CN104725185A - Preparation method of 4-iodobiphenyl - Google Patents
Preparation method of 4-iodobiphenyl Download PDFInfo
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- CN104725185A CN104725185A CN201510065843.4A CN201510065843A CN104725185A CN 104725185 A CN104725185 A CN 104725185A CN 201510065843 A CN201510065843 A CN 201510065843A CN 104725185 A CN104725185 A CN 104725185A
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Abstract
The invention provides a preparation method of 4-iodobiphenyl, belonging to the field of organic chemical synthesis. According to the preparation method, the technical problems that a product of a traditional synthesis method is low in purity, poor in appearance and color and tedious and complex to separate and purify are solved. By virtue of the method for synthesizing high-purity 4-iodobiphenyl by introducing a novel Cu-La silicon dioxide mesoporous composite catalyst into iodination reaction of biphenyl, the technical problems are solved. A new method having the advantages of low cost and pollution and high purity and selectivity is provided for the industrial production of liquid crystal material intermediate 4-iodobiphenyl.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to a kind of synthesis of liquid crystal material intermediate, particularly relate to a kind of preparation method of 4-iodine biphenyl.
Background technology
In recent years, liquid crystal material, because of the liquid flow dynamic characteristic of its uniqueness and solid crystals optical characteristics, is forward position and the focus of technique of display area research always.Scientific research personnel designs and have developed various liquid crystal material, has promoted the technical development of the high-technology fields such as indicating meter of new generation, luminescent device fast.
But the advantages such as biphenyls liquid crystal material has light, chemical stability is good, and the physical constants such as anisotropy, viscosity and double refraction are adjustable, thus enjoy favor in liquid crystal material.Wherein 4-iodine biphenyl and 4,4-diiodobiphenyl are the important liquid crystal intermediates of a class, and they play the vital role of bridging, end-blocking in the synthesis of biphenyls liquid crystal material.
As everyone knows, in the synthesis of liquid crystal material, the purity of starting material and intermediate is most important, even if there is trace impurity to there is the performance being also enough to affect material in the middle of them.Therefore, very harsh with single assorted content requirement to the purity of liquid crystal material intermediate on market.But the synthesis of 4-iodine biphenyl and 4,4-diiodobiphenyl is all take biphenyl as raw material, introduces iodine by catalysis, oxidation, first generate 4-iodine biphenyl in reaction, and then generate 4,4-diiodobiphenyl.The two is difficult to be separated by the means of routine because of its very similar stuctures and properties, impurity each other in respective product.Wherein 4, as long as 4-diiodobiphenyl ensures that in its preparation technology the excessive of iodine can the content of control 4-iodine biphenyl, ensure its product purity.Current 4,4-diiodobiphenyl techniques are ripe.Compare and 4,4-diiodobiphenyl, the synthesis of highly purified 4-iodine biphenyl is then very difficult.Because 8 of biphenyl very nearly the same with 8 activity of 4-iodine biphenyl, therefore be difficult in the reaction ensure that iodide ion only replaces a hydrogen, namely be difficult to go to control not generate 4 by correlation parameter in the synthesis of 4-iodine biphenyl, 4-diiodobiphenyl, Here it is market does not have the basic reason of high purity 4-iodine biphenyl.Current people can only be purified to 4-iodine biphenyl product by repeatedly recrystallization.On domestic and international market, common 4-iodine biphenyl purity is more than 95%, and single assorted (4,4-diiodobiphenyl) <1%, color is faint yellow.Therefore the key applied in liquid crystal material of 4-iodine biphenyl and difficult point are exactly the issues of purification of its product.
Summary of the invention
The object of the invention is to the defect overcoming prior art existence, provide a kind of selectivity high, energy consumption is low, and the reaction times is short, and product appearance is good, color and luster is good, purity is high, and post-reaction treatment is simple to operate, the preparation method of the 4-iodine biphenyl of easily separated purification.
For achieving the above object, invention introduces novel C u-La mesoporous SiO 2 composite catalyst, concrete scheme is as follows: in reaction flask, add raw material biphenyl, elemental iodine, solvent, a small amount of vitriol oil and concentrated nitric acid successively under room temperature, composite catalyst, slowly be warming up to 60-90 DEG C and start reaction, control temperature of reaction 60-90 DEG C, sampling detects and can stop heating without continuing stirring reaction 10-30min after biphenyl again to reaction solution; Be cooled to 40 DEG C, discharging cool, namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leave standstill, use organic solvent recrystallization, then filter, drying sterling;
Wherein, the mechanism of above-mentioned reaction is as shown in Equation 1:
(formula 1)
Above-mentioned solvent is acetic acid, and its consumption is 10-30 times of biphenyl quality.
Above-mentioned composite catalyst is Cu+La composite mesopore SiO
2composite catalyst, its consumption be the 0.1-0.4 of biphenyl quality doubly.
Above-mentioned raw material biphenyl, the mol ratio of elemental iodine are 1:0.3-0.7.
Above-mentioned recrystallization solvent is ethyl acetate.
The present invention has following beneficial effect: the present invention introduces novel C u-La mesoporous SiO 2 composite catalyst and reduces temperature of reaction on the one hand, usual 4-iodine biphenyl and 4, the synthesis reaction temperature of 4-diiodobiphenyl is 100-150 DEG C, after introducing catalyzer, the temperature of reaction of 4-iodine biphenyl can be realized at 60-90 DEG C, selectivity large 98%; Shorten the reaction times on the other hand, by contrast experiment and on-line monitoring, the reaction times of introducing catalyzer is 1-1.5 hour, and not adding the catalyst reaction time is 2-3 hour; By product 4 is greatly inhibit from these two aspects, the generation of 4-diiodobiphenyl, the aftertreatment of thus reacting only needs the simple recrystallization operation of a step can make the high purity 99.5% of product, and color is white, thus solve the issues of purification of difficult point-its product that 4-iodine biphenyl is applied in liquid crystal material.In addition, the present invention reduces temperature of reaction, Reaction time shorten, thus reduces energy consumption, reduces production cost, meets policy requirements that is energy-saving and cost-reducing, Green Chemistry.
Embodiment
Below in conjunction with embodiment, invention is described in further details, but protection scope of the present invention is not limited thereto.
Embodiment 1
In 500ml reaction flask, 14.52g biphenyl, 11.42g elemental iodine, 272ml acetic acid, the 1.22ml vitriol oil and 3ml concentrated nitric acid is added successively, 3g Cu-La composite mesopore SiO under room temperature
2catalyzer, be slowly warming up to 70 DEG C start reaction, control temperature of reaction be 70 DEG C, sampling GC detect to reaction solution without continue again after biphenyl stirring reaction 25min can stop heat; Be cooled to 40 DEG C, discharging cools, and namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leaves standstill, and by re-crystallizing in ethyl acetate, then filtration, drying obtain the white sterling 20.33g that purity is 99.5%.
Embodiment 2
In 500ml reaction flask, 14.52g biphenyl, 9.13g elemental iodine, 230ml acetic acid, the 1.22ml vitriol oil and 3ml concentrated nitric acid is added successively, 3.5g Cu-La composite mesopore SiO under room temperature
2catalyzer, be slowly warming up to 75 DEG C start reaction, control temperature of reaction be 75 DEG C, sampling GC detect to reaction solution without continue again after biphenyl stirring reaction 20min can stop heat; Be cooled to 40 DEG C, discharging cools, and namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leaves standstill, and by re-crystallizing in ethyl acetate, then filtration, drying obtain the white sterling 16.25 that purity is 99.5%.
Embodiment 3
In 500ml reaction flask, 14.52g biphenyl, 13.70g elemental iodine, 300ml acetic acid, the 1.22ml vitriol oil and 3ml concentrated nitric acid is added successively, 3.8g Cu-La composite mesopore SiO under room temperature
2catalyzer, be slowly warming up to 80 DEG C start reaction, control temperature of reaction be 80 DEG C, sampling GC detect to reaction solution without continue again after biphenyl stirring reaction 15min can stop heat; Be cooled to 40 DEG C, discharging cools, and namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leaves standstill, and by re-crystallizing in ethyl acetate, then filtration, drying obtain the white sterling 21.32 that purity is 99.5%.
