CN102363591A - Method for preparing 4,4'-difluorobenzil - Google Patents
Method for preparing 4,4'-difluorobenzil Download PDFInfo
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- CN102363591A CN102363591A CN2011103673512A CN201110367351A CN102363591A CN 102363591 A CN102363591 A CN 102363591A CN 2011103673512 A CN2011103673512 A CN 2011103673512A CN 201110367351 A CN201110367351 A CN 201110367351A CN 102363591 A CN102363591 A CN 102363591A
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Abstract
The invention discloses a method for preparing 4,4'-difluorobenzil, which comprises: preparing 1,2-bis(-4-fluorophenyl)-2-hydroxy ethanone by subjecting p-fluorobenzaldehyde serving as a raw material to a condensation reaction in saturated ethanol solution of NaOH in the presence of vitamin B1 or 3-propyl-4-methyl-5-ethoxy thiazole bromine serving as a catalyst; and oxidizing 1,2-bis(-4-fluorophenyl)-2-hydroxy ethanone to obtain 4,4'-difluorobenzil. The method for preparing 4,4'-difluorobenzil, which is disclosed by the invention, adopts readily available raw material, is simple in operation and suitable for industrial production, has high product yield and high practicality and can create great economic and social benefit.
Description
Technical field
The invention belongs to the organic cpds synthesis technical field, be specifically related to a kind of preparation 4, the method for 4 '-difluoro benzil.
Background technology
4,4 '-difluoro benzil is a kind of important organic synthesis intermediate, is widely used in the synthetic of luminescent material and medicine intermediate.Existing synthetic 4, in the method for 4 '-difluoro benzil, the main weak point that exists comprises that reaction raw materials obtains difficulty, and reactions step is loaded down with trivial details, and the catalyst system therefor kind is many, need be to synthetic 4, and the method for 4 '-difluoro benzil is improved and is innovated.
Summary of the invention
Goal of the invention: the deficiency to existing in the prior art, the purpose of this invention is to provide a kind of preparation 4, the method for 4 '-difluoro benzil, a kind of raw material cheaply is easy to get to realize providing, the synthesis technique of yield height, suitable suitability for industrialized production simple to operate.
Technical scheme: in order to realize the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of preparation 4, the method for 4 '-difluoro benzil is a raw material with the p-Fluorobenzenecarboxaldehyde; With VITMAIN B1 or 3-propyl group-4-methyl-5-hydroxy ethylthiazole bromine salt is catalyzer; In saturated NaOH ethanolic soln, carry out condensation reaction, make 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone; Oxidation 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone makes 4,4 '-difluoro benzil.Reaction formula is following:
Above-mentioned preparation 4, the method for 4 '-difluoro benzil, concrete steps are following:
(1) in reactor drum, add VITMAIN B1, saturated NaOH ethanolic soln slowly drips p-Fluorobenzenecarboxaldehyde, 60 ℃ of temperature controls, and reaction 6h is cooled to 0 ~ 5 ℃, and crystallization 4h has solid to separate out, and filters; Filter cake water and washing with alcohol obtain yellow solid, and drying obtains 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone;
(2) in reactor drum, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone and 50% (v/v) aqueous ethanolic solution and concentrated hydrochloric acid adds FeCl
3, heat up 70 ~ 75 ℃ reaction 3h; Be cooled to room temperature, add methylene dichloride and stir, filter, filter cake is with 50mL * 3 washed with dichloromethane; Merging filtrate and washing lotion are told organic layer, and water layer is with 150mL * 2 dichloromethane extractions, combining extraction liquid; Anhydrous sodium sulfate drying, the filtering siccative, filtrate decompression concentrates; Use the 20mL ethyl alcohol recrystallization, obtain yellow solid and be 4,4 '-difluoro benzil.
Beneficial effect: with existing 4; 4 '-difluoro benzil is the preparation method compare, preparation 4 of the present invention, and the outstanding advantage that 4 '-difluoro benzil method has comprises: this method raw material is easy to get; Suitability for industrialized production simple to operate and suitable; Product yield is high, has good practicability, can produce favorable economic benefit and social benefit.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation.
