CN102531887A - Method for preparing 2,4,5- trifluoro-3-methyl benzoic acid - Google Patents
Method for preparing 2,4,5- trifluoro-3-methyl benzoic acid Download PDFInfo
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- CN102531887A CN102531887A CN2012100017840A CN201210001784A CN102531887A CN 102531887 A CN102531887 A CN 102531887A CN 2012100017840 A CN2012100017840 A CN 2012100017840A CN 201210001784 A CN201210001784 A CN 201210001784A CN 102531887 A CN102531887 A CN 102531887A
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Abstract
The invention provides a method for preparing 2,4,5- trifluoro-3-methyl benzoic acid. The method is characterized in that 2,4,5-trifluorobenzoic acid reacts with mixed alkali under the condition of an organic solvent so as to obtain metal salt, of which the carboxylic group and the C3 site are substituted; mixed alkali comprises one of n-butyllithium or tert-butyllithium or lithium isopropoxide, one of potassium tert-butoxide or sodium methylate or potassium methoxide and one of 2,2,6,6-tetramethyl-piperidine or diisopropylamine or tetramethyl ethylenediamine or 2-hydrosulfuryl benzothiazole in a mixing manner, and organic solvent is alcohol ether solvent; metal salt reacts with methylating agents, and a substitution reaction is performed at the benzene ring C3 site so as to obtain 2,4,5- trifluoro-3-methyl benzoic acid; and the reaction temperature ranges from subzero 80 to 20 DEG C. The method has the advantages of high reaction temperature and low cost, and is easy for industrialized production.
Description
Technical field
The present invention relates to the synthetic field of organic chemistry, be specifically related to 2,4, the preparation method of 5-three fluoro-3-tolyl acids.
Background technology
Aromatic fluorine compound is mainly used the midbody of physiologically active compounds such as used as pesticides, medicine, has good thermostability and higher fat-soluble.For example, as weedicide, sterilant, antitumor drug worker ability dyestuff etc.Because fluorine itself is active high, in reaction, be difficult to control, especially on certain location, introduce and divide period of the day from 11 p.m. to 1 a.m difficulty bigger, so the preparation of fluorinated organic compound is still the field of a very challenging property.
2,4,5-three fluoro-3-tolyl acids are the midbodys that purposes is increasingly extensive, are the medicine intermediates of using always.The method Grignard reagent synthesis method that replaces methyl on the phenyl ring is to contain with the phenyl ring and the metal of halogen to process Grignard reagent, is reacting with methylating reagent; Butyllithium reagent method is to contain or do not have the phenyl ring of halogen to become lithium salts to go up methyl with the methylating reagent reaction again with the butyllithium reagent react, but these two kinds of methods all cannot carry out when on phenyl ring, carboxyl being arranged, therefore, must carboxy protective be got up.(Tetrahedron 61 (2005) 8394 – 8404) such as Guillaume Anquetin protect carboxyl with amino alcohol, and behind substituent methyl on n-Butyl Lithium/iodomethane reaction, the deprotection base obtains title product again.Vladimir Beylin, David C. Boyles, wait (Org. Process Res. Dev., 2007,11 (3), 441-449) do not use protective material to synthesize this compound, but will use the reagent hexamethyl two silica-based Lithamides of expensive.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, provide that a kind of technology is more reasonable, yield is high, cost is low 2,4, the preparation method of 5-three fluoro-3-tolyl acids.
Technical problem to be solved by this invention is to realize through following technical scheme.The present invention is a kind of 2,4, and the preparation method of 5-three fluoro-3-tolyl acids is characterized in that its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is-80-20 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:1.5 ~ 3; Described mixed base is by n-Butyl Lithium, a kind of (being designated as A) in tert-butyl lithium or the sec.-propyl lithium, a kind of (being designated as B) in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of (being designated as C) in the 2-thiohydroxy benzothiazole mixed and formed, and three (A, B, C) mass ratio successively is 1:0.2 ~ 5:0.2 ~ 5; Described organic solvent is pure ether solvent;
(2) with the reaction of metal-salt and methylating reagent, temperature of reaction is-80-20 ℃; In phenyl ring C3 position substitution reaction taking place obtains 2,4,5-three fluoro-3-tolyl acids; The mass ratio of metal-salt and methylating reagent is 1:1.1 ~ 3; Described methylating reagent is methyl-sulfate or methyl iodide.
The synthetic route of the inventive method is following:
In the preparing method's of the present invention step (1), described pure ether solvent is one or more combinations in glycol dimethyl ether, MTBE, THF, ether preferably.
