OA20268A - Process for preparation of anthranilamides - Google Patents
Process for preparation of anthranilamides Download PDFInfo
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- OA20268A OA20268A OA1202100293 OA20268A OA 20268 A OA20268 A OA 20268A OA 1202100293 OA1202100293 OA 1202100293 OA 20268 A OA20268 A OA 20268A
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- compound
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- chlorantraniliprole
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- 238000000034 method Methods 0.000 title claims abstract description 76
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical class NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 238000000746 purification Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 192
- 239000005886 Chlorantraniliprole Substances 0.000 claims description 140
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 claims description 140
- 239000002002 slurry Substances 0.000 claims description 121
- 239000012535 impurity Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 45
- 239000007795 chemical reaction product Substances 0.000 claims description 44
- 239000005889 Cyantraniliprole Substances 0.000 claims description 42
- DVBUIBGJRQBEDP-UHFFFAOYSA-N Cyantraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl DVBUIBGJRQBEDP-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 27
- 239000000543 intermediate Substances 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- -1 cyano, amino Chemical group 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- 239000011780 sodium chloride Substances 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000007086 side reaction Methods 0.000 claims description 9
- 150000001805 chlorine compounds Chemical class 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000003460 sulfonic acids Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 20
- 238000001914 filtration Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000749 insecticidal Effects 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- QARBMVPHQWIHKH-UHFFFAOYSA-N Methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 7
- 239000002917 insecticide Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QUBBAXISAHIDNM-UHFFFAOYSA-N 1-ethyl-2,3-dimethylbenzene Chemical compound CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 description 3
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 108091006220 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 3
- LRDFRRGEGBBSRN-UHFFFAOYSA-N 2-methylpropanenitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- FORBXGROTPOMEH-UHFFFAOYSA-N 5-bromo-2-(3-chloropyridin-2-yl)pyrazole-3-carboxylic acid Chemical compound OC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl FORBXGROTPOMEH-UHFFFAOYSA-N 0.000 description 2
- 241000238421 Arthropoda Species 0.000 description 2
- 241000255777 Lepidoptera Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000003389 potentiating Effects 0.000 description 2
- 102000037170 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KNDVJPKNBVIKML-UHFFFAOYSA-N 2-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-5-[[5-(trifluoromethyl)tetrazol-2-yl]methyl]pyrazole-3-carboxamide Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(CN2N=C(N=N2)C(F)(F)F)=NN1C1=NC=CC=C1Cl KNDVJPKNBVIKML-UHFFFAOYSA-N 0.000 description 1
- INKMAGKGDPLJDP-UHFFFAOYSA-N 2-[5-bromo-2-(3-chloropyridin-2-yl)pyrazol-3-yl]-8-methyl-4-oxo-3,1-benzoxazine-6-carbonitrile Chemical compound CC1=CC(C#N)=CC(C(O2)=O)=C1N=C2C1=CC(Br)=NN1C1=NC=CC=C1Cl INKMAGKGDPLJDP-UHFFFAOYSA-N 0.000 description 1
- KOPXCQUAFDWYOE-UHFFFAOYSA-N 2-amino-5-chloro-3-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC(C(O)=O)=C1N KOPXCQUAFDWYOE-UHFFFAOYSA-N 0.000 description 1
- RAMUASXTSSXCMB-UHFFFAOYSA-N 5-bromo-N-[2-bromo-4-chloro-6-(1-cyclopropylethylcarbamoyl)phenyl]-2-(3-chloropyridin-2-yl)pyrazole-3-carboxamide Chemical compound C1CC1C(C)NC(=O)C1=CC(Cl)=CC(Br)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl RAMUASXTSSXCMB-UHFFFAOYSA-N 0.000 description 1
- 102000003922 Calcium Channels Human genes 0.000 description 1
- 108090000312 Calcium Channels Proteins 0.000 description 1
- 240000000218 Cannabis sativa Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 240000006962 Gossypium hirsutum Species 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N O-Toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102000019027 Ryanodine Receptor Calcium Release Channel Human genes 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000001055 chewing Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 230000004220 muscle function Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Abstract
The present invention provides a process for preparation and purification anthranilamides.
Description
- PROCESS FOR PREPARATION OF ANTHRANILAMIDES
Technical field of the invention
The présent invention relates to the préparation of Anthranilamides. The présent invention further provides anthranilamide that is free from impurities. Particularly, the présent 10 invention provides a process for purifying anthranilamides that is free from impurities.
Background of the invention
Effective control of insect pest such as arthropods is essential for crop safety. Arthropods 15 are an important class of pests which cause huge damage to crop and household every year around the world. Anthranilamides are a new class of compounds with extremely potent insecticidal activity. These nitrogen-containing aromatic compounds selectively act on targeted ryanodine receptors in insects. Ryanodine receptors form calcium ion channels which are responsible for muscle function.
Examples of insecticidal anthranilamides are cyantraniliprole, chlorantraniliprole, cyclaniliprole, tetrachlorantraniliprole and tetraniliprole. Chlorantraniliprole is a highly potent and sélective activator of insect ryanodine receptor with exceptional activity on a broad range of Lepidoptera. It Controls a wide range of chewing pests (primarily 25 Lepidoptera, but also some Coleoptera, Diptera and Isoptera species) in a broad range of crops, including fruit, vegetables, vines, cotton, sugar cane, rice and grass.
US 7232836 discloses the préparation of chlorantraniliprole represented as compound of Formula IV (Scheme I).
