CN114874185A - Method for preparing o-formamido benzamide compound - Google Patents
Method for preparing o-formamido benzamide compound Download PDFInfo
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- CN114874185A CN114874185A CN202210269777.2A CN202210269777A CN114874185A CN 114874185 A CN114874185 A CN 114874185A CN 202210269777 A CN202210269777 A CN 202210269777A CN 114874185 A CN114874185 A CN 114874185A
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- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 benzamide compound Chemical class 0.000 title claims abstract description 20
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003222 pyridines Chemical class 0.000 claims abstract description 11
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- YVILNCAQKXEOFG-UHFFFAOYSA-N 1,2,4-trimethyl-2h-pyridine Chemical compound CC1C=C(C)C=CN1C YVILNCAQKXEOFG-UHFFFAOYSA-N 0.000 claims description 4
- HOPRXXXSABQWAV-UHFFFAOYSA-N 2,3,4-trimethylpyridine Chemical compound CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N alpha-methylpyridine Natural products CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- AWQZNAYKKKFWHS-UHFFFAOYSA-N 1,2,5-trimethyl-2h-pyridine Chemical compound CC1C=CC(C)=CN1C AWQZNAYKKKFWHS-UHFFFAOYSA-N 0.000 claims description 2
- FELIUMMSTCKVHC-UHFFFAOYSA-N CC1N(C)C=CC=C1C Chemical compound CC1N(C)C=CC=C1C FELIUMMSTCKVHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical class NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims 1
- RSAIIBFKUJGUQI-UHFFFAOYSA-N 2-methylpyridine Chemical group [CH2]C1=CC=CC=N1 RSAIIBFKUJGUQI-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000000575 pesticide Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 150000003936 benzamides Chemical class 0.000 abstract 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000005886 Chlorantraniliprole Substances 0.000 description 5
- 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 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- DGDAVTPQCQXLGU-UHFFFAOYSA-N 5437-38-7 Chemical compound CC1=CC=CC(C(O)=O)=C1[N+]([O-])=O DGDAVTPQCQXLGU-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- VSFYTPXXMLJNAU-UHFFFAOYSA-N methyl 2-amino-3-methylbenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1N VSFYTPXXMLJNAU-UHFFFAOYSA-N 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RWLPKYJTGUCBQH-UHFFFAOYSA-N 2-amino-5-bromo-3-methylbenzoic acid Chemical compound CC1=CC(Br)=CC(C(O)=O)=C1N RWLPKYJTGUCBQH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LFXSHFHOJMKZDE-UHFFFAOYSA-N 2-formamidobenzamide Chemical compound NC(=O)C1=CC=CC=C1NC=O LFXSHFHOJMKZDE-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000007098 aminolysis reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CEAJFNBWKBTRQE-UHFFFAOYSA-N methanamine;methanol Chemical compound NC.OC CEAJFNBWKBTRQE-UHFFFAOYSA-N 0.000 description 2
- NVJKMGDNYCDLGR-UHFFFAOYSA-N methyl 2-amino-5-bromo-3-methylbenzoate Chemical compound COC(=O)C1=CC(Br)=CC(C)=C1N NVJKMGDNYCDLGR-UHFFFAOYSA-N 0.000 description 2
- BOYQWVQNPIZDPU-UHFFFAOYSA-N methyl 2-amino-5-chloro-3-methylbenzoate Chemical compound COC(=O)C1=CC(Cl)=CC(C)=C1N BOYQWVQNPIZDPU-UHFFFAOYSA-N 0.000 description 2
- UHFVZQIOQVEYQM-UHFFFAOYSA-N methyl 2-amino-5-cyano-3-methylbenzoate Chemical compound COC(=O)C1=CC(C#N)=CC(C)=C1N UHFVZQIOQVEYQM-UHFFFAOYSA-N 0.000 description 2
- NJHDBIXFFZVJGZ-UHFFFAOYSA-N methyl 3-methyl-2-nitrobenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1[N+]([O-])=O NJHDBIXFFZVJGZ-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WNAJXPYVTFYEST-UHFFFAOYSA-N 2-Amino-3-methylbenzoate Chemical compound CC1=CC=CC(C(O)=O)=C1N WNAJXPYVTFYEST-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- MOXMPWAWQLBNGS-UHFFFAOYSA-N 5-bromo-2-(3-chloropyridin-2-yl)pyrazole-3-carbonyl chloride Chemical compound ClC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl MOXMPWAWQLBNGS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005889 Cyantraniliprole Substances 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 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 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a method for preparing o-formamido benzamide compounds, in particular to a method for preparing o-formamido benzamide pesticide compounds by reacting benzoate compounds with pyridyl substituted pyrazole acyl chloride compounds in the presence of optionally substituted pyridine compounds and then carrying out ammonolysis reaction. The invention improves the yield and purity of the product by adopting the optionally substituted pyridine compound, has the advantages of simple route operation, relatively uniform solvent and low cost, realizes less three wastes production and stable process, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a method for preparing an o-formamido benzamide compound.
