CN109928951B - Preparation method of 2-isopropyl thioxanthone - Google Patents
Preparation method of 2-isopropyl thioxanthone Download PDFInfo
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- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 230000007613 environmental effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- BRQKZKIYPNEMQZ-UHFFFAOYSA-N 2-(4-propan-2-ylphenyl)sulfanylbenzoic acid Chemical compound C1=CC(C(C)C)=CC=C1SC1=CC=CC=C1C(O)=O BRQKZKIYPNEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- ZEAJXCPGHPJVNP-UHFFFAOYSA-N fenyramidol Chemical compound C=1C=CC=CC=1C(O)CNC1=CC=CC=N1 ZEAJXCPGHPJVNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- COSXSGYUZSGBNE-UHFFFAOYSA-N 2-(4-propan-2-ylsulfanylphenyl)benzoic acid Chemical compound C1=CC(SC(C)C)=CC=C1C1=CC=CC=C1C(O)=O COSXSGYUZSGBNE-UHFFFAOYSA-N 0.000 description 3
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 3
- APDUDRFJNCIWAG-UHFFFAOYSA-N 4-propan-2-ylbenzenethiol Chemical compound CC(C)C1=CC=C(S)C=C1 APDUDRFJNCIWAG-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- -1 2, 2' -dithio diphenyl formic acid Chemical compound 0.000 description 2
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 2
- KCWPXUBWIXAVLB-UHFFFAOYSA-N CC(C)C(C=C1)=CC=C1S(C(C=CC=C1)=C1C(O)=O)(=O)=O Chemical compound CC(C)C(C=C1)=CC=C1S(C(C=CC=C1)=C1C(O)=O)(=O)=O KCWPXUBWIXAVLB-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003799 water insoluble solvent Substances 0.000 description 2
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2-isopropyl thioxanthone as a photoinitiator, in particular to a method for preparing 2-isopropyl thioxanthone by carrying out ring closure reaction on 2- (4-isopropylphenylthio) benzoic acid under the condition of reflux dehydration. The method has the advantages of less concentrated sulfuric acid, low environmental pressure, good product appearance and the like.
Description
Technical Field
The invention relates to a preparation method of 2-isopropyl thioxanthone as a photoinitiator, in particular to a method for preparing 2-isopropyl thioxanthone by carrying out ring closure reaction on 2- (4-isopropylphenylthio) benzoic acid under the condition of reflux dehydration.
Background
The 2-isopropyl thioxanthone is a high-efficiency free radical II type photoinitiator, is suitable for photocuring materials consisting of unsaturated polyester, acrylic monomers and the like, and can be used for colorless or colored UV curing ink, wooden furniture, decorative coatings, adhesives, automobile metal part coatings, optical fiber manufacturing, printed matter luminescent materials and the like. It has the function of a sensitizer when used with a cationic photoinitiator and can also be used as a photosensitizer to enhance the curing efficiency of photoinitiator 907.
According to the difference of the used raw materials, the preparation method of the 2-isopropyl thioxanthone which can be industrially produced at present mainly comprises the following steps:
1. taking 2, 2' -dithio diphenyl formic acid and isopropyl benzene as raw materials: 2-isopropyl thioxanthone (CN 1220666) is prepared by the catalytic reaction of concentrated sulfuric acid in the next step; or multi-step reaction, 2, 2' -dithio diphenyl formic acid is firstly converted into 2-chloro-sulfuration benzoyl chloride through reaction and then reacts with isopropyl benzene to prepare 2-isopropyl thioxanthone (CN 1461302);
2. the method comprises the following steps of taking o-chlorobenzoic acid (CN 101570534, CN101817812, CN 101830887) or anthranilic acid (CN 102174036) or o-chlorobenzonitrile (CN 2013106571115) as a raw material, reacting the raw material with 4-isopropylthiophenol to prepare an intermediate 2- (4-isopropylthiophenyl) benzoic acid, and then carrying out ring closure reaction under the catalysis of concentrated sulfuric acid to prepare 2-isopropylthioxanthone:
the main disadvantage of process 1 is that the product produced is a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone, where 4-isopropylthioxanthone is less active and therefore less active than pure thioxanthone. The method 2 has the advantages of short route and great advantages for preparing the pure 2-isopropyl thioxanthone, but has the defects. Firstly, concentrated sulfuric acid is a catalyst and a solvent, and the catalytic effect of the concentrated sulfuric acid is influenced by water generated in the reaction process, so that the consumption of the concentrated sulfuric acid is very large, a large amount of waste acid is generated, and the sewage treatment pressure is large; secondly, the product has poor appearance and dark color.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a process method for preparing 2-isopropyl thioxanthone, which uses less concentrated sulfuric acid, has low environmental pressure and good product appearance.
