CN109928951A - The preparation method of 2- isopropyl thioxanthone - Google Patents
The preparation method of 2- isopropyl thioxanthone Download PDFInfo
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- CN109928951A CN109928951A CN201711372522.4A CN201711372522A CN109928951A CN 109928951 A CN109928951 A CN 109928951A CN 201711372522 A CN201711372522 A CN 201711372522A CN 109928951 A CN109928951 A CN 109928951A
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- water
- isopropyl
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- isopropyl thioxanthone
- sulfuric acid
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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 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 34
- 239000002904 solvent Substances 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 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
- 229960000935 dehydrated alcohol Drugs 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
- 239000007791 liquid phase Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000013517 stratification Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012805 post-processing Methods 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
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MFURVJLMZSKTJQ-UHFFFAOYSA-N C1(=CC=CC=C1)S.C(C)(C)C=1C=CC=CC1 Chemical compound C1(=CC=CC=C1)S.C(C)(C)C=1C=CC=CC1 MFURVJLMZSKTJQ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 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
- 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 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
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- -1 sulfuric acid Isopropyl thioxanthone Chemical compound 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 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
- 238000009835 boiling Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006277 sulfonation 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
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of photoinitiator 2- isopropyl thioxanthone, more particularly to 2-(4- isopropyl thiophenyl) benzoic acid carries out ring closure reaction under the conditions of reflux dewatering and prepares 2- isopropyl thioxanthone.This method has many advantages, such as using the concentrated sulfuric acid is few, environmental pressure is small, product appearance is good.
Description
Technical field
The present invention relates to a kind of preparation methods of photoinitiator 2- isopropyl thioxanthone, more particularly to 2-(4- isopropyl
Thiophenyl) benzoic acid carries out ring closure reaction under the conditions of reflux dewatering and prepares 2- isopropyl thioxanthone.
Background technique
2- isopropyl thioxanthone is a kind of II type photoinitiator of efficient free radical, is suitable for unsaturated polyester (UP), acrylic acid
In the photo-curing material of the compositions such as monomer, can be used for colorless or colored UV cured printing ink, wood furniture, decorative paint, adhesive,
Automobile metal component coating, fiber manufacturing, printed matter luminescent material etc..Have when it is used together with cation light initiator quick
The effect of agent is alternatively arranged as photosensitizer and uses the solidification efficiency to enhance photoinitiator 907.
By the difference for using raw material, currently, can the preparation method of industrial 2- isopropyl thioxanthone mainly have:
1, using 2,2 '-two thiodiphenvl formic acid and cumene as raw material: reacting preparation 2- in next step in the catalysis of the concentrated sulfuric acid
Isopropyl thioxanthone (CN1220666)；Or multistep reaction, 2,2 '-two thiodiphenvl formic acid are first converted by reaction
2- chlorine vulcanizes chlorobenzoyl chloride, then reacts preparation 2- isopropyl thioxanthone (CN1461302) with cumene again；
2, with 0-chloro-benzoic acid (CN101570534, CN101817812, CN101830887) or ortho-aminobenzoic acid
(CN102174036) or o-chloro benzonitrile (CN2013106571115) is raw material, is reacted with 4- isopropylbenzene thiophenol, preparation is intermediate
Body 2-(4- isopropyl thiophenyl) benzoic acid, then ring closure reaction prepares 2-isopropylthioxanthone under the catalysis of the concentrated sulfuric acid:
The major defect of method 1 is that the product produced is 2- isopropyl thioxanthone and 4- isopropyl thioxanthone mixture,
Wherein the activity of 4- isopropyl thioxanthone is poor, therefore mixed position is good not as good as the activity of the thioxanthone of pure position.Method 2 is so system
The 2- isopropyl thioxanthone of standby pure position, route is shorter, has great advantage, but still has deficiency.The concentrated sulfuric acid is catalyst first
It is solvent again, and generates water during the reaction and will affect the catalytic effect of the concentrated sulfuric acid, therefore the dosage of the concentrated sulfuric acid is very big,
A large amount of spent acid are generated, treatment pressure of sewage is big；Secondly product appearance is bad, is a bit darkish in color.
Summary of the invention
Present invention aim to avoid in the prior art the problem provide it is a kind of using the concentrated sulfuric acid is few, environment pressure
The process for preparing 2- isopropyl thioxanthone that power is small, product appearance is good.
