CN117003731A - Preparation method of chlorantraniliprole or cyantraniliprole - Google Patents
Preparation method of chlorantraniliprole or cyantraniliprole Download PDFInfo
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- CN117003731A CN117003731A CN202210479157.1A CN202210479157A CN117003731A CN 117003731 A CN117003731 A CN 117003731A CN 202210479157 A CN202210479157 A CN 202210479157A CN 117003731 A CN117003731 A CN 117003731A
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- pyridine
- pyrazole
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- 239000005886 Chlorantraniliprole Substances 0.000 title claims abstract description 55
- 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 55
- 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 title claims abstract description 41
- 239000005889 Cyantraniliprole Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 53
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005859 coupling reaction Methods 0.000 claims abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008878 coupling Effects 0.000 claims abstract description 8
- 238000010168 coupling process Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 16
- 239000012320 chlorinating reagent Substances 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical group ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000007805 chemical reaction reactant Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003880 polar aprotic solvent Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 102000001424 Ryanodine receptors Human genes 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 108091052345 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- -1 pyridines) Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 102000034573 Channels Human genes 0.000 description 1
- 108091006146 Channels Proteins 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000329 smooth muscle myocyte Anatomy 0.000 description 1
- 210000002948 striated muscle cell Anatomy 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 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
Abstract
The application provides a preparation method of chlorantraniliprole or cyantraniliprole, which comprises the following steps: coupling 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxamide with an anthranilamide of formula (I) in the presence of an additive selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and combinations thereof to give a chlorantraniliprole or a cyantraniliprole of formula (II), wherein R is Cl or CN, and a solvent selected from the group consisting of acetonitrile, 1, 2-dioxane, tetrahydrofuran and combinations thereof, the coupling reaction temperature being 20 ℃ to the reflux temperature of the solvent, and the reaction system does not contain an alkaline substance.
Description
Technical Field
The application relates to a preparation method of chlorantraniliprole or cyantraniliprole.
Background
Chlorantraniliprole and cyantraniliprole are a class of efficient and selective ryanodine receptor inhibitor insecticides. The ryanodine receptor is a channel protein that controls the release of intracellular calcium ions. Chlorantraniliprole and cyantraniliprole cause the calcium ions stored in smooth muscle and striated muscle cells to be released without control until being exhausted by directly combining and activating ryanodine receptors in insects, thereby damaging the muscle movement regulation of the insects and causing paralysis of the insects until death.
WO03/015519A1 discloses a process for preparing chlorantraniliprole or cyantraniliprole comprising: 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid and aminobenzamide are reacted in the presence of methylsulfonyl chloride and pyridine to obtain chlorantraniliprole or cyantraniliprole, and the yield is 58% -65%.
However, there remains a need to develop alternatives for the preparation of chlorantraniliprole or cyantraniliprole in order to achieve the goals of environmental protection, cost saving, high yield, high purity and/or simple operation.
Disclosure of Invention
For this reason, through intensive studies, the inventors of the present application have proposed for the first time a method for preparing chlorantraniliprole or cyantraniliprole, which comprises the steps of:
coupling 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride with anthranilamide of formula (I) in the presence of additives and solvents to give chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the solvent is selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
In the prior art, long-term and general advocacy is that an alkaline substance is used as an acid binding agent to neutralize byproduct hydrochloric acid generated in the coupling reaction and form salt with reactants, so that the yield of the coupling reaction is improved.
Compared with the prior art, the application does not need to use basic compounds (such as pyridines), and the chlorantraniliprole and the cyantraniliprole can be obtained in high yield, high purity and low cost for the first time by adopting a small amount of specific additives.
The application also provides a method for preparing chlorantraniliprole or cyantraniliprole, which comprises the following steps:
i) Subjecting 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid to chlorination with a chlorinating agent in the presence of a solvent selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof to obtain a reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride,
II) coupling the reaction solution containing 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride with anthranilamide of formula (I) in situ in the presence of additives and the solvent to give chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
As described above, the present application eliminates the necessity of using basic compounds (e.g., pyridines) as compared with the prior art, and can obtain chlorantraniliprole and cyantraniliprole in high yield, high purity and low cost for the first time by using a small amount of specific additives. Furthermore, according to the present application, after the chlorination reaction of step i), the coupling reaction of step ii) is directly performed in situ without additional separation and purification of the reaction mixture of step i), and the operation is simple and cost-effective.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If there is a discrepancy, the definition provided by the present application controls.
