CN116535388A - Preparation method of chlorantraniliprole - Google Patents
Preparation method of chlorantraniliprole Download PDFInfo
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- CN116535388A CN116535388A CN202310302988.6A CN202310302988A CN116535388A CN 116535388 A CN116535388 A CN 116535388A CN 202310302988 A CN202310302988 A CN 202310302988A CN 116535388 A CN116535388 A CN 116535388A
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- Prior art keywords
- palladium
- chloro
- bis
- pyridine
- pyrazol
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- 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 title claims abstract description 51
- 239000005886 Chlorantraniliprole Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 31
- XHLGXCSAICVHNH-UHFFFAOYSA-N 3-chloro-2-(3,5-dibromopyrazol-1-yl)pyridine Chemical compound ClC1=CC=CN=C1N1C(Br)=CC(Br)=N1 XHLGXCSAICVHNH-UHFFFAOYSA-N 0.000 claims abstract description 30
- WOBVZGBINMTNKL-UHFFFAOYSA-N 2-amino-5-chloro-n,3-dimethylbenzamide Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1N WOBVZGBINMTNKL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- -1 benzyl bis (triphenylphosphine) palladium chloride Chemical compound 0.000 claims description 4
- RSJBEKXKEUQLER-UHFFFAOYSA-N dicyclohexyl(3-dicyclohexylphosphanylpropyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCCP(C1CCCCC1)C1CCCCC1 RSJBEKXKEUQLER-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QRPNDOFSVHOGCK-UHFFFAOYSA-N 3-di(propan-2-yl)phosphanylpropyl-di(propan-2-yl)phosphane Chemical compound CC(C)P(C(C)C)CCCP(C(C)C)C(C)C QRPNDOFSVHOGCK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002941 palladium compounds Chemical class 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- TYXWDMWSFQYDKQ-UHFFFAOYSA-N 4-diphenylphosphanylbutan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 TYXWDMWSFQYDKQ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 claims description 2
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 6
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 4
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 230000009471 action Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YTUFZVFTWQLIBQ-UHFFFAOYSA-N 1,3-bis[di(propan-2-yloxy)phosphoryl]propane Chemical compound CC(C)OP(=O)(OC(C)C)CCCP(=O)(OC(C)C)OC(C)C YTUFZVFTWQLIBQ-UHFFFAOYSA-N 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-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
- 241000251468 Actinopterygii Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 102000042094 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 1
- 108091052345 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of chlorantraniliprole, which comprises the following steps: 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, 2-amino-5-chloro-N, 3-dimethylbenzamide and CO are reacted in the presence of a palladium catalyst to obtain the chlorantraniliprole. The preparation method has the advantages of high reaction yield, simple and easily obtained raw materials, low cost, convenient operation, environmental friendliness and the like, and is more suitable for industrial production.
Description
Technical Field
The invention relates to the field of pesticide synthesis, in particular to a preparation method of chlorantraniliprole.
Background
The chlorantraniliprole is a new-generation novel, efficient and low-toxicity pesticide, has a special effect on lepidoptera pests by inducing an insect ryanodine receptor to regulate and control intracellular calcium ion release, has low toxicity on fish, bees, aquatic organisms and mammals, and is very environment-friendly. Chlorantraniliprole is used for lepidopteran pest control on rice, fruits and vegetables.
The preparation method of chlorantraniliprole is more, for example, dupont discloses that 2, 3-dichloropyridine is used as a raw material, a key intermediate 3-bromo-1- (3-chloro-2-pyridyl) -1H pyrazole-5-formic acid is generated through hydrazinization, cyclization, bromination, oxidation and hydrolysis, then 2- [ 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-yl ] -6-chloro-8-methyl-4H-3, 1-benzoxazine-4-ketone is generated with 2-amino-3-methyl-5-chlorobenzoic acid under the action of methanesulfonyl chloride and triethylamine, and chlorantraniliprole is finally generated under the action of methylamine; duPont, in turn, published in patent WO2006062978 the key intermediate 3-bromo-1- (3-chloro-2-pyridinyl) -1H pyrazole-5-carboxylic acid with 2-amino-5-chloro-N, 3-dimethylbenzamide under the action of methanesulfonyl chloride and 3-methylpyridine to form chlorantraniliprole. The two routes all need to use the virulent pipe product methanesulfonyl chloride, and the whole route is tedious, the operation is tedious and the three wastes are more.
