CN110845495B - Synthesis method of triplet photosensitizer - Google Patents
Synthesis method of triplet photosensitizer Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention relates to a triplet photosensitizer without any heavy atom and a synthesis method thereof, and aims to solve the problems that the conventional triplet photosensitizer is single in structure and expensive in price. The chemical structural formula of the triplet photosensitizer is as follows:
or
According to the invention, two triplet photosensitizers N-1 and N-2 without heavy atoms are synthesized in a conjugated and non-conjugated flexible connection mode, and the absorption spectra of the two photosensitizers are obviously red-shifted. Upon application of the above two photosensitizers to the reaction of photooxidation of DPBF, a significant decrease in the absorption of DPBF at 414nm was observed, indicating that both were effective in generating triplet excited states.
Description
Technical Field
The invention relates to a triplet photosensitizer without any heavy atom and a synthesis method thereof, which take an Excited State Intramolecular Proton Transfer (ESIPT) process as a theoretical basis and naphthalimide and 2- (2-Hydroxyphenyl) Benzothiazole (HBT) as basic structural units.
Background
The triplet photosensitizer is gradually combined with the fields of medicine, hydrogen energy development, dye-sensitized solar cells and the like, and is widely applied to the fields of hydrogen production by photolysis of water, photocatalytic organic reaction, photodynamic therapy, triplet-triplet annihilation up-conversion and the like. Triplet photosensitizers are those in which the molecule undergoes intersystem crossing (S) after photoexcitation1→Tn(n.gtoreq.1)) reaches the triplet excited state of the molecule (having higher energy), and then transfers its triplet energy to a molecule having no intersystem crossing (ISC) ability or low efficiency of intersystem crossing, or a compound participating in a redox reaction process as a catalyst.
Intersystem crossing is an essential pathway for triplet generation. The intersystem crossing can be effectively generated by utilizing the heavy atom effect, and at present, the research is more about transition metal triplet photosensitizers containing ruthenium, platinum and the like and heavy atoms, such as: bromine, iodine, sulfur, and the like. In addition, spin transfer units are introduced into the molecule, such as: c60Has 100% intersystem crossing ability, and when combined with an absorbent group with strong light capacity, can obtain a triplet photosensitizer without heavy atoms through an energy transfer mechanism. In addition, triplet excited states can also be obtained by n-pi transition and exciton coupling. However, the molecular structure with n-pi transition is modified to generate a large unpredictability of triplet state, and thus, there is still a great difficulty in designing such photosensitizers. The research on triplet states generated by exciton coupling is still in the initial stage.
The triplet photosensitizer can be obtained in the above mode, but the triplet photosensitizer containing heavy atoms is expensive and not environment-friendly; spin transfer units provide a viable route to the design of triplet photosensitizers that are free of heavy atoms, but it is difficult to find new compounds that can effectively act as spin transfer units, thus restricting further derivatization of such photosensitizers. In the absence of heavy atoms, the triplet state is largely unpredictable and difficult to derivatize further. Thus, whether new triplet photosensitizers can be obtained by other photophysical processes has become a hot issue in this field.
Disclosure of Invention
The invention aims to further solve the problems that the existing triplet photosensitizer has a single structure and the triplet photosensitizer containing heavy atoms is expensive, so that a cis-keto structure triplet excited state can be effectively generated in an excited intramolecular proton transfer (ESIPT) photophysical process, and a novel triplet photosensitizer without heavy atoms and a synthesis method thereof are synthesized.
The chemical structural formula of the triplet photosensitizer is as follows:
wherein R represents
The synthesis method of the triplet photosensitizer is realized according to the following steps:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. to a mixed solution of triethylamine and THF of bromo HBT (Compound 1), a catalytic amount of Pd (PPh) was added under argon protection3)4And CuI, then injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and carrying out column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and carrying out column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3);
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride (compound 4) and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification to obtain bromonaphthalimide;
thirdly, synthesizing a photosensitizer N-1:
d. under the protection of argon, bromonaphthalimide (compound 5) and ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) are dissolved in a mixed solution of triethylamine and THF, and a catalytic amount of Pd (PPh) is added3)4And cuprous iodide, heating the reaction solution to 65-80 ℃, reacting for 6-12 h, cooling, decompressing to remove the solvent, and purifying the crude product by column chromatography to obtain the triplet photosensitizer (N-1).