To overcome the steps of method 2, there are two improved ideas: firstly, the organic solvent is added, and the dosage of concentrated sulfuric acid is reduced; secondly, the catalytic effect of concentrated sulfuric acid is ensured, and water generated by the reaction is taken away from the reaction system. And the added organic solvent can carry water at the same time, so that the two problems are solved at the same time, and the solvent which is convenient for post-treatment and is insoluble in water is preferably selected.
According to the above thought, the process of the preparation method of 2-isopropyl thioxanthone provided by the invention comprises the following specific operation steps:
1) dissolving 2- (4-isopropylbenzene sulfenyl) benzoic acid in an organic solvent,
2) adding catalyst, heating to reflux and divide water,
3) after the reaction is finished, adding water to perform extraction and quenching reaction;
wherein the organic solvent is selected from cyclohexane, methylcyclohexane, dichloroethane; the catalyst is selected from concentrated sulfuric acid.
The preparation method of 2-isopropyl thioxanthone is characterized in that the dosage of concentrated sulfuric acid is 1-3 times of the dosage of 2- (4-isopropylthiophenyl) benzoic acid substance. The use amount of concentrated sulfuric acid is beneficial to accelerating the reaction rate, but if the use amount is too large, the color of the product is not good, and if the use amount of sulfuric acid is too small, the reaction time needs to be prolonged for a long time, so that the production cycle and the productivity are influenced.
The preparation method of 2-isopropyl thioxanthone is characterized in that the dosage of the organic solvent is 1.5 to 10 times of the weight of 2- (4-isopropylthiophenyl) benzoic acid. The principle of the method is that the raw materials can be dissolved or completely dissolved in a reflux state, and simultaneously, the water generated by the reaction can be completely separated when the water is separated in the reflux state. The dosage of the solvent is not too much, which affects the productivity.
First, the inventors first selected the organic solvents of the solvent and water-carrying agent as toluene and xylene, which first have a sufficiently high boiling point to ensure a sufficient reaction temperature; secondly, the intermediate 2- (4-isopropylbenzene sulfenyl) benzoic acid can be well dissolved in a hot state; again, their water carrying capacity is very good, see table 1.
TABLE 1 binary azeotrope formation of toluene, xylene and water
However, in the experimental process, the inventor finds that when toluene or xylene is used as a solvent and a water-carrying agent, a new side reaction, namely sulfonation reaction, is generated, so that the appearance of the product is influenced, and the product with qualified appearance cannot be obtained; and the byproduct benzenesulfonic acid generated by the side reaction can cause serious emulsification in the post-treatment, and the layering is obvious only by adding a large amount of water, so the environmental pressure is high. Thus neither toluene nor xylene are good solvents for this reaction.
The inventor gives up toluene and xylene with good water carrying effect and searches for a non-benzene solvent and a water-insoluble solvent, firstly, the non-benzene solvent can avoid sulfonation side reaction, and the water-insoluble solvent can be convenient for post-treatment.
