CN114890980B - Process for preparing ionic thiafluorene derivatives - Google Patents
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- CN114890980B CN114890980B CN202210526478.2A CN202210526478A CN114890980B CN 114890980 B CN114890980 B CN 114890980B CN 202210526478 A CN202210526478 A CN 202210526478A CN 114890980 B CN114890980 B CN 114890980B
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 23
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- -1 4- { N, N-bis [4- (6-bromohexyloxy) phenyl ] amino } phenylboronic acid pinacol ester Chemical compound 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 238000011403 purification operation Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- ZOMAQBACQSQOIL-UHFFFAOYSA-N 1,7-dibromo-9H-fluorene Chemical compound BrC1=CC=CC=2C3=CC=C(C=C3CC1=2)Br ZOMAQBACQSQOIL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000012216 imaging agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006053 organic reaction Methods 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
- 230000035515 penetration Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 238000007039 two-step reaction Methods 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of an ionic thiafluorene derivative, and relates to the field of organic synthesis. The invention has the advantages of shorter synthetic route, simpler separation and purification operation process of the product, higher yield and suitability for mass synthesis. The product molecule contains a plurality of quaternary ammonium salt groups, so that the problem of poor water solubility of the thiafluorene derivative can be effectively solved, and the product molecule has wide application prospect in the field of biomedicine.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of an ionic thiafluorene derivative.
Background
Thiafluorene is a tricyclic compound with fluorene as a carbon skeleton and is easy to modify, so that a thiafluorene group is introduced into various organic reactions. The thiafluorene derivative is widely applied to the fields of biomedical materials, organic photoelectric materials and the like, and is an important organic synthesis intermediate.
Of the numerous fields of application of thiafluorene derivatives, biomedical applications are certainly a very important part, most of which are in the development of bioluminescence imaging agents and their use. The thiafluorene has a planar conjugated structure, and the abundant electronic property of the thiafluorene can be used for constructing molecules with an electron donor-acceptor structure, so that the constructed molecules can form effective intramolecular charge transfer, thereby realizing red shift of emission wavelength. While longer emission wavelengths facilitate penetration through deeper body tissues, which is of great importance for in vivo imaging. However, in practical applications, the biological environment is a liquid environment filled with water, and most of the fluorene derivatives with good fluorescence properties are pure organic substances and have poor water solubility, which limits the application of the fluorene-based imaging agent. Therefore, it is of great importance to develop a thiafluorene derivative having good water solubility. The introduction of quaternary ammonium salt groups to form positive and negative ionic structures is a method which can effectively increase the water solubility of the compound.
Disclosure of Invention
The invention aims to provide a preparation method of ionic thiafluorene derivatives. The invention has the advantages of short synthesis route of the target product and simple and convenient separation and purification operation.
The preparation method of the ionic thiafluorene derivative is characterized in that the 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- (6-bromohexyl) phenyl ] amino } phenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and a certain amount of toluene 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 column chromatography to obtain a solution of a target product, and recovering the solvent to obtain the compound 1.
(2) Mixing a certain amount of compound 1, trimethylamine and a certain amount of toluene in a reaction bottle, heating to a certain temperature, stirring and reacting for a certain time at the temperature, and carrying out solid-liquid separation, washing, drying and the like on the reaction mixture to obtain a compound 2.
The preparation method of the compound 4 comprises the following steps:
(1) Mixing a certain amount of 2, 8-dibromo-dibenzothiophene, 4- { N, N-di [4- (6-chlorohexyl) phenyl ] amino } phenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and a certain amount of toluene 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 column chromatography to obtain a solution of a target product, and recovering the solvent to obtain the compound 3.
(2) A certain amount of compound 3, trimethylamine and a certain amount of toluene are mixed in a reaction bottle, heated to a certain temperature, stirred and reacted for a certain time at the temperature, and the reaction mixture is subjected to the steps of solid-liquid separation, washing, drying and the like to obtain the compound 4.