The synthesis method of the triplet photosensitizer is realized according to the following steps:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. to a mixed solution of triethylamine and THF of bromo HBT (Compound 1), a catalytic amount of Pd (PPh) was added under argon protection3)4And CuI, then injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and carrying out column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and carrying out column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3);
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride (compound 4) and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification to obtain bromonaphthalimide (a light yellow solid);
synthesis of azidoamino-substituted naphthalimides (Compound 6):
d. under the protection of argon, injecting excessive 3-azidopropylamine into ethylene glycol monomethyl ether solution of bromonaphthalimide, heating the reaction solution to 80-110 ℃, reacting for 6-10 h, removing the solvent under reduced pressure, and carrying out column chromatography on the crude product to obtain azido amino-substituted naphthalimide (compound 6);
fourthly, synthesis of photosensitizer N-2:
e. under the protection of argon, dissolving azidoamino-substituted naphthalimide (compound 6) and ethynyl-substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) in a mixed solvent of chloroform, ethanol and water, then adding a catalytic amount of sodium ascorbate and copper sulfate pentahydrate, reacting for 20-26 h at room temperature, extracting with dichloromethane, drying, removing the solvent under reduced pressure, and performing column chromatography separation on a crude product to obtain the triplet photosensitizer (N-2).
The synthetic routes of the triplet photosensitizers N-1 and N-2 of the present invention are shown below:
the synthesis method of the triplet photosensitizers N-1 and N-2 comprises the steps of taking cheap 5-bromosalicylaldehyde as a raw material, carrying out condensation reaction with o-aminothiophenol to obtain bromo HBT, introducing trimethylsilylethynyl in the first step, then introducing alkynyl in salicylaldehyde by deprotection, obtaining bromo naphthalene diimide by substitution reaction in the second step, and carrying out Sonogashira coupling reaction with the ethynyl HBT in the first step to obtain a target product N-1. In order to compare the differences of the non-conjugated connection modes, the flexible chain connected photosensitizer N-2 is synthesized by utilizing click reaction of azido-substituted naphthalimide and HBT-alkyne in the step one.
The photosensitizer N-1 and N-2 are respectively tested by ultraviolet spectrum, emission spectrum and the like, and further the fact that the N-1 generates Excited State Intramolecular Proton Transfer (ESIPT) is verified.
The triplet photosensitizer with Naphthalimide (NDI) and HBT as basic structural units, which is prepared by the invention, has the following beneficial effects:
1. according to the invention, two triplet photosensitizers N-1 and N-2 without heavy atoms are synthesized in a conjugated and non-conjugated flexible connection mode, the absorption spectra of the two photosensitizers are obviously red-shifted, and the light absorption capability of visible light is obviously enhanced.
2. The light emission spectrum of the photosensitizer N-1 has a dual emission phenomenon, namely: meanwhile, an enol type emission peak at 538nm of short wavelength and a ketone type structure emission peak at 682nm of long wavelength are observed, and Stokes shift reaches 144nm, which indicates that ESIPT occurs.
