CN115232037B - Preparation method of benzoyl sulfamoyl-N-substituted benzamide compound - Google Patents
Preparation method of benzoyl sulfamoyl-N-substituted benzamide compound Download PDFInfo
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- CN115232037B CN115232037B CN202210965968.2A CN202210965968A CN115232037B CN 115232037 B CN115232037 B CN 115232037B CN 202210965968 A CN202210965968 A CN 202210965968A CN 115232037 B CN115232037 B CN 115232037B
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- -1 benzamide compound Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 title claims description 9
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical group 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 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 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 4
- 239000003054 catalyst Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 18
- 239000000539 dimer Substances 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 125000001188 haloalkyl group Chemical group 0.000 abstract description 5
- 239000012320 chlorinating reagent Substances 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 abstract 1
- 150000003936 benzamides Chemical class 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000007787 solid Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- UCAGLBKTLXCODC-UHFFFAOYSA-N carzenide Chemical compound NS(=O)(=O)C1=CC=C(C(O)=O)C=C1 UCAGLBKTLXCODC-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PFYHAAAQPNMZHO-UHFFFAOYSA-N Methyl 2-methoxybenzoate Chemical compound COC(=O)C1=CC=CC=C1OC PFYHAAAQPNMZHO-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- OAWUUPVZMNKZRY-UHFFFAOYSA-N cyprosulfamide Chemical compound COC1=CC=CC=C1C(=O)NS(=O)(=O)C1=CC=C(C(=O)NC2CC2)C=C1 OAWUUPVZMNKZRY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OYEVFSJZQTUDDN-UHFFFAOYSA-N methanol;n-methylmethanamine Chemical compound OC.CNC OYEVFSJZQTUDDN-UHFFFAOYSA-N 0.000 description 2
- VAZWXPJOOFSNLB-UHFFFAOYSA-N methyl 4-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)C=C1 VAZWXPJOOFSNLB-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RETLCWPMLJPOTP-UHFFFAOYSA-N ethyl 2-chlorobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1Cl RETLCWPMLJPOTP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- CEAJFNBWKBTRQE-UHFFFAOYSA-N methanamine;methanol Chemical compound NC.OC CEAJFNBWKBTRQE-UHFFFAOYSA-N 0.000 description 1
- CPXCDEMFNPKOEF-UHFFFAOYSA-N methyl 3-methylbenzoate Chemical compound COC(=O)C1=CC=CC(C)=C1 CPXCDEMFNPKOEF-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PATCOXOSYWGZRL-UHFFFAOYSA-N n,n-dimethyl-4-sulfamoylbenzamide Chemical compound CN(C)C(=O)C1=CC=C(S(N)(=O)=O)C=C1 PATCOXOSYWGZRL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FWAXOFUGUZQYJS-UHFFFAOYSA-N n-cyclopropyl-4-sulfamoylbenzamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1C(=O)NC1CC1 FWAXOFUGUZQYJS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present application relates to a process for the preparation of benzoylsulfamoyl-N-substituted benzamide compounds. The method comprises the following synthetic routes:wherein X is selected from alkyl, alkoxy, haloalkyl, halogen, R 1 、R 2 Are independently selected from alkyl, R 3 、R 4 Each independently selected from H, alkyl, and cycloalkyl, n=1-3. The application uses the reaction of the ester compound and the amine compound to overcome the problem that the byproduct dimer compound is easy to generate in the reaction of the acylate and the amine in the prior art and the use of the chlorinating reagent is not environment-friendly, and has better industrial production application prospect.
Description
Technical Field
The application belongs to the field of chemical synthesis, and particularly relates to preparation of a benzoyl sulfamoyl-N-substituted benzamide compound.
Background
The benzoyl sulfamoyl-N-substituted benzamide compound is an important active compound, can be used as herbicide safeners and the like, is especially applied after seedling in preventing and controlling crops such as corn, rice or grains, and can widen the application range of related herbicides.
In patent WO99/16744, acylaminosulfonylbenzamide derivatives and their use as safeners for herbicide control of weeds are disclosed. The safener has excellent performance and wide application prospect.
The above document also discloses two preparation methods for preparing acyl sulfamoyl benzamide derivatives, but the first method of the described preparation methods uses more expensive raw materials, so that the method is difficult to realize large-scale industrial production; the second of these methods is inefficient in the process, resulting in lower overall yields.