Scheme I
CH3NH2
Chlorantraniliprole (Formula IV)
Intermediate 3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxylic acid is represented as compound of Formula I and intermediate 2-amino-5-chloro-3methylbenzoic acid is represented as compound of Formula IL 2-[3-bromo-l-(3chloropyridin-2-y 1)-1 H-pyrazol-5 -y 1] -6-chloro-8-methy 1-4H-3,1 -benzoxazin-4-one is referred to as compound of Formula III.
US 7247647 discloses the préparation of cyantraniliprole (Formula represented as compound of Formula VII (Scheme II).
Cyantraniliprole (Formula VII)
Intermediate 3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazole-5-carboxylic acid is represented as compound of Formula I and intermediate 2-amino-5-cyano-310 methylbenzoic acid is represented as compound of Formula V. 2-[3-bromo-l-(3chloropyridin-2-yl)-1 H-pyrazol-5-yl]-6-cyano-8-methyl-4H-3,1 -benzoxazin-4-one is referred to as compound of Formula VI.
Inventors of the présent invention noted that compound of Formula III is not physically stable enough to undergo appropriate purification. It has been further noted that impure compound of Formula III on further reaction with methyl amine, leads to chlorantraniliprole with inconsistent physical and Chemical properties which in tum leads to ineffective product for the intended use.
Further, it has been observed that low solubility of anthranilamides in water and/or organic solvents makes it challenging to conduct appropriate purification processes.
Therefore, there is a need to develop improved préparation and purification methods for anthranilamides.
Objects of the Invention
It is an object of the présent invention to provide anthranilamides that is free of impurities.
It is another object of the présent invention to provide a process for préparation of anthranilamides.
It is yet another object of the présent invention to provide a process for preparing chlorantraniliprole that is free from impurities.
Summary of the Invention
The présent invention provides compounds of Formula (A) that are substantially free from impurities:
wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, Nthio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (C1-C10) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (Ci-Cio) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3.
The présent invention provides a process for purifying compound of Formula A,
wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, Nthio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (Ci-Cio) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, 10 hydorxyl or linear or branched (C1-C10) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3;
said process comprising purifying the compound of formula A from an aqueous slurry comprising said compound of formula A.
The présent invention provides a process for purifying compound of Formula A,
wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, Nthio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (Ci-Cio) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, 10 hydorxyl or linear or branched (Ci-Cio) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3;
said process comprising the steps of:
a) feeding a reaction product mixture comprising compound of Formula A into a 15 reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating solids;
e) optionally repeating steps b), c) and d); and
f) drying to get purified compound of Formula A.
The présent invention further provides chlorantraniliprole substantially free of impurities.
The présent invention provides a process for purifying chlorantraniliprole, said process comprising purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole.
The présent invention provides a process for purifying chlorantraniliprole, said process comprising the steps of:
a) feeding a reaction product mixture comprising chlorantraniliprole into a reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating solids;
e) optionally repeating steps b), c) and d); and
f) drying to get purified Chlorantraniliprole.
The présent invention provides a process preparing chlorantraniliprole that is free from impurities, said process comprising purifying Chlorantraniliprole from an aqueous slurry comprising the reaction product of the compound of formula III with methylamine.
The présent invention provides a process preparing chlorantraniliprole that is free from impurities, said process comprising the steps of:
a) reacting compound of Formula III with methyl amine in an organic solvent;
b) separating and collecting solids;
c) preparing a slurry of step b) product in aqueous conditions;
d) stirring the slurry for a pre-determined time;
e) separating and collecting solids;
f) optionally repeating steps c), d) and e); and
g) drying to get chlorantraniliprole substantially free from impurities.
The présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities wherein purification of compound of Formula III is not essential.
The présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising purifying Chlorantraniliprole from an aqueous slurry, said aqueous slurry comprising a hydrophilic solvent admixed with the reaction product of a compound of formula III with methylamine.
The présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising the steps of:
a) preparing compound of Formula III by reacting compound of Formula I and compound of Formula II in an organic solvent;
b) optionally purifying compound of Formula III;
c) reacting compound of Formula III with methyl amine in an organic solvent;
d) separating and collecting solids;
e) preparing a slurry of step d) product in aqueous conditions;
f) stirring the slurry for a pre-determined time;
g) separating and collecting solids;
h) optionally repeating steps e), f) and g); and
i) drying to get chlorantraniliprole free from impurities.
The présent invention provides a process for purifying cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous slurry of cyantraniliprole.
The présent invention provides a process for purifying cyantraniliprole said process comprising the steps of:
a) feeding a reaction product mixture comprising cyantraniliprole into a reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating solids;
e) optionally repeating steps b), c) and d); and
f) drying to get purified cyantraniliprole.
The présent invention further provides a process for preparing cyantraniliprole that is free from impurities, said process comprising the steps of:
a) reacting compound of Formula VI with methyl amine in an organic solvent;
b) separating and collecting solids;
c) preparing a slurry of step b) product in aqueous conditions;
d) stirring the slurry for a pre-determined time;
e) separating and collecting solids;
f) optionally repeating steps c), d) and e); and
g) drying to get cyantraniliprole substantially free from impurities.
The présent invention further provides a process for preparing cyantraniliprole said process comprising purifying cyantraniliprole from an aqueous slurry, said aqueous slurry comprising a hydrophilic solvent admixed with the reaction product of a compound of formula VI with methylamine.