The ionic thiafluorene derivative provided by the invention can be synthesized through two-step reaction. By utilizing the characteristic that thiafluorene is easy to modify, triphenylamine groups modified by terminal haloalkoxy groups are respectively connected to two sides through suzuki coupling reaction; then synthesizing a target product through salifying reaction of the terminal halogen group and trimethylamine. The introduced quaternary ammonium salt groups can solve the problem of poor water solubility of the thiafluorene derivative, and can effectively widen the application range of the thiafluorene derivative.
The preparation method provided by the invention has the advantages of simple steps, easy operation of separation and purification processes, easy acquisition of raw materials and higher yield, and is suitable for large-scale synthesis and future large-scale industrial production.
Detailed Description
Example 1
(1) 445 mg of 2, 8-dibromofluorene, 1459 mg of pinacol 4- (N, N-bis (4- (6-bromohexyl) phenyl) amino) phenylborate, 174 mg tetrakis (triphenylphosphine) palladium, 415 mg potassium carbonate and 13 mL toluene were mixed in a reaction flask, stirred for 5 minutes to dissolve the raw materials sufficiently, and reacted under nitrogen at 100℃with stirring for 18 h. After the reaction was completed, the reaction solution was cooled to room temperature, diluted with 50 mL ethyl acetate and transferred to a separating funnel, the organic phase was washed twice with a saturated aqueous ammonium chloride solution, 60 mL each time, the organic phases were separated, the aqueous phase was combined and extracted twice with ethyl acetate, 30 mL each time, the organic phases were combined, dried with 5 g anhydrous sodium sulfate for 20 minutes, the dried organic phase was recovered by distillation under reduced pressure to give a crude product, the crude product was separated by column chromatography on 200-300 mesh silica gel, the eluent used was 1:2 petroleum ether and methylene chloride, the fourth zone was collected as a target product solution, and the solvent was recovered by distillation under reduced pressure to give 971 mg as a yellow solid, which was compound 1, in 70% yield.
(2) 694 mg Compound 1, 119 mg trimethylamine and 5 mL toluene were mixed in a reaction flask, and reacted under nitrogen with stirring at 100℃for 6h. After the reaction, cooling to room temperature, carrying out solid-liquid separation on the reaction mixture to obtain a solid crude product, washing the crude product once by using 8 mL dichloromethane and 8 mL ethyl acetate respectively, and naturally drying to obtain 739 mg yellow solid which is compound 2 with the yield of 91%.
Example 2
(1) 445 mg of 2, 8-dibromo-fluorene, 1281 mg of pinacol 4- (N, N-di (4- (6-chlorohexyl) phenyl) amino) phenylborate, 174 mg tetrakis (triphenylphosphine) palladium, 415 mg potassium carbonate and 13 mL toluene were mixed in a reaction flask, stirred for 5 minutes to fully dissolve the raw materials, and reacted under the protection of nitrogen at 100 ℃ with stirring for 18 h. After the reaction was completed, the reaction solution was cooled to room temperature, diluted with 50 mL ethyl acetate and transferred to a separating funnel, the organic phase was washed twice with a saturated aqueous ammonium chloride solution, 60 mL each time, the organic phases were separated, the aqueous phase was combined and extracted twice with ethyl acetate, 30 mL each time, the organic phases were combined, dried with 5 g anhydrous sodium sulfate for 20 minutes, the dried organic phase was recovered by distillation under reduced pressure to give a crude product, the crude product was separated by column chromatography on 200-300 mesh silica gel, the eluent used was 1:2 petroleum ether and methylene chloride, the fourth zone was collected as a target product solution, and the solvent was recovered by distillation under reduced pressure to give 871 mg as a yellow solid, which was compound 3, in a yield of 72%.
(2) Compound 605 and mg, 119 and mg trimethylamine, and 5 mL toluene were mixed in a reaction flask, and reacted under nitrogen with stirring at 100 ℃ for 6h. After the reaction, the reaction mixture is cooled to room temperature, the crude product is obtained after solid-liquid separation, the crude product is washed once by 8 mL methylene dichloride and 8 mL ethyl acetate respectively, and 636 mg yellow solid is obtained after natural drying, and the yield is 88 percent.
