CN108191709A - A kind of method for preparing unsaturated oximido ethers compound - Google Patents
A kind of method for preparing unsaturated oximido ethers compound Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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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Abstract
A kind of preparation method of unsaturated oximido ethers compound (I), reaction equation are as follows：
Description
Technical field
The invention belongs to organic synthesis field, more particularly to a kind of method for preparing unsaturated oximido ethers compound.
Background technology
Unsaturated oximido ethers compound is a kind of compound with high bactericidal activity.Chemical combination is disclosed in CN1309897A
Object-methoxyimino-N- methyl -2- [[[[[[4- (2,6- dimethyl) phenyl] -3- butene-2s-yl] imino group] oxygroup] first
Base] phenyl-acetamides (compound number：1), bioactivity research show the compound have wide sterilization spectrum, bactericidal activity it is high,
The features such as treatment and protective effect are had both, be commercialized exploitation, general entitled alkene oxime amine.
Although the preparation method of unsaturated oximido ethers compound is disclosed in CN1309897A：By styryl methyl ketone oxime
With (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate condensation reaction is carried out under alkaline condition, then react with methylamine
Obtain target product.But carry out styryl methyl ketone oxime in the method and (E) -2- (bromomethyl)-α-methoxy imino
Yield is relatively low when base methyl phenylacetate reacts, and in embodiment 1 is prepared, the reaction yield of the step is only 29.43%.Condensation product
It is relatively low that yield during aminolysis is carried out with methylamine again, yield 75%.This two-step reaction total recovery is only 22.07%, and is post-processed
Complexity seriously limits the industrialized production of such product.
And then technical staff is dedicated to constantly researching and developing new, more advanced reasonable, more environmentally-friendly preparation at this stage
The preparation method of unsaturated oximido ethers compound, to obtain efficient, the safe fungicide that quality is more excellent, price is lower.
Invention content
The purpose of the present invention is to provide a kind of more easy, more environmentally-friendly sides for preparing unsaturated oximido ethers compound
Method.
In order to achieve the object of the present invention, the present invention use technical solution for：
A kind of method for preparing unsaturated oximido ethers compound, reaction equation are as follows：
In formula：X1-X5Hydrogen, fluorine, chlorine, bromine, alkyl or alkoxy are respectively and independently selected from,
Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent, adds in logical formula (II) institute
Show the inorganic carbonate of .5-2.2 times mole of compound 20, add (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate
(III), it reacts and ether compound (IV) is made；Obtained ether compound (IV) is dissolved in alcohol, adds methylamine, reaction is made
Unsaturated oximido ethers compound shown in logical formula (I)；The organic solvent is selected from ketones solvent.
Preparation is preferably：Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent, is added
Enter the inorganic carbonate of .5-2.2 times mole of compound 20 shown in logical formula (II), add .85-1.1 times of compound 20 shown in logical formula (II)
Mole (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (III), 1-8h is reacted in the range of 40-90 DEG C, be made
Ether compound (IV)；Obtained ether compound (IV) is dissolved in alcohol, adds in 2-6 times mole of compound shown in logical formula (IV)
Methylamine reacts 1-5h in the range of 40-100 DEG C, and the unsaturated oximido ethers compound shown in logical formula (I) is made.
Preparation is more preferably：Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent,
The inorganic carbonate of 1.1-1.6 times mole of chemical combination shown in logical formula (II) is added in, adds .9-1.0 times of compound 20 shown in logical formula (II)
Mole (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (III), 2-5h is reacted in the range of 50-65 DEG C, be made
Ether compound (IV)；Obtained ether compound (IV) is dissolved in alcohol, adds in 3-5 times mole of compound shown in logical formula (IV)
In the presence of methylamine, 2-5h is reacted in the range of 60-80 DEG C, the unsaturated oximido ethers compound shown in logical formula (I) is made.
The inorganic carbonate is selected from sodium carbonate, potassium carbonate or cesium carbonate.It is preferred that inorganic carbonate is selected from potassium carbonate or carbon
Sour caesium.More preferable inorganic carbonate is selected from potassium carbonate.