In CN100429200C, a method for producing acyl sulfamoyl benzoyl is disclosed, but in this method, an acylating agent such as thionyl chloride is used, and thionyl chloride is toxic and has a strong pungent odor, and is not suitable for use in a large amount. The production line does not meet the environmental-friendly process requirements.
In addition, CN111517996a discloses that undesired dimers are formed due to the fact that acid para to sulfonamide is prone to undergo intermolecular polymerization itself after reaction with a chlorinating agent to form acid chloride, and discloses that those skilled in the art have studied related production processes all the time and have difficulty in overcoming the formation of related dimers. Therefore, in order to overcome the generation of related dimer products, a new synthetic route is provided in the patent document, pivaloyl chloride is reacted with carboxyl groups and then reacted with amine to prepare corresponding products, however, the technical personnel in the art know that pivaloyl chloride can have certain damage to human bodies, is environment-friendly, and meanwhile, the preparation process is environment-friendly and has high pressure, so that the method is not suitable for large-scale production.
Development of an environmentally friendly method for preparing a benzoylsulfamoyl-N-substituted benzamide compound is a subject of constant research by researchers.
Disclosure of Invention
Aims at solving the problems of high environmental protection pressure and dimer byproduct generation in the process route for preparing the benzoyl sulfamoyl-N-substituted benzoyl amide compound in the prior art. The application provides an industrial synthesis method of a benzoyl sulfamoyl-N-substituted benzamide compound, which has an environment-friendly process route and overcomes the defect of byproduct generation of a dimer. The application provides a preparation method of a benzoyl sulfamoyl-N-substituted benzamide compound shown in a formula I, which comprises the following reaction steps: the compound of the formula II and the compound of the formula III are prepared by the reaction under the catalysis of alkali.
The reaction route is as follows:
wherein X is selected from alkyl, alkoxy, haloalkyl, halogen, R 1 Selected from alkyl radicals, R 3 、R 4 Independently selected from H, alkyl and cycloalkyl, n=1-3, provided that R 3 、R 4 H is not selected at the same time.
Further, the application also provides a preparation method of the compound of the formula II, which comprises the compound of the formula V and R 3 R 4 NH reaction.
The reaction route is as follows:
wherein R is 2 Selected from alkyl radicals, R 3 、R 4 Each independently selected from H, alkyl and cycloalkyl.
The present application still further provides a process for the preparation of a compound of formula V comprising a compound of formula VI and R 2 OH is prepared under acid catalysis.
The reaction route is as follows:
wherein R is 2 Selected from alkyl groups.
The beneficial effects of the application are that
1. The method solves the problem of serious environmental pollution caused by using a chlorinating reagent, such as thionyl chloride, in the prior art, and the process is more environment-friendly.
2. In the reaction process, each step of reaction is not required to be treated, the next step of reaction can be directly carried out, the process efficiency can be improved, and the environmental protection pressure caused by each step of reaction treatment can be overcome.
3. The application has the advantages of easily obtained reaction raw materials, high reaction yield and reduced production cost.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated elements or steps without excluding other material elements or steps.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the application.
It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In some embodiments, materials, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application.
The subscripts n and m of Cn-Cm in the present application in each case denote the number of carbon atoms in the group.
Halogen in each case denotes fluorine, chlorine, bromine and iodine.
The term "alkyl" (and in other groups comprising alkyl groups, such as alkyl moieties of alkoxy groups) as used herein denotes in each case a radical having typically from 1 to 10 carbon atoms,alkyl groups, which are usually straight-chain or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. C (C) 1 -C 4 Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1-dimethylethyl (tert-butyl).
The term "alkoxy" in the present application is understood to mean an alkoxy group whose hydrocarbyl moiety has the meaning described for "alkyl". For example, "C 1 -C 6 Alkoxy "or" C 1 -C 4 Alkoxy ", preferably methoxy, ethoxy.
The term "haloalkyl" in the present application is understood to mean a haloalkyl group whose hydrocarbyl moiety has the meaning described for "alkyl", halo referring to the replacement of part or all of the hydrogen atoms on the alkyl group with halogen. For example, "C 1 -C 6 Haloalkyl "or" C 1 -C 4 Haloalkyl ", preferably trifluoromethyl.
