CN108424409A - A kind of method of solid acid catalysis synthesis photoinitiator 2,4- diethyl thioxanthones - Google Patents
A kind of method of solid acid catalysis synthesis photoinitiator 2,4- diethyl thioxanthones Download PDFInfo
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- CN108424409A CN108424409A CN201810216680.9A CN201810216680A CN108424409A CN 108424409 A CN108424409 A CN 108424409A CN 201810216680 A CN201810216680 A CN 201810216680A CN 108424409 A CN108424409 A CN 108424409A
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- Prior art keywords
- photoinitiator
- solid acid
- diethyl thioxanthones
- dithio
- organic solvent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
Abstract
The invention discloses a kind of solid acid catalysis to synthesize photoinitiator 2, the method of 4 diethyl thioxanthones, this method uses solid acid as catalyst, dithio-salicylic acid, NSC 62102 are added in the reaction kettle containing organic solvent and reacted, later by extraction, recrystallization, filter, be dried to obtain required product photoinitiator 2,4 diethyl thioxanthones, yield is improved the present invention compared with prior art, and greatly reduce side reaction, be it is a kind of it is suitable industrialization, environmentally protective production method.
Description
Technical field
The present invention relates to photoinitiator fields, are especially a kind of solid acid catalysis synthesis photoinitiator 2,4- diethyl sulfides
The method of miscellaneous anthrone.
Background technology
2,4- diethyl thioxanthones, English name 2,4-Diethyl Thioxanthone (vehicle economy TX), molecular formula：
C17H16OS, molecular weight：268.37 CAS registration numbers：[82799-44-8].2,4- diethyl thioxanthones are light yellow crystal powder
End, fusing point：70~71 DEG C.As a kind of important photoinitiator, 2,4- diethyl thioxanthones are widely used in UV solidifications
Type coating and ink.
The production technology of 2,4- diethyl thioxanthones mainly does solvent and catalyst simultaneously with the concentrated sulfuric acid at present
(J.Chem.Soc.1911,99,645, JPS 57163377 and CN 102250060 are all made of this technique), not only side reaction is more
(especially some sulfonated aromatic compounds), product appearance is poor, and product yield is low (80% or so), and post-processing difficulty is very
Greatly, while generating a large amount of spent acid, also production equipment is caused greatly to corrode, it is both not environmentally or uneconomical.
Invention content
The technical problem to be solved by the present invention is to the shortcomings that overcoming the above prior art：A kind of solid acid catalysis is provided
The method for synthesizing photoinitiator 2,4- diethyl thioxanthones.
Technical solution of the invention is as follows：
A kind of method of solid acid catalysis synthesis photoinitiator 2,4- diethyl thioxanthones includes the following steps：
(1) condensation reaction：Under conditions of temperature is 0~200 DEG C, by dithio-salicylic acid, NSC 62102, solid
Acid catalyst, which is added in the reaction kettle containing organic solvent, to react 4~30 hours.
(2) it waits for step (1) after reaction, reaction solution is cooled to room temperature, impurity screening obtains filtrate, and filtrate is through decompression
After concentration removes organic solvent, extractant is added and extracts, branch vibration layer, after organic layer is washed with water and saturated brine respectively,
Vacuum distillation removes extractant, finally by gained residue by recrystallizing, filtering, be drying to obtain required product photoinitiator
2,4- diethyl thioxanthones.
The dithio-salicylic acid that the relation with contents of dithio-salicylic acid and organic solvent is every mole in the step (1) needs
200~2000ml organic solvents are wanted, preferably need 600~1200ml organic solvents per mole salicylic acid.
The molar ratio of dithio-salicylic acid and NSC 62102 is 1 in the step (1)：1~5, preferably 1：1.1~1.5.
The mass percent concentration of solid acid catalyst accounts for the 0.5%~10% of total reaction mixture in the step (1),
Preferably 1%~2%.
Solid acid catalyst in the step (1) is storng-acid cation exchange resin, solid super-strong acid, tri-chlorination
One kind in aluminium, zinc chloride, ferric trichloride, ferric sulfate, wherein solid super-strong acid are SO4 2-/TiO2、SO4 2-/ZrO2In one kind.
