CN107759516B - Preparation method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative - Google Patents
Preparation method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative Download PDFInfo
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- C07D213/00—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
- 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
Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative. In the presence of excessive solvent, beta-diketone derivatives (general formula II), acrolein derivatives (general formula III) and ammonia source compounds are subjected to catalytic reaction or catalytic reaction without catalyst to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I); or reacting beta-diketone derivatives (general formula II) and acrolein derivatives (general formula III) under the catalysis of a catalyst or without the catalyst, and then adding a solvent and an ammonia source compound to react to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I); the invention provides a synthesis method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives with low cost and industrial prospect.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative.
Background
The alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative is a key intermediate for preparing the imidazolinone herbicide, has very important commercial value, and has great potential economic significance for any improvement of the synthetic process.
The literature shows the synthesis of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives, which can be broadly divided into two types, pre-alkoxylation and post-alkoxylation: the pre-alkoxylation method means that alkoxy is introduced into the structure of the compound before the pyridine ring is formed; the post-alkoxylation method means that an alkoxy group is introduced after a pyridine ring is formed.
In the substitution of pyridine-2, 3-dicarboxylic acids by alkyl radicals and alkyl ethersIn the imidazolinone series herbicides synthesized by the derivatives, the change of the substituent group not only has great influence on the activity and the efficacy of the herbicide (mutual toxic and side effects), but also has great influence on the difficulty and the yield of the synthesized pyridine-2, 3-dicarboxylic acid derivatives. Under similar reaction conditions, the yield of the pyridine-2, 3-dicarboxylic acid derivative varies, due to the difference in substituents, as: -C2H5＞90％，—CH3About 70%, -CH2OCH3Is less than 1%. Therefore, the synthesis of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives is extremely difficult, so that the conventional methoxyfenamic-n-ethyl in the imidazolinone series herbicides is produced by a post-methoxylation method, namely, 5-methyl-2, 3-pyridinecarboxylic acid diethyl ester is used as a raw material and is subjected to bromination, chlorination and methoxylation to obtain 5-methoxymethyl-2, 3-pyridinecarboxylic acid diethyl ester, and the method has the advantages of high raw material price, poor halogenation selectivity, low product yield and high cost. Therefore, the development of a low-cost (pre-alkoxylation method) process for producing alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives is an urgent issue for the market.
Compared with alkyl substituted derivatives, the synthesis methods of the alkyl ether substituted derivatives have fewer reports in documents, and mainly comprise the following synthesis methods: EP299362 and US5286868 take diethyl aminomaleate as a raw material to synthesize alkyl ether substituted derivatives, which are expensive and have long reaction time; EP461401 and EP548559 synthesize ammonia chloro diethyl maleate by taking dichloro diethyl maleate as a raw material, and then synthesize a target product, wherein the reaction time is long and the yield is low; EP461403 takes diethyl dichlorosuccinate as a raw material to carry out reactions such as ammonification, ring closure and the like to synthesize a target product; EP820987 uses 2, 3-dichloropyridine and derivatives thereof as raw materials, and palladium acetate as a catalyst in an autoclave is reacted with CO to synthesize a target product; US5892050 adopts a Weissmier reagent synthesis method, and the yield is only 17.7%; synthesis of 5-methoxymethyl-2, 3-pyridinedicarboxylic acid, Dumeng et al, agricultural chemicals (2011), 50(6) also reported a method for synthesizing a desired product using diethyl aminomaleate as a starting material. The methods generally have the problems of high raw material price, long reaction time, low product conversion rate and the like, and are not suitable for industrial production, and CN103965100 takes a 5-methyl (or methoxy) -2, 3-pyridine dicarboxylic ester N-substituted derivative as a raw material, and prepares a target product by reacting cerium ammonium nitrate in a polar solvent, because the raw material is high in price and is not easy to obtain, the method is not suitable for industrial production. The invention relates to a synthesis method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives, which is suitable for industrialization after CN 104447527.