The term "cycloalkyl" according to the application denotes in each case a radical having generally from 3 to 10 carbon atoms ("C 3 -C 10 Cycloalkyl "), preferably 3 to 7 carbon atoms (" C) 3 -C 7 Cycloalkyl ") is especially 3 to 6 carbon atoms (" C 3 -C 6 Cycloalkyl ") and a mono-or bicyclic cycloaliphatic radical. Examples of the monocyclic group having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The "boiling point" in the present application is the temperature at which the liquid boils, i.e., the temperature at which the saturated vapor pressure of the liquid is equal to the outside pressure. Boiling point refers to the temperature at which the pure material boils at 1 atm. For example, methanol has a boiling point of 64.8 ℃, ethanol has a boiling point of 78.3 ℃, n-propanol has a boiling point of 97.4 ℃, and butanol has a boiling point of 117 to 118 ℃.
The term "solid base" according to the present application includes metal salt solid bases and supported solid bases, preferably supported solid bases, including alumina supported solid bases, zirconia supported solid bases, molecular sieve supported solid bases and the like, such as KF/Al 2 O 3 、KOH/Al 2 O 3 、K 2 O/Al 2 O 3 、KNO 3 /Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、KNO 3 /ZrO 2 、K 2 CO 3 /ZrO 2 、MgO/ZrO 2 、MgO/KL、MgO/NaY、KNO 3 /KX、KOH/4A、KNO 3 MCM-41, mgO/SBA-15, etc.
The following descriptions of variables and preferred embodiments of variables for the compounds of formula (I), the features of the uses and methods of the application and the features of the compositions of the application are valid both on their own and preferably in combination with each other.
The application provides a preparation method of a benzoyl sulfamoyl-N-substituted benzamide compound shown in a formula I, which comprises the following reaction steps: the compound of the formula II and the compound of the formula III react under the catalysis of alkali to prepare the compound of the formula I, wherein the structures of the compounds of the formula I, the formula II and the formula III are as follows:
the reaction route is as follows:
wherein X is selected from alkyl, alkoxy, haloalkyl, halogen, R 1 Selected from alkyl radicals, R 3 、R 4 Independently selected from H, alkyl and cycloalkyl, n=1-3, provided that R 3 And R is 4 And not H at the same time. The present inventors have found that when R 3 、R 4 And at the same time, when H is selected, byproducts generated in the reaction of the compound of the formula III and the amide part in the formula II can occur. R is R 3 、R 4 Without simultaneous selection of H, the dimer by-products reported in the prior art do not appear under the conditions of the present application.
Preferably X is C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Haloalkyl, halogen.
Further preferred X is methoxy, ethoxy, methyl, ethyl, trifluoromethyl, fluoro, chloro, bromo and iodo.
Preferably R 1 Selected from C 1 -C 4 Alkyl groups, more preferably methyl and ethyl groups.
Preferably R 3 、R 4 H, C of a shape of H, C 1 -C 4 Alkyl and C 3 -C 6 Cycloalkyl, more preferably H, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
n is preferably 1, 2 and 3, more preferably 1.
The reaction is carried out under the action of alkali, wherein the alkali is one or more of triethylamine, DIPEA and solid alkali; the solid base includes a metal salt solid base and a supported solid base, such as: sodium carbonate, potassium bicarbonate, sodium bicarbonate; supported solid bases including alumina supported solid bases, zirconia supported solid bases, molecular sieve supported solid bases, and the like, e.g., KF/Al 2 O 3 、KOH/Al 2 O 3 、K 2 O/Al 2 O 3 、KNO 3 /Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、KNO 3 /ZrO 2 、K 2 CO 3 /ZrO 2 、MgO/ZrO 2 、MgO/KL、MgO/NaY、KNO 3 /KX、KOH/4A、KNO 3 MCM-41, mgO/SBA-15, etc. The research shows that the catalytic effect of the supported solid base in the reaction is more excellent.
The reaction is carried out in an organic solvent, wherein the organic solvent is an alcohol solvent, preferably methanol, ethanol, propanol and butanol, more preferably methanol and ethanol; the reaction temperature of the above reaction is 0℃to the boiling point of the solvent used, preferably 25℃to the boiling point of the solvent used, and the reaction time is 1 to 8 hours, preferably 1 to 5 hours. Further, the compound of formula II is prepared by the following method, wherein the compound of formula V and R 3 R 4 NH reaction.
The reaction route is as follows:
wherein R is 2 Selected from alkyl groups, preferably C 1 -C 4 Alkyl, more preferably methyl and ethyl, R 3 、R 4 As defined above.