Background
The DuPont successfully developed an o-formamidobenzamide pesticide in 2000, which not only has good activity to lepidoptera pests, but also has good activity to specific diptera pests, has wide application space and huge market prospect, and the representative compound chlorantraniliprole in the pesticide is the first pesticide in the global sales.
Two intermediates for synthesizing chlorantraniliprole are mainly 2-amino-5-chloro-3-methylbenzoic acid (intermediate I) containing an aromatic ring structure and 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid (intermediate II) containing a pyrazole ring structure. The existing synthesis methods mainly comprise the following steps:
the first method is to take anthranilic acid as a raw material, carry out oximation, cyclization, oxidation, ammonolysis and chlorination to obtain an intermediate I, and then carry out ammonolysis with the intermediate II to obtain chlorantraniliprole. The starting raw materials of the route are cheap and easy to obtain, but oximation and cyclization cause a large amount of waste salt wastewater, the total yield is only about 26%, and the total cost is high. A specific synthetic route is shown as the following formula:
the second method is to take 2-nitro-3-methyl benzoic acid as raw material and carry out H reaction 2 Reduction, chlorination of sulfonyl chloride, cyclization of phosgene, aminolysis of a methylamine water solution to obtain an intermediate 2-amino-5-chloro-N, 3-dimethylbenzamide, and amidation reaction of the intermediate II with methanesulfonyl chloride and an acid-binding agent, namely 3-methylpyridine to obtain chlorantraniliprole. The method has the advantages of good yield, large solvent consumption, frequent replacement and complicated post-treatment:
disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a method for preparing anthranilic acid diamide compounds, which has the advantages of cheap raw materials, simple and convenient post-treatment operation and mild reaction conditions.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing o-formamido-benzamide compounds, which comprises reacting a compound of formula III with a compound of formula IV in the presence of an optionally substituted pyridine compound to obtain a compound of formula II, and performing an ammonolysis reaction to obtain a compound of formula I:
in the formula, R 1 、R 2 、R 3 、R 4 Each independently represents H, halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl or C 1 -C 6 Alkoxy radical, R 5 Is represented by C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 Alkyl, X represents C 1 -C 6 Alkyl and Y represents halogen.
Further, the reaction of formula III with the compound of formula IV is carried out in a solvent; the solvent is one or more of chloroform, dichloroethane, acetonitrile, tetrahydrofuran and toluene.
Still further, the feeding molar ratio of the compound of formula III to the compound of formula IV is 1: 1.0 to 1.05;
still further, the compound of formula IV and the optionally substituted pyridine compound are fed in a molar ratio of 1:1 to 2.3.
Further, the reaction temperature of the reaction of the compound of the formula III and the compound of the formula IV is 10-40 ℃; the amidation reaction time is 1-3 h.