3. When the photosensitizer N-1 and the photosensitizer N-2 are applied to the reaction of photooxidation DPBF, the absorption of DPBF at 414nm is observed to be obviously reduced, which indicates that the photosensitizer N-1 and the photosensitizer N-2 both effectively generate triplet excited states, and the photosensitizer N-2 has potential application value in the fields of photodynamic therapy and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of photosensitizer N-1 obtained in example one;
FIG. 2 is a high resolution mass spectrum of photosensitizer N-1 obtained in the first example;
FIG. 3 is the NMR spectrum of photosensitizer N-2 obtained in example two;
FIG. 4 is a high resolution mass spectrum of photosensitizer N-2 obtained in example two;
FIG. 5 is a graph showing UV-VIS absorption spectra of photosensitizers N-1 and N-2 obtained in example, wherein 1 represents photosensitizer N-1 and 2 represents photosensitizer N-2;
FIG. 6 is a graph of the emission spectrum of photosensitizer N-1 obtained in example one, wherein □ represents toluene(PhCH3) And o represents Dichloromethane (DCM), Δ represents Tetrahydrofuran (THF), -represents ethyl acetate (EtOAC), -represents acetonitrile (CH)3CN), a represents methanol (MeOH);
FIG. 7 is a graph of the emission spectrum of photosensitizer N-2 obtained in example two, wherein-represents toluene (PhCH)3) And o represents Dichloromethane (DCM), Δ represents Tetrahydrofuran (THF), Δ represents ethyl acetate (EtOAC), and it represents acetonitrile (CH)3CN),. o denotes methanol (MeOH);
FIG. 8 is a graph showing changes in ultraviolet spectrum during the photooxidation of DPBF by the photosensitizer N-1 obtained in the first embodiment, wherein the irradiation time is 0s, 30s, 60s, 90s, 120s and 180s in sequence along the direction of an arrow;
FIG. 9 is a diagram showing the UV spectrum change of the photosensitizer N-2 obtained in example two during the DPBF photooxidation, wherein the irradiation time is 0s, 30s, 60s, 90s, 120s and 180s in sequence along the arrow direction;
FIG. 10 is a graph showing the kinetics of the photooxidation DPBF of the photosensitizers N-1 and N-2 obtained in example, wherein □ represents the photosensitizer N-1,
represents photosensitizer N-2.
Detailed Description
The first embodiment is as follows: the chemical structural formula of the triplet photosensitizer of the embodiment is as follows:
wherein
The second embodiment is as follows: the synthesis method of the triplet photosensitizer of the embodiment is implemented by the following steps:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. under the protection of argon, to the mixed solution of triethylamine and THF of bromo HBT (compound 1)To the solution, a catalytic amount of Pd (PPh) was added3)4And CuI, then injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and carrying out column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and carrying out column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3);
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride (compound 4) and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification to obtain bromonaphthalimide;
thirdly, synthesizing a photosensitizer N-1:
d. under the protection of argon, bromonaphthalimide (compound 5) and ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) are dissolved in a mixed solution of triethylamine and THF, and a catalytic amount of Pd (PPh) is added3)4And cuprous iodide, heating the reaction solution to 65-80 ℃, reacting for 6-12 h, cooling, decompressing to remove the solvent, and purifying the crude product by column chromatography to obtain the triplet photosensitizer (N-1).
The third concrete implementation mode: the difference between the embodiment and the second embodiment is that the volume ratio of triethylamine to THF in the mixed solution in the step a and the step d is 3-1: 1.
The fourth concrete implementation mode: the second or third difference between this embodiment and the first or second embodiment is that the reaction solution in step c is heated to 120 ℃ and reacted for 2 hours.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that the molar ratio of the 2-bromonaphthalene-1.4, 5.8-tetracarboxylic dianhydride to the 2-ethylhexylamine in the step c is 1:3 to 5.
The sixth specific implementation mode: the difference between this embodiment and one of the second to fifth embodiments is that the solid substance obtained by suction filtration in step c is washed with deionized water and ethanol in sequence.
