CN102942463B - A kind of preparation method of benzophenone compound - Google Patents
A kind of preparation method of benzophenone compound Download PDFInfo
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- CN102942463B CN102942463B CN201210468587.XA CN201210468587A CN102942463B CN 102942463 B CN102942463 B CN 102942463B CN 201210468587 A CN201210468587 A CN 201210468587A CN 102942463 B CN102942463 B CN 102942463B
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Abstract
The invention discloses a kind of preparation method of benzophenone compound, this preparation method with the aromatic compound shown in formula (I) and Benzoyl chloride for raw material, obtained benzophenone compound shown in formula III under Gemini surface active agent katalysis, reaction formula is as follows:
in formula (I), formula III, substituent R is-H ,-F ,-Cl ,-Br ,-(CH
2) n CH
3or-O (CH
2) nCH
3, wherein n=1 ~ 7.Compared with prior art, the reaction system have 1, using is cheap and easy to get, low cost of manufacture in the present invention, simple to operate, transformation efficiency is high, mild condition, and the three wastes are few, convenient post-treatment, little to equipment corrosion, and catalytic activity is high, long service life.2, utilizing reusable Gemini surface active agent system to substitute the influential organic solvent of environment, is economical and practical green environmental protection technique.
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 Recent study water-soluble light trigger the most widely, it is high, colourless, tasteless that water-based Benzophenone-type light initiator has light-initiated efficiency, the advantages such as high water soluble are had in very wide pH value range, considerable status is occupied in water-soluble photoinitiator, mainly on benzophenone parent nucleus, introduce ionic group, as quaternary ammonium salt or sulfonate groups, make it both maintain the Photoinitiation Property of parent, in turn enhance water-soluble.The low prices such as Benzophenone-type light initiator benzophenone, 4-methyl benzophenone, 2 methyl benzophenone, laser curing velocity are fast, raw material is easy to get, exploitation has the water-soluble photoinitiator kind of independent intellectual property right, Application and Development cost can be reduced, excellent Photoinitiation Property can be had again.Therefore, the synthesis of this photoinitiator is with a wide range of applications.This product in the past mainly the flourishing industrialized country such as Europe, North America and Japan produce and use this product.In recent years, domestic market is along with transition of China's economic and modernization, and quick rising tendency has appearred in the demand of China.The benzophenone that annual China produces can not only meet domestic demand, but also the developed countries such as a large amount of outlet America and Europes.Present whole world year, consumption rate of increase was about 5 ~ 7%, according to world market investigation and assessment, world's year volume of production and marketing of benzophenone, at about 6000 tons, is mainly used in industry and the fields such as photosensitizers, chemical synthetic drug, spices and essence and other special chemical synthesis.
Gemini surface active agent is a 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 multiple advantages such as good water-soluble and rheological, have wide practical use.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of utilize Gemini surface active agent effect under prepare the method for benzophenone compound, 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 with the aromatic compound shown in formula (I) and Benzoyl chloride for raw material, obtained benzophenone compound shown in formula III under Gemini surface active agent katalysis, and reaction formula is as follows:
（I） (Ⅲ)
In formula (I), formula III, substituent R is-H ,-F ,-Cl ,-Br ,-(CH
2) n CH
3or-O (CH
2) nCH
3, wherein n=1 ~ 7.
Further, this preparation method comprises the steps:
(1), add in reaction vessel by aromatic compound, Benzoyl chloride and the Gemini surface active agent shown in formula (I), heating, reaction, 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 as shown in formula II:
(Ⅱ)。
Further, in described step (1), the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 1-10: 1.
Further, in described step (1), the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 3-5: 1.
Further, in described step (1), temperature of reaction is 50-150 DEG C.
Further, in described step (1), temperature of reaction is 60-120 DEG C.
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 described step (2) comprises extraction, washing, organic layer drying, underpressure distillation desolventizing successively, obtains white crystalline product finally by column chromatography.
Compared with prior art, tool has the following advantages in the present invention: the reaction system 1, used is cheap and easy to get, low cost of manufacture, and operating process is simple, transformation efficiency is high, mild condition, the three wastes are few, convenient post-treatment, little to the corrosion of equipment, the activity of catalysis is high, long service life.2, utilize Gemini surface active agent system to substitute the influential organic solvent of environment, being a new synthesis technique, is a novelty production technology.And Gemini surface active agent is reusable, it is economical and practical green environmental protection technique.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, 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 grams are joined in 150 milliliters of there-necked flasks with electric stirring, thermometer, reflux condensing tube, be heated to 100 DEG C, react 8 hours, react complete, directly add 30 milliliters of toluene and extract 3 times, extraction liquid is successively through saturated NaHCO
3solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4dry, underpressure distillation removing toluene, be separated through column chromatography (sherwood oil: ethyl acetate=20:1) and obtain product 10.2g, yield is 56%, fusing point 46-47 DEG C (literature value 45-49 DEG C), HPLC(High Performance Liquid Chromatography high performance liquid chromatography) detect product purity and reach 99.5%.