After test exploration, the inventor finds that the reaction can be well promoted by selecting a solvent cyclohexane, methylcyclohexane or dichloroethane; water generated in the reaction can be effectively carried out in the reaction process; and the post-treatment has no emulsification phenomenon, the post-treatment is simple, and most importantly, the appearance of the product prepared by the reaction is very good.
According to the preparation method of 2-isopropylthioxanthone, the raw material 2- (4-isopropylphenylthio) benzoic acid can be conveniently prepared, the preparation of the 2- (4-isopropylphenylthio) benzoic acid is reported in many documents, and CN101570534, CN101817812, CN101830887, US4902826 and the like are obtained by firstly reacting under alkaline conditions to prepare sodium 2- (4-isopropylphenylthio) benzoate and then acidifying.
The preparation method of 2-isopropyl thioxanthone provided by the invention reduces the consumption of concentrated sulfuric acid from about 10 times in the prior art to 3 times or less, reduces the consumption of concentrated sulfuric acid, also reduces the consumption of water during the extraction and extinction reaction, thereby reducing the waste acid water after post-treatment, separating out acid water, washing an organic phase for the second time, and directly sleeving a water phase after the second time washing for the extraction and extinction of the next batch reaction. The amount of water used in the extraction and extinction reaction is 1-2 times of the mass of concentrated sulfuric acid, and the waste acid water obtained by the amount of water can be well layered without adding too much water, and the waste acid water obtained by the amount of water can also be used for acidifying sodium 2- (4-isopropylbenzene sulfenyl) benzoate, then generating 2- (4-isopropylbenzene sulfenyl) benzoic acid and a basically saturated sodium sulfate solution, purifying the sodium sulfate by cooling crystallization for sale, thereby obtaining the waste water with low salt content, and therefore, the environmental pressure of the post-treatment is not large.
The preparation method of the 2-isopropyl thioxanthone provided by the invention has the advantages that:
(a) the consumption of concentrated sulfuric acid is small, and the cost is saved;
(b) the acid water obtained by post-treatment is used for preparing raw materials, so that a pure by-product sodium sulfate can be prepared, and the environmental pressure is low;
(c) the prepared product has good appearance.
The specific embodiment is as follows:
in order to illustrate the invention more clearly, the following non-limiting examples are given for further illustration.
Example 1: preparation of 2- (4-isopropylphenylthio) benzoic acid
120.3g (0.79mol) of o-chlorobenzoic acid, 120g (0.79mol) of 4-isopropylthiophenol and 68.0g (1.70mol) of sodium hydroxide were heated to 80 ℃ and stirred to react for 0.5 hour, and 520mL of toluene was added, followed by heating, refluxing, dehydration and removal of 14mL of water. And protecting the obtained solution with nitrogen, sealing and pressurizing the solution at 1MPa, heating the solution to 210 ℃, reacting the solution for 10 hours, cooling the solution, desolventizing the solution to recover toluene, adjusting the pH of the solution to 2 with dilute hydrochloric acid or dilute sulfuric acid, performing suction filtration and drying to prepare 204g of 2- (4-isopropylphenylthio) benzoic acid with the melting point of 149-151 ℃.
Example 2: preparation of 2-isopropyl thioxanthone
Dissolving 136.2g (0.50 mol) of 2- (4-isopropylbenzene sulfenyl) benzoic acid in 250mL of dichloroethane, slowly dropwise adding 125.0g of 98% sulfuric acid (1.25 mol) in a water bath, after 30min of dripping, slowly heating and raising the temperature, refluxing and dehydrating, monitoring the reaction by TLC or a liquid phase according to the amount of separated water, after the reaction is completed, cooling, adding 150mL of water, stirring for 30min, standing and layering, separating an organic phase, and reserving an acid water phase for later use. The organic phase is washed with a further 150mL of water and then the solvent is recovered by distillation, and the residue is recrystallized from 250mL of absolute ethanol to yield 114.5g of a pale yellow solid, i.e.: 2-isopropyl thioxanthone, content 99.4%.