Disclosure of Invention
The invention aims to provide a preparation method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives, which is economical, safe, effective and environmentally-friendly.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives comprises the steps of carrying out catalytic or catalyst-free catalytic reaction on beta-diketone derivatives (general formula II), acrolein derivatives (general formula III) and ammonia source compounds in the presence of excessive solvent to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I);
or reacting beta-diketone derivatives (general formula II) and acrolein derivatives (general formula III) under the catalysis of a catalyst or without the catalyst, and then adding a solvent and an ammonia source compound to react to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I);
in the general formula, R1And R2Each of which may be the same or different is selected from H or C1-C6An alkyl group; r3Is selected from C1-C4Alkoxy-substituted C1-C6An alkyl group.
The product of formula I prepared above can be isolated and purified by conventional chemical methods, such as extraction, filtration, distillation, chromatography, and the like. The specific process is as follows:
scheme 1:
and (2) a flow scheme:
preferably:
reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at-20-160 ℃ in the presence of excessive solvent, and further reacting with ammonia source compounds at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I);
or reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at-20-160 ℃ in the presence of a catalyst and an excessive solvent, and further reacting with an ammonia source compound at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I);
or, the beta-diketone derivative (general formula II) and the acrolein derivative (general formula III) react at-20 to 160 ℃ to form a transition product, and the obtained transition product further reacts with a solvent and an ammonia source compound at 20 to 160 ℃ to obtain the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative shown in the general formula (I);
or, in the presence of a catalyst, reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at-20-160 ℃ to form transition products, and further reacting the obtained transition products with a solvent and an ammonia source compound at 20-160 ℃ to obtain the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I).
The molar ratio of the beta-diketone derivative (general formula II), the acrolein derivative (general formula III) and the ammonia source compound is 1:1-3: 1-4.
Wherein the addition amount of the solvent in each preparation process is that the weight ratio of the beta-diketone derivative (general formula II) to the solvent is 1: 3-10;
wherein, in the preparation processes, in the reaction catalyzed by the catalyst, the molar ratio of the catalyst to the beta-diketone derivative (general formula II) is 1: 2-50.
Further preferably: in the presence of excessive solvent, reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at-20-80 ℃ under the catalysis of a catalyst or without the catalyst, and further reacting with an ammonia source compound at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I).
Or reacting beta-diketone derivative (general formula II) with acrolein derivative (general formula III) at the temperature of-20-80 ℃ to form a transition product under the catalysis of a catalyst or without the catalyst, adding a solvent and an ammonia source, and reacting at the temperature of 20-160 ℃ to obtain the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative shown in the general formula (I).
More preferably: in the presence of an excessive solvent, reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at 10-60 ℃ under the catalysis of a catalyst or without the catalyst, and further reacting with an ammonia source compound at a reflux temperature to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I).
Or reacting beta-diketone derivatives (general formula II) and acrolein derivatives (general formula III) at the temperature of 10-60 ℃ to form transition products under the catalysis of a catalyst or without the catalyst, adding a solvent and an ammonia source, and further reacting at the reflux temperature to obtain the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in the general formula (I).
In the above reaction process of the present invention, the reaction temperature is generally in inverse proportion to the reaction time, that is, the reaction time is reduced by increasing the reaction temperature, however, an excessively high reaction temperature causes undesirable side reactions and decomposition, and a suitable reaction temperature is generally in the range of-20 to 160 ℃; preferably more than 0 ℃, the condensation reaction is preferably 10-60 ℃, and the ring-closure reaction with the ammonia source compound is preferably carried out at the reflux temperature of the solvent.
The solvent is selected from one or a combination of a plurality of solvents which can partially dissolve or completely dissolve the compound of the general formula II, the compound of the general formula III and the hydrocarbon, the alcohol, the ether and the ester of the ammonia source.
The hydrocarbon is aromatic hydrocarbon or halogenated hydrocarbon; the alcohol is alkanol; the ether is lower aliphatic ether; the esters are alkyl acetates.
