CN108137535A - The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound - Google Patents
The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound Download PDFInfo
- Publication number
- CN108137535A CN108137535A CN201680060148.1A CN201680060148A CN108137535A CN 108137535 A CN108137535 A CN 108137535A CN 201680060148 A CN201680060148 A CN 201680060148A CN 108137535 A CN108137535 A CN 108137535A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- sodium
- ester compound
- acid ester
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention belongs to organic synthesis field, more particularly to a kind of preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound.Reaction equation is as follows,
Description
The invention belongs to organic synthesis fields, more particularly to a kind of preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound.
Benzamide compound is a kind of novel pesticide efficiently, safe.Wherein the bromo- N- of 3- (2- methyl -4- chloro- 6- (carbamoyl group) phenyl) -1- (3- chloro-2-pyridyl) -1H- pyrazoles -5- formamide (general entitled chlorantraniliprole), the bromo- N- of 3- (2- methyl -4- cyano -6- (carbamoyl group) phenyl) -1- (3- chloro-2-pyridyl) -1H- pyrazoles -5- formamide (general entitled cyantraniliprole) have high insecticidal activity, and E.I.Du Pont Company has developed as insecticide.(the general entitled cyclaniliprole) of Ishihara Sangyo Kaisha, Ltd. bromo- N- of bisamide class compound 3- being developed (the bromo- 6- of the chloro- 4- of 2- ((1- cyclopropylethyl) acyl group) phenyl) -1- (3- chloro-2-pyridyl) -1H- pyrazoles -5- formamide, the insecticidal activity with wide spectrum.Shenyang Chemical Research Institute has found the bromo- N- (2 of the 3- with high insecticidal activity; 4- bis- chloro- 6- (carbamoyl group) phenyl) -1- (3; 5- dichloro-2-pyridyl base) -1H- pyrazoles -5- formamide, it has also developed as insecticide, general entitled tetrachloro insect amide.
1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylate is the shared key intermediate for synthesizing chlorantraniliprole, cyantraniliprole, cyclaniliprole, the synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylate is disclosed in WO2004011453, it is reacted and is made at a reflux temperature with maleic acid diester by hydrazino pyridine, reaction yield is only 55%.
Nankai University's Xu Feng wave etc. reports the method (bibliography: pesticide research and application .14 (2) for using the complicated diamine complex A containing anthracene nucleus as catalyst synthesis 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester, 14-15,2009), yield 70%.Catalyst specific structure is as follows:
All the time, technical staff is dedicated to constantly researching and developing new, more advanced reasonable pyridyl pyrazoles alkanone carboxylic acid ester compound preparation method, and to obtain, quality is more excellent, the lower benzamide insecticides of price.
Summary of the invention
The purpose of the present invention is to provide a kind of more easy, more efficiently pyridyl pyrazoles alkanone carboxylic acid ester compound preparation methods.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound, reaction equation are as follows:
In formula: R1Selected from H or Cl；R2Selected from C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C3-C6It is naphthenic base, halogen, unsubstituted or by most 6 C1-C4Alkyl-substituted benzyl；
Hydrazino pyridine (II) under alkaline condition, is reacted with maleic acid diester (III) by the effect of catalyst and pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made,
Wherein, 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:
It is described hydrazino pyridine (II) under alkaline condition, the step of pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made is reacted with maleic acid diester (III) by the effect of catalyst includes,
Hydrazino pyridine (II) used, alkali, maleic acid diester (III) and catalyst mol ratio be 1:1-2:1-5:0.00001-0.01.
The hydrazino pyridine (II), alkali, maleic acid diester (III) and catalyst mol ratio be 1:1.2-1.5:1.5-2:0.0001-0.001；
Hydrazino pyridine (II) reacts in the step of pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made with maleic acid diester (III) under alkaline condition, by the effect of catalyst, and control reaction temperature is 20-50 DEG C.
Under alkaline condition, the reaction for reacting obtained pyridyl pyrazoles alkanone carboxylic acid ester compound (I) with maleic acid diester (III) by the effect of catalyst carries out hydrazino pyridine (II) in following solvent:
The solvent is toluene, chlorobenzene, carboxylic acid esters, alkyl alcohols, ethers or polar aprotic solvent；
Used alkali is selected from the amide or alkyl alcoholates of the hydride of alkali metal, alkali metal.