Organic solvent in the step (1) is one or more in amide, sulfoxide, alcohol, halogenated hydrocarbons；Wherein, amide
For one kind in n,N-Dimethylformamide, n,N-dimethylacetamide；Sulfoxide is dimethyl sulfoxide (DMSO), thionyl chloride, phenyl Asia
One kind in sulfone, benzyl, sulfolane；Alcohol is one in cyclobutanol, amylalcohol, isoamyl alcohol, neopentyl alcohol, cyclohexanol, suberol
Kind；Halogenated hydrocarbons be dichloromethane, 1,2- dichloroethanes, chloroform, carbon tetrachloride, Benzene Chloride, o-dichlorohenzene, m-dichlorobenzene, to two
One kind in chlorobenzene.
Extractant in the step (2) is fat hydrocarbon, arene, alkyl halide hydro carbons, Polyhalogenated aromatic hydrocarbons, ether
One kind in class, esters.
The beneficial effects of the invention are as follows：
Compared with prior art, the yield of product of the present invention is increased to 85% or more less than 80% from original, reacts item
Part is mild, and the reaction time is short, and post-processing is simple, and waste is few, therefore production cost declines to a great extent with cost of material, and significantly
Alleviate prior art with the concentrated sulfuric acid do solvent bank come the influence to the technique such as more, the equipment burn into environmental pollution of side reaction,
Be it is a kind of it is suitable industrialization, environmentally protective production method.
Specific implementation mode
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact
Apply example.
Embodiment 1
(1) condensation reaction：Temperature be 100 DEG C under conditions of, by 25g dithio-salicylic acids, 26g NSC 62102s,
3g storng-acid cation exchange resins, which are added in the reaction kettle containing 75ml dimethyl sulfoxide (DMSO)s, to react；
(2) HPLC is reacted into line trace, until after dithio-salicylic acid disappears, reaction solution is cooled to room temperature, is filtered, filtrate
After being concentrated under reduced pressure and removing solvent, the extraction of 100g toluene is added, branch vibration layer, organic layer is washed with water and saturated brine respectively
Afterwards, vacuum distillation removes toluene, then recrystallizes gained residue with 95% ethyl alcohol, finally by filtering, drying
Yellow crystalline powder 38.9g is obtained, gained yellow crystalline powder is photoinitiator 2,4- diethyl thioxanthones.
Experimental result：Product yield is 88.9%, and fusing point is 70~72 DEG C, and it is 99.5% that HPLC, which detects product purity,.
Embodiment 2
(1) condensation reaction：Temperature be 100 DEG C under conditions of, by 25g dithio-salicylic acids, 26g NSC 62102s,
1.5g solid super-strong acids SO4 2-/TiO2It is added in the reaction kettle containing 75ml dimethyl sulfoxide (DMSO)s and reacts；
(2) HPLC is reacted into line trace, until after dithio-salicylic acid disappears, reaction solution is cooled to room temperature, is filtered, filtrate
After being concentrated under reduced pressure and removing solvent, the extraction of 100g toluene is added, branch vibration layer, organic layer is washed with water and saturated brine respectively
Afterwards, vacuum distillation removes toluene, then recrystallizes gained residue with 95% ethyl alcohol, finally by filtering, drying
Yellow crystalline powder 37.2g is obtained, gained yellow crystalline powder is photoinitiator 2,4- diethyl thioxanthones.
Experimental result：Product yield is 85.0%, and fusing point is 70~72 DEG C, and it is 99.5% that HPLC, which detects product purity,.
Embodiment 3
(1) condensation reaction：Temperature be 100 DEG C under conditions of, by 22g dithio-salicylic acids, 23g NSC 62102s,
1.3g solid acids SO4 2-/TiO2It is added to containing 70mlN, is reacted in the reaction kettle of N- dimethylacetylamides；
(2) HPLC is reacted into line trace, until after dithio-salicylic acid disappears, reaction solution is cooled to room temperature, is filtered, filtrate
After being concentrated under reduced pressure and removing solvent, the extraction of 100g toluene is added, branch vibration layer, organic layer is washed with water and saturated brine respectively
Afterwards, vacuum distillation removes toluene, then recrystallizes gained residue with 95% ethyl alcohol, finally by filtering, drying
Yellow crystalline powder 36.3g is obtained, gained yellow crystalline powder is photoinitiator 2,4- diethyl thioxanthones.
Experimental result：Product yield is 86.2%, and fusing point is 70~72 DEG C, and it is 99.0% that HPLC, which detects product purity,.