Unless otherwise indicated, the numerical ranges set forth herein are intended to include the endpoints of the ranges, and all numbers and subranges within the range.
The materials, amounts, methods, apparatus, and examples herein are illustrative and, unless otherwise indicated, should not be construed as limiting.
The terms "comprising," "including," and "having," as used herein, are intended to include other components or steps that do not affect the end result. These terms encompass the meanings of "consisting of … …" and "consisting essentially of … …". Products and methods according to the present disclosure may include or incorporate the necessary features described in this disclosure, as well as additional and/or optional components, ingredients, steps, or other limiting features described herein; or may consist of the essential features described in this disclosure, as well as additional and/or optional components, ingredients, steps, or other restrictive features described herein; or consist essentially of the essential features described in this disclosure, as well as additional and/or optional components, ingredients, steps, or other limitations described herein.
All materials and reagents used in the present disclosure are commercially available unless explicitly indicated otherwise.
Unless indicated otherwise or clearly contradicted by context, the operations performed herein may be performed at room temperature and at atmospheric pressure.
As used herein, the term "about" means that the numerical value it defines can have a deviation within the range of ± 10% of the numerical value, e.g., the term "about 55 ℃ means the range of" 55 ± 5.5 ℃.
As used herein, the term "atmospheric pressure" refers to about 1 atmosphere (about 1013.25 hPa).
As used herein, the term "room temperature" refers to about 20 to about 25 ℃, preferably about 25 ℃.
Examples of the present disclosure will be described in detail below.
Preparation method of chlorantraniliprole or cyantraniliprole
In one aspect, the application provides a method for preparing chlorantraniliprole or cyantraniliprole, which comprises the following steps:
coupling 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride with anthranilamide of formula (I) in the presence of additives and solvents to give chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the solvent is selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
In some examples, 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride is added to the reaction system in the form of a solution dissolved in a solvent. The solvent is the same as or different from the solvent of the coupling reaction, preferably the same, to facilitate handling and purification of the product.
In some examples, 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride is added directly to the reaction system.
In some examples, the solvent for the coupling reaction is acetonitrile. Acetonitrile helps to increase the yield and/or purity of the product chlorantraniliprole or cyantraniliprole.
In some examples, the solvent is acetonitrile and the reaction temperature is from about 20 to about 80 ℃, preferably from about 35 to about 75 ℃, more preferably from about 50 to about 60 ℃, and most preferably about 55 ℃.
The preferred schemes, reaction conditions and operating conditions described hereinafter for the coupling reaction or "step ii)" apply to this embodiment unless otherwise indicated or clearly contradicted.
In another aspect, the present application provides a method for preparing chlorantraniliprole or cyantraniliprole, comprising the steps of:
i) Subjecting 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid to chlorination with a chlorinating agent in the presence of a solvent selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof to obtain a reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride,
II) subjecting the reaction solution containing 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride to a coupling reaction with an anthranilamide of formula (I) (hereinafter abbreviated as "anthranilamide") in situ in the presence of an additive and the solvent to give a chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
When R is Cl, the structural formula (II) is chlorantraniliprole, namely the structural formula (II-A); when R is CN, the formula (II) is the structural formula of cyantraniliprole, namely the formula (II-B).
The inventors of the present application have found for the first time that the yield of the product chlorantraniliprole or cyantraniliprole can be unexpectedly improved by adding specific additives in the coupling reaction.
In the present application, in situ reaction means that the reaction solution obtained in step i) is distilled only to remove the excessive solvent, and can be directly used in step ii) without additional separation and purification.
The reaction starting materials 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid and anthranilamide are both in solid form. Thus, the dissolution of these reaction starting materials with a solvent allows both the coupling reaction and optionally the chlorination reaction to be carried out in the liquid phase, in order to increase the solubility and conversion of the reaction starting materials.
In step ii) and step i), the same or different solvents, preferably the same solvents, may be used, thereby simplifying the isolation and purification and increasing the purity of the final product.
In step ii) and optionally step i), the reaction is carried out at a temperature of 20 ℃ to the reflux temperature of the solvent, facilitating handling, thereby increasing the reaction rate, selectivity and/or yield.
