CN102329207A - Synthesis method of 2, 2'-dihydroxy-4, 4'-dimethoxybenzophenone - Google Patents
Synthesis method of 2, 2'-dihydroxy-4, 4'-dimethoxybenzophenone Download PDFInfo
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- CN102329207A CN102329207A CN201110316058A CN201110316058A CN102329207A CN 102329207 A CN102329207 A CN 102329207A CN 201110316058 A CN201110316058 A CN 201110316058A CN 201110316058 A CN201110316058 A CN 201110316058A CN 102329207 A CN102329207 A CN 102329207A
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- dihydroxyl
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Abstract
The invention relates to a synthesis method of 2, 2'-dihydroxy-4, 4'-dimethoxybenzophenone. The method comprises the following steps: 1) enabling m-dimethoxybenzene and oxalyl chloride to react in the presence of a catalyst at the temperature of 70-80 DEG C for getting an intermediate product 2, 2', 4, 4'-tetramethoxy benzophenone, wherein the weight ratio of the m-dimethoxybenzene to the oxalyl chloride is 1:1-20, the used catalyst is azo isobutyronitrile or benzoyl peroxide, and the using quantity of the catalyst is 0.5%-2% of the weight of the m-dimethoxybenzene; and 2) enabling the obtained intermediate product and Lewis acid to react under the condition of taking an organic reagent as a solvent, wherein the reaction temperature is 50 DEG C and the reaction time is 2-3 hours; and stopping the reaction, adding water for hydrolysis, skimming, performing rotary evaporation and recrystallizing to get the 2, 2'-dihydroxy-4, 4'-dimethoxybenzophenone. The Lewis acid is one of AlCl3, ZnCl2, BF3 and polyphosphoric acid; and the organic reagent is one of dichloroethane, toluene, xylene, nitrobenzene and chlorobenzene. According to the method, the reaction temperature is appropriate, the catalyst is simple and easy to get, the using quantity of the catalyst is low, the environmental pollution is small, and the method is closest to the requirements of green chemistry.
Description
Technical field
The present invention relates to a kind of compound method of water-soluble UV light absorber, specifically is benzophenone UVA 2,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone.
Background technology
Benzophenone compound is a kind of important organic intermediate, and its can strong absorption UV-light, is widely used in fields such as daily-use chemical industry, medicine, agricultural chemicals, plastics, coating.The traditional method of synthetic this compounds mainly is a phosgenation, but phosgene has severe toxicity, and it is dangerous to operate, and the cost of investment in industriallization is too high and because it is a gas, is not easy to transportation and stores, and is unfavorable for the development of Green Chemistry.The present invention provides a kind of environmental pollution few, and the high compound method of product yield.
Summary of the invention
The object of the invention aims to provide a kind of simple to operate, and reaction conditions is gentle, and cost is low, and is little to environmental influence, with green catalyst catalysis Synthetic 2,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone.
The technical scheme that the present invention adopts is following:
A kind of 2,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone, its method steps is:
1), by a phenylene dimethyl ether and oxalyl chloride in the presence of catalyzer; In 70-80 ℃, the reaction 1.5 hours, obtain intermediate product 2,2 ' 4; 4 '-tetramethoxy UVNUL MS-40; As shown in the formula (I), the ratio of the amount of substance of described phenylene dimethyl ether and oxalyl chloride is 1: 1-20, and the catalyzer that uses is azo isobutyronitrile or Lucidol;
2), step 1) gained intermediate product and Lewis acid are done at organic reagent to react 50 ℃ of temperature of reaction, time 2-3 hour under the condition of solvent; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, promptly get 2; 2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone is as shown in the formula (II);
Described Lewis acid is AlCl
3, ZnCl
2, BF
3, a kind of in the polyphosphoric acid; Described organic reagent is a kind of in ethylene dichloride, toluene, YLENE, oil of mirbane, the chlorobenzene;
Described 1), 2) step reaction is carried out in protection of inert gas.
Reaction equation:
In the technical scheme that the present invention adopts, in the step 1) amount of employed catalyzer be between the 0.5%-2% of phenylene dimethyl ether quality.
In the technical scheme that the present invention adopts, after the step 1) reaction,, directly reclaim oxalyl chloride, directly add water hydrolysis, separatory then, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone the reactant distillation.
