CN102108041A - Method for synthesizing 9,10-bis(chloromethyl)anthracene - Google Patents
Method for synthesizing 9,10-bis(chloromethyl)anthracene Download PDFInfo
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- CN102108041A CN102108041A CN2010105937328A CN201010593732A CN102108041A CN 102108041 A CN102108041 A CN 102108041A CN 2010105937328 A CN2010105937328 A CN 2010105937328A CN 201010593732 A CN201010593732 A CN 201010593732A CN 102108041 A CN102108041 A CN 102108041A
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- anthracene
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- dioxane
- trioxymethylene
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Abstract
The invention discloses a method for synthesizing 9,10-bis(chloromethyl)anthracene, which is characterized by comprising the following steps of: adding saturated solution of dioxane and concentrated hydrochloric acid into a reaction container, adding anthracene and trioxymethylene at one time, stirring, and raising the temperature for micro reflux reaction; and washing, filtering, drying and recrystallizing to obtain a product after the reaction is finished. The hydrogen chloride saturated solution of dioxane replaces the traditionally introduced hydrogen chloride gas, the equipment loss is reduced, the operation is simple, the dioxane solvent used in the reaction process can be recycled, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind ofly 9, the synthetic method of 10-two (chloromethyl) anthracene belongs to chemical methodology of organic synthesis technical field.
Background technology
Anthracene is a kind of good fluorescent material, is widely used in fields such as optics, electrooptics, decoration, safety, makeup, diagnosis, electric, electronics, semi-conductor, electroluminescent.
The easiest being substituted of hydrogen on 9 and 10 of anthracene, this 9, it also is a kind of good fluorescent material that 10-two replaces anthracene derivants, liquid crystal, agricultural and medical aspect widespread use.9,10-two (chloromethyl) anthracene is 9, and 10-two replaces in the anthracene derivants the most frequently used a kind of, because its preparation method is simple, raw material is easy to get, and product is the very high organic synthesis intermediate of a kind of activity, can be further synthetic as raw material once more.Existing method is that hydrogen chloride gas is fed the system that has added anthracene and trioxymethylene, makes 9 through backflow, 10-two (chloromethyl) anthracene.This method is to the corrodibility height of equipment, and loss is bigger, has improved the cost of equipment, and production efficiency is not high yet, and degree of purity of production can not reach requirement.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of 9, the synthetic method of 10-two (chloromethyl) anthracene, adopt the hydrogenchloride saturated solution of dioxane to react, reduce equipment loss and production cost, enhance productivity and product purity, and the recyclable utilization of solution.
The present invention realizes by following technical scheme:
A kind of 9, the synthetic method of 10-two (chloromethyl) anthracene, it is to realize: the saturated solution that in reaction vessel, adds dioxane and concentrated hydrochloric acid by following method, property adding anthracene and trioxymethylene again, stir, be warming up to little back flow reaction state, after the sustained reaction, stop heating, continue stirring reaction; Reaction end after scouring, filtration, drying, recrystallization get product.
The mass ratio of described feeding raw material is a concentrated hydrochloric acid: anthracene: trioxymethylene=(2.5-3.0): 1: (0.8-1.2).
The sustained reaction time of described little reflux state is 3-5h, and stopping to heat the reaction times of continuing to stir in the back is 10-15h.
Reaction formula of the present invention is:
Beneficial effect of the present invention is:
1, adopt the hydrogenchloride saturated solution of dioxane to replace hydrogen chloride gas to react, reduce the loss of equipment, make simple to operately, the purity of product is higher.
2, dioxane is recyclable utilizes again, reduces production costs.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
In the four-hole bottle of 5L, add 3.6L dioxane and 1000ml concentrated hydrochloric acid mixing solutions, and then adding 450g anthracene and 380g trioxymethylene, opening agitator stirs, slowly be warming up to little reflux state, keep little reflux state reaction 3h, stop heating, continue stirring reaction 10h, have yellow solid to separate out, stopped reaction filters, filter cake 500ml dioxane washed twice, filter again, and in funnel, wash, drain with the 800ml dioxane, filter cake is 40 ℃ of following vacuum-dryings, get 9 of 447g, the thick product of 10-two (chloromethyl) anthracene, yield is 76.2%.
The thick product of 447g of gained is carried out heating for dissolving in toluene, be stirred to fully dissolving after, filtered while hot is cooled to room temperature, oven dry, 9,10-two (chloromethyl) anthracene product 425g, content 99.5%.
Embodiment 2
In the four-hole bottle of 5L, add 3.6L dioxane and 1000ml concentrated hydrochloric acid mixing solutions, and then adding 393g anthracene and 471.6g trioxymethylene, opening agitator stirs, slowly be warming up to little reflux state, keep little reflux state reaction 5h, stop heating, continue stirring reaction 15h, have yellow solid to separate out, stopped reaction filters, filter cake 600ml dioxane washed twice, filter again, and in funnel, wash, drain with the 1000ml dioxane, filter cake is 40 ℃ of following vacuum-dryings, get 9 of 385g, the thick product of 10-two (chloromethyl) anthracene, yield is 78.5%.
The thick product of 385g of gained is carried out heating for dissolving in toluene, be stirred to fully dissolving after, filtered while hot is cooled to room temperature, oven dry, 9,10-two (chloromethyl) anthracene product 356g, content 99.2%.
