CN104447402A - Preparation method of 3-trifluoromethyl phenylacetonitrile - Google Patents
Preparation method of 3-trifluoromethyl phenylacetonitrile Download PDFInfo
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- CN104447402A CN104447402A CN201410707144.0A CN201410707144A CN104447402A CN 104447402 A CN104447402 A CN 104447402A CN 201410707144 A CN201410707144 A CN 201410707144A CN 104447402 A CN104447402 A CN 104447402A
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- benzyl cyanide
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Abstract
The invention relates to a preparation method of 3-trifluoromethyl phenylacetonitrile. According to the preparation method, aminobenzyl cyanide is taken as a raw material and has a trifluoromethylation reaction, a diazotization reaction and a reduction reaction sequentially to prepare 3-trifluoromethyl phenylacetonitrile. The preparation method has a reasonable process, high yield and few side effects and is applicable to industrial production.
Description
Technical field
The present invention relates to Chemicals, particularly a kind of preparation method of m-trifluoromethyl benzyl cyanide.
Background technology
M-trifluoromethyl benzyl cyanide is a kind of agricultural chemicals, medicine intermediate, and domestic and international public technology has part to report.
1), US4144265 discloses a kind of preparation method of m-trifluoromethyl benzyl cyanide, with phenylfluoroform, chloromethyl methyl ether and chlorsulfonic acid for raw material first synthesizes m-trifluoromethyl chlorine Bian, then m-trifluoromethyl chlorine Bian and sodium cyanide Reactive Synthesis m-trifluoromethyl benzyl cyanide.This method, raw material chloromethyl methyl ether is strong carcinogen, and chlorsulfonic acid is the hazardous substance of deep-etching, and sodium cyanide is the hazardous substance of high poison, so be not suitable for large production.
2), DE3717434 discloses and under 600-700 DEG C of high temperature, synthesizes m-trifluoromethyl benzyl cyanide with phenylfluoroform and highly toxic substance chlorine cyanogen, and the method is also unfavorable for large production.
3), US4966988 discloses with m-xylene is raw material, first chlorination synthesis a, a, a-tri-chloro-m-xylene; Use a again, a, a-tri-chloro-m-xylene in tetrachloroethylene solvent with hexachloroethane Reactive Synthesis a, a, a, à-four chloro-m-xylene, then fluoridize synthesis m-trifluoromethyl chlorine Bian through hydrogen fluoride gas, and then with sodium cyanide Reactive Synthesis m-trifluoromethyl benzyl cyanide.This technique, so poisonous and hazardous raw material, solvent are more, easily causes serious environmental hazard, is unfavorable for large production.
4), CN200410093014 discloses and first synthesizes m-trifluoromethyl chlorine Bian with phenylfluoroform, chlorsulfonic acid, paraformaldehyde, mineral acid (such as sulfuric acid) for raw material, then with the method for sodium cyanide Reactive Synthesis m-trifluoromethyl benzyl cyanide.The method can produce a large amount of Waste Sulfuric Acids, fluorine-containing by product, and reaction yield is low, the requirement of uncomfortable safety, cleaner production at present.
Summary of the invention
Object of the present invention, exactly in order to overcome the defect that above-mentioned prior art exists, provides that a kind of rational technology, productive rate are high, the preparation method of the m-trifluoromethyl benzyl cyanide that compares environmental protection.
Object of the present invention is achieved through the following technical solutions:
A preparation method for m-trifluoromethyl benzyl cyanide is with p-aminophenyl acetonitrile for raw material, prepares m-trifluoromethyl benzyl cyanide through trifluoromethylation reaction, diazotization reaction and reduction reaction.
Reaction formula is as follows:
The specific practice of described trifluoromethylation reaction is, p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate are added in reaction flask to stir and react, reaction product adds water and ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile; The specific practice of described diazotization reaction is, after the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, adds water and sulfuric acid, and cooling is added dropwise to sodium nitrite solution and carries out diazotization reaction and prepare diazonium salt; The specific practice of described reduction reaction is, drips Hypophosporous Acid, 50 to diazonium salt, adds vinyl acetic monomer and extract after reaction terminates, the first decompression and solvent recovery of oil reservoir, and then product m-trifluoromethyl benzyl cyanide is collected in rectification under vacuum.
