CN109912417A - A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method - Google Patents
A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method Download PDFInfo
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- CN109912417A CN109912417A CN201910283827.0A CN201910283827A CN109912417A CN 109912417 A CN109912417 A CN 109912417A CN 201910283827 A CN201910283827 A CN 201910283827A CN 109912417 A CN109912417 A CN 109912417A
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- methyl
- methylenedioxy phenoxy
- benzoylformate
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Abstract
The invention belongs to technical field of fine, are related to pharmaceutical chemicals synthetic technology, in particular to a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate.It is, by reacting under the effect of the catalyst with methanol, to prepare 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate using 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide as starting material.This method avoid using highly concentrated hydrogen chloride gas to prepare in traditional handicraft, so that reaction time is short, high conversion rate, product quality is excellent, and operating procedure is simple, and required equipment is simple, has the characteristics that low energy consumption, the period is short, production capacity is big, environmental protection.
Description
Technical field
The invention belongs to technical field of fine, are related to pharmaceutical chemicals synthetic technology, in particular to a kind of 2- (2- first
Base Phenoxymethyl)-methyl benzoylformate synthetic method.
Background technique
Kresoxim-methyl is a kind of methoxy acrylic acid class fungicide drug found earliest, and kresoxim-methyl is made in addition to having sterilization
With, and the growth of many cereal crops can also be promoted, and plant senescence can be delayed, enhance plant to oxygen, dioxy
The absorption and utilization for changing carbon, there is very big application prospect on the market.
Currently, preparation 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate has main method are as follows: in 2- (2- methylbenzene
Oxygen methyl) methylene chloride, methanol are added in benzoyl cyanide, then be passed through hydrogen chloride gas and obtain 2- (2- methylenedioxy phenoxy methyl) benzoyl first
Sour methyl esters.This kind of preparation method is very long reaction time, and the every batch of period was at 120 hours or more, and the hydrogen chloride gas used has
Corrosivity easily corrodes equipment, has security risk.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of synthesis of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate
Method.Using 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide as starting material, occur by under the effect of the catalyst with methanol anti-
It answers, prepares 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate.
Specific synthetic route is as follows:
Specific steps of the invention are as follows:
2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and dichloroethanes (content 99%) are warming up to dissolution,
Reaction solution is cooled down again to after 0-10 DEG C, and catalyst is added, water is added, methanol is added dropwise, is to slowly warm up to flow back, 2-6
Cooling system is to 20 DEG C after hour, filtering, and methanol is added after washing, vacuum distillation and is warming up to dissolution for filtrate, then is cooled to 5-
It 10 DEG C, filters, obtains 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate solid.
Wherein, the dosage of dichloroethanes is 2.8-3.5 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight；More preferably
, the dosage of dichloroethanes is 3 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight；The dosage of water is 2- (2- methylbenzene
Oxygen methyl) benzoyl cyanide 1.2-2.0 times of equivalent.
The purpose that methanol is added dropwise for the first time is using methanol as reactant, and second of purpose that methanol is added is to make methanol
For the solvent for purifying 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate.
Selected catalyst is one of phosphoric acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, taurine, iodine, highly acidic resin
Or it is several；
The catalyst amount is the 0.5%-10% of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight；
Further, catalyst amount is preferably the 1%-5% of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight；
The first time methanol usage is preferably 3-5 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide mole；
Second of addition methanol usage is 2-3 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
Relative to it has been reported that method, the present invention uses environment amenable reagent, reduces environmental pollution, at the same this
Invention is easy to operate in entire synthesis process, and not only high income, obtained target product purity are also relatively high, and every batch of is anti-
Answer the period at 15 hours or so.The present invention is a kind of low pollution, high yield, high-purity, low energy consumption synthesis 2- (2- methylenedioxy phenoxy first
Base)-methyl benzoylformate method.
Specific embodiment
The specific embodiment of form by the following examples does further specifically above content of the invention
It is bright, but the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention, and it is complete to be all made of conventional prior unless otherwise specified, in following embodiments
At.
Embodiment 1
A kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate, the specific steps are that:
125.5g 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide (content 96%) and 376.5g dichloroethanes are warming up to 35
DEG C dissolution, then cooling reaction solution are added 1.3g p-methyl benzenesulfonic acid, 13.0g water are added, 64g methanol is added dropwise, slowly rises to after 5 DEG C
Temperature was to reflux 2 hours, and cooling system is to 20 DEG C, filtering, and 251g methanol is added after washing, vacuum distillation and is warming up to 60 DEG C for filtrate
Dissolution, then 5 DEG C are cooled to, it filters, obtains 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate solid 127.9g.Through measuring
It calculates, yield 92%, content 98%.
