CN102942463A - Preparation method for benzophenone compound - Google Patents
Preparation method for benzophenone compound Download PDFInfo
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- CN102942463A CN102942463A CN201210468587XA CN201210468587A CN102942463A CN 102942463 A CN102942463 A CN 102942463A CN 201210468587X A CN201210468587X A CN 201210468587XA CN 201210468587 A CN201210468587 A CN 201210468587A CN 102942463 A CN102942463 A CN 102942463A
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Abstract
The invention discloses a preparation method for a benzophenone compound. According to the preparation method, an aromatic compound and a benzoyl chloride expressed by a formula (I) are taken as raw materials for preparing the benzophenone compound expressed by a formula (III) under a catalytic action of a dimeric surfactant. The reaction formula is as follows, wherein substituent groups R in the formula (I) and formula (III) are -H, -F, -Cl, -Br, -(CH2)nCH3 or -O(CH2)nCH3, and n is equal to 1-7. Compared with the prior art, the preparation method has the advantages that 1) the adopted reaction system is low-cost and easily obtained, the manufacturing cost is low, the operation is simple, the conversion rate is high, the condition is mild, the three wastes are few, the post-processing is conveniently performed, the corrosion to equipment is small, the catalytic activity is high and the service life is long, and 2) an organic solvent having influence on the environment is replaced by using a reusable dimeric surfactant system, and the preparation method is an economical and practical environment-friendly technology.
Description
Technical field
The present invention relates to a kind of light trigger, be specifically related to the preparation method of benzophenone compound.
Background technology
Benzophenone compound is the most widely water-soluble light trigger of Recent study, it is high, colourless, tasteless that water-based benzophenone photoinitiator has light-initiated efficient, the advantages such as high water soluble are arranged in very wide pH value scope, in water-soluble photoinitiator, occupy considerable status, mainly be to introduce ionic group at the benzophenone parent nucleus, such as quaternary ammonium salt or sulfonate groups, so that it had both kept the Photoinitiation Property of parent, strengthened again water-soluble.The prices such as benzophenone photoinitiator benzophenone, 4-methyldiphenyl ketone, 2 methyl benzophenone are cheap, laser curing velocity fast, raw material is easy to get, exploitation has the water-soluble photoinitiator kind of independent intellectual property right, can reduce the Application and Development cost, can have again excellent Photoinitiation Property.Therefore, the synthetic of this photoinitiator is with a wide range of applications.This product mainly is in the past that the flourishing industrialized countries such as Europe, North America and Japan produce and use this product.In recent years, the domestic market is along with transition and the modernization of China's economic, and rapid growth trend has appearred in the demand of China.The benzophenone that annual China produces can not only satisfy domestic demand, but also the developed countries such as a large amount of outlet America and Europes.Now the consumption rate of increase is about 5～7% whole world year, according to the world market investigation and assessment, world's year volume of production and marketing of benzophenone is mainly used in industry and the fields such as photosensitizers, chemical synthetic drug, spices and essence and other special chemicals be synthetic about 6000 tons.
Gemini surface active agent is the class spy with two hydrophilic radicals and two lipophilic groups
The tensio-active agent of different structure has higher better surfactivity than conventional surfactant (only having a hydrophilic radical and a lipophilic group).Gemini surface active agent is the novel surfactant of a class performance brilliance, has high surfactivity.The good multiple advantages such as water-soluble and rheological have wide practical use.
Summary of the invention
Technical problem to be solved by this invention is, a kind of method for preparing benzophenone compound under the Gemini surface active agent effect of utilizing is provided, and the method is easy to operate, and transformation efficiency is high, and the three wastes are few, convenient post-treatment.
Technical scheme of the present invention:
The preparation method of benzophenone compound of the present invention is take the aromatic compound shown in the formula (I) and Benzoyl chloride as raw material, makes the benzophenone compound shown in the formula III under the Gemini surface active agent katalysis, and reaction formula is as follows:
（I） (Ⅲ)
In formula (I), the formula III substituent R be-H ,-F ,-Cl ,-Br ,-(CH
2) n CH
3Or-O (CH
2) nCH
3, n=1～7 wherein.