The step of for conquering method 2, there are two improved thoughs: first is that increasing organic solvent, reducing the dosage of the concentrated sulfuric acid；
Second is that guaranteeing the catalytic effect of the concentrated sulfuric acid, the water that reaction generates is taken away from reaction system.And increased organic solvent is same
When can also be solved two problems simultaneously with water, preferably convenient post-treatment, water-immiscible solvent.
According to above-mentioned thinking, the concrete operation step of the technique of 2- isopropyl thioxanthone preparation method provided by the invention:
1) by 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in organic solvent,
2) catalyst is added, heating carries out reflux water-dividing,
3) end of reaction adds water to extract reaction of going out；
Wherein organic solvent is selected from hexamethylene, hexahydrotoluene, dichloroethanes；Catalyst is selected from the concentrated sulfuric acid.
2- isopropyl thioxanthone preparation method provided by the invention, it is characterised in that the dosage of the concentrated sulfuric acid is selected from 2-(4-
Isopropyl thiophenyl) 1-3 times of amount of benzoic acid species.The dosage of the concentrated sulfuric acid is conducive to accelerate reaction rate, but dosage greatly
Too big product colour is bad, and if sulfuric acid dosage is very little, the reaction time needs to extend for a long time, influences production cycle and production capacity.
2- isopropyl thioxanthone preparation method provided by the invention, it is characterised in that the dosage of organic solvent is selected from 2-
1.5-10 times of (4- isopropyl thiophenyl) benzoic acid weight.The type of solvent is different, and dosage also has difference, and principle is can be molten
Solution is completely dissolved reaction raw materials in the state of reflux, while point dereaction can generate completely when also guaranteeing reflux water-dividing
Water.Solvent usage can not be too many, influences production capacity.
Initially, the organic solvent of inventor's choice solvent and water entrainer is toluene and dimethylbenzene, first their boiling point foot
Enough height, guarantee enough reaction temperatures；Secondly intermediate 2-(4- isopropyl thiophenyl can be dissolved very well in the state of heat) benzene first
Acid；Their band outlet capacity is very good again, is shown in Table 1.
1 toluene of table, dimethylbenzene and water form binary azeotrope situation
But during the experiment, inventors have found that when doing solvent and water entrainer using toluene or dimethylbenzene, new pair can be generated
Reaction --- sulfonating reaction, this not only will affect the appearance of product, cannot get the product of qualified appearance；And side reaction generation
Byproduct benzene sulfonic acid will lead to post-processing emulsification it is very serious, needing to be added a large amount of water could be layered obviously, and environmental pressure is big.Cause
The solvent that this toluene and dimethylbenzene have not been for the reaction.
Inventor abandons the toluene and dimethylbenzene good with water effect, finds non-benzene series, water-immiscible solvent, benzene non-first
The solvent of system can be not soluble in water to can be convenient post-processing to avoid sulfonation side reaction, because using water or miscible with water is dissolved in
When solvent, first recycling design is needed, water-immiscible solvent is added and is extracted, kinetic energy is not only consumed, also has solvent
Cross contamination.
After experimental exploration, inventor has found to select solvent hexamethylene, hexahydrotoluene or dichloroethanes, not only can be very
Good promotion reaction；The water that reaction generates can also effectively be taken out of during the reaction；And post-processing does not have emulsion, after
Processing is simple, it is most important that the product appearance for reacting preparation is very good.
2- isopropyl thioxanthone preparation method provided by the invention, raw material 2-(4- isopropyl thiophenyl) benzoic acid can be with
Convenient to be made, 2-(4- isopropyl thiophenyl) preparation of benzoic acid had many document reports, CN101570534,
CN101817812, CN101830887, US4902826 etc. are that first to react the 2-(4- being prepared under alkaline condition different
Propyl benzene sulfenyl) sodium benzoate, then obtained by acidification.
2- isopropyl thioxanthone preparation method provided by the invention makes the dosage of the concentrated sulfuric acid by 10 times in the prior art
Left and right, is reduced to 3 times and hereinafter, reduce the dosage of the concentrated sulfuric acid, decreases extraction and goes out the dosage of water when reacting, to reduce
The waste acid water of post-processing, after separating sour water, organic phase carries out secondary washing, and the water phase after secondary washing can directly be covered and is used for
The extraction of next batch reaction is gone out.Extract 1-2 times that the dosage of water when reacting of going out is selected from concentrated sulfuric acid quality, does not need that too many water is added i.e.