The aromatic hydrocarbon is benzene, toluene, xylene, chlorobenzene or naphthalene, preferably toluene. The alkanol is methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, preferably ethanol. The ether is diethyl ether, propyl ether or isopropyl ether, preferably isopropyl ether. The ester is methyl acetate, ethyl acetate, propyl acetate or butyl acetate, preferably ethyl acetate. The mixture is a mixture of two or more of the above listed solvents in any ratio, preferably a mixture of benzene and toluene, a mixture of methanol and ethanol, a mixture of propyl ether and isopropyl ether, a mixture of methanol and toluene, a mixture of ethanol and toluene, a mixture of t-butanol and toluene, and a mixture of ethyl acetate and butyl acetate.
The ammonia source is one or more of ammonium sulfamate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium formate, ammonium acetate, hydroxylamine hydrochloride, hydroxylamine sulfate, hydroxylamine phosphate, liquid ammonia, ammonia water, ammonia gas, diethylamine and triethylamine, and the ammonium salt is preferably ammonium acetate or ammonium sulfamate.
The catalyst is amide, hydride, hydroxide and carbonate of alkali metal or alkaline earth metal, alkali metal alcoholate and organic amine compound. When in use, the catalyst can be one of the catalysts or a combination of the catalysts.
The alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives of formula I obtained in the above manner are useful intermediates for the preparation of highly effective, environmentally benign imidazolinone herbicide compounds of formula IV. That is, the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative of the general formula I can react with the aminocarboxamide compound in the presence of an inert solvent and a strong base to obtain the imidazolidinone compound of the general formula IV,
wherein the imidazolinone herbicide compounds of formula IV are as follows:
wherein R is3Is a quilt C1-C4Alkoxy-substituted C1-C6An alkyl group.
The preparation of the imidazolidinone compound of the formula IV is carried out as follows:
at the same time, the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative (diester compound) obtained in the above-mentioned general formula I can be hydrolyzed into the corresponding diacid, and the resulting diacid can be used for preparing the imidazolidinone of the general formula IV according to the route described in the patent literature (for example, U.S. Pat. No. 4,798,619).
The invention has the advantages that the adopted raw material beta-diketone derivative (general formula II) has simple structure, low price and easy obtainment; compared with the synthesis method reported in the literature and the current industrialized production method, the synthesis method disclosed by the invention has the advantages that the reaction time is greatly shortened (within 5 hours), the reaction condition is milder (the reflux temperature of a common solvent), the product yield is remarkably improved, and the synthesis method is a synthesis method of the alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative with lower raw material cost and better industrialized prospect.
Detailed Description
In order that the invention may be further understood, the following examples are set forth, primarily for the purpose of illustrating the invention in greater detail, and the invention is not limited by these examples.
Example 1
The specific process for preparing 5-methoxymethyl pyridine-2, 3-dicarboxylic acid ethyl ester is as follows:
500ml dry four-mouth bottle, load reflux condenser and thermometer, add 120ml toluene, 20g (folding hundred) butanone diacid diethyl ester, 0.5g 30% NaOH solution, under the condition of 20 deg.C, drip 11.2g (folding hundred) 2-methoxy methyl acrolein within 15min, keep warm for 1.0h, add 24.3g ammonium sulfamate, heat up to reflux, keep warm for 3.0h, cool to room temperature, add 40ml water, separate out the organic phase, the organic phase washes with 80ml moisture 2 times, evaporate solvent under reduced pressure, get the title product of orange viscous liquid, the yield of product is 85.5%. The product is identified as 5-methoxymethylpyridine-2, 3-dicarboxylate by HPLC, 13CNMR, 1HNMR and MS analysis.
