GB2463318A - Preparation of anthranilamide derivatives containing a pyridinylpyrazole moiety - Google Patents
Preparation of anthranilamide derivatives containing a pyridinylpyrazole moiety Download PDFInfo
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- GB2463318A GB2463318A GB0816754A GB0816754A GB2463318A GB 2463318 A GB2463318 A GB 2463318A GB 0816754 A GB0816754 A GB 0816754A GB 0816754 A GB0816754 A GB 0816754A GB 2463318 A GB2463318 A GB 2463318A
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- C07—ORGANIC CHEMISTRY
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- 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
- C07D401/14—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 three or more hetero rings
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Abstract
The invention relates to the preparation of an insecticide of formula (I) or agronomically acceptable salts, tautomers or N-oxides thereof, wherein X is a phenyl, naphthyl, quinolinyl, benzothiazolyl or benzimidazolyl bivalent moiety substituted at least with alkyl or halogen and optionally with alkoxy, cyano or nitro; R1is hydrogen, alkyl, cycloalkyl-alkyl, cyanoalkyl, cycloalkyl or cycloalkyl-cycloalkyl; and R2is halogen, alkoxy, haloalkyl or haloalkoxy. The process is depicted below and comprises (a) reacting an anhydride of formula (II) with an amine R1NH2, preferably isopropylamine, to give an ortho amido-substituted aromatic amine of formula (III); and (b) reacting the amine (III) with a chloropyridinylpyrazole acid chloride of formula (IV), preferably used in excess, to obtain the diamide (I). The preparation of 6-{[2-(3-chloropyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino}-5-methyl-1H-indazole-7-carboxylic acid isopropylamide is exemplified. Compounds of formula (III) and a subset of compounds of formula (IV) where R2is alkoxy, fluoro, chloro, iodo, haloalkyl or haloalkoxy are claimed separately.
Description
Process for the preparation of anthranilamide derivatives The present invention relates to a novel process for the preparation of insecticidally active anthranilamide derivatives.
Processes for the preparation of anthranilamide derivatives are described, for example, in WO 03/01 5519, WO 2004067528, W02005/085234, WO 2008/064891 and It is known from said references to prepare anthranilamide derivatives of formuI A, R (A), wherein Ra, Rx, Ry and Rz are organic substituents, by a) coupling of an anhyd ride of formula B (B), in the presence of acetonitrile and pyridine with a compound of formula C (C), ci tO a compoUnd of fOrmula D Ry (D), b aneaihg said compound with an amine of formula NHRxRx.
However, such process has the disadvantage that the selectivity of the ring opening is often not satisfactory, especially if the phenyl ring which carries the substituent Rz is replaced by a bicylic ring which contains nitrogen atoms, in particular by an 1-H-indazole moiety.
The present invention accordingly relates to a process for the preparation of compounds of formula I ci XOO N (I), HN.. R1
wherein X is a bivalent group selected from
R
R4 (X1), (X2), R4 (X3), R4 (X4), R4\ (X5), (X6), N (X7) and (X8);
N-NH
R1 is hydrogen, C1-C4alkyl or C1-C4alkyl substituted with one or two groups selected from C3-C6cycloalkyl and cyano; or R1 is C3-C6cycloalkyl or C3-C6cycloalkyl substituted by C3-C6cycloalkyl; R2 is halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; R3 is C1-C4alkyl or halogen; and R4 and R5 independently from each other, are hydrogen, C1-C4alkyl, C1-C4alkoxy, cyano, nitro, or halogen; and isomers/enantiomers/tautomers of those compounds,which process comprises a) reacting a compound of formula II (II), wherein X is as defined under formula I, in the presence of an amine of formula R1-NH2, wherein R1 is as defined under formula I, in the presence of a solvent to a compound of formula Ill xQ (Ill), HN.... R1
wherein X and R1 are as defined under formula I, and b) reacting said compound of formula Ill with compound of formula IV
R
o (Iv), wherein R2 is as defined under formula, in the presence of a solvent.
The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
Halogen is generally fluorine, chlorine, bromine or iodine.
