CN109651190A - A kind of synthetic method of kresoxim-methyl - Google Patents
A kind of synthetic method of kresoxim-methyl Download PDFInfo
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- CN109651190A CN109651190A CN201811627541.1A CN201811627541A CN109651190A CN 109651190 A CN109651190 A CN 109651190A CN 201811627541 A CN201811627541 A CN 201811627541A CN 109651190 A CN109651190 A CN 109651190A
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- methylenedioxy phenoxy
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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Abstract
The invention belongs to technical field of fine, are related to chemistry of pesticide product synthetic technology, in particular to a kind of synthetic method of kresoxim-methyl.The present invention is using 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide as starting material, it reacts with methoxamine hydrochloride, hydrogen chloride gas is passed through in backward system after completion of the reaction, this method is short reaction time, high conversion rate, product quality is excellent, and the kresoxim-methyl content of synthesis meets market to the technical requirements of kresoxim-methyl 99% or more.
Description
Technical field
The invention belongs to technical field of fine, are related to chemistry of pesticide product synthetic technology, in particular to a kind of kresoxim-methyl
Synthetic method.
Background technique
Kresoxim-methyl is a kind of methoxy acrylic acid class fungicide class 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 enhancing plant can be delayed for nitrogen, dioxy
The absorption and utilization for changing carbon, there is very big application prospect on the market.
Currently, the main method for preparing kresoxim-methyl is as follows:
Synthetic route one:
Using phthalide as raw material, phthalide is reacted with o-cresol generates 2- (2- methylenedioxy phenoxy methyl) benzoic acid, and then chlorination obtains
Acyl chlorides, then carry out cyanogenation with Cymag and obtain 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide, 2- (2- methylenedioxy phenoxy methyl)
Benzoyl cyanide be added methanol lead to hydrogen chloride gas obtain 2- (2- methylenedioxy phenoxy methyl) methyl benzoylformate, then with methoxy amido salt
Hydrochlorate oximation reaction, logical hydrogen chloride gas configuration are converted into kresoxim-methyl.
In method made above, overall reaction yield is low, and total recovery also only has 55%, and reaction step and period are long, and should
A large amount of hydrogen chloride gas has been used in synthetic method, cannot have been recycled after hydrogen chloride gas use, and environment is caused greatly to pollute.
Synthetic route two:
Using o-toluic acid as raw material, acyl chlorides is prepared by thionyl chloride chlorination reaction, then the system of reacting with Cymag
Standby o-methyl-benzene formyl cyanogen, then passes to hydrogen chloride gas and obtains o-methyl-benzene formic acid methyl esters, then with methoxamine hydrochloride oxime
Change, logical hydrogen chloride gas carries out configuration indexing and obtains (E) -2- methoxyl group imido grpup-[(2- o-methyl-phenyl)] methyl acetate, Jin Eryu
Bromine reaction, finally reacts to obtain kresoxim-methyl with o-cresol.The process route, total recovery only have 35%, and higher cost, still
So largely use hydrogen chloride gas.
Therefore selection one is relatively cheap, and easy to operate, safety and environmental protection, period short synthesis technology will have very big warp
Ji value.
Summary of the invention
In view of the above-mentioned problems, the present invention has high income, reaction week the present invention provides a kind of synthetic method of kresoxim-methyl
Phase is short, environmental protection and energy saving, feature at low cost；The present invention is with 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and methoxamine hydrochloride
Raw material is first dehydrated to obtain 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile through oximate, then pass through again
Pinner, which reacts, is made kresoxim-methyl.
Specific synthetic route is as follows:
Step are as follows:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile
2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and methoxamine hydrochloride are added in methanol, catalyst, heating are put into
To 55 DEG C -65 DEG C, heat preservation obtains 2- methoxy imino-until 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide residual residue 0.5%
The methanol solution of 2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile；
(2) kresoxim-methyl is prepared through pinner reaction
The methanol solution of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to 5-10 DEG C
Afterwards, it is passed through hydrogen chloride gas into system, after having led to hydrogen chloride gas, and is to slowly warm up to 15-30 DEG C, insulation reaction is until 2- methoxy imino
It is to slowly warm up to flow back when base -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residue 10%-15%, reflux is until 2- methoxy
End of reaction after imido grpup -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5%, rear cooling, which filters, obtains ether
Kresoxim-methyl crude product, is then added in aqueous methanol by bacterium ester crude product, filters after being cooled to 0-20 DEG C after the completion of mashing and obtains essence
Product kresoxim-methyl.