In the preparation of formula II above, preferably, the compound of formula V is reacted with R 3 R 4 NH reacts in the presence of alkali, wherein the alkali is selected from one or more of triethylamine, DIPEA and solid alkali; the solid base includes metal salt solid base and supported solid base, preferably solid base, for example, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alumina supported solid base, zirconia supported solid base, molecular sieve supported solid base and the like, most preferably KF/Al 2 O 3 、KOH/Al 2 O 3 、K 2 O/Al 2 O 3 、KNO 3 /Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、KNO 3 /ZrO 2 、K 2 CO 3 /ZrO 2 、MgO/ZrO 2 、MgO/KL、MgO/NaY、KNO 3 /KX、KOH/4A、KNO 3 MCM-41, mgO/SBA-15, etc. It is found that the selection of a suitable base in this step can achieve a good catalytic effect.
The reaction is carried out in an organic solvent, wherein the organic solvent is an alcohol solvent, preferably methanol, ethanol, propanol and butanol, more preferably methanol and ethanol; the reaction temperature of the above reaction is 0℃to the boiling point of the solvent used, preferably 25℃to the boiling point of the solvent used, and the reaction time is 1 to 8 hours, preferably 1 to 5 hours.
Further, the process for preparing the compound of formula V comprises the compound of formula VI and R 2 OH is prepared under the catalysis of acid.
The reaction route is as follows:
wherein R is 2 The definition is as described above.
The reaction is carried out in an organic solvent, wherein the organic solvent is an alcohol solvent, preferably methanol, ethanol, propanol and butanol, more preferably methanol and ethanol; the reaction temperature of the above reaction is 0℃to the boiling point of the solvent used, preferably 25℃to the boiling point of the solvent used, and the reaction time is 1 to 8 hours, preferably 1 to 5 hours.
The acid used in the above reaction is an organic acid or an inorganic acid, preferably an inorganic acid, more preferably sulfuric acid, hydrochloric acid or phosphoric acid.
The amount of acid used in the above reaction is 1% to 10% by weight of the compound of formula VI: preferably 3-8% by weight, the catalytic effect is insignificant when the amount of acid is too low, and too high an amount may produce certain by-product impurities.
In a further preferred embodiment, the compound of formula I is of formula I ', the compound of formula II is of formula II ', the compound of formula III is of formula III ',
wherein the compound of formula I ' is prepared by reacting the compound of formula II ' and the compound of formula III ' under alkaline conditions, wherein the alkali, the solvent and the reaction temperature are prepared under the preparation conditions, and the synthetic route is as follows:
wherein R is 1 Is defined as above.
The further synthetic route for formula II' is as follows:
wherein R is 2 The definition is as described above.
The compound of the formula I' can be obtained by synthesizing the compound of the formula VI as a starting material through the route, wherein the reactions in each step can be carried out by using the same solvent, and meanwhile, intermediates in the reaction process can be not required to be separated, so that the production process can be greatly simplified. The preparation method of the I' compound by adopting the route of the application has no generation of conventional dimer compound impurities and has wide application prospect.
The following examples are non-limiting for illustrating the application.
Unless otherwise specifically defined, amounts, relative amounts, percentages refer to weight, and raw materials used are commercially available or are obtained synthetically.
The liquid phase detection conditions are as follows: the chromatographic column is Shodex C18-100-5 (250 x 4.6 mm), the detection wavelength is 240nm, and the mobile phase is acetonitrile: 20mM sodium acetate solution: acetic acid=400: 600:1, a flow rate of 1.000ml/min and a column temperature of 25 ℃.
Example 1 preparation of N, N-dimethyl-4-sulfamoylbenzamide
10.76g of methyl p-aminosulfonyl benzoate is added into methanol, 8.3g of dimethylamine methanol solution (30%) and 4.1g of potassium carbonate are added for reaction for 2 hours at 60 ℃, after the reaction is finished, the solvent is removed, and the product is dried after washing with water to obtain 11.2g of target product, and the yield is 98%.
Example 2 preparation of N, N-dimethyl-4- (4-trifluoromethyl-benzoylsulfamoyl) -benzamide
11.2g g N of N-dimethyl-4-sulfamoyl benzamide is taken and added into methanol, 10.0g of 4-trifluoromethyl benzoic acid methyl ester and 6.9g of potassium carbonate are added for reaction for 5 hours at 60 ℃, after the reaction is finished, a large amount of liquid phase detection raw materials are remained, the target product contains about 39 percent, and no similar dimer product reported in the prior art is generated.