The seventh embodiment: the synthesis method of the triplet photosensitizer of the embodiment is implemented by the following steps:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. to a mixed solution of triethylamine and THF of bromo HBT (Compound 1), a catalytic amount of Pd (PPh) was added under argon protection3)4And CuI, then injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and carrying out column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and carrying out column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3);
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1.4, 5.8-tetracarboxylic dianhydride (compound 4) and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, carrying out suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and purifying by column chromatography to obtain bromonaphthalimide (a light yellow solid);
synthesis of azidoamino-substituted naphthalimides (Compound 6):
d. under the protection of argon, injecting excessive 3-azidopropylamine into ethylene glycol monomethyl ether solution of bromonaphthalimide, heating the reaction solution to 80-110 ℃, reacting for 6-10 h, removing the solvent under reduced pressure, and carrying out column chromatography on the crude product to obtain azido amino-substituted naphthalimide (compound 6);
fourthly, synthesis of photosensitizer N-2:
e. under the protection of argon, dissolving azidoamino-substituted naphthalimide (compound 6) and ethynyl-substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) in a mixed solvent of chloroform, ethanol and water, then adding a catalytic amount of sodium ascorbate and copper sulfate pentahydrate, reacting for 20-26 h at room temperature, extracting with dichloromethane, drying, removing the solvent under reduced pressure, and performing column chromatography separation on a crude product to obtain the triplet photosensitizer (N-2).
The specific implementation mode is eight: the second or seventh embodiment is different from the second or seventh embodiment in that the molar ratio of the brominated HBT to the trimethylsilylacetylene in the step a is 1 (2-3).
The specific implementation method nine: the difference between the present embodiment and the seventh embodiment is that the molar ratio of 3-azidopropylamine to bromonaphthalimide in step d is 5-10: 1.
The first embodiment is as follows: the synthesis of the triplet photosensitizers of this example was carried out as follows:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. to a mixed solution of bromo HBT (compound 1) (30.4mg,0.1mmol) in triethylamine and THF at a volume ratio of triethylamine to THF of 1:3 under argon protection, a catalytic amount of Pd (PPh) was added3)4(11.6mg,0.01mmol) and CuI (1.9mg,0.01mmol), injecting 0.1mL of trimethylsilylacetylene using a syringe, heating the reaction solution to 70 ℃, reacting for 8h, removing the solvent under reduced pressure, and separating by column chromatography (developing solvent is dichloromethane: petroleum ether ═ 1:1) to obtain 23.2 mg of compound 2, the yield is 71.8%;
b. dissolving a compound 2(64.6mg,0.2mmol) in anhydrous THF, then dropwise adding 1mL of 1mol/L tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15min, adding distilled water to quench the reaction, washing the reaction solution with water, extracting with dichloromethane, drying, removing the solvent under reduced pressure, and separating the crude product by column chromatography (a developing agent is dichloromethane: petroleum ether ═ 1:1) to obtain 35.6mg of ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) with the yield of 70.9%;
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1.4, 5.8-tetracarboxylic dianhydride (200mg,0.58mmol) and 2-ethylhexylamine (300 mg,2.32mmol) in 15mL of acetic acid, heating the reaction solution to 120 ℃, reacting for 2 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, sequentially leaching with water and ethanol, dissolving the leached solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification by using dichloromethane as a developing agent to obtain 190mg of bromonaphthoyl diimine (light yellow solid), wherein the yield is as follows: 57.7 percent;
thirdly, synthesizing a photosensitizer N-1:
d. bromonaphthalimide (60.0mg,0.1mmol) and ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (25.0mg,0.1mmol) are dissolved in a mixed solution of triethylamine and THF under the protection of argon gas, the volume ratio of the triethylamine to the THF is 3:1, and a catalytic amount of Pd (PPh) is added3)4(11.6mg,0.01mmol) and cuprous iodide (1.9mg,0.01mmol), heating the reaction solution to 70 ℃, reacting for 10h, cooling, removing the solvent under reduced pressure, and purifying the crude product by column chromatography to obtain the red solid triplet photosensitizer (N-1) with the yield of 54.1%.
Hydrogen nuclear magnetic resonance data of triplet photosensitizer obtained in this example1H NMR(400MHz,CDCl3) δ 8.84(s, 1H),8.78(d,1H, J ═ 7.6Hz),8.71(d,1H, J ═ 7.6Hz),8.11(d,1H, J ═ 1.7Hz),8.02(d,1H, J ═ 8.1Hz),7.97(d,1H, J ═ 8.1Hz),7.79(d,1H, J ═ 1.8Hz),7.55(t,1H, J ═ 7.2Hz),7.47(t,1H, J ═ 7.4Hz),7.18(d,1H, J ═ 7.5Hz),4.25-4.10(m,4H),2.06-1.93(m,2H),1.45-1.32(m,16H), 1.00-0.90 (ms, 12H, theoretical m: z/m: [ C ]45H44N3O5S-H]-738.2996, respectively; found 738.2955.