Detailed Description
It has been noted that many of the anthranilamides represented by general structure of Formula A hâve low solubility in water or in other hydrophilic solvents due to which isolation and purification of the compound is troublesome. Despite their low solubility in water and other hydrophilic solvents, it has been surprisingly found by the présent inventors that substantially pure anthranilamides i.e. which is substantially free of impurities, could be prepared by purifying the crude reaction product of the compound of formula III with methylamine, out of an aqueous slurry. Based on this finding, it has been made possible by the présent inventors to provide insecticidal anthranilamides that is free from impurities and to a process for preparing such substantially pure anthranilamides.
Chlorantraniliprole is an example of such anthranilamides which is difficult to préparé and to purify resulting in varying physico-chemical properties and to optimize the process for its préparation. It has been noted that compound of formula III is not stable enough to undergo effective purification processes and that previous processes that depended upon purifying the compound of formula III to obtain pure anthranilamides failed to provide such substantially pure anthranilamides and lead to yield loss, as has been made possible by the process of the présent invention. Impure compound of formula III on reacting further with methyl amine leads to chlorantraniliprole with various impurities and uneven physical properties and found to be ineffective for the intended use. The présent invention finds that purifying the anthranilamides out of an aqueous slurry is a surprisingly better strategy to préparé substantially pure anthanilamides than starting with pure compound of formula III.
Inventors of the présent invention noted that, by following the process of the présent invention, purification of compound of formula III can be avoided or is not required and chlorantraniliprole could still be obtained that is substantially free from impurities.
The présent invention thus provides compounds of Formula (A) that is free from impurities.
Formula A
Wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, N5 thio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (C1-C10) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (C1-C10) alkyl or linear or branched (C1-C10) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3.
In another aspect, the présent invention also provides a process for purifying compound of Formula A,
wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, Nthio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (Ci-Cio) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (C1-C10) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3;
said process comprising purifying the compound of formula A from an aqueous slurry comprising said compound of formula A.
In an embodiment, the aqueous slurry of the compound of formula A is provided in a reactor.
In an embodiment, the aqueous slurry of the compound of formula A comprises a reaction product mixture which comprises the compound of formula A.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine carried out in an organic solvent.
In an embodiment, the compound of formula III is reacted with methylamine without being purified or isolated.
In an embodiment, the aqueous slurry comprises a slurry comprises the reaction product mixture in water.
In an embodiment, purifying the compound of formula A from an aqueous slurry comprising said compound of formula A comprises stirring the aqueous slurry for a predetermined time before purifying said compound of formula A.
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula II.
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, the compound of formula III is used without being isolated or purified from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, purifying the compound of formula A from an aqueous slurry comprising said compound of formula A comprises stirring the aqueous slurry for a predetermined time, and subsequently purifying said compound of formula A.
In an embodiment, purifying the compound of formula A from an aqueous slurry comprising said compound of formula A comprises stirring the aqueous slurry for a predetermined time, purifying said compound of formula A, and separating said compound of formula A from the aqueous slurry.
In an embodiment, purifying the compound of formula A from an aqueous slurry comprising said compound of formula A comprises repeatedly: (a) stirring the aqueous slurry for a predetermined time, (b) purifying said compound of formula A, and (c) separating said compound of formula A from the aqueous slurry.
In an embodiment, steps (a), (b) and (c) may be repeated a plurality of times.
In an embodiment, purifying the compound of formula A from an aqueous slurry comprising said compound of formula A comprises stirring the aqueous slurry for a predetermined time, purifying said compound of formula A, separating said compound of formula A from the aqueous slurry, and drying said separated compound of formula A.
In an embodiment, the présent invention also provides a process for purifying compound of Formula A,
wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, Nthio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (Ci-Cio) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (Ci-Cio) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3;
said process comprising the steps of:
a) feeding a reaction product mixture comprising compound of Formula A into a reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating solids;
e) optionally repeating steps b), c) and d); and
f) drying to get purified compound of Formula A.
In an embodiment, the compound of Formula A is when Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, N-thio dérivatives, alkyl, substituted alkyl with halogen, cyano or amino heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydroxyl or linear or branched (C1-C10) alkyl compounds wherein m, n, p and q can be 0, 1, 2, or 3.
In one embodiment, the compound of Formula A is when Ri is CN, and CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 wherein m and q=2 as represented in the below structure.
Ο
Cyantraniliprole
In another embodiment, the compound of Formula A is when Ri is Cl and -CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 wherein m and q =2 as represented in the below structure.
O
Chlorantraniliprole
In another embodiment, the compound of Formula A is when Ri is Cl and Br R2 is Cl, R3 is Br and R4 is H and 1-cyclopropyl ethyl and wherein m and q =2 as represented in the below structure.
cyclanili proie
In yet another embodiment, the compound of Formula A is when Ri is Cl, R2 is Cl, R3 is Br and R4 is H, and -CH3, wherein m, n and q =2 as represented in the below structure.
tetrachlorantraniliprole
In another embodiment, the compound of Formula A is when Ri is CN, and -CH3, R2 is Cl, R3 is 5-(trifluoromethyl)-2H-tetrazol-2-yl] methyl and R4 is H and -CH3 wherein m and q =2 as represented in the below structure.
In an embodiment, the term ‘impurities’ refers to unreacted synthetic intermediates, reagents, solvents, organic and/or inorganic products of side reactions, organic and/or inorganic salts and/or other undesired materials.
Therefore, the compounds of the invention being substantially free of impurities is intended to mean the referred compound being substantially free of ail the unreacted synthetic intermediates, reagents, solvents, organic and/or inorganic products of side reactions, organic and/or inorganic salts and/or other undesired materials.
