CN104086452A - Method for preparing high-purity (3,4-diaminophenyl)(4-fluorophenyl) ketone by virtue of catalytic hydrogenation - Google Patents
Method for preparing high-purity (3,4-diaminophenyl)(4-fluorophenyl) ketone by virtue of catalytic hydrogenation Download PDFInfo
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- CN104086452A CN104086452A CN201410354529.3A CN201410354529A CN104086452A CN 104086452 A CN104086452 A CN 104086452A CN 201410354529 A CN201410354529 A CN 201410354529A CN 104086452 A CN104086452 A CN 104086452A
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Abstract
The invention relates to a method for preparing high-purity (3,4-diaminophenyl)(4-fluorophenyl) ketone by virtue of catalytic hydrogenation, belonging to the technical field of pharmaceutical and chemical engineering. The method comprises the following steps: adding (4-amino-3-nitrophenyl)(4-fluorophenyl) ketone (I) and a catalyst into an organic solvent, introducing hydrogen, and performing hydrogenation reduction reaction to obtain a flubendazole intermediate namely (3,4-diaminophenyl)(4-fluorophenyl) ketone (II). The method disclosed by the invention has the advantages that compared with a reduction method using sodium hydrosulfide, the method is simple in process, small in solvent dosage and short in reaction time, can be used for solving the problem that a large amount of sulfide-containing wastewater is difficult to be treated, and is beneficial for industrial production; meanwhile, a novel catalyst preparation method is simple, and has the characteristics of high reaction activity, good selectivity and recycled catalyst; compared with a pure Pt/C catalyst, the novel catalyst can be used for effectively inhibiting the phenomenon that carbanyl groups are reduced into methylene and inhibiting the occurrence of the defluorination phenomenon, and is relatively high in product yield and purity.
Description
Technical field
The present invention relates to a kind of Flubendazole intermediate, relates in particular to the shortening preparation method of a kind of Flubendazole intermediate (3,4-diamino-phenyl) (4-fluorophenyl) ketone, belongs to medicine and chemical technology field.
Background technology
(3,4-diamino-phenyl) (4-fluorophenyl) ketone is the key intermediate that conventional insect repellent Flubendazole is produced, mainly by (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone reduction preparation.The method of reducing of bibliographical information has iron powder, tin protochloride, sodium sulfide reducing method, silicon carbide catalysis, Pt/C shortening method, Raney Ni shortening method.Current industrial main employing Sodium sulfhydrate reduction method, general chemical reduction method is seriously polluted, produces a large amount of sulphide-containing waste waters difficult, and poor product quality; Victor in 1997, (Journal of Medicinal Chemistry, the vol.40 such as Frantz; Nb.24) reported in tetrahydrofuran (THF) by the preparation (3 in 12 hours of nickel shortening, 4-diamino-phenyl) (4-fluorophenyl) ketone, while using active nickel catalysis, its byproduct of reaction amount is larger, product yield is low, active nickel very easily catches fire in air simultaneously, exists huge potential safety hazard in production; The shortening method working pressure that US5693661 reports is larger, easily occur that carbonyl is reduced into methylene radical and generates by product 4-(4-fluorophenyl) phenyl-1, the by product (3 of 2-diamines and hydrogenation defluorinate, 4-diamino-phenyl) phenyl ketone, not only reduced reaction yield, and product purity is declined.Although add dehalogenation inhibitor can improve the selectivity of reaction, reduced product quality introduce defluorinate inhibitor in reaction system after, increased production cost.Therefore, the catalyzer of industrial exploitation highly selective, suppress (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone Hydrogenation standby (3,4-diamino-phenyl) defluorinate in the process of (4-fluorophenyl) ketone, also will suppress excessive hydrogenation reduction to cause carbonyl to be reduced into methylene radical very important simultaneously.
Summary of the invention
The object of the invention is: for deficiency of the prior art, provide the preparation method of a kind of environmental protection, simple, the high yield of technique, high purity (3,4-diamino-phenyl) (4-fluorophenyl) ketone.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of shortening is prepared the method for high purity (3,4-diamino-phenyl) (4-fluorophenyl) ketone, comprises the steps:
(4-amino-3-nitrophenyl) (4-fluorophenyl) ketone and catalyzer are added in organic solvent, pass into hydrogen, hydrogenation reduction, obtains Flubendazole intermediate (3,4-diamino-phenyl) (4-fluorophenyl) ketone; The consumption of wherein said catalyzer be raw material (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone quality 0.01%～15%, the consumption of described organic solvent is 1～20 times of quality of raw material (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, wherein said catalyzer is Pt-X/C catalyzer, wherein, X is Ru, La, Ce, Co, Li, K, Mg, Ti, Cu, a kind of in Mo element;
The consumption of catalyzer of the present invention be (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone quality 0.1%～10%, preferably 0.2%～2.0%, the consumption of described organic solvent is 3～15 times of quality of (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, preferably 3～6 times.