Further, this preparation method comprises the steps:
(1), the aromatic compound shown in the formula (I), Benzoyl chloride and Gemini surface active agent are added in the reaction vessel, heating, reaction is to reacting complete;
(2), step (1) products therefrom is obtained described benzophenone compound through aftertreatment.
Further, described Gemini surface active agent ditane Gemini surface active agent, structural formula is shown in formula II:
(Ⅱ)。
Further, the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 1-10 in the described step (1): 1.
Further, the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 3-5 in the described step (1): 1.
Further, temperature of reaction is 50-150 ℃ in the described step (1).
Further, temperature of reaction is 60-120 ℃ in the described step (1).
Further, the reaction times of described step (1) is 1-10 hour.
Further, the reaction times of described step (1) is 5-8 hour.
Further, the aftertreatment in the described step (2) comprises extraction, washing, organic layer drying, underpressure distillation desolventizing successively, obtains the white crystals product finally by column chromatography.
The present invention compared with prior art has following advantage: 1, employed reaction system is cheap and easy to get, low cost of manufacture, and operating process is simple, transformation efficiency is high, mild condition, and the three wastes are few, convenient post-treatment, corrosion to equipment is little, catalysis active high, long service life.2, utilizing the Gemini surface active agent system to substitute the influential organic solvent of environment, is a new synthesis technique, is a novelty production technology.And Gemini surface active agent is reusable, is economical and practical green environmental protection technique.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
Embodiments of the invention 1:
The preparation of benzophenone
Benzene 7.8 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 40 are restrained in 150 milliliters of there-necked flasks that join with electric stirring, thermometer, reflux condensing tube, be heated to 100 ℃, reacted 8 hours, react complete, directly add 30 milliliters of toluene extractions 3 times, extraction liquid is successively through saturated NaHCO
3Solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4Dry, toluene is removed in underpressure distillation, (sherwood oil: ethyl acetate=20:1) separation obtains product 10.2g through column chromatography, yield is 56%, fusing point 46-47 ℃ (literature value 45-49 ℃), HPLC(High Performance Liquid Chromatography high performance liquid chromatography) detects product purity and reach 99.5%.
Embodiments of the invention 2:
The preparation of 2,4-methyldiphenyl ketone
Toluene 9.2 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 30 are restrained in 150 milliliters of there-necked flasks that join with electric stirring, thermometer, reflux condensing tube, be heated to 110 ℃, reacted 5 hours, react complete, directly add 30 milliliters of toluene extractions 3 times, extraction liquid is successively through saturated NaHCO
3Solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4Drying, toluene is removed in underpressure distillation, and (sherwood oil: ethyl acetate=20:1) separation obtains product 11.4g, and yield is 58%, and fusing point 53-55 ℃ (literature value 54-57 ℃), HPLC detect product purity and reach 99.5% through column chromatography.
Embodiments of the invention 3:
The preparation of 3,4-chlorobenzophenone
Chlorobenzene 12 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 80 are restrained in 150 milliliters of there-necked flasks that join with electric stirring, thermometer, reflux condensing tube, be heated to 150 ℃, reacted 5 hours, react complete, directly add 30 milliliters of toluene extractions 3 times, extraction liquid is successively through saturated NaHCO
3Solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4Drying, toluene is removed in underpressure distillation, and (sherwood oil: ethyl acetate=20:1) separation obtains product 11.9g, and yield is 55%, and fusing point 74-76 ℃ (literature value 75-77 ℃), HPLC detect product purity and reach 99.5% through column chromatography.
Embodiments of the invention 4:
The preparation of 4,4-methoxy benzophenone
Methyl-phenoxide 11 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 60 are restrained in 150 milliliters of there-necked flasks that join with electric stirring, thermometer, reflux condensing tube, be heated to 60 ℃, reacted 10 hours, react complete, directly add 30 milliliters of toluene extractions 3 times, extraction liquid is successively through saturated NaHCO
3Solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4Drying, toluene is removed in underpressure distillation, and (sherwood oil: ethyl acetate=20:1) separation obtains product 12.1g, and yield is 57%, and fusing point 59-61 ℃ (literature value 58-562 ℃), HPLC detect product purity and reach 99.5% through column chromatography.
