CN103450021A - Preparation method of improved 2-(2'-bromomethylphenyl)-2-carbonyl methyl acetate - Google Patents
Preparation method of improved 2-(2'-bromomethylphenyl)-2-carbonyl methyl acetate Download PDFInfo
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- CN103450021A CN103450021A CN 201310412993 CN201310412993A CN103450021A CN 103450021 A CN103450021 A CN 103450021A CN 201310412993 CN201310412993 CN 201310412993 CN 201310412993 A CN201310412993 A CN 201310412993A CN 103450021 A CN103450021 A CN 103450021A
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- 0 Cc1c(*)cccc1 Chemical compound Cc1c(*)cccc1 0.000 description 3
- YCINJZQUXAFTQD-ZRDIBKRKSA-N Cc(cccc1)c1/C(/C(OC)=O)=N\OC Chemical compound Cc(cccc1)c1/C(/C(OC)=O)=N\OC YCINJZQUXAFTQD-ZRDIBKRKSA-N 0.000 description 1
- GPZXFICWCMCQPF-UHFFFAOYSA-N Cc(cccc1)c1C(Cl)=O Chemical compound Cc(cccc1)c1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a process synthesis method of an improved trifloxystrobin intermediate 2-(2'-bromomethylphenyl)-2-carbonyl methyl acetate. The innovation of the process is reflected in the following two reaction steps: (1) 2-methyl benzoyl chloride reacts with cyanide to generate 2-methyl benzoyl cyanide, and (2) 2-(2'-methylphenyl)-2-carbonyl methyl acetate is brominated to generate 2-(2'- bromomethylphenyl)-2-carbonyl methyl acetate. The method provided by the invention is used for solving the following problems that the hydrolysis of the 2-methyl benzoyl chloride causes low synthesis yield of the 2-methyl benzoyl cyanide, light is needed in the bromination process to waste energy source, a solvent with large toxicity is used, the numerous generated dibromides are difficult to separate and purify, the yield is low and the like in the previous synthesis. According to the method provided by the invention, the operation is simpler and the reaction conditions are milder. Especially, the yield is greatly increased and the production cost is reduced, so that the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of 2-(preparation method of 2 '-2-bromomethylphenyl-2-carbonylic acetic acid methyl esters
Technical background
Methoxy acrylic ester compounds is to take the series bactericidal agent that natural product Strobilurins successfully develops as the guide.As the respiration inhibitor of fungi, there is unique mechanism of action, it can be adsorbed consumingly by the plant wax layer, for plant surface provides excellent provide protection.The characteristics of such fungicide compound are partly to have carbon-carbon double bond or carbon-to-nitrogen double bon at its pharmacophore, 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters is to synthesize the key intermediate that drug effect regiment headquarters is divided into this compounds of carbon-to-nitrogen double bon, as oxime bacterium ester and kresoxim-methyl etc.In mesosome 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters synthetic, many routes are arranged under study for action both at home and abroad, but all exist weak point.Such as the route Raw self that the O-bromo methyl phenylo boric acid is raw material is rare, there is difficulty in expensive and reaction; The route that o-bromotoluene is raw material relates to grignard reagent, and operational difficulty is difficult to industrialization etc.By contrast, below, a route has very large Research Significance:
This route, not only raw material is easy to get, and to plant and instrument require relatively lowly, actually operating is simple.But also have the weak point in some industrialization: the 2-methyl benzoyl chloride easily is hydrolyzed into acid in reaction process, thereby causes 2-toluyl nitrile yield to reduce; Bromination process needs rayed to waste energy, and uses larger solvent (as the tetracol phenixin) contaminate environment of toxicity, use catalyzer to make cost raise, and in reaction process, the more by product of generation makes target compound be difficult to separation and purification etc.The solution of these problems will provide larger power to the exploitation of methoxy acrylic bactericide and the initiative of novel pesticide product, also will bring huge economic benefit for society.
Summary of the invention
In view of 2-, (problem occurred in the preparation of 2 '-2-bromomethylphenyl-2-carbonylic acetic acid methyl esters, the present invention has solved above problem by the factor of research reaction mechanism and discussion impact reaction and the reason that impurity produces.Avoided to a great extent the hydrolysis problem of 2-methyl benzoyl chloride by the condition of groping in the preparation of 2-toluyl nitrile; In the bromo process, we use Sodium Bromide and sodium bromate method, have avoided direct dropping bromine, and this method does not need light and any catalyzer simultaneously, and this makes operation more simple, and reaction conditions is gentleer, and environment is more friendly.Compared with the literature, yield improves greatly simultaneously, and production cost reduces, and is applicable to suitability for industrialized production.
