CN101585781B - Preparing method of N, N-dimethylbenzamide - Google Patents
Preparing method of N, N-dimethylbenzamide Download PDFInfo
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- CN101585781B CN101585781B CN200910088595XA CN200910088595A CN101585781B CN 101585781 B CN101585781 B CN 101585781B CN 200910088595X A CN200910088595X A CN 200910088595XA CN 200910088595 A CN200910088595 A CN 200910088595A CN 101585781 B CN101585781 B CN 101585781B
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- adjacent amino
- dimethyl benzamide
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- 0 *OC(c1ccccc1N)=O Chemical compound *OC(c1ccccc1N)=O 0.000 description 1
- DPXIIVXPZPOINE-UHFFFAOYSA-N CN(C)C(c1ccccc1N)=O Chemical compound CN(C)C(c1ccccc1N)=O DPXIIVXPZPOINE-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparing method of o-amino N, N-dimethylbenzamide, which is prepared by reacting isatoic anhydride and dimethylamine or dimethylamino aminic acid. The method has advantagesof easy-obtained and cheap production raw materials, high reaction yield, simple operation and easy industrial production.
Description
Technical field
The invention belongs to the organic synthesis field, specifically, relate to a kind of adjacent amino-N, the preparation method of N-dimethyl benzamide.
Background technology
Adjacent amino-N, N-dimethyl benzamide are the important intermediate of the phonetic aniline sulphur of preparation sulfonylurea herbicide grand (Orthosulfamuron) and some pharmaceutical prod.
Existing bibliographical information adjacent amino-N, the preparation method of N-dimethyl benzamide mainly contains following four kinds:
1, document (Tetrahedron; 1970,26:2007-2026) put down in writing by o-amino benzoyl chloride and the adjacent amino-N of n n dimetylaniline prepared in reaction, the method for N-dimethyl benzamide; But, cause that reaction preference is poor, yield is low because o-amino benzoyl chloride self can react;
2, document (Tetrahedron Letters; 1992; 33 (43): 6453-6456) put down in writing by cinnamyl o-aminobenzoate and n n dimetylaniline lithium salts and prepared adjacent amino-N, the method for N-dimethyl benzamide, but the preparation of n n dimetylaniline lithium salts and preservation condition are relatively harsher in this route;
3, document (Pesticide Science, 1996,46:151-156) put down in writing by 1,1-dimethylamino-3-phenylurea prepares adjacent amino-N through rearrangement reaction, the method for N-dimethyl benzamide, but raw material that should reaction is difficult for preparation;
4, document (Journal of the Chemical Society, PT1,1995,11:1349-1358; Journal of Medicinal Chemistry; 1997,40:2674-2687) and patent (US5985837, US5688795, US20080182852 etc.) put down in writing by adjacent nitro-N, N-dimethyl benzamide hydrogenating reduction prepares adjacent amino-N; The method of N-dimethyl benzamide; The reaction yield of this method is higher, but expensive raw materials, and the hydrogenation technique operational safety is poor.
Summary of the invention
The purpose of this invention is to provide a kind of adjacent amino-N, the novel preparation method of N-dimethyl benzamide.
Adjacent amino-N provided by the invention, the preparation method of N-dimethyl benzamide are made by isatoic anhydride (Isatoic anhydride) and n n dimetylaniline or the reaction of dimethylamino formic acid, and chemical reaction process is following:
Wherein, n n dimetylaniline or dimethylamino formic acid are 1.0-2.0, preferred 1.1-1.5 molar equivalent with the molar equivalent ratio of isatoic anhydride.
Above-mentionedly instead under organic solvent, carry out, said organic solvent is N, dinethylformamide, acetonitrile, THF, ETHYLE ACETATE, acetone, methyl alcohol, ethylene dichloride, toluene etc.
Said n n dimetylaniline is gaseous state, liquid state, the aqueous solution or alcoholic solution.
Adjacent amino-N provided by the invention, the preparation method of N-dimethyl benzamide have that raw materials for production are cheap and easy to get, reaction yield is high, and be simple to operate, advantages such as security height.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.
Embodiment 1 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add 400mL methyl alcohol, open and stir, be cooled to below-10 ℃, then import 34g (0.75mol, 99.9%) n n dimetylaniline gas with chilled brine.Subsequently, return to room temperature, stirring reaction 4 hours.The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 80.5g, and purity is 98.8%, yield is 96.8%.
Embodiment 2 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add the 400mL ethylene dichloride, open and stir, be cooled to below 10 ℃, then add 68g (0.6mol, 40%) dimethylamine agueous solution with chilled brine.Subsequently, return to room temperature, stirring reaction 5 hours.Layering with water with the ethylene dichloride extraction once, merges organic phase, and the negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 74.2g, and purity is 94.0%, yield is 85.0%.
Embodiment 3 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add the 400mL acetonitrile, open and stir, be cooled to below 10 ℃, then add 62g (0.55mol, 40%) dimethylamine agueous solution with chilled brine.Subsequently, return to room temperature, stirring reaction 4 hours.The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 77.8g, and purity is 96.5%, yield is 91.6%.
Embodiment 4 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add 320mL ETHYLE ACETATE; Open and stir; Be cooled to below 10 ℃ with chilled brine, then add the mixing solutions of 58.5g (0.65mol, 99%) dimethylamino formic acid and 80mL ETHYLE ACETATE.Subsequently, return to room temperature, stirring reaction 4 hours.The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 81.3g, and purity is 99.0%, yield is 98.0%.
