CN102887832B - Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction - Google Patents
Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a chloroacetamide compound with large steric hindrance by a water phase reaction, wherein the method comprises the following steps: taking inorganic alkali as an acid binding agent, enabling a secondary amine compound to react with chloroacetyl chloride in water to synthesize the corresponding chloroacetamide compound with large steric hindrance in the presence of an organic solvent. The method provided by the invention can be used for synthesizing pesticides s-metolachlor and metolachlor. The method provided by the invention has the advantages of simple operation, quick reaction, high product yield and good quality; the method provided by the invention is suitable for large-scale preparation.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to the method for the synthetic large steric hindrance chlor(o)acetamide compound of water react.
Background technology
Chloroacetamide-based compounds is the important organic compound of a class, and for example S-metolachlor is the chirality weedicide of international market share maximum, and acetochlor, the third careless amine etc. is all also agricultural chemicals common on market.Conventionally,, when the larger secondary amine compound acidylate of steric hindrance, need excessive more acyl chlorides or more loaded down with trivial details method.Chlor(o)acetamide synthetic is generally that chloroacetyl chloride and aminated compounds are under organic bases effect, in dry organic solvent, carry out (US5430188, WO9521151), the organic solvent that reaction needed is more, solvent needs stricter with water pretreatment, operation is more, and the use of organic bases also causes " three wastes " of reaction more.
Summary of the invention
The object of the present invention is to provide the method for the synthetic large steric hindrance chlor(o)acetamide compound of a kind of water react, this method reaction is fast, simple to operate, organism " three wastes " few, is applicable to extensive preparation.
In order to realize above-mentioned task, technical scheme of the present invention is as follows:
The method of the synthetic large steric hindrance chlor(o)acetamide compound of water react: taking mineral alkali as an acid binding agent, under organic solvent promotes, secondary amine compound and chloroacetyl chloride react synthetic corresponding large steric hindrance chlor(o)acetamide compound in water.Concrete reaction formula is as follows:
In formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, or on described group further with 1-3 following substituting group: fluorine, chlorine, C1-C4 alkyl, C1-C4 alkoxyl group, phenyl, phenoxy group, benzyl or benzyloxy; R is selected from C1-C4 alkyl or C1-C4 alkoxy carbonyl; The mol ratio of secondary amine and chloroacetyl chloride is: 1:1.0-2.0.
The consumption of water is 100-2000 milliliter/mole amine.
Described acid binding agent is sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole of acid binding agent/mole amine.
Described organic solvent is normal hexane, sherwood oil (boiling range 60-90 ° of C), methylene dichloride, trichloromethane, ethylene dichloride, methyl tertiary butyl ether, benzene, toluene, chlorobenzene or dimethylbenzene; Consumption of organic solvent is 40-2000 milliliter/mole amine.
According to above-mentioned synthetic method, reaction can complete in 2 hours, and the transformation efficiency of raw material amine is more than 95%, and most preferred reaction example Raw amine can transform completely.Compared with prior art, the method reaction of the synthetic large steric hindrance chlor(o)acetamide compound of water react disclosed by the invention is fast, simple to operate, organism " three wastes " few, is applicable to extensive preparation.
Embodiment
According to the method for the synthetic large steric hindrance chlor(o)acetamide compound of water react of the present invention, taking mineral alkali as acid binding agent, under organic solvent promotes, secondary amine compound and chloroacetyl chloride react synthetic corresponding large steric hindrance chlor(o)acetamide compound in water, and reaction formula is as follows:
In formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, or on described group further with 1-3 following substituting group: fluorine, chlorine, C1-C4 alkyl, C1-C4 alkoxyl group, phenyl, phenoxy group, benzyl or benzyloxy; R is selected from C1-C4 alkyl or C1-C4 alkoxy carbonyl; The mol ratio of secondary amine and chloroacetyl chloride is: 1:1.0-2.0.The consumption of water is 100-2000 milliliter/mole amine.
Concrete operations are as follows:
In the reactor with agitator, add raw material secondary amine, mineral alkali and appropriate organic solvent, water, vigorous stirring under room temperature condition, splashes into chloroacetyl chloride in reaction solution continuously.Standing, separatory after dripping off, organic phase precipitation obtains acid amides product.
In above-mentioned reaction formula, two kinds of compounds shown in secondary amine compound preferred structure formula I and II:
The acid binding agent that reacts used is sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole of acid binding agent/mole amine; In reaction, the consumption of water is 100-2000 milliliter/mole amine; The organic solvent that reaction adopts is normal hexane, sherwood oil (boiling range 60-90 ° of C), methylene dichloride, trichloromethane, ethylene dichloride, methyl tertiary butyl ether, benzene, toluene, chlorobenzene or dimethylbenzene; Consumption of organic solvent is 40-2000 milliliter/mole amine.