In an embodiment, aqueous conditions of step b) refers to water or a mixture of water and one or more solvents.
In a preferred embodiment, aqueous conditions of step b) refers to water.
In an embodiment, slurry of step b) is prepared by mixing reaction mass with water or with a mixture of water and one or more solvents.
In an embodiment, solvents are selected from the group comprising methanol, éthanol npropanol, n-butanol, acetone, ethyl acetate, dimethyl sulfoxide, acetonitrile and dimethylformamide.
In an embodiment, in step c), the reaction mass is stirred at a température from about 25°C to about 80°C.
In a preferred embodiment, in step c), the reaction mass is stirred at a température from about 40°C to about 60°C.
In an embodiment, in step c), the reaction mass is stirred for a period of at least 15 minutes.
In a preferred embodiment, in step c), the reaction mass is stirred for a period of at least 30 minutes.
In an embodiment, the solid séparation of step d) is conducted by filtration, sédimentation, décantation, or by solid-liquid centrifugation.
In a preferred embodiment the solid séparation of step d) is conducted by filtration.
The présent invention provides chlorantraniliprole substantially free of impurities.
In an embodiment the présent invention provides chlorantraniliprole that is substantially free of impurities.
In another embodiment the présent invention provides cyantraniliprole that is substantially free of impurities.
In another embodiment the présent invention provides chlorantraniliprole with purity > 95% by weight.
In another embodiment the présent invention provides chlorantraniliprole with purity > 97% by weight.
In another embodiment the présent invention provides cyantraniliprole with purity > 95% by weight.
In another embodiment the présent invention provides cyantraniliprole with purity > 97% by weight.
In an embodiment, the term ‘impurities’ refers to unreacted synthetic intermediates, reagents, solvents, organic and/or inorganic products of side reactions, organic and/or inorganic salts and/or other undesired materials.
In another embodiment, synthetic intermediates comprise compound of Formula I, compound of Formula II and compound of Formula III.
In another embodiment, synthetic intermediates comprise compound of Formula I, compound of Formula V and compound of Formula VI.
In an embodiment, reagent include methane sulfonyl chloride and methyl amine.
In an embodiment, the organic and/or inorganic products of side reactions include salts of compound of Formula I with sulfonic acids and/or chlorides.
In an embodiment organic and/or inorganic products of side reactions include salts of compound of Formula I with methane sulfonyl chloride.
In another embodiment organic and/or inorganic products of side reactions include salts of compound of Formula II with sulfonic acids and/or chlorides.
In another embodiment organic and/or inorganic products of side reactions include salts of compound of Formula V with sulfonic acids and/or chlorides.
In yet another embodiment, the présent invention provides chlorantraniliprole that is substantially free of compound of Formula I, compound of Formula II, compound of Formula III, salts of compound of Formula I with sulfonic acids and chlorides.
In yet another embodiment, the présent invention provides cyantraniliprole that is substantially free of compound of Formula I, compound of Formula V, compound of Formula VI, salts of compound of Formula I with sulfonic acids and chlorides.
In an aspect, the présent invention provides a process for purifying chlorantraniliprole, said process comprising purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole.
In an embodiment, the aqueous slurry of Chlorantraniliprole is provided in a reactor.
In an embodiment, the aqueous slurry of Chlorantraniliprole comprises a reaction product mixture which comprises Chlorantraniliprole.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine carried out in an organic solvent.
In an embodiment, the compound of formula III is reacted with methylamine without being purified or isolated.
In an embodiment, the aqueous slurry comprises a slurry comprises the reaction product mixture in water.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time before purifying said Chlorantraniliprole.
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula IL
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, the compound of formula III is used without being isolated or purified from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, and subsequently purifying said Chlorantraniliprole.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, purifying said Chlorantraniliprole, and separating said Chlorantraniliprole from the aqueous slurry.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said Chlorantraniliprole comprises repeatedly: (a) stirring the aqueous slurry for a predetermined time, (b) purifying said Chlorantraniliprole, and (c) separating Chlorantraniliprole from the aqueous slurry.
In an embodiment, steps (a), (b) and (c) may be repeated a plurality of times.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, purifying Chlorantraniliprole, separating Chlorantraniliprole from the aqueous slurry, and drying said separated Chlorantraniliprole.
Thus, the présent invention provides a process for purifying chlorantraniliprole, said process comprising the steps of:
a) feeding a reaction product mixture comprising chlorantraniliprole into a reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating and collecting solids;
e) optionally repeating steps b), c) and d); and
f) drying to get chlorantraniliprole substantially free from impurities.
In an embodiment, chlorantraniliprole of step a) can be prepared from a reaction of compound of Formula I, its dérivatives or salts and compound of Formula II, its dérivatives or salts.
In an embodiment, aqueous conditions of step b) refers to water or a mixture of water and one or more solvents.
In a preferred embodiment, aqueous conditions of step b) refers to water.
In an embodiment, slurry of step b) is prepared by mixing reaction mass with water or with a mixture of water and one or more solvents.
In an embodiment, in step c), the reaction mass is stirred at a température from about 25°C to about 80°C.
In a preferred embodiment, in step c), the reaction mass is stirred at a température from about 40°C to about 60°C.
In an embodiment, in step c), the reaction mass is stirred for a period of at least 15 minutes.
In a preferred embodiment, in step c), the reaction mass is stirred for a period of at least 30 minutes.
In an embodiment, the solid séparation of step d) is conducted by filtration, sédimentation, décantation, or by solid-liquid centrifugation.