Embodiment 5 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add 320mLN; Dinethylformamide is opened and is stirred, and is cooled to below 10 ℃ with chilled brine; Then add 62.9g (0.7mol, 99%) dimethylamino formic acid and 80mLN, the mixing solutions of dinethylformamide.Subsequently, return to room temperature, stirring reaction 4 hours.The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 77.1g, and purity is 98.2%, yield is 92.4%.
Embodiment 6 adjacent amino-N, the preparation of N-dimethyl benzamide
Get 82.3g (0.5mol, 99.0%) isatoic anhydride and place reaction flask, add 320mL toluene, open and stir, be cooled to below 10 ℃, then add the mixing solutions of 72.0g (0.8mol, 99%) dimethylamino formic acid and 80mL toluene with chilled brine.Subsequently, return to room temperature, stirring reaction 6 hours.The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 71.2g, and purity is 93.6%, yield is 81.3%.
Claims (5)
1. adjacent amino-N; The preparation method of N-dimethyl benzamide is characterized in that, the isatoic anhydride 82.3g that gets 0.5mol 99.0% places reaction flask; Add the 400mL ethylene dichloride; Open and stir, be cooled to below 10 ℃, then add the dimethylamine agueous solution 68g of 0.6mol 40% with chilled brine; Subsequently, return to room temperature, stirring reaction 5 hours; Layering with water with the ethylene dichloride extraction once, merges organic phase, and the negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 74.2g, and purity is 94.0%.
2. adjacent amino-N; The preparation method of N-dimethyl benzamide is characterized in that, the isatoic anhydride 82.3g that gets 0.5mol 99.0% places reaction flask; Add the 400mL acetonitrile; Open and stir, be cooled to below 10 ℃, then add the dimethylamine agueous solution 62g of 0.55mol 40% with chilled brine; Subsequently, return to room temperature, stirring reaction 4 hours; The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 77.8g, and purity is 96.5%.
3. adjacent amino-N; The preparation method of N-dimethyl benzamide is characterized in that, the isatoic anhydride 82.3g that gets 0.5mol 99.0% places reaction flask; Add 320mL ETHYLE ACETATE; Open and stir, be cooled to below 10 ℃, then add the mixing solutions of 0.65mol 99% dimethylamino formic acid 58.5g and 80mL ETHYLE ACETATE with chilled brine; Subsequently, return to room temperature, stirring reaction 4 hours; The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 81.3g, and purity is 99.0%.
4. adjacent amino-N, the preparation method of N-dimethyl benzamide is characterized in that; The isatoic anhydride 82.3g that gets 0.5mol 99.0% places reaction flask, adds 320mLN, dinethylformamide; Open and stir; Be cooled to below 10 ℃ with chilled brine, then add 0.7mol99% dimethylamino formic acid 62.9g and 80mLN, the mixing solutions of dinethylformamide; Subsequently, return to room temperature, stirring reaction 4 hours; The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 77.1g, and purity is 98.2%.
5. adjacent amino-N; The preparation method of N-dimethyl benzamide is characterized in that, the isatoic anhydride 82.3g that gets 0.5mol 99.0% places reaction flask; Add 320mL toluene; Open and stir, be cooled to below 10 ℃, then add the mixing solutions of 0.8mol 99% dimethylamino formic acid 72.0g and 80mL toluene with chilled brine; Subsequently, return to room temperature, stirring reaction 6 hours; The negative pressure precipitation obtains the adjacent amino-N of target compound, N-dimethyl benzamide 71.2g, and purity is 93.6%.
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| CN200910088595XA CN101585781B (en) | 2009-07-08 | 2009-07-08 | Preparing method of N, N-dimethylbenzamide |
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| CN200910088595XA CN101585781B (en) | 2009-07-08 | 2009-07-08 | Preparing method of N, N-dimethylbenzamide |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136039A (en) * | 1994-11-08 | 1996-11-20 | 弗·哈夫曼-拉罗切有限公司 | [3-(4-phenylpiperazin-1-yl)propyl-amino, thio and oxy]-pyridine, pyrimidine and benzene derivatives as alpha1-adrenoceptor antagonists |
| WO2000066563A1 (en) * | 1999-04-30 | 2000-11-09 | Glaxo Group Limited | Imidazoline derivatives as alpha-1a adrenoceptor ligands |
| WO2008092049A1 (en) * | 2007-01-26 | 2008-07-31 | Smithkline Beecham Corporation | Anthranilamide inhibitors of aurora kinase |
-
2009
- 2009-07-08 CN CN200910088595XA patent/CN101585781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136039A (en) * | 1994-11-08 | 1996-11-20 | 弗·哈夫曼-拉罗切有限公司 | [3-(4-phenylpiperazin-1-yl)propyl-amino, thio and oxy]-pyridine, pyrimidine and benzene derivatives as alpha1-adrenoceptor antagonists |
| WO2000066563A1 (en) * | 1999-04-30 | 2000-11-09 | Glaxo Group Limited | Imidazoline derivatives as alpha-1a adrenoceptor ligands |
| WO2008092049A1 (en) * | 2007-01-26 | 2008-07-31 | Smithkline Beecham Corporation | Anthranilamide inhibitors of aurora kinase |
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