In some examples, the chlorinating agent is thionyl chloride or has the general formula XS (O) 2 Cl compound, X is C 1 -C 4 Alkyl, C 1 -C 2 Haloalkyl, or optionally substituted with 1 to 3 groups selected from halogen, C 1 -C 3 Phenyl substituted by substituents of alkyl and nitro. Preferably, the chlorinating agent is one or more of thionyl chloride, methanesulfonyl chloride, propanesulfonyl chloride, benzenesulfonyl chloride and p-toluenesulfonyl chloride. More preferably, inexpensive and environmentally friendly thionyl chloride is used as chlorinating agent.
In some examples, in step i), the molar ratio of chlorinating agent to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid is from about 1:1 to about 1.3:1.
In some examples, in step i), the solvent and the chlorinating agent are added sequentially to the 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, or the chlorinating agent and the solvent are added simultaneously to the 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid.
In some examples, in step i), the chlorination reaction is carried out with stirring.
In some examples, in step i), the weight of the solvent is from about 2 to about 10 times, preferably from about 4 to about 8 times, more preferably from about 6 to about 7 times the weight of the 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid.
In some examples, in step i), the solvent is acetonitrile and the reaction temperature is from about 20 to about 80 ℃, preferably from about 35 to about 75 ℃, more preferably from about 50 to about 60 ℃, most preferably about 55 ℃.
In some examples, in step i), the reaction time is from about 1 hour to about 5 hours, preferably from about 3 hours to about 4 hours.
In some examples, step i) is performed at atmospheric pressure.
In some examples, step ii) is performed at atmospheric pressure.
In some examples, prior to performing step ii), further comprising distilling the reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride under reduced pressure.
In some examples, prior to step ii), reduced pressure distillation is performed at a reaction temperature of step i) to a temperature about 10 ℃ below the reaction temperature of step i) and an internal pressure of 10hPa to 500hPa to remove solvent.
In some examples, prior to step ii), distillation under reduced pressure is performed at an internal temperature of about 55 ℃ and an internal pressure of about 80hPa to remove acetonitrile as a solvent.
In some examples, in step ii), the reaction system comprises a basic substance.
In some examples, the basic substance includes an inorganic substance, such as an alkali metal or alkaline earth metal carbonate or bicarbonate; and organic substances such as tertiary amines, in particular pyridine and its derivatives, for example pyridine, 2-methylpyridine, 3-methylpyridine and 2, 6-dimethylpyridine.
In some examples, in step ii), the reaction system does not contain an alkaline substance.
According to the present application, the basic material is no longer necessary for the coupling reaction, nor is the presence or absence of the basic material significantly affected by the outcome of the coupling reaction (e.g., product yield and/or product purity).
In some examples, in step ii), the solvent and the additive are added sequentially to the anthranilamide, or the additive and the solvent are added sequentially to the anthranilamide, or the solvent and the additive are added simultaneously to the anthranilamide.
In some examples, in step ii), the coupling reaction is performed with stirring.
In some examples, in step ii), the reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride is added, preferably dropwise, to a mixture of the anthranilamide of formula (I), the solvent and the additive.
In some examples, in step ii), the additive is N, N-dimethylformamide or N, N-dimethylacetamide.
In some examples, in step i) and step ii), the solvent is acetonitrile. Acetonitrile helps to increase the yield and/or purity of the product chlorantraniliprole or cyantraniliprole.
In some examples, in step ii), the solvent is acetonitrile and the reaction temperature is from about 20 to about 80 ℃, preferably from about 35 to about 75 ℃, more preferably from about 50 to about 60 ℃, most preferably about 55 ℃.
In some examples, the molar ratio of anthranilamide of formula (I) to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid is from about 0.9:1 to about 1.1:1, preferably from about 1:1 to about 1.05:1, for example, from about 1:1, about 1.01:1, about 1.02:1, about 1.03:1, about 1.04:1, or about 1.05:1, more preferably from about 1.02:1 to about 1.03:1, and most preferably about 1.03:1. Under the molar ratio, the expensive raw material 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid can be completely reacted, the anthranilamide of the formula (I) can not be wasted, and good balance between economic cost and yield is realized.
