CN101153037A - Method of producing 10-(4-xenyl)-2-isopropyl thioxanthone sulfur onium phosphorofluoric acid salt - Google Patents
Method of producing 10-(4-xenyl)-2-isopropyl thioxanthone sulfur onium phosphorofluoric acid salt Download PDFInfo
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- CN101153037A CN101153037A CNA2006101135552A CN200610113555A CN101153037A CN 101153037 A CN101153037 A CN 101153037A CN A2006101135552 A CNA2006101135552 A CN A2006101135552A CN 200610113555 A CN200610113555 A CN 200610113555A CN 101153037 A CN101153037 A CN 101153037A
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Abstract
The present invention relates to a preparation method of novel cationic photoinitiator10-(4-biphenyl)-2-isopropyl-thiadiazole ketone sulfur hexafluorophosphate. The 2-isopropyl thioxanthone is used as raw material; the mixed oxidant of cerium ammonium nitrate and sodium hypochlorite is used; the hydrohalogenic acid is added for catalysis. After the oxidation reaction, the intermediate sulfoxide can be made; the sulfoxide and biphenyl react to get the intermediate of sulfonium salt through salt reaction. Finally, the mixed solvent of alcohol categories and water is used; and the aqueous solution potassium hexafluorophosphate is dropped into the solution of the intermediate sulfoxide to get the product. The method of the present invention can reduce the dosage of expensive oxidant, and quicken the speed of oxidation reaction. Besides, the ion exchange reaction is complete and the solvent is easy to be recycled and reused; the purity of the target product is high; the optical solidification effects are good; the whole process is easy for the realization of industrial production.
Description
Technical field
Content involved in the present invention is the preparation method of the sulfosalt compound that the novel no benzene of a class discharges in the cation light initiator.
Background technology
People prepared cation photocuring coating in the past, be extensive use of the triaryl sulfonium salts photoinitiator such as UVI6992, they produce simple phenyl compound such as benzene after photolysis, brought poisonous residue to printing material, and may be penetrated into and cause more serious problem in the packed article.Toxicological harmless environmental requirement based on the food product pack field, producing starting material volatile, that easily move the benzene series small-molecule substance all will not allow to use, impel people to develop as the described long-chain substituted-phenyl of patent US4882201 sulfosalt, or the xenyl that allowing described in the patent W003/072567 comes across in the food replaces sulfosalt, be 10-(4-xenyl)-2-isopropyl thioxanthone sulfur hexafluorophosphate, structure is suc as formula shown in (I).The preparation method who describes in this patent is to be that 2-isopropyl thioxanthone (compd A) oxidation obtains sulfoxide (compd B) through a thioether, sulfoxide and biphenyl salify obtain bisulfate ion sulfosalt (Compound C), be dissolved in the acetic acid, carry out ion-exchange with the phosphofluoric acid aqueous solutions of potassium and obtain target product.
Carry out the sulfide oxidation reaction and used the oxygenant ceric ammonium nitrate, its selectivity is better, and speed of response is fast, and the content of over oxidation by product sulfone is less in the product, is no more than 5%.But because the ceric ammonium nitrate amount of using in this technology is excessive, and its price is expensive especially, causes the target product production cost very high, does not have the industrial value of realization.In Japanese Patent JP0240354A, make sulfide oxidation prepare sulfoxide as oxygenant with sodium hypobromite, hypochlorous sodium replaces sodium hypobromite in the experiment, discovery is that the oxidizing reaction speed of raw material is very slow with 2-isopropyl thioxanthone (compd A), raw material still has 50% behind the reaction 72h, and in the oxidation later stage, oxidation rate slows down gradually, and causes material thioether to be difficult to react completely.
Oxidizing reaction obtains intermediate sulfoxide (compd B) and generates bisulfate ion sulfosalt (Compound C) with biphenyl under the vitriol oil, acetic anhydride effect, patent WO03/072567 method is that Compound C is diluted to solution with small amount of acetic acid, splash into and carry out ion-exchange in the phosphofluoric acid aqueous solutions of potassium, experimental result proves, ion-exchange effect is poor, exchange rear section PF6-does not combine with sulfonium ion, be thick, be difficult for crystallization and obtain the crystalline powder product, and the small amount of crystalline product quality that obtains is relatively poor, and its fusing point is lower than 5～10 ℃ of standard substance all the time.
At above-mentioned defective, the present inventor has carried out intensive research, on the basis of above-mentioned synthetic method, makes improvements, and overcomes it and has raw materials for production cost height, and the shortcoming of product quality difference is so finished the present invention.
