CN103073432B - Synthetic method of 5-(2-chlorine-4-(trifluoromethyl) phenoxyl)-2-nitrobenzoic acid - Google Patents
Synthetic method of 5-(2-chlorine-4-(trifluoromethyl) phenoxyl)-2-nitrobenzoic acid Download PDFInfo
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- CN103073432B CN103073432B CN201310015369.5A CN201310015369A CN103073432B CN 103073432 B CN103073432 B CN 103073432B CN 201310015369 A CN201310015369 A CN 201310015369A CN 103073432 B CN103073432 B CN 103073432B
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Abstract
The invention discloses a synthetic method of 5-{2-chlorine-4-(trifluoromethyl) phenoxyl}-2-nitrobenzoic acid. The method comprises the following steps: firstly, 5-chlorine-2-nitryl-benzoic acid and alkaline solution are reacted in the condition of normal pressure or high pressure, so as to obtain 5-hydroxy-2-nitryl-benzoic acid; and secondly, 5-hydroxy-2-nitryl-benzoic acid and 3,4-dichlorobenzotrifluoride are conducted to etherification reaction in solvent, so as to obtain the 5-{2-chlorine-4-(trifluoromethyl) phenoxyl}-2-nitrobenzoic acid). The synthetic method is safer and convenient, and simultaneously can avoid the generation of isomer.
Description
Technical field
The present invention relates to the preparation method of agricultural chemicals or pesticide intermediate, specifically the chloro-4-(trifluoromethyl of a kind of 5-[2-) phenoxy group] synthetic method of-2-nitrobenzoic acid.
Background technology
The chloro-4-(trifluoromethyl of 5-[2-) phenoxy group]-2-nitrobenzoic acid, be commonly called as acifluorfen, it is protoporphyrin oxidase inhibitor, it is a kind of fluorine-contained diphenyl ether herbicide, also can be used as the intermediate of producing the diphenyl ether herbicides such as lactofen, main anti-broadleaved herb, is mainly used in the field weeding agent of soybean, peanut and other crops.
The chloro-4-(trifluoromethyl of 5-[2-) phenoxy group] structural formula of-2-nitrobenzoic acid:
The chloro-4-(trifluoromethyl of 5-[2-according to the literature) phenoxy group]-2-nitrobenzoic acid synthetic have the route that two classes are different:
Synthetic line one: take meta-cresol as raw material, first and KOH reaction generation sylvite, then with 3,4-, bis-chlorobenzotrifluoride generation etherification reactions, then through peroxidation, nitrated obtaining:
This method oxidizing reaction yield is very low maybe will use noble metal catalyst, and catalyst recovery is more difficult.
Synthetic route two: take m-Salicylic acid as raw material, first and potassium hydroxide reaction obtains m-Salicylic acid sylvite, then with 3,4-, bis-chlorobenzotrifluoride generation etherificate condensation reactions, more acidified, nitrated obtaining:
This method condensation reaction is difficult to thoroughly complete, and by product and raw material resorcylic acid are similar with target product character, are difficult to separation.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that above-mentioned prior art exists, provide a kind of new 5-[2-chloro-4-(trifluoromethyl) phenoxy group] synthetic method of-2-nitrobenzoic acid, make synthetic operation safer, simultaneously convenient, building-up process can be avoided the generation of isomer.
For this reason, the present invention adopts following technical scheme: the chloro-4-(trifluoromethyl of a kind of 5-[2-) phenoxy group] synthetic method of-2-nitrobenzoic acid, it is characterized in that: comprise the following steps: the chloro-2-nitro-phenylformic acid of A, 5-reacts with basic solution and obtains 5-hydroxyl-2-nitro-phenylformic acid; B, 5-hydroxyl-2-nitro-phenylformic acid and 3,4-, bis-chlorobenzotrifluorides carry out etherification reaction in solvent, obtain the chloro-4-(trifluoromethyl of 5-[2-) phenoxy group]-2-nitrobenzoic acid.
In foregoing invention content, basic solution is the mixing solutions of aqueous sodium hydroxide solution or potassium hydroxide aqueous solution or water and organic solvent composition.
In foregoing invention content, it is cupric oxide or Red copper oxide or copper or cuprous salt that steps A adopts catalyzer.
In foregoing invention content, the normal pressure of steps A or reaction under high pressure are carried out in normal pressure reactor or autoclave.
In foregoing invention content, the etherification reaction solvent in step B is DMF or dimethyl sulfoxide (DMSO) or tetramethylene sulfone.
In foregoing invention content, the etherification reaction in step B adopts catalyst oxidation copper or Red copper oxide or copper or cuprous salt.
In foregoing invention content, in steps A, add dimethyl sulfoxide (DMSO).
In foregoing invention content, the mixing solutions that water and organic solvent form is ethylenediamine solution or the trolamine aqueous solution or the thanomin aqueous solution.
Method of the present invention compared with prior art, have the following advantages: total recovery is high, starting raw material is inexpensive and be easy to get, used catalyst is common agents, and production cost is low, only generates target product in reaction process, avoided the generation of nitration reaction isomer, reduce the formation of impurity, be conducive to the separation and purification of target product, be more convenient for promoting the use of in industrial production.Therefore, it is a large amount of synthetic that method of the present invention is more suitable for, and is the synthetic chloro-4-(trifluoromethyl of 5-[2-) phenoxy group] diphenyl ether herbicide such as-2-nitrobenzoic acid or lactofen provides a synthetic method with practical value.
