CN108137535B - Method for preparing pyridyl pyrazolidinone carboxylic acid compounds - Google Patents
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Abstract
The invention belongs to the field of organic synthesis, and particularly relates to a pyridyl groupA preparation method of pyrazolidone carboxylic ester compounds. The reaction formula is as follows,
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of pyridyl pyrazolidone carboxylic ester compounds.
Background
The benzamide compound is a novel pesticide with high efficiency and safety. Among them, 3-bromo-N- (2-methyl-4-chloro-6- (methionyl) phenyl) -1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide (common name: chlorantraniliprole), 3-bromo-N- (2-methyl-4-cyano-6- (methionyl) phenyl) -1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide (common name: cyantariniprole) has high insecticidal activity, and dupont has been developed as an insecticide. The bisamide-based compound 3-bromo-N- (2-chloro-4-bromo-6- ((1-cyclopropylethyl) acyl) phenyl) -1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxamide (commonly known as cyclaniliprole) developed by shichen corporation has a broad spectrum of insecticidal activity. Shenyang chemical research institute found that 3-bromo-N- (2, 4-dichloro-6- (methionyl) phenyl) -1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxamide, which has high pesticidal activity, has also been developed as a pesticide, commonly known as tetrachlorantraniliprole.
1- (3-chloropyridin-2-yl) -3-pyrazolidone-5-carboxylic ester is a common key intermediate for synthesizing chlorantraniliprole, cyclopaniprole and cyclopaniprole, and WO2004011453 discloses the synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidone-5-carboxylic ester, which is prepared by reacting hydrazinopyridine with maleic diester at reflux temperature, wherein the reaction yield is only 55%.
Xufengbo et al at southern Kai university report a method for synthesizing ethyl 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylate using anthracycline-containing diamine complex A with a complex structure as a catalyst (reference: pesticide research and application. 14(2), 14-15, 2009), with a yield of 70%. The specific structure of the catalyst is as follows:
in the past, technicians are dedicated to continuously research and develop new, more advanced and reasonable preparation methods of pyridyl pyrazolidone carboxylic ester compounds, so as to obtain benzamide insecticides with better quality and lower price.
Disclosure of Invention
The invention aims to provide a simpler and more efficient preparation method of pyridyl pyrazolidone carboxylic ester compounds.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of pyridyl pyrazolidone carboxylic ester compounds has the following reaction formula:
in the formula: r1Selected from H or Cl; r2Is selected from C1-C6Alkyl radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C3-C6Cycloalkyl, halogen, unsubstituted or substituted by up to 6C1-C4Alkyl-substituted benzyl of (a);
under the alkaline condition, hydrazinopyridine (II) reacts with maleic acid diester (III) under the action of a catalyst to prepare pyridyl pyrazolidone carboxylic ester compound (I),
wherein the catalyst is selected from: cu (L1) Cl, Cu (L1) Br, Cu (L1) I, Cu (L2)2Cl、Cu(L2)2Br、Cu(L2)2I、Ni(L1)Cl2、Ni(L1)Br2、Ni(L1)I2、Ni(L2)2Cl2、Ni(L2)2Br2Or Ni (L2)2I2；
Wherein L1 is selected from:
l2 is selected from:
the catalyst is selected from Cu (L1) Br, Cu (L1) I, Cu (L2)2Br or Cu (L2)2I; wherein
L1 is selected from:
l2 is selected from:
the catalyst is selected from Cu (L1) I or Cu (L2)2I, wherein
L1 is selected from:
l2 is selected from:
the step of preparing the pyridyl pyrazolidone carboxylic ester compound (I) by reacting hydrazinopyridine (II) with maleic diester (III) under the action of a catalyst under the alkaline condition comprises the following steps,
the molar ratio of the hydrazinopyridine (II), the alkali, the maleic diester (III) and the catalyst is 1: 1-2: 1-5: 0.00001-0.01.
The molar ratio of the hydrazinopyridine (II), the alkali, the maleic acid diester (III) and the catalyst is 1: 1.2-1.5: 1.5-2: 0.0001-0.001;
in the step of preparing the pyridyl pyrazolidone carboxylic ester compound (I) by reacting the hydrazinopyridine (II) with the maleic diester (III) under the action of a catalyst under an alkaline condition, the reaction temperature is controlled to be 20-50 ℃.