Can be layered very well, and the waste acid water that the water of this dosage obtains can be also used for acidification 2-(4- isopropyl thiophenyl) benzoic acid
Then sodium generates 2-(4- isopropyl thiophenyl) benzoic acid and the metabisulfite solution that is substantially saturated, sulfuric acid is purified by decrease temperature crystalline
Sodium, for selling, to obtain the low waste water of salt, therefore the environmental pressure post-processed is little.
2- isopropyl thioxanthone preparation method advantage provided by the invention are as follows:
(a) dosage of the concentrated sulfuric acid is small, save the cost；
(b) sour water that post-processing obtains is used for the preparation of raw material, and pure byproduct sulfite, environmental pressure can be prepared
It is small；
(c) product appearance being prepared is good.
Specific embodiment:
In order to illustrate more clearly of the present invention, hereinafter nonlimiting examples is taken to further illustrate.
Embodiment 1:2-(4- isopropyl thiophenyl) benzoic acid preparation
By 120.3g(0.79mol) 0-chloro-benzoic acid, 120g (0.79mol) 4- isopropylbenzene thiophenol, 68.0g (1.70mol) hydrogen
Sodium oxide molybdena is heated to 80 DEG C and is stirred to react 0.5 hour, and toluene 520mL is added, dehydration is heated to reflux, after sloughing 14mL water.By institute
Solution nitrogen protection is obtained, closed pressurization 1MPa is heated to 210 DEG C, reacts 10 hours, cools, and precipitation recycles toluene, uses
The pH that dilute hydrochloric acid or dilute sulfuric acid adjust solution is 2, filters, drying, 204g 2-(4- isopropyl thiophenyl is prepared) benzoic acid,
Fusing point is 149-151 DEG C.
The preparation of embodiment 2:2- isopropyl thioxanthone
Take 136.2g(0.50mol) 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in 250mL dichloroethanes, slowly drips under water-bath
Add 98% sulfuric acid of 125.0g (1.25mol), 30min drop finishes, slow heating heating, reflux dewatering, according to the amount TLC for separating water or
Liquid phase monitoring reaction, after fully reacting, 150mL water is added in cooling, stirs 30min, and stratification separates organic phase, sour water phase
It is spare.Organic phase is washed with 150mL again, is then distilled to recover solvent, residue is recrystallized with 250mL dehydrated alcohol, obtained
114.5g faint yellow solid, it may be assumed that 2- isopropyl thioxanthone, content 99.4%.
The preparation of embodiment 3:2- isopropyl thioxanthone
Take 136.2g(0.50mol) 2-(4- isopropyl thiophenyl) benzoic acid is scattered in 400mL hexamethylene, slowly drips under water-bath
Add 98% sulfuric acid of 125.0g (1.25mol), 30min drop finishes, slow heating heating, reflux dewatering, according to the amount TLC for separating water or
Liquid phase monitoring reaction, after fully reacting, 150mL water is added in cooling, stirs 30min, and stratification separates organic phase, then uses
Then 150mL washing is distilled to recover solvent, residue is recrystallized with 250mL dehydrated alcohol, obtains 115.8g faint yellow solid,
That is: 2- isopropyl thioxanthone, content 99.3%.
The preparation of embodiment 4:2- isopropyl thioxanthone
Take 136.2g(0.50mol) 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in 250mL dichloroethanes, slowly drips under water-bath
Add 98% sulfuric acid of 75.0g (0.75mol), 30min drop finishes, slow heating heating, reflux dewatering, according to the amount or TLC for separating water
Or liquid phase monitoring reaction, after fully reacting, 75mL water is added in cooling, stirs 30min, and stratification separates organic phase, then uses
Then 75mL washing is distilled to recover solvent, residue is recrystallized with 250mL dehydrated alcohol, obtains 113.2g faint yellow solid,
That is: 2- isopropyl thioxanthone, content 99.0%.
The preparation (applying for acid pickle) of embodiment 5:2- isopropyl thioxanthone
By 120.3g(0.79mol) 0-chloro-benzoic acid, 120g (0.79mol) 4- isopropylbenzene thiophenol, 68.0g (1.70mol) hydrogen
Sodium oxide molybdena is heated to 80 DEG C and is stirred to react 0.5 hour, and toluene 520mL is added, dehydration is heated to reflux, after sloughing 14mL water.By institute
Solution nitrogen protection is obtained, closed pressurization 1MPa is heated to 210 DEG C, reacts 10 hours, cools, and precipitation recycles toluene, uses
The pH that the sour water that embodiment 2 separates adjusts reaction solution is 2, and keeping the temperature of reaction system is 40 DEG C or so, is filtered, drying, system
It is standby to obtain 200g 2-(4- isopropyl thiophenyl) benzoic acid.Filtrate is cooled to 0 DEG C, is filtered again, and natural drying obtains
The sal glauberi of 145g.