In a preferred embodiment the solid séparation of step d) is conducted by filtration.
In another embodiment, the présent invention provides a process for purifying chlorantraniliprole, said process comprising the steps of:
a) feeding a reaction product mixture comprising chlorantraniliprole into a reactor;
b) preparing a slurry of the mixture in water;
c) stirring the slurry at 25°-60°C for at least 30 minutes;
d) filtering;
e) optionally repeating steps b), c) and d); and
f) drying to get chlorantraniliprole substantially free from impurities.
In yet another embodiment, the présent invention provides a process for purifying chlorantraniliprole, said process comprising the steps of:
a) feeding a reaction product mixture comprising chlorantraniliprole into a reactor;
b) preparing a slurry of the reaction mass in water;
c) stirring at 25°-60°C for at least 30 minutes;
d) filtering;
e) repeating steps b), c) and d) at least once; and
f) drying to get chlorantraniliprole substantially free from impurities.
The présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities.
The présent invention also provides a process preparing chlorantraniliprole that is free from impurities, said process comprising purifying Chlorantraniliprole from an aqueous slurry comprising the reaction product of the compound of formula III with methylamine.
In an embodiment, the aqueous slurry of Chlorantraniliprole is provided in a reactor.
In an embodiment, the aqueous slurry of Chlorantraniliprole comprises a reaction product mixture which comprises Chlorantraniliprole.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine.
In an embodiment, the reaction product mixture is a reaction product of a compound of formula III with methylamine carried out in an organic solvent.
In an embodiment, the compound of formula III is reacted with methylamine without being purified or isolated.
In an embodiment, the aqueous slurry comprises a slurry comprises the reaction product mixture in water.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time before purifying said Chlorantraniliprole.
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula IL
In an embodiment, the compound of formula III is a reaction product produced from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, the compound of formula III is used without being isolated or purified from a reaction between a compound of formula I and a compound of formula II carried out in an organic solvent.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, and subsequently purifying said Chlorantraniliprole.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said 10 Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, purifying said Chlorantraniliprole and separating said Chlorantraniliprole from the aqueous slurry.
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said 15 Chlorantraniliprole comprises repeatedly: (a) stirring the aqueous slurry for a predetermined time, (b) purifying said Chlorantraniliprole, and (c) separating Chlorantraniliprole from the aqueous slurry.
In an embodiment, steps (a), (b) and (c) may be repeated a plurality of times. 20
In an embodiment, purifying Chlorantraniliprole from an aqueous slurry comprising said Chlorantraniliprole comprises stirring the aqueous slurry for a predetermined time, purifying Chlorantraniliprole, separating Chlorantraniliprole from the aqueous slurry, and drying said separated Chlorantraniliprole.
The présent invention provides a process for purifying cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous slurry of cyantraniliprole.
The présent invention provides a process for purifying cyantraniliprole said process 30 comprising the steps of:
a) feeding a reaction product mixture comprising cyantraniliprole into a reactor;
b) preparing a slurry of the mixture in aqueous conditions;
c) stirring the slurry for a pre-determined time;
d) separating solids;
e) optionally repeating steps b), c) and d); and
f) drying to get purified cyantraniliprole.
In an embodiment, the présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising the steps of:
a) reacting compound of Formula III and methyl amine in an organic solvent;
b) separating and collecting solids;
c) preparing a slurry of step b) product in aqueous conditions;
d) stirring for a pre-determined time;
e) separating and collecting solids;
f) optionally repeating steps c), d) and e); and
g) drying to get chlorantraniliprole substantially free from impurities.
In an embodiment, reaction of step a) is conducted in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene and dioxane.
In a preferred embodiment reaction of step a) is conducted in ethyl acetate.
In an embodiment, in step a) methyl amine is used as an aqueous solution.
In an embodiment, aqueous conditions of step c) refers to water or a mixture of water and one or more solvents.
In a preferred an embodiment, aqueous conditions of step c) refers to water.
In an embodiment, slurry of step c) is prepared by mixing reaction mass with water or with a mixture of water and one or more solvents.
In an embodiment, in step d), the reaction mass is stirred at a température from about 25 °C to about 80°C.
In a preferred embodiment, in step d), the reaction mass is stirred at a température from about 40°C to about 60°C.
In an embodiment, in step d), the reaction mass is stirred for a period of at least 15 minutes.
In a preferred embodiment, in step d), the reaction mass is stirred for a period of at least 30 minutes.
In an embodiment, the solid séparation of step e) is conducted by filtration, sédimentation, décantation, or by solid-liquid centrifugation.
In a preferred embodiment the solid séparation of step e) is conducted by filtration.
The présent invention also provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising purifying Chlorantraniliprole from an aqueous slurry, said aqueous slurry comprising a hydrophilic solvent admixed with the reaction product of a compound of formula III with methylamine.
In an embodiment, hydrophilic solvents are selected from the group comprising methanol, éthanol n-propanol, n-butanol, acetone, ethyl acetate, dimethyl sulfoxide, acetonitrile and dimethylformamide.
In a preferred embodiment, the présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising the steps of:
a) reacting compound of Formula III and aqueous methyl amine solution in an organic solvent;
b) filtering the reaction mass;
c) preparing a slurry of the réaction mass in water;
d) stirring at 25°-60°C for at least 30 minutes;
e) filtering;
f) repeating steps c), d) and e) at least once; and
g) drying to get purified chlorantraniliprole.
