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| H.E.THOMPSON.NEW GROWTH-REGULATING COMPOUNDS.I.SUMMARY OF GROWTH-INHIBITORY ACTIVITIES OF SOME ORGANIC COMPOUNDS AS DETERMINED BY THREE TESTS.《BONTANICAL GAZETTE》.1946, * |
| 王红.N-甲基-2-(4-氯苯氧基)乙酰胺的合成.《精细石油化工》.2008,第25卷(第1期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101391969A (en) | 2009-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106278862B (en) | A kind of new technique for synthesizing of 2,4 dichlorophenoxyacetic acid | |
| CN104119211B (en) | A kind of prepare ɑ-mono-bromo ketone and ɑ, ɑ-two method of brominated ketone compound by ketone compounds selective bromination | |
| CN102015649A (en) | Method for manufacturing aryl carboxamides | |
| CN103951627B (en) | Method for synthesizing sulfentrazone midbody and sulfentrazone | |
| CN105566215B (en) | A kind of Rui Gefeini preparation method | |
| CN107056675A (en) | A kind of synthetic method of silodosin and its intermediate | |
| CN101391969B (en) | Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide | |
| CN106045876B (en) | A kind of synthetic method of p-hydrochloride | |
| CN107056756A (en) | A kind of method for preparing high-purity Losartan | |
| CN108558759A (en) | The method that one kettle way prepares celecoxib | |
| CN109096119B (en) | A method of preparing cinacalcet hydrochloride | |
| CN102516236B (en) | Preparation method of antipsychotic drug iloperidone | |
| EP1757597B1 (en) | Method for producing 2-oxo-1-phenyl-3-oxabicyclo[3.1.0]hexane | |
| CN102757390B (en) | Method for preparing 2-methoxy-4-diazanyl-5-fluoropyrimidine | |
| CN105330550B (en) | A kind of preparation method of optically active 1 cyclohexylethylamine | |
| CN106496031B (en) | A method of improving dimethyl malenate yield | |
| CN107417606A (en) | N cyanogen methyl is double（Trifluoromethyl）Niacinamide is converted into method and the application of flonicamid | |
| CN105130972B (en) | Benzoic acid emtricitabine salt, its preparation method and the method for preparing emtricitabine with benzoic acid emtricitabine salt | |
| CN104402813B (en) | Novel method for synthesizing sorafenib | |
| CN106336352A (en) | Synthesis method of 6-fluorosalicylic acid | |
| CN105503646A (en) | Synthesis method of 3-amino-6-chloro-N,4-dimethylbenzamidedimethyl formamide | |
| CN105237529A (en) | Refining method for high-purity anhydrous dasatinib | |
| CN103086962A (en) | Synthetic method for 5-chlorine-2,4-dyhydroxyl pyridine | |
| CN106167453B (en) | A kind of preparation method of 2,4 dichlorophenoxyacetic acid methyl esters | |
| CN104672180A (en) | Chiral preparation method of [(1S)-3-methyl-1-[[(2R)-2-methylepoxyethyl]carbonyl]butyl]tert-butyl carbamate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120509 Termination date: 20141030 |
|
| EXPY | Termination of patent right or utility model |