CN114262286A - One-pot synthesis method of triphenyl sulfonium salt - Google Patents
One-pot synthesis method of triphenyl sulfonium salt Download PDFInfo
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- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 23
- 230000000977 initiatory effect Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000005457 ice water Substances 0.000 claims abstract description 14
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 14
- 239000011630 iodine Substances 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 10
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 230000002431 foraging effect Effects 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 18
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 9
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 9
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-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
- 125000005843 halogen group Chemical group 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims description 5
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 claims description 3
- FKFGHOKKBPBWDZ-UHFFFAOYSA-N chloro-phenyl-propan-2-ylsilane Chemical compound CC(C)[SiH](Cl)c1ccccc1 FKFGHOKKBPBWDZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical group OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- HEUIAKTUJMENAO-UHFFFAOYSA-N tert-butyl-chloro-phenylsilane Chemical compound CC(C)(C)[SiH](Cl)C1=CC=CC=C1 HEUIAKTUJMENAO-UHFFFAOYSA-N 0.000 claims description 3
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 phenyl sulfoxide compound Chemical class 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CALUPIZUADHGNN-UHFFFAOYSA-N silane trimethyl-lambda3-bromane Chemical compound [SiH4].CBr(C)C CALUPIZUADHGNN-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 1
- XHQDTKZEDBRQLR-UHFFFAOYSA-N [SiH4].CI(C)C Chemical compound [SiH4].CI(C)C XHQDTKZEDBRQLR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is suitable for the technical field of synthesis, and provides a one-pot synthesis method of triphenyl sulfonium salt, which comprises the following steps: s01, under the protection of first inert gas, adding magnesium chips and iodine particles into a first organic solvent, then dropwise adding an initiation solution into the first organic solvent to perform initiation reaction, and after initiation, dropwise adding a substrate solution to obtain a first reaction solution; adding a catalyst solution into the first reaction solution for aging reaction to obtain a second reaction solution; s02, under the protection of a second inert gas, cooling the second reaction liquid to 0 ℃, adding thionyl chloride into the second reaction liquid, and reacting at 20-30 ℃ for 12 hours to obtain a mixed liquid; placing the mixed solution in hydrogen halide ice water, and carrying out halogenation reaction at 10 ℃ to obtain a halogenation reaction solution; and (3) filtering the halogenation reaction solution, taking the filtrate, standing for layering, taking the aqueous phase layer, and washing with a second organic solvent to obtain the aqueous solution of the triphenyl sulfonium salt. The method has the advantages of high reaction speed, short production period, high atom utilization rate, low environmental pollution and high reaction yield.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and particularly relates to a one-pot synthesis method of triphenyl sulfonium salt.
Background
Due to the structural particularity, the triphenyl sulfonium salt and the derivative thereof have extremely important application in the photoresist and the photoresist material part. Compounds containing triphenylsulfonium salts and derivatives thereof are often used as important intermediates for photoacid generators.
In the prior art, there are various synthesis routes for triphenyl sulfonium salt and derivatives thereof, for example, diphenyl sulfide is used as an initial raw material, and is mixed with an oxidant in a solution to react under the action of a catalyst to obtain a reaction solution containing a phenyl sulfoxide compound, and then phenyl magnesium halide is used as an intermediate containing diphenyl sulfoxide to obtain a product containing triphenyl sulfonium salt through Grignard reaction; the product containing triphenyl sulfonium salt is obtained by taking phenyl as a starting material, taking anhydrous aluminum trichloride and thionyl chloride as auxiliary materials, reacting under anhydrous and oxygen-free conditions, finally quenching, and repeatedly separating, wherein benzene which is a high-toxicity compound is used as a reaction raw material. Most of the existing preparation methods have harsh reaction conditions, low conversion rate and yield, long reaction time, many byproducts, complex and fussy post-treatment, and large environmental pollution, and are not suitable for industrial mass production.
Disclosure of Invention
The embodiment of the invention provides a one-pot synthesis method of triphenylsulfonium salt, aiming at solving the problems of harsh reaction conditions, low conversion rate and yield, long reaction time, more byproducts, complex and tedious post-treatment, great environmental pollution and unsuitability for industrial mass production in the existing preparation method.