Example two: the synthesis of the triplet photosensitizers of this example was carried out as follows:
preparation of ethynyl substituted 2- (2-Hydroxyphenyl) Benzothiazole (HBT) (compound 3):
a. to a mixed solution of bromo HBT (compound 1) (30.4mg,0.1mmol) in triethylamine and THF at a volume ratio of triethylamine to THF of 1:3 under argon protection, a catalytic amount of Pd (PPh) was added3)4(11.6mg,0.01mmol) and CuI (1.9mg,0.01mmol), injecting 0.1mL of trimethylsilylacetylene using a syringe, heating the reaction solution to 70 ℃, reacting for 8h, removing the solvent under reduced pressure, and separating by column chromatography (developing solvent is dichloromethane: petroleum ether ═ 1:1) to obtain 23.2 mg of compound 2, the yield is 71.8%;
b. dissolving a compound 2(64.6mg,0.2mmol) in anhydrous THF, then dropwise adding 1mL of tetrahydrofuran solution of 1mol/L tetrabutylammonium fluoride, reacting at room temperature for 15min, adding distilled water to quench the reaction, washing the reaction solution with water, extracting with dichloromethane, drying, decompressing and removing the solvent, separating and developing a crude product by column chromatography by using dichloromethane, petroleum ether is 1:1, and obtaining 35.6mg of ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole (compound 3) with the yield of 70.9%;
synthesis of bis, bromonaphthalimide (Compound 5):
c. under the protection of argon, dissolving 2-bromonaphthalene-1.4, 5.8-tetracarboxylic dianhydride (200mg,0.58mmol) and 2-ethylhexylamine (300 mg,2.32mmol) in 15mL of acetic acid, heating the reaction solution to 120 ℃, reacting for 2 hours, cooling to room temperature, pouring the reaction solution into cold water, carrying out suction filtration on the obtained solid phase, respectively eluting with water and ethanol, dissolving the solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and carrying out column chromatography purification by taking dichloromethane as a developing agent to obtain 190mg of bromonaphthalimide (light yellow solid), wherein the yield is as follows: 57.7 percent;
synthesis of azidoamino-substituted naphthalimides (Compound 6):
d. under the protection of argon, injecting excessive 3-azidopropylamine (0.1mL,1.0mmol) into a glycol monomethyl ether solution of bromonaphthalimide (56 mg,0.1mmol), heating the reaction solution to 80 ℃, reacting for 8h, removing the solvent under reduced pressure, and performing column chromatography (dichloromethane is used as a developing agent) on the crude product to obtain 52mg of red solid azidoamino-substituted naphthalimide (compound 6), wherein the yield is as follows: 88.4 percent;
fourthly, synthesis of photosensitizer N-2:
e. azidoamino-substituted naphthalimide (50.0mg,0.085mmol) and ethynyl-substituted 2- (2-hydroxyphenyl) benzothiazole (30.0mg,0.12mmol) were dissolved in a mixed solvent of chloroform, ethanol, water (volume ratio 6:1:1) under argon protection, then catalytic amount of sodium ascorbate (7.2mg) and copper sulfate pentahydrate (4.5mg) were added, reacted for 24h at room temperature, extracted with dichloromethane, dried, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography to obtain red solid triplet photosensitizer (N-2), yield: 67.3 percent.