Haloalkyl groups preferably have a chain length of from ito 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1 -d ifluoro-2,2,2-trichloroethyl, 2,2, 3,3-tetrafluoroethyl and 2,2,2-trichioroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluorornethyl.
Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2-chloroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoroethoxy and 2,2,2-trichloroethoxy; preferably difluorochioromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy and 2,2,2-trifluoroethoxy.
Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms.
Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.
The cycloalkyl groups have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The process of the present invention is especially advantageous for the preparation of compounds of formula I, wherein X is X8.
The present invention is especially suitable for the preparation of compounds selected from the compounds of formula I, wherein a) R1 is cyclopropyl substituted by cyclopropyl at the 1-position, R2 is bromine, R3 is methyl, R4 is CN and X is X1; b) R1 is methyl substituted by cyclopropyl, R2 is CF3, R3 is methyl, R4 is Cl and X is X1; C) R1 is cyclopropyl substituted by cyclopropyl at the 1-position, R2 is CE3, R3 is methyl, R4 is Cl and X is X1; d) R1 is cyclopropyl substituted by cyclopropyl at the 1-position, R2 is CF3, R3 is methyl, R4 is CN and X is X1; e) R1 is cyclopropyl substituted by cyclopropyl at the 1-position, R2 is OCH2CF3, R3 is methyl, R4 is CN and X is X1; f) R1 is isopropyl, R2 is methoxy; R3 is methyl, R4 is hydrogen and X is X8; g) R1 is isopropyl, R2 is trifluoromethyl, R3 is chlorine, R4 is hydrogen and X is X6; h) R1 is isopropyl, R2 is trifluoromethyl, R3 is methyl, R4 is hydrogen and X is X8; i) R1 is methyl, R2 is bromine, R3 is methyl, R4 is CN and X is X1; and j) R1 is methyl, R2 is bromine, R3 is methyl, R4 is Cl and X is X1.
Reaction step a): It is preferred to perform reaction step a) in the presence of I to 20 equivalents of an amine of formula R1-NH2, preferably ito 10 equivalents, most preferably 3 to 6 equivalents. Preferred organic solvents are ethyl acetate, I,4-dioxane, acetonitrile, tetrahydrofurane, N,N-dimethylformamide, N, N-dimethyl acetamide, toluene, xylene, acetic acid and mixtures thereof, in particular acetic acid, most preferably acetic acid if X is X8. The reaction can be performed at temperatures of from 0°C to 100°C, preferably of from 80 to 100°C, most preferably of from 95° to 100°C. The process of the present invention is especially advantageous for the preparation of compounds of formula I, wherein X is X8. For compounds of formula I, wherein X is X8, reaction step a) can be performed with a surprising high selectivity, good yield and gives a product of formula Ill with high purity.
Reaction step b): Suitable solvent for reaction step b) are ethyl acetate, 1,4-dioxane, acetonitrile, tetrahydrofurane, N, N-dimethylformamide, N, N-dimethyl acetamide, toluene, xylene, or a mixture thereof. Preferred temperatures are of from -20°C to 100°C, preferred is ambient temperature. A general advantage over the prior art processes is that no base such as pyridine is required for the process according to the invention.
Surprisingly it was found that an excess of the compound of formula IV in relation to the compound of formula Ill, in particular an excess of 0,1 to 10%, preferably 0,5 to 3% of the compound of formula IV leads to a significant increase in yield and purity especially for the preparation of compounds of formula I, wherein X is X8. Therefore, the use of an excess of the compound of formula IV in relation to the compound of formula Ill, in particular of 0,1 to 10%, preferably 0.5 to 3% of the compound of formula IV in process step b) is especially preferred, in particular for the preparation of compounds of formula I, wherein X is X8.
