CN108129349A - The synthetic method of one kind (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide - Google Patents
The synthetic method of one kind (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide Download PDFInfo
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- CN108129349A CN108129349A CN201711377676.2A CN201711377676A CN108129349A CN 108129349 A CN108129349 A CN 108129349A CN 201711377676 A CN201711377676 A CN 201711377676A CN 108129349 A CN108129349 A CN 108129349A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention discloses a kind of synthetic methods of 2 (2 phenoxy phenyl) acetamide of (E) 2 methoxy imino N methyl, it is reacted using diphenyl ether as starting material with dimethyl oxalate and prepares intermediate 2 (2 phenoxy group benzene) 2 oxoacetic acid methyl esters, then oxime compounds are made with azanol reaction, 2 (2 phenoxy phenyl) acetamide of (E) 2 methoxy imino N methyl most is made through amination afterwards.The preparation method of the present invention has many advantages, such as that raw material is cheap and easily-available, simple for process, the three wastes are few, avoids using hypertoxic raw material, is suitble to industrialized production.(E) 2 methoxy imino N methyl 2 (2 phenoxy phenyl) acetamides are a kind of efficient agricultural bactericide, have stronger preventive and therapeutic effect to diseases such as rice blast, banded sclerotial blight, powdery mildew of cucumber, downy mildew.
Description
Technical field
The present invention relates to a kind of preparation methods of agriculture chemicals fungicide, and in particular to one kind (E) -2- methoxy imino-N- first
The synthetic method of base -2- (2- phenoxy phenyls) acetamide.
Background technology
(E) -2- methoxy iminos-N- methyl -2- (2- phenoxy phenyls) acetamide belongs to methoxy acrylic acid (as shown in I)
Esters fungicide has stronger preventive and therapeutic effect to diseases such as rice blast, banded sclerotial blight, powdery mildew of cucumber, downy mildew；To phycomycete
The fungi imperfects such as class, ascomycetes, basidiomycetes and fungi imperfect have very high inhibition mycelia growth left and right.The longevity of residure
Long, 80d still has 80% preventive effect after processing, efficient to panicle blast, which has prevention and therapeutic effect quickly.
The prior art is disclosed about (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide synthesis side
Method mainly has following three kinds：
(1) EP0547825 is disclosed uses 0-chloro-benzoic acid with phenol ether metaplasia into 2- phenoxy benzoic acids, by acylation
It is reacted with methyl isocyanideization and N- methyl -2- (2- phenoxy groups benzene) -2- oxoaGetamides is made, then dimethyl suflfate carries out methyl
Change, obtain (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide.The shortcomings that route, uses severe toxicity
Methyl isocyanide, the compound are gas, and the leakage of methyl isocyanide is strictly controlled in use, right there are great security risk
Equipment and protective device requirement are high, are not suitable for industrialized production.
(2) EP0596692 is disclosed is obtained by the reaction target product for starting material to 2- (phenoxy group) toluene through 6 steps.
The route is longer, to use severe poisonous chemicals Cymag, security context pressure is larger, and the intermediate product 2- (benzene of the route
Oxygroup) bromobenzyl is larger to eyes and skin irritatin.
(3) disclosed use benzene diether be starting material through acylation synthesis, cyan-hydrolysis, hydroxyl oximate to CN102603563A
Target product is combined to methyl.Acylated yield is low, and uses hydrofluoric acid, and seriously corroded in preparation process is high to equipment requirement,
Preparation process pollution corrosion is big.
In conclusion prior art yield is low, three waste discharge is more, and used poisonous reagent methyl isocyanide and Cymag or
The shortcomings of reagent hydrofluoric acid of high corrosion is high there are security risk, and equipment requirement is high, this results in (E) -2- methoxy iminos-N-
Methyl -2- (2- phenoxy phenyls) acetamide can not mass produce.
Invention content
The technical problem to be solved in the present invention is to provide a kind of high income, three waste discharge is few, safe, equipment requirement
It is low, it is suitble to the synthesis side of (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide of bulk industrial production
Method.