Detailed summary of the invention
The invention provides the preparation method of a kind of improved 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters, on the bromination two-step reaction of especially synthetic at 2-toluyl nitrile and 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters, carried out process innovation.Not only reaction method is improved, and yield has a more substantial increase.
1.2-the preparation of toluyl nitrile (B): with toluene, make solvent, to the tindichloride and the iodine that add A, sodium cyanide, Tetrabutyl amonium bromide, catalytic amount in reaction flask, system is heated to 70～100 ℃, the system after 4 hours of reacting is cooled to 15-25 ℃, again to the aqueous sodium hydroxide solution that adds pH=10 in system, continue stirring reaction 1 hour, reaction finishes.
2.2-in the preparation of toluyl nitrile (B), Heating temperature is 70～100 ℃, wherein yield is the highest 80 ℃ the time.
3.2-the tindichloride added in the preparation of toluyl nitrile (B) and iodine are the co-catalysis agent.
The preparation of (4.2-2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E): add D, ethyl acetate, water, Sodium Bromide and sodium bromate stirring and dissolving in reaction flask, start to drip hydrochloric acid, solution becomes red-brown, reacts solution after 5 hours and becomes glassy yellow, and reaction finishes.
5. during synthetic 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E), solvent, except ethyl acetate, can also be acetonitrile, methylene dichloride, chloroform etc.
6. during synthetic 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E), the mol ratio of Sodium Bromide, sodium bromate and D is 5～6: 1～1.2: 3, and when the mol ratio of Sodium Bromide, sodium bromate and D is 5.2: 1.1: 3, yield is the highest.
7. during synthetic 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E), Sodium Bromide can replace with sodium bisulfite or sodium sulphite.
8. during synthetic 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E), temperature of reaction is 20～40 ℃, and wherein Optimal Temperature is 25～30 ℃.
9. during synthetic 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E), in reaction, the volume ratio of solvent and water is that 3: 1 o'clock effects are best.
Embodiment
In order to understand better the present invention, below by embodiment, it is described further:
(1) technique of compd B is synthetic
Embodiment 1
Add A27.9g (180mmol) in the 500ml round-bottomed flask, sodium cyanide 9.3g (190mmol), Tetrabutyl amonium bromide 1.5g (4.6mmol), tindichloride 0.11g (0.6mmol), iodine 0.15g (0.6mmol) and toluene 200ml.System is warming up to 70 ℃, and reacts 4 hours at this temperature, extract reaction solution the gas chromatographic analysis feed stock conversion and be about 65%.Now system is dropped to room temperature (20 ℃) and, to the aqueous sodium hydroxide solution 50ml that adds pH=10 in reaction flask, continue stirring reaction 1 hour, the TLC detection reaction completes.The sodium bicarbonate aqueous solution that system is 5% by concentration is treated to neutrality, filters, and separatory, use respectively 50ml toluene aqueous phase extracted twice, merges organic phase dry.Precipitation obtains crude product 24.2g, content 79.3%, yield 73%.
Embodiment 2
Add A27.9g (180mmol) in the 500ml round-bottomed flask, sodium cyanide 9.3g (190mmol), Tetrabutyl amonium bromide 1.5g (4.6mmol), tindichloride 0.11g (0.6mmol), iodine 0.15g (0.6mmol) and toluene 200ml.System is warming up to 80 ℃, and reacts 4 hours at this temperature, extract reaction solution the gas chromatographic analysis feed stock conversion and be about 75%.Now system is dropped to room temperature (20 ℃) and, to the aqueous sodium hydroxide solution 50ml that adds pH=10 in reaction flask, continue stirring reaction 1 hour, the TLC detection reaction completes.The sodium bicarbonate aqueous solution that system is 5% by concentration is treated to neutrality, filters, and separatory, use respectively 50ml toluene aqueous phase extracted twice, merges organic phase dry.Precipitation obtains crude product 23.7g, content 88.7%, yield 80%.
Embodiment 3
Add A27.9g (180mmol) in the 500ml round-bottomed flask, sodium cyanide 9.3g (190mmol), Tetrabutyl amonium bromide 1.5g (4.6mmol) and toluene 200ml.System is warming up to 80 ℃, and reacts 4 hours at this temperature, extract reaction solution the gas chromatographic analysis feed stock conversion and be about 45%.Now system is dropped to room temperature (20 ℃) and, to the aqueous sodium hydroxide solution 50ml that adds pH=10 in reaction flask, continue stirring reaction 1 hour, the TLC detection reaction completes.The sodium bicarbonate aqueous solution that system is 5% by concentration is treated to neutrality, filters, and separatory, use respectively 50ml toluene aqueous phase extracted twice, merges organic phase dry.Precipitation obtains crude product 22.9g, content 60%, yield 52%.