The hydride of the alkali metal is lithium hydride, sodium hydride or hydrofining；
The amide of alkali metal is lithium amide, Sodamide or potassamide；Alkyl alcoholates are sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, amylalcohol sodium, sodium isopropylate, isobutyl sodium alkoxide, sec-butyl alcohol sodium, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide or potassium tert-butoxide；
The carboxylic acid esters are acetic acid esters, dimethyl ester or maleic acid diester；Alkyl alcohols is methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol；Ethers is tetrahydrofuran, 2- methyltetrahydrofuran or dioxane；Polar aprotic solvent is acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide or dimethyl sulfoxide.
The alkali is selected from sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, amylalcohol sodium, sodium isopropylate, isobutyl sodium alkoxide, sec-butyl alcohol sodium or sodium tert-butoxide；
The suitable solvent is selected from methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
The alkali is selected from sodium ethoxide；The suitable solvent is selected from ethyl alcohol.
In synthetic method given above and each general formula compound in the definition of group, collects term used and is generally defined as follows:
Alkyl refers to the groups such as linear chain or branched chain form, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl.Naphthenic base refers to including groups such as closed chain forms, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, methylcyclopropyl groups, cyclopropylcyclopropyl.Alkenyl refers to linear chain or branched chain alkenyl, such as 1- acrylic, 2- acrylic and different cyclobutenyls.Alkynyl refers to linear chain or branched chain alkynes, such as 1- propinyl, 2-propynyl and different butynyls.Halogen refers to fluorine, chlorine, bromine, iodine.
The present invention has a little: the present invention uses catalyst of the simply unazotized phenyl phosphine compound of structure as the synthesis of catalytic pyridine base pyrazolidone carboxylate, can greatly improve the yield of reaction, so as to complete the present invention.
Optionally, the reaction of preparation method of the present invention can carry out under the conditions of 20-50 DEG C, and the temperature is easily controllable, greatly improve the safety of reaction.In addition, catalyst of the invention is there is also simple and easy, cheap advantage is synthesized, only needing metal salt and Phenylphosphine to react in ethanol be can be prepared by.Therefore, catalyst of the invention is easier to the application in industrialized production.
Carry out the present invention will be described in more detail pyridyl pyrazoles alkanone carboxylic acid ester compound preparation method below by embodiment is enumerated, but is not intended to limit the present invention.
Embodiment 1
The synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester
1000 milliliters of dehydrated alcohols and sodium ethoxide (65.7 grams, 0.966 mole) are added in 2000 milliliters of reaction flasks,
3- chloride-2-hydrazinopyridine (101.04 grams, 98%, 0.69 mole), adds catalyst Cu (PPh3)2(0.15 gram of I, 0.00021 mole) (bi triphenyl phosphine cuprous iodide, synthetic method is participated in: Chemistry-A European Journal, 16 (39), 11822-11826,2010) mixture is heated to 40 DEG C, is added dropwise diethyl maleate (145.7 grams, 0.83 mole).This temperature 4h is kept, then neutralizes reaction mixture with (60 grams) of glacial acetic acid.Mixture is diluted with 1000 milliliters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is washed with 3 × 150 milliliter 40% of ethanol water.149.91 grams of orange solids of pyrazolidone -5- Ethyl formate of 1- (3- chloro-2-pyridyl) -3- are obtained after drying, it is 98% that quantified by external standard method, which analyzes its content, yield 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 synthetic method of catalyst is as follows:
1000 milliliters of dehydrated alcohols, triphenylphosphine (500 grams, 1,9mol), CuI (181 grams, 0.95mol) are sequentially added in 2000 milliliters of reaction flasks, after being warming up to 80 DEG C of reaction 1h, it is naturally cooling to room temperature, is filtered, it is dry, 644.9 grams of product are obtained, yield 95%.
The suitable raw material of following other catalyst choices can prepare in this manner.