Further, the optionally substituted pyridine compound is unsubstituted pyridine or substituted pyridine, and the substituted pyridine is substituted by 1 to 3C 1 -C 6 Alkyl substituent substituted pyridines.
Further, the quilt has 1-3C 1 -C 6 The alkyl substituent substituted pyridine is any one of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 6-dimethylpyridine, 1,2, 3-trimethylpyridine, 1,2, 4-trimethylpyridine, 1,2, 5-trimethylpyridine, 2,3, 4-trimethylpyridine or 1,2, 4-trimethylpyridine.
Further, the ammonolysis reaction is a reaction in a methanol solution of monomethylamine or a reaction in an ethanol solution of ethylamine.
Further, the reaction temperature of the ammonolysis reaction is 45-80 ℃; the reaction time of the ammonolysis reaction is 1-3 h.
Still further, the feeding molar ratio of the compound shown in the formula II to monomethylamine or ethylamine is 1: 1-1.3.
Further, the preparation route of the compound of formula III is as follows:
further, when R is 3 When Cl, the compound of formula III is prepared by reacting a III' compound with SO 2 Cl 2 The compound is prepared by reaction.
And further, 3-methyl-2-nitrobenzoic acid is taken as a raw material, and is subjected to acyl chlorination reaction and esterification reaction to obtain 3-methyl-2-nitrobenzoic acid methyl ester, reduction reaction is carried out to obtain 2-amino-3-methylbenzoic acid methyl ester, and chlorination reaction or cyanidation reaction is carried out to obtain 2-amino-5-chloro-3-methylbenzoic acid methyl ester.
Further, the reaction temperature of the acyl chlorination reaction is 50-80 ℃, and the reaction time is 0.5-1 h; the esterification reaction temperature is 25-50 ℃, and the reaction time is 1-3 h.
Furthermore, the solvent is one or more of chloroform, dichloroethane, acetonitrile, tetrahydrofuran and toluene;
the acyl chlorination reagent is PCl 3 、SOCl 2 One of MSCl;
the alcohol is one of methanol, ethanol, isopropanol and n-butanol;
the feeding molar ratio of the 3-methyl-2-nitrobenzoic acid to the acyl chlorination reagent to the alcohol is 1: 1-1.3: 1 to 1.2.
Further, the reduction reaction is carried out on 2-nitro-3-methyl benzoate and hydrogen in methanol under the condition of a catalyst, and the catalyst is 5-10% of palladium carbon.
Furthermore, the feeding mass ratio of the 2-nitro-3-methyl benzoate to the palladium carbon is 1: 0.005-0.01; the hydrogen pressure is 0.5MPa to 1.6 MPa; the reaction temperature of the reduction reaction is 50-100 ℃; the reaction time of the reduction reaction is 3-9 h.
Still further, the chlorination reaction is carried out in a solvent.
Furthermore, the solvent is one or more of chloroform, dichloroethane, acetonitrile, tetrahydrofuran and toluene;
the chlorination reagent is one or more of chlorine, sulfonyl chloride and NCS;
the chlorination temperature is-5 ℃ to 20 ℃; the mass of the solvent and the 2-amino-5-chloro-3-methylbenzoate is 5-12 times.
Still further, the cyanation reaction is carried out in a solvent.
Still further, the cyanidation reaction solvent is a glacial acetic acid aqueous solution.
Still further, the cyanidation reaction step specifically comprises: dropwise adding 40% hydrobromic acid into a glacial acetic acid aqueous solution of 40-60%, heating to 30 ℃ after dropwise adding, dropwise adding 30% hydrogen peroxide, reacting for 15min, adjusting the pH to 5-6 by alkali, filtering, washing with water, and drying to obtain 2-amino-5-bromo-3-methylbenzoate; adding 2-amino-5-bromo-3-methylbenzoate, N-methylpyrrolidone and cuprous cyanide at room temperature, stirring, heating, refluxing for 3-5 h, naturally cooling, adding 15% ammonia water and 3 times of dichloroethane, stirring, separating liquid, and desolventizing an organic layer to obtain a yellow solid product.