In the mixed base of preparing method's of the present invention step (1), three's mass ratio successively is preferably 1:1 ~ 2:1 ~ 2.
Compared with prior art, of the present invention 2,4,5-three fluoro-3-tolyl acid preparing methods are reasonable in design, and product yield is high, and cost is low, are prone to suitability for industrialized production.
Description of drawings
Fig. 1 is 2,4, the HNMR spectrogram of 5-three fluoro-3-tolyl acids.
Embodiment
Below further describe the concrete technical scheme of the utility model,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1, and is a kind of 2,4, the preparation method of 5-three fluoro-3-tolyl acids, and its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is-80 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:1.5; Described mixed base is by n-Butyl Lithium, a kind of in tert-butyl lithium or the sec.-propyl lithium, a kind of in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of mixing in the 2-thiohydroxy benzothiazole is formed, and three's mass ratio successively is 1:0.2:5; Described organic solvent is pure ether solvent;
(2) with metal-salt and methylating reagent reaction, temperature of reaction is-80 ℃; In phenyl ring C3 position substitution reaction taking place obtains 2,4,5-three fluoro-3-tolyl acids; The mass ratio of metal-salt and methylating reagent is 1:1.1; Described methylating reagent is methyl-sulfate or methyl iodide.
Embodiment 2, and is a kind of 2,4, the preparation method of 5-three fluoro-3-tolyl acids, and its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is 20 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:3; Described mixed base is by n-Butyl Lithium, a kind of in tert-butyl lithium or the sec.-propyl lithium, a kind of in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of mixing in the 2-thiohydroxy benzothiazole is formed, and three's mass ratio successively is 1:5:0.2; Described organic solvent is pure ether solvent;
(2) with metal-salt and methylating reagent reaction, temperature of reaction is 20 ℃; In phenyl ring C3 position substitution reaction taking place obtains 2,4,5-three fluoro-3-tolyl acids; The mass ratio of metal-salt and methylating reagent is 1:3; Described methylating reagent is methyl-sulfate or methyl iodide.
Embodiment 3, and is a kind of 2,4, the preparation method of 5-three fluoro-3-tolyl acids, and its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is-20 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:2.5; Described mixed base is by n-Butyl Lithium, a kind of in tert-butyl lithium or the sec.-propyl lithium, a kind of in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of mixing in the 2-thiohydroxy benzothiazole is formed, and three's mass ratio successively is 1:1:1; Described organic solvent is pure ether solvent;
(2) with metal-salt and methylating reagent reaction, temperature of reaction is-20 ℃; In phenyl ring C3 position substitution reaction taking place obtains 2,4,5-three fluoro-3-tolyl acids; The mass ratio of metal-salt and methylating reagent is 1:2; Described methylating reagent is methyl-sulfate or methyl iodide.
Embodiment 4, and is a kind of 2,4, the preparation method of 5-three fluoro-3-tolyl acids, and its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is 0 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:2; Described mixed base is by n-Butyl Lithium, a kind of in tert-butyl lithium or the sec.-propyl lithium, a kind of in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of mixing in the 2-thiohydroxy benzothiazole is formed, and three's mass ratio successively is 1:2:2; Described organic solvent is pure ether solvent;
(2) with metal-salt and methylating reagent reaction, temperature of reaction is 0 ℃; In phenyl ring C3 position substitution reaction taking place obtains 2,4,5-three fluoro-3-tolyl acids; The mass ratio of metal-salt and methylating reagent is 1:2.5; Described methylating reagent is methyl-sulfate or methyl iodide.
Embodiment 5; Embodiment 1-4 2 described in any one; 4, in the preparing method's of 5-three fluoro-3-tolyl acids the step (1), described pure ether solvent is selected from one or more combinations in glycol dimethyl ether, MTBE, THF, the ether.
Embodiment 6,2,4, and the preparation method of 5-three fluoro-3-tolyl acids tests one:
In the 20L anhydrous response bottle, drop into the n-Butyl Lithium 2.1L of 2.5M, cool to-60 ° of following Dropwise 5 40g of C Diisopropylamines; Finish, insulation reaction 0.5 hour, controlled temperature is not higher than-60 ° of C; Drip 900g 2,4, the solution of 3.6 liters of THFs of 5-trifluoro-benzoic acid.Finished insulation reaction 1-2 hour.Add 600 gram potassium tert.-butoxides, insulation reaction is after 1 hour, and controlled temperature is not higher than-60 ° of C, slowly drips the methyl-sulfate of 895 grams, insulation reaction 1 hour, and the HPLC detection reaction finishes.Keep low temperature to add earlier that 100ml water is overworked to go out, again with 3N hydrochloric acid accent reacting liquid pH value to 3-4.Layering, water layer be with ethyl acetate extraction 3 times, each 500ml.Merge organic phase, washing, anhydrous magnesium sulfate drying again, the decompression precipitation gets bullion.Bullion gets pure article through the ethanol/water recrystallization.Content, 98.6%.Quality 720 grams, yield 74%.