Embodiment 2
The synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester
300 milliliters of dehydrated alcohols and (16.97 grams of sodium ethoxide are added in 1000 milliliters of reaction flasks, 0.249 mole), (30.75 grams of 3- chloride-2-hydrazinopyridine, 98%, 0.21 mole), it adds (0.017 gram of I of catalyst Cu (binap), 0.000021 mole) (2,2'- is bis--(diphenyl phosphine) -1,1'- dinaphthalene abbreviation binap, synthetic method participates in: Chemistry-A European Journal, 16 (39), 11822-11826,2010) mixture is heated to 30 DEG C, drop
Add diethyl maleate (44.23 grams, 0.252 mole).This temperature 4h is kept, then neutralizes reaction mixture with glacial acetic acid (15 grams).Mixture is diluted with 300 milliliters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is washed with 3 × 50 milliliter 40% of ethanol water.47.06 grams of orange solids of pyrazolidone -5- Ethyl formate of 1- (3- chloro-2-pyridyl) -3- are obtained after drying, it is 95% that quantified by external standard method, which analyzes its content, yield 79%.
Embodiment 3
The synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester
300 milliliters of dehydrated alcohols are added in 1000 milliliters of reaction flasks and sodium ethoxide (16.97 grams, 0.249 mole), 3- chloride-2-hydrazinopyridine (30.75 grams, 98%, 0.21 mole) add catalyst Cu (PPh3)2(0.042 gram of Br, 0.000063 mole) (bi triphenyl phosphine cuprous bromide, synthetic method is participated in: Chemistry-A European Journal, 16 (39), 11822-11826,2010), mixture is heated to 35 DEG C, it is added dropwise diethyl maleate (44.23 grams, 0.252 mole).This temperature 4h is kept, then neutralizes reaction mixture with (15 grams) of glacial acetic acid.Mixture is diluted with 300 milliliters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is washed with 3 × 50 milliliter 40% of ethanol water.It is orange that 1- (3- chloro-2-pyridyl) -3- pyrazolidone -5- Ethyl formate is obtained after drying
45.98 grams of solid, it is 96% that quantified by external standard method, which analyzes its content, yield 78%.
Embodiment 4
The synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester
300 milliliters of dehydrated alcohols are added in 1000 milliliters of reaction flasks and sodium ethoxide (16.97 grams, 0.249 mole), 3- chloride-2-hydrazinopyridine (30.75 grams, 98%, 0.21 mole) add catalyst n i (PPh3)2Br2(0.047 gram, 0.000063 mole) (bi triphenyl phosphine Nickel Bromide synthetic method is participated in: Appl.Organometal.Chem., and 23,455-459,2009), mixture is heated to 45 DEG C, it is added dropwise diethyl maleate (44.23 grams, 0.252 mole).This temperature 4h is kept, then neutralizes reaction mixture with (15 grams) of glacial acetic acid.Mixture is diluted with 300 milliliters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is washed with 3 × 50 milliliter 40% of ethanol water.45.98 grams of orange solids of pyrazolidone -5- Ethyl formate of 1- (3- chloro-2-pyridyl) -3- are obtained after drying, it is 96% that quantified by external standard method, which analyzes its content, yield 78%.
According to the method in embodiment 1, catalyst Cu (PPh is used3)2I (bi triphenyl phosphine cuprous iodide) can high yield obtained 1- (3,5- dichloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester.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).
Embodiment 5
The synthesis of 1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester
600 liters are added in 1000 liters of reaction kettles without dehydrated alcohol and sodium ethoxide (34.6 kilograms, 500 moles), 3- chloride-2-hydrazinopyridine (61.5 kilograms, 98%, 420 kilomol) adds catalyst Cu (PPh3)2I (90 grams), mixture are heated to 35 DEG C, are added dropwise diethyl maleate (88.4 kilograms, 500 moles).This temperature 4h is kept, then neutralizes reaction mixture with (20 kilograms) of glacial acetic acid.Mixture is diluted with 300 liters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is beaten with 100 liter 40% of ethanol water.After centrifugal filtration, dry, 92 kilograms of orange solids of pyrazolidone -5- Ethyl formate of 1- (3- chloro-2-pyridyl) -3- are obtained, it is 96% that quantified by external standard method, which analyzes its content, yield 78%.