Claims (5)
1. a kind of solid acid catalysis synthesizes photoinitiator 2, the method for 4- diethyl thioxanthones, which is characterized in that including following
Step：
(1) condensation reaction：Under conditions of temperature is 0~200 DEG C, dithio-salicylic acid, NSC 62102, solid acid are urged
Agent, which is added in the reaction kettle containing organic solvent, reacts 4~30 hours；
(2) it waits for step (1) after reaction, reaction solution is cooled to room temperature, impurity screening obtains filtrate, and filtrate is through being concentrated under reduced pressure
After removing organic solvent, extractant extraction is added, branch vibration layer after organic layer is washed with water and saturated brine respectively, depressurizes
Extractant is distilled off, finally by gained residue by recrystallizing, filtering, be drying to obtain required product photoinitiator 2,4-
Diethyl thioxanthone.
2. solid acid catalysis according to claim 1 synthesizes photoinitiator 2, the method for 4- diethyl thioxanthones is special
Sign is that the dithio-salicylic acid that the relation with contents of dithio-salicylic acid and organic solvent is every mole in the step (1) needs
Want the organic solvent of 200~2000ml；The molar ratio of NSC 62102 and dithio-salicylic acid is 1~5：1；Solid acid catalyst
Mass percent concentration accounts for the 0.5%~10% of total reaction mixture.
3. solid acid catalysis according to claim 1 synthesizes photoinitiator 2, the method for 4- diethyl thioxanthones is special
Sign is that the solid acid catalyst is storng-acid cation exchange resin, solid super-strong acid, alchlor, zinc chloride, three
One kind in iron chloride, ferric sulfate.
4. solid acid catalysis according to claim 1 synthesizes photoinitiator 2, the method for 4- diethyl thioxanthones is special
Sign is that the organic solvent in the step (1) is one or more in amide, sulfoxide, alcohol, halogenated hydrocarbons.
5. solid acid catalysis according to claim 1 synthesizes photoinitiator 2, the method for 4- diethyl thioxanthones is special
Sign is that the extractant in the step (2) is fat hydrocarbon, arene, alkyl halide hydro carbons, Polyhalogenated aromatic hydrocarbons, ether
One kind in class, esters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845471A (en) * | 2019-11-20 | 2020-02-28 | 吉安市东庆精细化工有限公司 | Process for synthesizing photoinitiator 2,4-diethyl thioxanthone by one-pot method |
| CN112778269A (en) * | 2020-12-30 | 2021-05-11 | 山东久日化学科技有限公司 | Preparation method of thioxanthone photoinitiator |
Citations (5)
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|---|---|---|---|---|
| CN1461302A (en) * | 2000-11-15 | 2003-12-10 | 波隆有限公司 | Friedel-crafts process for the preparation of thioxanthones |
| CN102250060A (en) * | 2011-05-27 | 2011-11-23 | 连云港升南化学有限公司 | Preparation method of 2,4-diethyl thioxanthone |
| CN102746271A (en) * | 2012-07-31 | 2012-10-24 | 浙江扬帆精细化工有限公司 | Preparation method of 2-isopropyl thioxanthone (ITX) |
| CN102863422A (en) * | 2012-09-07 | 2013-01-09 | 浙江工业大学 | Preparation method of 2-isopropylthioxanthone |
| CN107540580A (en) * | 2016-06-20 | 2018-01-05 | 深圳市有为化学技术有限公司 | The preparation method of acyl chlorides and thioxanthone |
-
2018
- 2018-03-16 CN CN201810216680.9A patent/CN108424409A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461302A (en) * | 2000-11-15 | 2003-12-10 | 波隆有限公司 | Friedel-crafts process for the preparation of thioxanthones |
| CN102250060A (en) * | 2011-05-27 | 2011-11-23 | 连云港升南化学有限公司 | Preparation method of 2,4-diethyl thioxanthone |
| CN102746271A (en) * | 2012-07-31 | 2012-10-24 | 浙江扬帆精细化工有限公司 | Preparation method of 2-isopropyl thioxanthone (ITX) |
| CN102863422A (en) * | 2012-09-07 | 2013-01-09 | 浙江工业大学 | Preparation method of 2-isopropylthioxanthone |
| CN107540580A (en) * | 2016-06-20 | 2018-01-05 | 深圳市有为化学技术有限公司 | The preparation method of acyl chlorides and thioxanthone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845471A (en) * | 2019-11-20 | 2020-02-28 | 吉安市东庆精细化工有限公司 | Process for synthesizing photoinitiator 2,4-diethyl thioxanthone by one-pot method |
| CN112778269A (en) * | 2020-12-30 | 2021-05-11 | 山东久日化学科技有限公司 | Preparation method of thioxanthone photoinitiator |
| CN112778269B (en) * | 2020-12-30 | 2022-09-02 | 山东久日化学科技有限公司 | Preparation method of thioxanthone photoinitiator |
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Application publication date: 20180821 |