CN107459464A - One kind synthesis 2（The nitro-phenoxy of 5 fluorine 2）The method of methyl acetate - Google Patents
One kind synthesis 2（The nitro-phenoxy of 5 fluorine 2）The method of methyl acetate Download PDFInfo
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- CN107459464A CN107459464A CN201710788402.6A CN201710788402A CN107459464A CN 107459464 A CN107459464 A CN 107459464A CN 201710788402 A CN201710788402 A CN 201710788402A CN 107459464 A CN107459464 A CN 107459464A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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Abstract
The invention discloses a kind of method of 2 (nitro-phenoxy of 5 fluorine 2) methyl acetates of synthesis, with 2,4 difluoro nitrobenzenes are raw material, are substituted by hydroxyl, etherification reaction obtains 2 (nitro-phenoxy of 5 fluorine 2) methyl acetates (flumioxazin intermediate).The synthetic method of the present invention, it is cheap and easy to get with 2,4 difluoro nitrobenzenes for raw material, production cost is reduced to a certain extent；Intermediate 1 is directly reacted with methyl chloroacetate, simple to operate, and raw material is repeated and applied mechanically, and reduces production cost；Etherification reaction reclaims by-product hydrochloric acid, and no by-product sylvite produces, environment-friendly and green, and post-processing operation is easy；Other raw material is cheap and easy to get, and reaction condition is gentle, easy to operate, is advantageous to extend to large-scale production.
Description
Technical field
The present invention relates to herbicide preparing technical field, is specially a kind of synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) acetic acid
The method of methyl esters.
Background technology
Flumioxazin is wider with quick active and herbicidal spectrum of burning to weeds, has efficient, less toxic, selectivity by force,
The features such as to non-target organism safety and small environmental pollution, therefore the herbicide is widely used in terms of agricultural production, and
And there is very big economic value.2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate is that wherein mesosome, chemical structural formula are as follows：
Flumioxazin is the wide variety of herbicide of agricultural production, and 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate is
Wherein mesosome, at present domestic technique announced several preparation technologies.Have with 2,4- difluoro nitrobenzenes for initiation material, but such a side
Solvent needed for formula nitrification and etherification reaction is more, and dichloroethanes and triethylamine need to reclaim, and increases energy consumption and running cost；This
It is outer also to have so that using 2,4- difluoro nitrobenzenes, for initiation material, but solvent acetone needs to reclaim, increase Operating Complexity, Er Qiehui
A large amount of by-product sylvite are produced, processing is difficult, pollutes environment.Therefore a variety of synthetic routes announced, it is easy to accomplish industrial metaplasia
That produces is less.
It is domestic at present that prior art discloses the technique road on preparing 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate
Line mainly has several.
Chinese Patent Application No. is that CN105837563A discloses a kind of method for synthesizing flumioxazin intermediate.Using
2,4- difluoro nitrobenzenes are initiation material, dinitro substituent are obtained by nitrification, afterwards in 1,2- dichloroethanes and triethylamine
Ehter bond intermediate is obtained to carry out etherification reaction with Butyl Glycolate under conditions of solvent；The route initiation material is inexpensively easy
, but the shortcomings that certain be present in this method：Solvent is more needed for reaction, and dichloroethanes and triethylamine need to reclaim, and increases energy
Consumption and running cost.
Liu Anchang etc. discloses a kind of synthetic method (conjunction of new herbicides flumioxazin of flumioxazin intermediate
Into research, Liu Anchang etc., world pesticide, the 2nd phase of volume 33).This method with 2,4- difluoro nitrobenzenes for initiation material, by hydroxyl
Base obtains 2- nitro -5- fluorophenols, afterwards under conditions of using acetone as solvent, with quantitative solid potassium carbonate and bromoacetic acid second
Ester reacts to obtain ehter bond intermediate；The synthetic route reaction condition is gentle, but not only solvent acetone needs to reclaim this method, increase
Operating Complexity, and a large amount of by-product sylvite can be produced, processing is difficult, pollutes environment.
The content of the invention
It is an object of the invention to provide a kind of method of synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, with 2,
4- difluoro nitrobenzenes are raw material, it is not necessary to which adding solvent can be reacted, not only simple to operate, and raw material is repeated and applied mechanically, and is dropped
Low production cost, reaction recovery by-product hydrochloric acid, is generated without by-product sylvite, green, and reacts gentle, safe, with
Solve the problems, such as to propose in above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：One kind synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-)
The method of methyl acetate, with 2,4- difluoro nitrobenzenes for raw material, substituted by hydroxyl, etherification reaction obtains 2- (the fluoro- 2- nitre of 5-
Base-phenoxy group) methyl acetate (flumioxazin intermediate).