Hydrogen nuclear magnetic resonance data of triplet photosensitizer obtained in this example1H NMR(400MHz,CDCl3): δ 12.71(s, 1H),10.22(t,1H, J ═ 7.8Hz),8.64(d,1H, J ═ 7.8Hz),8.35(d,1H, J ═ 7.8Hz),8.20(d,1H, J ═ 1.9Hz),8.17(s,1H),8.02(d,1H, J ═ 8.1Hz),7.94(d,1H, J ═ 7.9Hz),7.84(s,1H),7.74(d,1H, J ═ 2.0Hz),7.53(t,1H, J ═ 7.2Hz),7.44(t,1H, J ═ 7.2Hz),7.15(d,1H, J ═ 7.5), 4.66(t,2H, 6.6, J ═ 4.6, 3.86 (H, 3-3.86, 3.3H-3.86 Hz), 3.3-38H, 3-3.86 (m-3.86 Hz), 7.3H, 3-3.86 (m: m/z theoretical value [ C.48H53N7O5S-H]-839.3823, respectively; found 839.3814.
The application example is as follows: the photosensitizer N-1 and the photosensitizer N-2 are respectively prepared into a constant volume with the concentration of 1 x 10-3M mother liquor, adding a proper amount of mother liquor into a cuvette filled with 3mL of toluene, ensuring that the absorbance value at the excitation wavelength is between 0.2 and 0.3, and adding a quantitative DPBF dichloromethane solution (the addition amount is determined by that the absorbance value at 414nm is close to 1); and testing the absorption spectrum of the non-illuminated mixed liquid, then obtaining monochromatic light with a fixed wavelength through a monochromator, and illuminating the liquid for 30s every time to test the ultraviolet absorption spectrum. The photosensitizer sensitizes oxygen to generate singlet oxygen as the irradiation time increases, and the highly reactive singlet oxygen photo-oxidizes DPBF such that its absorbance at 414nm gradually decreases as the irradiation time increases (see FIGS. 8 and 9).
From FIG. 6, it can be seen that photosensitizer N-1 has a double emission peak in a weakly polar organic solvent such as toluene, indicating that ESIPT occurs.
From the kinetic diagram of FIG. 10, it can be seen that both photosensitizer N-1 and photosensitizer N-2 have photo-oxidation effects, where the photo-oxidation effect of N-2 is slightly better than that of N-1.
Claims (8)
1. A method for synthesizing a triplet photosensitizer, characterized in that the method is carried out according to the following steps:
preparation of ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole:
a. adding a catalytic amount of Pd (PPh) into a mixed solution of triethylamine and THF of brominated HBT under the protection of argon gas3)4And CuI, injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and performing column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole;
synthesis of bis (bromonaphthalimide):
c. under the protection of argon, dissolving 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification to obtain bromonaphthalimide;
thirdly, synthesizing a photosensitizer N-1:
d. bromonaphthalimide and ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole are dissolved in a mixed solution of triethylamine and THF under the protection of argon gas, and a catalytic amount of Pd (PPh) is added3)4And cuprous iodide, heating the reaction solution to 65-80 ℃, reacting for 6-12 h, cooling and reducingRemoving the solvent under pressure, and purifying the crude product by column chromatography to obtain the triplet state photosensitizer.
2. The method for synthesizing the triplet photosensitizer according to claim 1, wherein the volume ratio of triethylamine to THF in the mixed solution in step a and step d is 3-1: 1.
3. The method of claim 1, wherein the reaction solution in step c is heated to 120 ℃ and reacted for 2 hours.
4. The method for synthesizing a triplet photosensitizer according to claim 1, wherein the molar ratio of 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride and 2-ethylhexylamine in step c is 1: 3-5.
5. The method according to claim 1, wherein the solid phase obtained by suction filtration in step c is washed with deionized water and ethanol in sequence.