Examples 2 to 8
Different solvents are adopted, other operation conditions are the same as example 1, the reaction temperature is the reflux temperature of the solvents, and the experimental results are shown in Table 1
TABLE 1 Experimental results under different solvent conditions
| Examples | Solvent(s) | Reflux temperature (. degree.C.) | Product yield (%) |
| 2 | Benzene and its derivatives | 80 | 83.6 |
| 3 | Ethanol | 78 | 82.3 |
| 4 | Methanol | 64 | 75.5 |
| 5 | Tert-butyl alcohol | 82 | 78.2 |
| 6 | Ethyl acetate | 77 | 70.8 |
| 7 | Ethanol and toluene (volume ratio 1: 1) | 76 | 83.1 |
| 8 | Methanol and toluene (volume ratio 1: 1) | 63 | 77.5 |
Examples 9 to 15
Using different catalysts, the operating conditions were otherwise the same as in example 1, and the results are given in Table 2
TABLE 2 Experimental results under different catalyst conditions
| Examples | Solvent(s) | Catalyst and process for preparing same | Product yield (%) |
| 9 | Toluene | Is free of | 61.2 |
| 10 | Toluene | KOH | 84.5 |
| 11 | Toluene | NaH | 83.7 |
| 12 | Toluene | Na2CO3 | 75.6 |
| 13 | Toluene | K2CO3 | 76.2 |
| 14 | Toluene | CH3ONa | 79.1 |
| 15 | Toluene | CH3CH2ONa | 80.2 |
Example 16
The specific process for preparing 5-methoxymethyl pyridine-2, 3-dicarboxylic acid ethyl ester is as follows:
500ml dry four-mouth bottle, load reflux condenser and thermometer, add 20g (break away) butanone diacid diethyl ester, 0.5g 30% NaOH solution, under 20 degrees C, drip 11.2g (break away) of 2-methoxy methyl acrolein in 15min, keep warm for 1.0h, add 120ml ethanol, 24.3g ammonium sulfamate, heat up to the reflux, keep warm for 3.0h, cool to the room temperature, evaporate ethanol under reduced pressure, add 120ml toluene, 40ml water to stir for 10min, separate out the organic phase, evaporate solvent under reduced pressure 2 times washing, get the title product of viscous liquid of orange, the yield of the product is 86.8%. The product is identified as 5-methoxymethylpyridine-2, 3-dicarboxylate by HPLC, 13CNMR, 1HNMR and MS analysis.
Example 17 to example 23
Using different solvents, the operating conditions were the same as in example 16, the initial reaction temperature was 20 ℃ and the temperature after the addition of the ammonia source was the reflux temperature of the solvent, and the results are shown in Table 3
TABLE 3 Experimental results under different solvent conditions
Examples 24 to 30
The same operation conditions as in example 16 were carried out using different catalysts, the reaction temperatures were the reflux temperatures of the solvents, and the results are shown in Table 4
TABLE 4 Experimental results under different solvent conditions
| Examples | Solvent(s) | Catalyst and process for preparing same | Product yield (%) |
| 24 | Ethanol | Is free of | 65.5 |
| 25 | Ethanol | KOH | 85.2 |
| 26 | Ethanol | NaH | 84.3 |
| 27 | Ethanol | Na2CO3 | 77.5 |
| 28 | Ethanol | K2CO3 | 76.8 |
| 29 | Ethanol | CH3ONa | 81.5 |
| 30 | Ethanol | CH3CH2ONa | 82.7 |
Example 31
Implementation scheme of industrialization
Adding 240L of ethanol, 40kg of diethyl butanone diacid and 1.0kg of 30% NaOH solution into a 1000L dry enamel kettle, adding 22.4kg of 2-methoxymethylacrolein in a trickle within 30min at the temperature of 20 ℃, preserving heat for 1.0h, adding 48.6kg of ammonium sulfamate, heating to reflux, preserving heat for 3.0h, cooling to room temperature, evaporating out ethanol under reduced pressure, adding 240L of toluene and 80L of water, stirring for 10min, separating out an organic phase, washing with 80L of water for 2 times, and evaporating out a solvent under reduced pressure to obtain an orange viscous liquid title product, wherein the product yield is 85.2%.
The alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative of the general formula I prepared by the embodiment of the invention can be used for preparing efficient and environmentally-friendly imidazolinone herbicide compounds of the general formula IV. That is, alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives of formula I can be reacted with aminocarboxamide compounds in the presence of inert solvents and strong bases to give imidazolidinone compounds of formula IV, while the diesters of formula I prepared using the examples of the present invention can also be hydrolyzed to the corresponding diacids and then used in any of the process routes described in the patent literature for preparing imidazolidinones of formula IV, as described in U.S. Pat. No. 4,798,619.
Claims (7)
1. A preparation method of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives is characterized by comprising the following steps: reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at-20-160 ℃ in the presence of excessive solvent, and further reacting with ammonia source compounds at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I);
or, in the presence of a catalyst and an excessive solvent, reacting beta-diketone derivatives shown in a general formula (II) with acrolein derivatives shown in a general formula (III) at-20-160 ℃, and further reacting with ammonia source compounds at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in a general formula (I);
or reacting beta-diketone derivatives shown in the general formula (II) with acrolein derivatives shown in the general formula (III) at-20-160 ℃ to form transition products, and further reacting the obtained transition products with a solvent and an ammonia source compound at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in the general formula (I);
or, in the presence of a catalyst, reacting beta-diketone derivatives shown in a general formula (II) with acrolein derivatives shown in a general formula (III) at-20-160 ℃ to form transition products, and further reacting the obtained transition products with a solvent and an ammonia source compound at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in a general formula (I);
in the general formula, R1And R2Each of which may be the same or different is selected from H or Cl-C6An alkyl group; r3Is selected from Cl-C4Alkoxy-substituted C1-C6An alkyl group;
the solvent is selected from one or a combination of a plurality of solvents which can partially dissolve or completely dissolve the compound of the general formula II, the compound of the general formula III and the hydrocarbon, the alcohol, the ether and the ester of the ammonia source;
the ammonia source is one or more of ammonium sulfamate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium formate, ammonium acetate, liquid ammonia, ammonia water and ammonia gas;
the catalyst is hydride, hydroxide and carbonate of alkali metal or alkaline earth metal, and alkali metal alcoholate.
2. A process for the preparation of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives according to claim 1, characterized in that: the molar using amount ratio of the beta-diketone derivative shown in the general formula (II), the acrolein derivative shown in the general formula (III) and the ammonia source compound is 1:1-3: 1-4.
3. A process for the preparation of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives according to claim 1 or 2, characterized in that: in the presence of excessive solvent, reacting beta-diketone derivatives shown in a general formula (II) with acrolein derivatives shown in a general formula (III) at-20-80 ℃ under the catalysis of a catalyst or without the catalyst, and further reacting the beta-diketone derivatives with ammonia source compounds at 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in a general formula (I).
4. A process for the preparation of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives according to claim 1 or 2, characterized in that: reacting beta-diketone derivatives shown in a general formula (II) with acrolein derivatives shown in a general formula (III) at the temperature of-20-80 ℃ to form transition products under the catalysis of a catalyst or without the catalyst, adding a solvent and an ammonia source, and reacting at the temperature of 20-160 ℃ to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in a general formula (I).
5. The process for producing an alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative according to claim 4, wherein: in the presence of an excessive solvent, reacting beta-diketone derivatives (general formula II) with acrolein derivatives (general formula III) at 10-60 ℃ under the catalysis of a catalyst or without the catalyst, and further reacting with an ammonia source compound at a reflux temperature to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in general formula (I).
6. The process for producing an alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivative according to claim 5, wherein: reacting beta-diketone derivatives shown in a general formula (II) with acrolein derivatives shown in a general formula (III) at the temperature of 10-60 ℃ to form transition products under the catalysis of a catalyst or without the catalyst, adding a solvent and an ammonia source, and further reacting at the reflux temperature to obtain alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives shown in a general formula (I).
7. A process for the preparation of alkyl ether substituted pyridine-2, 3-dicarboxylic acid derivatives according to claim 1, characterized in that: the hydrocarbon is aromatic hydrocarbon or halogenated hydrocarbon; the alcohol is alkanol; the ether is diethyl ether, propyl ether or isopropyl ether; the esters are alkyl acetates.
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