Embodiments of the invention 2:
the preparation of 2,4-methyl benzophenone
Toluene 9.2 grams (0.1 mole), Benzoyl chloride 30 grams (0.2 mole), Gemini surface active agent 30 grams are joined in 150 milliliters of there-necked flasks with electric stirring, thermometer, reflux condensing tube, be heated to 110 DEG C, react 5 hours, react complete, directly add 30 milliliters of toluene and extract 3 times, extraction liquid is successively through saturated NaHCO
3solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4drying, underpressure distillation removing toluene, be separated through column chromatography (sherwood oil: ethyl acetate=20:1) and obtain product 11.4g, yield is 58%, fusing point 53-55 DEG C (literature value 54-57 DEG C), and HPLC detects product purity and reaches 99.5%.
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 grams are joined in 150 milliliters of there-necked flasks with electric stirring, thermometer, reflux condensing tube, be heated to 150 DEG C, react 5 hours, react complete, directly add 30 milliliters of toluene and extract 3 times, extraction liquid is successively through saturated NaHCO
3solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4drying, underpressure distillation removing toluene, be separated through column chromatography (sherwood oil: ethyl acetate=20:1) and obtain product 11.9g, yield is 55%, fusing point 74-76 DEG C (literature value 75-77 DEG C), and HPLC detects product purity and reaches 99.5%.
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 grams are joined in 150 milliliters of there-necked flasks with electric stirring, thermometer, reflux condensing tube, be heated to 60 DEG C, react 10 hours, react complete, directly add 30 milliliters of toluene and extract 3 times, extraction liquid is successively through saturated NaHCO
3solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4drying, underpressure distillation removing toluene, be separated through column chromatography (sherwood oil: ethyl acetate=20:1) and obtain product 12.1g, yield is 57%, fusing point 59-61 DEG C (literature value 58-562 DEG C), and HPLC detects product purity and reaches 99.5%.
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 grams are joined in 150 milliliters of there-necked flasks with electric stirring, thermometer, reflux condensing tube, be heated to 80 DEG C, react 10 hours, react complete, directly add 30 milliliters of toluene and extract 3 times, extraction liquid is successively through saturated NaHCO
3solution, saturated NaCl solution, distilled water wash, the anhydrous MgSO of toluene layer
4drying, underpressure distillation removing toluene, be separated through column chromatography (sherwood oil: ethyl acetate=20:1) and obtain product 12.7g, yield is 56%, fusing point 46-48 DEG C (literature value 46-48 DEG C), and HPLC detects product purity and reaches 99.5%.
Through following alkylation, sulfonation and neutralization reaction, obtained (this preparation method can with reference to " the synthesis and property research of Shuangzi face tensio-active agent " successively for the present invention's ditane Gemini surface active agent used, Hu Longjiang, Daqing Petroleum Institute's Master's thesis, 2004):
(1) alkylation, in four mouthfuls of reaction flasks 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 DEG C, dropwise adding in 20-30 minute with the mol ratio of ditane is the alkene of 2:1, then gradually temperature of reaction is risen to 70 DEG C, and remains unchanged, react end in 8 hours, catalyzer in removing system, is washed to neutrality, obtains alkylate for sulfonation;
(2) sulfonation, in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel, HCl gas absorbing device are housed, dropwise add alkylate and chlorsulfonic acid that mol ratio is 2:1 under vigorous stirring, time for adding is l hour, temperature of reaction controls at 20-25 DEG C, reacts 2 hours, after making the abundant sulfonation of alkylate, product is placed some hours, the HCl of generation is discharged as far as possible;
(3) neutralization reaction, sulfonated products is added in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed, temperature of reaction is controlled at 35 ~ 40 DEG C with water-bath, with dropping funnel by 15%(weight) sodium hydroxide solution slowly adds, regulation system pH value is 7 ~ 8, makes sulfonic acid all generate sodium sulfonate.
Claims (4)
1. the preparation method of a benzophenone compound, it is characterized in that, this preparation method with the aromatic compound shown in formula I and Benzoyl chloride for raw material, obtained benzophenone compound shown in formula III under Gemini surface active agent katalysis, reaction formula is as follows:
In formula I, formula III, substituent R is-H ,-F ,-Cl ,-Br ,-(CH
2)
ncH
3or-O (CH
2)
ncH
3, wherein n=1 ~ 7, this preparation method comprises the steps:
(1) add in reaction vessel by aromatic compound, Benzoyl chloride and the Gemini surface active agent shown in formula (1), heating, reaction, to reacting complete;
(2) step (1) products therefrom is obtained described benzophenone compound through aftertreatment.
Described Gemini surface active agent is ditane Gemini surface active agent, structural formula such as formula
(II) shown in:
In described step (1), the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 1-10:1, temperature of reaction is 50-150 DEG C, reaction times is 1-10 hour, aftertreatment in described step (2) comprises extraction, washing, organic layer drying, underpressure distillation desolventizing successively, obtains white crystalline product finally by column chromatography.
2. the preparation method of benzophenone compound according to claim 1, is characterized in that, in step (1), the mass ratio that feeds intake of Gemini surface active agent and aromatic compound is 3-5:1.
3. the preparation method of benzophenone compound according to claim 1, is characterized in that, in described step (1), temperature of reaction is 60-120 DEG C.
4. the preparation method of benzophenone compound according to claim 1, is characterized in that, in reactions steps (1), the reaction times is 5-8 hour.
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| 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 |
| CN103833496B (en) * | 2014-01-26 | 2015-10-07 | 浙江工业大学 | A kind of preparation method of plant polyphenol esterified derivative |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| 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 |
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| 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;于涛等;《大庆石油学院学报》;20040229;第28卷(第1期);第35-37页 * |
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