Description of drawings
Fig. 1 is 2,2 ' 4, and the IR figure of 4 '-tetramethoxy UVNUL MS-40
Fig. 2 is 2,2 '-dihydroxyl-4, the IR figure of 4 '-dimethoxy-benzophenone
Embodiment
Below through specific embodiment the present invention is described, but protection scope of the present invention is not limited thereto.
Embodiment 1
2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone is synthetic, and its operation steps is following:
The first step reaction: get that phenylene dimethyl ether places there-necked flask between 13.8g, add the 0.15g azo isobutyronitrile and make catalyzer, add magneton and put up device; In flask, add the 30ml oxalyl chloride, regulate temperature and stirring; Controlled temperature 70-80 ℃, the reaction 1.5 hours; Stop reaction, add water hydrolysis oxalyl chloride, filter and collect intermediate product and oven dry, intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40 infared spectrum such as Fig. 1,
1HNMR (400MHz, DMSO-d6) δ: 7.35-7.30 (m, 2H), 6.56 (s, 4H), 3.81 (s, 6H), 3.58 (s, 6H);
Second step reaction: with 30g AlCl
3Place flask with the first step intermediate product, add the 100ml ethylene dichloride again, stir temperature control; Controlled temperature is at 50 ℃, time 2-3 hour; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone.The HPLC detection level is 99.2%, yield 72%.Product 2,2 '-dihydroxyl-4, the infared spectrum of 4 '-dimethoxy-benzophenone such as Fig. 2,
1HNMR (400MHz, CDCl
3) δ: 11.33 (s, 2H), 6.55-6.53 (m, 2H), 6.50-6.45 (m, 4H), 3.67 (s, 6H).
Embodiment 2
The first step reaction; Get that phenylene dimethyl ether places there-necked flask between 13.8g, add 0.16g azo isobutyronitrile catalyzer, add magneton and put up device; In flask, add the 30ml oxalyl chloride, regulate temperature and stirring; Controlled temperature 70-80 ℃, the reaction 1.5 hours; Stop reaction, add water hydrolysis oxalyl chloride, filter and collect intermediate product and oven dry; Intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40 infared spectrum such as Fig. 1;
Second step reaction: with 30g ZnCl
2Place flask with the first step intermediate product, add the 100ml ethylene dichloride again, stir temperature control; Controlled temperature about 50 ℃, time 2-3 hour; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, the HPLC detection level is 99.1%, yield 70%.Product 2,2 '-dihydroxyl-4, the infared spectrum of 4 '-dimethoxy-benzophenone such as Fig. 2.
Embodiment 3
The first step reaction: get that phenylene dimethyl ether places there-necked flask between 13.8g, add 0.14g azo isobutyronitrile catalyzer, add magneton and put up device; In flask, add the 30ml oxalyl chloride, regulate temperature and stirring; Controlled temperature 70-80 ℃, the reaction 1.5 hours; Stop reaction, add water hydrolysis oxalyl chloride, filter and collect intermediate product and oven dry; Intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40 infared spectrum such as Fig. 1;
Second step reaction: with 30g AlCl
3Place flask with the first step intermediate product, add the 100ml chlorobenzene again, stir, temperature control: controlled temperature is at 50 ℃, time 2-3 hour; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, the HPLC detection level is 99.0%, yield 67%.Product 2,2 '-dihydroxyl-4, the infared spectrum of 4 '-dimethoxy-benzophenone such as Fig. 2.
Embodiment 4
The first step reaction: get that phenylene dimethyl ether places there-necked flask between 13.8g, add the 0.15g benzoylperoxide catalyst, add magneton and put up device; In flask, add the 30ml oxalyl chloride, regulate temperature and stirring; Controlled temperature 70-80 ℃, the reaction 1.5 hours; Stop reaction, add water hydrolysis oxalyl chloride, filter and collect intermediate product and oven dry; Intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40 infared spectrum such as Fig. 1;
Second step reaction: with 30g AlCl
3Place flask with the first step intermediate product, add 100m toluene again, stir temperature control; Controlled temperature is at 50 ℃, time 2-3 hour; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, the HPLC detection level is 99.0%, yield 69%.Product 2,2 '-dihydroxyl-4, the infared spectrum of 4 '-dimethoxy-benzophenone such as Fig. 2.