Comparative examples
1- (3- chloropyridine -2- base) -3- pyrazolidone -5- carboxylic acid, ethyl ester has been synthesized according to Nankai University's published method (bibliography: pesticide research and application .14 (2), 14-15,2009).
300 milliliters of dehydrated alcohols and sodium (5.22 grams, 0.227 mole) are added in 1000 milliliters of reaction flasks, stirring to bubble-free generates, and is added 3- chloride-2-hydrazinopyridine (30.00 grams, 0.205 mole), mixture is heated to
Flow back 5min, adds 0.003 gram of catalyst A, is added dropwise diethyl maleate (36.00 grams, 0.209 mole).30min is maintained the reflux for, reaction mixture is then cooled to 65 DEG C and is neutralized with (25.2 grams) of glacial acetic acid.Mixture is diluted with 300 milliliters of water, is cooled to room temperature, there is solid precipitation.Solid is collected by filtration, is washed with 3 × 50 milliliter 40% of ethanol water.1- (3- chloro-2-pyridyl) -3- pyrazolidone -5- Ethyl formate is obtained after drying, 45.2 grams of orange solids, normalizing content 96%, it is 85.4% that quantified by external standard method, which analyzes its content, yield 70%.
From the various embodiments described above and comparative example as it can be seen that pyridyl pyrazoles alkanone carboxylic acid ester compound has been made as catalyst with higher yields in the unazotized phenyl phosphine compound that the present invention uses structure simple, cheap and easy to get, and industrial amplification application is obtained.After catalyst of the invention, which can carry out at a lower temperature, reduce production energy consumption, while greatly improve the safety of reaction, this plays important function to reduction production cost, raising reaction safety in production process.
Application example
According to above-mentioned reaction equation, above-described embodiment is prepared into gained 3- chloropyridine base pyrazolidone carboxylic acid, ethyl ester and obtains 3- bromo -1- pyridyl pyrazoles -5- carboxylic acid through bromination, hydrolysis.Hydrolysis gained pyrazole carboxylic acid is using acylation, oxidation; pyrazole acyl chloride is made; it is reacted again with 2- amino -3- methyl-5-chloro benzoyl methylamine and commercial varieties chlorantraniliprole is made, the total recovery of reaction is 56.7% (in terms of 3- chloropyridine base pyrazolidone carboxylic acid, ethyl ester).
Claims (10)
- A kind of preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound, it is characterised in that:Reaction equation is as follows:In formula: R1Selected from H or Cl；R2Selected from C1-C6Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C3-C6It is naphthenic base, halogen, unsubstituted or by most 6 C1-C4Alkyl-substituted benzyl；Hydrazino pyridine (II) under alkaline condition, is reacted with maleic acid diester (III) by the effect of catalyst and pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made,Wherein, 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 preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 1, it is characterised in that:The catalyst is selected from Cu (L1) Br, Cu (L1) I, Cu (L2)2Br or Cu (L2)2I；WhereinL1 is selected from:L2 is selected from:
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound as described in claim 2, it is characterised in that: the catalyst is selected from Cu (L1) I or Cu (L2)2I, whereinL1 is selected from:L2 is selected from:
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 1, it is characterized by: hydrazino pyridine (II) under alkaline condition, reacting the step of pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made with maleic acid diester (III) by the effect of catalyst includesHydrazino pyridine (II) used, alkali, maleic acid diester (III) and catalyst mol ratio be 1:1-2:1-5:0.00001-0.01.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 4, it is characterised in that: the hydrazino pyridine (II), alkali, maleic acid diester (III) and catalyst mol ratio be 1:1.2-1.5:1.5-2:0.0001-0.001.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 1, it is characterized by: hydrazino pyridine (II) is under alkaline condition, it is reacted in the step of pyridyl pyrazoles alkanone carboxylic acid ester compound (I) is made by the effect of catalyst with maleic acid diester (III), control reaction temperature is 20-50 DEG C.