The embodiment of the invention is realized in such a way that a one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, under the protection of first inert gas, adding magnesium chips and iodine particles into a first organic solvent, then dropwise adding an initiation solution into the first organic solvent to perform initiation reaction, and after initiation, dropwise adding a substrate solution to obtain a first reaction solution; adding a catalyst solution into the first reaction solution for aging reaction to obtain a second reaction solution; 3.1-4.8 g of the magnesium chips are contained in each 100ml of the first organic solvent;
s02, under the protection of a second inert gas, cooling the second reaction liquid to 0 ℃, adding a thionyl chloride solution into the second reaction liquid, and reacting at 20-30 ℃ for 12 hours to obtain a mixed liquid; placing the mixed solution in hydrogen halide ice water, and carrying out halogenation reaction at 10 ℃ to obtain a halogenation reaction solution; and filtering the halogenation reaction solution, taking the filtrate, standing for layering, taking the aqueous phase layer, and washing with a second organic solvent to obtain the aqueous solution of the triphenyl sulfonium salt.
Further, in step S01,
the first inert gas is preferably nitrogen or argon.
The first organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether.
The dropping temperature is 50 ℃, and the dropping time is 1-1.5 h.
When the mass of the magnesium chips is 2.40g-19.01g, the dosage of the iodine particles is 1-2, and each iodine particle is 0.5g-2 g.
The initiator is contained in an amount of 5-15 g per 100ml of the first organic solvent.
The initiator is at least one of bromoethane, dibromoethane, dichloroethane or methyl iodide, and is preferably dibromoethane, dichloroethane or methyl iodide.
The thionyl chloride solution is tetrahydrofuran solution containing thionyl chloride or dimethyl tetrahydrofuran solution containing thionyl chloride or diethyl ether solution containing thionyl chloride; the thionyl chloride is contained in an amount of 1.74g to 2.65g per 40ml of tetrahydrofuran or 40ml of dimethyltetrahydrofuran or 40ml of diethyl ether.
Further, in step S02,
the second inert gas is preferably nitrogen or argon.
17.9g to 19.5g of the catalyst per 100ml of the first organic solvent are added.
The catalyst is trimethyl chlorosilane, trimethyl bromine silane, trimethyl iodine silane, dimethyl phenyl chlorosilane, triphenyl chlorosilane, tert-butyl phenyl chlorosilane, isopropyl phenyl chlorosilane or triphenyl phosphine, and preferably is trimethyl chlorosilane, trimethyl bromine silane or dimethyl phenyl chlorosilane.
The hydrogen halide is preferably hydrogen chloride or hydrogen bromide.
The second organic solvent is an ether solvent, preferably diethyl ether, tert-butyl methyl ether, 2-methyl tetrahydrofuran or tetrahydrofuran.
The general formula of the triphenylsulfonium salt is as follows:
wherein R is1\R2\R3Is an optional substituent, R1\R2\R3Is hydrogen, alkyl, halogen atom, ester group, methoxyl or hydrocarbyl; x is a halogen atom or hydrogen sulfate.
The method adopts a one-pot method, obtains the triphenyl sulfonium salt through synthesis of cheap and easily-obtained industrial raw materials, has the advantages of high reaction speed, short production period, lower energy consumption and high atom utilization rate, reduces the generation of byproducts, greatly lightens the environmental pollution, simultaneously well improves the yield of the synthesis reaction, and can improve the total yield by about 23 percent compared with the traditional production process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention is realized in such a way that a one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, adding magnesium chips and iodine particles into a first organic solvent under the protection of first inert gas, then dropwise adding an initiation solution into the first organic solvent to perform initiation reaction, and after initiation (a bubbling phenomenon and weak solvent reflux can be seen), dropwise adding a substrate solution to obtain a first reaction solution; adding a catalyst solution into the first reaction solution for aging reaction to obtain a second reaction solution; 3.1-4.8 g of the magnesium chips are contained in each 100ml of the first organic solvent;
s02, under the protection of a second inert gas, cooling the second reaction liquid to 0 ℃, adding a thionyl chloride solution into the second reaction liquid, and reacting at 20-30 ℃ for 12 hours to obtain a mixed liquid; placing the mixed solution in hydrogen halide ice water, and carrying out halogenation reaction at 10 ℃ to obtain a halogenation reaction solution; and filtering the halogenation reaction solution, taking the filtrate, standing for layering, taking the aqueous phase layer, and washing with a second organic solvent to obtain the aqueous solution of the triphenyl sulfonium salt.