Embodiment 7,2,4, and the preparation method of 5-three fluoro-3-tolyl acids tests two:
In the 20L anhydrous response bottle, drop into the n-Butyl Lithium 2.1L of 2.5M, cool to and drip the 620g Tetramethyl Ethylene Diamine below-60 ° of C; Finish, insulation reaction 0.5 hour, controlled temperature is not higher than-60 ° of C; Drip 900g 2,4, the solution of 3.6 liters of THFs of 5-trifluoro-benzoic acid.Finished insulation reaction 1-2 hour.Add 600 gram potassium tert.-butoxides, insulation reaction is after 1 hour, and controlled temperature is not higher than-60 ° of C, slowly drips the methyl-sulfate of 895 grams, insulation reaction 1 hour, and the HPLC detection reaction finishes.Keep low temperature to add earlier that 100ml water is overworked to go out, again with 3N hydrochloric acid accent reacting liquid pH value to 3-4.Layering, water layer be with ethyl acetate extraction 3 times, each 500ml.Merge organic phase, washing, anhydrous magnesium sulfate drying again, the decompression precipitation gets bullion.Bullion gets pure article through the ethanol/water recrystallization.Content, 98.2%.Quality 685 grams, yield 71%.
Embodiment 8,2,4, and the preparation method of 5-three fluoro-3-tolyl acids tests three:
In the 20L anhydrous response bottle, drop into the tert-butyl lithium 3.5L of 1.5M, cool to and drip the 620g Tetramethyl Ethylene Diamine below-60 ° of C; Finish, insulation reaction 0.5 hour, controlled temperature is not higher than-60 ° of C; Drip 900g 2,4, the solution of 3.6 liters of ether of 5-trifluoro-benzoic acid.Finished insulation reaction 1-2 hour.Add 600 gram potassium tert.-butoxides, insulation reaction is after 1 hour, and controlled temperature is not higher than-60 ° of C, slowly drips the methyl-sulfate of 895 grams, insulation reaction 1 hour, and the HPLC detection reaction finishes.Keep low temperature to add earlier that 100ml water is overworked to go out, again with 3N hydrochloric acid accent reacting liquid pH value to 3-4.Layering, water layer be with ethyl acetate extraction 3 times, each 500ml.Merge organic phase, washing, anhydrous magnesium sulfate drying again, the decompression precipitation gets bullion.Bullion gets pure article through the ethanol/water recrystallization.Content, 95.2%.Quality 725 grams, yield 75%.
Embodiment 9,2,4, and the preparation method of 5-three fluoro-3-tolyl acids tests four:
In the 20L anhydrous response bottle, drop into the tert-butyl lithium 3.5L of 1.5M, cool to and drip the 620g Tetramethyl Ethylene Diamine below-60 ° of C; Finish, insulation reaction 0.5 hour, controlled temperature is not higher than-60 ° of C; Drip 900g 2,4, the solution of 3.6 liters of ether of 5-trifluoro-benzoic acid.Finished insulation reaction 1-2 hour.Add 600 gram potassium tert.-butoxides, insulation reaction is after 1 hour, and controlled temperature is not higher than-60 ° of C, slowly drips the methyl-sulfate of 895 grams, insulation reaction 1 hour, and the HPLC detection reaction finishes.Keep low temperature to add earlier that 100ml water is overworked to go out, again with 3N hydrochloric acid accent reacting liquid pH value to 3-4.Layering, water layer be with ethyl acetate extraction 3 times, each 500ml.Merge organic phase, washing, anhydrous magnesium sulfate drying again, the decompression precipitation gets bullion.Bullion gets pure article through the ethanol/water recrystallization.Content, 96.2%.Quality 780 grams, yield 80%.