In some examples, in step ii), the additive is used in an amount of about 10 wt% to about 50 wt%, preferably about 10 wt% to about 30 wt%, for example about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt% and about 50 wt% of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid. In the dosage range of the additive, the reaction yield can be effectively improved, and the difficulty of purifying the product is not increased due to the introduction of excessive additive.
In some examples, in step ii), the solvent is about 2 to about 10 times, preferably about 4 to about 8 times, more preferably about 6 to about 7 times the weight of the 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid.
In some examples, in step ii), the reaction time is from about 0.5 hours to about 2 hours, preferably about 1 hour.
In some examples, after step ii) is performed, a post-treatment step iii) is further included: separating and purifying chlorantraniliprole or cyantraniliprole.
In some examples, after performing step ii), post-treatment step iii) comprises: the reaction system is allowed to naturally cool to room temperature, water is added dropwise in an amount of about 0.2 to about 1.5 times the weight of the solvent in the coupling reaction of step ii), and then filtered and dried. Water was added dropwise to the reaction solution to facilitate precipitation of the product. The amount of water added dropwise is about 0.2 to about 1.5 times, preferably about 0.5 to about 0.7 times or about 0.8 to about 1.2 times, for example about 0.2 times, about 0.29 times, about 0.33 times, about 0.36 times, about 0.42 times, about 0.5 times, about 0.57 times, about 0.64 times, about 0.66 times, about 0.7 times, about 0.71 times, about 0.75 times, about 0.8 times, about 0.83 times, about 0.86 times, about 1 times, about 1.14 times, about 1.2 times, about 1.33 times or about 1.5 times, preferably about 0.57 times, about 0.64 times, about 0.75 times, about 0.83 times, about 1 times or about 1.14 times the weight of the solvent in the coupling reaction of step ii). When the amount of water added dropwise to the reaction system is within the above-mentioned range, a good balance between the yield and purity of the product can be achieved.
In some examples, in step iii), the temperature of the water added dropwise to the reaction system is room temperature, e.g., about 20 to about 25 ℃.
In some examples, in step iii), the water added dropwise to the reaction system is tap water or deionized water.
When the product of formula (II) is chlorantraniliprole (II-a), the weight of water added dropwise to the reaction system after performing step II) is preferably from about 0.2 to about 1.0, preferably from about 0.5 to about 0.7 times the weight of the solvent in the coupling reaction of step II).
When the product of formula (II) is cyantraniliprole (II-B), the weight of water added dropwise to the reaction system after carrying out step II) is preferably from about 0.2 to about 1.5 times, preferably from about 0.8 to about 1.2 times the weight of the solvent in the coupling reaction of step II).
In some examples, the present application provides a method of preparing chlorantraniliprole comprising the steps of:
i) Subjecting 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid and thionyl chloride to chlorination reaction in the presence of acetonitrile at a molar ratio of about 1:1 to 1:1.3 at a temperature of about 50 to about 60 ℃ to obtain a reaction solution containing 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride, wherein acetonitrile is about 4 to 5 times by weight as much as 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, distillation under reduced pressure, and
II) coupling the reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid chloride in situ with an anthranilamide of formula (I-A) in the presence of acetonitrile and DMF or DMAc and at a temperature of about 50 to about 60℃to give a chlorantraniliprole of formula (II-A), wherein the molar ratio of anthranilamide to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid is about 1:1 to about 1.05:1, the weight of acetonitrile is about 4 to 5 times the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, and the weight of DMF or DMAc is about 10 to about 50% by weight of the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid
And iii) allowing the reaction system to naturally cool to room temperature, and dropping water in an amount of about 0.2 to about 1.0 times, preferably about 0.5 to about 0.7 times the weight of acetonitrile in step ii) into the reaction system.
And then filtered and dried.
In some examples, the present application provides a method of preparing cyantraniliprole comprising the steps of:
i) Subjecting 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid and thionyl chloride to chlorination reaction in the presence of acetonitrile at a molar ratio of about 1:1 to 1:1.3 at a temperature of about 50 to about 60 ℃ to obtain a reaction solution containing 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride, wherein acetonitrile is about 4 to 5 times by weight as much as 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, distillation under reduced pressure, and
II) coupling the reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid chloride with anthranilamide of formula (I-B) in situ in the presence of acetonitrile and DMF or DMAc at a temperature of about 50 to about 60℃to give cyantraniliprole of formula (II-B), wherein the molar ratio of anthranilamide to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid is about 1:1 to about 1.05:1, the weight of acetonitrile is about 4 to 5 times the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, and the weight of DMF or DMAc is about 10 to about 50% by weight of the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid
iii) The reaction system is allowed to naturally cool to room temperature and water is added dropwise in an amount of about 0.2 to about 1.5 times, preferably about 0.8 to about 1.2 times the weight of acetonitrile in step ii).