The further technical scheme of the present invention, comprises the following steps：
(1) hydroxyl substitutes
Put into a certain amount of 2,4- difluoro nitrobenzenes, water and potassium hydroxide successively into reactor, temperature meeting nature is raised to
70~90 DEG C, 1 hour is incubated after 70-90 degree is incubated about 2 hours and added, is sampled to 2,4- difluoro nitrobenzenes ＜ 0.5%.Sampling
After qualified, a certain amount of hydrochloric acid is added, side edged has product and water azeotropic to come out, heat temperature raising after stirring, with vapor
Distillation mode steams product.92 DEG C or so start product.Distillation finishes, product barrelling, and intermediate 1 is treated to react in next step.
Wherein, the intermediate 1 is C6H4FNO3, product C6H4FNO3With potassium fluoride KF；C6H4FNO3With potassium fluoride KF's
Mass ratio is 157: 58；
(2) etherification reaction
Put into the fluoro- 2- hydroxyls nitrobenzene of a certain amount of 4- successively into reactor, open and be added dropwise one at 80-100 DEG C of air inducing
Quantitative methyl chloroacetate, control is added dropwise in 4-5 hours, recovery hydrochloric acid by-product.Add rear 120-130 DEG C of insulation reaction 2 hours,
Mixture gradually becomes yellow, sampling raw material ＜ 0.5%.0-5 DEG C of filtering is cooled to after qualified, obtain 2- (the fluoro- 2- nitros of 5--
Phenoxy group) methyl acetate.
Preferably, in step (1), 2, the 4- difluoro nitrobenzenes C6H3F2NO2, potassium hydroxide KOH mass ratio be
159∶56。
Preferably, in step (2), the intermediate 1C6H4FNO3, methyl chloroacetate C3H5ClO2Mass ratio be 314:
217。
Preferably, in step (2), it is described be filtrated to get 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate after, filtrate
Continue to apply mechanically.
Preferably, in step (1-2), hydroxyl substitution reaction, the conversion ratio of etherification reaction are all higher than 99.5%.With it is existing
Technology is compared, the beneficial effects of the invention are as follows：
1st, the method for present invention synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, it is original with 2,4- difluoro nitrobenzenes
Material, it is cheap and easy to get, production cost is reduced to a certain extent；
2nd, the method for present invention synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, intermediate 1 is directly and monoxone
Methyl esters is reacted, simple to operate, and raw material is repeated and applied mechanically, and reduces production cost.
3rd, the method for present invention synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, etherification reaction recovery by-product salt
Acid, no by-product sylvite produce, environment-friendly and green, and post-processing operation is easy.
4th, the method for present invention synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, reaction step number is few, and each step is anti-
Mild condition is answered, it is safe, it is easy to operate, be advantageous to extend to large-scale production.
Brief description of the drawings
Fig. 1 is the flumioxazin intermediate synthetic reaction equation of the present invention；
The hydroxyl that Fig. 2 is the present invention substitutes equation；
Fig. 3 is the etherification reaction equation of the present invention；
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Referring to Fig. 1, a kind of method of synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, with 2,4- difluoroanilines
For raw material, substituted by hydroxyl, etherification reaction obtains 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate (among flumioxazin
Body).
The further technical scheme of the present invention, comprises the following steps：
(1) hydroxyl substitutes
Put into a certain amount of 2,4- difluoro nitrobenzenes, water and potassium hydroxide successively into reactor, temperature meeting nature is raised to
70~90 DEG C, 1 hour is incubated after 70-90 degree is incubated about 2 hours and added, is sampled to 2,4- difluoro nitrobenzenes ＜ 0.5%.Sampling
After qualified, a certain amount of hydrochloric acid is added, side edged has product and water azeotropic to come out, heat temperature raising after stirring, with vapor
Distillation mode steams product.92 DEG C or so start product.Distillation finishes, product barrelling, and intermediate 1 is treated to react in next step.
Wherein, the intermediate 1 is C6H4FNO3, product C6H4FNO3With potassium fluoride KF；C6H4FNO3With potassium fluoride KF's
Mass ratio is 157: 58；
Wherein, 2, the 4- difluoro nitrobenzenes C6H3F2NO2, potassium hydroxide KOH mass ratio be 159: 56.
(2) etherification reaction
Put into the fluoro- 2- hydroxyls nitrobenzene of a certain amount of 4- successively into reactor, open and be added dropwise one at 80-100 DEG C of air inducing
Quantitative methyl chloroacetate, control is added dropwise in 4-5 hours, recovery hydrochloric acid by-product.Add rear 120-130 DEG C of insulation reaction 2 hours,
Mixture gradually becomes yellow, sampling raw material ＜ 0.5%.0-5 DEG C of filtering is cooled to after qualified, obtain 2- (the fluoro- 2- nitros of 5--
Phenoxy group) methyl acetate.
Wherein, the intermediate 1C6H4FNO3, methyl chloroacetate C3H5ClO2Mass ratio be 314: 217.
In step (1-2), hydroxyl substitution reaction, the conversion ratio of etherification reaction are all higher than 99.5%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (6)
1. the method for one kind synthesis 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate, it is characterised in that with 2,4- difluoro nitros
Benzene is raw material, is substituted by hydroxyl, etherification reaction obtains 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate (in flumioxazin
Mesosome).
