CN114890981A - Preparation method of amino-substituted dibenzothiophene sulfoxide derivatives - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 title claims abstract description 10
- -1 amino-substituted dibenzothiophene Chemical class 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 32
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical class C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 18
- WNEXSUAHKVAPFK-UHFFFAOYSA-N 2,8-dibromodibenzothiophene Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3SC2=C1 WNEXSUAHKVAPFK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 9
- 235000011009 potassium phosphates Nutrition 0.000 claims description 9
- 229940126214 compound 3 Drugs 0.000 claims description 8
- 229940125898 compound 5 Drugs 0.000 claims description 8
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 7
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 4
- LBQQNHMLQQLHPI-UHFFFAOYSA-N CC1(C)OB(C(C=C2)=CC=C2N(C(C=C2)=CC=C2N(C)C)C(C=C2)=CC=C2N(C)C)OC1(C)C Chemical compound CC1(C)OB(C(C=C2)=CC=C2N(C(C=C2)=CC=C2N(C)C)C(C=C2)=CC=C2N(C)C)OC1(C)C LBQQNHMLQQLHPI-UHFFFAOYSA-N 0.000 claims description 3
- BTJQFRZWDBZGJA-UHFFFAOYSA-N CCN(CC)C(C=C1)=CC=C1N(C1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1)C(C=C1)=CC=C1N(CC)CC Chemical compound CCN(CC)C(C=C1)=CC=C1N(C1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1)C(C=C1)=CC=C1N(CC)CC BTJQFRZWDBZGJA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 6
- 230000035484 reaction time Effects 0.000 claims 3
- YTMVIIRAWJJGCT-UHFFFAOYSA-N 1-n,1-n-diphenyl-4-n-[4-(n-phenylanilino)phenyl]-4-n-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]benzene-1,4-diamine Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 YTMVIIRAWJJGCT-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000012074 organic phase Substances 0.000 description 25
- 239000002904 solvent Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- 238000007865 diluting Methods 0.000 description 11
- 239000012043 crude product Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 2
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical group 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
Abstract
The invention provides a preparation method of an amino-substituted dibenzothiophene sulfoxide derivative, and relates to the field of organic synthesis. The compound of the invention has short synthetic route, simple operation process for separating and purifying the product, high yield and suitability for mass synthesis. The product molecule of the invention has strong electron donor, enhances the charge transfer property in the molecule, and enables the product to have light emission with longer wavelength, thereby having wide application prospect in the field of organic photoelectric materials.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of an amino-substituted dibenzothiophene sulfoxide derivative.
Background
Dibenzothiophene sulfoxide is an important organic synthesis intermediate, has the characteristics of good photophysical property, easiness in modification and the like, and is often used for constructing organic room temperature phosphorescent materials. The organic room temperature phosphorescent material has unique time resolution property and good biocompatibility, and can be used for time resolution imaging of organisms. In addition, the organic room temperature phosphorescent material can realize multiple light emitting modes of fluorescence, delayed fluorescence and room temperature phosphorescence, can be used for multi-mode encryption, and improves the safety of information storage and transmission.
At present, research of organic room temperature phosphorescent materials based on dibenzothiophene sulfoxide derivatives in the fields of biological imaging and diagnosis, encryption anti-counterfeiting and the like attracts many people. Therefore, the design and synthesis of the novel dibenzothiophene sulfoxide derivative have important significance.
Disclosure of Invention
The invention aims to provide a preparation method of an amino-substituted dibenzothiophene sulfoxide derivative. The target product provided by the invention has short synthetic route and simple and convenient separation and purification operation.
The invention provides a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative, which is characterized in that a target product has the following structure:
the invention provides a preparation method of the compound, which comprises the following synthesis steps:
the preparation method of the compound 2 comprises the following steps:
(1) mixing a certain amount of 2, 8-dibromo dibenzothiophene, 4- [ N, N-di (4-dimethylaminophenyl) amino ] phenylboronic acid pinacol ester, tri (dibenzylideneacetone) dipalladium, potassium phosphate and a certain amount of tetrahydrofuran in a reaction bottle, heating to a certain temperature, stirring at the temperature for reacting for a certain time, diluting the reaction mixture with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, separating by using column chromatography to obtain a solution of a target product, and recovering the solvent to obtain a compound 1.
