CN101817735A - Method for synthesizing 2,3,4,4'-tetrahydroxybenzophenone - Google Patents
Method for synthesizing 2,3,4,4'-tetrahydroxybenzophenone Download PDFInfo
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- CN101817735A CN101817735A CN201010171290A CN201010171290A CN101817735A CN 101817735 A CN101817735 A CN 101817735A CN 201010171290 A CN201010171290 A CN 201010171290A CN 201010171290 A CN201010171290 A CN 201010171290A CN 101817735 A CN101817735 A CN 101817735A
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Abstract
The invention relates to a method for synthesizing 2,3,4,4'-tetrahydroxybenzophenone. In the method, methanol solution of boron trifluoride is used as a catalyst, pyrogallic acid and p-hydroxybenzoic acid are used as the raw materials to synthesize the 2,3,4,4'-tetrahydroxybenzophenone. The method is characterized in that: the methanol solution of boron trifluoride is used as a catalyst; and the pyrogallic acid and the p-hydroxybenzoic acid undergo an acylation reaction at a certain temperature to form the 2,3,4,4'-tetrahydroxybenzophenone.
Description
Technical field
The present invention relates to a kind of Synthetic 2,3,4,4 '-processing method of tetrahydroxybenzophenone: with boron trifluoride is catalyzer, is the raw material Synthetic 2 with pyrogallol and P-hydroxybenzoic acid, 3,4,4 '-tetrahydroxybenzophenone.
Background technology
2,3,4,4 '-tetrahydroxybenzophenone (THBP) is a kind of important organic intermediate, can be used for photo-resist, medicine intermediate, UV light absorber, resin stabilizer, dyestuff of microelectronic integrated circuit industry etc.Particularly in today that microelectronics industry develops rapidly, the demand as the THBP of ultraviolet positive photoresist sensitizer intermediate is sharply increased.China is one of IC industry major country of production in the world, and large-scale integrated circuit output accounts for more than 1/6 of global output, and the Application Areas of product and range of application enlarge rapidly.At present, the correlative study of THBP product also is in the starting stage in China, and domestic have only a few manufacturer production, and industrial scale is less, output is very limited, is difficult to satisfy domestic demand.Along with the development of microelectronics industry, the demand of this product sharply rises especially, and therefore, the exploitation of THBP has good market outlook.
The synthetic of THBP is classical Friedel-Crafts acylation reaction.The THBP synthetic method of bibliographical information mainly contains zinc chloride catalytie esterification method, resin catalysis, boron trifluoride catalysis method etc.Zinc chloride catalytie esterification method is that equimolar pyrogallol is mixed with P-hydroxybenzoic acid; react under zinc chloride and exsiccant ether existence condition, the shortcoming of this method is a long reaction time, the temperature of reaction height; strengthened the energy consumption of producing, and used inflammable ether as solvent.Resin catalysis is that equimolar pyrogallol and P-hydroxybenzoic acid mixing are reacted by resin column, though the productive rate of this method is higher, the resin regeneration time is long, and complex process is not suitable for large-scale production.The boron trifluoride catalysis method is to be raw material with pyrogallol and P-hydroxybenzoic acid, and tetrachloroethane is a solvent, and synthetic under boron trifluoride ether solution catalysis, temperature of reaction is 120 ℃, and the reaction times is 10h.The reaction conditions gentleness of this method, but long reaction time, the waste liquid amount of generation is big.
The emphasis of acylation reaction research concentrates on the gentle reaction medium of searching and catalyzer improves productive rate, simplification technology, reduction consumes and pollution efficiently.Therefore, seek the development trend that synthetic method efficient, energy-conservation, safety and environmental protection is this compounds research.
Summary of the invention
In order to solve the boron trifluoride diethyl etherate that prior art exists is that catalyzer, tetrachloroethane are solvent, and the shortcoming inflammable, that waste liquid amount is big the invention provides a kind of Synthetic 2,3,4,4 '-method of tetrahydroxybenzophenone, have productive rate height, raw material and advantage of low energy consumption.