In the present invention, the preparation method of Pt-X/C catalyzer is: 1 part of gac be impregnated in to the H that 0.01-1 doubly measures
2ptCl
6in mixing solutions containing 0.01-1 X ion (X=Ru, La, Ce, Co, Li, K, Mg, Ti, Cu or Mo) doubly, infiltrate, flood after 10-13 hour, use reductive agent at 81 ℃～95 ℃ heat reduction 1-1.5 hour, after having reduced, be cooled to room temperature, filter, be washed to neutrality, make Pt-X/C catalyzer, wherein in Pt-X/C catalyzer, the charge capacity of Pt is 1-5%, and the charge capacity of X is 0.1-5%.
In Pt-X/C catalyzer of the present invention, the charge capacity of Pt is 1-5%, and the charge capacity of X is 0.1-5%.
The reductive agent that Pt-X/C catalyzer of the present invention is used in preparation process is formaldehyde, hydrazine hydrate, phosphorous acid, KBH
4, CH
3a kind of in COONa or their mixture.
Organic solvent of the present invention is that one or more in methyl alcohol, ethanol, Virahol, benzene,toluene,xylene, ethyl acetate, oil of mirbane, normal hexane, hexanaphthene, tetrahydrofuran (THF) mix with arbitrary proportion.
Hydrogenation reduction temperature of the present invention is 20 ℃～80 ℃, and hydrogenation reduction pressure is 0.4MPa～1.5MPa, and the hydrogenation reduction time is 2～8 hours.
Adopt the beneficial effect of technical scheme of the present invention to be:
(1) new catalyst preparation method is simple, has that reactive behavior is high, selectivity good and catalyzer such as is repeatedly used at the feature.
(2) with by Sodium sulfhydrate reduction method compare, have that technique is simple, solvent load is few, the reaction times is short, and has avoided the unmanageable problem of a large amount of sulphide-containing waste waters, is conducive to suitability for industrialized production;
(3) new catalyst is compared with pure Pt/C catalyzer, can effectively suppress the generation that carbonyl in shortening process is reduced into methylene radical and defluorinate phenomenon, carbonyl reduction impurity 4-(4-fluorophenyl) phenyl-1 in product, 2-diamines and defluorinate impurity (3,4-diamino-phenyl) phenyl ketone is all less than 0.1%, product purity reaches more than 99.8%, and yield reaches more than 95%.
Accompanying drawing explanation
Fig. 1 is (3,4-diamino-phenyl) (4-fluorophenyl) ketone infrared spectrum.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
Shortening: in the autoclave of 1L, add 75.0g (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, 300ml methyl alcohol, 0.5g3%Pt/C catalyzer (Jiangxi Han Shi Bo Ye company limited), then build kettle cover, nitrogen replacement 3 times, use again hydrogen exchange 3 times, stir and be warming up to 50 ℃, start to pass into hydrogen, make temperature in the kettle be no more than 60 ℃, pressure keeps 0.4-0.6MPa, when hydrogen no longer absorbs, keep still internal pressure 0.6MPa, , continue reaction 1h, cooling, pressure release, extract fast reaction solution in still out, filtration catalizer, after the methyl alcohol of recovery 75%, this residual solution is poured in the water of 750ml, separate out glassy yellow solid, filter, vacuum drying (60 ℃), obtain (3, 4-diamino-phenyl) (4-fluorophenyl) ketone 62.8g, yield 94.6%.Product liquid chromatography-spectrometer analysis, the content of each component is (3,4-diamino-phenyl) (4-fluorophenyl) ketone 95.01%, (3,4-diamino-phenyl) phenyl ketone 2.52%, 4-(4-fluorophenyl) phenyl-1,2-diamines 1.95%.
Embodiment 2
Catalyzer preparation: by 0.135g H
2ptCl
6with 0.03g RuCl
3be dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 10 h, are heated to 95 ℃, drip NaOH solution and Glacial acetic acid, and heat reduction 1 hour reduce rear coolingly, and filtration, is washed to neutrality, makes Pt-Ru/C catalyzer.
