CN114380740A - Synthesis method of polysubstituted pyridine-2-oxygen ether compound - Google Patents
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- CN114380740A CN114380740A CN202111594242.4A CN202111594242A CN114380740A CN 114380740 A CN114380740 A CN 114380740A CN 202111594242 A CN202111594242 A CN 202111594242A CN 114380740 A CN114380740 A CN 114380740A
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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Abstract
The invention relates to a synthesis method of a polysubstituted pyridine-2-oxygen ether compound, which comprises the steps of directly mixing and reacting a polysubstituted pyridine derivative with phenol, distilling and recovering redundant phenol after the reaction is finished, adding a solvent into a distillation residue for dissolving, cooling, crystallizing, filtering and drying to obtain the polysubstituted pyridine-2-oxygen ether compound. The synthesis method of the polysubstituted pyridine-2-oxygen ether compound has no alkali participation, and the polysubstituted pyridine-2-oxygen ether compound is prepared by directly carrying out etherification reaction on phenol and polysubstituted pyridine derivatives, so that the generation of waste water and waste salt is avoided, the post-treatment process is simplified, and the synthesis method is an environment-friendly technical route.
Description
Technical Field
The invention belongs to the technical field of pesticide production, and particularly relates to a synthesis method of a polysubstituted pyridine-2-oxygen ether compound.
Background
The polysubstituted pyridine-2-oxygen ether compound is widely used as a bactericide and a herbicide and is widely applied to the field of pesticides. The synthesis route of the polysubstituted pyridine-2-oxygen ether compound is generally as follows: under the action of a phase transfer catalyst, potassium hydroxide or sodium hydroxide reacts with phenol to obtain potassium phenolate/sodium phenolate, and then nucleophilic substitution reaction is carried out on the potassium phenolate/sodium phenolate and halogen atoms at the 2-position of pyridine heterocycle to obtain the polysubstituted pyridine-2-oxygen ether compound, wherein the reaction principle is as follows:
wherein: r1 is a carboxylic acid, ester, amide, or substituted amide;
r4 is phenyl or a derivative thereof;
x is halogen;
m is sodium or potassium.
However, the synthetic route can generate a large amount of waste water and waste salt in production, which brings environmental protection pressure. Therefore, how to reduce waste water and waste salt in the synthesis process is a problem which is continuously studied by those skilled in the art.
Disclosure of Invention
The invention aims to provide a synthesis method of a polysubstituted pyridine-2-oxygen ether compound, which has the advantages of simple process, no generation of wastewater and waste salt and small environmental protection pressure.
The technical scheme adopted by the invention for solving the problems is as follows: a method for synthesizing polysubstituted pyridine-2-oxygen ether compounds comprises the step of directly mixing polysubstituted pyridine derivatives and phenol for reaction to obtain the polysubstituted pyridine-2-oxygen ether compounds.
The reaction principle is as follows:
wherein: r1 is a carboxylic acid, ester, amide, or substituted amide;
r2, R3 is H, halogen, alkyl or alkyl derivative;
r4 is phenyl or a derivative thereof;
x is halogen.
Preferably, the synthesis method of the polysubstituted pyridine-2-oxygen ether compound comprises the following steps:
(1) adding the pyridine derivative into an organic solvent for distillation and dehydration;
(2) adding phenol into an organic solvent for distillation and dehydration;
(3) continuously dropwise adding the solution obtained in the step (2) into the step (1), after dropwise adding, heating and refluxing for etherification reaction to obtain a reaction solution;
(4) carrying out negative pressure distillation on the reaction liquid obtained in the step (3) to recover redundant phenol;
(5) and (4) adding an organic solvent into the distillation residual liquid in the step (4), heating to dissolve, cooling, filtering and drying to obtain the polysubstituted pyridine-2-oxygen ether compound.
More preferably, the organic solvent in step (1), step (2) and step (5) is toluene, xylene, cyclohexane, heptane or chlorobenzene.