Embodiment 3
In the four-hole bottle of 5L, add 3.6L dioxane and 1000ml concentrated hydrochloric acid mixing solutions, and then adding 421g anthracene and 420g trioxymethylene, opening agitator stirs, slowly be warming up to little reflux state, keep little reflux state reaction 4h, stop heating, continue stirring reaction 13h, have yellow solid to separate out, stopped reaction filters, filter cake 500ml dioxane washed twice, filter again, and in funnel, wash, drain with the 800ml dioxane, filter cake is 40 ℃ of following vacuum-dryings, get 9 of 405g, the thick product of 10-two (chloromethyl) anthracene, yield is 81.0%.
The thick product of 405g of gained is carried out heating for dissolving in toluene, be stirred to fully dissolving after, filtered while hot is cooled to room temperature, oven dry, 9,10-two (chloromethyl) anthracene product 375g, content 99.7%.
Claims (3)
1. one kind 9, the synthetic method of 10-two (chloromethyl) anthracene, it is characterized in that being realizing: the saturated solution that in reaction vessel, adds dioxane and concentrated hydrochloric acid by following method, property adding anthracene and trioxymethylene again, stir, be warming up to little back flow reaction state, after the sustained reaction, stop heating, continue stirring reaction; Reaction end after scouring, filtration, drying, recrystallization get product.
2. as claimed in claim 19, the synthetic method of 10-two (chloromethyl) anthracene, the mass ratio that it is characterized in that described feeding raw material is a concentrated hydrochloric acid: anthracene: trioxymethylene=(2.5-3.0): 1: (0.8-1.2).
3. as claimed in claim 19, the synthetic method of 10-two (chloromethyl) anthracene is characterized in that the sustained reaction time of described little reflux state is 3-5h, and stopping to heat the reaction times of continuing to stir in the back is 10-15h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201010593732 CN102108041B (en) | 2010-12-17 | 2010-12-17 | Method for synthesizing 9,10-bis(chloromethyl)anthracene |
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| CN 201010593732 CN102108041B (en) | 2010-12-17 | 2010-12-17 | Method for synthesizing 9,10-bis(chloromethyl)anthracene |
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| CN102108041A true CN102108041A (en) | 2011-06-29 |
| CN102108041B CN102108041B (en) | 2013-09-11 |
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| CN 201010593732 Active CN102108041B (en) | 2010-12-17 | 2010-12-17 | Method for synthesizing 9,10-bis(chloromethyl)anthracene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130732A (en) * | 2011-11-22 | 2013-06-05 | 上海博康精细化工有限公司 | Preparation method of 3,5-dimethyl-4-chloromethyl isoxazole |
| CN105218303A (en) * | 2015-10-31 | 2016-01-06 | 高大元 | The synthetic method of a kind of 9-chloro-10-bromine benzanthrene |
| WO2018178439A1 (en) * | 2017-03-29 | 2018-10-04 | Universidad De Castilla La Mancha | Method for the synthesis of 9,10-bis(chloromethyl)anthracene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061085A (en) * | 2004-09-23 | 2007-10-24 | Zymes有限公司 | A practical, cost-effective synthesis of chloromethylated 1,4-benzoquinones |
-
2010
- 2010-12-17 CN CN 201010593732 patent/CN102108041B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061085A (en) * | 2004-09-23 | 2007-10-24 | Zymes有限公司 | A practical, cost-effective synthesis of chloromethylated 1,4-benzoquinones |
Non-Patent Citations (1)
| Title |
|---|
| GREGORY J.LESTINA等: "The syhthesis of 2-Chloromethyl-5-alkylhydroquinone Dimethyl Ethers by a Cointrolled Chloromethylation", 《J.ORG.CHEM.》, vol. 25, no. 8, 31 December 1960 (1960-12-31), pages 154 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130732A (en) * | 2011-11-22 | 2013-06-05 | 上海博康精细化工有限公司 | Preparation method of 3,5-dimethyl-4-chloromethyl isoxazole |
| CN105218303A (en) * | 2015-10-31 | 2016-01-06 | 高大元 | The synthetic method of a kind of 9-chloro-10-bromine benzanthrene |
| WO2018178439A1 (en) * | 2017-03-29 | 2018-10-04 | Universidad De Castilla La Mancha | Method for the synthesis of 9,10-bis(chloromethyl)anthracene |
| ES2686136A1 (en) * | 2017-03-29 | 2018-10-16 | Universidad De Castilla La Mancha | SYNTHESIS PROCEDURE OF 9,10-BIS (CHLOROMETHYL) ANTHRACEN (Machine-translation by Google Translate, not legally binding) |
| CN110461805A (en) * | 2017-03-29 | 2019-11-15 | 卡斯蒂利亚-拉曼查大学 | Method for synthesizing bis- (chloromethyl) anthracenes of 9,10- |
| US10597342B2 (en) * | 2017-03-29 | 2020-03-24 | Universidad De Castilla La Mancha | Method for the synthesis of 9,10-bis(chloromethyl)anthracene |
| JP2020515549A (en) * | 2017-03-29 | 2020-05-28 | ウニヴェルシダッド デ カスティーリャ ラ マンチャ | Method for synthesizing 9,10-bis(chloromethyl)anthracene |
| JP7066737B2 (en) | 2017-03-29 | 2022-05-13 | ウニヴェルシダッド デ カスティーリャ ラ マンチャ | Method for synthesizing 9,10-bis (chloromethyl) anthracene |
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|---|---|
| CN102108041B (en) | 2013-09-11 |
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