6. A method for synthesizing a triplet photosensitizer, characterized in that the method is carried out according to the following steps:
preparation of ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole:
a. adding a catalytic amount of Pd (PPh) into a mixed solution of triethylamine and THF of brominated HBT under the protection of argon gas3)4And CuI, injecting excessive trimethylsilylacetylene, heating the reaction solution to 65-85 ℃, reacting for 8-10 h, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a compound 2;
b. dissolving the compound 2 in anhydrous THF, dropwise adding a tetrahydrofuran solution of tetrabutylammonium fluoride, reacting at room temperature for 15-30 min, adding distilled water to quench and react, washing the reaction solution with water, drying, removing the solvent under reduced pressure, and performing column chromatography separation on a crude product to obtain ethynyl substituted 2- (2-hydroxyphenyl) benzothiazole;
synthesis of bis (bromonaphthalimide):
c. under the protection of argon, dissolving 2-bromonaphthalene-1, 4,5, 8-tetracarboxylic dianhydride and excessive 2-ethylhexylamine in acetic acid, heating the reaction solution to 110-130 ℃, reacting for 2-2.5 hours, cooling to room temperature, pouring the reaction solution into cold water, performing suction filtration to obtain a solid phase, dissolving the washed solid phase with dichloromethane, drying, removing the solvent under reduced pressure to obtain a crude product, and performing column chromatography purification to obtain bromonaphthalimide;
and thirdly, synthesizing azido amino substituted naphthalimide:
d. under the protection of argon, injecting excessive 3-azidopropylamine into ethylene glycol monomethyl ether solution of bromonaphthalimide, heating the reaction solution to 80-110 ℃, reacting for 6-10 h, removing the solvent under reduced pressure, and carrying out column chromatography on the crude product to obtain azido amino-substituted naphthalimide;
fourthly, synthesis of photosensitizer N-2:
e. under the protection of argon, dissolving azidoamino-substituted naphthalimide and ethynyl-substituted 2- (2-hydroxyphenyl) benzothiazole in a mixed solvent of chloroform, ethanol and water, then adding a catalytic amount of sodium ascorbate and copper sulfate pentahydrate, reacting for 20-26 h at room temperature, extracting by dichloromethane, drying, removing the solvent under reduced pressure, and performing column chromatography separation on a crude product to obtain the triplet photosensitizer.
7. The method for synthesizing the triplet photosensitizer according to claim 1 or 6, wherein the molar ratio of the brominated HBT to the trimethylsilylacetylene in the step a is 1 (2-3).
8. The method for synthesizing the triplet photosensitizer according to claim 6, wherein the molar ratio of 3-azidopropylamine to bromonaphthalimide in step d is 5-10: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980322A (en) * | 2014-05-23 | 2014-08-13 | 中国石油大学(华东) | Preparation method of up-conversion luminescent material based on triplet-triplet annihilation |
| CN107556333A (en) * | 2017-09-19 | 2018-01-09 | 广东工业大学 | A kind of triplet sensitising agent and preparation method thereof and a kind of upper converting system |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107556333A (en) * | 2017-09-19 | 2018-01-09 | 广东工业大学 | A kind of triplet sensitising agent and preparation method thereof and a kind of upper converting system |
Non-Patent Citations (4)
| Title |
|---|
| Accessing the Long-Lived Triplet Excited States in Bodipy-Conjugated 2-(2-Hydroxyphenyl) Benzothiazole/Benzoxazoles and Applications as Organic Triplet Photosensitizers for Photooxidations;Pei Yang 等;《J. Org. Chem.》;20120628;第77卷(第14期);第6166-6178页 * |
| Broadband Visible Light-Harvesting Naphthalenediimide (NDI) Triad:Study of the Intra-/Intermolecular Energy/Electron Transfer and the Triplet Excited State;Shuang Wu 等;《J. Phys. Chem.》;20150428;第20卷;第4787-4799页，尤其是文章摘要以及第4788页流程图1 * |
| Intramolecular Energy and Electron Transfers in Bodipy Naphthalenediimide Triads;Mushraf Hussain 等;《J. Phys. Chem. A》;20180701;第122卷(第29期);第6081-6088页 * |
| New excited state intramolecular proton transfer (ESIPT) dyes based on naphthalimide and observation of long-lived triplet excited statesw;Jie Ma 等;《Chem. Commun.》;20120810;第48卷;第9720-9722页，尤其是文章摘要以及第9720页流程图1中化合物N-1 * |
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