Embodiments of the invention 5:
The preparation of 4-oxethyl-diphenyl-ketone
Phenyl ethyl ether 12 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 36 are restrained in 150 milliliters of there-necked flasks that join with electric stirring, thermometer, reflux condensing tube, be heated to 80 ℃, reacted 10 hours, react complete, directly add 30 milliliters of toluene extractions 3 times, extraction liquid is successively through saturated NaHCO
3Solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4Drying, toluene is removed in underpressure distillation, and (sherwood oil: ethyl acetate=20:1) separation obtains product 12.7g, and yield is 56%, and fusing point 46-48 ℃ (literature value 46-48 ℃), HPLC detect product purity and reach 99.5% through column chromatography.
The used ditane Gemini surface active agent of the present invention makes through following alkylation, sulfonation and neutralization reaction successively that (this preparation method can be with reference to " the synthetic and performance study of Shuangzi face tensio-active agent ", Hu Longjiang, Daqing Petroleum Institute's Master's thesis, 2004):
(1) alkylation in the four-hole reaction flask that electric mixer, thermometer, reflux condensing tube, dropping funnel, HCl gas access equipment are housed, adds ditane, the AlC1 of catalytic amount
3, fully stir and make AlC1
3Be uniformly dispersed, pass into HCl gas, regulate temperature at 45-50 ℃, the mol ratio that dropwise adds in 20-30 minute with ditane is the alkene of 2:1, then temperature of reaction is risen to 70 ℃ gradually, and remains unchanged, react end in 8 hours, remove the catalyzer in the system, be washed to neutrality, get alkylate and be used for sulfonation;
(2) sulfonation, in the four-hole reaction flask that electric mixer, thermometer, reflux condensing tube, dropping funnel, HCl gas absorbing device are housed, under violent stirring, dropwise add alkylate and chlorsulfonic acid that mol ratio is 2:1, time for adding is l hour, temperature of reaction is controlled at 20-25 ℃, reacts 2 hours, make the abundant sulfonation of alkylate after, product was placed some hours, the HCl of generation is discharged as far as possible get final product;
(3) neutralization reaction, the sulfonated products adding is equipped with in the four-hole reaction flask of electric mixer, thermometer, reflux condensing tube, dropping funnel, control temperature of reaction at 35～40 ℃ with water-bath, with dropping funnel with 15%(weight) sodium hydroxide solution slowly adds, regulation system pH value is 7～8, makes sulfonic acid all generate sodium sulfonate.
Claims (10)
1. the preparation method of a benzophenone compound, it is characterized in that this preparation method is take the aromatic compound shown in the formula (I) and Benzoyl chloride as raw material, make the benzophenone compound shown in the formula III under the Gemini surface active agent katalysis, reaction formula is as follows:
(Ⅲ)
In formula (I), the formula III substituent R be-H ,-F ,-Cl ,-Br ,-(CH
2) n CH
3Or-O (CH
2) nCH
3, n=1～7 wherein.
2. the preparation method of benzophenone compound according to claim 1 is characterized in that this preparation method comprises the steps:
(1), the aromatic compound shown in the formula (I), Benzoyl chloride and Gemini surface active agent are added in the reaction vessel, heating, reaction is to reacting complete;
(2), step (1) products therefrom is obtained described benzophenone compound through aftertreatment.
3. the preparation method of benzophenone compound according to claim 1 and 2 is characterized in that described Gemini surface active agent ditane Gemini surface active agent, and structural formula is shown in formula II:
(Ⅱ)。
4. the preparation method of benzophenone compound according to claim 2 is characterized in that the mass ratio that feeds intake of the middle Gemini surface active agent of described step (1) and aromatic compound is 1-10: 1.
5. the preparation method of benzophenone compound according to claim 4 is characterized in that the mass ratio that feeds intake of the middle Gemini surface active agent of described step (1) and aromatic compound is 3-5: 1.
6. the preparation method of benzophenone compound according to claim 2 is characterized in that temperature of reaction is 50-150 ℃ in the described step (1).
