CN102746271A - Preparation method of 2-isopropyl thioxanthone (ITX) - Google Patents
Preparation method of 2-isopropyl thioxanthone (ITX) Download PDFInfo
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- CN102746271A CN102746271A CN2012102680119A CN201210268011A CN102746271A CN 102746271 A CN102746271 A CN 102746271A CN 2012102680119 A CN2012102680119 A CN 2012102680119A CN 201210268011 A CN201210268011 A CN 201210268011A CN 102746271 A CN102746271 A CN 102746271A
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- isopropyl thioxanthone
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Abstract
The invention discloses a preparation method of 2-ITX. The method includes the following steps: step one, adding 2-mercaptobenzoic acid,cumeneand a solid-acid catalyst into a reaction vessel, reacting under a heating condition, to obtain a reaction solution until the reaction ends; step two, cooling the reaction solution obtained in the step one, and obtaining the 2-ITX after postprocessing. According to the method, under the action of the solid-acid catalyst, the mercaptobenzoic acid is used as a starting raw material and the target product 2-ITX is synthesized through a one-pot method, and the method is a green chemical synthetic technique with an application prospect. The adopted bamboo charcoal sulfoacid catalyst is high in catalytic activity, good in selectivity, low in production cost and capable of being recycled. A reaction postprocessing method is simplified.
Description
Technical field
The present invention relates to a kind of preparation method of light trigger, be specifically related to the preparation method of 2-isopropyl thioxanthone.
Background technology
Photosensitive polymer is one type very important in the non-silver sensitive material, and range of application is increasingly extensive.It can be used as photo-resist, light-curable ink, photocuring coating material of printing plate material, PC board etc.And photopolymerisable initiator is the very important component in the synthetic photosensitive polymer compound system.The thioxanthone compounds is one type of light trigger preferably.Have good optical property, can be used as the initiator in the synthetic intermediate, DNA fluorescent probe, Raolical polymerizable of ultraviolet photocureable material, the molecular weight in the may command polyreaction, this compounds also has biological activitys such as antitumor in addition.At present, the compound method of thioxanthone is summarized and is had following several method.1) polyphosphoric acid catalyzed synthetic thioxanthone compound; 2) utilize sulphuric acid catalysis to synthesize the thioxanthone compound; 3) insert the synthetic thioxanthone compound of metal reaction; 4) through the synthetic thioxanthone compound of benzyne intermediate.People are also doing many improvement aspect the starting raw material of reaction in addition.
Solid acid catalyst is a kind of solid acid catalyst that causes that in recent years people pay much attention to.Utilize solid acid as heterogeneous catalyst, generally have not etching apparatus, pollution is little, high temperature resistant, aftertreatment is simple, easily separated, cost is low and advantage such as reusable, and has obtained broad research and application in the acid catalysis field.In traditional synthesis technique, use a large amount of liquid acid and organic solvent at present, environment is had certain influence.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of under the solid acid catalyst effect, the method for solvent-free one kettle way Synthetic 2-isopropyl thioxanthone.
Technical scheme of the present invention: for solving the problems of the technologies described above, the preparation method of 2-isopropyl thioxanthone of the present invention in turn includes the following steps:
(1), add o-mercaptobenzoic acid, isopropyl benzene and solid acid catalyst in the reaction vessel, react under the melt temperature condition, finish to reaction, reaction solution;
(2), with step (1) gained reaction solution cooling, get the 2-isopropyl thioxanthone through aftertreatment, reaction formula is following:
Preferably, the described solid acid catalyst of step (1) is the bamboo charcoal sulfonic acid catalyst.
Preferably, the said solid acid of step (1) quality that feeds intake is o-mercaptobenzoic acid 1%～30% of the quality that feeds intake.
Preferably, the said solid acid of step (1) quality that feeds intake is o-mercaptobenzoic acid 10% of the quality that feeds intake.
Preferably, the said aftertreatment of step (2) comprises successively:
Add extracted in toluene;
Extraction liquid concentrates and removes toluene;
Recrystallization gets the 2-isopropyl thioxanthone.
