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Preparation method of 2, 3-dipicolinic acid ester derivative intermediate and 2, 3-dipicolinic acid ester derivative

A technology of dicarboxylic acid esters and derivatives, which is applied in the field of pesticide chemistry, can solve the problems of many side reactions, unfavorable industrial production, and difficult to control reactions, and achieves the effect of high atom utilization.

Pending Publication Date: 2022-07-26
JIANGSU FLAG CHEM IND
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AI Technical Summary

Problems solved by technology

[0007] Chinese invention patent CN104447527A discloses a method for dialkyl pyridine-2,3-dicarboxylate, although the yield can be 82-96%, but it needs to use dangerous catalyst sodium amide, sodium hydrogen or triphenyl Sodium methyl is not conducive to industrial production. In addition, the reaction temperature is high, causing many side reactions, and it is difficult to control the reaction, and the process is complicated
[0008] Therefore, as an important intermediate in the synthesis of imidazolinone compounds, the existing synthetic methods of pyridine-2,3-dicarboxylates are not ideal enough, and there is an urgent need for a method with short reaction steps, easy-to-obtain raw materials, mild reaction and high product yield. Synthetic method of pyridine-2,3-dicarboxylate with higher yield and purity

Method used

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  • Preparation method of 2, 3-dipicolinic acid ester derivative intermediate and 2, 3-dipicolinic acid ester derivative
  • Preparation method of 2, 3-dipicolinic acid ester derivative intermediate and 2, 3-dipicolinic acid ester derivative
  • Preparation method of 2, 3-dipicolinic acid ester derivative intermediate and 2, 3-dipicolinic acid ester derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] ① Preparation of methyl 3-chloro-3-cyano-2-oxopropionate:

[0036]

[0037] 118.09 g (1 mol) of dimethyl oxalate and 180.1 g of 30% sodium methoxide methanol solution (1 mol) were stirred and dissolved at room temperature, and 90.60 g of chloroacetonitrile (1.2 mol) was slowly added dropwise at 15 to 20°C for 3 hours. , and stirring for 1 h after the addition was completed. After sampling qualified, it was cooled to 5~10 ℃, slowly added 182.5g of 30% hydrochloric acid methanol solution (1.5mol), acidified to pH value less than 4, filtered, evaporated to dryness methanol to obtain 160g of 3-chloro-3-cyano-2 -Methyl oxopropionate, qualitative content 94%, yield 93.4%. 1 H NMR(400MHz,DMSO)δ7.07(s,1H),3.83(s,3H).

[0038] ② Preparation of methyl 5-methylpyridine-2,3-dicarboxylate:

[0039]

[0040] 160g of 94% methyl 3-chloro-3-cyano-2-oxopropionate (0.93mol) obtained in step (1) was added to 136g of 30% hydrochloric acid methanol solution (1.1mol), and the tempera...

Embodiment 2

[0042] ① Preparation of methyl 3-chloro-3-cyano-2-oxopropionate:

[0043]

[0044] 118.09 g of dimethyl oxalate (1 mol) and 270.1 g of 30% sodium methoxide methanol solution (1.5 mol) were stirred and dissolved at room temperature, and 98.15 g of chloroacetonitrile (1.3 mol) was slowly added dropwise at 15 to 20°C. 3h, keep stirring for 1h after the dropwise addition. After sampling qualified, the temperature was lowered to 5-10° C., 304.17g of 30% hydrochloric acid methanol solution (2.5mol) was slowly added, and the pH value was acidified to less than 4 to obtain 593.89g of 3-chloro-3-cyano-2-oxopropane The acidification reaction solution of methyl acid is directly carried out to the next step without separation.

[0045] ② Preparation of methyl 5-methylpyridine-2,3-dicarboxylate:

[0046]

[0047]The acidification reaction solution of 593.89g of methyl 3-chloro-3-cyano-2-oxopropionate obtained in step 1 in Example 2 was heated to 60°C, and 78.2g of 2-methacrolein ( ...

Embodiment 3

[0049] ① Preparation of ethyl 3-methoxy-3-cyano-2-oxopropionate:

[0050]

[0051] Dissolve 146.14 g of diethyl oxalate (1 mol) and 102.1 g of sodium ethoxide (1.5 mol) in 500 g of toluene, and slowly add 78.1 g of chloroacetonitrile (1.03 mol) dropwise at 30 to 35°C for 2 hours. After the dropwise addition was completed, the mixture was kept stirring for 2h. After sampling qualified, it was cooled to 5-10°C, slowly added 158.28g of 30% hydrochloric acid ethanol solution (1.3mol), acidified to a pH value of less than 4, filtered, and evaporated to dryness to obtain 154.04g of 3-methoxy-3-cyanide Ethyl-2-oxopropionate, qualitative content 95%, yield 85.5%. 1 H NMR (400MHz, DMSO) δ 10.85(s, 1H), 4.28-4.22(m, 2H), 3.71(s, 3H), 1.26(t, J=7.1Hz, 3H).

[0052] ② Preparation of ethyl 5-ethylpyridine-2,3-dicarboxylate:

[0053]

[0054] 154.04g of 95% ethyl 3-methoxy-3-cyano-2-oxopropionate obtained in step ① of Example 3 was added to 117.5g of 30% hydrochloric acid ethanol s...

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Abstract

The invention relates to the field of pesticide chemistry, in particular to a preparation method of a 2, 3-dipicolinic acid ester derivative intermediate and a 2, 3-dipicolinic acid ester derivative, which comprises the following steps: dissolving a general formula II and a general formula III in an organic solvent, adding a strong base for reaction, filtering, washing, and drying to obtain the 2, 3-dipicolinic acid ester derivative intermediate. After the reaction is finished, carrying out acidification treatment by using an alcoholic solution of anhydrous acid to obtain an acidification reaction solution of the intermediate I; carrying out heat treatment on an acidification reaction solution of the intermediate I, then dropwise adding a general formula IV, and after the reaction is finished, carrying out simple post-treatment to obtain a general formula V; according to the method for preparing the 2, 3-dipicolinic acid ester and the derivative thereof, the two-step reaction can be carried out through a one-pot boiling method, free ammonia generated in the second step provides an ammonia source for pyridine ring formation, and the whole process is safe, environmentally friendly, high in atom utilization rate, economical, efficient and suitable for industrial production.

Description

technical field [0001] The invention relates to the field of pesticide chemistry, in particular to a preparation method of a 2,3-pyridinedicarboxylate derivative intermediate and a 2,3-pyridinedicarboxylate derivative. Background technique [0002] As high-efficiency herbicides, imidazolinones mainly inhibit the activity of acetate hydroxy acid synthases (AHAs) and affect the biosynthesis of three branched-chain amino acids—valine, leucine and isoleucine. Ultimately destroy protein synthesis, interfere with DNA synthesis and cell division and growth. Imazethapyr, imazethapyr and imazethapyr are important components of imidazolinone herbicides. [0003] Patents US4948896A and US5047542A disclose methods for synthesizing pyridine-2,3-dicarboxylate from dialkyl maleate derivatives, the overall yield is 66-88%, the product purity is 69-93%, and the yield and purity are equal. It is not ideal, and there is also the problem of high organic waste, which is difficult to solve. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/21C07D213/80C07D213/803
CPCC07C253/30C07C255/21C07D213/80C07D213/803
Inventor 赵渭张璞黄瑞琦吴耀军
Owner JIANGSU FLAG CHEM IND
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