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 1, it is characterized by: hydrazino pyridine (II) is under alkaline condition, the reaction for reacting obtained pyridyl pyrazoles alkanone carboxylic acid ester compound (I) with maleic acid diester (III) by the effect of catalyst carries out in following solvent:The solvent is toluene, chlorobenzene, carboxylic acid esters, alkyl alcohols, ethers or polar aprotic solvent；Used alkali is selected from the amide or alkyl alcoholates of the hydride of alkali metal, alkali metal.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 7, it is characterised in that: the hydride of the alkali metal is lithium hydride, sodium hydride or hydrofining；The amide of alkali metal is lithium amide, Sodamide or potassamide；Alkyl alcoholates are sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, amylalcohol sodium, sodium isopropylate, isobutyl sodium alkoxide, sec-butyl alcohol sodium, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide or potassium tert-butoxide；The carboxylic acid esters are acetic acid esters, dimethyl ester or maleic acid diester；Alkyl alcohols is methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol；Ethers is tetrahydrofuran, 2- methyltetrahydrofuran or dioxane；Polar aprotic solvent is acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide or dimethyl sulfoxide.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 8, it is characterised in that: the alkali is selected from sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, amylalcohol sodium, sodium isopropylate, isobutyl sodium alkoxide, sec-butyl alcohol sodium or sodium tert-butoxide；The solvent is selected from methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, isopropanol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
- The preparation method of pyridyl pyrazoles alkanone carboxylic acid ester compound according to claim 9, it is characterised in that: the alkali is selected from sodium ethoxide；The solvent is selected from ethyl alcohol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511009005.1A CN106928183B (en) | 2015-12-29 | 2015-12-29 | The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound |
| CN2015110090051 | 2015-12-29 | ||
| PCT/CN2016/108984 WO2017114121A1 (en) | 2015-12-29 | 2016-12-08 | Method for preparing pyridylpyrazolidone carboxylic acid compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108137535A true CN108137535A (en) | 2018-06-08 |
| CN108137535B CN108137535B (en) | 2021-02-19 |
Family
ID=59224566
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511009005.1A Active CN106928183B (en) | 2015-12-29 | 2015-12-29 | The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound |
| CN201680060148.1A Active CN108137535B (en) | 2015-12-29 | 2016-12-08 | Method for preparing pyridyl pyrazolidinone carboxylic acid compounds |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511009005.1A Active CN106928183B (en) | 2015-12-29 | 2015-12-29 | The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN106928183B (en) |
| BR (1) | BR112018013249B1 (en) |
| WO (1) | WO2017114121A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057687A (en) * | 2020-08-05 | 2022-02-18 | 沈阳中化农药化工研发有限公司 | Method for preparing pyridyl pyrazolidinone carboxylic acid compounds |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317016A (en) * | 2016-08-24 | 2017-01-11 | 河北艾林国际贸易有限公司 | Insect cyclopropanecarboxamide compound and preparing method thereof and application |
| 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 |
| CN108484572A (en) * | 2018-04-29 | 2018-09-04 | 江苏省农用激素工程技术研究中心有限公司 | Novel bisamide class compound and its preparation method and application |
| 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 |
| EP4003962A4 (en) * | 2019-08-21 | 2023-08-09 | Gharda Chemicals Limited | Process for synthesis of pyrazolidinone compounds |
| WO2021033165A1 (en) * | 2019-08-21 | 2021-02-25 | Gharda Chemicals Limited | Process for synthesis of pyrazolidinone compounds |
| CN113072472A (en) * | 2021-04-07 | 2021-07-06 | 湖南科技学院 | Synthesis method of 2-methylmercapto-maleic diester compound |