Technical scheme of the present invention is: a kind of Synthetic 2; 3,4,4 '-method of tetrahydroxybenzophenone; with pyrogallol and P-hydroxybenzoic acid is raw material; carry out acylation reaction in the presence of catalyzer, reaction finishes postcooling, and adjust pH is to neutral; separate out crystallization; filter; washing; drying gets 2,3; 4; 4 '-the thick product of tetrahydroxybenzophenone, after activated carbon decolorizing is refining, get 2,3 again; 4; 4 '-the tetrahydroxybenzophenone purified product, described catalyzer is a boron trifluoride methanol solution, the mass volume ratio of pyrogallol and boron trifluoride methanol solution is 1: 4g/mL.
Synthetic method is more specifically:
The first step, synthetic: by pyrogallol and P-hydroxybenzoic acid charging capacity ratio is 1: 1.1 (mol: mol), pyrogallol and P-hydroxybenzoic acid are being carried out acylation reaction 2～6h in the presence of the catalyzer under 100～120 ℃; reaction finishes postcooling; reaction solution neutralizes with alkali lye, and adjust pH to 6～7 neutrality is separated out crystallization; after filtration; the washing after drying gets 2,3; 4,4 '-the thick product of tetrahydroxybenzophenone.Described catalyzer is a boron trifluoride methanol solution, and its consumption is 4: 1 (mL: g) with the volume mass ratio of pyrogallol; Described alkali lye is that the quality volumetric concentration is the sodium hydrogen carbonate solution of 3～5% (g/mL), uses the alkali lye amount to be limit with control pH value of solution value to neutrality.
Second step, refining: with the first step reaction obtain 2,3,4,4 '-the thick product of tetrahydroxybenzophenone is dissolved in the boiling water, add activated carbon decolorizing 10～20min, filtered while hot, filtrate crystallisation by cooling, filtration, drying, 2,3,4,4 '-the tetrahydroxybenzophenone purified product.Described boiling water consumption is 2,3,4,4 '-40～60 times of the thick quality product of tetrahydroxybenzophenone; Described activated carbon dosage is 5～15% of a thick quality product.
The synthetic method that the present invention addresses belongs to typical Friedel-Crafts reaction, being with a kind of lewis acid---boron trifluoride methanol solution is as catalyzer, need not use other solvent, make the reaction of pyrogallol (pyrogallol) and P-hydroxybenzoic acid, generate 2,3,4,4 '-tetrahydroxybenzophenone.Reaction formula is as follows:
This law and comparing with the method that with the tetrachloroethane is solvent synthesis of polyhydroxy benzophenone as catalyzer with boron trifluoride ether solution of having reported, though based on same reaction mechanism, materials are different with processing condition, have tangible beneficial effect.
Beneficial effect:
(1) the catalyzer boron trifluoride methanol solution of the present invention's selection is compared with the boron trifluoride diethyl etherate that existing report uses, and is safer.Though the two all is a boron trifluoride catalyst, its complex compound is respectively methyl alcohol and ether.16 ℃ of methyl alcohol boiling points, flash-point-45 ℃, limits of explosion 6.0～36.5% (percent by volume); And 34.6 ℃ of ether boiling points, volatility is big, and the people is had narcoticness, flash-point-45 ℃, limits of explosion 1.85～48.0%.
(2) boron trifluoride methanol solution is catalyzer in the synthesis technique of the present invention, also be solvent, do not need again when common use boron trifluoride diethyl etherate catalysis, to add other solvents such as tetrachloroethane, greatly reduce raw material consumption and waste liquid amount, reduce preparation cost, reduce and pollute.
(3) reaction times of the present invention short, when at 120 ℃ down during reaction, can in 2h, finish reaction, with reported method reaction times be that 10h compares the time of having saved greatly, this energy efficient greatly when carrying out suitability for industrialized production is raised the efficiency.The present invention can finish reaction under 100 ℃ of temperature of reaction, be that 120 ℃ of temperature have reduced by 20 ℃ than reported method temperature of reaction, and only this item will be saved a large amount of energy consumptions in factory's actual production.