The present invention is the synthetic method of (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide, with hexichol
Ether is raw material, and synthetic route is as follows：
Its synthetic method, includes the following steps：
(1) diphenyl ether and butyl lithium react in solvent A at -20 DEG C~-15 DEG C is made 2- Phenoxyphenyl lithiums, then
Dimethyl oxalate is added dropwise, after reacting 2h, adds in mass percent concentration and obtains 2- (2- phenoxy groups benzene) -2- oxygen for 10% hydrochloric acidolysis
For methyl acetate, the solvent A is petroleum ether, n-hexane, hexamethylene or tetrahydrofuran；The volume mass of solvent A and diphenyl ether
Than for 5ml~10ml：1g；The molar ratio of dimethyl ether, butyl lithium and dimethyl oxalate is 1.0：1.0~2.0：1~2.0；
(2) salt of (2- phenoxy groups the benzene) -2- oxoacetic acid methyl esters of 2- first and azanol in solvent B in 50 DEG C~120 DEG C
It reacts and then is reacted again with dimethyl suflfate, methylate to obtain 2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetate, described
Solvent B is methanol or ethyl alcohol；The volume mass of solvent B and 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters is than 3ml~8ml：
1g；2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters, hydroxylamine salt, the molar ratio of dimethyl suflfate are 1.0：1.0~1.2：1.0
~1.2；
(3) 2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetates and methylamine solution in solvent C in 60 DEG C~100
DEG C reaction, reactant it is post-treated (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide, it is described organic
Combination of the solvent for one or more of benzene,toluene,xylene and methanol；Solvent C and 2- methoxy imino -2- (2-
Phenoxy phenyl) methyl acetate volume mass ratio be 2ml~6ml：1g；2- methoxy iminos -2- (2- phenoxy phenyls) acetic acid first
The molar ratio of ester and methylamine is 1.0：1.0~2.0.
Optimal technical solution is：
1) first under nitrogen protection, diphenyl ether, petroleum ether are added in the there-necked flask of 250mL, are cooled to -15 DEG C, is protected
It holds temperature and n-butyllithium solution is added dropwise, after dripping, then dimethyl oxalate is added dropwise in insulation reaction 1h again, after reacting 2h, -5
Acidolysis is neutralized to neutrality at DEG C, then is washed with water, extracts, dries and is distilled successively, obtains intermediate 2- (2- phenoxy groups benzene) -2-
Oxoacetic acid methyl ester；The volume mass of petroleum ether and diphenyl ether ratio is 5ml：1；Dimethyl ether, butyl lithium and dimethyl oxalate rub
You are than being 1.0：1.1：1.05.
2) 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters, hydroxylamine hydrochloride and methanol is added in three-necked flask, is warming up to
60 DEG C -65 DEG C, dimethyl suflfate reaction 8h is then added dropwise, is cooled to room temperature later, adds water washing, layering, saturated common salt washing
It washs, anhydrous magnesium sulfate drying, decompression steams solvent, filtration drying obtains 25.1g2- methoxy iminos -2- (2- phenoxy phenyls) acetic acid
Methyl esters；The volume mass of methanol and 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters compares 3.7ml：1g；2- (2- phenoxy groups benzene)-
2- oxoacetic acid methyl esters, hydroxylamine salt, the molar ratio of dimethyl suflfate are 1.0：1.0：1.2.
3) toluene, 2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetates and methylamine are added in there-necked flask, is heated to
75 DEG C -80 DEG C, react 4h；It is cooled to room temperature, adds water washing, layering, saturated common salt water washing, anhydrous magnesium sulfate drying, decompression
Steam solvent, filtration drying obtains (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide；Toluene and 2- methoxies
The volume mass ratio of imido grpup -2- (2- phenoxy phenyls) methyl acetate is 2ml：1g；2- methoxy iminos -2- (2- phenoxy phenyls)
The molar ratio of methyl acetate and methylamine is 1.0：1.0.
Compared with prior art, the present invention has the following advantages：
(1) using butyl lithium in step (1), which reaches 98%, and yield is more than 80%, avoids using
Hypertoxic raw material, safer environmental protection.
(2) corrosion reagent is not polluted by force in the present invention, low for equipment requirements, the three wastes are few.
(3) in synthetic method of the invention harmful and corrosivity is not also generated without using the chemicals of severe toxicity, reaction process
Substance such as hydrogen chloride etc.；Recycled solvent, production cost are low.
In short, the technical problem to be solved in the present invention is to provide a kind of high income, three waste discharge is few, safe, equipment
It is required that it is low,
Specific embodiment
It is the embodiment that invention provides below, to be further explained explanation to technical scheme of the present invention.