Example 3: preparation of 2-isopropyl thioxanthone
Dispersing 136.2g (0.50 mol) of 2- (4-isopropylbenzenesulfonyl) benzoic acid in 400mL of cyclohexane, slowly dropwise adding 125.0g of 98% sulfuric acid (1.25 mol) in a water bath, slowly heating and raising the temperature after 30min of dripping, refluxing and dehydrating, monitoring the reaction by TLC or a liquid phase according to the amount of separated water, cooling and adding 150mL of water after the reaction is completed, stirring for 30min, standing and layering, separating an organic phase, washing with 150mL of water, distilling and recovering the solvent, and recrystallizing the residue with 250mL of anhydrous ethanol to obtain 115.8g of light yellow solid, namely: 2-isopropyl thioxanthone, content 99.3%.
Example 4: preparation of 2-isopropyl thioxanthone
Dissolving 136.2g (0.50 mol) of 2- (4-isopropylbenzenesulfonyl) benzoic acid in 250mL of dichloroethane, slowly dropwise adding 75.0g of 98% sulfuric acid (0.75 mol) in a water bath, slowly heating and raising the temperature after 30min of dripping, refluxing and dehydrating, monitoring the reaction according to the amount of separated water or TLC or a liquid phase, cooling and adding 75mL of water after the reaction is completed, stirring for 30min, standing and layering, separating an organic phase, washing with 75mL of water, distilling and recovering the solvent, and recrystallizing the residue with 250mL of anhydrous ethanol to obtain 113.2g of light yellow solid, namely: 2-isopropyl thioxanthone, content 99.0%.
Example 5: preparation of 2-isopropyl thioxanthone (use of waste acid liquor)
120.3g (0.79mol) of o-chlorobenzoic acid, 120g (0.79mol) of 4-isopropylthiophenol and 68.0g (1.70mol) of sodium hydroxide were heated to 80 ℃ and stirred to react for 0.5 hour, and 520mL of toluene was added, followed by heating, refluxing, dehydration and removal of 14mL of water. And (3) protecting the obtained solution with nitrogen, sealing and pressurizing the solution at 1MPa, heating the solution to 210 ℃, reacting the solution for 10 hours, cooling the solution, desolventizing and recovering toluene, adjusting the pH of the reaction solution to 2 by using the acid water separated from the example 2, keeping the temperature of the reaction system at about 40 ℃, performing suction filtration and drying to prepare 200g of 2- (4-isopropylphenylthio) benzoic acid. The filtrate was cooled to 0 deg.C, filtered again, and dried naturally to obtain 145g of sodium sulfate decahydrate.
Dissolving 136.2g (0.50 mol) of 2- (4-isopropylphenylthio) benzoic acid prepared above in 250mL of dichloroethane, slowly dropwise adding 125.0g of 98% sulfuric acid (1.25 mol) in a water bath, after 30min of dripping, slowly heating to raise the temperature, refluxing and dehydrating, monitoring the reaction according to the amount of separated water, TLC or a liquid phase, after the reaction is completed, cooling, adding 150mL of water, stirring for 30min, standing and layering, separating an organic phase, washing with 150mL of water, distilling and recovering the solvent, and recrystallizing the residue with 250mL of anhydrous ethanol to obtain 115.7g of light yellow solid, namely: 2-isopropyl thioxanthone, content 99.3%.
