CN109970582A - A method of preparing the chloro- 3- methyl benzoic acid of 2- amino -5- - Google Patents
A method of preparing the chloro- 3- methyl benzoic acid of 2- amino -5- Download PDFInfo
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- CN109970582A CN109970582A CN201910370497.9A CN201910370497A CN109970582A CN 109970582 A CN109970582 A CN 109970582A CN 201910370497 A CN201910370497 A CN 201910370497A CN 109970582 A CN109970582 A CN 109970582A
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- amino
- benzoic acid
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- methyl benzoic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for preparing the chloro- 3- methyl benzoic acid of 2- amino -5-, the following steps are included: by 2- amino -3- methyl benzoic acid (compound-I), it is added in reaction dissolvent, reaction density is 5-10 times (solvent volume/compound I weight), reaction temperature 20-40oC is added portionwise Cyanuric Chloride (compound-II), and liquid phase monitors reaction process, and after the reaction was completed, filtering, hot water washs, and recrystallizing methanol obtains the chloro- 3- methyl benzoic acid of 2- amino -5- (compound-III).A kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- of the present invention, with 2- amino -3- methyl benzoic acid (compound-I) for starting material, Cyanuric Chloride (compound-II) is used as chlorization condition, obtains the chloro- 3- methyl benzoic acid of 2- amino -5- (compound-III).This method raw material is simple and easy to get, and post-processing is simple, and total recovery is high, can provide important references for industrialized production.
Description
Technical field
The present invention relates to a kind of methods for preparing the chloro- 3- methyl benzoic acid of 2- amino -5-.
Background technique
The chloro- 3- methyl benzoic acid of 2- amino -5- be synthesis 2- amino -3- methyl-5-chloro benzamide insecticides (by
The new pesticide of the exploitations such as Japanese pesticide company, DuPont Corporation and Bayer pesticide science and technology, product name are " health is wide ")
Key intermediate.Since prior art limits, lead to synthetic intermediate 2- amino -3- methyl-5-chloro benzamide cost very
High, limiting maximum step is to synthesize the chloro- 3- methyl benzoic acid of 2- amino -5- by 2- amino -3- methyl benzoic acid.It is existing
The chlorination reagent of document patent report is N- chlorosuccinimide, and benefit is to react very clean, but price is very expensive,
The reaction dissolvent for being only suitable for more high value-added product (CN103450154, CN104031026), and reporting is high boiling
DMF, it is difficult to be post-processed.
Summary of the invention
The purpose of the present invention is to provide a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5-, this method can be with
The chloro- 3- methyl benzoic acid of 2- amino -5- is efficiently obtained, post-processing is simple, and total recovery is high, provides important ginseng for industrialized production
It examines.
To achieve the goals above, the chloro- 3- methylbenzene first of 2- amino -5- is prepared the technical scheme is to design a kind of
The method of acid, comprising the following steps: by 2- amino -3- methyl benzoic acid (compound-I), be added in reaction dissolvent, reaction density
For 5-10 times (solvent volume/compound I weight), reaction temperature 20-40oCyanuric Chloride (compound-II) is added portionwise in C,
Liquid phase monitors reaction process, and after the reaction was completed, filtering, hot water washs, and recrystallizing methanol obtains the chloro- 3- methylbenzene of 2- amino -5-
Formic acid (compound-III).
Further, the reaction dissolvent is ethyl acetate, methylene chloride, dichloroethanes, the medium solvent of water.
Preferably, the molar ratio of the 2- amino -3- methyl benzoic acid (compound-I) and Cyanuric Chloride (compound-II)
For 1:0.3-1, preferably 1:0.35；Reaction temperature is 25-30 oC, reaction time are 10 hours.
Preferably, the reaction dissolvent is dichloroethanes, and reaction density is 6 times (solvent volume/isatoic anhydride weight).
The advantages and beneficial effects of the present invention are: a kind of side for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- of the present invention
Method, with 2- amino -3- methyl benzoic acid (compound-I) for starting material, Cyanuric Chloride (compound-II) is used as chlorization condition,
Obtain the chloro- 3- methyl benzoic acid of 2- amino -5- (compound-III).This method raw material is simple and easy to get, and post-processing is simple, total recovery
Height can provide important references for industrialized production.
Detailed description of the invention
Fig. 1 is reaction equation of the invention.
Specific embodiment
With reference to the accompanying drawings and examples, further description of the specific embodiments of the present invention.Following embodiment is only
For clearly illustrating technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1:
At room temperature, it in 1000ml round-bottomed flask, is added isatoic anhydride (60g, 396.92mmol), dichloroethanes 180ml, 25-30
At DEG C, Cyanuric Chloride (25.62g, 138.92mmol) slowly is added in batches.After adding, it is followed by stirring for about 10h, liquid phase detection
Indigo raw material is cooled to 5 DEG C or less less than 1%.It filters, is washed solid 2 times, drained with 50 DEG C of water (150ml).It is transferred to reaction flask
In, it is added anhydrous methanol (250ml), is heated to system dissolution, be cooled to 5 DEG C hereinafter, filtering, drying obtains off-white powder
62.6g, yield 85%, it is 98.5% that liquid phase, which detects purity,.