Embodiment 1：
1) first under nitrogen protection, by diphenyl ether (20g, 0.12mol), petroleum ether 100mL, add in three mouthfuls of 250mL
In bottle, -15 DEG C are cooled to, keeps temperature that n-butyllithium solution is added dropwise, after dripping, then oxalic acid is added dropwise in insulation reaction 1h again
Dimethyl ester reacts 2h, then -5 DEG C plus 10% hydrochloric acid in and to neutrality, be washed with water, extract, dry and distill successively,
Obtain 21.7g intermediates 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters, content 95%, yield 80%.mp:122~124 DEG C.
IR(cm-1)：3075,2963,1760,1723,1209,1190,1060.
1H NMR(δppm)：3.69 (3H, s), 6.90-7.5 (8H, m), 7.75 (1H, d).
2) 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters (21.5g, 0.1mol), hydrochloric acid hydroxyl are added in three-necked flask
Amine (21.5g, 0.1mol) and methanol 80ml, are warming up to 60 DEG C -65 DEG C, and dimethyl suflfate (10.8g, 0.12mol) is then added dropwise
8h is reacted, is cooled to room temperature later, adds water 50ml washings, layering, the drying of 20ml saturated common salts water washing, anhydrous magnesium sulfate, subtract
Pressure steams solvent, filtration drying, cools to less than 40 DEG C addition water 60ml, neutrality is finally washed with water, filtration drying obtains
25.1g2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetate, content 95%, yield 85%.
IR(cm-1)：3096,2966,1768,1746,1205,1176,1066.
1H NMR(δppm)：3.65 (3H, s), 3.95 (3H, s), 7.70~7.30 (8H, m), 7.45 (H, d).
3) in there-necked flask add in toluene 60ml, 2- methoxy imino -2- (2- phenoxy phenyls) methyl acetate (14g,
0.05mol) with methylamine (6.15g, 0.05mol), 75 DEG C -80 DEG C are heated to, reacts 4h；It is cooled to room temperature, adds water washing, divides
Layer, the drying of saturated common salt water washing, anhydrous magnesium sulfate, decompression steams solvent, filtration drying obtains 15.4g target products, content
98.7%, yield 80%, 88-95 DEG C of fusing point.
IR (KBr, cm-1)：3090,2934,1732,1698,1269,1117,1089.
1H NMR (DMSO, δ ppm)：2.89 (3H, d), 4.01 (3H, s), 6.65 (1H, s), 6.90-7.21 (8H, m),
7.32 (1H, d).
Synthesis target product total recovery is counted as 54.4% using diphenyl ether.
Embodiment 2：
1) first under nitrogen protection, by diphenyl ether (20g, 0.12mol), petroleum ether 100mL, tetramethylethylenediamine (2g,
It 0.02mol) adds in the there-necked flask of 250mL, is cooled to -15 DEG C, keep temperature that n-butyllithium solution is added dropwise, after dripping, protect
Temperature reaction 1h, is then added dropwise diethy-aceto oxalate again, after reacting 2h, in the hydrochloric acid that -5 DEG C add 10% and to neutrality, uses water successively
Washing, extraction, dry and distillation, obtain 21.7g intermediates 2- (2- phenoxy groups benzene) -2- ethyls, and content 96% is received
Rate 70%.
2) 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters (21.5g, 0.1mol), methyl hydroxyl are added in three-necked flask
Amine (21.5g, 0.1mol) and ethyl alcohol 80ml are warming up to 60 DEG C of -65 DEG C of reaction 8h, be cooled to room temperature later, water 50ml is added to wash,
Layering, the drying of 20ml saturated common salts water washing, anhydrous magnesium sulfate, decompression steam solvent, filtration drying, cool to less than 40 DEG C and add
Entering water 60ml, neutrality is finally washed with water, filtration drying obtains 25.1g2- methoxy iminos -2- (2- phenoxy phenyls) ethyl acetate,
Content 95%, yield 80%.
3) with step (3) in embodiment 1
Synthesis target product total recovery is counted as 44.8% using diphenyl ether.
Embodiment 3：
The embodiment and embodiment 1 the difference lies in：Solvent for use A is tetrahydrofuran in step (1), and yield is
83%.
Embodiment 4：
The embodiment and embodiment 1 the difference lies in：Lithiumation agent used is tert-butyl lithium in step (1), and yield is
84%.
Embodiment 5：
The embodiment and embodiment 1 the difference lies in：Solvent for use A is the mixing of toluene and methanol in step (3)
Solvent, yield 84%.
Embodiment 6：
The embodiment and embodiment 2 the difference lies in：Agents useful for same methyl hydroxylamine becomes hydroxyl sulfate in step (1)
And dimethyl suflfate, yield 77%.