EXAMPLE 3 preparation of N-cyclopropyl-4- (2-methoxy-benzoylsulfamoyl) -benzamide
12g N-cyclopropyl-4-sulfamoyl benzamide is taken and added into ethanol, 8.5g of 2-methoxyl methyl benzoate and 2.8g of potassium hydroxide are added for reaction for 5 hours at 70 ℃, after the reaction is finished, a large amount of liquid phase detection raw materials are remained, the target product contains about 48 percent, and no similar dimer product reported in the prior art is generated.
EXAMPLE 4 preparation of N-cyclopropyl-4- (2-methoxy-benzoylsulfamoyl) -benzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in methanol, adding 0.3g of concentrated sulfuric acid, heating and refluxing for reaction for 3 hours; cooling and adding 9.3g KOH/Al 2 O 3 (15% loading, weight percent) and 3.4g cyclopropylamine, at 60℃for 3h; after cooling, 8.4g of methyl 2-methoxybenzoate is added for reaction for 3 hours at 60 ℃, after the reaction is finished, the filtrate is filtered, the solvent is removed, 17.6g of target product is obtained through recrystallization, the purity is 99.8%, the total yield is 94%, and no similar dimer product reported in the prior art is generated.
1H NMR(300MHz，DMSO):11.99(br，1H),8.65(br，1H),7.91～7.99(m,4H),7.45～7.51(t,1H),7.33～7.35(d,1H),7.08～7.11(d,1H),6.93～6.98(t,1H),3.80(s，3H),2.83～2.87(m，1H),0.57-0.70(m,4H)
EXAMPLE 5 preparation of N-isopropyl-4- (3-methyl-benzoylsulfamoyl) -benzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in methanol, adding 0.3g of concentrated sulfuric acid, heating and refluxing for reaction for 2 hours; cooling and adding 27.6. 27.6g K 2 CO 3 /ZrO 2 (15% loading, weight percent) and 3.3g isopropyl amine, at 60 ℃ for 1h; 7.5g of methyl 3-methylbenzoate is added after cooling, the reaction is carried out for 1h at 60 ℃, after the reaction is finished, the filtrate is filtered, the solvent is removed, 17.3g of target product is obtained through recrystallization, the purity is 99.2%, the total yield is 96%, and no similar dimer product reported in the prior art is generated.
1H NMR(300MHz，DMSO):11.83(br，1H),8.57(br，1H),7.90～7.97(m,4H),7.69～7.71(m,2H),7.28～7.31(m,2H),3.84～3.87(m，1H),2.31(s，3H),1.23～1.26(d,6H)
EXAMPLE 6 preparation of 4- (3-chloro-benzoylsulfamoyl) -benzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in ethanol, adding 0.8g of concentrated sulfuric acid, and heating and refluxing for reaction for 2 hours; cooling and adding 10.7g of NaOH/Al 2 O 3 (15% of load rate, weight percent) and 4.1g of ammonia water (25% of mass percent), and reacting for 1h at 70 ℃; cooling, adding 8.6g of 3-methyl chlorobenzoate, reacting at 50deg.C for 2h, filtering, removing solvent, detecting liquid phase to find that the target product contains 65%, and analyzing to determine R 3 R 4 At the same time, when H is used, the amide functional group reacts with the ester group, corresponding byproducts are generated, and similar dimer products reported in the prior art are not generated.
EXAMPLE 7 preparation of 4- (2-chloro-benzoylsulfamoyl) -N-cyclohexylbenzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in ethanol, adding 0.5g of concentrated sulfuric acid, and heating and refluxing for reaction for 2 hours; after cooling, 16g MgO/KL (load factor 5 percent by weight) and 5.0g cyclohexylamine are added for reaction for 2 hours at 40 ℃; after cooling, 9.3g of ethyl 2-chlorobenzoate is added for reaction for 2 hours at 50 ℃, after the reaction is finished, the filtrate is filtered, the solvent is removed, and the recrystallization is carried out to obtain 19.4g of target product, the purity is 99.2%, the total yield is 92%, and no similar dimer product is reported in the prior art.