1H NMR (DMSO-d6) 7.55 (s, IH), 7.22 (s, IH), δ 2.11 (s, 3H)。
Embodiment 2:
At room temperature, it in 50L reaction kettle, is added isatoic anhydride (5kg, 33.08mol), dichloroethanes 30L, at 25-30 DEG C, slowly
Cyanuric Chloride (2.13kg, 11.58mol) is added in batches.After adding, it is followed by stirring for about 10h, liquid phase detection indigo raw material is less than
1%, it is cooled to 5 DEG C or less.It filters, is washed solid 2 times, drained with 50 DEG C of water (15L).It is transferred in reaction flask, is added without water beetle
Alcohol (20L) is heated to system dissolution, is cooled to 5 DEG C hereinafter, filtering, and drying obtains off-white powder 5.1kg, yield 83%,
It is 98.8% that liquid phase, which detects purity,.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5-, which comprises the following steps: by 2- ammonia
Base -3- methyl benzoic acid (compound-I) is added in reaction dissolvent, and reaction density is 5-10 times of (solvent volume/compound I weight
Amount), reaction temperature 20-40oC is added portionwise Cyanuric Chloride (compound-II), and liquid phase monitors reaction process, and reaction is completed
Afterwards, it filters, hot water washing, recrystallizing methanol obtains the chloro- 3- methyl benzoic acid of 2- amino -5- (compound-III).
2. a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- according to claim 1, which is characterized in that institute
Stating reaction dissolvent is one of ethyl acetate, methylene chloride, dichloroethanes, water or a variety of.
3. a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- according to claim 1, which is characterized in that institute
The molar ratio for stating 2- amino -3- methyl benzoic acid (compound-I) and Cyanuric Chloride (compound-II) is 1:0.3-1；Reaction temperature
Degree is 25-30 oC, reaction time are 10 hours.
4. a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- according to claim 2, which is characterized in that institute
The molar ratio for stating 2- amino -3- methyl benzoic acid (compound-I) and Cyanuric Chloride (compound-II) is 1:0.35.
5. a kind of method for preparing the chloro- 3- methyl benzoic acid of 2- amino -5- according to claim 1, which is characterized in that institute
Stating reaction dissolvent is dichloroethanes, and reaction density is 6 times (solvent volume/isatoic anhydride weight).
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| CN201910370497.9A CN109970582A (en) | 2019-05-06 | 2019-05-06 | A method of preparing the chloro- 3- methyl benzoic acid of 2- amino -5- |
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| CN201910370497.9A CN109970582A (en) | 2019-05-06 | 2019-05-06 | A method of preparing the chloro- 3- methyl benzoic acid of 2- amino -5- |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142620A (en) * | 2020-10-12 | 2020-12-29 | 江西省科学院应用化学研究所 | Synthetic method of 2-amino-3, 5-dichloro-N-methylbenzamide |
Citations (3)
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|---|---|---|---|---|
| US20070299265A1 (en) * | 2004-12-07 | 2007-12-27 | Rafael Shapiro | Method for Preparing N-Phenylpyrazole-1-Carboxamides |
| CN102093335A (en) * | 2010-11-26 | 2011-06-15 | 贵州大学 | Acylhydrazone and hydrazide derivatives and application thereof |
| CN105198859A (en) * | 2015-09-21 | 2015-12-30 | 西安近代化学研究所 | Anthranilic diamide compound containing dichloropropene base and application |
-
2019
- 2019-05-06 CN CN201910370497.9A patent/CN109970582A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070299265A1 (en) * | 2004-12-07 | 2007-12-27 | Rafael Shapiro | Method for Preparing N-Phenylpyrazole-1-Carboxamides |
| CN102093335A (en) * | 2010-11-26 | 2011-06-15 | 贵州大学 | Acylhydrazone and hydrazide derivatives and application thereof |
| CN105198859A (en) * | 2015-09-21 | 2015-12-30 | 西安近代化学研究所 | Anthranilic diamide compound containing dichloropropene base and application |
Non-Patent Citations (2)
| Title |
|---|
| M. ABID MASOOD，等: "Lead diversification. Application to existing drug molecules: Mifepristone 1 and antalarmin 8", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| 郭长彬，等: "氯虫酰胺的合成工艺改进", 《广州化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142620A (en) * | 2020-10-12 | 2020-12-29 | 江西省科学院应用化学研究所 | Synthetic method of 2-amino-3, 5-dichloro-N-methylbenzamide |
| CN112142620B (en) * | 2020-10-12 | 2023-03-31 | 江西省科学院应用化学研究所 | Synthetic method of 2-amino-3, 5-dichloro-N-methylbenzamide |
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Application publication date: 20190705 |