Claims (3)
- The synthetic method of one kind 1. (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide, which is characterized in that Using diphenyl ether as raw material, include the following steps：(1) diphenyl ether and butyl lithium react in solvent A at -20 DEG C~-15 DEG C is made 2- Phenoxyphenyl lithiums, is then added dropwise Dimethyl oxalate after reacting 2h, adds in mass percent concentration and obtains 2- (2- phenoxy groups benzene) -2- oxo second for 10% hydrochloric acidolysis Sour methyl esters, the solvent A are petroleum ether, n-hexane, hexamethylene or tetrahydrofuran；The volume mass of solvent A and diphenyl ether ratio is 5ml~10ml：1g；The molar ratio of dimethyl ether, butyl lithium and dimethyl oxalate is 1.0：1.0~2.0：1~2.0；(2) salt of (2- phenoxy groups the benzene) -2- oxoacetic acid methyl esters of 2- first and azanol in solvent B in 50 DEG C~120 DEG C react, Then it is reacted again with dimethyl suflfate, methylate to obtain 2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetate, the solvent B For methanol or ethyl alcohol；The volume mass of solvent B and 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters is than 3ml~8ml：1g；2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters, hydroxylamine salt, the molar ratio of dimethyl suflfate are 1.0：1.0~1.2：1.0~1.2；(3) 2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetates and methylamine solution are anti-in 60 DEG C~100 DEG C in solvent C Should, reactant is post-treated to obtain (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide, the organic solvent Combination for one or more of benzene,toluene,xylene and methanol；Solvent C and 2- methoxy iminos -2- (2- benzene oxygen Phenyl) methyl acetate volume mass ratio be 2ml~6ml：1g；2- methoxy iminos -2- (2- phenoxy phenyls) methyl acetates and The molar ratio of methylamine is 1.0：1.0~2.0.
- 2. the synthetic method of 2- (2- phenoxy groups benzene) -2- oxoacetic acid methyl esters as described in claim 1, which is characterized in that step Suddenly the post processing in (1) is followed successively by hydrochloric acid acidification, layering, extraction, washing, dry and distillation.
- 3. the synthesis side of (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide as described in claim 1 Method, which is characterized in that the post processing of step (3), which is followed successively by, is cooled to 25 DEG C plus water washing, layering, saturated common salt water washing, nothing Water magnesium sulfate is dried, and decompression steams solvent, filtration drying.
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| CN201711377676.2A CN108129349A (en) | 2017-12-19 | 2017-12-19 | The synthetic method of one kind (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide |
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| CN201711377676.2A CN108129349A (en) | 2017-12-19 | 2017-12-19 | The synthetic method of one kind (E) -2- methoxy imino-N- methyl -2- (2- phenoxy phenyls) acetamide |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254426A2 (en) * | 1986-07-18 | 1988-01-27 | Zeneca Limited | Fungicides |
| EP0468775A1 (en) * | 1990-07-26 | 1992-01-29 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Process for producing methoxyiminoacetamide compounds and intermediates |
| WO1999051567A1 (en) * | 1998-04-07 | 1999-10-14 | Shionogi & Co., Ltd. | Process for producing hydroxyiminoacetamide derivative and process for producing methoxyiminoacetamide derivative with the same |
| CN102603563A (en) * | 2012-01-16 | 2012-07-25 | 山东康乔生物科技有限公司 | Preparation method of metominostrobin |
-
2017
- 2017-12-19 CN CN201711377676.2A patent/CN108129349A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254426A2 (en) * | 1986-07-18 | 1988-01-27 | Zeneca Limited | Fungicides |
| EP0468775A1 (en) * | 1990-07-26 | 1992-01-29 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Process for producing methoxyiminoacetamide compounds and intermediates |
| WO1999051567A1 (en) * | 1998-04-07 | 1999-10-14 | Shionogi & Co., Ltd. | Process for producing hydroxyiminoacetamide derivative and process for producing methoxyiminoacetamide derivative with the same |
| CN102603563A (en) * | 2012-01-16 | 2012-07-25 | 山东康乔生物科技有限公司 | Preparation method of metominostrobin |
Non-Patent Citations (1)
| Title |
|---|
| ROSSI, RENZO 等: "A novel method for the efficient synthesis of methyl 2-oxo-2-arylacetates and its application to the preparation of fungicidal methyl (E)-O-methyloximino-2-arylacetates and their (Z)-stereoisomers", 《TETRAHEDRON》 * |
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