7. the preparation method of benzophenone compound according to claim 6 is characterized in that temperature of reaction is 60-120 ℃ in the described step (1).
8. the preparation method of benzophenone compound according to claim 2, the reaction times that it is characterized in that described step (1) is 1-10 hour.
9. the preparation method of benzophenone compound according to claim 8, the reaction times that it is characterized in that described step (1) is 5-8 hour.
10. the preparation method of benzophenone compound according to claim 2 is characterized in that the aftertreatment in the described step (2) comprises extraction, washing, organic layer drying, underpressure distillation desolventizing successively, obtains the white crystals product finally by column chromatography.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664590A (en) * | 2013-12-20 | 2014-03-26 | 广东鑫钰新材料股份有限公司 | Method for synthesizing compound containing 4-(2-hydroxy ethoxy) diphenylketone structure or acetate thereof |
| CN103833496A (en) * | 2014-01-26 | 2014-06-04 | 浙江工业大学 | Preparation method of plant polyphenol esterification derivatives |
| CN105967985A (en) * | 2016-06-01 | 2016-09-28 | 上海应用技术学院 | Preparation method of 4-methyl-4'-fluorine-diphenyl ketone |
| CN108947785A (en) * | 2017-05-25 | 2018-12-07 | 湖南大学 | A kind of highly selective photocatalytic synthesis at benzophenone method |
| CN111960933A (en) * | 2020-07-20 | 2020-11-20 | 唐山龙泉化学助剂有限公司 | Synthesis of ultraviolet absorbent 4-n-hexyloxy benzophenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295546A (en) * | 2011-06-30 | 2011-12-28 | 浙江工业大学 | Method for preparing benzophenone compound |
| CN102746243A (en) * | 2012-07-23 | 2012-10-24 | 浙江常山科润化学有限公司 | Method for preparing 2-(2-hydroxy-3-chloracetyl-5-methylphenyl)benzotriazol |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295546A (en) * | 2011-06-30 | 2011-12-28 | 浙江工业大学 | Method for preparing benzophenone compound |
| CN102746243A (en) * | 2012-07-23 | 2012-10-24 | 浙江常山科润化学有限公司 | Method for preparing 2-(2-hydroxy-3-chloracetyl-5-methylphenyl)benzotriazol |
Non-Patent Citations (1)
| Title |
|---|
| 于涛等: "新型表面活性剂——双烷基双磺酸钠基二苯甲烷的合成与性能", 《大庆石油学院学报》, vol. 28, no. 1, 29 February 2004 (2004-02-29), pages 35 - 37 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664590A (en) * | 2013-12-20 | 2014-03-26 | 广东鑫钰新材料股份有限公司 | Method for synthesizing compound containing 4-(2-hydroxy ethoxy) diphenylketone structure or acetate thereof |
| CN103833496A (en) * | 2014-01-26 | 2014-06-04 | 浙江工业大学 | Preparation method of plant polyphenol esterification derivatives |
| CN103833496B (en) * | 2014-01-26 | 2015-10-07 | 浙江工业大学 | A kind of preparation method of plant polyphenol esterified derivative |
| CN105967985A (en) * | 2016-06-01 | 2016-09-28 | 上海应用技术学院 | Preparation method of 4-methyl-4'-fluorine-diphenyl ketone |
| CN105967985B (en) * | 2016-06-01 | 2019-01-04 | 上海应用技术学院 | A kind of preparation method of 4- methyl -4 '-fluoro- benzophenone |
| CN108947785A (en) * | 2017-05-25 | 2018-12-07 | 湖南大学 | A kind of highly selective photocatalytic synthesis at benzophenone method |
| CN108947785B (en) * | 2017-05-25 | 2021-03-26 | 湖南大学 | Method for synthesizing benzophenone by photocatalysis |
| CN111960933A (en) * | 2020-07-20 | 2020-11-20 | 唐山龙泉化学助剂有限公司 | Synthesis of ultraviolet absorbent 4-n-hexyloxy benzophenone |
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| CN102942463B (en) | 2015-08-26 |
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