Shortening: in the autoclave of 1L, add 75.0g (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, 300ml methyl alcohol, 0.5gPt-Ru/C catalyzer, then build kettle cover, nitrogen replacement 3 times, use again hydrogen exchange 3 times, stir and be warming up to 50 ℃, start to pass into hydrogen, make temperature in the kettle be no more than 60 ℃, pressure keeps 0.4-0.6MPa, when hydrogen no longer absorbs, keep still internal pressure 0.6MPa, , continue reaction 1h, cooling, pressure release, extract fast reaction solution in still out, filtration catalizer, after the methyl alcohol of recovery 75%, this residual solution is poured in the water of 750ml, separate out glassy yellow solid, filter, vacuum drying (60 ℃), obtain (3, 4-diamino-phenyl) (4-fluorophenyl) ketone 64.6g, yield 97.3%.Fusing point 113.0-114.1 ℃.Product liquid chromatography-spectrometer analysis, the content of each component is (3,4-diamino-phenyl) (4-fluorophenyl) ketone 99.91%, (3,4-diamino-phenyl) phenyl ketone 0.04%, 4-(4-fluorophenyl) phenyl-1,2-diamines 0.02%.
Embodiment 3
Catalyzer preparation: by 0.135g H
2ptCl
6with 0.4g TiCl
4be dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 12 h, are heated to 90 ℃, drip KBH
4solution, heat reduction 1.5 hours, has reduced rear coolingly, filters, and is washed to neutrality, makes Pt-Ti/C catalyzer.
Shortening: in the autoclave of 1L, add 80.0g (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, 480ml toluene, 1.2gPt-Ti/C catalyzer, then build kettle cover, nitrogen replacement 3 times, use again hydrogen exchange 3 times, stir and be warming up to 50 ℃, start to pass into hydrogen, make temperature in the kettle be no more than 60 ℃, pressure keeps 0.5-0.9MPa, when hydrogen no longer absorbs, keep still internal pressure 1.0MPa, , continue reaction 1h, cooling, pressure release, extract fast reaction solution in still out, filtration catalizer, after the toluene of recovery 70%, glassy yellow solid is separated out in cooling, filter, vacuum drying (70 ℃), obtain (3, 4-diamino-phenyl) (4-fluorophenyl) ketone 67.7g, yield 95.6%.Fusing point 113.2-114.1 ℃.Product liquid chromatography-spectrometer analysis, the content of each component is (3,4-diamino-phenyl) (4-fluorophenyl) ketone 99.88%, (3,4-diamino-phenyl) phenyl ketone 0.06%, 4-(4-fluorophenyl) phenyl-1,2-diamines 0.03%.
Embodiment 4
Catalyzer preparation: by 0.135g H
2ptCl
6with 1.0g La (NO
3)
3be dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 12 h, are heated to 85 ℃, drip hydrazine hydrate solution, and heat reduction 1 hour reduce rear coolingly, and filtration, is washed to neutrality, makes Pt-La/C catalyzer.
Shortening: in the autoclave of 1L, add 80.0g (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone, 400ml ethyl acetate, 0.8gPt-La/C catalyzer, then build kettle cover, nitrogen replacement 3 times, use again hydrogen exchange 3 times, stir and be warming up to 70 ℃, start to pass into hydrogen, make temperature in the kettle be no more than 80 ℃, pressure keeps 0.6-1.0MPa, when hydrogen no longer absorbs, keep still internal pressure 1.0MPa, , continue reaction 1h, cooling, pressure release, extract fast reaction solution in still out, filtration catalizer, after the ethyl acetate of recovery 80%, glassy yellow solid is separated out in cooling, filter, vacuum drying (70 ℃), obtain (3, 4-diamino-phenyl) (4-fluorophenyl) ketone 68.4g, yield 96.8%.Product liquid chromatography-spectrometer analysis, the content of each component is (3,4-diamino-phenyl) (4-fluorophenyl) ketone 99.90%, (3,4-diamino-phenyl) phenyl ketone 0.04%, 4-(4-fluorophenyl) phenyl-1,2-diamines 0.01%.
Embodiment 5
The impact of catalyzer time to standby (3,4-diamino-phenyl) (4-fluorophenyl) the reactive ketone performance of (4-amino-3-nitrophenyl) (4-fluorophenyl) Hydrogenation
The Pt-Ti/C catalyzer that embodiment 2 suction filtrations are obtained is reused as catalyzer after methanol wash is dried for 3 times, and other operation steps is with embodiment 2.Test-results is in Table 1:
Table 1 catalyzer is applied mechanically test catalyst Catalytic Hydrogenation Properties
The invention is not restricted to above-described embodiment, that all foundations technical spirit of the present invention is done above-described embodiment is any simple, equivalent variations or modification, all belongs within the scope of the technology of the present invention.