Embodiment 1
In the 500mL there-necked flask, add the 1.0g VITMAIN B1 under the room temperature, saturated NaOH ethanolic soln 300mL slowly drips p-Fluorobenzenecarboxaldehyde 15g, and controlled temperature is at 60 ℃, and reaction 6h is cooled to 0 ~ 5 ℃, and crystallization 4h has solid to separate out, and filters.Filter cake water and washing with alcohol obtain yellow solid, and drying obtains 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone 15g, yield 50%.
In the 250mL there-necked flask, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone 15g and 50% aqueous ethanolic solution 150mL and 0.5mL concentrated hydrochloric acid add FeCl
315g, 70 ~ 75 ℃ of reaction 3h heat up.Be cooled to room temperature, add the 250mL methylene dichloride and stir, filter, filter cake is with 50mL * 3 washed with dichloromethane; Merging filtrate and washing lotion are told organic layer, and water layer is with 150mL * 2 dichloromethane extractions, combining extraction liquid; Anhydrous sodium sulfate drying, the filtering siccative, filtrate decompression concentrates, and uses the 20mL ethyl alcohol recrystallization; Obtain yellow solid and be 4,4 '-difluoro benzil 10g, m.p:118 ~ 120 ℃, yield 67%.
Embodiment 2
In the 500mL there-necked flask, add 3-propyl group-4-methyl-5-hydroxy ethylthiazole bromine salt 1.6g under the room temperature, saturated NaOH ethanolic soln 300mL slowly drips p-Fluorobenzenecarboxaldehyde 30g; Controlled temperature is at 60 ℃, and reaction 6h is cooled to 0 ~ 5 ℃; Crystallization 4h has solid to separate out, and filters.Filter cake water and washing with alcohol obtain yellow solid, and drying obtains 15.8g, yield 55%.
In the 250mL there-necked flask, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone 15g and 50% aqueous ethanolic solution 150mL and 0.5mL concentrated hydrochloric acid add FeCl
315g, 70 ~ 75 ℃ of reaction 3h heat up.Be cooled to room temperature, add the 250mL methylene dichloride and stir, filter, filter cake is with 50mL * 3 washed with dichloromethane; Merging filtrate and washing lotion are told organic layer, and water layer is with 150mL * 2 dichloromethane extractions, combining extraction liquid; Anhydrous sodium sulfate drying, the filtering siccative, filtrate decompression concentrates, and uses the 20mL ethyl alcohol recrystallization; Obtain yellow solid and be 4,4 '-difluoro benzil, m.p:118 ~ 120 ℃, yield 68%.
Embodiment 3
In the 500mL there-necked flask, add the 2g VITMAIN B1 under the room temperature, saturated NaOH ethanolic soln 350mL slowly drips p-Fluorobenzenecarboxaldehyde 25g, and controlled temperature is at 60 ℃, and reaction 7h is cooled to 0 ~ 5 ℃, and crystallization 5h has solid to separate out, and filters.Filter cake is water and washing with alcohol successively, obtains yellow solid, and drying obtains 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone.
In the 500mL there-necked flask, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone 20g and 50% aqueous ethanolic solution 200mL and 0.8mL concentrated hydrochloric acid add FeCl
320g, 70 ~ 75 ℃ of reaction 4h heat up.Be cooled to room temperature, add the 200mL methylene dichloride and stir, filter, filter cake is with 60mL * 3 washed with dichloromethane; Merging filtrate and washing lotion are told organic layer, and water layer is with 180mL * 3 dichloromethane extractions, combining extraction liquid; Anhydrous sodium sulfate drying, the filtering siccative, filtrate decompression concentrates, and uses the 30mL ethyl alcohol recrystallization; Obtain yellow solid and be 4,4 '-difluoro benzil, m.p:118 ~ 120 ℃, yield 69%.
Embodiment 4
In the 500mL there-necked flask, add 3-propyl group-4-methyl-5-hydroxy ethylthiazole bromine salt 2.0g under the room temperature, saturated NaOH ethanolic soln 350mL slowly drips p-Fluorobenzenecarboxaldehyde 35g; Controlled temperature is at 60 ℃, and reaction 4.5h is cooled to 0 ~ 5 ℃; Crystallization 4.5h has solid to separate out, and filters.Filter cake water and washing with alcohol obtain yellow solid, and drying obtains 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone.