The patent US20100317864 improves the DuPont, firstly, a key intermediate 3-bromo-1- (3-chloro-2-pyridyl) -1H pyrazole-5-formic acid is prepared into acyl chloride, and then the acyl chloride is condensed with 2-amino-5-chloro-N, 3-dimethylbenzamide to generate chlorantraniliprole, and the improvement route avoids the use of a virulent tubular product methanesulfonyl chloride, but prolongs the reaction steps and reduces the overall yield.
In conclusion, the preparation method with high yield, low cost, simple and safe operation and environmental protection is developed, and has important significance for industrial production of chlorantraniliprole.
Disclosure of Invention
The invention aims to provide a preparation method of chlorantraniliprole, which has the advantages of high yield, low cost, simple and safe operation and environmental friendliness.
In order to solve the problems, the invention adopts the following technical scheme:
the invention provides a preparation method of chlorantraniliprole, which comprises the following steps of reacting 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, 2-amino-5-chloro-N, 3-dimethylbenzamide and CO in the presence of a palladium catalyst to obtain the chlorantraniliprole.
Preferably, the feeding mole ratio of the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine to the 2-amino-5-chloro-N, 3-dimethylbenzamide is 1: (1 to 1.2), for example, 1:1.02, 1:1.05, 1:1.08, 1:1.12, 1:1.16, 1:1.8, etc.
Further preferably, the molar ratio of the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine to the 2-amino-5-chloro-N, 3-dimethylbenzamide is 1: (1-1.1).
Preferably, the palladium catalyst is selected from palladium-containing compounds having a palladium oxidation state of 0 and/or palladium-containing compounds having a palladium oxidation state of 2.
Preferably, the palladium-containing compound having a palladium oxidation state of 0 is selected from one or more of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, bis (tri-t-butylphosphine) palladium, and metallic palladium supported on an inert carrier; the palladium compound with the palladium oxidation state of 2 is selected from one or more of palladium chloride, palladium acetate, bis (acetonitrile) palladium dichloride, bis (triphenylphosphine) palladium chloride, bis (tricyclohexylphosphine) palladium dichloride, bis (methyl diphenylphosphine) palladium dichloride and benzyl bis (triphenylphosphine) palladium chloride.
Further preferably, the inert support is selected from one or more of activated carbon, alumina, barium sulfate or barium carbonate.
According to a specific and preferred embodiment, the palladium-containing compound having a palladium oxidation state of 0 is selected from one or more of tris (dibenzylideneacetone) dipalladium, bis (tri-t-butylphosphine) palladium, tetrakis (triphenylphosphine) palladium.
According to another specific and preferred embodiment, the palladium compound having a palladium oxidation state of 2 is selected from palladium chloride and/or palladium acetate.
Preferably, the feeding mole ratio of the palladium catalyst to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001-0.002): 1, for example 0.0002: 1. 0.0003: 1. 0.0004: 1. 0.0005: 1. 0.001: 1. 0.0015:1, etc.
Further preferably, the molar ratio of the palladium catalyst to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001 to 0.001): 1.
preferably, the palladium catalyst is matched with a ligand to participate in the reaction, the ligand is selected from one or more of triphenylphosphine, 1, 3-bis (diisopropylphosphino) propane, 1, 3-bis (diphenylphosphino) butane, 1, 3-bis (dicyclohexylphosphino) propane, 2-dimethyl-1, 3-bis (diphenylphosphino) propane and 2-dicyclohexylphosphine-2, 6-dimethoxybiphenyl, and the feeding mole ratio of the ligand to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001-0.002): 1.
further preferably, the ligand is selected from one or more of 1, 3-bis (diphenylphosphino) propane, triphenylphosphine, 1, 3-bis (diisopropylphosphino) propane, 1, 3-bis (diphenylphosphino) propane, 1, 3-bis (dicyclohexylphosphino) propane.
Further preferably, the molar ratio of the ligand to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001 to 0.001): 1, for example 0.0002: 1. 0.0003: 1. 0.0004: 1. 0.0005: 1. 0.0006:1, etc.