Further, the preparation route of the compound of formula IV is as follows:
further, the compound of formula IV is prepared by reacting IV' with SO 2 Y 2 The compound is prepared by reaction.
Further, in the formula (I), the,
R 1 is selected from CH 3 A group of compounds selected from the group consisting of Cl and Br,
R 2 is a compound of formula (I) in the formula (H),
R 3 is Cl or CN, and can be used as a catalyst,
R 4 is H, F or OCH 3 ，
R 5 Represents CH 3 Or
X represents CH 3 Or CH 2 CH 3 ，
Y represents Cl.
Further, in the formula (I), the,
R 1 is CH 3 ，R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is CH 3 ，R 2 Is H, R 3 Is CN, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is F, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is OCH 3 ，R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Br, R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is composed of
X is CH 3 And Y is Cl.
Due to the adoption of the technology, compared with the prior art, the invention has the remarkable advantages that:
1) the invention adopts pyridine and substitutes as organic base, and compared with inorganic base, the pyridine-organic acid-binding agent has the effects of acid-binding agent, reaction temperature reduction and impurity generation inhibition; meanwhile, pyridine and substitutes can play a catalytic role in the reactions of acid anhydride cyclization, hydrolysis, esterification and the like.
2) In the invention, the methyl alcohol or ethanol solution of methylamine is adopted in the aminolysis reaction, and a proper amount of sodium alkoxide is added to accelerate the reaction speed; the problem that acetonitrile is a solvent and is easy to generate impurities in a high-temperature alkaline system is avoided, and the cost of the acetonitrile is high.
Detailed Description
For a better understanding of the present invention, the present invention is described in further detail below with reference to specific embodiments. These examples are provided to illustrate the main reactions and essential features of the present invention, and are not limited by the following embodiments, and the implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not mentioned are generally the conditions in routine experiments.
The present invention will be further illustrated by the following description of examples in conjunction with the accompanying drawings.
Example 1
1) Synthesis of methyl 2-nitro-3-methylbenzoate:
36.9g of 2-nitro-3-methylbenzoic acid and 110.8g of dichloroethane were charged in a four-necked flask, the mixture was heated to 50 ℃ with stirring, and 28.6g of SOCl was slowly added dropwise 2 After the dropwise addition is finished within 0.5h, heating to 65 ℃, preserving heat for 0.5h, cooling to 40 ℃ after the reaction of the raw materials is finished, beginning to dropwise add 7.8g of methanol, after the dropwise addition is finished within 0.5h, preserving heat for 1.5h, desolventizing under negative pressure after the reaction is finished, and adding 158g of methanol for later use.
2) Synthesis of methyl 2-amino-3-methylbenzoate:
transferring the product solution obtained in the step (1) into a hydrogenation kettle, adding 0.2g of 10% palladium carbon, closing the hydrogenation kettle, replacing the nitrogen for 3 times, introducing 0.5MPa hydrogen, starting stirring, heating to 60 ℃, reacting for 5 hours, filtering while the reaction is hot after the reaction is finished, distilling the filtrate under reduced pressure to obtain 32.1g of 2-amino-3-methyl benzoate, determining the purity by HPLC (high performance liquid chromatography) to be 98.7%, and combining the two steps to obtain the yield of 94.2%.
3) Synthesis of methyl 2-amino-5-chloro-3-methylbenzoate:
putting 30g of methyl 2-amino-3-methylbenzoate into a four-mouth bottle, adding 150g of dichloroethane, stirring and dropwise adding sulfonyl chloride at 5-10 ℃, heating to 30 ℃ after dropwise adding is completed for 3 hours, keeping the temperature for 1 hour, filtering after the reaction is completed, and washing a filter cake with 30g of dichloroethane and storing for later use. The product of this step was dried to yield 86.4g with 98.6% purity by HPLC and 97.1% yield.