Is then filtered and dried.
It is noted that the following examples are only for illustrative purposes and are not intended to limit the present application.
In the following examples, high performance liquid chromatography was used to measure the relative amounts of the ingredients in the final product.
Synthesis example 1 (examples 2-12): preparation of Chlorantraniliprole ("Compound II-A")
Step i) to a three-necked flask, 20g (0.0661 mol,1.0 eq) of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, 80g of acetonitrile and 10.2g (0.0859 mol,1.3 eq) of thionyl chloride were added, and the mixture was heated to an internal temperature of 55℃to react until the reaction solution became clear, and the reaction solution was allowed to stand for about 3 to 4 hours. Excess acetonitrile was removed by distillation under reduced pressure at about 80hPa, and the internal temperature was 55℃by distillation under reduced pressure to give 60g of a brown liquid.
Step ii) to a four-necked flask, 13.8g (0.0694 mol,1.05 eq) of anthranilamide of the formula (I-A), 120g of acetonitrile and 2g of DMAc were charged, warmed to an internal temperature of 55℃and stirred for 20min. The brown liquid obtained in the step i) is dripped into a four-necked flask, the dripping temperature is 55-60 ℃, and the dripping lasts for about 1.0h. After the completion of the dropwise addition, the internal temperature was maintained at 55℃for 1 hour. Naturally cooling to room temperature, and dripping 80g of water (water temperature 25 ℃). After the completion of the dropwise addition, the mixture was stirred at 25℃for 2 hours. The filter cake was filtered, rinsed with 160g of water and dried under vacuum at 70℃to give 30.3g of chlorantraniliprole as a white solid (compound II-A).
As shown in table 1, the coupling reaction conditions were changed and the reaction results were recorded.
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In Table 1, the column "reaction liquid (215 nm)" indicates the reaction liquid after the completion of the coupling reaction and when water crystallization has not been added yet; 215nm represents the liquid phase detection wavelength. The column "product content" indicates the content of each component in the precipitated product after crystallization by adding water. Unless otherwise indicated or clearly contradicted, references to yield, purity (i.e., product content) and absolute yield hereinafter refer to yield, purity and absolute yield after water addition crystallization.
As can be seen from Table 1, in examples 1-1, examples 1-2 and examples 1-4, when N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP) as a polar aprotic solvent containing nitrogen was used as an additive, the yield of chlorantraniliprole was higher than 94% and the absolute yield was higher than 91.5%. In examples 1-3 and examples 1-5, both the yield and absolute yield of chlorantraniliprole were significantly reduced when using the polar aprotic solvent containing sulfur, dimethyl sulfoxide (DMSO) or sulfolane (TMSO) as an additive.
In examples 2-4 and examples 2-5, the yield of chlorantraniliprole can be significantly improved by using a relatively large amount of N, N-dimethylacetamide (DMAc) as a solvent and an additive, but DMAc is not easily removed, and the purity of the product is affected by the excessive residual DMAc contained in the product chlorantraniliprole. In examples 2 to 6, when DMAc was used in an amount of 50% by weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA), the residual DMAc content in the product chlorantraniliprole was reduced to 0.21%.
In examples 2 to 7 and examples 2 to 8, the yield (94.5% yield before crystallization by adding water) of the reaction starting material chlorantraniliprole was significantly higher than the yield (89.1% yield before crystallization by adding water) of 1.02:1 in terms of the equivalent ratio of chlorantraniliprole to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA) than in terms of the equivalent ratio of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA).
In examples 2 to 7, after the coupling reaction was completed, the reaction solution was not added dropwise with water, but was cooled directly to 0℃and then filtered, and the yield was only 87.8%, demonstrating that adding an appropriate amount of water dropwise to the reaction solution significantly improved the final yield of the product.