Still more preferably, the molar ratio of the ligand to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is from (0.0001 to 0.0008): 1.
preferably, the reaction is carried out in the presence of a base selected from one or more of potassium carbonate, sodium acetate, triethylamine, pyridine, 3-methylpyridine, 3, 5-dimethylpyridine and potassium bicarbonate, and the molar ratio of the base to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (1-2): 1.
further preferably, the base is selected from one or more of potassium carbonate, sodium acetate, triethylamine and pyridine.
Further preferably, the molar ratio of the base to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (1 to 1.5): 1, for example 1.1: 1. 1.2: 1. 1.3: 1. 1.4:1, etc.
Preferably, the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine and the 2-amino-5-chloro-N, 3-dimethylbenzamide are reacted in the presence of a solvent selected from one or more of N, N-dimethylformamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, dichloroethane, toluene, N-methylpyrrolidone and chlorobenzene.
Further preferably, the solvent is selected from one or more of tetrahydrofuran, dichloroethane, toluene and acetonitrile.
Preferably, the CO pressure is controlled to be 0.5-20 bar, e.g. 1bar, 2bar, 3bar, 4bar, 6bar, 8bar, 12bar, 16bar, 18bar, etc.
Further preferably, the CO pressure is controlled to be 2-4 bar.
Preferably, the temperature of the reaction is 90 to 150 ℃, e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, etc.
Further preferably, the temperature of the reaction is 100 to 120 ℃.
Preferably, the duration of the reaction is from 10 to 15 hours, such as 11 hours, 12 hours, 13 hours, 14 hours, etc.
Further preferably, the duration of the reaction is between 10 and 12 hours.
Preferably, the preparation method comprises the following specific steps: n (N) 2 Mixing the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, the 2-amino-5-chloro-N, 3-dimethylbenzamide, the palladium catalyst, the ligand, the base and the solvent in an autoclave, stirring and mixing uniformly, and carrying out N 2 3 times of replacement, 3 times of replacement by CO, heating reaction, and filtering after the reaction is finished to obtain the chlorantraniliprole.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the preparation method provides a new thought for the synthesis of chlorantraniliprole, has the advantages of high yield, simple and easily obtained raw materials, obvious reduction in cost, environment-friendly and safe used reagent, simple and safe operation, simple post-treatment and the like, and is more suitable for industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, which are to be understood as illustrative of the basic principles, main features and advantages of the present invention, but the present invention is not limited by the following examples. The implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
The invention relates to a method for preparing 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 2-amino-5-chloro-N, 3-dimethylbenzamide (K2) and CO in the presence of a palladium catalystThe reaction was carried out to obtain chlorantraniliprole (KK). Specifically, at N 2 Under the protection, 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 2-amino-5-chloro-N, 3-dimethylbenzamide (K2), palladium catalyst, ligand, alkali and solvent are mixed, and after mixing, the reaction system is subjected to N 2 CO replacement after replacement, heating reaction, and filtering after the reaction is finished to obtain chlorantraniliprole.
The preparation route of the invention is as follows:
through the preparation method, the yield of chlorantraniliprole is improved, the reaction raw materials are simple and easy to obtain, the cost is greatly reduced, the preparation method also has the advantages of simplicity in operation, simplicity in post-treatment, environment friendliness and the like, is suitable for industrial production, and solves the problems of complex operation, complex post-treatment, low reaction yield, high cost and multiple three wastes in the prior art.
The schemes of the present application are discussed further below.
Example 1
Preparation of chlorantraniliprole (KK)
N 2 Into a autoclave under protection, 10g (29.6 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 6.5g (32.7 mmol) of 2-amino-5-chloro-N, 3-dimethylbenzamide (K2), 13.6mg (0.0148 mmol) of tris (dibenzylideneacetone) dipalladium, 3.9mg (0.0148 mmol) of triphenylphosphine, 4.9g (35.5 mmol) of potassium carbonate and 30g of tetrahydrofuran were charged, and stirring was started, the system was replaced with N 2 After three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 5bar, then the temperature is raised to 130 ℃ for reaction for 13 hours, the reaction is completed, the temperature is reduced to room temperature, the crude chlorantraniliprole product is obtained by filtration, and 13.8g of chlorantraniliprole is obtained by pulping, filtering and drying the crude chlorantraniliprole product with water, and the yield is 96.5%.