Further, with the molar ratio computing of pure material, 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide in step (1), (2):
Methoxamine hydrochloride: catalyst: the ratio of hydrogen chloride gas is 1:(1.02-1.1): (0.005-1.05): 1.1；Preferably, 2- (2-
Methylenedioxy phenoxy methyl) benzoyl cyanide: methoxamine hydrochloride: catalyst: the ratio of hydrogen chloride gas is 1:1.05:0.01:1.1.
Further, the catalyst in the step (1) is at least one of organic base or phase transfer catalyst；It is preferred that
, the organic base is selected from triethylamine, triethylene diamine, 1,8- diazabicylo, 11 carbon -7- alkene (DBU), 1,5- diaza
Appointing in bicyclic [4.3.0] -5- nonene (DBN), 4-dimethylaminopyridine, N-methylmorpholine, tetramethylethylenediamine or tri-n-butylamine
It anticipates one kind；
The phase transfer catalyst be selected from 18 hat 6,15 hat 5, cyclodextrin, benzyltriethylammoinium chloride, tetrabutylammonium bromide,
Tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or myristyl three
Any one in ammonio methacrylate；Preferably tetrabutylammonium chloride.
Further, in the step (2) the aqueous range of aqueous methanol in 10%-50%；Preferably 20%.
Further, by 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile in the step (2)
After methanol solution is cooled to 5-10 DEG C, it is passed through hydrogen chloride gas into system, after having led to hydrogen chloride gas, and is to slowly warm up to 28 DEG C, keeps the temperature
Reaction is to slowly warm up to when 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residue 10%-15%
Reflux, reflux after 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5% until reacted
Finish, rear cooling, which filters, obtains kresoxim-methyl crude product, and then kresoxim-methyl crude product is added in aqueous methanol, is cooled to after the completion of mashing
It is filtered after 15 DEG C and obtains fine work kresoxim-methyl.
The present invention has the advantage that compared with prior art
The present invention provides a kind of synthetic method of kresoxim-methyl, this method selects 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide
React with pinner and carry out simultaneously with methoxamine hydrochloride elder generation oximate, configuration conversion, direct synthesis is simultaneously simply refining to obtain height and contains
The kresoxim-methyl of amount.The process recovery ratio that oximate, configuration convert after more traditional 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide is first esterified
15% or more raising, the operation cycle every batch of material reduction the period 60 hours or more, and hydrogen chloride gas dosage operating method saving
60% or more, the amount for handling by-product hydrochloric acid saves 60% or more, and the present invention is a kind of at low cost, easy to operate, safety and environmental protection, week
Phase short synthetic method.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art answer
It should be appreciated that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form repair
Change or replace, but these modifications and replacement are fallen within the protection scope of the present invention.
Embodiment 1
A kind of synthetic method of kresoxim-methyl, the specific steps are that:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile
2- (the 2- methylenedioxy phenoxy methyl) benzoyl cyanide and 1.1mol methoxamine hydrochloride of 1mol are added to the first of 5 times of volumes
In alcohol, the benzyltriethylammoinium chloride of 0.01mol is put into, is warming up to 60 DEG C, heat preservation is until 2- (2- methylenedioxy phenoxy methyl) benzene first
Acyl cyanogen residual residue 0.5%, obtains the methanol solution of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile；
(2) kresoxim-methyl is prepared through pinner reaction
The above-mentioned methanol solution for obtaining 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to
After 5 DEG C, hydrogen chloride gas is passed through into system, hydrogen chloride gas dosage is 1.1mol, after having led to hydrogen chloride gas, and is to slowly warm up to 15 DEG C, is protected
Temperature reaction is to slowly warm up to back when 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residue 11%
Stream, until thinking to have reacted after 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5%
Finish, rear cooling, which filters, obtains kresoxim-methyl crude product, is then added to kresoxim-methyl crude product in aqueous 15% methanol, after the completion of mashing
It is filtered after being cooled to 9 DEG C and obtains fine work kresoxim-methyl.Total recovery 90%, content 99.3%.