The hydrazinopyridine (II) reacts with the maleic acid diester (III) under the action of a catalyst under the alkaline condition to prepare the pyridyl pyrazolidone carboxylic ester compound (I) in the following solvents:
the solvent is toluene, chlorobenzene, carboxylic acid esters, alkyl alcohols, ethers or polar aprotic solvents;
the base used is selected from alkali metal hydride, alkali metal amide or alkyl alcohol.
The hydride of the alkali metal is lithium hydride, sodium hydride or potassium hydride;
the amide of alkali metal is lithium amide, sodium amide or potassium amide; the alkyl alcoholate is sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentanoate, sodium isopropoxide, sodium isobutoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide or potassium tert-butoxide;
the carboxylic acid ester is acetic ester, fumaric diester or maleic diester; the alkyl alcohol is methanol, ethanol, propanol, butanol, pentanol, isopropanol, isobutanol, sec-butanol or tert-butanol; the ethers are tetrahydrofuran, 2-methyltetrahydrofuran or dioxane; the polar aprotic solvent is acetonitrile, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
The alkali is selected from sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentanoate, sodium isopropoxide, sodium isobutoxide, sodium sec-butoxide or sodium tert-butoxide;
the suitable solvent is selected from methanol, ethanol, propanol, butanol, pentanol, isopropanol, isobutanol, sec-butanol or tert-butanol.
The base is selected from sodium ethoxide; the suitable solvent is selected from ethanol.
In the synthesis given above and in the definition of the radicals in the compounds of the formulae, the terms used are generally defined as follows:
alkyl means straight or branched chain forms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and the like. Cycloalkyl is meant to include cyclic chain forms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopropyl, cyclopropylcyclopropyl and the like. Alkenyl means straight or branched chain alkenyl groups such as 1-propenyl, 2-propenyl, and the various butenyl groups and the like. Alkynyl means straight or branched alkynes such as 1-propynyl, 2-propynyl and the various butynyl groups and the like. Halogen means fluorine, chlorine, bromine, iodine.
The invention has the following advantages: the invention adopts the nitrogen-free phenylphosphine compound with simple structure as the catalyst for catalyzing the synthesis of pyridyl pyrazolidone carboxylic ester, and can greatly improve the yield of the reaction, thereby completing the invention.
Optionally, the reaction of the preparation method can be carried out at 20-50 ℃, and the temperature is easy to control, so that the safety of the reaction is greatly improved. In addition, the catalyst has the advantages of simple and feasible synthesis and low cost, and can be prepared only by reacting metal salt and phenylphosphine in ethanol. Therefore, the catalyst of the invention is easier to be applied to industrial production.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
Synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester
1000 ml of absolute ethanol and sodium ethoxide (65.7 g, 0.966 mol), 3-chloro-2-hydrazinopyridine (101.04 g, 98%, 0.69 mol) were added to a 2000 ml reaction flask, and the catalyst Cu (PPh) was added3)2I (0.15 g, 0.00021 mol) (copper bistriphenylphosphine iodide, synthesis method: Chemistry-A European Journal, 16(39), 11822-phase 11826, 2010) mixture was heated to 40 ℃ and diethyl maleate (145.7 g, 0.83 mol) was added dropwise. The temperature is kept for 4 hours, and the temperature is kept,the reaction mixture was then neutralized with glacial acetic acid (60 g). The mixture was diluted with 1000 ml of water, cooled to room temperature and a solid precipitated. The solid was collected by filtration and washed with 3X 150 ml of 40% aqueous ethanol. After drying, 149.91 g of 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate orange solid is obtained, and the content is 98% by external standard method quantitative analysis, and the yield is 79%.1H NMR(300MHz，DMSO)：8.289-8.269(q，1H)，7.956-7.190(q，1H)，7.231-7.190(q，1H)，4.862-4.816(q，1H)，4.236-4.165(q，2H)，2.967-2.879(q，1H)，2.396-2.336(q，1H)，1.250-1.202(t，3H)。
The synthesis method of the catalyst comprises the following steps:
1000 ml of absolute ethyl alcohol, triphenylphosphine (500 g, 1,9mol) and CuI (181 g, 0.95mol) are sequentially added into a 2000 ml reaction bottle, the temperature is increased to 80 ℃, the reaction is carried out for 1h, then the temperature is naturally reduced to the room temperature, the filtration and the drying are carried out, 644.9 g of the product is obtained, and the yield is 95%.