The présent invention further provides a process for preparing chlorantraniliprole that is substantially free from impurities wherein purification of compound of Formula III is not essential.
The présent invention provides a process for preparing chlorantraniliprole that is substantially free from impurities, said process comprising the steps of:
a) preparing compound of Formula III by reacting compound of Formula I and compound of Formula II in an organic solvent;
b) optionally purifying compound of Formula III;
c) reacting compound of Formula III with methyl amine in an organic solvent;
d) separating and collecting solids;
e) preparing a slurry of step d) product in aqueous conditions;
f) stirring the slurry for a pre-determined time;
g) separating and collecting solids;
h) optionally repeating steps e), f) and g); and
i) drying to get chlorantraniliprole substantially free from impurities.
In an embodiment, reaction of step a) is conducted in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene and dioxane.
In another embodiment reaction of step a) is conducted in presence of a base.
In an embodiment, step b) purification of compound of Formula III can be optional.
In another embodiment, in step (b), compound of Formula III can be purified partially.
In yet another embodiment, according to the présent invention, purification of compound of Formula III is not essential.
In an embodiment, step b) purification of compound of Formula III can be avoided.
In an embodiment, the process of the présent invention leads to chlorantraniliprole that is substantially free from impurities which are produced during step a) reaction.
In another embodiment, the process of the présent invention avoids the purification of less stable compound of Formula III.
In an embodiment, reaction of step c) is conducted in an organic solvent selected from the group comprising acetonitrile, tetrahydrofuran, ethyl acetate, toluene, xylene and dioxane.
In a preferred embodiment reaction of step c) is conducted in ethyl acetate.
In an embodiment, in step c) methyl amine is used as an aqueous solution.
In an embodiment, aqueous conditions of step e) refers to water or a mixture of water and one or more solvents.
In a preferred an embodiment, aqueous conditions of step e) refers to water.
In an embodiment, slurry of step e) is prepared by mixing reaction mass with water or with a mixture of water and one or more solvents.
In an embodiment, in step f), the reaction mass is stirred at a température from about 25°C to about 80°C.
In a preferred embodiment, in step f), the reaction mass is stirred at a température from 30 about 40°C to about 60°C.
In an embodiment, in step f), the reaction mass is stirred for a period of at least 15 minutes.
In a preferred embodiment, in step f), the reaction mass is stirred for a period of at least 30 minutes.
In an embodiment, the solid séparation of step g) is conducted by filtration, sédimentation, décantation, or by solid-liquid centrifugation.
In a preferred embodiment the solid séparation of step g) is conducted by filtration.
In an embodiment, the présent invention provides Chlorantraniliprole having a purity of at least about 97.0%.
In an embodiment, the présent invention provides Chlorantraniliprole having a purity of at least about 97.5%.
In an embodiment, the présent invention provides an anthanilamide insecticide having less than 0.5% of intermediates of formulae I, II, and III.
In an embodiment, the présent invention provides an anthranilamide insecticide having less than 0.2% of intermediates of formulae I, II and III.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 0.5% of intermediates of formulae I, II, and III.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 0.2% of intermediates of formulae I, II and III.
In an embodiment, the présent invention provides an anthranilamide insecticide having less than 1.0% of the salts of intermediates of formulae I, II, and III.
In an embodiment, the présent invention provides an anthranilamide insecticide having less than 0.5% of the salts of intermediates of formulae I, II and III.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 1.0% of the salts of intermediates of formulae I, II, and III.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 0.5% ofthe salts of intermediates of formulae I, II and III.
In these embodiments, the salts of intermediates of formulae I, II or III includes the salts of these intermediates of methane sulfonyl chloride.
In an embodiment, the présent invention provides an anthranilamide insecticide having less than 2.0% of the inorganic impurities.
In an embodiment, the présent invention provides an anthranilamide insecticide having less than 0.5% of the inorganic impurities.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 2.0% of the inorganic impurities.
In an embodiment, the présent invention provides Chlorantraniliprole having less than 0.5% of the inorganic impurities.
The présent invention further provides a process for preparing cyantraniliprole that is free from impurities, said process comprising the steps of:
a) reacting compound of Formula VI with methyl amine in an organic solvent;
b) separating and collecting solids;
c) preparing a slurry of step b) product in aqueous conditions;
d) stirring the slurry for a pre-determined time;
e) separating and collecting solids;
f) optionally repeating steps c), d) and e); and
g) drying to get cyantraniliprole substantially free from impurities.
The présent invention further provides a process for preparing cyantraniliprole said process comprising purifying cyantraniliprole from an aqueous slurry, said aqueous slurry 5 comprising a hydrophilic solvent admixed with the reaction product of a compound of formula VI with methylamine.
The advantages and other parameters of the présent invention is illustrated by the below given examples. However, the scope of the présent invention is not limited by the 10 examples in any manner. It will be appreciated by any person skilled in this art that the présent invention includes aforesaid examples and further can be modified and altered within the technical scope of the présent invention.
Examples:
Example 1 : Préparation of compound of Formula III
Methane sulphonyl chloride (56g) in acetonitrile (108g) was added to the mixture of compound of Formula I (54g), compound of Formula II (35g) and pyridine (73g) in acetonitrile (162g) with stirring at 5-10°C followed by stirring for 3 hours at 25°C. The mixture was then filtered and washed with acetonitrile followed by drying to get 20 compound of Formula III (75g, Yield = 93%)
Example 2: Préparation of chlorantraniliprole
Compound of Formula III (75g) was stirred in ethyl acetate (225 g) in a reactor at 1520°C while stirring. Aqueous solution of methyl amine (43 g) was added to the reaction 25 mixture in 2 hours at 15-25°C and stirred for 3 hours. The mass was then cooled to 30°C, filtered and washed with ethyl acetate to get chlorantraniliprole (98 g, ~93%purity).