Preferably, the 2-isopropyl thioxanthone is obtained by dioxane: water=5:1 (volume ratio) recrystallization.
Preferably, said being reflected under 120～200 ℃ the temperature condition of step (1) carried out.
Preferably, said being reflected under 160～180 ℃ of step (1) carried out.
Preferably, the time of the said reaction of step (1) is 1～10 hour.
Preferably, the time of the said reaction of step (1) is 3～6 hours.
Solid acid catalyst of the present invention is the bamboo charcoal sulfonic acid catalyst, " preparation of sulfonation bamboo charcoal, sign and acid catalysis performances thereof " such as its preparation method reference literature Xu Qiong,
New carbon,
2011,
26 (2), 103-108.
Concrete preparation method is with dry bamboo bits and 30～80%H
3PO
4The mass ratio of the aqueous solution is after 1:3～10 soak 1～20, to use the B suction filtration, obtains the bamboo bits of impregnation of phosphoric acid again at 100 ℃ of following dry 24h; In tube furnace, carry out pyrolysis then; Be warming up to 110 ℃ with 30 ℃/minute temperature rise rates, be incubated 3 hours, cool to room temperature naturally; Products therefrom to neutral, obtains the bamboo charcoal sample with deionized water wash after the drying.The oleum that then the bamboo charcoal sample is added massfraction 50%; Bamboo charcoal sample and 50% oleum mass ratio are 1:1～5; Be warming up to 100 ℃ of constant temperature sulfonation 2h, add deionized water cooling termination reaction, the washing of gained sulfonation bamboo charcoal is extremely neutral; Detect till the sulfate radical-free ion with barium chloride solution, obtain the sulfonation bamboo charcoal catalyst after the drying.
Among the present invention, under the solid acid catalyst effect, utilize o-mercaptobenzoic acid to be starting raw material, the method for the synthetic title product 2-isopropyl thioxanthone of solvent-free one kettle way is a kind of Green Chemistry synthetic technology that application prospect is arranged.The bamboo charcoal sulfonic acid catalyst catalytic activity that is adopted is high, and selectivity is good, and production cost is low, and is reusable, simplified reaction postprocessing method.Solid acid is repeatedly using after washing, dry reusable.In a word, the present invention compared with prior art, because of utilizing solid acid, condition of no solvent, technology is easy to operate, transformation efficiency is good, the three wastes are few, convenient post-treatment, solid acid is reusable, is economical and practical green environmental protection technique.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Preparation of catalysts
Embodiments of the invention 1:
1, carbonization process: with the H of dry bamboo bits 100 grams and 30%
3PO
4The aqueous solution 1000 grams soaked 20 hours, used the B suction filtration, obtained the bamboo bits of impregnation of phosphoric acid again at 100 ℃ of following dry 24h; In tube furnace, carry out pyrolysis then; Be warming up to 110 ℃ with 30 ℃/minute temperature rise rates, be incubated 3 hours, cool to room temperature naturally; Products therefrom to neutral, obtains the bamboo charcoal sample with deionized water wash after the drying.
2, sulfonation process: get above-mentioned bamboo charcoal sample 2 grams; Oleum 10 grams that add massfraction 50%; Be warming up to 100 ℃ of constant temperature sulfonation 2 hours, add deionized water cooling termination reaction, the washing of gained sulfonation bamboo charcoal is extremely neutral; Detect till the sulfate radical-free ion with barium chloride solution, obtain sulfonation bamboo charcoal catalyst 2.2 grams after the drying.
Embodiments of the invention 2:
1, carbonization process: with the H of dry bamboo bits 100 grams and 80%
3PO
4The aqueous solution 300 grams 3 hours are used the B suction filtration, again at 100 ℃ of dry down bamboo bits that obtained impregnation of phosphoric acid in 24 hours; In tube furnace, carry out pyrolysis then; Be warming up to 110 ℃ with 30 ℃/minute temperature rise rates, be incubated 3 hours, cool to room temperature naturally; Products therefrom to neutral, obtains the bamboo charcoal sample with deionized water wash after the drying.