Embodiment 2
A kind of synthetic method of kresoxim-methyl, the specific steps are that:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is by 2- (the 2- methyl of 2mol
Phenoxymethyl) benzoyl cyanide and 2.1mol methoxamine hydrochloride be added in the methanol of 6 times of volumes, put into the tetrabutyl of 0.02mol
Ammonium bromide is warming up to 58 DEG C, and heat preservation obtains 2- methoxy until 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide residual residue 0.5%
The methanol solution of imido grpup -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile；
(2) kresoxim-methyl is prepared through pinner reaction
The above-mentioned methanol solution for obtaining 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to
After 8 DEG C, hydrogen chloride gas is passed through into system, hydrogen chloride gas dosage is 2.3mol, after having led to hydrogen chloride gas, and is to slowly warm up to 20 DEG C, is protected
Temperature reaction is to slowly warm up to flow back when 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile remains 13%,
Until end of reaction is thought after 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5%, after
Cooling filters and obtains kresoxim-methyl crude product, is then added to kresoxim-methyl crude product in aqueous 20% methanol, cools down after the completion of mashing
It is filtered after to 15 DEG C and obtains fine work kresoxim-methyl.Total recovery 92.5%, content 99.1%.
Embodiment 3
A kind of synthetic method of kresoxim-methyl, the specific steps are that:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is by 2- (the 2- first of 2.5mol
Base Phenoxymethyl) benzoyl cyanide and 2.7mol methoxamine hydrochloride be added in the methanol of 3 times of volumes, put into the 4- diformazan of 2.7mol
Aminopyridine is warming up to 55 DEG C, and heat preservation obtains 2- first until 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide residual residue 0.5%
The methanol solution of oxygen imido grpup -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile.
(2) kresoxim-methyl is prepared through pinner reaction
The above-mentioned methanol solution for obtaining 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to
After 10 DEG C, hydrogen chloride gas is passed through into system, hydrogen chloride gas dosage is 3.1mol, after having led to hydrogen chloride gas, and 18 DEG C are to slowly warm up to,
Insulation reaction is until 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is to slowly warm up to back when remaining 10%
Stream, until thinking to have reacted after 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5%
Finish, rear cooling, which filters, obtains kresoxim-methyl crude product, is then added to kresoxim-methyl crude product in aqueous 17% methanol, after the completion of mashing
It is filtered after being cooled to 17 DEG C and obtains fine work kresoxim-methyl.Total recovery 92%, content 98.9%.
Embodiment 4
A kind of synthetic method of kresoxim-methyl, the specific steps are that:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is by 2- (the 2- first of 1.3mol
Base Phenoxymethyl) benzoyl cyanide and 1.5mol methoxamine hydrochloride be added in the methanol of 4 times of volumes, put into the N- methyl of 1.4mol
Morpholine is warming up to 55 DEG C, and it is sub- to obtain 2- methoxy until 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide residual residue 0.5% for heat preservation
The methanol solution of amido -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile.
(2) kresoxim-methyl is prepared through pinner reaction
The above-mentioned methanol solution for obtaining 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to
After 5 DEG C, hydrogen chloride gas is passed through into system, hydrogen chloride gas dosage is 2.5mol, after having led to hydrogen chloride gas, and is to slowly warm up to 28 DEG C, is protected
Temperature reaction is to slowly warm up to flow back when 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile remains 12%,
Until end of reaction is thought after 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile residual residue 0.5%, after
Cooling filters and obtains kresoxim-methyl crude product, is then added to kresoxim-methyl crude product in aqueous 20% methanol, cools down after the completion of mashing
It is filtered after to 15 DEG C and obtains fine work kresoxim-methyl.Total recovery 94%, content 99.3%.
Control experiment synthesizes kresoxim-methyl technique
It is added 2- (2- methylenedioxy phenoxy methyl) benzoyl nitrile 54g (0.2mol) of 94% content in flask, 200g toluene,
After being cooled to -5 DEG C, it is passed through dry hydrogen chloride gas 90g (2.4mol), leads to the time about 2h of hydrogen chloride.It is to slowly warm up to 20-
25 DEG C of reaction 10h are added back flow reaction 6 hours again methanol 50g, water 100g are then added into system, heats up 60 DEG C and keeps the temperature 4 hours
It cuts out lower water for 60 DEG C afterwards, adds secondary water 100g, carry out secondary washing, organic phase carries out vacuum distillation and recycles toluene, obtains
To 2- (2- methylenedioxy phenoxy methyl) methyl benzoylformate.