Described amide compound is two kinds of compounds shown in formula II I and IV:
Following instance is for further describing the present invention's water acid amides synthetic method.It is raw material that example adopts secondary amine compound I, prepares amide compound III and illustrates the present invention.But the present invention only limits to absolutely not following instance.Raw material secondary amine in claim limited range all can be prepared corresponding acid amides according to method provided by the invention.Gas-chromatography for reaction process (GC) (chromatographic column DB-1701,30m × 0.320mm × 0.25 μ m, 150 ° of C of column temperature, 10 ° of C/min, 300 ° of C of vaporizer temperature, 300 ° of C of detector temperature) detects.
Embodiment 1:
In the reactor with agitator, add 20.7 grams of (0.1mol) Compound I, 10.6 grams of (0.1mol) sodium carbonate, 4 ml n-hexanes and 100 ml waters, vigorous stirring under room temperature condition, splashes into 22.6 grams of (0.2mol) chloroacetyl chlorides in reaction solution continuously.Within 0.5 hour, drip off, standing, separatory, organic phase precipitation obtains 27.6 grams of acid amides products, yield 97.3%, content 96.5%.
Embodiment 2:
In the reactor with agitator, add 1036.5 grams of (5mol) Compound I, 220 grams of (5.5mol) sodium hydroxide, 500 milliliters of toluene and 2000 ml waters, vigorous stirring under room temperature condition, splashes into 592.9 grams of (5.25mol) chloroacetyl chlorides in reaction solution continuously.Within 2 hours, drip off, standing, separatory, organic phase precipitation obtains 1409 grams of acid amides products, yield 99.3%, content 97.5%.
Claims (5)
1. the method for the synthetic large steric hindrance chlor(o)acetamide compound of water react, it is characterized in that, taking mineral alkali as acid binding agent, under organic solvent promotes, secondary amine compound and chloroacetyl chloride react synthetic corresponding large steric hindrance chlor(o)acetamide compound in water, and reaction formula is as follows:
In formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, or on described group further with 1-3 following substituting group: fluorine, chlorine, C1-C4 alkyl, C1-C4 alkoxyl group, phenyl, phenoxy group, benzyl or benzyloxy; R is selected from C1-C4 alkyl or C1-C4 alkoxy carbonyl;
The mol ratio of secondary amine and chloroacetyl chloride is: 1:1.0-2.0;
The consumption of water is 100-2000 milliliter/mole amine.
2. the method for claim 1, is characterized in that: described acid binding agent is sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole of acid binding agent/mole amine.
3. method as claimed in claim 1 or 2, is characterized in that, described organic solvent is normal hexane, sherwood oil, methylene dichloride, trichloromethane, ethylene dichloride, methyl tertiary butyl ether, benzene, toluene, chlorobenzene or dimethylbenzene; Consumption of organic solvent is 40-2000 milliliter/mole amine.
4. the method for claim 1, is characterized in that, described secondary amine compound is selected from two kinds of compounds shown in structural formula I and II:
5. the method for claim 1, is characterized in that, described large steric hindrance chlor(o)acetamide compound is two kinds of compounds shown in formula II I and IV:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104356017B (en) * | 2014-11-21 | 2016-08-24 | 山东侨昌化学有限公司 | A kind of method of solvent-free acylated synthesis isopropyl methoxalamine |
| CN110117233A (en) * | 2018-02-05 | 2019-08-13 | 潍坊中农联合化工有限公司 | A kind of synthetic method of chloroacetamide-based compounds |
| CN109096137A (en) * | 2018-07-30 | 2018-12-28 | 山东万豪肥业有限公司 | A kind of synthetic method of S-metolachlor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093700A (en) * | 1992-12-29 | 1994-10-19 | 希巴-盖吉股份公司 | The preparation method of 2-alkyl-6-methyl-N-(1 ＇-methoxyl group-2 ＇-propyl group)-aniline and their N-chloroacetanilide |
| CN1721392A (en) * | 2004-07-15 | 2006-01-18 | 上海化学试剂研究所 | Process for preparing N,N-dimethyl chloroacetamide |
| CN101677538A (en) * | 2007-05-04 | 2010-03-24 | 联合磷化物有限公司 | Process for manufacture of high purity d-(-)-n,n-diethyl-2-(alpha-naphthoxy) propionamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093700A (en) * | 1992-12-29 | 1994-10-19 | 希巴-盖吉股份公司 | The preparation method of 2-alkyl-6-methyl-N-(1 ＇-methoxyl group-2 ＇-propyl group)-aniline and their N-chloroacetanilide |
| CN1721392A (en) * | 2004-07-15 | 2006-01-18 | 上海化学试剂研究所 | Process for preparing N,N-dimethyl chloroacetamide |
| CN101677538A (en) * | 2007-05-04 | 2010-03-24 | 联合磷化物有限公司 | Process for manufacture of high purity d-(-)-n,n-diethyl-2-(alpha-naphthoxy) propionamide |
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