Further, in step S01,
the first inert gas is preferably nitrogen or argon.
The first organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether.
The dropping temperature is 50 ℃, and the dropping time is 1-1.5 h.
When the mass of the magnesium chips is 2.40g-19.01g, the dosage of the iodine particles is 1-2, and each iodine particle is 0.5g-2 g.
The initiator is contained in an amount of 5-15 g per 100ml of the first organic solvent.
The substrate is chlorobenzene, bromobenzene or p-bromotoluene; the initiator is at least one of bromoethane, dibromoethane, dichloroethane or methyl iodide, and is preferably dibromoethane, dichloroethane or methyl iodide.
The thionyl chloride solution is tetrahydrofuran solution containing thionyl chloride or dimethyl tetrahydrofuran solution containing thionyl chloride or diethyl ether solution containing thionyl chloride; the thionyl chloride is contained in an amount of 1.74g to 2.65g per 40ml of tetrahydrofuran or 40ml of dimethyltetrahydrofuran or 40ml of diethyl ether.
Further, in step S02,
the second inert gas is preferably nitrogen or argon.
17.9g to 19.5g of the catalyst per 100ml of the first organic solvent are added.
The catalyst is at least one of trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, dimethylphenylchlorosilane, triphenylchlorosilane, tert-butylphenyl chlorosilane, isopropylphenyl chlorosilane or triphenylphosphine, and preferably is trimethylchlorosilane, trimethylbromosilane or dimethylphenylchlorosilane.
The hydrogen halide is preferably hydrogen chloride or hydrogen bromide.
The second organic solvent is an ether solvent, preferably diethyl ether, tert-butyl methyl ether, tetrahydrofuran or 2-methyl tetrahydrofuran.
The general formula of the triphenylsulfonium salt is as follows:
wherein R is1\R2\R3Is an optional substituent, R1\R2\R3Is hydrogen, alkyl, halogen atom, ester group, methoxyl or hydrocarbyl; x is a halogen atom or hydrogen sulfate.
The method adopts a one-pot method, obtains the triphenyl sulfonium salt through synthesis of cheap and easily-obtained industrial raw materials, has the advantages of high reaction speed, short production period, lower energy consumption and high atom utilization rate, reduces the generation of byproducts, greatly lightens the environmental pollution, simultaneously well improves the yield of the synthesis reaction, and can improve the total yield by about 23 percent compared with the traditional production process.
Different from the existing fractional step preparation method, the method adopts a one-pot method, obtains the triphenyl sulfonium salt by synthesizing cheap and easily-obtained industrial raw materials, has high atom utilization rate, reduces the generation of byproducts, can save a large amount of post-treatment time, does not need to purify intermediate diphenyl sulfoxide, can remove impurities in final post-treatment, and can effectively avoid the loss in the product purification process.