| WO2023012081A1 (en) | 2021-08-05 | 2023-02-09 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
| CN114478365A (en) * | 2022-02-11 | 2022-05-13 | 大连九信作物科学有限公司 | Purification method of 2-aminomethyl-3-chloro-5-trifluoromethylpyridine acetate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826332A (en) * | 2002-07-31 | 2006-08-30 | 纳幕尔杜邦公司 | Method for preparing 3-halo-4,5-dihydro-1H-pyrazoles |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0314497A (en) * | 2002-10-04 | 2005-08-02 | Du Pont | Invertebrate pest control compound, method and composition, spray composition, bait composition and invertebrate pest control device |
| TWI367882B (en) * | 2003-03-26 | 2012-07-11 | Du Pont | Preparation and use of 2-substituted-5-oxo-3-pyrazolidinecarboxylates |
-
2015
- 2015-12-29 CN CN201511009005.1A patent/CN106928183B/en active Active
-
2016
- 2016-12-08 WO PCT/CN2016/108984 patent/WO2017114121A1/en active Application Filing
- 2016-12-08 BR BR112018013249-7A patent/BR112018013249B1/en active IP Right Grant
- 2016-12-08 CN CN201680060148.1A patent/CN108137535B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826332A (en) * | 2002-07-31 | 2006-08-30 | 纳幕尔杜邦公司 | Method for preparing 3-halo-4,5-dihydro-1H-pyrazoles |
Non-Patent Citations (1)
| Title |
|---|
| 张奉志，等，: "《1-（3-氯吡啶-2-基）-3-吡唑烷酮-5-羧酸乙酯合成方法的改进》", 《农药研究与应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057687A (en) * | 2020-08-05 | 2022-02-18 | 沈阳中化农药化工研发有限公司 | Method for preparing pyridyl pyrazolidinone carboxylic acid 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108137535B (en) | 2021-02-19 |
| BR112018013249B1 (en) | 2022-03-22 |
| CN106928183B (en) | 2019-09-24 |
| BR112018013249A2 (en) | 2019-02-12 |
| CN106928183A (en) | 2017-07-07 |
| WO2017114121A1 (en) | 2017-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108137535A (en) | The preparation method of pyridyl pyrazoles alkanone carboxylic acid compound | |
| CN101945861A (en) | A kind of preparation method of benzamide compound | |
| CN106061972A (en) | 5-fluoro-4-imino-3-(alkyl/substituted alkyl)-1-(arylsulfonyl)-3,4-dihydropyrimidin-2(1h)-one and processes for their preparation | |
| CN110028489B (en) | Method for preparing benzamide compound by pressure reduction method | |
| CN108864144B (en) | Synthetic method of pinoxaden | |
| EP2501682A1 (en) | Method for producing 5-fluorine-1-alkyl-3-fluoralkyl-1h-pyrazol-4 carbolic acid chlorides | |
| DK2414345T3 (en) | METHOD FOR PRODUCING of pyridyl-substituted pyrazoles | |
| WO2022028258A1 (en) | Preparation method for bromopyrazole carboxylate compound | |
| WO2006136529A1 (en) | Pyrazolium alkylsulfates as ionic liquids | |
| EP2850066B1 (en) | Method for producing 1-alkyl-3-fluoralkyl-1h-pyrazol-carboxylic acid chlorides | |
| WO2007094225A9 (en) | Process for production of 5-alkoxy-4-hydroxymethylpyrazole compound | |
| JPH0784423B2 (en) | 3-Amino-2-substituted benzoyl acrylic acid derivative | |
| KR100720220B1 (en) | Process for producing substituted aniline compound | |
| CN114057687B (en) | Preparation method of pyridyl pyrazolone carboxylic ester compound | |
| CN102603508A (en) | Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate | |
| CN110396079A (en) | A kind of preparation method and applications of Rynaxypyr intermediate | |
| AU2006240772B2 (en) | Method for producing nicotinic acid derivative or salt thereof | |
| CN106831705B (en) | Synthesis method of pyridyl pyrazolidone carboxylic ester compound | |
| CN102304014B (en) | Method for preparing epoxiconazole intermediate | |
| US5925795A (en) | Processes for the preparation of aryl-β-diketones, arylpyrimidine ketones and crop protection intermediates | |
| CN115974729B (en) | Preparation method of 2- (2, 2-difluoroethoxy) -6-trifluoromethyl benzenesulfonyl chloride | |
| JP4979170B2 (en) | Process for producing 5-[(4-chlorophenyl) methyl] -2,2-dimethylcyclopentanone | |
| US20040019221A1 (en) | Processes for the preparation of pyrazole compounds | |
| CN107162999B (en) | Synthetic method of 2-phenyl-4-p-hydroxyphenyl thiazole | |
| CN106631842A (en) | Synthetic method for N-substituent-3-aminoacrolein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |