CN101029041B - Aryl-folinic phenol acetic acid and 1,4-dioxane complex, its production and use - Google Patents
Aryl-folinic phenol acetic acid and 1,4-dioxane complex, its production and use Download PDFInfo
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- CN101029041B CN101029041B CN2006100579787A CN200610057978A CN101029041B CN 101029041 B CN101029041 B CN 101029041B CN 2006100579787 A CN2006100579787 A CN 2006100579787A CN 200610057978 A CN200610057978 A CN 200610057978A CN 101029041 B CN101029041 B CN 101029041B
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Abstract
An match of arylformacyl phenyloxyacetic acid and 1,4-dioxyhexacyclane used for preparing macro-molecular phototrigger and its preparing process are disclosed.
Description
Technical field
The present invention relates to a kind of aryl-folinic phenol acetic acid and 1,4-dioxane complex and preparation method thereof and application.
Background technology
The aryl-folinic phenol acetic acid compounds is an a class meticulous organic compound of great use, can carry out reactions such as esterification, amidation and obtain corresponding derivative.An ongoing important innovation is exactly that the light trigger that will have aromatic ring originally links to each other with polymkeric substance in the ultraviolet photocureable material field, increases molecular weight, reduces molecular migration.The method that links to each other with polymkeric substance has multiple, wherein important a kind ofly by esterification acid and pure base polymer are linked together exactly, and carboxymethoxylization is exactly one of main mode of introducing on aromatic ring active group.The macromoleization of many existing structure photoinitiator compounds realizes by the carboxymethoxyl resterification that all the macromolecular photoinitiator that the WO03/033452 patent is described has just adopted this route.Therefore, become very important as the preparation purifying of the important intermediate aryl-folinic phenol acetic acid of light trigger macromoleization, it is directly connected to the purity of esterification products, color, important indicators such as photocuring efficient.Aryl-folinic phenol acetic acid is difficult to dissolving in common solvent; even as the solubleness reflux temperature in toluene, ethylene dichloride, chloroform all less than 5%; but experiment is found at oxo solvent as 1; more easily dissolving also can finely be dissolved in intensive polar solvent such as DMF and DMSO in 4-dioxane and the tetrahydrofuran (THF).But solvency power is too strong and boiling point is higher than 100 ℃ or be lower than 60 ℃ solvent and be not suitable for the purifying recrystallization and use, and is not that the recovery difficulty is exactly that loss is too big.In research 1, find during 4-dioxane dissolving benzoyl phenoxy acetic acid (BBA): the composition of crystallisate is not the benzoyl phenoxy acetic acid, and the composition of the data presentation crystallisate of nucleus magnetic resonance is two molecule BBA and a part 1, the complex compound of 4-dioxane.This phenomenon has also illustrated 1, and the 4-dioxane is to make the BBA crystal that lyolysis take place to the reason that BBA has excellent dissolution power, can destroy the hydrogen bond action between the original crystal of BBA.
French document Bulletin de la Societe Chimique de France (1954) in 1954,687-8. has described trifluoroacetic acid and 1, the character of 4-dioxane complex (CA registration number 854841-50-2).German document Justus Liebigs Annalen der Chemie (1966) in 1966,693182-6. has mentioned replacement dipropionic acid and 1, the preparation of 1: 1 title complex of 4-dioxane (CA registration number 7200-73-9).
At the problems referred to above, the inventor creates technical scheme of the present invention through long term studies and test.
Summary of the invention
The purpose of this invention is to provide a kind of aryl-folinic phenol acetic acid and 1, the 4-dioxane complex is characterized in that this title complex comprises following structure:
Wherein X is H or CH
3
A further object of the present invention provides a kind of aryl-folinic phenol acetic acid and 1, the preparation method of 4-dioxane complex.
Specifically, the invention provides a kind of aryl-folinic phenol acetic acid and 1, the preparation method of 4-dioxane complex, this method comprises the steps:
1) mixes aryl-folinic phenol acetic acid, 1,4-dioxane and solvent;
2) after the dissolving fully, stir cooling, crystallization obtains the purpose product.
Present method can adopt for example following specific embodiments:
1) with aryl-folinic phenol acetic acid, 1,4-dioxane and solvent, heated and stirred;
2) after the dissolving fully, target product is isolated in cooling, crystallization, and target product is two molecule aryl-folinic phenol acetic acids and a part 1, and the molecule that 4-dioxane complex form exists is similar to the crystal water phenomenon of some organic acid or inorganic salt.
Aryl-folinic phenol acetic acid of the present invention can be 4-benzoyl phenoxy acetic acid or 4-(4-methyl benzoyl) phenoxy acetic acid;
Service temperature of the present invention is 0-100 ℃;
Aryl-folinic phenol acetic acid of the present invention and 1, the mol ratio of 4-dioxane are 1: 1-6;
Solvent of the present invention is the little solvent of polarity, as toluene, ethylene dichloride etc.
The present invention has following advantage:
The present invention is simple to operate, yield is high, purity is high, convenient post-treatment.
Embodiment
The present invention can be further described with indefiniteness embodiment hereinafter.
Embodiment 1
4-benzoyl phenoxy acetic acid crude product; HPLC purity assay 95%; taking by weighing 0.074mol (20.0g) drops in the there-necked flask; measure 60ml ethylene dichloride and 0.117mol (10ml) 1; the 4-dioxane is heated with stirring to little backflow, the pressed powder dissolving; carry out heat filtering with cloth formula funnel, remove insoluble mechanical impurity.Filtrate is stirred nature cooling gently in another there-necked flask, the adularescent crystal is separated out in the time of about 35 ℃, cools to put into the low temperature bath after the room temperature and continue to be cooled to 0 ℃.Suction filtration with a little ethylene dichloride washing leaching cake, gets white crystals to filtration cakes torrefaction.50 ℃ of oven dry 4 hours obtain 0.033mol (20.0g) target product, yield 89.2%, product purity (HPLC analysiss) 99.5%, nuclear magnetic resonance spectroscopy calculating 1,4-dioxane content 14.6%, with the mol ratio of benzoyl phenoxy acetic acid be 1: 2.Ultimate analysis data C
34H
32O
10: C67.75% (theoretical value 67.99%): H5.42% (theoretical value 5.37%).
Embodiment two
4-(4-methyl benzoyl) phenoxy acetic acid crude product; HPLC purity assay 95%; taking by weighing 0.070mol (20.0g) drops in the there-necked flask; measure 60ml ethylene dichloride and 0.234mol (20ml) 1; the 4-dioxane, stirring heating, pressed powder dissolving; carry out heat filtering with cloth formula funnel, remove insoluble mechanical impurity.Filtrate is stirred nature cooling gently in another there-necked flask, the adularescent crystal is separated out in the time of about 65 ℃, cools to put into the low temperature bath after the room temperature and continue to be cooled to 15 ℃.Suction filtration with a little ethylene dichloride washing leaching cake, gets white crystals to filtration cakes torrefaction.50 ℃ of oven dry 4 hours, the 0.030mol that weighs (19.0g), yield 85.7%, product purity (HPLC analysiss) 99.5%, nuclear magnetic resonance spectroscopy calculating 1,4-dioxane content 14.0%, with the mol ratio of 4-(4-methyl benzoyl) phenoxy acetic acid be 1: 2.Ultimate analysis data C
34H
32O
10: C68.26% (theoretical value 68.39%); H5.64% (theoretical value 5.57%).
Embodiment three
4-(4-methyl benzoyl) phenoxy acetic acid crude product; HPLC purity assay 95%; taking by weighing 0.070mol (20.0g) drops in the there-necked flask; measure 60ml toluene and 0.409mol (35ml) 1; the 4-dioxane, stirring heating, pressed powder dissolving; carry out heat filtering with cloth formula funnel, remove insoluble mechanical impurity.Filtrate is stirred nature cooling gently in another there-necked flask, the adularescent crystal is separated out in the time of about 90 ℃, cools to put into the low temperature bath after the room temperature and continue to be cooled to 20 ℃.Suction filtration with a little ethylene dichloride washing leaching cake, gets white crystals to filtration cakes torrefaction.50 ℃ of oven dry 4 hours, the 0.032mol that weighs (20.2g), yield 91.9%, product purity (HPLC analysiss) 99.4%, nuclear magnetic resonance spectroscopy calculating 1,4-dioxane content 14.0%, with the mol ratio of 4-(4-methyl benzoyl) phenoxy acetic acid be 1: 2.Ultimate analysis data C
34H
32O
10: C68.26% (theoretical value 68.39%); H5.64% (theoretical value 5.57%).