The organic solvent is selected from ketones solvent.It is preferred that ketones solvent is different selected from acetone, butanone, methyl propyl ketone, methyl
The mixing of one or more of propyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), ethyl isobutylo ketone；More preferable ketone is molten
Agent is selected from the mixing of one or more of acetone, butanone, methyl propyl ketone, methyl iso-butyl ketone (MIBK).
It is preferred that alcohols solvent is selected from the mixing of one or more of methanol, ethyl alcohol, propyl alcohol, isopropanol；More preferable alcohols
Solvent is selected from methanol and/or ethyl alcohol.
The invention described above preparation method can be used conveniently to prepare X in above-mentioned reaction equation1-X5Insatiable hunger selected from hydrogen, fluorine, chlorine or bromine
And oximido ether compound.
The preparation method ginseng of (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate shown in above-mentioned logical formula (III)
See EP254426.The preparation method of styryl methyl ketone oxime compound shown in logical formula (II) is referring to CN1309897A.
In the definition of logical formula (I) compound given above, collect term used and be generally defined as follows：Alkyl refers to straight chain
Or branched form, such as it is n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, 2- methyl butyls, n-pentyl, different
The groups such as amyl.Alkoxy refers to that alkyl end is connected with the group of oxygen atom, such as methoxyl group, ethyoxyl, positive propoxy, isopropyl
Oxygroup, tert-butoxy etc..
Advantage for present invention：
Inorganic carbonate is selected not only to accelerate the speed of reaction in reaction process of the present invention, but also to the yield of target product
There is very big influence.Meanwhile make alkali using inorganic carbonate in reaction and play vital work to achieving the object of the present invention
With.In addition, using inorganic carbonate and corresponding solvent is coordinated reaction yield can be made further to be carried in reaction process
It is high.And further optimize reaction condition, adjust appropriate reaction temperature, select suitable alkali and appropriate dosage, Yu Shi
In suitable solvent, and then reaction yield is greatly improved, prepare the E formula unsaturated oximido ethers compounds of high bactericidal activity
Object is closed, the method for unsaturated oximido ethers compound provided by the present invention, not only with high yield, and last handling process is more
Add simplicity, the method is easier to industrialized production.
Specific embodiment
Below by the preparation for enumerating the unsaturated oximido ethers compound shown in the logical formula (I) of embodiment further description
Method, but the present invention is not limited only to these embodiments.
Embodiment 1
Methoxyimino-N- methyl -2- [[[[[[4- (2,6- dimethyl) phenyl] -3- butene-2s-yl] imino group] oxygen
Base] methyl] phenyl-acetamides synthesis
To reaction bulb sequentially add (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (75.5g, 0.2mol),
Acetone (390g), 2,6- dichlorostyrene ylmethyl ketoximes (46.1g, 0.20mol), potassium carbonate (44.6g, 0.32mol), heating
To 58 DEG C of reflux heat preservations, back flow reaction 5h.After reaction, 80 DEG C of water-bath heating normal pressures recycle acetone to substantially without fraction when stop
Anti-avulsion is molten.Add methylene chloride (350mL) and water 150g, stirs to complete molten rear stratification, separates organic phase and washed with water (150g)
It washs primary, separates after washing after organic phase, the first air-distillations of 70 DEG C of heating of water-bath after fraction to substantially without continuing after depressurizing 10min
Stopping adds in methanol (122g) after slightly cooling down, temperature rising reflux to material dispersion uniformly cools down, filters afterwards, methanol (12g) washs,
It drains, obtains white solid 82g, quantitative levels 97.0%, yield 91.4%.
White solid obtained in the previous step is added in reaction bulb, sequentially adds the methanol of methanol (480g) and methylamine
Solution (82.6g, 30%, 0.8mol) after 10min is stirred at room temperature, is warming up to reflux, keeps the temperature 3h.After reaction, normal pressure steams
It evaporating, stops distillation when collecting fraction 390g, room temperature filtering is down in cooling, drying, obtains white solid 76.9g, 131-132 DEG C,
Quantitative levels 98.8%, yield 95.8%.