The other catalysts described below can be prepared in this manner by selecting the appropriate starting materials.
Example 2
Synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester
A1000 ml reaction flask is charged with 300 ml of anhydrous ethanol and sodium ethoxide (16.97 g, 0.249 mol), 3-chloro-2-hydrazinopyridine (30.75 g, 98%, 0.21 mol), then added with Cu (bin) I (0.017 g, 0.000021 mol) (2, 2 '-bis- (diphenylphosphino) -1, 1' -binaphthyl, abbreviated as bin, the synthesis method is shown in Chemistry-A European Journal, 16(39), 11822-11826, 2010) mixture, heated to 30 ℃, and dripped
Diethyl maleate (44.23 g, 0.252 mol) was added. The temperature was maintained for 4h, after which the reaction mixture was neutralized with glacial acetic acid (15 g). The mixture was diluted with 300 ml of water and cooled to room temperature, and a solid precipitated. The solid was collected by filtration and washed with 3X 50 ml of 40% aqueous ethanol. 47.06 g of 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate orange solid is obtained after drying, the content is 95% by external standard method quantitative analysis, and the yield is 79%.
Example 3
Synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester
A1000 ml reaction flask was charged with 300 ml of absolute ethanol and sodium ethoxide (16.97 g, 0.249 mol), 3-chloro-2-hydrazinopyridine (30.75 g, 98%, 0.21 mol), and then catalyst Cu (PPh) was added3)2Br (0.042 g, 0.000063 mol) (cuprous bis-triphenylphosphine bromide, synthesis method: Chemistry-A European Journal, 16(39), 11822-11826, 2010), the mixture was heated to 35 ℃ and diethyl maleate (44.23 g, 0.252 mol) was added dropwise. The temperature was maintained for 4h, after which the reaction mixture was neutralized with glacial acetic acid (15 g). The mixture was diluted with 300 ml of water and cooled to room temperature, and a solid precipitated. The solid was collected by filtration and washed with 3X 50 ml of 40% aqueous ethanol. After drying, 45.98 g of 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate orange solid is obtained, and the content of the orange solid is 96 percent by external standard method quantitative analysis, and the yield is 78 percent.
Example 4
Synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester
A1000 ml reaction flask was charged with 300 ml of absolute ethanol and sodium ethoxide (16.97 g, 0.249 mol), 3-chloro-2-hydrazinopyridine (30.75 g, 98%, 0.21 mol), and catalyst Ni (PPh) was added3)2Br2(0.047 g, 0.000063 mol) (Synthesis of nickel bis (triphenylphosphine) dibromide, part of which was applied, organic chemical, 23, 455-459, 2009), the mixture was heated to 45 ℃ and diethyl maleate (44.23 g, 0.252 mol) was added dropwise. The temperature was maintained for 4h, after which the reaction mixture was usedGlacial acetic acid (15 g) was neutralized. The mixture was diluted with 300 ml of water and cooled to room temperature, and a solid precipitated. The solid was collected by filtration and washed with 3X 50 ml of 40% aqueous ethanol. After drying, 45.98 g of 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate orange solid is obtained, and the content of the orange solid is 96 percent by external standard method quantitative analysis, and the yield is 78 percent.