Embodiment 2
A kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate, the specific steps are that:
25.1g 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide (content 95.8%) and 75.3g dichloroethanes are warming up to 32
DEG C dissolution, then cooling reaction solution are added 1.5g phosphoric acid, 2.6g water are added, 9.7g methanol is added dropwise, is to slowly warm up to back to after 6 DEG C
Stream 3 hours, cooling system is to 20 DEG C, filtering, and 75g methanol is added after washing, vacuum distillation and is warming up to 58 DEG C of dissolutions for filtrate, then
4 DEG C are cooled to, filters, obtains 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate solid 25.1g.Through survey calculation, yield
It is 91%, content 98.5%.
Embodiment 3
A kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate, the specific steps are that:
251.1g 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide (content 96.4%) is warming up to 753.3g dichloroethanes
35 DEG C of dissolutions, then cooling reaction solution are added 2g p-methyl benzenesulfonic acid, 26g water are added, 144g methanol is added dropwise, slowly heats up to after 3 DEG C
To reflux 5 hours, cooling system was to 20 DEG C, filtering, filtrate through washing, be added after vacuum distillation 600g methanol be warming up to 57 DEG C it is molten
Solution, then 6 DEG C are cooled to, it filters, obtains 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate solid 258.3g.Through meter
It calculates, yield 93%, content 98.6%.
Embodiment 4
A kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate, the specific steps are that:
75.3g 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide (content 95.3%) is warming up to 225.9g dichloroethanes
36 DEG C of dissolutions, then cooling reaction solution are added 0.4g iodine, 7.8g water are added, 45g methanol is added dropwise, is to slowly warm up to after 4 DEG C
Reflux 2.5 hours, cooling system is to 20 DEG C, filtering, filtrate through washing, be added after vacuum distillation 200g methanol be warming up to 54 DEG C it is molten
Solution, then 2 DEG C are cooled to, it filters, obtains 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate solid 76.3g.Yield is
92.5%, content 98.4%.
Claims (9)
1. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate, which is characterized in that specific steps are as follows:
2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and dichloroethanes (content 99%) are warming up to dissolution, then cool down reaction solution to 0-10
After DEG C, catalyst is added, water is added, methanol is added dropwise, is to slowly warm up to flow back, cooling system is to 20 DEG C after 2-6 hours, filtering,
Methanol is added after washing, vacuum distillation and is warming up to dissolution for filtrate, then is cooled to 5-10 DEG C, filters, obtains 2- (2- methylenedioxy phenoxy
Methyl)-methyl benzoylformate solid.
2. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1, special
Sign is: the dosage of dichloroethanes is 2.8-3.5 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
3. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 2, special
Sign is: the dosage of dichloroethanes is 3 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
4. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1, special
Sign is: the dosage of water is 1.2-2.0 times of equivalent of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide.
5. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1, special
Sign is: the catalyst is one of phosphoric acid, p-methyl benzenesulfonic acid, benzene sulfonic acid, taurine, iodine, highly acidic resin
Or it is several.
6. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1 or 5,
It is characterized by: catalyst amount is the 0.5%-10% of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
7. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1 or 5,
It is characterized by: catalyst amount is the 1%-5% of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
8. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1, special
Sign is: 3-5 times that quantity of methyl alcohol is 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide mole being added dropwise for the first time.
9. a kind of synthetic method of 2- (2- methylenedioxy phenoxy methyl)-methyl benzoylformate according to claim 1, special
Sign is: second of addition quantity of methyl alcohol is 2-3 times of 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478241A (en) * | 2021-12-31 | 2022-05-13 | 山东京博生物科技有限公司 | Preparation method of arylformyl formic ether |
| CN114773193A (en) * | 2022-05-17 | 2022-07-22 | 荆州瑞东医药科技有限公司 | Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478241A (en) * | 2021-12-31 | 2022-05-13 | 山东京博生物科技有限公司 | Preparation method of arylformyl formic ether |
| CN114773193A (en) * | 2022-05-17 | 2022-07-22 | 荆州瑞东医药科技有限公司 | Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester |
| CN114773193B (en) * | 2022-05-17 | 2024-07-05 | 荆州瑞东医药科技有限公司 | Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } methyl acetate |
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