Through two-step reaction, the total recovery that object is made is 87.6% (with (E) -2- (bromomethyl)-α-methoxy imino benzene
Methyl acetate meter).
Embodiment 2
Methoxyimino-N- methyl -2- [[[[[[4- (2,6- dimethyl) phenyl] -3- butene-2s-yl] imino group] oxygen
Base] methyl] phenyl-acetamides synthesis (solvent butanone)
To reaction bulb sequentially add (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (75.5g, 0.2mol),
Butanone (350g), 2,6- dichlorostyrene ylmethyl ketoximes (46.1g, 0.2mol), potassium carbonate (41.4g, 0.30mol), heating
To 60 DEG C, insulation reaction 4h.After reaction, heating water bath be recovered under reduced pressure butanone to substantially without fraction when stop precipitation.Add two
Chloromethanes (350mL) and water 150g are stirred to complete molten rear stratification, are separated organic phase and washed once with water (150g), separate
After washing after organic phase, the first air-distillations of 70 DEG C of water-bath heating to without continuing to stop after depressurizing 10min after fraction, slightly cooling down substantially
Methanol (122g) is added in afterwards, and temperature rising reflux to material dispersion uniformly cools down, filters afterwards, methanol (12g) washing, drains, and obtains white
Color solid 80.7g, quantitative levels 97.0%, yield 90%.
White solid obtained in the previous step is added in reaction bulb, sequentially adds the methanol of methanol (470g) and methylamine
Solution (93g, 30%, 0.9mol) after 10min is stirred at room temperature, is warming up to reflux, keeps the temperature 3h.After reaction, air-distillation,
Stop distillation when collecting fraction 365g, room temperature filtering is down in cooling, drying, must expect 75.4g, 131-132 DEG C, quantitative levels
98.5%, yield 95%.
Through two-step reaction, the total recovery that object is made is 85.5% (with (E) -2- (bromomethyl)-α-methoxy imino benzene
Methyl acetate meter).
Embodiment 3
Methoxyimino-N- methyl -2- [[[[[[4- (2,6- dimethyl) phenyl] -3- butene-2s-yl] imino group] oxygen
Base] methyl] phenyl-acetamides synthesis
To reaction bulb sequentially add (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (75.5g, 0.2mol),
Acetone (390g), 2,6- dichlorostyrene ylmethyl ketoximes (46.1g, 0.20mol), cesium carbonate (97.7g, 0.30mol), heating
To 58 DEG C of reflux heat preservations, back flow reaction 4h.After reaction, 80 DEG C of water-bath heating normal pressures recycle acetone to substantially without fraction when stop
Anti-avulsion is molten.Add methylene chloride (350mL) and water 150g, stirs to complete molten rear stratification, separates organic phase and washed with water (150g)
It washs primary, separates after washing after organic phase, the first air-distillations of 70 DEG C of heating of water-bath to stopping without continuing to depressurize 10min after fraction substantially
Only, methanol (122g) is added in after slightly cooling down, temperature rising reflux to material dispersion uniformly cools down, filters afterwards, methanol (12g) washing, takes out
It is dry, obtain white solid 82.3g, quantitative levels 97.0%, yield 91.8%.
White solid obtained in the previous step is added in reaction bulb, sequentially adds the methanol of methanol (490g) and methylamine
Solution (93g, 30%, 0.9mol) after 10min is stirred at room temperature, is warming up to reflux, keeps the temperature 3h.After reaction, air-distillation,
Stop distillation when collecting fraction 400g, room temperature filtering is down in cooling, and drying obtains white solid 77.2g, fusing point 131-132
DEG C, quantitative levels 99.1%, yield 96%.
Through two-step reaction, the total recovery that object is made is 87.6% (with (E) -2- (bromomethyl)-α-methoxy imino benzene
Methyl acetate meter).