Upper step is obtained into 2- (2- methylenedioxy phenoxy methyl) methyl benzoylformate, 150g methanol, 20g methoxamine hydrochloride liter
Warm back flow reaction 6 hours, is cooled to 20 DEG C, is uniformly passed through dry hydrogen chloride gas 50g into reaction kettle in 2 hours,
It reacts 16 hours, filters after completion of the reaction, filter cake is eluted with fresh methanol, is obtained at 20-25 DEG C after having led to hydrogen chloride
Kresoxim-methyl.Kresoxim-methyl content 95%, two-step reaction total recovery 75%.
Claims (9)
1. a kind of synthetic method of kresoxim-methyl, it is characterised in that: with 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and methoxy amine salt
Hydrochlorate is raw material, first obtains 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile through oximation reaction, then leads to
Enter hydrogen chloride gas and the obtained kresoxim-methyl of pinner reaction occurs.
2. the synthetic method of kresoxim-methyl according to claim 1, it is characterised in that: the specific steps are that:
(1) preparation of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile
2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide and methoxamine hydrochloride are added in methanol, catalyst is put into, is warming up to 55
It DEG C -65 DEG C, keeps the temperature to fully reacting, obtains the methanol of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile
Solution；
(2) kresoxim-methyl is prepared through pinner reaction
After the methanol solution of 2- methoxy imino -2- [2- (2- methylenedioxy phenoxy methyl) phenyl] acetonitrile is cooled to 5-10 DEG C, to
It is passed through hydrogen chloride gas in system, after having led to hydrogen chloride gas, controls certain temperature range until end of reaction.Cooling is taken out after completion of the reaction
Filter obtains kresoxim-methyl crude product, and then kresoxim-methyl crude product is added in aqueous methanol, takes out after being cooled to 0-20 DEG C after the completion of mashing
Filter obtains fine work kresoxim-methyl.
3. the synthetic method of kresoxim-methyl according to claim 2, it is characterised in that: with the molar ratio computing of pure material, step
(1), 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide in (2): methoxamine hydrochloride: catalyst: the ratio of hydrogen chloride gas is 1:
(1.02-1.1):(0.005-1.05):1.1。
4. the synthetic method of kresoxim-methyl according to claim 3, it is characterised in that: with the molar ratio computing of pure material, step
(1), 2- (2- methylenedioxy phenoxy methyl) benzoyl cyanide in (2): methoxamine hydrochloride: catalyst: the ratio of hydrogen chloride gas is 1:1.05:
0.01:1.1。
5. the synthetic method of kresoxim-methyl according to claim 2, it is characterised in that: the catalyst in step (1) is organic
At least one of alkali or phase transfer catalyst.
6. the synthetic method of kresoxim-methyl according to claim 5, it is characterised in that: the organic base is selected from triethylamine, three
Ethylene diamine, 11 carbon -7- alkene (DBU) of 1,8- diazabicylo, 1,5- diazabicyclo [4.3.0] -5- nonene (DBN), 4-
Any one in dimethylamino naphthyridine, N-methylmorpholine, tetramethylethylenediamine or tri-n-butylamine；
The phase transfer catalyst be selected from 18- crown- 6,15- crown- 5, cyclodextrin, benzyltriethylammoinium chloride, tetrabutylammonium bromide,
Tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or myristyl three
Any one in ammonio methacrylate.
7. the synthetic method of kresoxim-methyl according to claim 5, it is characterised in that: the phase transfer catalyst is the tetrabutyl
Ammonium bromide.
8. the synthetic method of kresoxim-methyl according to claim 2, it is characterised in that: aqueous methanol is aqueous in step (2)
Range is in 10%-50%.
9. the synthetic method of kresoxim-methyl according to claim 8, it is characterised in that: aqueous methanol is aqueous in step (2)
Amount is 20%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142587A (en) * | 2019-06-27 | 2020-12-29 | 长沙嘉桥生物科技有限公司 | Benzoetonic acid and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112142587A (en) * | 2019-06-27 | 2020-12-29 | 长沙嘉桥生物科技有限公司 | Benzoetonic acid and preparation method and application thereof |
| CN112142587B (en) * | 2019-06-27 | 2023-05-12 | 长沙嘉桥生物科技有限公司 | Acetophenone acid and preparation method and application thereof |
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