Summary of the invention
The purpose of this invention is to provide a kind of 2-isopropyl thioxanthone is feedstock production structure improving one's methods suc as formula 10-shown in (I) (4-xenyl)-2-isopropyl thioxanthone sulfur hexafluorophosphate, this method obtains intermediate sulfoxide (compd B) through oxidation earlier with 2-isopropyl thioxanthone (compd A), sulfoxide obtains bisulfate ion sulfosalt (Compound C) with the biphenyl salify again, last and phosphofluoric acid aqueous solutions of potassium carries out ion-exchange and obtains formula (I) compound, the improvement that the inventive method is done has following 3 points: 1) adopt ceric ammonium nitrate and clorox blending oxidizing agent to carry out the oxidation of 2-isopropyl thioxanthone in oxidising process, and the adding haloid acid carries out catalysis; 2) in the ion exchange reaction process, adopt the aqueous solution with Potassium Hexafluorophosphate to be added drop-wise to method in the alcoholic solution of intermediate (Compound C).The inventive method overcomes and has raw materials for production cost height, the shortcoming of product quality difference in the art methods.
Specifically, the invention provides the method for a kind of preparation formula (I) 10-(4-xenyl)-2-isopropyl thioxanthone sulfur hexafluorophosphate, it comprises the steps:
1) in aqueous solvent system, in the presence of the oxidation system of ceric ammonium nitrate and clorox, 2-isopropyl thioxanthone (compd A) oxidation is obtained intermediate sulfoxide (compd B), and sulfoxide obtains the bisulfate ion sulfosalt (Compound C) of formula (II) again with the biphenyl salify;
2) with formula (II) compound dissolution in the alcoholic solvent system, the aqueous solution of Potassium Hexafluorophosphate is added drop-wise in the alcoholic solution of formula (II) gradually, collect formula (I) compound of from mixed solvent, separating out with the solid particulate precipitation forms.
The present invention also provides the method for 10-shown in a kind of preparation formula (II) (4-xenyl)-2-isopropyl thioxanthone sulfur acid hydrogen root sulfosalt,
This method comprises the steps:
In aqueous solvent system, in the presence of the oxidation system of ceric ammonium nitrate and clorox, 2-isopropyl thioxanthone (compd A) oxidation is obtained intermediate sulfoxide (compd B), and sulfoxide obtains the bisulfate ion sulfosalt (Compound C) of formula (II) again with the biphenyl salify.
The present invention also provides a kind of separation purification formula (I) compound method, and described method comprises the steps:
Formula (II) compound dissolution in the alcoholic solvent system, is added drop-wise to the aqueous solution of Potassium Hexafluorophosphate in the alcoholic solution of formula (II) gradually, collects formula (I) compound of from mixed solvent, separating out with the solid particulate precipitation forms.
In the methods of the invention, the mol ratio of ceric ammonium nitrate and clorox is 0.95～1.1, and the mol ratio of ceric ammonium nitrate and 2-isopropyl thioxanthone (compd A) is 0.05-0.5: 1.
In addition, can add an amount of haloid acid in the described oxidation system and carry out catalysis, can make the reaction times foreshorten to 30h by 72h.Described haloid acid can be hydrochloric acid or Hydrogen bromide, preferred Hydrogen bromide, and suitable concentration (by solution W/V densitometer) is 0.1～2%, and is preferred 0.3～1%, most preferably 0.5～1%.
In the methods of the invention, described alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol, 1,2-propylene glycol, 1, and one or more in ammediol and the glycerol, wherein particular methanol and ethanol, methyl alcohol most preferably, consumption is 30～50% of a water.
By in oxidizing reaction, adopting ceric ammonium nitrate and clorox blending oxidizing agent, utilized ceric ammonium nitrate that sulfide oxidation is become the outstanding selectivity of sulfoxide on the one hand, and the adding by clorox, the Ce (II) that generates in the system can be oxidized to Ce (IV), recover its oxidation susceptibility, making that the ceric ammonium nitrate in the system can recycle, significantly reduced its consumption, only is 3.5% of former consumption.Simultaneously unexpected the discovery adds an amount of haloid acid in this oxidation system, make the reaction times foreshorten to 30h by 72h, and haloid acid can be hydrochloric acid and Hydrogen bromide, preferred Hydrogen bromide, and suitable concentration (V/V) is 0.1～2%, and is preferred 0.3～1%, most preferably 0.5～1%.