The comparative example
Take by weighing 4-benzoyl phenoxy acetic acid, measure the 60ml ethylene dichloride and add there-necked flask, be heated with stirring to little backflow, pressed powder does not dissolve, and can not purify.
Claims (6)
1. an aryl-folinic phenol acetic acid and 1, the 4-dioxane complex is characterized in that this title complex is following structure:
Wherein X is H or CH
3
2. title complex as claimed in claim 1, wherein aryl-folinic phenol acetic acid is 4-benzoyl phenoxy acetic acid or 4-(4-methyl benzoyl) phenoxy acetic acid.
3. aryl-folinic phenol acetic acid as claimed in claim 2 and 1, the preparation method of 4-dioxane complex is, with aryl-folinic phenol acetic acid, 1,4-dioxane and solvent, heated and stirred; After treating dissolving fully, target product is isolated in cooling, crystallization;
Wherein, solvent is toluene or ethylene dichloride; Aryl-folinic phenol acetic acid is 4-benzoyl phenoxy acetic acid or 4-(4-methyl benzoyl) phenoxy acetic acid.
4. method according to claim 3, wherein, service temperature is 0-100 ℃.
5. method according to claim 3, wherein, aryl-folinic phenol acetic acid and 1, the mol ratio of 4-dioxane is 1: 1-6.
6. title complex according to claim 1 is applied to the ultraviolet photocureable material field as important intermediate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006100579787A CN101029041B (en) | 2006-03-02 | 2006-03-02 | Aryl-folinic phenol acetic acid and 1,4-dioxane complex, its production and use |
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| CN2006100579787A CN101029041B (en) | 2006-03-02 | 2006-03-02 | Aryl-folinic phenol acetic acid and 1,4-dioxane complex, its production and use |
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| CN101029041B true CN101029041B (en) | 2010-06-23 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894311A (en) * | 1986-10-29 | 1990-01-16 | Fuji Photo Film Co., Ltd. | Positive-working photoresist composition |
| EP0374760A1 (en) * | 1988-12-19 | 1990-06-27 | Hoechst Aktiengesellschaft | Dioxane addition compounds of aromatic meta- or para-hydroxy-carboxylic acids, and process for their preparation |
| CN1559713A (en) * | 2004-03-12 | 2005-01-05 | 李明锁 | Technology of manufacturing hollow steel |
-
2006
- 2006-03-02 CN CN2006100579787A patent/CN101029041B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894311A (en) * | 1986-10-29 | 1990-01-16 | Fuji Photo Film Co., Ltd. | Positive-working photoresist composition |
| EP0374760A1 (en) * | 1988-12-19 | 1990-06-27 | Hoechst Aktiengesellschaft | Dioxane addition compounds of aromatic meta- or para-hydroxy-carboxylic acids, and process for their preparation |
| CN1559713A (en) * | 2004-03-12 | 2005-01-05 | 李明锁 | Technology of manufacturing hollow steel |
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Assignee: Jiangsu Yingli Technology Development Co., Ltd. Assignor: Yingli Science and Technology Development Co., Ltd., Beijing Contract record no.: 2011990001046 Denomination of invention: Aryl-folinic phenol acetic acid and 1,4-dioxane complex, its production and use Granted publication date: 20100623 License type: Exclusive License Open date: 20070905 Record date: 20111116 |
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Address after: Beijing City, Haidian District Zhongguancun 100190 South 1 1 horse Baxter 10 storey building Patentee after: Yingli Science and Technology Development Co., Ltd., Beijing Address before: 100084 Haidian District Thunis International Exchange Center, Zhongguancun East Road, Beijing, four Patentee before: Yingli Science and Technology Development Co., Ltd., Beijing |
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Effective date of registration: 20160825 Address after: 226121 18 Daqing Road, three factory, Haimen, Jiangsu Patentee after: Jiangsu Yingli Technology Development Co., Ltd. Address before: Beijing City, Haidian District Zhongguancun 100190 South 1 1 horse Baxter 10 storey building Patentee before: Yingli Science and Technology Development Co., Ltd., Beijing |