Simultaneously according to method provided by the present invention, carbonate and reaction condition described in foregoing invention content are selected
It is optionally combined different combination conditions, and by X in logical formula (II) and logical formula (III)1-X5It is replaced accordingly, you can prepare logical
Unsaturated oximido ethers compound shown in formula (I)；Referring specifically to table 1
The structure of 1. partial Formula of table (I) compound
Comparative examples
(the compound number in CN1309897A of compound 1 in the method synthesis table 1 provided according to CN1309897A：1).
Methoxyimino-N- methyl -2- [[[[[[4- (2,6- dimethyl) phenyl] -3- butene-2s-yl] imino group] oxygen
Base] methyl] phenyl-acetamides synthesis
By the N of 2,6- dichlorostyrene ylmethyl ketoximes (2.3g, 0.01mol), N-dimethylformamide solution (10mL) drop
The suspension (10mL) of sodium hydroxide (0.4g, 0.01mol) n,N dimethylformamide is added to, after 0.5h, by (E) -2- (bromine first
Base)-α-methoxy imino methyl phenylacetate (2.86g, 0.01mol) N, the suspension (10mL) of N-dimethylformamide adds in
Into said mixture, continue to stir 2h at room temperature.After reaction, reaction mixture is poured into water, uses ethyl acetate
Extraction 2 times, merges extracting solution and washes 3 times, and then dry, concentration obtains crude product.With ethyl acetate and the mixed liquor of petroleum ether
(1:5) column chromatography is carried out for eluent to purify to obtain yellow oil 1.34g, quantitative levels 96.0%, yield 29.5%.
Yellow oil will be obtained above to be dissolved in methanol (40g), add methylamine water solution (0.7g, 40%,
0.009mol), reaction solution is added in reflux, keeps the temperature 3h.After reaction, air-distillation is extracted to no fraction with ethyl acetate
It takes twice, merges extract and be washed with water 3 times, then dry, concentrate, obtain target compound 1.0g, white solid, fusing point
131-133, quantitative levels 95%, yield 75%.
The total recovery of object is made as 22.1% (with (E) -2- (bromomethyl)-α-methoxy imino benzene through two-step reaction
Methyl acetate meter).
Claims (9)
1. a kind of method for preparing unsaturated oximido ethers compound, reaction equation are as follows：
In formula：X1-X5It is respectively and independently selected from hydrogen, fluorine, chlorine, bromine, alkyl or alkoxy, it is characterised in that：
Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent, adds in logical formula (II) shownization
0.5-2.2 times mole of inorganic carbonate is closed, adds (E) -2- (bromomethyl)-α-methoxy imino methyl phenylacetate (III),
Ether compound (IV) is made in reaction；Obtained ether compound (IV) is dissolved in alcohol, adds methylamine, reacts and general formula is made
(I) the unsaturated oximido ethers compound shown in.
2. the method described in accordance with the claim 1 for preparing unsaturated oximido ethers compound, it is characterised in that：
Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent, adds in logical formula (II) shownization
0.5-2.2 times mole of inorganic carbonate is closed, adds (E) -2- (bromine first of .85-1.1 times mole of compound 20 shown in logical formula (II)
Base)-α-methoxy imino methyl phenylacetate (III), 1-8h is reacted in the range of 40-90 DEG C, ether compound (IV) is made；It will
Ether compound (IV) is made to be dissolved in alcohol, the methylamine of 2-6 times mole of compound shown in logical formula (IV) is added in, in 40-100 DEG C of model
Interior reaction 1-5h is enclosed, the unsaturated oximido ethers compound shown in logical formula (I) is made.
3. according to the method for preparing unsaturated oximido ethers compound described in claims 1 or 2, it is characterised in that：
Styryl methyl ketone oxime compound shown in logical formula (II) is dissolved in organic solvent, adds in logical formula (II) shownization
1.1-1.6 times mole of inorganic carbonate is closed, adds (E) -2- (bromine first of .9-1.0 times mole of compound 20 shown in logical formula (II)
Base)-α-methoxy imino methyl phenylacetate (III), 2-5h is reacted in the range of 50-65 DEG C, ether compound (IV) is made；
Obtained ether compound (IV) is dissolved in alcohol, is added in the presence of the methylamine of 3-5 times mole of compound shown in logical formula (IV),
2-5h is reacted in the range of 60-80 DEG C, the unsaturated oximido ethers compound shown in logical formula (I) is made.