In case of the preparation of compounds of formula I, wherein X is X8, the use of an excess of a compound of formula IV surprisingly results in yields of at least 85%. If no excess is used, undesired by-products are formed which can decrease the yield significantly. A further significant advantage of the process according to the present invention is that no base is needed for reaction step b). The use of a base would lead to undesired side reactions. For example, acylation of compounds of the formula lila wherein X is X8, with compounds of formula IV in the presence of a base, such as triethylamine or pyridine, optionally in the presence of a catalyst such as dimethylamino-pyridine, at temperatures between 0°C to 50°C, in a suitable solvent such as acetonitrile, methylene chloride, or THF, or mixtures thereof, leads to compounds of the formula V acylated at the indazole ring nitrogen, with no trace of compounds of the formula I being detected in the reaction mixture as summarised in the following scheme: R4° + THF (Wa) (IV) R 2 CI (V) Compounds of formula II and their preparation are described in G. M. Coppola, Synthesis, 1980, 505. Compounds of formula IV and their preparation are described e.g. in W003/01 5518 (p. 31).
Compounds of formula Ill (ill), wherein X is a bivalent group selected from
R
(X2), R4 (X3), R4 (X4), R3(('L{ R4-_--I1JI�JI (X5), (X6), N5 (X7) and R4 (X8);
N-NH
and R1, R3, R4 and R5 are as defined under formula I, are novel, and are especially developed for the process according to the present invention and therefore constitute a further object of the present invention. Especially of interest are compounds of formula Ill, wherein X is X8.
Compounds of formula IVa
R
o (IVa), wherein R6 is C1-C4alkoxy, fluoro, chioro, iodo, C2-C4haloalkyl or C1-C4haloalkoxy, are novel, are especially developed for the process according to the present invention and therefore constitute a further object of the present invention. Especially of interest are compounds of formula IVa, wherein R2 is methoxy, chioro, difluoromethyl, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy. Particularly of interest are compounds of formula IVa, wherein R6 is methoxy, chloro or 2,2,2-trifluoroethoxy, especially methoxy.
Preparatory examples: Example Hi: Preparation of 6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyll-amino} -5-methyl-1 H-indazole-7-carboxylic acid isopropylamide: Step 1: Preparation of 5-methyl-i,6-dihydro-8-oxa-1,2,6-triaza-cyclopenta[a}naphthalene-7, 9-dione: çJIIIj;'I( triphosgen <,,c;IIIIII:rO N-NH N-NH 0 In a solution of 180 ml 1,4-dioxane and 100 ml THF, 10 g (52.2 nimol) 6-amino-5-methyl-i H-indazole-7-carboxylic acid was suspended. Triphosgen (31 g, 104.6 mmol) was added and the suspension was heated at a temperature of 50°C for 18 hours. The suspension was filtered and washed with diethylether. The mother liquor was diluted with 200 ml diethylether and the precipitated crystals were filtered. The solids were combined and directly submitted to the next step.
Step 2 (reaction step a) according to the invention): Preparation of 6-amino-5-methyl- 1 H-indazole-7-carboxylic acid isopropylamide: IPrNH2 17-L(NH2 N-NH 0 N-NH HN CH3
H CH3
5-Methyl-i,6-dihydro-8-oxa-1,2,6-triaza-cyclopenta[a]naphthalene-7,9-d ione (1.1 g, 5.1 mmol) obtained from step 1 was suspended in 30 ml acetic acid and 1.5 ml isopropylamine (36.9 mmol) was added. The suspension was heated at reflux for 18 hours. Another 1.5 ml (36.9 mmol) isopropylamine was added and the mixture was heated 8 h at reflux. The mixture was cooled down and poured on 200 nil water. After minutes stirring, the crystalline material was filtered and washed with water. The solid was dissolved in ethyl acetate and filtered over a short pad of silicagel. The -9-.
compound obtained can be crystallized from petrol ether and diisopropylether. Melting point: 173.5°C.
Step 3: Preparation of 2-(3-chloro-pyridin-2-yI)-5-methoxy-2H-pyrazole-3-carboxylic acid: O-CH O-CH3 H3C"\-\0 NJ7CI HO NjCI To a solution of 324 mg (1 mmol) 2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carboxylic acid pentyl ester in 6 ml dioxan was added a solution of 79 mg KOH (1.2 rnmol) in 3 ml water. The yellowish solution was stirred for 1.5 hours and the dioxan was evaporated. The aqueous solution was diluted with water, washed with ethyl acetate.