The procedure is as in example 1, using the catalyst Cu (PPh)3)2The 1- (3, 5-dichloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester can be prepared with high yield by I (copper bis (triphenylphosphine) iodide).1H NMR(300MHz，CDCl3)：8.146(q，1H)，7.658(q，1H)，5.073(dd，1H)，4.241(q，2H)，3.029(dd，1H)，2.721(dd，1H)，1.258(t，3H)。
Example 5
Synthesis of 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylic acid ethyl ester
600L of absolute ethyl alcohol and sodium ethoxide (34.6 kg, 500 mol), 3-chloro-2-hydrazinopyridine (61.5 kg, 98%, 420 kmol) are added into a 1000L reaction kettle, and catalyst Cu (PPh) is added3)2I (90 g), the mixture was heated to 35 ℃ and diethyl maleate (88.4 kg, 500 mol) was added dropwise. The temperature was maintained for 4h, after which the reaction mixture was neutralized with glacial acetic acid (20 kg). The mixture was diluted with 300 l of water and cooled to room temperature, and a solid precipitated. The solid was collected by filtration and slurried with 100 liters of 40% aqueous ethanol. After centrifugal filtration and drying, 92 kg of 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate orange solid is obtained, and the content is 96 percent by external standard method quantitative analysis, and the yield is 78 percent.
Comparative example
Ethyl 1- (3-chloropyridin-2-yl) -3-pyrazolidinone-5-carboxylate was synthesized according to the published methods of southern kakai university (reference: pesticide research and application 14(2), 14-15, 2009).
Into a 1000 ml reaction flask were added 300 ml of absolute ethanol and sodium (5.22 g, 0.227 mol), stirred until no bubble was generated, 3-chloro-2-hydrazinopyridine (30.00 g, 0.205 mol) was added, the mixture was heated to reflux for 5min, catalyst a 0.003 g was added, and diethyl maleate (36.00 g, 0.209 mol) was added dropwise. Reflux was maintained for 30min, after which the reaction mixture was cooled to 65 ℃ and neutralized with glacial acetic acid (25.2 g). The mixture was diluted with 300 ml of water and cooled to room temperature, and a solid precipitated. The solid was collected by filtration and washed with 3X 50 ml of 40% aqueous ethanol. Drying to obtain 1- (3-chloro-2-pyridyl) -3-pyrazolidinone-5-ethyl formate, 45.2 g of orange solid with normalization content of 96%, and the yield is 70% after the content is analyzed quantitatively by an external standard method and the normalization content is 85.4%.
As can be seen from the above examples and comparative examples, the pyridyl pyrazolidone carboxylic ester compound is prepared with high yield by using the nitrogen-free phenylphosphine compound which is simple in structure, cheap and easy to obtain as a catalyst, and is industrially applied in an enlarged manner. After the catalyst is used, the reaction can be carried out at a lower temperature, the production energy consumption is reduced, and the reaction safety is greatly improved, so that the catalyst plays an important role in reducing the production cost and improving the reaction safety in the production process.
Examples of the applications
According to the reaction formula, the 3-chloropyridyl pyrazolidone carboxylic acid ethyl ester prepared in the embodiment is brominated and hydrolyzed to obtain the 3-bromo-1-pyridylpyrazole-5-carboxylic acid. The pyrazole carboxylic acid obtained by hydrolysis is acylated and oxidized to prepare pyrazole acyl chloride, and then reacts with 2-amino-3-methyl-5-chlorobenzoyl methylamine to prepare commercial chroraranilprole, wherein the total yield of the reaction is 56.7 percent (calculated by 3-chloropyridyl pyrazolidone carboxylic acid ethyl ester).
Claims (10)
1. A preparation method of pyridyl pyrazolidone carboxylic ester compounds is characterized by comprising the following steps:
the reaction formula is as follows:
in the formula: r1Selected from H or Cl; r2Is selected from C1-C6Alkyl radical, C3-C6Cycloalkyl, unsubstituted or substituted by up to 6C1-C4Alkyl-substituted benzyl of (a);
under the alkaline condition, hydrazinopyridine (II) reacts with maleic acid diester (III) under the action of a catalyst to prepare pyridyl pyrazolidone carboxylic ester compound (I),
wherein the catalyst is selected from: cu (L1) Cl, Cu (L1) Br, Cu (L1) I, Cu (L2)2Cl、Cu(L2)2Br or Cu (L2)2I; wherein L1 is selected from:
l2 is selected from:
2. the process for preparing pyridylpyrazolone carboxylic acid esters according to claim 1, wherein:
the catalyst is selected from Cu (L1) Br, Cu (L1) I, Cu (L2)2Br or Cu (L2)2I; wherein
L1 is selected from:
l2 is selected from:
3. the process for preparing pyridylpyrazolone carboxylic acid esters according to claim 2, characterized in that: the catalyst is selected from Cu (L1) I or Cu (L2)2I, wherein
L1 is selected from:
l2 is selected from:
4. the process for preparing pyridylpyrazolone carboxylic acid esters according to claim 1, wherein: the preparation method of the pyridyl pyrazolidone carboxylic ester compound (I) by reacting hydrazinopyridine (II) with maleic diester (III) under the action of a catalyst under the alkaline condition comprises the following steps,
the molar ratio of the hydrazinopyridine (II), the alkali, the maleic diester (III) and the catalyst is 1: 1-2: 1-5: 0.00001-0.01.
5. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 4, wherein: the molar ratio of the hydrazinopyridine (II), the alkali, the maleic acid diester (III) and the catalyst is 1: 1.2-1.5: 1.5-2: 0.0001-0.001.
6. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 1, wherein: in the step of preparing the pyridyl pyrazolidone carboxylic ester compound (I) by reacting the hydrazinopyridine (II) with the maleic diester (III) under the action of a catalyst under an alkaline condition, the reaction temperature is controlled to be 20-50 ℃.
7. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 1, wherein: the hydrazinopyridine (II) reacts with the maleic acid diester (III) under the action of a catalyst under the alkaline condition to prepare the pyridyl pyrazolidone carboxylic ester compound (I) in the following solvents:
the solvent is toluene, chlorobenzene, carboxylic acid esters, alkyl alcohols, ethers or polar aprotic solvents;
the base used is selected from alkali metal hydride, alkali metal amide or alkyl alcohol.
8. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 7, wherein: the hydride of the alkali metal is lithium hydride, sodium hydride or potassium hydride;
the amide of alkali metal is lithium amide, sodium amide or potassium amide; the alkyl alcoholate is sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentanoate, sodium isopropoxide, sodium isobutoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide or potassium tert-butoxide;
the carboxylic acid ester is acetic ester, fumaric diester or maleic diester; the alkyl alcohol is methanol, ethanol, propanol, butanol, pentanol, isopropanol, isobutanol, sec-butanol or tert-butanol; the ethers are tetrahydrofuran, 2-methyltetrahydrofuran or dioxane; the polar aprotic solvent is acetonitrile, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
9. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 8, wherein: the alkali is selected from sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentanoate, sodium isopropoxide, sodium isobutoxide, sodium sec-butoxide or sodium tert-butoxide;
the solvent is selected from methanol, ethanol, propanol, butanol, pentanol, isopropanol, isobutanol, sec-butanol or tert-butanol.
10. The process for preparing pyridylpyrazolone carboxylic acid esters according to claim 9, wherein: the base is selected from sodium ethoxide; the solvent is selected from ethanol.
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| CN109988150B (en) * | 2017-12-29 | 2022-04-12 | 江苏中旗科技股份有限公司 | N-alkyl-N-cyanoalkyl benzamide compounds and application thereof |
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| CN110330455B (en) * | 2019-05-31 | 2023-04-28 | 湖北省生物农药工程研究中心 | Amide derivative, preparation method and application thereof |
| WO2021033165A1 (en) * | 2019-08-21 | 2021-02-25 | Gharda Chemicals Limited | Process for synthesis of pyrazolidinone compounds |
| BR112022003171A2 (en) * | 2019-08-21 | 2022-05-17 | Gharda Chemicals Ltd | Process for the synthesis of pyrazolidinone compounds |
| CN114057687B (en) * | 2020-08-05 | 2023-11-14 | 沈阳中化农药化工研发有限公司 | Preparation method of pyridyl pyrazolone carboxylic ester compound |
| CN113072472A (en) * | 2021-04-07 | 2021-07-06 | 湖南科技学院 | Synthesis method of 2-methylmercapto-maleic diester compound |
| EP4380363A1 (en) | 2021-08-05 | 2024-06-12 | Syngenta Crop Protection AG | Method for controlling diamide resistant pests & compounds therefor |
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| CN108137535A (en) | 2018-06-08 |
| WO2017114121A1 (en) | 2017-07-06 |
| BR112018013249B1 (en) | 2022-03-22 |
| CN106928183A (en) | 2017-07-07 |
| BR112018013249A2 (en) | 2019-02-12 |
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