Claims (6)
1. a shortening is prepared high purity (3,4-diamino-phenyl) method of (4-fluorophenyl) ketone, the method is that (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone and catalyzer are added in organic solvent, pass into hydrogen, hydrogenation reduction, obtain Flubendazole intermediate (3,4-diamino-phenyl) (4-fluorophenyl) ketone;
The consumption of wherein said catalyzer be raw material (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone quality 0.1%～10%;
The consumption of described organic solvent is 3～15 times of quality of raw material (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone;
Wherein said catalyzer is Pt-X/C catalyzer, and wherein, X is Ru, La, Ce, Co, Li, K, Mg, Ti, Cu, a kind of in Mo element; In described Pt-X/C catalyzer, the charge capacity of Pt is 1-5%, and the charge capacity of X is 0.1-5%.
The chemical formula of described (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone is:
The chemical formula of described (3,4-diamino-phenyl) (4-fluorophenyl) ketone is:
2. a kind of shortening according to claim 1 is prepared high purity (3,4-diamino-phenyl) method of (4-fluorophenyl) ketone, it is characterized in that: the consumption of described catalyzer is the quality of (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone 0.2%～2.0%, the consumption of described organic solvent is 3～6 times of quality of (4-amino-3-nitrophenyl) (4-fluorophenyl) ketone.
3. a kind of shortening according to claim 1 is prepared high purity (3,4-diamino-phenyl) method of (4-fluorophenyl) ketone, is characterized in that: described Pt-X/C catalyzer is prepared by the following method: 1 part of gac be impregnated in to the H that 0.01-1 doubly measures
2ptCl
6in mixing solutions containing 0.01-1 X ion doubly, infiltrate, dipping is after 10-13 hour, uses reductive agent at 81 ℃～95 ℃ heat reduction 1-1.5 hour, after reduce, is cooled to room temperature, filtration, is washed to neutrality, makes Pt-X/C catalyzer.
4. a kind of shortening according to claim 3 is prepared high purity (3,4-diamino-phenyl) method of (4-fluorophenyl) ketone, is characterized in that: the reductive agent that described Pt-X/C catalyzer is used in preparation process is formaldehyde, hydrazine hydrate, phosphorous acid, KBH
4, CH
3a kind of in COONa or their mixture.
5. a kind of shortening according to claim 5 is prepared high purity (3,4-diamino-phenyl) method of (4-fluorophenyl) ketone, is characterized in that: described organic solvent is that one or more in methyl alcohol, ethanol, Virahol, benzene,toluene,xylene, ethyl acetate, oil of mirbane, normal hexane, hexanaphthene, tetrahydrofuran (THF) mix with arbitrary proportion.
6. a kind of shortening is prepared high purity (3 according to claim 1,4-diamino-phenyl) method of (4-fluorophenyl) ketone, it is characterized in that: described hydrogenation reduction temperature is 20 ℃～80 ℃, hydrogenation reduction pressure 0.4MPa～1.5MPa, the hydrogenation reduction time is 2～8 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106083622A (en) * | 2016-06-16 | 2016-11-09 | 常州齐晖药业有限公司 | A kind of preparation method of mebendazole intermediate 3,4 diaminobenzophenone |
| CN112138651A (en) * | 2020-09-30 | 2020-12-29 | 西安凯立新材料股份有限公司 | Platinum-carbon catalyst for synthesizing flufenacet intermediate and preparation method and application thereof |
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| CN102276490A (en) * | 2011-06-30 | 2011-12-14 | 常州寅盛药业有限公司 | Method for preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083622A (en) * | 2016-06-16 | 2016-11-09 | 常州齐晖药业有限公司 | A kind of preparation method of mebendazole intermediate 3,4 diaminobenzophenone |
| CN106083622B (en) * | 2016-06-16 | 2018-06-19 | 常州齐晖药业有限公司 | A kind of preparation method of mebendazole intermediate 3,4- diaminobenzophenones |
| CN112138651A (en) * | 2020-09-30 | 2020-12-29 | 西安凯立新材料股份有限公司 | Platinum-carbon catalyst for synthesizing flufenacet intermediate and preparation method and application thereof |
| CN112138651B (en) * | 2020-09-30 | 2023-03-03 | 西安凯立新材料股份有限公司 | Platinum-carbon catalyst for synthesizing flufenacet intermediate and preparation method and application thereof |
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