The temperature of described trifluoromethylation reaction controls at 15-60 DEG C, and the molar ratio of p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate is: 1: 1-5: 1-5.
The temperature of described diazotization reaction controls at-10-20 DEG C, and the mol ratio of p-aminophenyl acetonitrile, sulfuric acid and Sodium Nitrite is: 1: 2-5: 1-2.
The temperature of described reduction reaction controls at-10-20 DEG C, and the mol ratio of p-aminophenyl acetonitrile and Hypophosporous Acid, 50 is: 1: 1-5.
The temperature of described trifluoromethylation reaction controls at 20-30 DEG C, and the molar ratio of p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate is: 1: 1.5-2: 1.2-2; The temperature of diazotization reaction controls at-5-5 DEG C, and the mol ratio of p-aminophenyl acetonitrile, sulfuric acid and Sodium Nitrite is: 1: 2.5-3: 1.2-1.5; The temperature of reduction reaction controls at 0-5 DEG C, and the mol ratio of p-aminophenyl acetonitrile and Hypophosporous Acid, 50 is 1: 1.5-2.
Compared with prior art, present invention process is reasonable, productive rate is high, product assay is high, and solvent can use by simple distillation Posterior circle, and the three wastes are few, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
33 grams of (0.25 mole) p-aminophenyl acetonitriles, 45 grams of (0.5 mole) tertbutyl peroxides and 78 grams of (0.5 mole) Sodium trifluoromethanesulfinates are added stirring at room temperature in reaction flask and carries out reaction 4 hours, reaction product adds 500 ml waters and 200 milliliters of ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile.After the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, add 100 ml waters and 62.5 grams of (0.625 mole) 98% vitriol oils, be cooled to 0 DEG C, be incubated-2-5 DEG C to be added dropwise to 129.4 grams of (0.375 mole) 20% sodium nitrite in aqueous solution and to carry out diazotization reaction, drip and terminate stirring 30 minutes, prepared that diazonium salt mixture is used for next step reaction.
In preparation-obtained diazonium salt mixture above, be incubated 0-5 DEG C be added dropwise to 66 grams of (0.5 mole) 50% Hypophosporous Acid, 50, drip and terminate to continue stirring 1 hour, add 200 milliliters of vinyl acetic monomers to extract, the first decompression and solvent recovery of oil reservoir, then 92-93 DEG C/4mmHg cut is collected in rectification under vacuum, obtain 39.5 grams of product m-trifluoromethyl benzyl cyanides, productive rate: 85.4%.
Embodiment 2
33 grams of (0.25 mole) p-aminophenyl acetonitriles, 112.5 grams of (1.25 moles) tertbutyl peroxides and 195 grams of (1.25 moles) Sodium trifluoromethanesulfinates are added stirring at room temperature in reaction flask and carries out reaction 2.5 hours, reaction product adds 1500 ml waters and 200 milliliters of ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile.After the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, add 200 ml waters and 125 grams of (1.25 moles) 98% vitriol oils, be cooled to 0 DEG C, be incubated-2-5 DEG C to be added dropwise to 172.5 grams of (0.5 mole) 20% sodium nitrite in aqueous solution and to carry out diazotization reaction, drip and terminate stirring 30 minutes, prepared that diazonium salt mixture is used for next step reaction.
In preparation-obtained diazonium salt mixture above, be incubated 0-5 DEG C be added dropwise to 165 grams of (1.25 moles) 50% Hypophosporous Acid, 50, drip and terminate to continue stirring 1 hour, add 200 milliliters of vinyl acetic monomers to extract, the first decompression and solvent recovery of oil reservoir, then 92-93 DEG C/4mmHg cut is collected in rectification under vacuum, obtain 32 grams of product m-trifluoromethyl benzyl cyanides, productive rate: 69.2%.
Embodiment 3
33 grams of (0.25 mole) p-aminophenyl acetonitriles, 22.5 grams of (0.25 mole) tertbutyl peroxides and 39 grams of (0.25 mole) Sodium trifluoromethanesulfinates are added 55-60 DEG C of stirring in reaction flask and carries out reaction 2 hours, reaction product adds 400 ml waters and 200 milliliters of ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile.After the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, add 100 ml waters and 50 grams of (0.5 mole) 98% vitriol oils, be cooled to 0 DEG C, be incubated 10-20 DEG C to be added dropwise to 86.25 grams of (0.25 mole) 20% sodium nitrite in aqueous solution and to carry out diazotization reaction, drip and terminate stirring 30 minutes, prepared that diazonium salt mixture is used for next step reaction.