1H NMR(300MHz，DMSO):12.12(br，1H),8.73(br，1H),7.96～8.05(m,4H),7.87～7.92(d,1H),7.41～7.49(m,2H),7.29～7.34(t,1H),3.50-3.56(m，1H),1.69～1.73(m,4H),1.40～1.46(m,6H)
Example 8 preparation of N, N-dimethyl-4- (4-trifluoromethyl-benzoylsulfamoyl) -benzamide
10.1g of p-aminosulfonyl benzoic acid was taken,dissolving with methanol, adding 0.6g of concentrated sulfuric acid, heating and refluxing for reaction for 1.5h; cooling and adding 36.8. 36.8g K 2 CO 3 /Al 2 O 3 (15% loading, weight percent) and 9.0g dimethylamine methanol solution (30%), at 25℃for 3h; 10.2g of methyl 4-trifluoromethyl benzoate is added, the reaction is carried out for 3 hours at 25 ℃, after the reaction is finished, the filtration is carried out, the filtrate is taken to remove the solvent, 18.4g of target product is obtained by recrystallization, the purity is 99.3%, the total yield is 92%, and no similar dimer product is reported in the prior art.
1H NMR(300MHz，DMSO):11.96(br，1H),7.93～7.98(m,4H),7.74-7.82(d,2H),7.64～7.69(d,2H),2.92(s，6H)
EXAMPLE 9 preparation of 4- (2, 4-dimethoxy-benzoylsulfamoyl) -N-methyl-benzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in methanol, adding 0.4g of concentrated sulfuric acid, and heating and refluxing for reaction for 4 hours; after cooling, 14g KOH/4A (load factor 10% by weight) and 7.8g monomethylamine methanol solution (30%) were added and reacted at 50℃for 2 hours; after cooling, 9.9g of 2, 4-dimethoxy methyl benzoate is added for reaction for 2 hours at 50 ℃, after the reaction is finished, the solution is filtered, the filtrate is taken to remove the solvent, 17.8g of target product is obtained through recrystallization, the purity is 99.6%, the total yield is 94%, and no similar dimer product reported in the prior art is generated.
1H NMR(300MHz，DMSO):11.91(br，1H),8.69(br，1H),7.92～7.97(m,4H),7.65～7.71(d,1H),6.51～6.54(d,1H),6.49(s，1H),3.78(s，6H),2.73(s，3H)
EXAMPLE 10 preparation of 4- (4-chloro-3-methyl-benzoylsulfamoyl) -N-ethyl-benzamide
Dissolving 10.1g of p-aminosulfonyl benzoic acid in ethanol, adding 0.5g of concentrated sulfuric acid, and heating and refluxing for reaction for 2 hours; cooling, adding 5.1g of sodium bicarbonate and 2.3g of ethylamine, and reacting for 2 hours at 70 ℃; after cooling, 9.9g of 3-methyl-4-ethyl chlorobenzoate is added for reaction for 2 hours at 70 ℃, after the reaction is finished, the solvent is removed, and after water washing, 7.8g of target product is obtained through repeated recrystallization, the purity is 98.4%, the total yield is 41%, and no similar dimer product reported in the prior art is generated.
1H NMR(300MHz，DMSO):12.09(br，1H),8.69(br，1H),7.95～8.04(m,4H),7.69～7.72(m,2H),7.24～7.31(d,1H),3.25～3.29(m,2H),2.38(s，3H),1.23-1.29(t，3H),
The above description is only a preferred embodiment of the present application, and is not intended to limit the technical solution of the present application in any way. Any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present application fall within the protection scope of the present application.
Claims (18)
1. A process for the preparation of a benzoylsulfamoyl-N-substituted benzamide compound of formula I comprising the steps of: the compound of the formula II and the compound of the formula III react under the catalysis of alkali to prepare the compound of the formula I, wherein the structures of the compounds of the formula I, the formula II and the formula III are as follows:
；/>；/>the method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Haloalkyl, halogen, R 1 Selected from C 1 -C 4 Alkyl, R 3 、R 4 Are respectively and independently selected from H, C 1 -C 4 Alkyl and C 3 -C 6 Cycloalkyl, n is 1, 2 and 3, provided that R 3 And R is 4 Not simultaneously H; the base is selected from KOH/Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、K 2 CO 3 /ZrO 2 One or more of MgO/KL and KOH/4A.