Example one
A one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, under the protection of nitrogen gas, adding 4.8g of magnesium chips and 2 iodine particles into a first organic solvent (100ml of tetrahydrofuran), then dropwise adding an initiator (2ml of dibromoethane, 50 ℃, obvious bubbles and a reflux solution are visible after initiation, and the initiation is finished), then dropwise adding a substrate solution (a mixed solution of 100ml of tetrahydrofuran and 20g of chlorobenzene) to perform reaction (the dropwise adding temperature is 50 ℃, the dropwise adding time is 3 hours, and after the dropwise adding is finished, the temperature is kept at 50 ℃ for 2 hours), detecting by GC that chlorobenzene is less than 0.5% and stopping the reaction to obtain a first reaction liquid, adding an aging solution (40 ml of tetrahydrofuran solution containing 2.6g of trimethylchlorosilane) into the first reaction liquid to perform aging reaction for 2 hours to obtain a second reaction liquid (the GC detection raw material is less than 5%);
s02, under the protection of nitrogen gas, cooling the second reaction liquid to 0 ℃, adding a thionyl chloride solution into the second reaction liquid, dropwise adding the solution at the temperature of 0 ℃, and dropwise adding the solution for 3 hours to obtain a mixed solution; placing the mixed solution into (5% hydrogen chloride solution, 30g) hydrogen chloride ice water (each hundred milliliters of hydrogen chloride ice water contains 3g of hydrogen chloride), and carrying out chlorination reaction at 10 ℃ to obtain chlorination reaction solution, wherein the pH value is 2-5; filtering the chlorination reaction solution, taking filtrate, standing for layering, taking a water phase layer, and washing with a second organic solvent (diethyl ether, 40ml × 3) to obtain an aqueous solution of the triphenyl sulfonium salt; conversion of the triphenylsulfonium salt by HPLC calibration was 67%.
Example two
A one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, under the protection of nitrogen gas, adding 95.04g of magnesium chips and 5 iodine particles into a first organic solvent (2000ml of 2-methyltetrahydrofuran), then dropwise adding (the dropwise adding temperature is 50 ℃, the dropwise adding time is 0.5h, after the dropwise adding is finished, the temperature is kept at 50 ℃ for 2h) an initiator (3ml of dibromoethane, obvious bubbles can be seen after the initiation and reaction liquid backflow) into the first organic solvent, then dropwise adding a substrate reaction liquid (a mixed solution of 2000ml of 2-methyltetrahydrofuran and 400g of chlorobenzene) for reaction, and stopping the reaction when the content of chlorobenzene is detected to be less than 0.5% by GC (gas chromatography) to obtain a first reaction liquid; adding 800ml of a 2-methyltetrahydrofuran solution containing 52.9g of trimethylchlorosilane in a catalyst solution into the first reaction solution to obtain a second reaction solution (the content of raw material chlorobenzene is less than 5 percent by GC detection);
s02, under the protection of nitrogen gas, cooling the second reaction liquid to 0 ℃, adding 386g of thionyl chloride solution into the second reaction liquid, and reacting at 30 ℃ for 3.5 hours to obtain a mixed liquid; placing the mixed solution into hydrogen chloride ice water (each hundred milliliters of the hydrogen chloride ice water contains 15g of hydrogen chloride), and carrying out chlorination reaction at 10 ℃ to obtain chlorination reaction liquid; filtering the chlorination reaction solution, taking filtrate, standing for layering, taking a water phase layer, and washing with a second organic solvent (diethyl ether, 800ml × 3) to obtain an aqueous solution of the triphenyl sulfonium salt; conversion of the triphenylsulfonium salt by HPLC calibration was 49%.
EXAMPLE III
A one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, under the protection of nitrogen gas, adding 3.4g of magnesium chips and 1 iodine particle into a first organic solvent (100ml of tetrahydrofuran), then dropwise adding (the dropwise adding temperature is 50 ℃, the dropwise adding time is 0.5h, and after the dropwise adding is finished, the temperature is kept at 50 ℃ for 1h) an initiator (0.5g of dibromoethane and 10ml of tetrahydrofuran solution) into the first organic solvent, finishing the initiation, showing obvious bubbles and weak reflux phenomena, dropwise adding a substrate solution (a mixed solution of 100ml of tetrahydrofuran and 20g of bromobenzene) for reaction, and stopping the reaction when the content of bromobenzene is detected to be less than 0.5% by GC (gas chromatography) to obtain a first reaction solution; adding a catalyst solution (40 ml of tetrahydrofuran solution containing 19.5g of trimethylchlorosilane) into the first reaction solution to carry out an aging reaction for 2 hours to obtain a second reaction solution (GC detects that the bromobenzene as a raw material is less than 5%);
s02, under the protection of nitrogen gas, cooling the second reaction liquid to 0 ℃, adding a tetrahydrofuran solution containing 1.9g of thionyl chloride into the second reaction liquid, and reacting at 23-30 ℃ for 3.5 hours to obtain a mixed liquid; placing the mixed solution into hydrogen bromide ice water (each hundred milliliters of hydrogen bromide ice water contains 35g of hydrogen bromide), and carrying out bromination reaction at 10 ℃ to obtain bromination reaction solution; filtering the bromination reaction solution, taking filtrate, standing for layering, taking a water phase layer, and washing the water phase layer with a second organic solvent (diethyl ether, 40ml of x 3) to obtain an aqueous solution of the triphenyl sulfonium salt; conversion of the triphenylsulfonium salt by HPLC calibration was 71%.