In preparation-obtained diazonium salt mixture above, be incubated 10-20 DEG C be added dropwise to 33 grams of (0.25 mole) 50% Hypophosporous Acid, 50, drip and terminate to continue stirring 1 hour, add 200 milliliters of vinyl acetic monomers to extract, the first decompression and solvent recovery of oil reservoir, then 92-93 DEG C/4mmHg cut is collected in rectification under vacuum, obtain 25.2 grams of product m-trifluoromethyl benzyl cyanides, productive rate: 54.5%.
Embodiment 4
33 grams of (0.25 mole) p-aminophenyl acetonitriles, 45 grams of (0.5 mole) tertbutyl peroxides and 78 grams of (0.5 mole) Sodium trifluoromethanesulfinates are added 15-20 DEG C of stirring in reaction flask and carries out reaction 4 hours, reaction product adds 500 ml waters and 200 milliliters of ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile.After the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, add 100 ml waters and 62.5 gram of (0.625) 98% vitriol oil, be cooled to 0 DEG C, be incubated-10-0 DEG C to be added dropwise to 129.4 grams of (0.375 mole) 20% sodium nitrite in aqueous solution and to carry out diazotization reaction, drip and terminate stirring 30 minutes, prepared that diazonium salt mixture is used for next step reaction.
In preparation-obtained diazonium salt mixture above, insulation-10-0 DEG C is added dropwise to 66 grams of (0.5 mole) 50% Hypophosporous Acid, 50, drip and terminate to continue stirring 1 hour, add 200 milliliters of vinyl acetic monomers to extract, the first decompression and solvent recovery of oil reservoir, then 92-93 DEG C/4mmHg cut is collected in rectification under vacuum, obtain 36.5 grams of product m-trifluoromethyl benzyl cyanides, productive rate: 78.9%.
Embodiment 5
33 grams of (0.25 mole) p-aminophenyl acetonitriles, 45 grams of (0.5 mole) tertbutyl peroxides and 58.5 grams of (0.375 mole) Sodium trifluoromethanesulfinates are added stirring at room temperature in reaction flask and carries out reaction 4 hours, reaction product adds 500 ml waters and 200 milliliters of ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile.After the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, add 100 ml waters and 75 grams of (0.75 mole) 98% vitriol oils, be cooled to 0 DEG C, be incubated 0-5 DEG C to be added dropwise to 129.4 grams of (0.375 mole) 20% sodium nitrite in aqueous solution and to carry out diazotization reaction, drip and terminate stirring 30 minutes, prepared that diazonium salt mixture is used for next step reaction.
In preparation-obtained diazonium salt mixture above, be incubated 0-5 DEG C be added dropwise to 66 grams of (0.5 mole) 50% Hypophosporous Acid, 50, drip and terminate to continue stirring 1 hour, add 200 milliliters of vinyl acetic monomers to extract, the first decompression and solvent recovery of oil reservoir, then 92-93 DEG C/4mmHg cut is collected in rectification under vacuum, obtain 40.2 grams of product m-trifluoromethyl benzyl cyanides, productive rate: 86.9%.
Claims (6)
1. a preparation method for m-trifluoromethyl benzyl cyanide, is characterized in that, with p-aminophenyl acetonitrile for raw material, prepares m-trifluoromethyl benzyl cyanide through trifluoromethylation reaction, diazotization reaction and reduction reaction.
2. the preparation method of m-trifluoromethyl benzyl cyanide according to claim 1, it is characterized in that, the specific practice of described trifluoromethylation reaction is, p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate are added in reaction flask to stir and react, reaction product adds water and ethyl acetate, stir layering, oil reservoir is the ethyl acetate solution of intermediate 3-trifluoromethyl-4-aminophenyl acetonitrile; The specific practice of described diazotization reaction is, after the ethyl acetate solution solvent concentration of 3-trifluoromethyl-4-aminophenyl acetonitrile, adds water and sulfuric acid, and cooling is added dropwise to sodium nitrite solution and carries out diazotization reaction and prepare diazonium salt; The specific practice of described reduction reaction is, drips Hypophosporous Acid, 50 to diazonium salt, adds vinyl acetic monomer and extract after reaction terminates, the first decompression and solvent recovery of oil reservoir, and then product m-trifluoromethyl benzyl cyanide is collected in rectification under vacuum.