2, sulfonation process: get bamboo charcoal sample 2 grams; Oleum 10 grams that add massfraction 50%; Be warming up to 100 ℃ of constant temperature sulfonation 2 hours, add deionized water cooling termination reaction, the washing of gained sulfonation bamboo charcoal is extremely neutral; Detect till the sulfate radical-free ion with barium chloride solution, obtain sulfonation bamboo charcoal catalyst 2.2 grams after the drying.
Embodiments of the invention 3:
1, carbonization process: with the H of dry bamboo bits 100 grams and 50%
3PO
4The aqueous solution 600 grams soaked 10 hours, used the B suction filtration, again at 100 ℃ of dry down bamboo bits that obtained impregnation of phosphoric acid in 24 hours; In tube furnace, carry out pyrolysis then; Be warming up to 110 ℃ with 30 ℃/minute temperature rise rates, be incubated 3 hours, cool to room temperature naturally; Products therefrom to neutral, obtains the bamboo charcoal sample with deionized water wash after the drying.
2, sulfonation process: get bamboo charcoal sample 2 grams; Oleum 10 grams that add massfraction 50%; Be warming up to 100 ℃ of constant temperature sulfonation 2 hours, add deionized water cooling termination reaction, the washing of gained sulfonation bamboo charcoal is extremely neutral; Detect till the sulfate radical-free ion with barium chloride solution, obtain sulfonation bamboo charcoal catalyst 2.2 grams after the drying.
The preparation of isopropyl thioxanthone
Embodiments of the invention 4:
In 250 milliliters of there-necked flasks, add o-mercaptobenzoic acid 154 grams (1 mole) and isopropyl benzene 122 grams (1.1 moles), sulfonation bamboo charcoal catalyst 15 grams; Reacted 5 hours down at 180 ℃, with the reaction solution cooling, in reaction solution, add toluene and extract for 500 milliliters after reaction finishes; Extraction liquid concentrates and removes toluene, uses dioxane: water=5:1 (volume ratio) recrystallization obtains light yellow crystal product 226 grams, yield 89%; 73～75 ℃ of fusing points, HPLC detect product purity and reach 99.5%.
Embodiments of the invention 5:
In 250 milliliters of there-necked flasks, add o-mercaptobenzoic acid 154 grams (1 mole) and isopropyl benzene 122 grams (1.1 moles), sulfonation bamboo charcoal catalyst 46 grams; Reacted 10 hours down at 150 ℃, with the reaction solution cooling, in reaction solution, add toluene and extract for 500 milliliters after reaction finishes; Extraction liquid concentrates and removes toluene, uses dioxane: water=5:1 (volume ratio) recrystallization obtains light yellow crystal product 225 grams, yield 88.5%; 73～75 ℃ of fusing points, HPLC detect product purity and reach 99.5%.
Embodiments of the invention 6:
In 250 milliliters of there-necked flasks, add o-mercaptobenzoic acid 154 grams (1 mole) and isopropyl benzene 122 grams (1.1 moles), sulfonation bamboo charcoal catalyst 1.6 grams; Reacted 10 hours down at 200 ℃, with the reaction solution cooling, in reaction solution, add toluene and extract for 500 milliliters after reaction finishes; Extraction liquid concentrates and removes toluene, uses dioxane: water=5:1 (volume ratio) recrystallization obtains light yellow crystal product 202 grams, yield 81%; 73～75 ℃ of fusing points, HPLC detect product purity and reach 99.5%.
Embodiments of the invention 7:
In 250 milliliters of there-necked flasks, add o-mercaptobenzoic acid 154 grams (1 mole) and isopropyl benzene 122 grams (1.1 moles), sulfonation bamboo charcoal catalyst 15 grams; Reacted 10 hours down at 200 ℃, with the reaction solution cooling, in reaction solution, add toluene and extract for 500 milliliters after reaction finishes; Extraction liquid concentrates and removes toluene, uses dioxane: water=5:1 (volume ratio) recrystallization obtains light yellow crystal product 218 grams, yield 86%; 73～75 ℃ of fusing points, HPLC detect product purity and reach 99.5%.