(2) Mixing a certain amount of compound 1, 30% hydrogen peroxide, trifluoroacetic acid and a certain amount of dichloromethane in a reaction bottle, stirring and reacting for a certain time at room temperature, neutralizing the reaction mixture, diluting with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, and purifying by recrystallization to obtain compound 2.
A method for preparing compound 4:
(1) mixing a certain amount of 2, 8-dibromo dibenzothiophene, 4- [ N, N-bis (4-diethylaminophenyl) amino ] phenylboronic acid pinacol ester, tris (dibenzylideneacetone) dipalladium, potassium phosphate and a certain amount of tetrahydrofuran in a reaction bottle, heating to a certain temperature, stirring and reacting for a certain time at the temperature, diluting the reaction mixture with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, separating by using column chromatography to obtain a solution of a target product, and recovering the solvent to obtain a compound 3.
(2) Mixing a certain amount of compound 3, 30% hydrogen peroxide, trifluoroacetic acid and a certain amount of dichloromethane in a reaction bottle, stirring and reacting for a certain time at room temperature, neutralizing the reaction mixture, diluting with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, and purifying by recrystallization to obtain compound 4.
The preparation method of the compound 6 comprises the following steps:
(1) mixing a certain amount of 2, 8-dibromo dibenzothiophene, 4- [ N, N-di (4-diphenylamine-phenyl) amino ] phenylboronic acid pinacol ester, tri (dibenzylidene acetone) dipalladium, potassium phosphate and a certain amount of tetrahydrofuran in a reaction bottle, heating to a certain temperature, stirring at the temperature for reacting for a certain time, diluting the reaction mixture with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, separating by using column chromatography to obtain a solution of a target product, and recovering the solvent to obtain a compound 5.
(2) Mixing a certain amount of compound 5, 30% hydrogen peroxide, trifluoroacetic acid and a certain amount of dichloromethane in a reaction bottle, stirring and reacting for a certain time at room temperature, neutralizing the reaction mixture, diluting with a solvent, extracting, separating, drying, recovering the solvent and the like to obtain a crude product, and purifying by recrystallization to obtain compound 6.
The amino-substituted dibenzothiophene sulfoxide derivative provided by the invention has a donor-acceptor-donor structure, and can be synthesized through Suzuki coupling reaction and oxidation reaction in sequence. Dibenzothiophene sulfoxide in the structure of the compound is used as an acceptor, and two sides of the dibenzothiophene sulfoxide are respectively connected with triphenylamine groups with strong electron donating property, so that the intramolecular charge transfer property of the compound is enhanced, and the compound is favorable for emitting with longer wavelength. The unique sulfoxide structure can not only enhance the electron-withdrawing ability of the acceptor, but also enhance the intersystem crossing rate of electrons in the compound, and realize the efficient transfer of excitons from a singlet state to a triplet state.
The preparation method provided by the invention has the advantages of simple steps, easy operation of separation and purification processes, easily available raw materials, high yield and suitability for large-scale synthesis and future large-scale production.
Detailed Description
Example 1
(1) 171 mg of 2, 8-dibromodibenzothiophene, 526 mg of 4- [ N, N-bis (4-dimethylaminophenyl) amino ] phenylboronic acid pinacol ester, 32 mg of tris (dibenzylideneacetone) dipalladium, 318 mg of potassium phosphate and 8 mL of tetrahydrofuran were mixed in a reaction flask, stirred for 5 min to fully dissolve the raw materials, and stirred for reaction at 65 ℃ for 18 h under the protection of nitrogen. After the reaction is finished, cooling to room temperature, diluting the reaction liquid with 30 mL of ethyl acetate, transferring the reaction liquid into a separating funnel, washing an organic phase twice with 40 mL of saturated ammonium chloride aqueous solution each time, separating out the organic phase, combining the aqueous phases, extracting twice with 20 mL of ethyl acetate each time, drying the combined organic phase for 20 min with 3 g of anhydrous sodium sulfate, recovering the solvent from the dried organic phase through reduced pressure distillation to obtain a crude product, performing column chromatography separation with 200-mesh and 300-mesh silica gel, wherein the used eluent is 10:1 petroleum ether and ethyl acetate, collecting the fourth zone as a target product solution, and recovering the solvent through reduced pressure distillation to obtain 316 mg of yellow solid, namely the compound 1, and the yield is 75%.