In examples 2 to 12, examples 2 to 13, examples 2 to 14 and examples 2 to 15, after the end of the coupling reaction, water was added dropwise to the reaction system in an amount of 0.63 times, 0.57 times, 0.64 times and 0.71 times the weight of acetonitrile in the coupling reaction, respectively, the yield of chlorantraniliprole was higher than 93%, the absolute yield was higher than 91.5% and the purity was higher than 96%. In particular, in examples 2 to 14, water was added dropwise to the reaction system in an amount of 0.64 times by weight of acetonitrile in the coupling reaction, the yield of chlorantraniliprole was as high as 95.4%, the absolute yield was as high as 93.11%, the purity was as high as 97.6%, and it was confirmed that water of 0.64:1: the mass ratio of acetonitrile is more conducive to improving the yield and purity of chlorantraniliprole.
In examples 2-14, examples 2-18, examples 2-19 and examples 2-20, respectively, different coupling reaction temperatures were used: absolute yields of chlorantraniliprole were 93.11%, 90.99%, 92.24% and 92.53% at 55 ℃, 15 ℃,35 ℃ and 75 ℃, respectively. It can be seen that the preferred reaction temperature range is 35-75deg.C, with an optimum reaction temperature around 55deg.C.
In examples 2-13, examples 2-16 and examples 2-17, respectively, different coupling reaction temperatures were used: absolute yields of chlorantraniliprole were 92.91%, 88.81% and 89.94% at 55 ℃,30 ℃ and 75 ℃, respectively. It can be seen that about 55℃is the preferred reaction temperature.
In examples 2-17 and examples 2-20, the coupling reaction temperature was 75 ℃, the weight of water added dropwise to the reaction system was 0.57 and 0.64 times the weight of acetonitrile in the coupling reaction, the yields of chlorantraniliprole were 93.2% and 95.1%, respectively, the absolute yields were 89.94% and 92.53, respectively, demonstrating 0.64:1 water: the mass ratio of acetonitrile is more conducive to improving the yield and purity of chlorantraniliprole.
In examples 2-14, 4-2, 4-3 and 4-4, the amount of DMAc used was 10%, 20%, 30% and 50% by weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA), respectively, the yields of chlorantraniliprole were higher than 95% and the absolute yields were higher than 92.5%, respectively.
The preferred amount of additive is shown to be 10% to 50% by weight, preferably 10% to 30% by weight, based on the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA), with 30% by weight being the optimum amount of additive for both yield and purity, and 10% by weight being the cost-effective amount of additive for both yield, purity and economy.
In example 4-1, without the use of additives, the yield of chlorantraniliprole was reduced to 93.1% and the absolute yield was reduced to 89.75%. Example 4-1 demonstrates that not all polar aprotic solvents added help to increase the yield of the coupling reaction compared to examples 1-3 and examples 1-5, and further demonstrates that the nitrogen-containing polar aprotic solvents selected in accordance with the present application provide a significant improvement in product yield.
In examples 4-5, DMAc was used as both solvent and additive, and DMF at 2.5% by weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid (KA) was used as additive, with yields of chlorantraniliprole as high as 98.7%, however, excessive DMAc remained in chlorantraniliprole, resulting in purity of chlorantraniliprole of only 94.3%.
Synthesis example 2 (examples 3-4): preparation of cyantraniliprole (Compound II-B)
Step i) to a three-necked flask, 20g (0.0661 mol,1.0 eq) of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid, 80g of acetonitrile and 10.2g (0.0859 mol,1.3 eq) of thionyl chloride were added, and the mixture was heated to an internal temperature of 55℃to react until the reaction solution became clear, and the reaction solution was allowed to stand for about 3 to 4 hours. Excess acetonitrile was removed by distillation under reduced pressure at about 80hPa, and the internal temperature was 55℃by distillation under reduced pressure to give 50g of a brown liquid.
Step ii) to a four-necked flask, 12.5g (0.0661 mol,1.0 eq) of anthranilamide of the formula (I-B), 140g of acetonitrile and 2g of DMAc were charged, warmed to an internal temperature of 55℃and stirred for 20min. The brown liquid obtained in the step i) is dripped into a four-necked flask, the dripping temperature is 55-60 ℃, and the dripping time is about 1.0h. After the completion of the dropwise addition, the internal temperature was maintained at 55℃for 1 hour. Naturally cooling to room temperature, and dripping 100g of water (water temperature 25 ℃). After the completion of the dropwise addition, the mixture was stirred at 25℃for 2 hours. The filter cake was rinsed with 100g of water and dried in vacuo at 70℃to give 28.6g of cyantraniliprole (Compound II-B) as an off-white solid.