Example 6: preparation of 2-isopropyl thioxanthone
Dissolving 136.2g (0.50 mol) of 2- (4-isopropylbenzene sulfenyl) benzoic acid in 300mL of toluene, slowly dropwise adding 125.0g of 98% sulfuric acid (1.25 mol) in a water bath, slowly heating and raising the temperature after 30min of dripping, refluxing and dehydrating, monitoring the reaction according to the amount of separated water, TLC or a liquid phase, cooling and adding 150mL of water after the reaction is completed, stirring for 30min, standing for 4h, completely not layering, adding 150mL of water, stirring and standing, adding 150mL of water, adding a small part of an emulsifying intermediate layer, and separating the emulsifying layer into the water phase. The organic phase separated off is washed with a further 150mL of water and then distilled to recover the solvent, and the residue is recrystallized from 250mL of absolute ethanol to yield 95.4g of a tan solid, i.e.: 2-isopropyl thioxanthone, content 98.8%.
Example 7: preparation of 2-isopropyl thioxanthone
Dissolving 136.2g (0.50 mol) of 2- (4-isopropylbenzene sulfenyl) benzoic acid in 300mL of toluene, slowly dropwise adding 200.0g of 98% sulfuric acid (2.00 mol) in a water bath, after 30min of dropwise addition, slowly heating and raising the temperature, keeping the temperature at 60 ℃ for reaction, carrying out TLC or liquid phase monitoring reaction, after the reaction is completed, cooling to room temperature, adding 600mL of water, stirring for 30min, standing for layering, slightly forming an emulsifying intermediate layer, and separating the emulsifying layer into the water phase. The organic phase separated off is washed with 200mL of water and then distilled to recover the solvent, and the residue is recrystallized from 250mL of absolute ethanol to yield 101.8g of a dark yellow solid, i.e.: 2-isopropyl thioxanthone, content 98.7%.
Example 8: preparation of 2-isopropyl thioxanthone (concentrated sulfuric acid as solvent)
496.8g of concentrated sulfuric acid (270 mL) was taken, stirred, cooled to about 10 ℃ in an ice-water bath, and 136.2g (0.50 mol) of 2- (4-isopropylphenylthio) benzoic acid was added to the concentrated sulfuric acid in portions over 2 hours. And (3) after the addition is finished, carrying out heat preservation reaction, pouring into 600mL of ice water after the reaction is completed, stirring for 30min, adding 300mL of toluene for extraction, standing for layering, separating an organic phase, washing the organic phase with 200mL of water, distilling to recover the solvent, and recrystallizing the residue with 250mL of absolute ethyl alcohol to obtain 100.0g of dark yellow solid, namely: 2-isopropyl thioxanthone, content 98.7%.
The yield, appearance, amount of sulfuric acid used, and sulfuric acid waste water conditions of the products prepared in the examples are shown in Table 2.
TABLE 2
Claims (1)
1. A preparation method of 2-isopropyl thioxanthone with small post-treatment environmental pressure comprises the following operation steps:
1) dissolving 2- (4-isopropylbenzene sulfenyl) benzoic acid in an organic solvent;
2) adding concentrated sulfuric acid, heating, refluxing and dividing water; the dosage of the concentrated sulfuric acid is 1 to 3 times of the dosage of the 2- (4-isopropylbenzene sulfenyl) benzoic acid substance;
2) after the reaction is finished, adding water to quench the reaction, wherein the water consumption of the quenching reaction is 1-2 times of the mass of concentrated sulfuric acid, and the obtained waste acid water is used for acidifying sodium 2- (4-isopropylbenzene sulfenyl) benzoate;
wherein the organic solvent of step 1) is selected from cyclohexane, dichloroethane;
the organic solvent is used in an amount of 1.5-10 times the weight of 2- (4-cumylthio) benzoic acid.
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| CN101570534A (en) * | 2008-04-28 | 2009-11-04 | 大丰市天生化学工业有限公司 | Preparation process of 2-isopropyl thioxanthone |
| 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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Denomination of invention: Preparation method of 2-isopropylthioanthracene ketone Effective date of registration: 20231213 Granted publication date: 20220308 Pledgee: Binzhou Wudi Branch of Qilu Bank Co.,Ltd. Pledgor: SHANDONG JIURI CHEMICAL TECHNOLOGY Co.,Ltd. Registration number: Y2023980071450 |