4. the method described in accordance with the claim 2 for preparing unsaturated oximido ethers compound, it is characterised in that：The inorganic carbonate
Salt is selected from sodium carbonate, potassium carbonate or cesium carbonate.
5. according to the method for preparing unsaturated oximido ethers compound described in claim 4, it is characterised in that：The inorganic carbonate
Salt is selected from potassium carbonate or cesium carbonate.
6. according to the method for preparing unsaturated oximido ethers compound described in claim 5, it is characterised in that：The inorganic carbonate
Salt is selected from potassium carbonate.
7. the method described in accordance with the claim 1 for preparing unsaturated oximido ethers compound, it is characterised in that：The organic solvent
Selected from ketones solvent.
8. according to the method for preparing unsaturated oximido ethers compound described in claim 7, it is characterised in that：The ketones solvent
In acetone, butanone, methyl propyl ketone, methyl isopropyl Ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), ethyl isobutylo ketone
One or more of mixing；Alcohols solvent is selected from the mixing of one or more of methanol, ethyl alcohol, propyl alcohol, isopropanol.
9. according to the method according to any one of claims 8 for preparing unsaturated oximido ethers compound, it is characterised in that：The ketone is molten
Agent is selected from the mixing of one or more of acetone, butanone, methyl propyl ketone, methyl iso-butyl ketone (MIBK)；Alcohols solvent is selected from methanol
And/or ethyl alcohol.
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|---|---|---|---|---|
| CN1065658A (en) * | 1991-01-30 | 1992-10-28 | 帝国化学工业公司 | Mycocide |
| CN1062711C (en) * | 1998-02-10 | 2001-03-07 | 化工部沈阳化工研究院 | Pesticide and fungicide of unsaturated oximido ethers |
| WO2001056358A2 (en) * | 2000-01-28 | 2001-08-09 | Rohm And Haas Company | Enhanced propertied pesticides |
| CN1309897A (en) * | 2000-02-24 | 2001-08-29 | 沈阳化工研究院 | Unsaturated oximino ether bactericide |
| CN103140136A (en) * | 2010-09-01 | 2013-06-05 | 杜邦公司 | Fungicidal pyrazoles and their mixtures |
| CN104884437A (en) * | 2012-10-25 | 2015-09-02 | 纳幕尔杜邦公司 | Substituted tolyl fungicides |
| WO2015157005A1 (en) * | 2014-04-10 | 2015-10-15 | E I Du Pont De Nemours And Company | Substituted tolyl fungicide mixtures |
-
2016
- 2016-12-08 CN CN201611120635.0A patent/CN108191709B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1065658A (en) * | 1991-01-30 | 1992-10-28 | 帝国化学工业公司 | Mycocide |
| CN1062711C (en) * | 1998-02-10 | 2001-03-07 | 化工部沈阳化工研究院 | Pesticide and fungicide of unsaturated oximido ethers |
| WO2001056358A2 (en) * | 2000-01-28 | 2001-08-09 | Rohm And Haas Company | Enhanced propertied pesticides |
| CN1309897A (en) * | 2000-02-24 | 2001-08-29 | 沈阳化工研究院 | Unsaturated oximino ether bactericide |
| CN103140136A (en) * | 2010-09-01 | 2013-06-05 | 杜邦公司 | Fungicidal pyrazoles and their mixtures |
| CN104884437A (en) * | 2012-10-25 | 2015-09-02 | 纳幕尔杜邦公司 | Substituted tolyl fungicides |
| WO2015157005A1 (en) * | 2014-04-10 | 2015-10-15 | E I Du Pont De Nemours And Company | Substituted tolyl fungicide mixtures |
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| 于春睿等: "肟菌酯合成方法述评", 《农药》 * |
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