2. the synthetic method of 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate according to claim 1, it is characterised in that：
Synthetic method comprises the following steps：
(1) hydroxyl substitutes
Put into a certain amount of 2,4- difluoro nitrobenzenes, water and potassium hydroxide successively into reactor, temperature can nature be raised to 70~
90 DEG C, 1 hour is incubated after 70-90 degree is incubated about 2 hours and added, is sampled to 2,4- difluoro nitrobenzenes ＜ 0.5%.It is qualified to sample
Afterwards, a certain amount of hydrochloric acid is added, side edged has product and water azeotropic to come out, heat temperature raising after stirring, with steam distillation
Mode steams product.92 DEG C or so start product.Distillation finishes, product barrelling, and intermediate 1 is treated to react in next step.
Wherein, the intermediate 1 is C6H4FNO3, product C6H4FNO3With potassium fluoride KF；C6H4FNO3With potassium fluoride KF quality
Than for 157: 58；
(2) etherification reaction
Put into the fluoro- 2- hydroxyls nitrobenzene of a certain amount of 4- successively into reactor, be added dropwise at 80-100 DEG C of air inducing of opening a certain amount of
Methyl chloroacetate, control is added dropwise in 4-5 hours, reclaims hydrochloric acid by-product.Add rear 120-130 DEG C of insulation reaction 2 hours, mix
Thing gradually becomes yellow, sampling raw material ＜ 0.5%.0-5 DEG C of filtering is cooled to after qualified, obtains 2- (the fluoro- 2- nitros-benzene oxygen of 5-
Base) methyl acetate.
3. the synthetic method of 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate according to claim 2, it is characterised in that：
In step (1), 2, the 4- difluoro nitrobenzenes C6H3F2NO2, potassium hydroxide KOH mass ratio be 159: 56.
4. the synthetic method of 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate according to claim 2, it is characterised in that：
In step (2), the intermediate 1C6H4FNO3, methyl chloroacetate C3H5ClO2Mass ratio be 314: 217.
5. the synthetic method of 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate according to claim 2, it is characterised in that：
In step (2), it is described be filtrated to get 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate after, filtrate continues to apply mechanically.
6. the synthetic method of 2- (the fluoro- 2- nitro-phenoxies of 5-) methyl acetate according to claim 2, it is characterised in that：
In step (1-2), hydroxyl substitution reaction, the conversion ratio of etherification reaction are all higher than 99.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710788402.6A CN107459464A (en) | 2017-08-23 | 2017-08-23 | One kind synthesis 2（The nitro-phenoxy of 5 fluorine 2）The method of methyl acetate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710788402.6A CN107459464A (en) | 2017-08-23 | 2017-08-23 | One kind synthesis 2（The nitro-phenoxy of 5 fluorine 2）The method of methyl acetate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976129A (en) * | 2018-08-16 | 2018-12-11 | 淮安国瑞化工有限公司 | A kind of fluoro- 2,4- 2,4-dinitrophenoxy of 2-(5-) acetic acid esters preparation method |
| CN109503506A (en) * | 2018-11-21 | 2019-03-22 | 内蒙古世杰化工有限公司 | A kind of intermediate production method of flumioxazin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227535A (en) * | 1991-10-09 | 1993-07-13 | Hoechst Aktiengesellschaft | Process for the preparation of 2-nitro-5-fluoro- or -5-chlorophenol |
| WO2014122674A1 (en) * | 2013-02-08 | 2014-08-14 | Rallis India Limited | Process for preparation of derivatives of tetrahydrophthalimide |
-
2017
- 2017-08-23 CN CN201710788402.6A patent/CN107459464A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227535A (en) * | 1991-10-09 | 1993-07-13 | Hoechst Aktiengesellschaft | Process for the preparation of 2-nitro-5-fluoro- or -5-chlorophenol |
| WO2014122674A1 (en) * | 2013-02-08 | 2014-08-14 | Rallis India Limited | Process for preparation of derivatives of tetrahydrophthalimide |
Non-Patent Citations (1)
| Title |
|---|
| 刘安昌 等: "新型除草剂丙炔氟草胺的合成研究", 《世界农药》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976129A (en) * | 2018-08-16 | 2018-12-11 | 淮安国瑞化工有限公司 | A kind of fluoro- 2,4- 2,4-dinitrophenoxy of 2-(5-) acetic acid esters preparation method |
| CN108976129B (en) * | 2018-08-16 | 2022-10-28 | 安徽宁亿泰科技有限公司 | Preparation method of 2- (5-fluoro-2, 4-dinitrophenoxy) acetate |
| CN109503506A (en) * | 2018-11-21 | 2019-03-22 | 内蒙古世杰化工有限公司 | A kind of intermediate production method of flumioxazin |
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Application publication date: 20171212 |