Example four
A one-pot synthesis method of triphenyl sulfonium salt comprises the following steps:
s01, under the protection of nitrogen gas, adding 3.1g of magnesium chips and 1 iodine particle into a first organic solvent (100ml of tetrahydrofuran), then dropwise adding (the dropwise adding temperature is 50 ℃, the dropwise adding time is 0.5h, and after the dropwise adding is finished, the temperature is kept at 50 ℃ for 0.5h) an initiator (2ml of dichloroethane and 20ml of tetrahydrofuran), wherein obvious bubbles and weak reflux phenomena can be seen after the initiation, then carrying out initiation reaction on a substrate solution (a mixed solution of 100ml of tetrahydrofuran and 20g of p-bromotoluene), wherein the dropwise adding time is 3h, and the reaction is stopped when the content of p-bromotoluene is detected to be less than 0.5% by GC (gas chromatography) to obtain a first reaction solution; adding a catalyst solution (40 ml of tetrahydrofuran solution containing 17.9g of trimethylchlorosilane) into the first reaction solution to carry out an aging reaction for 2 hours to obtain a second reaction solution (GC detects that the content of p-bromotoluene is less than 5 percent);
s02, under the protection of nitrogen gas, cooling the second reaction liquid to 0 ℃, adding a tetrahydrofuran solution containing 1.74g of thionyl chloride into the second reaction liquid, and reacting at 23-30 ℃ for 3.5 hours to obtain a mixed liquid; placing the mixed solution into hydrogen bromide ice water (each hundred milliliters of hydrogen bromide ice water contains 15g of hydrogen bromide), and carrying out bromination reaction at 10 ℃ to obtain bromination reaction solution; filtering the bromination reaction solution, taking filtrate, standing for layering, taking a water phase layer, and washing the water phase layer with a second organic solvent (diethyl ether, 40ml of x 3) to obtain an aqueous solution of the triphenyl sulfonium salt; conversion of triphenylsulfonium salt by HPLC calibration was 73%.
The conventional process for preparing diphenyl sulfoxide by oxidizing diphenyl sulfide generates peroxidation impurities in the oxidation process, and the impurities reduce the conversion rate of the reaction. The method adopts a one-pot method, obtains the triphenyl sulfonium salt by synthesizing cheap and easily-obtained industrial raw materials, has no oxidation problem, and avoids uncontrollable intermediate due to oxidation. The whole reaction of this application is more controllable, and each step reaction all uses GC, HPLC to detect qualified aftertreatment, can accomplish the reaction through 4 mouthfuls of flasks, can save the use and the area of cauldron, can directly reduce the emission of waste liquid, useless solid, waste water in the aftertreatment process, reduces the cost of handling the waste liquid.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A one-pot synthesis method of triphenyl sulfonium salt is characterized by comprising the following steps:
s01, under the protection of a first inert gas, adding magnesium chips and iodine particles into a first organic solvent, then dropwise adding an initiator into the first organic solvent to carry out initiation reaction, and after initiation, dropwise adding a substrate solution to obtain a first reaction solution; adding a catalyst solution into the first reaction solution for aging reaction to obtain a second reaction solution; 3.1-4.8 g of the magnesium chips are contained in each 100ml of the first organic solvent;
s02, under the protection of a second inert gas, cooling the second reaction liquid to 0 ℃, adding a thionyl chloride solution into the second reaction liquid, and reacting at 20-30 ℃ for 12 hours to obtain a mixed liquid; placing the mixed solution in hydrogen halide ice water, and carrying out halogenation reaction at 10 ℃ to obtain a halogenation reaction solution; and filtering the halogenation reaction solution, taking the filtrate, standing for layering, taking the aqueous phase layer, and washing with a second organic solvent to obtain the aqueous solution of the triphenyl sulfonium salt.