Claims (10)
1. the preparation method of a 2-isopropyl thioxanthone is characterized in that this preparation method in turn includes the following steps:
(1), add o-mercaptobenzoic acid, isopropyl benzene and solid acid catalyst in the reaction vessel, heating condition is reaction down, finish to reaction, reaction solution;
(2), with step (1) gained reaction solution cooling, get the 2-isopropyl thioxanthone through aftertreatment, reaction formula is following:
2. according to the preparation method of the said 2-isopropyl thioxanthone of claim 1, it is characterized in that the described solid acid catalyst of step (1) is the bamboo charcoal sulfonic acid catalyst.
3. according to the preparation method of claim 1 or 2 said 2-isopropyl thioxanthones, it is characterized in that the said solid acid of step (1) quality that feeds intake is o-mercaptobenzoic acid 1%～30% of the quality that feeds intake.
4. according to the preparation method of the said 2-isopropyl thioxanthone of claim 3, it is characterized in that the said solid acid of step (1) quality that feeds intake is o-mercaptobenzoic acid 10% of the quality that feeds intake.
5. according to the preparation method of the said 2-isopropyl thioxanthone of claim 1, it is characterized in that the said aftertreatment of step (2) comprises successively:
Add extracted in toluene;
Extraction liquid concentrates and removes toluene;
Recrystallization gets the 2-isopropyl thioxanthone.
6. according to the preparation method of the said 2-isopropyl thioxanthone of claim 5, it is characterized in that the 2-isopropyl thioxanthone is obtained by dioxane: water=5:1 (volume ratio) recrystallization.
7. according to the preparation method of the said 2-isopropyl thioxanthone of claim 1, it is characterized in that said being reflected under 120～200 ℃ the temperature condition of step (1) carry out.
8. according to the preparation method of the said 2-isopropyl thioxanthone of claim 7, it is characterized in that said being reflected under 160～180 ℃ of step (1) carry out.
9. according to the preparation method of the said 2-isopropyl thioxanthone of claim 1, it is characterized in that the time of the said reaction of step (1) is 1～10 hour.
10. according to the preparation method of the said 2-isopropyl thioxanthone of claim 9, it is characterized in that the time of the said reaction of step (1) is 3～6 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424409A (en) * | 2018-03-16 | 2018-08-21 | 吉安市东庆精细化工有限公司 | A kind of method of solid acid catalysis synthesis photoinitiator 2,4- diethyl thioxanthones |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915507A (en) * | 2006-09-05 | 2007-02-21 | 湖南师范大学 | Method for preparing solid sulfonic acid from reproducible vegetable material |
| CN101817812A (en) * | 2010-05-11 | 2010-09-01 | 天津久日化学工业有限公司 | Preparation method of 2-isopropyl thioxanthone and derivatives thereof |
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- 2012-07-31 CN CN2012102680119A patent/CN102746271A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915507A (en) * | 2006-09-05 | 2007-02-21 | 湖南师范大学 | Method for preparing solid sulfonic acid from reproducible vegetable material |
| CN101817812A (en) * | 2010-05-11 | 2010-09-01 | 天津久日化学工业有限公司 | Preparation method of 2-isopropyl thioxanthone and derivatives thereof |
Non-Patent Citations (2)
| Title |
|---|
| YEONSIL PARK ET AL.: "Investigation of Process Optimization in Synthesis of Thioxanthone from 2,2"-Dithiobisbenzoic Acid and Cumene", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》, vol. 6, no. 6, 30 November 2000 (2000-11-30), pages 431 - 436 * |
| 徐琼等: "磺化竹炭的制备、表征及其酸催化性能", 《新型碳材料》, vol. 26, no. 2, 30 April 2011 (2011-04-30), pages 103 - 108 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424409A (en) * | 2018-03-16 | 2018-08-21 | 吉安市东庆精细化工有限公司 | A kind of method of solid acid catalysis synthesis photoinitiator 2,4- diethyl thioxanthones |
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Application publication date: 20121024 |