In the 500mL there-necked flask, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone 18g and 50% aqueous ethanolic solution 180mL and 0.7mL concentrated hydrochloric acid add FeCl
316g, 70 ~ 75 ℃ of reaction 4h heat up.Be cooled to room temperature, add the 260mL methylene dichloride and stir, filter, filter cake is with 55mL * 3 washed with dichloromethane; Merging filtrate and washing lotion are told organic layer, and water layer is with 170mL * 3 dichloromethane extractions, combining extraction liquid; Anhydrous sodium sulfate drying, the filtering siccative, filtrate decompression concentrates, and uses the 20mL ethyl alcohol recrystallization; Obtain yellow solid and be 4,4 '-difluoro benzil, m.p:118 ~ 120 ℃, yield 69%.
Claims (2)
1. one kind prepares 4; The method of 4 '-difluoro benzil; It is characterized in that: being raw material with the p-Fluorobenzenecarboxaldehyde, is catalyzer with VITMAIN B1 or 3-propyl group-4-methyl-5-hydroxy ethylthiazole bromine salt, in saturated NaOH ethanolic soln, carries out condensation reaction; Make 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone; Oxidation 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone makes 4,4 '-difluoro benzil.
2. preparation 4 according to claim 1, the method for 4 '-difluoro benzil is characterized in that, concrete steps are following:
(1) in reactor drum, add VITMAIN B1 or 3-propyl group-4-methyl-5-hydroxy ethylthiazole bromine salt, saturated NaOH ethanolic soln slowly drips p-Fluorobenzenecarboxaldehyde; 60 ℃ of temperature controls, reaction 5 ~ 7h is cooled to 0 ~ 5 ℃; Crystallization 4 ~ 5h filters filter cake water and washing with alcohol; Obtain yellow solid, drying obtains 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone;
(2) in reactor drum, add 1,2-two (4-fluorophenyl)-2-hydroxyl ethyl ketone, alcohol, concentrated hydrochloric acid and FeCl
3, heat up 70 ~ 75 ℃ reaction 3 ~ 4h; Be cooled to room temperature, add methylene dichloride and stir, filter; Filter cake is used washed with dichloromethane, and merging filtrate and washing lotion are told organic layer; Water layer is used dichloromethane extraction, anhydrous sodium sulfate drying extraction liquid, concentrating under reduced pressure extraction liquid; Use ethyl alcohol recrystallization, obtain yellow solid and be 4,4 '-difluoro benzil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916113A (en) * | 2017-04-21 | 2017-07-04 | 常州佳德医药科技有限公司 | 2,3 pairs of (4 fluorophenyl) 6,7 Difluoroquinoxalins and preparation method thereof |
| CN108558628A (en) * | 2018-04-03 | 2018-09-21 | 宁夏医科大学 | Benzoic preparation method |
| CN109020996A (en) * | 2018-09-03 | 2018-12-18 | 常州工程职业技术学院 | One kind having photoactive miscellaneous polycyclic compound and preparation method thereof |
-
2011
- 2011-11-18 CN CN2011103673512A patent/CN102363591A/en active Pending
Non-Patent Citations (3)
| Title |
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| 俞善信: "氯化铁对安息香的氧化", 《化学试剂》 * |
| 陈益民等: "苯甲醛安息香缩合反应催化合成苯偶姻新方法", 《精细化工中间体》 * |
| 高妍等: "间二硝基苯偶酰的合成新工艺", 《鞍山科技大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916113A (en) * | 2017-04-21 | 2017-07-04 | 常州佳德医药科技有限公司 | 2,3 pairs of (4 fluorophenyl) 6,7 Difluoroquinoxalins and preparation method thereof |
| CN108558628A (en) * | 2018-04-03 | 2018-09-21 | 宁夏医科大学 | Benzoic preparation method |
| CN108558628B (en) * | 2018-04-03 | 2021-06-25 | 宁夏医科大学 | Preparation method of benzoin |
| CN109020996A (en) * | 2018-09-03 | 2018-12-18 | 常州工程职业技术学院 | One kind having photoactive miscellaneous polycyclic compound and preparation method thereof |
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Application publication date: 20120229 |