Embodiment 4
Add A27.9g (180mmol) in the 500ml round-bottomed flask, sodium cyanide 9.3g (190mmol), Tetrabutyl amonium bromide 1.5g (4.6mmol), tindichloride 0.11g (0.6mmol) and toluene 200ml.System is warming up to 80 ℃, and reacts 6 hours at this temperature, extract reaction solution the gas chromatographic analysis feed stock conversion and be about 58%.Now system is dropped to room temperature (20 ℃) and, to the aqueous sodium hydroxide solution 50ml that adds pH=10 in reaction flask, continue stirring reaction 1 hour, the TLC detection reaction completes.The sodium bicarbonate aqueous solution that system is 5% by concentration is treated to neutrality, filters, and separatory, use respectively 50ml toluene aqueous phase extracted twice, merges organic phase dry.Precipitation obtains crude product 24.1g, content 63.3%, yield 58%.
Embodiment 5
Add A55.8g (360mmol) in the 500ml round-bottomed flask, sodium cyanide 18.6g (380mmol), Tetrabutyl amonium bromide 3.0g (9.2mmol), tindichloride 0.22g (1.2mmol), iodine 0.30g (1.2mmol) and toluene 200ml.System is warming up to 80 ℃, and reacts 6 hours at this temperature, extract reaction solution the gas chromatographic analysis feed stock conversion and be about 76%.Now system is dropped to room temperature (20 ℃) and, to the aqueous sodium hydroxide solution 50ml that adds PH=10 in reaction flask, continue stirring reaction 1 hour, the TLC detection reaction completes.The sodium bicarbonate aqueous solution that system is 5% by concentration is treated to neutrality, filters, and separatory, use respectively 50ml toluene aqueous phase extracted twice, merges organic phase dry.Precipitation obtains crude product 47.7g, content 89.3%, yield 81%.
(2) technique of compd E is synthetic
Embodiment 6
Add D12.4g (60mmol) in the 500ml round-bottomed flask, Sodium Bromide 10.7g (104mmol), sodium bromate 3.2g (20.9mmol), ethyl acetate 150ml and water 50ml are in 25 ℃ of lower stirring and dissolving of room temperature.Drip about 20ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively by twice of 50ml ethyl acetate aqueous phase extracted and merge organic phase, drying, precipitation obtains crude product 17.0g, content 88.8%, yield 88%.
Embodiment 7
Add D12.4g (60mmol) in the 500ml round-bottomed flask, Sodium Bromide 10.7g (104mmol), sodium bromate 3.2g (20.9mmol), trichloromethane 150ml and water 50ml are 25 ℃ of lower stirring and dissolving.Drip about 20ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively with twice of 50ml chloroform extraction water and merge organic phase, drying, precipitation obtains crude product 16.7g, content 75.0%, yield 73%.
Embodiment 8
Add D12.4g (60mmol) in the 500ml round-bottomed flask, Sodium Bromide 10.7g (104mmol), sodium bromate 3.2g (20.9mmol), acetonitrile 150ml and water 50ml are 25 ℃ of lower stirring and dissolving.Drip about 20ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively by twice of 50ml acetonitrile aqueous phase extracted and merge organic phase, drying, precipitation obtains crude product 16.9g, yield 80%.
Embodiment 9
Add D12.4g (60mmol) in the 500ml round-bottomed flask, Sodium Bromide 10.3g (100mmol), sodium bromate 3.0g (20mmol), ethyl acetate 150ml and water 50ml are in 25 ℃ of lower stirring and dissolving of room temperature.Drip about 20ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively by twice of 50ml ethyl acetate aqueous phase extracted and merge organic phase, drying, precipitation obtains crude product 16.5g, content 86.3%, yield 83%.
Embodiment 10
Add D12.4g (60mmol) in the 500ml round-bottomed flask, Sodium Bromide 11.1g (108mmol), sodium bromate 3.3g (22mmol), ethyl acetate 150ml and water 50ml are in 25 ℃ of lower stirring and dissolving of room temperature.Drip about 20ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively by twice of 50ml ethyl acetate aqueous phase extracted and merge organic phase, drying, precipitation obtains crude product 16.7g, content 83.2%, yield 81%.