More preferably, the step (1) is specifically: adding the pyridine derivative into an organic solvent at the temperature of 0-160 ℃ for distillation and dehydration, wherein the mass ratio of the pyridine derivative to the organic solvent is 10: 1-1: 50, and the distillation and dehydration temperature is 100-150 ℃.
More preferably, the mass ratio of the polysubstituted pyridine derivative to the organic solvent in the step (1) is 2: 1-1: 5.
More preferably, the step (2) is specifically: adding phenol into an organic solvent at the temperature of 0-160 ℃ for distillation and dehydration, wherein the mass ratio of the phenol to the organic solvent is 10: 1-1: 50, and the distillation and dehydration temperature is 100-150 ℃.
More preferably, the mass ratio of the phenol to the organic solvent in the step (2) is 2: 1-1: 3.
More preferably, the step (3) is specifically: and (3) continuously dropwise adding the solution obtained in the step (2) into the step (1), after dropwise adding, heating and refluxing for etherification reaction, evaporating the organic solvent or supplementing fresh organic solvent to control the temperature of the reaction system to be 90-200 ℃, reacting for 1-25h, sampling and controlling, wherein the content of the polysubstituted pyridine derivative as the raw material is less than 0.5%.
More preferably, the etherification temperature in step (3) is 125-160 ℃.
More preferably, the step (4) is specifically: and (4) distilling the reaction liquid obtained in the step (3) under negative pressure to recover the redundant phenol, wherein the distillation temperature is 80-180 ℃, and the vacuum is-0.04 to-0.1 Mpa.
More preferably, the distillation temperature in step (4) is 115-165 ℃.
More preferably, the step (5) is specifically: and (4) adding an organic solvent into the distillation residual liquid in the step (4), heating to dissolve, cooling at 0-30 ℃, filtering, and drying at 40-140 ℃ in sequence to obtain the polysubstituted pyridine-2-oxygen ether compound.
Compared with the prior art, the invention has the advantages that:
the synthesis method of the polysubstituted pyridine-2-oxygen ether compound has no alkali participation, and the polysubstituted pyridine-2-oxygen ether compound is prepared by directly carrying out etherification reaction on phenol and polysubstituted pyridine derivatives, so that the generation of waste water and waste salt is avoided, the post-treatment process is simplified, and the synthesis method is an environment-friendly technical route.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A method for synthesizing polysubstituted pyridine-2-oxygen ether compounds N- (2, 4-difluorophenyl) -2- [ (3-trifluoromethyl) phenoxy ] -3-pyridine carboxamide comprises the following steps:
dissolving N- (2, 4-difluorophenyl) -2-chloro-3-pyridinecarboxamide in cyclohexane solvent, and distilling and dehydrating to obtain a cyclohexane solution of N- (2, 4-difluorophenyl) -2-chloro-3-pyridinecarboxamide, wherein the mass ratio of the N- (2, 4-difluorophenyl) -2-chloro-3-pyridinecarboxamide to the cyclohexane is 1:1, and the distilling and dehydrating temperature is 145 ℃; dissolving m-trifluoromethylphenol in cyclohexane, and distilling and dehydrating to obtain a m-trifluoromethylphenol cyclohexane solution, wherein the mass ratio of the m-trifluoromethylphenol to the cyclohexane is 2:1, and the distillation and dehydration temperature is 140 ℃; dropwise adding the m-trifluoromethyl phenol cyclohexane solution into the N- (2, 4-difluorophenyl) -2-chloro-3-pyridinecarboxamide cyclohexane solution, heating to 145-155 ℃ for etherification reaction, keeping the temperature at 145-155 ℃, distilling out part of cyclohexane to maintain the temperature at 145-155 ℃ if the system temperature is lower than 145 ℃, replenishing part of cyclohexane to maintain the temperature at 145-155 ℃ if the system temperature is higher than 155 ℃, stopping the reaction until the content of the raw material N- (2, 4-difluorophenyl) -2-chloro-3-pyridinecarboxamide is less than 0.5 percent, and reacting for 8 hours; distilling and recovering m-trifluoromethylphenol at 135 deg.C under-0.095 Mpa to obtain distillation residue; adding cyclohexane with the theoretical yield of 3 times of N- (2, 4-difluorophenyl) -2- [ (3-trifluoromethyl) phenoxy ] -3-pyridinecarboxamide into the distillation residue, heating to dissolve, cooling at 5 ℃, filtering and drying at 120 ℃ to obtain the product of N- (2, 4-difluorophenyl) -2- [ (3-trifluoromethyl) phenoxy ] -3-pyridinecarboxamide.