Embodiment 10,2,4, and the preparation method of 5-three fluoro-3-tolyl acids tests five:
In the 20L anhydrous response bottle, drop into the n-Butyl Lithium 2.1L of 2.5M, cool to-40 ° of following Dropwise 5 40g of C Diisopropylamines; Finish, insulation reaction 0.5 hour, controlled temperature is not higher than-40 ° of C; Drip 900g 2,4, the solution of 3.6 liters of THFs of 5-trifluoro-benzoic acid.Finished insulation reaction 1-2 hour.Add 600 gram potassium tert.-butoxides, insulation reaction is after 1 hour, and controlled temperature is not higher than-60 ° of C, slowly drips 1.01 kilograms methyl iodide, insulation reaction 1 hour, and the HPLC detection reaction finishes.Keep low temperature to add earlier that 100ml water is overworked to go out, again with 3N hydrochloric acid accent reacting liquid pH value to 3-4.Layering, water layer be with ethyl acetate extraction 3 times, each 500ml.Merge organic phase, washing, anhydrous magnesium sulfate drying again, the decompression precipitation gets bullion.Bullion gets pure article through the ethanol/water recrystallization.Content, 95.6%.Quality 620 grams, yield 64%.: change into: bullion gets 620g white solid powder, yield 64% through the ethanol/water recrystallization.HPLC:97.6%, fusing point: 102.2-103.5 ° C, ultimate analysis: C
8H
5F
3O
2, theoretical [reality]: 50.54 [50.65]; H2.65 [2.75]; 1H NMR [DMSO] d 2.29 [s, 3H], 7.72 [m, 1H], 13.55 [m, 1H].Sample 2,4, the HNMR spectrogram of 5-three fluoro-3-tolyl acids is referring to Fig. 1, and the sample detection data see the following form.
| Test event | Salable product | Detected result |
| Proterties | White solid | Meet |
| Content | ≥98. 0% | 98.2% |
| Weight loss on drying | ≤0.1% NMT0.1% | 0.03% NMT0.03% |
| Heavy metal | ≤5ppm NMT10ppm | 3ppm NMT3ppm |
Claims (3)
1. one kind 2,4, the preparation method of 5-three fluoro-3-tolyl acids is characterized in that its step is following:
(1) 2,4, the 5-trifluoro-benzoic acid obtains all substituted metal-salt of carboxyl and C3 position with the mixed base reaction under the organic solvent condition; Temperature of reaction is-80-20 ℃; 2,4, the mass ratio of 5-trifluoro-benzoic acid and mixed base is 1:1.5 ~ 3; Described mixed base is by n-Butyl Lithium, a kind of in tert-butyl lithium or the sec.-propyl lithium, a kind of in potassium tert.-butoxide, sodium methylate or the potassium methylate; And 2,2,6; The 6-tetramethyl piperidine, diisopropylamine, Tetramethyl Ethylene Diamine; A kind of mixing in the 2-thiohydroxy benzothiazole is formed, and three's mass ratio successively is 1:0.2 ~ 5:0.2 ~ 5; Described organic solvent is pure ether solvent;
(2) with the reaction of metal-salt and methylating reagent, temperature of reaction be-substitution reaction acquisition 2,4, take place, 5-three fluoro-3-tolyl acids in 80-20 ℃ in phenyl ring C3 position; The mass ratio of metal-salt and methylating reagent is 1:1.1 ~ 3; Described methylating reagent is methyl-sulfate or methyl iodide.
2. preparation method according to claim 1 is characterized in that: the pure ether solvent described in the step (1) is selected from one or more combinations in glycol dimethyl ether, MTBE, THF, the ether.
3. preparation method according to claim 1 is characterized in that: in the mixed base of step (1), three's mass ratio successively is 1:1 ~ 2:1 ~ 2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215913A (en) * | 1994-02-03 | 1995-08-15 | Hokuriku Seiyaku Co Ltd | Production of 2,4,5-trihalogeno-3-methylbenzoic acid |
| CN1746148A (en) * | 2005-09-02 | 2006-03-15 | 中国科学院上海有机化学研究所 | A kind of Synthetic 2,4, the method for 5-three fluoro-3-methoxybenzoic acids |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215913A (en) * | 1994-02-03 | 1995-08-15 | Hokuriku Seiyaku Co Ltd | Production of 2,4,5-trihalogeno-3-methylbenzoic acid |
| CN1746148A (en) * | 2005-09-02 | 2006-03-15 | 中国科学院上海有机化学研究所 | A kind of Synthetic 2,4, the method for 5-three fluoro-3-methoxybenzoic acids |
Non-Patent Citations (2)
| Title |
|---|
| GUILLAUME ANQUETIN，ET AL: "Synthesis of mono- and di-substituted 2,4,5-trifluorobenzoic acid synthons, key precursors for biologically active 6-fluoroquinolones", 《TETRAHEDRON》 * |
| VLADIMIR BEYLIN，ET AL.: "The Preparation of Two, Preclinical Amino-quinazolinediones as Antibacterial Agents", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》 * |
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