CN115594684A - Organic photocatalyst based on isoazatruxene skeleton and preparation method and application thereof - Google Patents

Organic photocatalyst based on isoazatruxene skeleton and preparation method and application thereof Download PDF

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CN115594684A
CN115594684A CN202211377216.0A CN202211377216A CN115594684A CN 115594684 A CN115594684 A CN 115594684A CN 202211377216 A CN202211377216 A CN 202211377216A CN 115594684 A CN115594684 A CN 115594684A
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张霄
安伯杭
高蓉
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Fujian Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Abstract

The invention discloses an organic photocatalyst based on an isoazatruxene skeleton, and a preparation method and application thereof, and belongs to the technical field of photocatalysis. The chemical general formula of the organic photocatalyst is as follows:
Figure 100004_DEST_PATH_IMAGE002
wherein R is 1 Is H, acyl, ester group, substituted or unsubstituted C 1 ‑C 30 Alkyl radical, C 3 ‑C 30 Alkenyl radical, C 3 ‑C 30 Alkynyl, C 1 ‑C 30 Alkoxy radical, C 3 ‑C 12 Cycloalkyl radical, C 1 ‑C 10 Heterocycloalkyl radical, C 3 ‑C 12 Cycloalkenyl radical, C 1 ‑C 10 Heterocycloalkenyl, C 6 ‑C 30 Aryl radical, C 1 ‑C 30 A heteroaryl group; r 2 Is H, acetyl, hydroxyl, methoxyl, formyl, carboxyl, cyano, ester group, substituted or unsubstituted aryl or halogen; r is 3 Is H, formyl, carboxyl, ester group or halogen. The organic photocatalyst shows excellent photocatalytic efficiency in the reductive coupling and intramolecular dearomatization reaction of visible light catalysis, and has wide practical application value.