Example 2
A synthesis method of polysubstituted pyridine-2-oxygen ether compound 2- [4- (3-chloro-5-trifluoromethylpyridyl-2-yl) phenoxy ] methyl propionate comprises the following steps:
dissolving 2- (4-hydroxyphenoxy) propionic acid in a solvent toluene, and carrying out distillation dehydration to obtain a 2- (4-hydroxyphenoxy) propionic acid toluene solution, wherein the mass ratio of the 2- (4-hydroxyphenoxy) propionic acid to the toluene is 1:2.5, and the distillation dehydration temperature is 112 ℃; dissolving 3-chloro-2, 5-bis (trifluoromethyl) pyridine in toluene, distilling and dehydrating to obtain a 3-chloro-2, 5-bis (trifluoromethyl) pyridine toluene solution, wherein the mass ratio of the 3-chloro-2, 5-bis (trifluoromethyl) pyridine to the toluene is 2: 1; dropwise adding the 3-chloro-2, 5-bis (trifluoromethyl) pyridine toluene solution into the 2- (4-hydroxyphenoxy) propionic acid toluene solution, heating to carry out etherification reaction, keeping the temperature at 145 ℃ of 140-; distilling 2- (4-hydroxyphenoxy) propionic acid at 165 deg.C under-0.095 Mpa; adding toluene with 5 times of theoretical yield of 2- [4- (3-chloro-5-trifluoromethylpyridyl-2-yl) phenoxy ] methyl propionate into the distillation residue, heating to dissolve, cooling at 5 ℃, filtering and drying at 100 ℃ to obtain a product of 2- [4- (3-chloro-5-trifluoromethylpyridyl-2-yl) phenoxy ] methyl propionate.
Example 3
A method for synthesizing polysubstituted pyridine-2-oxygen ether compound (E) -A-methoxymethylene-2- (3-trifluoromethyl-2-pyridyloxymethyl) benzyl acetate comprises the following steps:
dissolving (E) -2- (2-hydroxyphenyl) -3-methoxy methyl acrylate in chlorobenzene as a solvent, and distilling and dehydrating to obtain a chlorobenzene solution of (E) -2- (2-hydroxyphenyl) -3-methoxy methyl acrylate, wherein the mass ratio of (E) -2- (2-hydroxyphenyl) -3-methoxy methyl acrylate to chlorobenzene is 1:3, and the distillation and dehydration temperature is 144 ℃; dissolving 2-chloro-6 (trifluoromethyl) pyridine in chlorobenzene, and distilling and dehydrating to obtain a 2-chloro-6 (trifluoromethyl) pyridine chlorobenzene solution, wherein the mass ratio of the 2-chloro-6 (trifluoromethyl) pyridine to the cyclohexane is 2:1, and the distillation and dehydration temperature is 140 ℃; dropwise adding a 2-chloro-6 (trifluoromethyl) pyridine chlorobenzene solution into a (E) -2- (2-hydroxyphenyl) -3-methoxy methyl acrylate solution, heating to carry out etherification reaction, keeping the temperature at 170-175 ℃, distilling out part of chlorobenzene to maintain the temperature at 170-175 ℃ if the system temperature is lower than 170 ℃, and supplementing part of chlorobenzene to maintain the temperature at 170-175 ℃ if the system temperature is higher than 175 ℃, stopping the reaction until the content of the raw material (E) -2- (2-hydroxyphenyl) -3-methoxy methyl acrylate is less than 0.5 percent, and reacting for 7 hours; distilling (E) -methyl 2- (2-hydroxyphenyl) -3-methoxyacrylate at 165 deg.C under-0.095 MPa; adding toluene with 5 times of theoretical yield of (E) -A-methoxymethylene-2- (3-trifluoromethyl-2-pyridyloxymethyl) benzyl acetate into distillation residue, heating to dissolve, cooling at 5 deg.C, filtering, and drying at 100 deg.C to obtain (E) -A-methoxymethylene-2- (3-trifluoromethyl-2-pyridyloxymethyl) benzyl acetate product.