The aqueous solution was acidified with HCI 4N and the title compound precipitated as a solid, which was colfected by filtration (F: 231-2°C). The filtrate was extracted with ethyl acetate. After drying of the organic phase (MgSO4) and evaporation of the solvent, a second crop of the title compound was isolated (white crystals, F: 227-8°C).
Step 4: Preparation of 2-(3-Chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl chloride: O-CH3 O-CH3 ON (COd)2, DMF HO CI NL5' 2-(3-Chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carboxylic acid (110 g, 434 mmol) was solved in 1200 ml methylene chloride. Oxalyl chloride (74.5 ml, 867 mmol) was slowly added at ambient temperature. After addition of 2 ml dimethylformamide, the mixture was stirred for 18 hours at ambient temperature. Oxalyl chloride (10 ml, 116 mmol) was added and the mixture was heated at a temperature of 40°C for 30 minutes. -10-
The mixture was concentrated at the rotary, evaporated, dried, and directly used in the next step.
Step 5 (reaction step b) of the invention): Preparation of 6-{[2-(3-chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-amino} -5-methyl-1 H-indazole-7-carboxylic acid isopropyla m ide:
O-CH
NH2 O-CH3 CHO IIHHNCH + CH3CN HH]<CH3 CH3 6-Amino-5-methyl-1H-indazole-7-carboxylic acid isopropylamide (1.0 g, 4.3 mmol) was suspended in 20 ml CH3CN. 2-(3-Chloro-pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl chloride (1.23 g, 4.51 mmol) was added in several portions. The mixture was stirred at ambient temperature for 39 hours. A saturated solution of NaHCO3 in water (15 ml) was added and the mixture was stirred for a few minutes. After filtration, 6-{[2-(3-chloro- pyridin-2-yl)-5-methoxy-2H-pyrazole-3-carbonyl]-ami no}-5-methyl-I H-i ndazole-7-carboxylic acid isopropylarnide was isolated as a solid material, which can be triturateded in diethyl ether or diisopropylether. The purified compound was isolated with a yield of 85%. 1H-NMR (400 MHz, CDGI3, reference TMS); (ppm): 10.8 (broad s, 1 H), 9.6 (broad s, 1H), 8.40 (d, 1H), 7.86 (s, 1H), 7.81 (d, 1H), 7.30 (dd, 1H), 7.20 (s, 1H), 6.95-6.70 (broad s, 1H), 6.82 (s, IH), 4.27-4.18 (m, 1H), 4.03 (s, 3H), 2.03 (s, 3H), 1.13 (d, 6H). -11 -
Claims (5)
- What is claimed is: 1. A process for the preparation of compounds of formula I xQ: N wherein X is a bivalent group selected fromRR4 R4 (X2), R4 (x3), R4N (X4), (X5), (X6), N (X7) and R4 (X5);N-NHR1 is hydrogen, C1-C4alkyl or C1-C4alkyl substituted with one or two groups selected from C3-C6cycloalkyl and cyano; or R1 is C3-C6cycloalkyl or C3-C6cycloalkyl substituted by C3-C6cycloalkyl;R2 is halogen, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; R3 is C1-C4aIkyl or halogen; and R4 and R5 independently from each other, are hydrogen, C1-C4alkyl, C1-C4alkoxy, cyano, nitro, or halogen; and agronomically acceptable salts/isomers/enantiomers/tautomers/N-oxides of those compoundswhich process comprises a) reacting a compound of formula II -12-xo wherein X is as defined under formula I, in the presence of an amine of formula R1-NH2, wherein R1 is as defined under formula I, in the presence of a solvent to a compound of formula Ill (Ill), HN... R1wherein X and R1 are as defined under formula I, and b) reacting said compound of formula Ill with compound of formula IV (IV),CIwherein R2 is as defined under formula I, in the presence of a solvent.