Embodiment 4
In 500ml reaction flask, 14.52g biphenyl, 12.52g elemental iodine, 260ml acetic acid, the 1.22ml vitriol oil and 3ml concentrated nitric acid is added successively, 4.0g Cu-La composite mesopore SiO under room temperature
2catalyzer, be slowly warming up to 82 DEG C start reaction, control temperature of reaction be 82 DEG C, sampling GC detect to reaction solution without continue again after biphenyl stirring reaction 15min can stop heat; Be cooled to 40 DEG C, discharging cools, and namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leaves standstill, and by re-crystallizing in ethyl acetate, then filtration, drying obtain the white sterling 20.89 that purity is 99.5%.
Claims (7)
1. a preparation method for 4-iodine biphenyl, is characterized in that: it is achieved by introducing composite catalyst in the iodination reaction of biphenyl, and its preparation process specifically comprises the steps:
In reaction flask, raw material biphenyl, elemental iodine, solvent, a small amount of vitriol oil and concentrated nitric acid is added successively under room temperature, composite catalyst, slowly be warming up to 60-90 DEG C and start reaction, control temperature of reaction is 60-90 DEG C, and sampling detects and can stop heating without continuing stirring reaction 10-30min after biphenyl again to reaction solution; Be cooled to 40 DEG C, discharging cool, namely centrifuging obtain thick product, adds activated carbon decolorizing to thick product, leave standstill, use organic solvent recrystallization, then filter, drying sterling;
Wherein, the mechanism of described reaction is as shown in Equation 1:
(formula 1).
2. the preparation method of a kind of 4-iodine biphenyl as claimed in claim 1, is characterized in that: described solvent is acetic acid.
3. the preparation method of a kind of 4-iodine biphenyl as described in any one of claim 1 or 2, is characterized in that: described solvent quality is 10-30 times of biphenyl quality.
4. the preparation method of a kind of 4-iodine biphenyl as claimed in claim 1, is characterized in that: described composite catalyst is Cu+La composite mesopore SiO
2composite catalyst.
5. the preparation method of a kind of 4-iodine biphenyl as claimed in claim 1, is characterized in that: described Cu+La composite mesopore SiO
2composite catalyst consumption be the 0.1-0.4 of biphenyl quality doubly.
6. the preparation method of a kind of 4-iodine biphenyl as claimed in claim 1, is characterized in that: described raw material biphenyl, the mol ratio of elemental iodine are 1:0.3-0.7.
7. the preparation method of a kind of 4-iodine biphenyl as claimed in claim 1, is characterized in that: described recrystallization solvent is ethyl acetate.
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| CN201510065843.4A CN104725185A (en) | 2015-02-09 | 2015-02-09 | Preparation method of 4-iodobiphenyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517912A (en) * | 2020-06-11 | 2020-08-11 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of 4-iodobiphenyl |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4792641A (en) * | 1987-03-25 | 1988-12-20 | Eastman Kodak Company | Process for preparing iodinated aromatic compounds |
| CN1747910A (en) * | 2003-02-10 | 2006-03-15 | 三菱瓦斯化学株式会社 | Process for production of iodine compounds and process for production of high-purity 5-iodo-2-methylbenzoic acid |
| CN101481291A (en) * | 2007-11-28 | 2009-07-15 | 霍尼韦尔国际公司 | Method for pretreating and regenerating catalysts used in a process for making fluoroiodoalkanes |
-
2015
- 2015-02-09 CN CN201510065843.4A patent/CN104725185A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4792641A (en) * | 1987-03-25 | 1988-12-20 | Eastman Kodak Company | Process for preparing iodinated aromatic compounds |
| CN1747910A (en) * | 2003-02-10 | 2006-03-15 | 三菱瓦斯化学株式会社 | Process for production of iodine compounds and process for production of high-purity 5-iodo-2-methylbenzoic acid |
| CN101481291A (en) * | 2007-11-28 | 2009-07-15 | 霍尼韦尔国际公司 | Method for pretreating and regenerating catalysts used in a process for making fluoroiodoalkanes |
Non-Patent Citations (1)
| Title |
|---|
| TOSHIO SUGITA ET AL.: "AROMATIC IODINATION WITH ALUMINUM AND COPPER(II) CHLORIDES AND IODINE", 《CHEMISTRY LETTERS》, 31 December 1982 (1982-12-31), pages 1481 - 1484 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517912A (en) * | 2020-06-11 | 2020-08-11 | 中昊(大连)化工研究设计院有限公司 | Synthetic method of 4-iodobiphenyl |
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