Bigger, not soluble in water owing to midbody compound C hydrophobic grouping volume in permutoid reaction, and be soluble in the organic solvent, as methylene dichloride, ethylene dichloride, acetone, acetate, alcohols.Intermediate acetic acid solution with high density in the former technology directly is added drop-wise in the phosphofluoric acid aqueous solutions of potassium, just directly cause midbody compound C separating out from system, exchange anionic chance and lose, make permutoid reaction be difficult for carrying out with hexafluoro-phosphate radical soluble in water.Through screening, find that the aqueous solution with Potassium Hexafluorophosphate is added drop-wise to the reactive mode in the alcoholic solution of intermediate (Compound C) gradually, can obtain purer product, fusing point conformance with standard product.Increased the solvability of intermediate in reaction system on the one hand, the intermediate that does not exchange fully is dissolved in and carries out homogeneous reaction in the system on the other hand, and the product that obtains after the exchange is separated out with solid form from system, help carry out of permutoid reaction, exchange effect completely thereby reach to positive dirction.Promptly from mixed solvent, separate out through the ion exchange reaction after product with the solid particulate precipitation forms, suction filtration can obtain solid crude product, and purity is more than 96%, and crude product product after crystallization reaches the standard substance requirement, and the easy recovery set usefulness of solvent easily realizes industrialization in this technology.Alcoholic solvent consumption suitable in the permutoid reaction is the scope of 30～50 (V/V) % of water.Alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol, 1,2-propylene glycol, 1, one or more in ammediol and the glycerol, wherein particular methanol and ethanol, most preferably methyl alcohol.
Embodiment
Following indefiniteness example will further specify content of the present invention, but the content of claim of the present invention is not limited to cited embodiment.
Embodiment 1
In 1000 milliliters of four-hole bottles, add 60.0 gram (0.24 mole) 2-ITX (2-isopropyl thioxanthone), 450 milliliters of acetonitriles and 100 ml waters, 18.0 gram ceric ammonium nitrate (0.0328 mole), 10.0 grams, 48% hydrobromic acid solution is after stirring, temperature remains on 25～30 ℃, drip the chlorine bleach liquor of 200 gram (0.24 mole) 10% content from dropping funnel, stir 24 hours sampling analysis, raw material 2-ITX content is 1.1%.In reaction solution, add 400 milliliters in water, stir suction filtration after 1 hour, and with 100 ml water washing leaching cakes, drying obtains the light yellow oxidation products of 56.1 grams.The HPLC purity assay is 97.4%, and yield is 88.4%.
Embodiment 2
20.5 gram (0.076 mole) 2-ITX oxidation products (embodiment 1 gained) and biphenyl 18.0 grams (0.117 mole), 70 milliliters of acetate, 70 milliliters of acetic anhydrides, 18 milliliters of methylene dichloride, stirring and dissolving in 250 milliliters of four-hole bottles, place the low temperature bath to be cooled to below 15 ℃ then, drip 26 milliliters of the vitriol oils, keep reacting liquid temperature not to be higher than 15 ℃.Drip at 15 ℃ and stirred 2 hours down.Reaction solution is transferred in 2500 milliliters of reaction flasks, added 1000 ml waters and 1000 milliliters of methylene dichloride, stir after 30 minutes, put and carry out layering in the separating funnel, tell lower floor's dichloromethane solution.Methylene dichloride evaporate to dryness on rotatory evaporator is obtained the hydrosulfate intermediate.
This intermediate is dissolved in 150 ml methanol, and the 250 ml water drips of solution that will contain 14 gram (0.076 mole) Potassium Hexafluorophosphates are added in this solution, add and continue to stir 5 hours, separate out pulverulent solids.Suction filtration, the washing filter cake.Oven dry obtains yellow solid product.
Comparative examples 1
20.5 gram (0.076 mole) 2-ITX oxidation products (embodiment 1 gained) and biphenyl 18.0 grams (0.117 mole), 70 milliliters of acetate, 70 milliliters of acetic anhydrides, 18 milliliters of methylene dichloride, stirring and dissolving in 250 milliliters of four-hole bottles, place the low temperature bath to be cooled to below 15 ℃ then, drip 26 milliliters of the vitriol oils, keep reacting liquid temperature not to be higher than 15 ℃.Drip at 15 ℃ and stirred 2 hours down.Reaction solution is transferred in 2500 milliliters of reaction flasks, added 1000 ml waters and 1000 milliliters of methylene dichloride, stir after 30 minutes, put and carry out layering in the separating funnel, tell lower floor's dichloromethane solution.Methylene dichloride evaporate to dryness on rotatory evaporator is obtained the hydrosulfate intermediate.
This intermediate is dissolved in 30 milliliters of acetate forms solution, and be added drop-wise in the 800 ml water solution that contain 40 gram Potassium Hexafluorophosphates, stir and leave standstill after 5 hours, as seen lower floor has thick product to separate out, with 200 milliliters of ethylene dichloride extracting and demixing, and use the dried over mgso dichloroethane solution, on rotatory evaporator, steam methylene dichloride and obtain the semi-solid product.