- 2. A process according to claim 1, for the preparation of compounds of formula I, wherein X is X8,
- 3. A process according to claim 2, wherein in reaction step b) the compound of formula IV is used in excess with regard to the compound of formula Ill.
- 4. A compound of formula III (Wy' HN...wherein X is a bivalent group selected fromNR(X2), (X3), (X4), R4 R5 R R3 (X5), (X6), (X7) andJN I R3 (X8); R4N-NHwherein R1, R3, R4 and R5 are as defined for formula I ii, claim 1.
- 5. A compound of formula IVa,R oNN (IVa), CIN3 wherein R6 is C1-C4alkoxy, fluoro, chioro, iodo, C2-C4haloalkyl or C1-C4haloalkoxy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0816754A GB2463318A (en) | 2008-09-12 | 2008-09-12 | Preparation of anthranilamide derivatives containing a pyridinylpyrazole moiety |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0816754A GB2463318A (en) | 2008-09-12 | 2008-09-12 | Preparation of anthranilamide derivatives containing a pyridinylpyrazole moiety |
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| Publication Number | Publication Date |
|---|---|
| GB0816754D0 GB0816754D0 (en) | 2008-10-22 |
| GB2463318A true GB2463318A (en) | 2010-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0816754A Withdrawn GB2463318A (en) | 2008-09-12 | 2008-09-12 | Preparation of anthranilamide derivatives containing a pyridinylpyrazole moiety |
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| GB (1) | GB2463318A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021508688A (en) * | 2017-12-20 | 2021-03-11 | ピーアイ インダストリーズ リミテッドＰｉ Ｉｎｄｕｓｔｒｉｅｓ Ｌｔｄ | Pyrazolopyridine-diamides, their use as pesticides and methods of their manufacture |
| WO2023012081A1 (en) | 2021-08-05 | 2023-02-09 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005115972A1 (en) * | 2004-05-25 | 2005-12-08 | Astrazeneca Ab | Therapeutic compounds |
| WO2007093402A1 (en) * | 2006-02-16 | 2007-08-23 | Syngenta Participations Ag | Pesticides containing a bicyclic bisamide structure |
| WO2008010897A2 (en) * | 2006-07-19 | 2008-01-24 | E. I. Du Pont De Nemours And Company | Process for making 3-substituted 2-amino-5-halobenzamides |
| WO2008031549A1 (en) * | 2006-09-11 | 2008-03-20 | Syngenta Participations Ag | Process for the preparation of anthranilamide derivatives |
| WO2008064891A1 (en) * | 2006-12-01 | 2008-06-05 | Syngenta Participations Ag | N-cyanoalkylanthranilamides as insecticides |
-
2008
- 2008-09-12 GB GB0816754A patent/GB2463318A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005115972A1 (en) * | 2004-05-25 | 2005-12-08 | Astrazeneca Ab | Therapeutic compounds |
| WO2007093402A1 (en) * | 2006-02-16 | 2007-08-23 | Syngenta Participations Ag | Pesticides containing a bicyclic bisamide structure |
| WO2008010897A2 (en) * | 2006-07-19 | 2008-01-24 | E. I. Du Pont De Nemours And Company | Process for making 3-substituted 2-amino-5-halobenzamides |
| WO2008031549A1 (en) * | 2006-09-11 | 2008-03-20 | Syngenta Participations Ag | Process for the preparation of anthranilamide derivatives |
| WO2008064891A1 (en) * | 2006-12-01 | 2008-06-05 | Syngenta Participations Ag | N-cyanoalkylanthranilamides as insecticides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021508688A (en) * | 2017-12-20 | 2021-03-11 | ピーアイ インダストリーズ リミテッドＰｉ Ｉｎｄｕｓｔｒｉｅｓ Ｌｔｄ | Pyrazolopyridine-diamides, their use as pesticides and methods of their manufacture |
| WO2023012081A1 (en) | 2021-08-05 | 2023-02-09 | Syngenta Crop Protection Ag | Method for controlling diamide resistant pests & compounds therefor |
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| GB0816754D0 (en) | 2008-10-22 |
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