Embodiment 5
The first step reaction: get that phenylene dimethyl ether places there-necked flask between 13.8g, add the 0.16g benzoylperoxide catalyst, add magneton and put up device; In flask, add the 30ml oxalyl chloride, regulate temperature and stirring; Controlled temperature 70-80 ℃, the reaction 1.5 hours; Stop reaction, add water hydrolysis oxalyl chloride, filter and collect intermediate product and oven dry; Intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40 infared spectrum such as Fig. 1;
Second step reaction: with 10gBF
3Place flask with the first step intermediate product, add 100ml YLENE again, stir temperature control; Controlled temperature is at 50 ℃, time 2-3 hour; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, get product 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, the HPLC detection level is 99.1%, yield 71%.Product 2,2 '-dihydroxyl-4, the infared spectrum of 4 '-dimethoxy-benzophenone such as Fig. 2.
Claims (3)
1. one kind 2,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone is characterized in that method steps is:
1), by a phenylene dimethyl ether and oxalyl chloride in the presence of catalyzer; In 70-80 ℃, the reaction 1.5 hours; Obtain intermediate product 2,2 ' 4,4 '-tetramethoxy UVNUL MS-40; The ratio of the amount of substance of described phenylene dimethyl ether and oxalyl chloride is 1: 1-20, and the catalyzer that uses is azo isobutyronitrile or Lucidol;
2), step 1) gained intermediate product and Lewis acid are done at organic reagent to react 50 ℃ of temperature of reaction, time 2-3 hour under the condition of solvent; After stopping reaction, add water hydrolysis, separatory, revolve steaming, recrystallization, promptly get 2; 2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone;
Described Lewis acid is AlCl
3, ZnCl
2, BF
3, a kind of in the polyphosphoric acid; Described organic reagent is a kind of in ethylene dichloride, toluene, YLENE, oil of mirbane, the chlorobenzene;
Described 1), 2) step reaction is carried out in protection of inert gas.
2. as claimed in claim 12,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone is characterized in that, in the step 1) amount of employed catalyzer be between the 0.5%-2% of quality of phenylene dimethyl ether.
3. as claimed in claim 12,2 '-dihydroxyl-4, the compound method of 4 '-dimethoxy-benzophenone; It is characterized in that, after the step 1) reaction, reactant is distilled; Directly reclaim oxalyl chloride, directly add water hydrolysis, separatory then, revolve steaming, recrystallization, get product 2; 2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467268A (en) * | 2013-09-26 | 2013-12-25 | 山东午阳化工股份有限公司 | Preparation method of 2,2'- dyhydroxyl-4,4'-dimethoxybenzophenone |
| CN104292136A (en) * | 2014-09-19 | 2015-01-21 | 浙江科技学院 | Preparation method of sulfogaiacol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181376A (en) * | 1996-11-01 | 1998-05-13 | 武田药品工业株式会社 | Production of benzophenone derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181376A (en) * | 1996-11-01 | 1998-05-13 | 武田药品工业株式会社 | Production of benzophenone derivatives |
Non-Patent Citations (4)
| Title |
|---|
| 《J.Org.Chem.》 19581130 J.A.Vanallan "Derivatives of Benzoylresorcinol" p1679-1682 1-3 第23卷, 第11期 * |
| 《武汉科技大学学报(自然科学版)》 20050930 伍林等 "苯与草酰氯反应机理的探讨" 第247-248，278页 1-3 第28卷, 第3期 * |
| J.A.VANALLAN: ""Derivatives of Benzoylresorcinol"", 《J.ORG.CHEM.》 * |
| 伍林等: ""苯与草酰氯反应机理的探讨"", 《武汉科技大学学报(自然科学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467268A (en) * | 2013-09-26 | 2013-12-25 | 山东午阳化工股份有限公司 | Preparation method of 2,2'- dyhydroxyl-4,4'-dimethoxybenzophenone |
| CN103467268B (en) * | 2013-09-26 | 2015-03-25 | 山东午阳化工股份有限公司 | Preparation method of 2,2'- dyhydroxyl-4,4'-dimethoxybenzophenone |
| CN104292136A (en) * | 2014-09-19 | 2015-01-21 | 浙江科技学院 | Preparation method of sulfogaiacol |
| CN104292136B (en) * | 2014-09-19 | 2016-03-09 | 浙江科技学院 | A kind of preparation method of thiocol |
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