(2) 84 mg of Compound 1, 170 mg of 30% hydrogen peroxide, 2 mL of trifluoroacetic acid and 7 mL of dichloromethane were mixed in a reaction flask, and the reaction was stirred at room temperature for 4 hours. After the reaction, neutralizing the reaction solution with 3 mL of saturated aqueous sodium bicarbonate solution, diluting the neutralized reaction solution with 15 mL of dichloromethane and transferring the reaction solution into a separating funnel, washing an organic phase twice with 20 mL of saturated aqueous ammonium chloride solution, separating an organic phase, combining aqueous phases, extracting with 15 mL of dichloromethane once, combining organic phases, drying with 1.5 g of anhydrous sodium sulfate for 20 min, distilling the dried organic phase under reduced pressure to recover the solvent, recrystallizing with 15 mL of a mixed solvent of dichloromethane and n-hexane in a volume ratio of 1:4 to obtain 59 mg of yellow solid which is compound 2 after heating dissolution, filtration, cooling crystallization, suction filtration, washing and natural drying, wherein the yield is 69%.
Example 2
(1) 171 mg of 2, 8-dibromodibenzothiophene, 591 mg of 4- [ N, N-bis (4-diethylaminophenyl) amino ] phenylboronic acid pinacol ester, 32 mg of tris (dibenzylideneacetone) dipalladium, 318 mg of potassium phosphate and 8 mL of tetrahydrofuran are mixed in a reaction flask, stirred for 5 min to fully dissolve the raw materials, and stirred and reacted for 18 h at 65 ℃ under the protection of nitrogen. After the reaction is finished, cooling to room temperature, diluting the reaction liquid with 30 mL of ethyl acetate, transferring the reaction liquid into a separating funnel, washing an organic phase twice with 40 mL of saturated ammonium chloride aqueous solution each time, separating out the organic phase, combining the aqueous phases, extracting twice with 20 mL of ethyl acetate each time, drying the combined organic phase for 20 min with 3 g of anhydrous sodium sulfate, recovering the solvent from the dried organic phase through reduced pressure distillation to obtain a crude product, performing column chromatography separation with 200-mesh and 300-mesh silica gel, wherein the used eluent is 10:1 petroleum ether and ethyl acetate, collecting the fourth zone as a target product solution, and recovering the solvent through reduced pressure distillation to obtain 334 mg of yellow solid, namely the compound 3, and the yield is 70%.
(2) 96 mg of Compound 3, 170 mg of 30% hydrogen peroxide, 2 mL of trifluoroacetic acid and 7 mL of dichloromethane were mixed in a reaction flask, and the reaction was stirred at room temperature for 4 hours. After the reaction is finished, neutralizing the reaction liquid with 3 mL of saturated sodium bicarbonate aqueous solution, diluting the neutralized reaction liquid with 15 mL of dichloromethane, transferring the reaction liquid into a separating funnel, washing an organic phase twice with 20 mL of saturated ammonium chloride aqueous solution, separating an organic phase, combining aqueous phases, extracting once with 15 mL of dichloromethane, drying the combined organic phase for 20 min with 1.5 g of anhydrous sodium sulfate, recovering the solvent from the dried organic phase through reduced pressure distillation to obtain a yellow solid, recrystallizing the yellow solid with 15 mL of dichloromethane and n-hexane mixed solvent with the volume ratio of 1:4, heating, dissolving, filtering, cooling, crystallizing, filtering, washing and naturally drying to obtain 61 mg of yellow solid which is compound 4 with the yield of 63%.