Embodiment
Embodiment 1:
Steps A,
In reaction flask, add 4.4 g(0.11 mol) sodium hydroxide, 5 mL water, 20 mL dimethyl sulfoxide (DMSO), the chloro-2-nitro-phenylformic acid of 7.2 g (0.036 mol) 5-, reflux keeps reaction 20 hours under atmospheric pressure state, add 50 mL water, concentrated hydrochloric acid is acidified to pH=3,3 * 50 mL ethyl acetate extractions, combining extraction liquid, decompression steams ethyl acetate and obtains faint yellow solid, ethyl alcohol recrystallization obtains 5.2 g products, yield 80 %, 168～173 ℃ of fusing points.
The chloro-4-(trifluoromethyl of step B, 5-[2-) phenoxy group] preparation of-2-nitrobenzoic acid
In reaction flask, add 2.24 g(0.04 mol) potassium hydroxide solid, the water of 5 mL, then add 30 mL toluene, 3.66 g (0.02 mol) 5-hydroxyl-2-nitrobenzoic acid, reflux is to anhydrous separating, steam toluene, the dimethyl sulfoxide (DMSO) that adds 50 mL, the cuprous chloride of 0.01 g, 3 of 8.6 g (0.04 mol), 4-bis-chlorobenzotrifluorides, 140 ℃ are reacted 20 hours.After reacting completely, decompression steams dimethyl sulfoxide (DMSO), adds 100 mL water, decolorizing with activated carbon, and hydrochloric acid is adjusted pH=3, and ethyl alcohol recrystallization obtains 6.1 g products, yield 85%, 155～160 ℃ of fusing points.
Embodiment 2:
The preparation of steps A, 5-hydroxyl-2-nitrobenzoic acid
In autoclave, add 7 g(0.175 mol) sodium hydroxide, 80 mL water, 10 g(0.05 mol) the chloro-2-nitrobenzoic acid of 5-, 0.7 g(0.005 mol) Red copper oxide, be heated to 160 ℃, under atmospheric pressure state, react 10 hours, cold house's temperature, suction filtration reclaims Red copper oxide, and filtrate is acidified to pH=3 with concentrated hydrochloric acid.With 3 * 50 mL ethyl acetate extractions, combining extraction liquid, decompression steams ethyl acetate and obtains faint yellow solid, and ethyl alcohol recrystallization obtains 9.0 g products, yield 98.3 %, 168～173 ℃ of fusing points.
The chloro-4-(trifluoromethyl of step B, 5-[2-) phenoxy group] preparation of-2-nitrobenzoic acid
In reaction flask, add 2.24 g(0.04 mol) potassium hydroxide solid, the water of 5 mL, then add 30 mL toluene, 3.66 g (0.02 mol) 5-hydroxyl-2-nitrobenzoic acid, reflux, to anhydrous separating, steams toluene, the tetramethylene sulfone that adds 60 mL, 3 of 8.6 g (0.04 mol), 4-bis-chlorobenzotrifluorides, 140 ℃ are reacted 20 hours.After reacting completely, decompression steams dimethyl sulfoxide (DMSO), adds 100 mL water, decolorizing with activated carbon, and hydrochloric acid is adjusted pH=3, and ethyl alcohol recrystallization obtains 5.9 g products, yield 84.6%, 155～160 ℃ of fusing points.
Dimethyl sulfoxide (DMSO) described in above-mentioned two embodiment and tetramethylene sulfone can be replaced with DMF, and the steps A in two embodiment and step B can recombinate arbitrarily.
Protection scope of the present invention is not limited to above-described embodiment, and technical scheme all and of the present invention technology contents identical or that be equal to all falls in its protection domain.
Claims (1)
1. the chloro-4-(trifluoromethyl of 5-[2-) phenoxy group] synthetic method of-2-nitrobenzoic acid, it is characterized in that: comprise the following steps:
1) preparation of steps A, 5-hydroxyl-2-nitrobenzoic acid:
The sodium hydroxide, the 80mL water that in autoclave, add 7g, the chloro-2-nitrobenzoic acid of 10g 5-, 0.7g Red copper oxide, be heated to 160 ℃, under atmospheric pressure state, react cold house's temperature 10 hours, suction filtration reclaims Red copper oxide, filtrate is acidified to pH=3 with concentrated hydrochloric acid, with the extraction of 3 * 50mL ethyl acetate, combining extraction liquid, decompression steams ethyl acetate and obtains faint yellow solid, ethyl alcohol recrystallization obtains 9.0g product, yield 98.3%, 168～173 ℃ of fusing points;
2) the chloro-4-(trifluoromethyl of step B, 5-[2-) phenoxy group] preparation of-2-nitrobenzoic acid:
The potassium hydroxide solid that adds 2.24g in reaction flask, the water of 5mL, then add 30mL toluene, 3.66 g5-hydroxyl-2-nitrobenzoic acids, reflux is to anhydrous separating, steam toluene, the dimethyl sulfoxide (DMSO) that adds 50mL, the cuprous chloride of 0.01g, 3 of 8.6g, 4-bis-chlorobenzotrifluorides, 140 ℃ are reacted 20 hours.After reacting completely, decompression steams dimethyl sulfoxide (DMSO), adds 100mL water, decolorizing with activated carbon, and hydrochloric acid is adjusted pH=3, and ethyl alcohol recrystallization obtains 6.1g product, yield 85%, 155～160 ℃ of fusing points.
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| US4031131A (en) * | 1975-09-29 | 1977-06-21 | Rohm And Haas Company | Process for preparing phenoxybenzoic acids |
| EP0080312A1 (en) * | 1981-11-16 | 1983-06-01 | Rohm And Haas Company | The preparation of certain diphenyl ethers especially 5-(4-trifluoromethylphenoxy)- and 5-(2-halo-4-trifluoromethylphenoxy)-2-nitrobenzoic acid and salts and esters and amides |
| JPS6089451A (en) * | 1983-10-24 | 1985-05-20 | Toray Ind Inc | Production of 6-nitro-3-hydroxybenzoic acid |
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