CN103881700A - Thienyl phosphorescent iridium complex as well as preparation method and application thereof - Google Patents
Thienyl phosphorescent iridium complex as well as preparation method and application thereof Download PDFInfo
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- CN103881700A CN103881700A CN201410096083.9A CN201410096083A CN103881700A CN 103881700 A CN103881700 A CN 103881700A CN 201410096083 A CN201410096083 A CN 201410096083A CN 103881700 A CN103881700 A CN 103881700A
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Abstract
The invention discloses a thienyl phosphorescent iridium complex. A preparation method for the thienyl phosphorescent iridium complex comprises the following steps: weighing 3,8-dibromoiridium phenanthroline-2-phenylpyridine complex (or 3,8-dibromoiridium phenanthroline-2-phenylquinoline complex) and 2-thiophene pinacol borate at a molar ratio of 1:(0.1-12), and adding tetra(triphenyl phosphine) palladium with the molar percentage of 1-20%; adding sodium carbonate aqueous solution with a proper concentration of 2 M, adding an appropriate amount of DMF (dimethyl formamide), and stirring at a temperature of 25-75 DEG C for 1-75 hours; after the reaction is finished, cooling the reaction solution to a room temperature, pouring the reaction solution in water, and stirring for 1-30 minutes; extracting a water phase by use of dichloromethane, combining an organic phase, and drying the organic phase by use of anhydrous magnesium sulphate; filtering the solution, removing the filtrate, and removing a solvent in vacuum to obtain a crude product. The iridium complex obtained by the preparation method disclosed by the invention is used for generating singlet oxygen from a steady-state near-infrared light, good in stability, and expected to be applied in the aspect of near-infrared photodynamic therapy.
Description
Technical field
The invention belongs to material science, be specifically related to a class thienyl phosphorescent iridium complex 3,8-(2-thiophene)-phenanthroline iridium-2-phenylpyridine and 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline and its preparation method and application.
Background technology
The photosensitizers that tissue is absorbed by the laser radiation of specific wavelength is excited, the photosensitizers of excited state is given oxygen around transmission ofenergy again, generate active very strong singlet oxygen, singlet oxygen and adjacent biomacromolecule generation oxidizing reaction, produce cytotoxicity and cause cell impaired and even dead, thereby reach the effect of photodynamic therapy.Therefore, the generation of singlet oxygen is the basis of the treatment of photodynamic therapy.
Photodynamic therapy, as a kind of therapy with deep scientific basic, to the result for the treatment of of some cancer not second to operation, chemotherapy or radiotherapy; To some early-stage cancer, can reach healing object.It has the following advantages: (1) main destruction of cancer cells, not injuring normal cell; (2) photosensitizers nontoxicity, safety, can not suppress people's immunologic function, also can not suppress marrow and cause white corpuscle, red corpuscle and thrombopenia; (3) with the effect of complementing each other of operation, radiation and chemotherapy, can apply simultaneously; (4) can do many courses for the treatment of, can not produce resistance; Treatment time short, generally after 48-72 hour, can there is curative effect.
In addition, due near infrared light, it is less to the injury of human body, and its unique penetrance that skin is had, and near infrared light photodynamic therapy has very important significance.At present, first-generation Porphyrin-Based Sensitizer, s-generation phthalocyanines photosensitizers by some state approvals as clinical application.But these photosensitizerss exist the unstable for light, hold labile shortcoming under illumination condition, the photosensitizer, particularly near infrared light photosensitizers of a new generation need exploitation.
Summary of the invention
The object of the present invention is to provide a kind of thienyl complex of iridium with near infrared continuous laser generation singlet oxygen ability and preparation method thereof.
Thienyl phosphorescent iridium complex 3 provided by the invention, 8-(2-thiophene)-phenanthroline iridium-2-phenylpyridine and 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline, structural formula is:
Its preparation method is as follows:
(1) take 3,8-dibromo-o phenanthroline iridium-2-phenylpyridine title complex (or 3,8-dibromo-o phenanthroline iridium-2-phenylquinoline title complex) and 2-thiophene tetramethyl ethylene ketone boric acid ester, its mol ratio is 1:0.1～12, adding mole number is four (triphenyl phosphorus) palladium of 1～20%;
(2) adding concentration is the aqueous sodium carbonate of 2M;
(3) add DMF, 25 DEG C～75 DEG C of temperature, stir 1～75 hour;
(4) after reaction finishes, reaction solution is cooled to room temperature, pours in water, stir 1～30min;
(5) use dichloromethane extraction water, merge organic phase, organic phase anhydrous magnesium sulfate drying;
(6) filter above-mentioned solution, go filtrate, solvent removed in vacuo, obtains crude product.The sterling of Thin Cylindrical chromatography.
Above-mentioned gained complex of iridium can be used for singlet oxygen and produces, and therefore produces the medicine of singlet oxygen for the preparation of near infrared light.
Gained complex of iridium of the present invention produces and has advantages of good stability for singlet oxygen, and under near infrared continuous laser is irradiated, such cationic iridium complex can produce singlet oxygen, is desirably near infrared light photodynamic therapy aspect and is applied; In addition, preparation method of the present invention is simple.