(4) the present invention is the catalyzer Synthetic 2 with boron trifluoride methanol solution, 3,4,4 '-the reaction conditions gentleness of tetrahydroxybenzophenone, simple for process, consume with pollute relative less.
Description of drawings
Figure 12,3,4,4 '-infrared spectrogram of tetrahydroxybenzophenone.
Figure 22,3,4,4 '-the tetrahydroxybenzophenone hydrogen nuclear magnetic resonance (
1H-NMR) wave spectrogram.
Figure 32,3,4,4 '-the tetrahydroxybenzophenone hydrogen nuclear magnetic resonance (
1H-NMR) wave spectrum partial enlarged drawing.
Through the fusing point instrument measure 2,3,4,4 '-tetrahydroxybenzophenone product fusing point is 199～204 ℃, through IR,
1H-NMR determines its chemical structure.With the KBr compressing tablet, product is carried out Infrared spectroscopy, the infrared signature absorption peak of main group is: 3365.66cm
-1(HO-Ar); 1636.56cm
-1(C=O); 1607.53cm
-1, 1587.88cm
-1, 1432.30cm
-1(phenyl ring skeletal vibration) is with the main group infrared signature absorption basically identical in the target product structure.
1H-NMR analyzes: and δ 6.3976～6.4151 (d, 1H, HAr), δ 6.9588～6.9763 (d, 1H, HAr), δ 6.8744～6.8969 (m, 2H, 2 * HAr), δ 7.5350～7.5660 (m, 2H, 2 * HAr), δ 8.6084 (s, 1H ,-HO), δ 10.0215 (s, 1H ,-OH), δ 10.2278 (s, 1H,-OH), δ 12.0917 (s, 1H ,-HO), identify thus its chemical structure be 2,3,4,4 '-tetrahydroxybenzophenone.
Embodiment
Embodiment 1:
A kind of Synthetic 2,3,4,4 '-processing method of tetrahydroxybenzophenone, step is:
(1) be 1: 1.1 (mol: mol) by pyrogallol and P-hydroxybenzoic acid amount of substance ratio; the acylation reaction under certain catalyzer and temperature action with pyrogallol and P-hydroxybenzoic acid; reaction finishes postcooling, and reaction solution neutralizes with alkali lye, separates out crystallization; after filtration; the washing after drying gets 2,3; 4,4 '-the thick product of tetrahydroxybenzophenone.The catalyzer that acylation reaction adopted is a boron trifluoride methanol solution, and consumption is 4: 1 (mL: g) with the ratio of pyrogallol quality; Alkali lye is 3～5% (g/mL) sodium hydrogen carbonate solution, uses the alkali lye amount to be limit with control pH value of solution value in neutrality; Temperature of reaction is 100～120 ℃; Reaction times is 2～6h.
(2) reaction is obtained 2,3,4,4 '-the thick product of tetrahydroxybenzophenone is dissolved in the boiling water, adds activated carbon decolorizing, filtered while hot, the filtrate crystallisation by cooling, after filtration, drying, 2,3,4,4 '-the tetrahydroxybenzophenone purified product.The boiling water consumption is 2,3,4,4 '-50～60 times of the thick quality product of tetrahydroxybenzophenone; The gac add-on is 2,3,4,4 '-the thick quality product fractional 5% of tetrahydroxybenzophenone, bleaching time is 10～30min.
Embodiment 2:
(1) takes by weighing pyrogallol 6.3g and P-hydroxybenzoic acid 7.6g, add in three mouthfuls of reaction flasks of 500mL, add catalyzer boron trifluoride methanol solution 25mL, reaction 6h under 110 ℃, reaction finishes postcooling, and reaction solution neutralizes with 3% (g/mL) sodium hydrogen carbonate solution, adjust pH is to neutral, separate out crystallization, after filtration, the washing after drying, get 2,3,4,4 '-the thick product 10.06g of tetrahydroxybenzophenone.
(2) above-mentioned thick product is dissolved in the 500mL boiling water, adds 1.5g activated carbon decolorizing 20min, filtered while hot, the filtrate crystallisation by cooling filters, the pure water washing, drying, 2,3,4,4 '-tetrahydroxybenzophenone purified product 7.72g.
Embodiment 3:
Take by weighing pyrogallol 6.3g and P-hydroxybenzoic acid 7.6g, add in three mouthfuls of reaction flasks of 500mL, add catalyzer boron trifluoride methanol solution 25mL, reaction 2h under 120 ℃, reaction finishes postcooling, and reaction solution neutralizes with 5% (g/mL) sodium hydrogen carbonate solution, adjust pH is to neutral, separate out crystallization, after filtration, the washing after drying, get 2,3,4,4 '-the thick product 9.1g of tetrahydroxybenzophenone.
Embodiment 4:
(1) takes by weighing pyrogallol 12.6g and P-hydroxybenzoic acid 15.2g, add in three mouthfuls of reaction flasks of 250mL, add catalyzer boron trifluoride methanol solution 50mL, reaction 5h under 100 ℃, reaction finishes postcooling, and reaction solution neutralizes with 5% (g/mL) sodium hydrogen carbonate solution, adjust pH is to neutral, separate out crystallization, after filtration, the washing after drying, get 2,3,4,4 '-the thick product 18.0g of tetrahydroxybenzophenone.190～202 ℃ of fusing points.
(2) take by weighing thick product 3.0g, add 125mL water, add the 0.5g gac, add heat decoloring 15min, filtered while hot, the filtrate crystallisation by cooling, after filtration, drying, 2,3,4,4 '-tetrahydroxybenzophenone purified product 2.2g.204.5～213.2 ℃ of fusing points.
Comparative Examples:
Take by weighing pyrogallol 6.3g and P-hydroxybenzoic acid 7.6g, add in three mouthfuls of reaction flasks of 500mL, add catalyzer boron trifluoride acetic acid solution 25mL, react 6h down in 110 ℃, reaction finishes postcooling, and reaction solution neutralizes with 3% (g/mL) sodium hydrogen carbonate solution, and adjust pH is to neutral, separate out crystallization, after filtration, the washing after drying gets 2,3, the thick product of 4-trihydroxy-acetophenone.
By Comparative Examples as can be seen, but be not that equal this reaction of catalysis of all boron trifluoride solution obtains target product 2,3,4,4 '-tetrahydroxybenzophenone.Optimize boron trifluoride methanol and can obtain best effect by experiment repeatedly as catalyzer.
Claims (4)
1. Synthetic 2; 3,4,4 '-method of tetrahydroxybenzophenone; with pyrogallol and P-hydroxybenzoic acid is raw material; carry out acylation reaction in the presence of catalyzer, reaction finishes postcooling, and adjust pH is to neutral; separate out crystallization; filter; washing; drying gets 2,3; 4; 4 '-the thick product of tetrahydroxybenzophenone, after activated carbon decolorizing is refining, get 2,3 again; 4; 4 '-the tetrahydroxybenzophenone purified product, it is characterized in that: described catalyzer is a boron trifluoride methanol solution, the mass volume ratio of pyrogallol and boron trifluoride methanol solution is 1: 4g/mL.
2. Synthetic 2 as claimed in claim 1,3,4,4 '-method of tetrahydroxybenzophenone, it is characterized in that concrete steps are:
The first step, synthetic: by pyrogallol and P-hydroxybenzoic acid mol ratio is 1: 1.1, and pyrogallol and P-hydroxybenzoic acid are being carried out acylation reaction 2～6h under 100～120 ℃ in the presence of the catalyzer, reaction finishes postcooling, reaction solution neutralizes with alkali lye, and crystallization is separated out in adjust pH to 6～7, after filtration, the washing after drying gets 2,3,4,4 '-the thick product of tetrahydroxybenzophenone;
Second step, refining: with the first step reaction obtain 2,3,4,4 '-the thick product of tetrahydroxybenzophenone is dissolved in the boiling water, add activated carbon decolorizing 10～20min, filtered while hot, filtrate crystallisation by cooling, filtration, drying, 2,3,4,4 '-the tetrahydroxybenzophenone purified product.