4) Synthesis of 3-bromo-1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid chloride:
61.7g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid and 250g of dichloroethane were charged in a four-necked flask, stirred and heated to 50 ℃ and 28.6g of SOCl was slowly added dropwise 2 After 0.5h of dropwise addition, heating to 65 ℃ and preserving heat for 0.5h, and after the reaction of the raw materials is finished, removing residual SOCl in the system under negative pressure 2 HCl and SO 2 261g of reaction solution was obtained and stored for further use.
5) Synthesis of 3-bromo-N- [ 4-chloro-2-methyl-6- ((oxy) carbonyl) phenyl ] -1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-amide:
putting wet 2-amino-5-chloro-3-methyl benzoate powder into a dry four-neck flask, adding 100g of dichloroethane for uniform dispersion, after detecting that the water content is qualified, adding 35g of 3-methylpyridine, cooling to 10 ℃, slowly dripping 261g of the reaction solution containing 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-acyl chloride obtained in the step, after dripping is completed for 0.5H, heating to 30 ℃, preserving the temperature for 1H, filtering and leaching after the reaction is completed, and putting a filter cake into the next step.
6) Synthesis of chlorantraniliprole:
putting the wet powder of the 3-bromine-N- [ 4-chlorine-2-methyl-6- ((oxy) carbonyl) phenyl ] -1- (3-chlorine-2-pyridyl) -1H-pyrazole-5-amide obtained in the previous step into a four-mouth flask, adding 190g of methanol, stirring and heating to 60 ℃, slowly dripping 20.9g of 30% monomethylamine methanol solution, keeping the temperature at 60 ℃ for 1H after finishing dripping, filtering after the reaction is finished, adding 100g of water into a filter cake, heating and pulping for 0.5H, filtering while hot, and drying the product to obtain 89.9g of off-white powder, wherein the yield is 95.8% (calculated by 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-acyl chloride), and the purity is determined to be 98.8% by HPLC (high performance liquid chromatography).
Example 2
1) Synthesis of methyl 2-amino-5-bromo-3-methylbenzoate:
putting 30g of methyl 2-amino-3-methylbenzoate into a four-mouth bottle, adding 100g of 50% glacial acetic acid, stirring at room temperature, dropwise adding 40g of 40% hydrobromic acid, after 0.5H of dropwise addition, heating to 30 ℃, and slowly dropwise adding 12.5g of 30% H 2 O 2 And after 15min of dropwise addition, preserving heat for 0.5h until the reaction is finished, adding 1.5g of sodium bisulfite and NaOH to adjust the system ph to 5-6, cooling, performing suction filtration, and drying to obtain 42.8g of a product, wherein the purity is 97.9% by HPLC (high performance liquid chromatography) and the yield is 94.5%.
2) Synthesis of methyl 2-amino-5-cyano-3-methylbenzoate:
and (3) putting the methyl 2-amino-5-bromo-3-methylbenzoate, 200g N-methylpyrrolidone and 16.2g of cuprous cyanide into a reaction bottle, heating to reflux, keeping the temperature for 3-5 hours, adding 120g of 15% ammonia water and 140g of dichloroethane after the reaction is finished, stirring for 10min, standing for liquid separation, desolventizing an organic layer to obtain 31.8g of yellow solid, wherein the purity is 98.1% by HPLC (high performance liquid chromatography) and the yield is 95.5%.