Brief description of the drawings
Fig. 1 is 3,8-(2-thiophene) nucleus magnetic hydrogen spectrum of-phenanthroline iridium-2-phenylpyridine title complex characterizes.
Fig. 2 is 3,8-(2-thiophene) nucleus magnetic hydrogen spectrum of-phenanthroline iridium-2-phenylquinoline title complex characterizes.
Fig. 3 is 3,8-(2-thiophene) ultra-violet absorption spectrum of-phenanthroline iridium-2-phenylpyridine title complex.
Fig. 4 is 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline u. v spectra of complex
Fig. 5 is 3,8-(2-thiophene) fluorescence emission spectrum of-phenanthroline iridium-2-phenylpyridine title complex.
Fig. 6 is 3,8-(2-thiophene) fluorescence emission spectrum of-phenanthroline iridium-2-phenylquinoline title complex.
Fig. 7 is 3,8-(2-thiophene) singlet oxygen of-phenanthroline iridium-2-phenylpyridine title complex produces the evaluation of ability.
Fig. 8 is 3,8-(2-thiophene) singlet oxygen of-phenanthroline iridium-2-phenylquinoline title complex produces the evaluation of ability.
Embodiment
Below by embodiment, the present invention will be further described, but be not used for limiting the present invention.
Embodiment 1:
Prepare complex of iridium 3,8-(2-thiophene)-phenanthroline iridium-2-phenylpyridine title complex: take 3,8-dibromo-o phenanthroline iridium-2-phenylpyridine title complex 1mmol and 2-thiophene tetramethyl ethylene ketone boric acid ester 2.4mmol; Adding mole number is four (triphenyl phosphorus) palladium of 5%; Adding wherein concentration is the aqueous sodium carbonate 20mL of 2M; Add the DMF of 40mL, temperature 70 C, stirs 36 hours; After reaction finishes, reaction solution is cooled to room temperature, pours in water, stir 30min; With methylene dichloride, repeatedly aqueous phase extracted, merges organic phase, organic phase anhydrous magnesium sulfate drying; Filter above-mentioned solution, go filtrate, solvent removed in vacuo.Obtain crude product, Thin Cylindrical chromatography obtains sterling.
The nucleus magnetic hydrogen spectrum of this title complex characterizes as shown in Figure 1.
As shown in Figure 3 and Figure 5, this title complex has good phosphorescent emissions in methylene dichloride for its absorption spectrum and emmission spectrum, rubescent orange phosphorescence.
Embodiment 2:
Prepare complex of iridium 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline title complex: take 3,8-dibromo-o phenanthroline iridium-2-phenylpyridine title complex 1mmol and 2-thiophene tetramethyl ethylene ketone boric acid ester 2.4mmol; Adding mole number is four (triphenyl phosphorus) palladium of 5%; Adding wherein concentration is the aqueous sodium carbonate 20mL of 2M; Add the DMF of 40mL, temperature 70 C, stirs 36 hours; After reaction finishes, reaction solution is cooled to room temperature, pours in water, stir 30min; With methylene dichloride, repeatedly aqueous phase extracted, merges organic phase, organic phase anhydrous magnesium sulfate drying; Filter above-mentioned solution, go filtrate, solvent removed in vacuo.Obtain crude product, Thin Cylindrical chromatography obtains sterling.
The nucleus magnetic hydrogen spectrum of this title complex characterizes as shown in Figure 2.
As shown in Figure 4 and Figure 6, this title complex has good phosphorescent emissions in methylene dichloride for its absorption spectrum and emmission spectrum, rubescent orange phosphorescence.
Embodiment 3: singlet oxygen produces experiment
Its singlet oxygen produces tests at ethanol: in the mixing solutions of water=4:1 volume ratio, carry out, investigate the singlet oxygen and 1 that title complex produces under near infrared light shines, 3-phenylbenzene isobenzofuran (DPBF) reaction, with consuming 1,3-phenylbenzene isobenzofuran indicate singlet oxygen generation, the generation ability that changes instruction singlet oxygen in the uv-absorbing at 410nm place, result as shown in Figure 7 and Figure 8.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.Do not depart from the equivalence or the amendment that under principles of this disclosure, complete so every, all fall into the scope of protection of the invention.
Claims (4)
1. a class thienyl phosphorescent iridium complex: 3,8-(2-thiophene)-phenanthroline iridium-2-phenylpyridine and 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline, structural formula is:
2. thienyl phosphorescent iridium complex 3 according to claim 1,8-(2-thiophene) preparation method of-phenanthroline iridium-2-phenylpyridine, it is characterized in that, comprise the following steps:
(1) take 3,8-dibromo-o phenanthroline iridium-2-phenylpyridine title complex and 2-thiophene tetramethyl ethylene ketone boric acid ester, its mol ratio is 1:0.1～12, and adding mole number is four (triphenyl phosphorus) palladium of 1～20%;
(2) adding concentration is the aqueous sodium carbonate of 2M;
(3) add DMF, 25 DEG C～75 DEG C of temperature, stir 1～75 hour;
(4) after reaction finishes, reaction solution is cooled to room temperature, pours in water, stir 1～30min;
(5) use dichloromethane extraction water, merge organic phase, organic phase anhydrous magnesium sulfate drying;
(6) filter above-mentioned solution, go filtrate, solvent removed in vacuo, obtains crude product.