2. The one-pot synthesis method of triphenylsulfonium salt according to claim 1, wherein in step S01, the first organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether; the dropping temperature is 0-50 ℃, and the dropping time is 1-1.5 h.
3. The one-pot synthesis method of triphenylsulfonium salt according to claim 1, wherein in step S01, when the mass of the magnesium chips is 2.40g-19.01g, the iodine particle is used in an amount of 1-2 particles, and each iodine particle is 0.5g-2 g.
4. The one-pot synthesis method of triphenylsulfonium salt according to claim 1, wherein in step S01, 3-15g of the initiator is added per 100ml of the first organic solvent; the initiator is at least one of bromoethane, dibromoethane, dichloroethane or methyl iodide.
5. The one-pot synthesis method of triphenylsulfonium salt according to claim 4, wherein the substrate is chlorobenzene, bromobenzene or p-bromotoluene.
6. The one-pot synthesis method of triphenylsulfonium salt according to claim 1, wherein in step S01, 17.9g to 19.5g of the catalyst is added per 100ml of the first organic solvent.
7. The one-pot synthesis method of triphenylsulfonium salt according to claim 1, wherein in step S02, the thionyl chloride solution is tetrahydrofuran solution containing thionyl chloride or dimethyltetrahydrofuran solution containing thionyl chloride or diethyl ether solution containing thionyl chloride; 1.74g-2.65g of thionyl chloride is contained in 40ml of tetrahydrofuran or 40ml of dimethyl tetrahydrofuran or 40ml of diethyl ether; the hydrogen halide ice water contains 5-35 g of hydrogen halide per 100ml of hydrogen halide ice water.
8. The one-pot synthesis method of triphenylsulfonium salts according to claim 1, wherein in step S02, the catalyst is trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, dimethylphenylchlorosilane, triphenylchlorosilane, tert-butylphenyl chlorosilane, isopropylphenyl chlorosilane or triphenylphosphine.
9. The one-pot synthesis method of triphenylsulfonium salt according to claim 7, wherein in step S02, the hydrogen halide is hydrogen chloride or hydrogen bromide; the second organic solvent is diethyl ether, tert-butyl methyl ether, 2-methyl tetrahydrofuran or tetrahydrofuran.
10. The one-pot synthesis method of a triphenylsulfonium salt according to claim 1, wherein in step S02, the triphenylsulfonium salt has a general formula as follows:
wherein R is1\R2\R3Is an optional substituent, R1\R2\R3Is hydrogen, alkyl, halogen atom, ester group, methoxyl or hydrocarbyl; x is a halogen atom or hydrogen sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004315430A (en) * | 2003-04-16 | 2004-11-11 | Fuji Photo Film Co Ltd | Method for producing sulfonium salt |
| CN102838518A (en) * | 2012-09-11 | 2012-12-26 | 西安彩晶光电科技股份有限公司 | Preparation method of triphenyl sulfonium salt |
| CN106892847A (en) * | 2015-12-19 | 2017-06-27 | 西安瑞联新材料股份有限公司 | A kind of synthetic method of three (tert-butyl-phenyl) sulphur bromines |
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| JP2004315430A (en) * | 2003-04-16 | 2004-11-11 | Fuji Photo Film Co Ltd | Method for producing sulfonium salt |
| CN102838518A (en) * | 2012-09-11 | 2012-12-26 | 西安彩晶光电科技股份有限公司 | Preparation method of triphenyl sulfonium salt |
| CN106892847A (en) * | 2015-12-19 | 2017-06-27 | 西安瑞联新材料股份有限公司 | A kind of synthetic method of three (tert-butyl-phenyl) sulphur bromines |
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