3. the preparation method of m-trifluoromethyl benzyl cyanide according to claim 1 and 2, it is characterized in that, the temperature of described trifluoromethylation reaction controls at 15-60 DEG C, and the molar ratio of p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate is: 1: 1-5: 1-5.
4. the preparation method of m-trifluoromethyl benzyl cyanide according to claim 1 and 2, is characterized in that, the temperature of described diazotization reaction controls at-10-20 DEG C, and the mol ratio of p-aminophenyl acetonitrile, sulfuric acid and Sodium Nitrite is: 1: 2-5: 1-2.
5. the preparation method of m-trifluoromethyl benzyl cyanide according to claim 1 and 2, is characterized in that, the temperature of described reduction reaction controls at-10-20 DEG C, and the mol ratio of p-aminophenyl acetonitrile and Hypophosporous Acid, 50 is: 1: 1-5.
6. the preparation method of m-trifluoromethyl benzyl cyanide according to claim 1 and 2, it is characterized in that, the temperature of described trifluoromethylation reaction controls at 20-30 DEG C, and the molar ratio of p-aminophenyl acetonitrile, tertbutyl peroxide and Sodium trifluoromethanesulfinate is: 1: 1.5-2: 1.2-2; The temperature of diazotization reaction controls at-5-5 DEG C, and the mol ratio of p-aminophenyl acetonitrile, sulfuric acid and Sodium Nitrite is: 1: 2.5-3: 1.2-1.5; The temperature of reduction reaction controls at 0-5 DEG C, and the mol ratio of p-aminophenyl acetonitrile and Hypophosporous Acid, 50 is 1: 1.5-2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085226A (en) * | 2015-08-28 | 2015-11-25 | 烟台九目化学制品有限公司 | Preparing method of 3,5-halogeno benzene carboxylic acid |
| CN105669613A (en) * | 2016-01-12 | 2016-06-15 | 江苏明化合晟生物科技有限公司 | Production method of high-efficiency herbicide flurtamone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144265A (en) * | 1978-07-17 | 1979-03-13 | The Dow Chemical Company | Process for the manufacture of m-trifluoromethyl benzyl nitrile |
| US4824987A (en) * | 1987-05-23 | 1989-04-25 | Degussa Aktiengesellschaft | Method of preparing m-trifluoromethylphenyl acetonitrile |
| US4966988A (en) * | 1989-02-17 | 1990-10-30 | Chevron Research Company | Process for preparing acetonitrile 3-trifluoromethyl benzene |
| CN1660789A (en) * | 2004-12-15 | 2005-08-31 | 上海试四赫维化工有限公司 | Method for synthesizing m-trifluoromethyl benzyl cyanide |
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2014
- 2014-11-27 CN CN201410707144.0A patent/CN104447402B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144265A (en) * | 1978-07-17 | 1979-03-13 | The Dow Chemical Company | Process for the manufacture of m-trifluoromethyl benzyl nitrile |
| US4824987A (en) * | 1987-05-23 | 1989-04-25 | Degussa Aktiengesellschaft | Method of preparing m-trifluoromethylphenyl acetonitrile |
| US4966988A (en) * | 1989-02-17 | 1990-10-30 | Chevron Research Company | Process for preparing acetonitrile 3-trifluoromethyl benzene |
| CN1660789A (en) * | 2004-12-15 | 2005-08-31 | 上海试四赫维化工有限公司 | Method for synthesizing m-trifluoromethyl benzyl cyanide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085226A (en) * | 2015-08-28 | 2015-11-25 | 烟台九目化学制品有限公司 | Preparing method of 3,5-halogeno benzene carboxylic acid |
| CN105669613A (en) * | 2016-01-12 | 2016-06-15 | 江苏明化合晟生物科技有限公司 | Production method of high-efficiency herbicide flurtamone |
| CN105669613B (en) * | 2016-01-12 | 2018-07-27 | 江苏明化合晟生物科技有限公司 | The production method of highy potent herbicide flurtamone |
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