Embodiment 3
20.5 gram (0.076 mole) 2-ITX oxidation products (embodiment 1 gained) and biphenyl 18.0 grams (0.117 mole), 70 milliliters of acetate, 70 milliliters of acetic anhydrides, 18 milliliters of methylene dichloride, stirring and dissolving in 250 milliliters of four-hole bottles, place the low temperature bath to be cooled to below 15 ℃ then, drip 26 milliliters of the vitriol oils, keep reacting liquid temperature not to be higher than 15 ℃.Drip at 15 ℃ and stirred 2 hours down.Add 1000 ml waters and 1000 milliliters of methylene dichloride, stir, then reaction solution is transferred in 2500 milliliters of reaction flasks, after 30 minutes, put and carry out layering in the separating funnel, tell lower floor's dichloromethane solution.Methylene dichloride evaporate to dryness on rotatory evaporator is obtained the hydrosulfate intermediate.
This intermediate is dissolved in 150 milliliters of ethanol, and the 250 ml water drips of solution that will contain 14 gram (0.076 mole) Potassium Hexafluorophosphates are added in this solution, add and continue to stir 5 hours, separate out pulverulent solids.Suction filtration, the washing filter cake.Oven dry obtains yellow solid product.
Claims (11)
1. the method for the 10-of a preparation formula (I) (4-xenyl)-2-isopropyl thioxanthone sulfur hexafluorophosphate,
It comprises the steps:
1) in aqueous solvent system, in the presence of the oxidation system of ceric ammonium nitrate and clorox, the oxidation of 2-isopropyl thioxanthone is obtained the intermediate sulfoxide, this sulfoxide obtains the bisulfate ion sulfosalt of formula (II) again with the biphenyl salify;
2) with formula (II) compound dissolution in the alcoholic solvent system, the aqueous solution of Potassium Hexafluorophosphate is added drop-wise in the alcoholic solution of formula (II) gradually, collect formula (I) compound of from mixed solvent, separating out with the solid particulate precipitation forms.
2. the method for 10-shown in the preparation formula (II) (4-xenyl)-2-isopropyl thioxanthone sulfur acid hydrogen root sulfosalt,
This method comprises the steps:
In aqueous solvent system, in the presence of the oxidation system of ceric ammonium nitrate and clorox, the oxidation of 2-isopropyl thioxanthone is obtained the intermediate sulfoxide, this sulfoxide obtains the bisulfate ion sulfosalt of formula (II) again with the biphenyl salify.
3. according to the method for claim 1 or 2, wherein, the mol ratio of described clorox and 2-isopropyl thioxanthone (compd A) is 0.95～1.1, and the mol ratio of ceric ammonium nitrate and 2-isopropyl thioxanthone (compd A) is 0.05-0.5: 1.
4. according to arbitrary method of claim 1-3, add haloid acid in the described oxidation system as catalyzer.
5. according to the method for claim 4, wherein, described haloid acid is hydrochloric acid or Hydrogen bromide.
6. according to the method for claim 5, wherein, described haloid acid is a Hydrogen bromide.
7. according to the method for claim 4-6, wherein the concentration of haloid acid is counted 0.1～2V/V% by solution system.
8. one kind is separated purification formula (I) compound method, and described method comprises the steps:
Formula (II) compound dissolution in the alcoholic solvent system, is added drop-wise to the aqueous solution of Potassium Hexafluorophosphate in the alcoholic solution of formula (II) gradually, collects formula (I) compound of from mixed solvent, separating out with the solid particulate precipitation forms.
9. method according to Claim 8, wherein, described alcoholic solvent system can be an alcoholic solvent, consumption is the scope of 30～50 (V/V) % of water.
10. according to the method for claim 9, wherein said alcoholic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol, 1,2-propylene glycol, 1, one or more in ammediol and the glycerol.
11. according to the method for claim 10, wherein, described alcoholic solvent is methyl alcohol or ethanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9061979B2 (en) | 2011-07-29 | 2015-06-23 | Insight High Technology (Beijing) Co. Ltd. | Mercapto benzophenone compounds, compositions and preparations method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9061979B2 (en) | 2011-07-29 | 2015-06-23 | Insight High Technology (Beijing) Co. Ltd. | Mercapto benzophenone compounds, compositions and preparations method thereof |
| US9409861B2 (en) | 2011-07-29 | 2016-08-09 | Insight High Technology (Beijing) Co. Ltd. | Mercapto benzophenone compounds, compositions and preparation method thereof |
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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, No. 1 Zhongguancun East Road, Beijing, Tsinghua Science Park No. 10 building, east gate of Tsinghua University, four building, purple building, Haidian District Patentee before: Yingli Science and Technology Development Co., Ltd., Beijing |