Claims (1)
1. The preparation method of the ionic thiafluorene derivative is characterized by comprising the following steps of: the ionic thiafluorene derivative has the following structure:
the preparation method of the compound 2 comprises the following steps:
(1) Mixing a certain amount of 2, 8-dibromo-dibenzothiophene, 4- { N, N-bis [4- (6-bromohexyloxy) phenyl ] amino } phenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and a certain amount of toluene 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 and recovering the solvent to obtain a crude product, separating by column chromatography to obtain a solution of a target product, and recovering the solvent to obtain a compound 1; wherein the mass ratio of the reactants is that 2, 8-dibromo-thiofluorene: 4- { N, N-bis [4- (6-bromohexyloxy) phenyl ] amino } phenylboronic acid pinacol ester: tetrakis (triphenylphosphine) palladium: potassium carbonate=1: 3.279:0.391:0.932; the reaction temperature is 100 ℃ and the reaction time is 18 hours;
(2) Mixing a certain amount of compound 1, trimethylamine and a certain amount of toluene in a reaction bottle, heating to a certain temperature, stirring and reacting for a certain time at the temperature, and carrying out solid-liquid separation, washing and drying on a reaction mixture to obtain a compound 2; wherein, the mass ratio of the reactants is that the compound 1: trimethylamine=1: 0.171; the reaction temperature is 100 ℃ and the reaction time is 6 hours;
the preparation method of the compound 4 comprises the following steps:
(a) Mixing a certain amount of 2, 8-dibromo-dibenzothiophene, 4- { N, N-bis [4- (6-chlorohexyloxy) phenyl ] amino } phenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and a certain amount of toluene 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 and recovering the solvent to obtain a crude product, separating by column chromatography to obtain a solution of a target product, and recovering the solvent to obtain a compound 3; wherein the mass ratio of the reactants is that 2, 8-dibromo-thiofluorene: 4- { N, N-bis [4- (6-chlorohexyloxy) phenyl ] amino } phenylboronic acid pinacol ester: tetrakis (triphenylphosphine) palladium: potassium carbonate=1: 2.879:0.391:0.932; the reaction temperature is 100 ℃ and the reaction time is 18 hours;
(b) Mixing a certain amount of compound 3, trimethylamine and a certain amount of toluene in a reaction bottle, heating to a certain temperature, stirring and reacting for a certain time at the temperature, and carrying out solid-liquid separation, washing and drying on a reaction mixture to obtain a compound 4; wherein, the mass ratio of the reactants is that the compound 3: trimethylamine=1: 0.197; the reaction temperature was 100℃and the reaction time was 6 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864042A (en) * | 2010-06-07 | 2010-10-20 | 南京邮电大学 | Water-soluble fluorine-containing grafting conjugated polymer and preparation method and application method thereof |
| CN105198697A (en) * | 2015-06-02 | 2015-12-30 | 湖北和昌新材料科技股份有限公司 | Synthetic method for 2-bromofluorene derivatives |
| CN112080156A (en) * | 2020-10-10 | 2020-12-15 | 华东理工大学 | Water-soluble dye containing pyrene and preparation method thereof |
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- 2022-05-16 CN CN202210526478.2A patent/CN114890980B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864042A (en) * | 2010-06-07 | 2010-10-20 | 南京邮电大学 | Water-soluble fluorine-containing grafting conjugated polymer and preparation method and application method thereof |
| CN105198697A (en) * | 2015-06-02 | 2015-12-30 | 湖北和昌新材料科技股份有限公司 | Synthetic method for 2-bromofluorene derivatives |
| CN112080156A (en) * | 2020-10-10 | 2020-12-15 | 华东理工大学 | Water-soluble dye containing pyrene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚集诱导发光分子的设计合成及生物医学应用研究;王晓鹏;《中国优秀硕士学位论文全文数据库基础科学辑》;A006-371 * |
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