3. Synthetic 2 as claimed in claim 2,3,4,4 '-method of tetrahydroxybenzophenone, it is characterized in that described alkali lye is that the quality volumetric concentration is the sodium hydrogen carbonate solution of 3～5%g/mL, use the alkali lye amount to be limit with control pH value of solution value to 6～7.
4. Synthetic 2 as claimed in claim 2,3,4,4 '-method of tetrahydroxybenzophenone, it is characterized in that, described activated carbon dosage is 2,3,4,4 '-the thick quality product of tetrahydroxybenzophenone 5～15%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120608A (en) * | 2010-12-23 | 2011-07-13 | 广西民族大学 | Novel method for studying in-situ growth process of cadmium sulfide nanosphere |
| CN103449998A (en) * | 2013-08-26 | 2013-12-18 | 曹庸 | Method for heterogeneous synthesis of 2,3,4,4'-tetrahydroxy benzophenone |
| CN106349036A (en) * | 2016-08-28 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | 2,3,4,4'-tetrahydroxy benzophenone preparation method |
| CN106365961A (en) * | 2016-08-28 | 2017-02-01 | 遵义市倍缘化工有限责任公司 | Method for preparing 2,3,4,4' tetrahydroxy diphenyl ketone at normal pressure |
| CN109232205A (en) * | 2018-11-14 | 2019-01-18 | 大晶信息化学品（徐州）有限公司 | A kind of preparation method of tetracarboxylic benzophenone |
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| JPH06172252A (en) * | 1992-12-09 | 1994-06-21 | Taoka Chem Co Ltd | Production of benzophenones |
| CN101643398A (en) * | 2009-09-07 | 2010-02-10 | 湖南先伟实业有限公司 | Preparation method of 2,3,4,4'-tetrahydroxyldiphenylketone |
-
2010
- 2010-05-13 CN CN201010171290A patent/CN101817735A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172252A (en) * | 1992-12-09 | 1994-06-21 | Taoka Chem Co Ltd | Production of benzophenones |
| CN101643398A (en) * | 2009-09-07 | 2010-02-10 | 湖南先伟实业有限公司 | Preparation method of 2,3,4,4'-tetrahydroxyldiphenylketone |
Non-Patent Citations (2)
| Title |
|---|
| 《精细化工中间体》 20020228 王振宇等 2，3，4，4'-四羟基二苯甲酮合成研究 第18-20页 1-4 第32卷, 第1期 * |
| 王振宇等: "2，3，4，4′-四羟基二苯甲酮合成研究", 《精细化工中间体》, vol. 32, no. 1, 28 February 2002 (2002-02-28), pages 18 - 20 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120608A (en) * | 2010-12-23 | 2011-07-13 | 广西民族大学 | Novel method for studying in-situ growth process of cadmium sulfide nanosphere |
| CN103449998A (en) * | 2013-08-26 | 2013-12-18 | 曹庸 | Method for heterogeneous synthesis of 2,3,4,4'-tetrahydroxy benzophenone |
| CN106349036A (en) * | 2016-08-28 | 2017-01-25 | 遵义市倍缘化工有限责任公司 | 2,3,4,4'-tetrahydroxy benzophenone preparation method |
| CN106365961A (en) * | 2016-08-28 | 2017-02-01 | 遵义市倍缘化工有限责任公司 | Method for preparing 2,3,4,4' tetrahydroxy diphenyl ketone at normal pressure |
| CN109232205A (en) * | 2018-11-14 | 2019-01-18 | 大晶信息化学品（徐州）有限公司 | A kind of preparation method of tetracarboxylic benzophenone |
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Application publication date: 20100901 |