Example 3: Purification of chlorantraniliprole g of chlorantraniliprole (as prepared in example 2) and 200g of water were charged 30 into a reactor. The mass was stirred at 40°-50°C for one hour. The mass was then filtered.
The wet mass was then charged into the reactor and 200g of water was added. The slurry was then stirred at 40°-50°C for one hour. The mass was then fdtered and washed with hot water. The wet mass thus obtained was dried at 70°C. 51 g, purity 97.5%.
Example 4: Préparation of compound of Formula III
Methane sulphonyl chloride (56g) in Tetrahydrofuran (75 g) was added to the mixture of compound of Formula I (54g), compound of Formula II (35g) and pyridine (73g) in Tetrahydrofuran (75 g) with stirring at 5-10°C followed by stirring for 3 hours at 25°C. The mixture was then filtered and washed with acetonitrile followed by drying to get compound of Formula III (68g, Yield = 84.3%)
Example 5: Préparation of chlorantraniliprole
Compound of Formula III (68g) was stirred in ethyl acetate (175 g) in a reactor at 1520°C while stirring. Aqueous solution of methyl amine (41 g) was added to the reaction mixture in 2 hours at 15-25°C and stirred for 3 hours. The mass was then cooled to 30°C, Add 200 gms water and maintain for 1 hr then filtered and washed with ethyl acetate to get chlorantraniliprole (58 g, ~93%purity).
Example 6: Purification of chlorantraniliprole g of chlorantraniliprole (as prepared in example 5) 200g of water and 100g of ethyl acetate were charged into a reactor. The mass was stirred at 40°-50°C for one hour. The mass was then filtered and washed with hot water. The wet mass thus obtained was dried at 70°C. 49 g, purity 97.5%.
Example 7: Analytical results of chlorantraniliprole prepared and purified by process according to the présent invention
The analytical results of chlorantraniliprole prepared (Example 2) and purified (Example
3) by the présent invention is presented in the below table (Table 1):
Table 1:
| Sample | Chlorantraniliprole (% purity) | Intermediates (%) | Salts of intermed | Inorganics (%) | Others (%) |
| iates (%) | |||||
| Example 2 | 93 | 0.5-1 | 1-2 | 2-4 | <1 |
| Example 3 | >97 | <0.2 | <0.5 | <0.5 | <0.1 |
Intermediates include compound of Formula I, compound of Formula II and compound of Formula III. Salts of intermediates include sait of compound of Formula I with methane sulfonyl chloride. Inorganics include chlorides. Traces of solvents, bases and other 5 unidentified impurities are also getting removed by the process of the présent invention.
From the above experiments it is established that the process according to the présent invention can be used to produce chlorantraniliprole of high purity as well as consistent properties.
Example 8: Préparation of compound of Formula VI
Methane sulphonyl chloride (60g) in acetonitrile (115g) was added to the mixture of compound of Formula I (55g), compound of Formula V (38g) and pyridine (75g) in acetonitrile (165g) with stirring at 5-10°C followed by stirring for 4 hours at 25°C. The mixture was then filtered and washed with acetonitrile followed by drying to get 15 compound of Formula VI (73g, Yield = 92%)
Example 9: Préparation of cyantraniliprole (formula VII)
Compound of Formula VI (73g) was stirred in ethyl acetate (220 g) in a reactor at 1520°C while stirring. Aqueous solution of methyl amine (43 g) was added to the reaction 20 mixture in 2 hours at 15-25°C and stirred for 3 hours. The mass was then cooled to 30°C, filtered and washed with ethyl acetate to get cyantraniliprole (95 g, ~93%purity).
Example 10: Purification of cyantraniliprole (formula VII) g of cyantraniliprole (as prepared in example 6) and 200g of water were charged into a 25 reactor. The mass was stirred at 35°-40°C for one hour. The mass was then filtered. The wet mass was then charged into the reactor and 200g of water was added. The slurry was then stirred at 35°-40°C for one hour. The mass was then filtered and washed with hot water. The wet mass thus obtained was dried at 70°C. (49 g, purity 97.5%).
Claims (26)
- CLAIMS :1. Compounds of Formula (A) that are substantially free from impurities:wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, N-thio dérivatives, hydroxyl, unsubstituted or substituted linear or10 branched (C1-C10) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (C1-C10) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3.
- 2. A compound of Formula A that is substantially free from impurities according to 15 claim 1 wherein Ri is CN, and CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 and wherein m and q =2.
- 3. A compound of Formula A that is substantially free from impurities according to claim 1 wherein Ri is Cl and -CH3, R2 is Cl, R3 is Br and R4 is H and -CH3 and20 wherein m and q =2.
- 4. A compound of Formula A that is substantially free from impurities according to claim 1 wherein Ri is Cl and Br R2 is Cl, R3 is Br and R4 is H and 1-cyclopropyl ethyl and wherein m and q =2.
- 5. A compound of Formula A that is substantially free from impurities according to claim 1 wherein Ri is Cl, R2 is Cl, R3 is Br and R4 is H, and -CH3, wherein m, n and q =2.
- 6. A compound of Formula A that is substantially free from impurities according to claim 1 wherein Ri is CN, and -CH3, R2 is Cl, R3 is 5-(trifluoromethyl)-2Htetrazol-2-yl]methyl and R4 is H and -CH3 wherein m and q =2.