Take the 136.2g(0.50mol of above-mentioned preparation) 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in 250mL dichloroethanes,
98% sulfuric acid of 125.0g (1.25mol) is slowly added dropwise under water-bath, 30min drop finishes, slow heating heating, reflux dewatering, according to
Amount, TLC or the liquid phase monitoring reaction for separating water, after fully reacting, cooling addition 150mL water, stirring 30min, stratification, point
Organic phase out, then washed with 150mL, it is then distilled to recover solvent, residue is recrystallized with 250mL dehydrated alcohol, obtained
115.7g faint yellow solid, it may be assumed that 2- isopropyl thioxanthone, content 99.3%.
The preparation of embodiment 6:2- isopropyl thioxanthone
Take 136.2g(0.50mol) 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in 300mL toluene, is slowly added dropwise under water-bath
98% sulfuric acid of 125.0g (1.25mol), 30min drop finish, slow heating heating, reflux dewatering, according to separate the amount of water, TLC or
Liquid phase monitoring reaction, after fully reacting, 150mL water is added in cooling, stirs 30min, stands 4h, completely not stratified, adds 150mL
Water stirring is stood, and still some is emulsified, and adds 150mL water, still there is sub-fraction Middle emulsion layer, by emulsion layer also one
It rises and assigns in water phase.The organic phase separated, then organic phase is washed with 150mL, then it is distilled to recover solvent, residue 250mL
Dehydrated alcohol recrystallization, obtains 95.4g Tan solid, it may be assumed that 2- isopropyl thioxanthone, content 98.8%.
The preparation of embodiment 7:2- isopropyl thioxanthone
Take 136.2g(0.50mol) 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in 300mL toluene, is slowly added dropwise under water-bath
98% sulfuric acid of 200.0g (2.00mol), 30min drop finish, slow heating heating, 60 DEG C of insulation reactions, and TLC or liquid phase monitoring are anti-
It answers, after fully reacting, is down to room temperature, 600mL water is added, stir 30min, stratification slightly has Middle emulsion layer, will emulsify
Layer is also assigned in water phase together.The organic phase separated, then organic phase is washed with 200mL, it is then distilled to recover solvent, residue is used
250mL dehydrated alcohol recrystallization, obtains 101.8g dark yellow solid, it may be assumed that 2- isopropyl thioxanthone, content 98.7%.
The preparation of embodiment 8:2- isopropyl thioxanthone (concentrated sulfuric acid makees solvent)
The 496.8g concentrated sulfuric acid (270mL) is taken, stirring is cooled to 10 DEG C or so with ice-water bath, and 136.2g(0.50mol) 2-(4- is different
Propyl benzene sulfenyl) benzoic acid is added portionwise in the concentrated sulfuric acid with 2h.Charging finishes insulation reaction, after fully reacting, is poured into 600mL
In ice water, 30min is stirred, the extraction of 300mL toluene, stratification, the organic phase separated is added, then wash organic phase with 200mL,
Then it is distilled to recover solvent, residue is recrystallized with 250mL dehydrated alcohol, obtains 100.0g dark yellow solid, it may be assumed that 2- isopropyl
Thioxanthone, content 98.7%.
The product that each embodiment is prepared, yield, appearance, sulfuric acid dosage, sulfuric acid wastewater containing situation are shown in Table 2.
Table 2
Claims (3)
1. a kind of preparation method of 2- isopropyl thioxanthone preparation method, operating procedure include:
1) by 2-(4- isopropyl thiophenyl) benzoic acid is dissolved in organic solvent；
2) concentrated sulfuric acid is added, heating carries out reflux water-dividing；
2) end of reaction adds water to extract reaction of going out；
Wherein organic solvent described in step 1) is selected from hexamethylene, hexahydrotoluene, dichloroethanes.
2. 2- isopropyl thioxanthone preparation method according to claim 1, it is characterised in that the dosage of the concentrated sulfuric acid is selected from
2-(4- isopropyl thiophenyl) 1-3 times of amount of benzoic acid species.
3. 2- isopropyl thioxanthone preparation method according to claim 1, it is characterised in that the dosage of organic solvent is selected
From 2-(4- isopropyl thiophenyl) 1.5-10 times of benzoic acid weight.
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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 |