2. The method of claim 1, wherein X is methyl, ethyl, methoxy, ethoxy, trifluoromethyl, fluoro, chloro, bromo, or iodo.
3. The method of claim 2, wherein R is 1 Selected from methyl and ethyl; r is R 3 、R 4 Each independently selected from the group consisting of H, methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
4. A method of preparing according to claim 3, wherein n is 1.
5. The process according to claim 1, wherein the reaction is carried out in an organic solvent which is an alcoholic solvent which is methanol, ethanol, propanol or butanol, and the reaction temperature of the above reaction is from 0 ℃ to the boiling point of the solvent used; the reaction time is 1-8h.
6. The method according to claim 5, wherein the alcohol solvent is methanol or ethanol; the reaction temperature is 25 ℃ to the boiling point of the solvent used; the reaction time is 1-5h.
7. The process according to any one of claims 1 to 6, wherein the compound of formula II is obtained by reacting a compound of formula V with R 3 R 4 The NH is reacted to prepare the catalyst,
the reaction route is as follows:
wherein R is 2 Selected from C 1 -C 4 Alkyl group；R 3 、R 4 As defined in any one of claims 1 to 6.
8. The process of claim 7, wherein R 2 Selected from methyl and ethyl.
9. The process of claim 7, wherein the compound of formula V is a compound of formula V and R 3 R 4 NH is reacted in the presence of a base selected from KOH/Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、K 2 CO 3 /ZrO 2 One or more of MgO/KL and KOH/4A.
10. The method according to claim 9, wherein the reaction is carried out in an organic solvent, which is an alcoholic solvent, which is methanol, ethanol, propanol or butanol; the reaction temperature of the reaction is 0 ℃ to the boiling point of the solvent, and the reaction time is 1-8h.
11. The method according to claim 10, wherein the alcoholic solvent is methanol or ethanol; the reaction temperature of the reaction is 25 ℃ to the boiling point of the solvent, and the reaction time is 1-5h.
12. The process of claim 7, wherein the compound of formula V is prepared by reacting a compound of formula VI with R 2 OH is prepared under the catalysis of acid;
the reaction route is as follows:
wherein R is 2 The definition is as defined in claim 7.
13. The method according to claim 12, wherein the reaction is carried out in an organic solvent, wherein the organic solvent is an alcohol solvent, and the alcohol solvent is one of methanol, ethanol, propanol and butanol; the reaction temperature of the reaction is 0 ℃ to the boiling point of the solvent used; the reaction time is 1-8h.
14. The method of claim 13, wherein the alcoholic solvent is methanol or ethanol; the reaction temperature of the reaction is 25 ℃ to the boiling point of the solvent used; the reaction time is 1-5h.
15. The method of claim 12, wherein the acid is an organic acid or an inorganic acid; the acid is used in an amount of 1% to 10% by weight of formula VI.
16. The process of claim 12 wherein the acid is an organic or inorganic acid and the amount of acid is 3% to 8% by weight of formula VI.
17. The method of claim 15 or 16, wherein the acid is an inorganic acid; the inorganic acid is selected from sulfuric acid, hydrochloric acid or phosphoric acid.
18. The process according to claim 1, wherein the compound of formula I is of formula I ', the compound of formula II is of formula II ', the compound of formula III is of formula III ',，/>，。
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| CN1272106A (en) * | 1997-09-29 | 2000-11-01 | 阿温提斯作物科学有限公司 | Acylsulfamoylbenzamides, crop protection compositions containing them and processes for their preparation |
| CN1812962A (en) * | 2003-06-25 | 2006-08-02 | 拜尔作物科学有限公司 | Process for preparing acylsulfamoylbenzamides |
| CN111517996A (en) * | 2020-06-11 | 2020-08-11 | 河北兰升生物科技有限公司 | Preparation method and preparation intermediate of benzoyl sulfamoyl benzamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1272106A (en) * | 1997-09-29 | 2000-11-01 | 阿温提斯作物科学有限公司 | Acylsulfamoylbenzamides, crop protection compositions containing them and processes for their preparation |
| CN1812962A (en) * | 2003-06-25 | 2006-08-02 | 拜尔作物科学有限公司 | Process for preparing acylsulfamoylbenzamides |
| CN111517996A (en) * | 2020-06-11 | 2020-08-11 | 河北兰升生物科技有限公司 | Preparation method and preparation intermediate of benzoyl sulfamoyl benzamide |
Non-Patent Citations (1)
| Title |
|---|
| Yang Zheng 等.Design of novel CSA analogues as potential safeners and fungicides.《Bioorganic & Medicinal Chemistry Letters》.2015,第25卷791-794. * |
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