- 7. Compounds of Formula (A) according to claim 1 that is substantially free from impurities wherein said impurities include unreacted synthetic intermediates, reagents, solvents, organic and/or inorganic products of side reactions, organic and/or inorganic salts and/or other undesired materials.
- 8. A process for purifying compound of Formula A,wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, amino, N-thio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (C1-C10) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (C1-C10) alkyl and5 wherein m, n, p and q can be 0, 1, 2, or 3;said process comprising purifying the compound of formula A from an aqueous slurry of said compound of formula A.10
- 9. A process for purifying compound of Formula A,wherein Ri, R2, R3 and R4 can be independently a hydrogen, halogen, cyano, 15 amino, N-thio dérivatives, hydroxyl, unsubstituted or substituted linear or branched (C1-C10) alkyl or cycloalkyl, heterocyclic unsubstituted or substituted with halogen, cyano, amino, hydorxyl or linear or branched (C1-C10) alkyl and wherein m, n, p and q can be 0, 1, 2, or 3; according to claim 8, said process comprising the steps of:a) feeding a reaction product mixture of compound of Formula A into a reactor;b) preparing a slurry of the mixture in aqueous conditions;c) stirring the slurry for a pre-determined time;d) separating solids;e) optionally repeating steps b), c) and d); andf) drying to get purified compound of Formula A.
- 10. A process according to claim 9 wherein said aqueous conditions comprise water or a mixture of water and one or more solvents.
- 11. Chlorantraniliprole substantially free from impurities.
- 12. Chlorantraniliprole according to claim 11 that are substantially free from impurities wherein said impurities include unreacted synthetic intermediates, reagents, solvents, organic and/or inorganic products of side reactions, organic and/or inorganic salts and/or other undesired materials
- 13. Chlorantraniliprole according to claim 11 that are substantially free from impurities wherein said impurities include compound of Formula I, compound of Formula II, compound of Formula III, salts of compound of Formula I with sulfonic acids and chlorides.
- 14. Chlorantraniliprole according to claim 11 having a purity of at least about 97.0%.
- 15. Chlorantraniliprole according to claim 11 having less than 0.5% of intermediates of formula I, II, and III.
- 16. Chlorantraniliprole according to claim 11 having less than 0.5% of the salts of intermediates of formula I, II and III.
- 17. A process for purifying chlorantraniliprole, said process comprising purifying Chlorantraniliprole from an aqueous slurry of Chlorantraniliprole.
- 18. A process for purifying chlorantraniliprole according to claim 17, said process comprising the steps of:a) feeding a reaction product mixture comprising chlorantraniliprole into a reactor;b) preparing a slurry of the mixture in aqueous conditions;c) stirring the slurry for a pre-determined time;d) separating solids;e) optionally repeating steps b), c) and d); andf) drying to get purified Chlorantraniliprole.
- 19. A process for preparing chlorantraniliprole that is free from impurities, said process comprising the steps of:a) reacting compound of Formula III with methyl amine in an organic solvent;b) separating and collecting solids;c) preparing a slurry of step b) product in aqueous conditions;d) stirring the slurry for a pre-determined time;e) separating and collecting solids;f) optionally repeating steps c), d) and e); andg) drying to get chlorantraniliprole substantially free from impurities.
- 20. A process for preparing chlorantraniliprole according to claim 19 wherein purification of compound of Formula III is not essential.
- 21. A process for preparing chlorantraniliprole according to claim 19, said process comprising purifying Chlorantraniliprole from an aqueous slurry, said aqueous slurry comprising a hydrophilic solvent admixed with the reaction product of a compound of formula III with methylamine.
- 22. A process for preparing chlorantraniliprole according to claim 19, said process comprising the steps of:a) preparing compound of Formula III by reacting compound of Formula I and compound of Formula II in an organic solvent;b) optionally purifying compound of Formula III;c) reacting compound of Formula III with methyl amine in an organic solvent;d) separating and collecting solids;e) preparing a slurry of step d) product in aqueous conditions;f) stirring the slurry for a pre-determined time;g) separating and collecting solids;h) optionally repeating steps e), f) and g); andi) drying to get chlorantraniliprole free from impurities.
- 23. A process for purifying cyantraniliprole, said process comprising purifying cyantraniliprole from an aqueous slurry of cyantraniliprole.
- 24. A process for purifying cyantraniliprole according to claim 23, said process comprising the steps of:a) feeding a reaction product mixture comprising cyantraniliprole into a reactor;b) preparing a slurry of the mixture in aqueous conditions;c) stirring the slurry for a pre-determined time;d) separating solids;e) optionally repeating steps b), c) and d); andf) drying to get purified cyantraniliprole.
- 25. A process for preparing cyantraniliprole that is free from impurities, said process comprising the steps of:a) reacting compound of Formula VI with methyl amine in an organic solvent;b) separating and collecting solids;c) preparing a slurry of step b) product in aqueous conditions;d) stirring the slurry for a pre-determined time;e) separating and collecting solids;f) optionally repeating steps c), d) and e); andg) drying to get cyantraniliprole substantially free from impurities.
- 26. A process for preparing cyantraniliprole according to claim 25, said process comprising purifying cyantraniliprole from an aqueous slurry, said aqueous slurry comprising a hydrophilic solvent admixed with the reaction product of a5 compound of formula VI with methylamine.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN201831048884 | 2018-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA20268A true OA20268A (en) | 2022-04-14 |
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