Example 3
(1) 171 mg of 2, 8-dibromodibenzothiophene, 812 mg of 4- [ N, N-bis (4-dianilinophenyl) amino ] phenylboronic acid pinacol ester, 32 mg of tris (dibenzylideneacetone) dipalladium, 318 mg of potassium phosphate and 8 mL of tetrahydrofuran were mixed in a reaction flask, stirred for 5 min to fully dissolve the raw materials, and stirred for reaction at 65 ℃ for 18 h under the protection of nitrogen. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is diluted by 30 mL of ethyl acetate and transferred to a separating funnel, an organic phase is washed twice by saturated ammonium chloride aqueous solution, 40 mL of the organic phase is separated, after the organic phase is separated, an aqueous phase is combined, extracted by ethyl acetate twice, 20 mL of the ethyl acetate is separated for each time, the combined organic phase is dried for 20 min by 3 g of anhydrous sodium sulfate, the dried organic phase is subjected to reduced pressure distillation to recover a solvent to obtain a crude product, the crude product is separated by 200-mesh 300-mesh silica gel column chromatography, the used eluent is 10:1 petroleum ether and ethyl acetate, the fourth zone is collected to be a target product solution, the solvent is recovered by reduced pressure distillation to obtain 429 mg of yellow solid, namely a compound 5, and the yield is 64%.
(2) 134 mg of Compound 5, 170 mg of 30% hydrogen peroxide, 2 mL of trifluoroacetic acid and 7 mL of dichloromethane were mixed in a reaction flask, and the reaction was stirred at room temperature for 4 hours. After the reaction is finished, neutralizing the reaction solution with 3 mL of saturated aqueous sodium bicarbonate solution, diluting the neutralized reaction solution with 15 mL of dichloromethane, transferring the reaction solution into a separating funnel, washing an organic phase twice with 20 mL of saturated aqueous ammonium chloride solution, separating an organic phase, combining aqueous phases, extracting with 15 mL of dichloromethane once, drying the combined organic phase with 1.5 g of anhydrous sodium sulfate for 20 min, distilling the dried organic phase under reduced pressure to recover the solvent, recrystallizing with 15 mL of a mixed solvent of dichloromethane and n-hexane with a volume ratio of 1:4 to obtain a yellow solid, heating for dissolving, filtering, cooling for crystallization, performing suction filtration, washing and naturally drying to obtain 98 mg of yellow solid, namely the compound 6, wherein the yield is 72%.
Claims (13)
1. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the amido-substituted dibenzothiophene sulfoxide has the following structure:
2. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the mass ratio of reactants in the preparation method of the compound 1 is that 2, 8-dibromo dibenzothiophene: 4- [ N, N-bis (4-dimethylaminophenyl) amino ] phenylboronic acid pinacol ester: tris (dibenzylideneacetone) dipalladium: potassium phosphate = 1: 3.076: 0.187: 1.860.
3. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction temperature in the preparation process of compound 1 was 65 ℃.
4. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction time in the preparation method of the compound 1 is 18 h.
5. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the mass ratio of reactants in the preparation method of the compound 2 is that the mass ratio of the compound 1: 30% hydrogen peroxide = 1: 2.024.
6. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the mass ratio of reactants in the preparation method of the compound 3 is that 2, 8-dibromo dibenzothiophene: 4- [ N, N-bis (4-diethylaminophenyl) amino ] phenylboronic acid pinacol ester: tris (dibenzylideneacetone) dipalladium: potassium phosphate = 1: 3.456: 0.187: 1.860.
7. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction temperature in the preparation method of the compound 3 is 65 ℃.
8. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction time in the preparation method of the compound 3 is 18 h.
9. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: in the preparation method of the compound 4, the mass ratio of reactants is that the mass ratio of a compound 3: 30% hydrogen peroxide = 1: 1.771.
10. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the mass ratio of reactants in the preparation method of the compound 5 is that 2, 8-dibromo dibenzothiophene: 4- [ N, N-bis (4-diphenylaminophenyl) amino ] phenylboronic acid pinacol ester: tris (dibenzylideneacetone) dipalladium: potassium phosphate = 1: 4.749: 0.187: 1.860.
11. a preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction temperature in the preparation process of the compound 5 is 65 ℃.
12. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: the reaction time in the preparation method of the compound 5 is 18 h.
13. A preparation method of an amido-substituted dibenzothiophene sulfoxide derivative is characterized by comprising the following steps: in the preparation method of the compound 6, the mass ratio of reactants is that the mass ratio of a compound 5: 30% hydrogen peroxide = 1: 1.269.
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| JP2009053518A (en) * | 2007-08-28 | 2009-03-12 | Fujifilm Corp | Resist composition for electron beam, x-ray or euv and pattern-forming method using the same |
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