Example 2
Preparation of chlorantraniliprole (KK)
N 2 Into the autoclave under protection, 30g (88.9 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 21.0g (105.7 mmol) were charged2-amino-5-chloro-N, 3-dimethylbenzamide (K2), 9.1mg (0.0178 mmol) of bis (tri-t-butylphosphine) palladium, 4.9mg (0.0178 mmol) of 1, 3-bis (diisopropylphosphono) propane, 8g (97.7 mmol) of sodium acetate and 75g of acetonitrile, and stirring was started, the system was prepared with N 2 After three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 10bar, then the temperature is raised to 120 ℃ for reaction for 15 hours, the reaction is completed, the room temperature is reduced, the crude chlorantraniliprole product is obtained by filtration, and 41.5g of chlorantraniliprole is obtained by pulping, filtering and drying the crude chlorantraniliprole product with water, and the yield is 96.7%.
Example 3
Preparation of chlorantraniliprole (KK)
N 2 Into a autoclave under protection, 50g (148.2 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 30.9g (155.6 mmol) of 2-amino-5-chloro-N, 3-dimethylbenzamide (K2), 17.1mg (0.0148 mmol) of tetrakis (triphenylphosphine) palladium, 6.1mg (0.0148 mmol) of 1, 3-bis (diphenylphosphino) propane, 15g (148.2 mmol) of triethylamine and 100g of toluene were charged, and stirring was started, the system was replaced with N 2 After three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 4bar, then the temperature is raised to 100 ℃ for reaction for 12 hours, the reaction is cooled to room temperature after the reaction is finished, 70.7g of chlorantraniliprole is obtained through filtration and drying, and the yield is 98.7%.
Example 4
Preparation of chlorantraniliprole (KK)
N 2 Into a autoclave under protection were charged 60g (177.8 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 37g (186.3 mmol) of 2-amino-5-chloro-N, 3-dimethylbenzamide (K2), 3.1mg (0.0178 mmol) of palladium chloride, 7.3mg (0.0178 mmol) of 1, 3-bis (diphenylphosphino) propane, 18g (177.8 mmol) of triethylamine and 180g of toluene, and stirring was started, the system was prepared with N 2 After three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 2bar, then the temperature is raised to 120 ℃ for reaction for 10 hours, after the reaction is finished, the temperature is reduced to room temperature, 84.6g of chlorantraniliprole is obtained through filtration and drying, and the yield is 98.5%.
Example 5
Preparation of chlorantraniliprole (KK)
N 2 Into a protected autoclave were charged 100g (296 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 65g (327 mmol) of 2-amino group-5-chloro-N, 3-dimethylbenzamide (K2), 19.9mg (0.0888 mmol) of palladium acetate, 38.8mg (0.0888 mmol) of 1, 3-bis (dicyclohexylphosphino) propane, 24.6g (310.8 mmol) of pyridine and 200g of dichloroethane, stirring is turned on and the system is replaced with N 2 After three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 4bar, then the temperature is raised to 150 ℃ for reaction for 11 hours, the reaction is completed, the room temperature is reduced, the crude chlorantraniliprole product is obtained by filtration, 137.4g of chlorantraniliprole is obtained by pulping the crude chlorantraniliprole product with water, filtering and drying, and the yield is 96.1%.
Example 6
Preparation of chlorantraniliprole (KK)
N 2 Into a autoclave under protection were charged 40g (118.6 mmol) of 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine (K1), 28.2g (142.0 mmol) of 2-amino-5-chloro-N, 3-dimethylbenzamide (K2), 179.8mg (0.237 mmol) of benzyl bis (triphenylphosphine) palladium chloride, 97.3mg (0.237 mmol) of 2-dicyclohexylphosphine-2, 6-dimethoxybiphenyl, 23.7g (237.2 mmol) of potassium bicarbonate and 80g of chlorobenzene, and the stirring was turned on, and the system was stirred with N 2 And after three times of replacement, CO is used for three times of replacement, the CO pressure is controlled at 20bar, then the temperature is raised to 150 ℃ for reaction for 15 hours, the reaction is completed, the room temperature is reduced, the crude chlorantraniliprole product is obtained by filtration, and 47.0g of chlorantraniliprole is obtained by pulping, filtering and drying the crude chlorantraniliprole product with water, and the yield is 82.0%.