3. thienyl phosphorescent iridium complex 3 according to claim 1,8-(2-thiophene) preparation method of-phenanthroline iridium-2-phenylquinoline, it is characterized in that, comprise the following steps:
(1) take 3,8-dibromo-o phenanthroline iridium-2-phenylquinoline title complex and 2-thiophene tetramethyl ethylene ketone boric acid ester, its mol ratio is 1:0.1～12, and adding mole number is four (triphenyl phosphorus) palladium of 1～20%;
(2) adding concentration is the aqueous sodium carbonate of 2M;
(3) add DMF, 25 DEG C～75 DEG C of temperature, stir 1～75 hour;
(4) after reaction finishes, reaction solution is cooled to room temperature, pours in water, stir 1～30min;
(5) use dichloromethane extraction water, merge organic phase, organic phase anhydrous magnesium sulfate drying;
(6) filter above-mentioned solution, go filtrate, solvent removed in vacuo, obtains crude product.
4. thienyl phosphorescent iridium complex 3 claimed in claim 1,8-(2-thiophene)-phenanthroline iridium-2-phenylpyridine and 3,8-(2-thiophene)-phenanthroline iridium-2-phenylquinoline produces the medicine of singlet oxygen for the preparation of near infrared light.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188149A (en) * | 2016-07-05 | 2016-12-07 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN110025794A (en) * | 2019-05-06 | 2019-07-19 | 上海师范大学 | Purposes of the metal iridium complex in the long Phosphorescence imaging reagent of preparation medicine or drug |
| CN112661795A (en) * | 2020-12-24 | 2021-04-16 | 玉林师范学院 | Human ovarian cancer cell inhibitor, preparation method and application thereof |
| CN112679549A (en) * | 2020-12-24 | 2021-04-20 | 玉林师范学院 | 8-hydroxyquinoline derivative iridium (III) complex and preparation method and application thereof |
| CN113278036A (en) * | 2021-05-31 | 2021-08-20 | 赣南师范大学 | Phenothiazine-containing iridium complex and preparation method and application thereof |
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| US20050176624A1 (en) * | 2003-08-07 | 2005-08-11 | Thompson Mark E. | Organometallic complexes as singlet oxygen sensitizers |
| WO2006011090A1 (en) * | 2004-07-21 | 2006-02-02 | Koninklijke Philips Electronics N.V. | Light-emitting electrochemical cell |
| CN103130837A (en) * | 2013-03-13 | 2013-06-05 | 上海师范大学 | Water-soluble cationic phosphorous iridium complex as well as preparation method and application thereof |
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Patent Citations (3)
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| US20050176624A1 (en) * | 2003-08-07 | 2005-08-11 | Thompson Mark E. | Organometallic complexes as singlet oxygen sensitizers |
| WO2006011090A1 (en) * | 2004-07-21 | 2006-02-02 | Koninklijke Philips Electronics N.V. | Light-emitting electrochemical cell |
| CN103130837A (en) * | 2013-03-13 | 2013-06-05 | 上海师范大学 | Water-soluble cationic phosphorous iridium complex as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| SHIN-YA TAKIZAWA等: "Photooxidation of 1,5-dihydroxynaphthalene with iridium complexes as singlet oxygen sensitizers", 《PHOTOCHEM. PHOTOBIOL. SCI.》, vol. 10, 31 December 2011 (2011-12-31), pages 895 - 903 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188149A (en) * | 2016-07-05 | 2016-12-07 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN106188149B (en) * | 2016-07-05 | 2019-03-22 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN110025794A (en) * | 2019-05-06 | 2019-07-19 | 上海师范大学 | Purposes of the metal iridium complex in the long Phosphorescence imaging reagent of preparation medicine or drug |
| CN110025794B (en) * | 2019-05-06 | 2021-12-03 | 上海师范大学 | Application of metal iridium complex in preparation of medical long-phosphorescence imaging reagent or medicine |
| CN112661795A (en) * | 2020-12-24 | 2021-04-16 | 玉林师范学院 | Human ovarian cancer cell inhibitor, preparation method and application thereof |
| CN112679549A (en) * | 2020-12-24 | 2021-04-20 | 玉林师范学院 | 8-hydroxyquinoline derivative iridium (III) complex and preparation method and application thereof |
| CN112679549B (en) * | 2020-12-24 | 2022-09-20 | 玉林师范学院 | 8-hydroxyquinoline derivative iridium (III) complex and preparation method and application thereof |
| CN113278036A (en) * | 2021-05-31 | 2021-08-20 | 赣南师范大学 | Phenothiazine-containing iridium complex and preparation method and application thereof |
| CN113278036B (en) * | 2021-05-31 | 2022-04-12 | 赣南师范大学 | Phenothiazine-containing iridium complex and preparation method and application thereof |
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