Example 4
A method for synthesizing polysubstituted pyridine-2-oxygen ether compound 2- (2-chlorine-4- (trifluoromethyl) phenoxy) nicotinic acid comprises the following steps:
dissolving 2-chloronicotinic acid in heptane as a solvent, and carrying out distillation and dehydration to obtain a heptane solution of 2-chloronicotinic acid, wherein the mass ratio of 2-chloronicotinic acid to heptane is 1:1, and the distillation and dehydration temperature is 82 ℃; dissolving 2-chloro-4- (trifluoromethyl) phenol in heptane, and distilling and dehydrating to obtain 2-chloro-4- (trifluoromethyl) phenol heptane solution, wherein the mass ratio of 2-chloro-4- (trifluoromethyl) phenol to heptane is 2: 1; dropwise adding the 2-chloro-4- (trifluoromethyl) phenol heptane solution into the 2-chloronicotinic acid heptane solution, heating to carry out etherification reaction, keeping the temperature at 155-165 ℃, distilling out part of heptane to maintain the temperature at 155-165 ℃ if the system temperature is lower than 155 ℃, supplementing part of heptane to maintain the temperature at 155-165 ℃ if the system temperature is higher than 165 ℃, stopping the reaction until the content of the raw material 2-chloronicotinic acid is less than 0.5%, and reacting for 8 hours; distilling and recovering 2-chloro-4- (trifluoromethyl) phenol at the temperature of 145 ℃ and the pressure of-0.095 Mpa; adding heptane with 3 times of theoretical yield of 2- (2-chloro-4- (trifluoromethyl) phenoxy) nicotinic acid into the distillation residue, heating to dissolve, cooling at 5 ℃, filtering, and drying at 120 ℃ to obtain the 2- (2-chloro-4- (trifluoromethyl) phenoxy) nicotinic acid product.
Example 5
A synthetic method of polysubstituted pyridine-2-oxygen ether compound 2- (4- (trifluoromethyl) phenoxy) methyl nicotinate comprises the following steps:
dissolving 2-chloronicotinic acid methyl ester in cyclohexane solvent, and distilling and dehydrating to obtain 2-chloronicotinic acid methyl ester cyclohexane solution, wherein the mass ratio of 2-chloronicotinic acid methyl ester to cyclohexane is 1:1, and the distillation and dehydration temperature is 140 ℃; dissolving 4- (trifluoromethyl) phenol in cyclohexane, and distilling and dehydrating to obtain 4- (trifluoromethyl) phenol cyclohexane solution, wherein the mass ratio of 4- (trifluoromethyl) phenol to cyclohexane is 2: 1; dripping the 4- (trifluoromethyl) phenol cyclohexane solution into the 2-chloronicotinic acid methyl ester cyclohexane solution, heating to carry out etherification reaction, keeping the temperature at 145-155 ℃, if the system temperature is lower than 145 ℃, distilling out part of cyclohexane to keep the temperature at 145-155 ℃, and if the system temperature is higher than 155 ℃, replenishing part of cyclohexane to keep the temperature at 145-155 ℃, stopping the reaction until the content of the raw material 2-chloronicotinic acid methyl ester is less than 0.5 percent, and reacting for 6 hours; distilling and recovering m-4- (trifluoromethyl) phenol at 140 ℃ and under the pressure of-0.095 Mpa; adding cyclohexane with the yield 3 times that of 2- (4- (trifluoromethyl) phenoxy) methyl nicotinate into the distillation residue, heating to dissolve, cooling at 5 ℃, filtering and drying at 120 ℃ to obtain a product of 2- (4- (trifluoromethyl) phenoxy) methyl nicotinate.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (8)
1. A method for synthesizing polysubstituted pyridine-2-oxygen ether compounds is characterized by comprising the following steps: directly mixing and reacting the polysubstituted pyridine derivative with phenol to obtain the polysubstituted pyridine-2-oxygen ether compound.
2. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 1, wherein: the method comprises the following steps:
(1) adding the polysubstituted pyridine derivative into an organic solvent for distillation and dehydration;
(2) adding phenol into an organic solvent for distillation and dehydration;
continuously dropwise adding the solution obtained in the step (2) into the step (1), after dropwise adding, heating and refluxing for etherification reaction to obtain a reaction solution;
(4) carrying out negative pressure distillation on the reaction liquid obtained in the step (3) to recover redundant phenol;
(5) and (4) adding an organic solvent into the distillation residual liquid in the step (4), heating to dissolve, cooling, filtering and drying to obtain the polysubstituted pyridine-2-oxygen ether compound.
3. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: the step (1) is specifically as follows: adding a polysubstituted pyridine derivative into an organic solvent for distillation dehydration, wherein the mass ratio of the pyridine derivative to the organic solvent is 10: 1-1: 50, and the distillation dehydration temperature is 100-150 ℃.
4. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: the step (2) is specifically as follows: adding phenol into an organic solvent for distillation dehydration, wherein the mass ratio of the phenol to the organic solvent is 10: 1-1: 50, and the distillation dehydration temperature is 100-150 ℃.
5. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: the step (3) is specifically as follows: and (3) continuously dropwise adding the solution obtained in the step (2) into the step (1), after dropwise adding, heating and refluxing for etherification reaction, evaporating the organic solvent or supplementing fresh organic solvent to control the temperature of the reaction system to be 90-200 ℃, reacting for 1-25h, sampling and controlling, wherein the content of the polysubstituted pyridine derivative as the raw material is less than 0.5%.
6. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: the step (4) is specifically as follows: and (4) distilling the reaction liquid obtained in the step (3) under negative pressure to recover the redundant phenol, wherein the distillation temperature is 80-180 ℃, and the vacuum is-0.04 to-0.1 Mpa.
7. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: the step (5) is specifically as follows: and (4) adding an organic solvent into the distillation residual liquid in the step (4), heating to dissolve, cooling at 0-30 ℃, filtering, and drying at 40-140 ℃ in sequence to obtain the polysubstituted pyridine-2-oxygen ether compound.
8. The method for synthesizing polysubstituted pyridine-2-oxoether compounds according to claim 2, wherein: in the step (1), the step (2) and the step (5), the organic solvent is toluene, xylene, cyclohexane, heptane or chlorobenzene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267336A (en) * | 1979-04-19 | 1981-05-12 | Ishihara Sangyo Kaisha Ltd. | Process for producing 4-(pyridyl-2-oxy)-phenoxyalkanecarboxylic acid or its derivatives |
| CN101209992A (en) * | 2006-12-28 | 2008-07-02 | 张月亮 | Preparation method of biological anthelmintic fluazuron |
| CN110894188A (en) * | 2018-09-13 | 2020-03-20 | 江苏丰山集团股份有限公司 | Preparation method of 2-substituted halogenated pyridine compound |
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2021
- 2021-12-24 CN CN202111594242.4A patent/CN114380740A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267336A (en) * | 1979-04-19 | 1981-05-12 | Ishihara Sangyo Kaisha Ltd. | Process for producing 4-(pyridyl-2-oxy)-phenoxyalkanecarboxylic acid or its derivatives |
| CN101209992A (en) * | 2006-12-28 | 2008-07-02 | 张月亮 | Preparation method of biological anthelmintic fluazuron |
| CN110894188A (en) * | 2018-09-13 | 2020-03-20 | 江苏丰山集团股份有限公司 | Preparation method of 2-substituted halogenated pyridine compound |
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