CN102887832A - 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
- Publication number
- CN102887832A CN102887832A CN2012103750532A CN201210375053A CN102887832A CN 102887832 A CN102887832 A CN 102887832A CN 2012103750532 A CN2012103750532 A CN 2012103750532A CN 201210375053 A CN201210375053 A CN 201210375053A CN 102887832 A CN102887832 A CN 102887832A
- Authority
- CN
- China
- Prior art keywords
- compound
- steric hindrance
- binding agent
- acid binding
- water
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
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 the 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. also all is agricultural chemicals common on the market.Usually, during 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 generally is that chloroacetyl chloride and aminated compounds are under the 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 " that react 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 a kind of water react: take mineral alkali as acid binding agent, under organic solvent promoted, secondary amine compound and chloroacetyl chloride reacted synthetic corresponding large steric hindrance chlor(o)acetamide compound in water.Concrete reaction formula is as follows:
In the formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, perhaps on the 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 yellow soda ash, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole 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 be finished in 2 hours, and the transformation efficiency of raw material amine is more than 95%, and most preferred reaction example Raw amine can transform fully.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, take mineral alkali as acid binding agent, under organic solvent promoted, secondary amine compound and chloroacetyl chloride reacted synthetic corresponding large steric hindrance chlor(o)acetamide compound in water, and reaction formula is as follows:
In the formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, perhaps on the 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 an amount of organic solvent, water, vigorous stirring under the room temperature condition splashes into chloroacetyl chloride in the reaction solution continuously.Leave standstill after dripping off, separatory, the organic phase precipitation namely obtains the acid amides product.
In the above-mentioned reaction formula, two kinds of compounds shown in secondary amine compound preferred structure formula I and the II:
The acid binding agent that reacts used is yellow soda ash, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole acid binding agent/mole amine; The consumption of water is 100-2000 milliliter/mole amine in the reaction; The organic solvent that reaction is adopted 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 the IV:
Following instance is used for further describing the present invention's water acid amides synthetic method.It is raw material that example adopts secondary amine compound I, and preparation amide compound III specifies the present invention.But the present invention only limits to absolutely not following instance.Raw material secondary amine in the claim limited range all can prepare corresponding acid amides according to method provided by the invention.Reaction process detects with gas-chromatography (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).
Embodiment 1:
In the reactor with agitator, add 20.7 gram (0.1mol) compound I, 10.6 gram (0.1mol) yellow soda ash, 4 ml n-hexanes and 100 ml waters, vigorous stirring under the room temperature condition splashes into 22.6 gram (0.2mol) chloroacetyl chlorides in the reaction solution continuously.0.5 hour drip off, leave standstill, separatory, the organic phase precipitation namely obtains acid amides product 27.6 grams, yield 97.3%, content 96.5%.
Embodiment 2:
In the reactor with agitator, add 1036.5 gram (5mol) compound I, 220 gram (5.5mol) sodium hydroxide, 500 milliliters of toluene and 2000 ml waters, vigorous stirring under the room temperature condition splashes into 592.9 gram (5.25mol) chloroacetyl chlorides in the reaction solution continuously.Dripped off in 2 hours, and left standstill, separatory, the organic phase precipitation namely obtains acid amides product 1409 grams, yield 99.3%, content 97.5%.
Claims (5)
1. the method for the synthetic large steric hindrance chlor(o)acetamide compound of a water react, it is characterized in that, take 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, reaction formula is as follows:
In the formula: Ar is selected from phenyl, pyridyl, pyrryl, thienyl or furyl, perhaps on the 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. it is characterized in that in accordance with the method for claim 1: described acid binding agent is yellow soda ash, sodium bicarbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, calcium hydroxide; The add-on of acid binding agent is 0.5-5.0 mole acid binding agent/mole amine.
3. according to claim 1 or 2 described methods, it is characterized in that, 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.
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 the II:
5. the method for claim 1 is characterized in that, described amide compound is two kinds of compounds shown in formula II I and the IV:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375053.2A CN102887832B (en) | 2012-09-29 | 2012-09-29 | Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375053.2A CN102887832B (en) | 2012-09-29 | 2012-09-29 | Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102887832A true CN102887832A (en) | 2013-01-23 |
| CN102887832B CN102887832B (en) | 2014-07-16 |
Family
ID=47531533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210375053.2A Active CN102887832B (en) | 2012-09-29 | 2012-09-29 | Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102887832B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356017A (en) * | 2014-11-21 | 2015-02-18 | 山东侨昌化学有限公司 | Method for synthesizing metolachlor by means of solvent-free acylation |
| 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 |
| 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 |
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 | N, the preparation method of 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 |
-
2012
- 2012-09-29 CN CN201210375053.2A patent/CN102887832B/en active Active
Patent 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 | N, the preparation method of 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356017A (en) * | 2014-11-21 | 2015-02-18 | 山东侨昌化学有限公司 | Method for synthesizing metolachlor by means of solvent-free acylation |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102887832B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NZ599549A (en) | Methods of synthesis and purification of heteroaryl compounds | |
| MX342850B (en) | Process for the preparation of chiral triazolones. | |
| CN102887832B (en) | Method for synthesizing chloroacetamide compound with large steric hindrance by water phase reaction | |
| CN103664561B (en) | The preparation method of a kind of metconazole and intermediate thereof | |
| CN104744394B (en) | A kind of method of asymmetric synthesis containing trifluoromethyl chirality quaternary carbon compound | |
| Liu et al. | An efficient and mild iron-mediated synthesis of alkenyl halides via direct C–C bond formation of benzyl alcohols and aryl alkynes | |
| CN102898329A (en) | Method for synthesizing N-aryl ketoimine by acidic catalytic dehydration | |
| CN102076677B (en) | Method for producing 3-methyl-2-thiophenecarboxylic acid | |
| CN109293491A (en) | A kind of method of aryl diazonium salt de-acyl group on diazonium | |
| CN102049301B (en) | High-efficiency ionic liquid and cross-linked polystyrene-supported palladium catalyst and application thereof | |
| CN103787916B (en) | A kind of preparation method of trifloxystrobin | |
| CN101302150B (en) | Synthetic method of 2-(2,4- dichlorophenoxy) propionic acid | |
| CN104860857B (en) | Methylthiosemicarbazone synthesis technique | |
| CN102786492B (en) | Preparation method of 3-isothiazolinone compound | |
| CN103351376B (en) | Synthetic method of 2-thiophene ethylamine | |
| CN102950024B (en) | Catalyst for asymmetric catalytic hydrogenation of imine | |
| CN104672180B (en) | Chiral preparation method of [(1S)-3-methyl-1-[[(2R)-2-methylepoxyethyl]carbonyl]butyl]tert-butyl carbamate | |
| CN105254611B (en) | The preparation method of the carboxylic acid of benzothiophene 2 | |
| Grellepois et al. | Diastereoselective Addition of Organomagnesium and Organolithium Reagents to Chiral Trifluoromethyl N‐tert‐Butanesulfinyl Hemiaminals | |
| CN103396347B (en) | Method for synthesizing p-hydroxyl thiobenzamide | |
| CN102285997A (en) | Method for preparing chloroallyl beta-lactam antibiotic intermediate | |
| CN105017232A (en) | Synthesis method of triazole bactericide | |
| CN105017126B (en) | Perfluoroalkyl azole derivatives and its synthetic method | |
| CN103333078B (en) | The synthetic method of a kind of anagrelide key intermediate, analogue or its salt | |
| CN103288780A (en) | Preparation method of 1-phenyl-1-cyclopentyl epoxy ethane |
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 |