Embodiment 11
Add D24.8g (120mmol) in the 500ml round-bottomed flask, Sodium Bromide 21.4g (208mmol), sodium bromate 6.4g (41.8mmol), ethyl acetate 150ml and water 150ml are in 25 ℃ of lower stirring and dissolving of room temperature.Drip about 40ml concentrated hydrochloric acid again in system, solution becomes red-brown, reacts after 5 hours and becomes glassy yellow.The TLC detection reaction completes.The aqueous sodium carbonate that is 5% by concentration by reaction solution be treated to neutral after separatory, respectively by twice of 50ml ethyl acetate aqueous phase extracted and merge organic phase, drying, precipitation obtains crude product 33.4g, content 87.3%, yield 85%.
Claims (10)
1. the preparation method of an improved 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters, improvement shows that 2-toluyl nitrile synthesizes the process innovation aspect of bromination (step D → E) two-step reaction of (steps A → B) and 2-(2 '-aminomethyl phenyl)-2-carbonylic acetic acid methyl esters, not only reaction method is improved, and yield has a more substantial increase.
2. as prepared the step of 2-toluyl nitrile (B) in claims 1: with toluene, make solvent, to the tindichloride and the iodine that add A, sodium cyanide, Tetrabutyl amonium bromide, catalytic amount in reaction flask, system is heated to 70～100 ℃, the system after 4 hours of reacting is cooled to 15-25 ℃, again to the aqueous sodium hydroxide solution that adds pH=10 in system, continue stirring reaction 1 hour, reaction finishes.
3. as the method for synthetic B in claims 2, it is characterized in that Heating temperature is 70～100 ℃, optimum temps is 80 ℃.
4. as the method for synthetic B in claims 2, it is characterized in that the tindichloride and the iodine that add are the co-catalysis agent.
5. as prepared the step of 2-(2 '-2-bromomethylphenyl)-2-carbonylic acetic acid methyl esters (E) in claims 1: add D, ethyl acetate, water, Sodium Bromide and sodium bromate stirring and dissolving in reaction flask, start to drip hydrochloric acid, solution becomes red-brown, react solution after 5 hours and become glassy yellow, reaction finishes.
6. as the method for synthetic E in claims 5, it is characterized in that solvent is except ethyl acetate, can also be acetonitrile, methylene dichloride, and chloroform etc., optimum solvent is ethyl acetate.
7. as the method for synthetic E in claims 5, the mol ratio that it is characterized in that Sodium Bromide, sodium bromate and D is 5～6: 1～1.2: 3.The optimum molar ratio of Sodium Bromide, sodium bromate and D is 5.2: 1.1: 3.
8. as the method for synthetic E in claims 5, it is characterized in that Sodium Bromide can replace with sodium bisulfite or sodium sulphite.
9. as the method for synthetic E in claims 5, it is characterized in that temperature of reaction is 20～40 ℃, Optimal Temperature is 25～30 ℃.
10. as the method for synthetic E in claims 5, in it is characterized in that reacting, the optimum volume ratio of organic solvent and water is 3: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557609A (en) * | 2014-12-18 | 2015-04-29 | 北京颖泰嘉和生物科技有限公司 | Method for preparing 2-benzyl bromide compound |
| CN104744303A (en) * | 2015-02-15 | 2015-07-01 | 北京欣奕华科技有限公司 | 2-R-4'-bromomethyl biphenyl and preparation method thereof |
| CN110396054A (en) * | 2019-07-31 | 2019-11-01 | 京博农化科技有限公司 | A kind of green synthesis method of kresoxim-methyl |
| CN115974834A (en) * | 2022-12-30 | 2023-04-18 | 北京理工大学 | A method for preparing thiazepine compound by continuous reaction |
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2013
- 2013-09-11 CN CN 201310412993 patent/CN103450021A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557609A (en) * | 2014-12-18 | 2015-04-29 | 北京颖泰嘉和生物科技有限公司 | Method for preparing 2-benzyl bromide compound |
| CN104557609B (en) * | 2014-12-18 | 2017-11-17 | 北京颖泰嘉和生物科技股份有限公司 | A kind of preparation method of 2 bromomethyl benzene-like compounds |
| CN104744303A (en) * | 2015-02-15 | 2015-07-01 | 北京欣奕华科技有限公司 | 2-R-4'-bromomethyl biphenyl and preparation method thereof |
| CN110396054A (en) * | 2019-07-31 | 2019-11-01 | 京博农化科技有限公司 | A kind of green synthesis method of kresoxim-methyl |
| CN110396054B (en) * | 2019-07-31 | 2022-09-20 | 京博农化科技有限公司 | Green synthesis method of kresoxim-methyl |
| CN115974834A (en) * | 2022-12-30 | 2023-04-18 | 北京理工大学 | A method for preparing thiazepine compound by continuous reaction |
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Application publication date: 20131218 |