According to the embodiment, the reaction yield of chlorantraniliprole prepared by the preparation method is high and reaches more than 82%, and particularly, the reaction yield of the obtained product is more than 98% by adopting the technical scheme of the embodiment 3 or the embodiment 4, so that the reaction yield is remarkably improved. According to the preparation method provided by the invention, 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, 2-amino-5-chloro-N, 3-dimethylbenzamide and CO are used as raw materials to prepare the chlorantraniliprole, so that the reaction yield is improved, the raw materials are simple and easy to obtain, the cost is low, the operation is convenient, the post-treatment is simple, and the preparation method is environment-friendly. Therefore, the preparation method is more suitable for industrial production.
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of chlorantraniliprole is characterized in that 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, 2-amino-5-chloro-N, 3-dimethylbenzamide and CO are reacted in the presence of a palladium catalyst to obtain the chlorantraniliprole.
2. The preparation method according to claim 1, wherein the molar ratio of the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine to the 2-amino-5-chloro-N, 3-dimethylbenzamide is 1: (1-1.2).
3. The preparation method according to claim 1, wherein the molar ratio of the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine to the 2-amino-5-chloro-N, 3-dimethylbenzamide is 1: (1-1.1).
4. The method of claim 1, wherein the palladium catalyst is selected from palladium-containing compounds having a palladium oxidation state of 0 and/or palladium-containing compounds having a palladium oxidation state of 2; and/or the feeding mole ratio of the palladium catalyst to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001-0.002): 1.
5. the method of claim 4, wherein the palladium-containing compound having a palladium oxidation state of 0 is selected from one or more of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, bis (tri-t-butylphosphine) palladium, and metallic palladium supported on an inert carrier; the palladium compound with the palladium oxidation state of 2 is selected from one or more of palladium chloride, palladium acetate, bis (acetonitrile) palladium dichloride, bis (triphenylphosphine) palladium chloride, bis (tricyclohexylphosphine) palladium dichloride, bis (methyl diphenylphosphine) palladium dichloride and benzyl bis (triphenylphosphine) palladium chloride.
6. The production method according to claim 1, wherein the palladium catalyst participates in the reaction in cooperation with a ligand selected from one or more of triphenylphosphine, 1, 3-bis (diisopropylphosphino) propane, 1, 3-bis (diphenylphosphino) butane, 1, 3-bis (dicyclohexylphosphino) propane, 2-dimethyl-1, 3-bis (diphenylphosphino) propane and 2-dicyclohexylphosphine-2, 6-dimethoxybiphenyl, and the molar ratio of the ligand to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (0.0001 to 0.002): 1.
7. the preparation method according to claim 1, wherein the reaction is carried out in the presence of a base selected from one or more of potassium carbonate, sodium acetate, triethylamine, pyridine, 3-methylpyridine, 3, 5-dimethylpyridine and potassium hydrogencarbonate, and the molar ratio of the base to the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine is (1-2): 1.
8. the production method according to claim 1, wherein the 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine and the 2-amino-5-chloro-N, 3-dimethylbenzamide are reacted in the presence of a solvent selected from one or more of N, N-dimethylformamide, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, dichloroethane, toluene, N-methylpyrrolidone and chlorobenzene.
9. The method according to claim 1, wherein the CO pressure is controlled to be 0.5 to 20bar; and/or, the temperature of the reaction is 90-150 ℃; and/or the duration of the reaction is 10-15 h.
10. The preparation method according to any one of claims 1 to 9, characterized in that the specific steps of the preparation method are: n (N) 2 The 3-chloro-2- (3, 5-dibromo-1H-pyrazol-1-yl) pyridine, the 2-amino-5-chloro-N, 3-dimethylbenzamide, and the palladium catalyst are reacted in an autoclave under an atmosphereMixing the ligand, alkali and solvent, stirring, and passing through N 2 3 times of replacement, 3 times of replacement by the CO, heating reaction, and filtering after the reaction is finished to obtain the chlorantraniliprole.
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