As shown in table 2, the coupling reaction conditions were changed and the reaction results were recorded.
As can be seen from Table 2, the use of DMAc as an additive in the coupling reaction improves both the yield and absolute yield of cyantraniliprole in examples 3-4 compared to example 3-1, examples 3-5 compared to example 3-2, and examples 3-6 compared to example 3-3.
In examples 3 to 4, examples 3 to 5, examples 3 to 6 and examples 3 to 7, the weight of water added dropwise to the reaction system was 0.71 times, 0.86 times, 1 time and 1.14 times, respectively, the weight of acetonitrile in the coupling reaction, and the amounts of water of 1 time and 1.14 times were found to be more conducive to improving the yield and purity of cyantraniliprole.
Examples 3-8 compared to examples 3-6, examples 3-9 compared to examples 3-7, the yield and purity of cyantraniliprole were reduced when DMF was added as an additive in addition to DMAc.
Various modifications of the application, in addition to those described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. Each reference cited in this disclosure (including all patents, patent applications, journal articles, books, and any other publications) is hereby incorporated by reference in its entirety.
Claims (10)
1. The preparation method of chlorantraniliprole or cyantraniliprole comprises the following steps:
coupling 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride with anthranilamide of formula (I) in the presence of additives and solvents to give chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the solvent is selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
2. The preparation method of chlorantraniliprole or cyantraniliprole comprises the following steps:
i) Subjecting 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid to chlorination with a chlorinating agent in the presence of a solvent selected from acetonitrile, 1, 2-dioxane, tetrahydrofuran, and combinations thereof to obtain a reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride,
II) coupling the reaction solution containing 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride with anthranilamide of formula (I) in situ in the presence of additives and the solvent to give chlorantraniliprole or cyantraniliprole of formula (II)
Wherein R is Cl or CN,
the additive is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and combinations thereof, and
the temperature of the coupling reaction is about 20 ℃ to the reflux temperature of the solvent.
3. The method of claim 1 or 2, wherein the additive is N, N-dimethylformamide or N, N-dimethylacetamide.
4. A process according to claim 2 or 3, wherein in steps i) and ii) the solvent is acetonitrile and
the reaction temperatures of step i) and step ii) are the same or different and are independently from each other about 20 to about 80 ℃, preferably about 35 to about 75 ℃, more preferably about 50 to about 60 ℃, most preferably about 55 ℃.
5. The process according to any one of claims 2-4, wherein in step ii) the molar ratio of anthranilamide of formula (I) to 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid is from about 0.9:1 to about 1.1:1, preferably from about 1:1 to about 1.05:1, more preferably from about 1.02:1 to about 1.03:1.
6. The method of any of claims 2-5, wherein the additive is used in an amount of about 10 wt.% to about 50 wt.%, preferably about 10 wt.% to 30 wt.% of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid.
7. The process according to any one of claims 2-6, wherein in step ii) the weight of the solvent is about 2 to about 10 times, preferably about 4 to about 8 times, more preferably about 6 to about 7 times the weight of 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carboxylic acid.
8. The process of any one of claims 2-7, wherein prior to performing step ii), further comprising distilling the reaction solution comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride from step i) under reduced pressure.
9. The method according to any one of claims 2-8, wherein after performing step ii), further comprising a post-treatment step iii): separating and purifying the product chlorantraniliprole or cyantraniliprole,
preferably, the post-treatment step iii) comprises: naturally cooling the reaction system to room temperature, adding dropwise water in an amount of about 0.2 to about 1.5 times, preferably about 0.5 to about 0.7 times or about 0.8 to about 1.2 times the weight of the solvent in the coupling reaction of step ii), filtering, and drying.
10. The process according to any one of claims 2-9, wherein in step ii) a reaction liquid comprising 3-bromo-1- (3-chloro-2-pyridine) -1H-pyrazole-5-carbonyl chloride is added dropwise to a mixture of anthranilamide of formula (I), the solvent and the additive.
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