3) Synthesis of 3-bromo-N- [ 4-cyano-2-methyl-6- ((oxy) carbonyl) phenyl ] -1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-amide:
putting 13g of methyl 2-amino-5-cyano-3-methylbenzoate into a dry four-neck flask, adding 120g of dichloroethane for uniform dispersion, after detecting that the water content is qualified, adding 7.4g of 3-methylpyridine, cooling to 10 ℃, slowly dropwise adding 52.5g of 40 mass percent 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-acyl chloride dichloroethane solution, after dropwise adding for 0.5H, heating to 45 ℃, preserving the temperature for 1H, filtering and leaching after the reaction is finished, and putting a filter cake into the next step.
4) Synthesizing cyantraniliprole:
putting 3-bromo-N- [ 4-cyano-2-methyl-6- ((oxy) carbonyl) phenyl ] -1- (3-chloro-2-pyridyl) -1H-pyrazole-5-amide wet powder into a four-neck flask, adding 120g of methanol, stirring, heating to 60 ℃, slowly dropping 9.5g of 30% monomethylamine methanol solution, after dropping for 2H, keeping the temperature at 60 ℃ for 1H, filtering after the reaction is finished, drying the product to obtain 30.1g of white powder, wherein the yield is 95.4% (calculated by 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-acyl chloride), and the purity is 98.2% determined by HPLC (high performance liquid chromatography).
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. A process for the preparation of anthranilic acid amides, characterized in that a compound of formula III is reacted with a compound of formula IV in the presence of an optionally substituted pyridine compound to obtain a compound of formula II, which is then subjected to an ammonolysis reaction to obtain a compound of formula I:
in the formula, R 1 、R 2 、R 3 、R 4 Each independently represents H, halogen, CN, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl or C 1 -C 6 Alkoxy radical, R 5 Is represented by C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 Alkyl, X represents C 1 -C 6 Alkyl and Y represents halogen.
2. The process according to claim 1, wherein the optionally substituted pyridine compound is unsubstituted pyridine or substituted pyridine, and the substituted pyridine is substituted by 1,2 or 3 carbon atoms 1 -C 6 Alkyl substituent substituted pyridines.
3. The method of claim 2, wherein the coating contains 1 to 3C' s 1 -C 6 The alkyl substituent substituted pyridine is 2-methylpyridine,Any one of 3-methylpyridine, 4-methylpyridine, 2, 6-dimethylpyridine, 1,2, 3-trimethylpyridine, 1,2, 4-trimethylpyridine, 1,2, 5-trimethylpyridine, 2,3, 4-trimethylpyridine or 1,2, 4-trimethylpyridine.
4. The process of claim 1, wherein the ammonolysis reaction is a reaction in a methanol solution of monomethylamine or a reaction in an ethanol solution of ethylamine.
5. The process of claim 1, wherein the compound of formula III is prepared by the following route:
。
6. the method of claim 5, wherein when R is 3 When Cl, the compound of formula III is prepared by reacting a III' compound with SO 2 Cl 2 The compound is prepared by reaction.
7. The process of claim 1, wherein the compound of formula IV is prepared by the following route:
。
8. the method of claim 7, wherein the compound of formula IV is prepared by reacting IV' with SO 2 Y 2 The compound is prepared by reaction.
9. The process according to claim 1, wherein in the formula,
R 1 is selected from CH 3 A group of compounds selected from the group consisting of Cl and Br,
R 2 is a compound of formula (I) in the formula (H),
R 3 is Cl or CN, and can be used as a catalyst,
R 4 is H, FOr OCH 3 ，
R 5 Represents CH 3 Or
，
X represents CH 3 Or CH 2 CH 3 ，
Y represents Cl.
10. The process according to claim 9, wherein in the formula,
R 1 is CH 3 ，R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is CH 3 ，R 2 Is H, R 3 Is CN, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is F, R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Cl, R 2 Is H, R 3 Is Cl, R 4 Is OCH 3 ，R 5 Is CH 3 X is CH 3 Y is Cl; or the like, or, alternatively,
R 1 is Br, R 2 Is H, R 3 Is Cl, R 4 Is H, R 5 Is composed of
X is CH 3 And Y is Cl.
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