Description

Organic photocatalyst based on isoazatruxene skeleton and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to an organic photocatalyst based on an isoazatruxene skeleton, and a preparation method and application thereof.
Background
Visible light catalyzed reactions have been one of the hot research topics in the last decade of organic chemistry. Since most organics do not directly absorb visible light, the reaction usually requires the addition of an additional photocatalyst. Photocatalysts based on noble metal (Ru, ir, etc.) complexes have been used most conventionally, but have problems of high price, significant toxicity, metal residue, etc. In order to solve the problems, chemists develop various pure organic photocatalysts which have the characteristics of simple synthesis, various performances, adjustable structure, relatively low cost and the like and are fully complementary with the traditional noble metal complex photocatalyst.
The skeleton of isoazatriindene was discovered by Bergman et al as early as 1979, and in the middle of the 90's last century, mount et al also prepared a variety of isoazatriindene derivatives by electrochemical trimerization of indole in acetonitrile, but the chemistry was left to stand for a long time after that. So far, only a few documents preliminarily study the photophysical properties of the isoazatrimer indene and the derivatives thereof, and the application examples of the isoazatrimer indene and the derivatives thereof in organic synthesis are never reported.
Disclosure of Invention
Aiming at the defects, the invention provides an organic photocatalyst based on an isoazatruxene skeleton, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic photocatalyst based on an isoazatruxene skeleton has a structural general formula as follows:
Figure DEST_PATH_IMAGE001
，
wherein R is 1 Is H, substituted or unsubstituted C 1 -C 30 Alkyl, substituted or unsubstituted C 3 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Alkynyl, substituted or unsubstituted C 1 -C 30 Alkoxy, substituted or unsubstituted C 3 -C 12 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Heterocycloalkyl, substituted or unsubstituted C 3 -C 12 Cycloalkenyl, substituted or unsubstituted C 1 -C 10 Heterocycloalkenyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 1 -C 30 Heteroaryl, acyl, ester groups; r is 2 Is H, acetyl, hydroxyl, methoxyl, formyl, carboxyl, cyano, ester group, halogen, substituted or unsubstituted aryl; r 3 Is H, formyl, carboxyl, ester group or halogen.
Further, the specific structural formula of the organic photocatalyst is as follows:
Figure 697720DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
。
the preparation of the organic catalyst based on the isoazatruxene skeleton takes indole or 5-bromoindole as a reaction raw material; specifically, when indole is used as a reaction raw material, the reaction process is as follows:
Figure 411598DEST_PATH_IMAGE004
，
which comprises the following steps:
1) Adding reaction raw materials of indole 1 and chloroacetic acid into dichloromethane to completely dissolve indole, then dropwise adding nitrosobenzene dissolved in dichloromethane, continuously stirring in the dropwise adding process, and then filtering and separating to obtain a compound 2;
2) Dissolving the obtained compound 2 in acetonitrile, slowly dropwise adding an acetonitrile solution of phenylhydrazine into the system, and filtering and separating after the reaction is finished to obtain a compound 3;
3) Carrying out N-terminal substitution reaction on the obtained compound 3 and different electrophilic reagents, and separating and purifying to obtain a compound 4;
4) Carrying out N-end para-position aromatic electrophilic substitution reaction on the obtained compound 4 to obtain a compound 5;
when 6-bromoindole is used as a reaction raw material, the reaction process is as follows:
Figure DEST_PATH_IMAGE005
，
which comprises the following steps:
1) Adding reaction raw materials 5-bromoindole 6 and chloroacetic acid into dichloromethane to completely dissolve indole, then dropwise adding nitrosobenzene dissolved in dichloromethane, continuously stirring in the dropwise adding process, and then filtering and separating to obtain a compound 7;
2) Dissolving the obtained compound 7 in acetonitrile, slowly dropwise adding an acetonitrile solution of phenylhydrazine into the system, and filtering and separating after the reaction is finished to obtain a compound 8;
3) Carrying out N-terminal substitution reaction on the obtained compound 8 and different electrophilic reagents, and separating and purifying to obtain a compound 9;
4) Converting the obtained compound 9 through metal organic reaction to obtain a compound 10;
5) Continuing the reaction of the obtained compound 10 with R 2 The aromatic electrophilic substitution at the ortho position gives the compound 11.
The obtained organic photocatalyst based on the isoindoline skeleton can be used for visible light-catalyzed organic reactions, including but not limited to carbonyl reduction coupling and intra-indole molecular dearomatization.
The invention has the beneficial effects that:
the organic photocatalyst is simple in preparation process, and has excellent photocatalytic efficiency in organic reactions such as carbonyl reduction coupling of visible light catalysis and dearomatization in indole molecules, so that the organic photocatalyst has practical application value.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
An organic photocatalyst based on an isoaza truxene skeleton, which comprises the following synthetic process and a specific preparation method:
Figure 548925DEST_PATH_IMAGE006
；
(1) Synthesis of compound 3 a:
the reactants indole 1 (133.88 mmol) and chloroacetic acid (133.88 mmol) were weighed into a 100mL round bottom flask, then 30 mL dichloromethane was added and the indole was completely dissolved. Nitrosobenzene (133.88 mmol) was weighed, dissolved in 30 mL dichloromethane and placed in a constant pressure dropping funnel. Dropwise adding a dichloromethane solution of nitrosobenzene into a round-bottom flask filled with indole at a controlled dropping speed of 5s, and continuously stirring during the dropping process. After reaction at 10 h, solid 2 was isolated by filtration. Weighing solid 2 (7.24 mmol) and placing the solid in a 100mL round-bottom flask, then weighing reactants phenylhydrazine (7.86 mmol) and 25 mL acetonitrile, mixing the reactants, and then dropwise adding the solution of phenylhydrazine in acetonitrile into the round-bottom flask containing the solid 2, wherein the dropwise adding speed is controlled to be 5s per drop, and stirring is carried out continuously during the dropwise adding process. After 2 h is reacted, the mixture is filtered and separated, and a filter cake is washed by acetonitrile and dried to obtain a gray solid compound 3a (product)Rate 45%). 1 H NMR (400 MHz, DMSO) δ 11.87 (s, 1H), 11.48 (s, 1H), 11.38 (s, 1 H), 8.91-8.75 (m, 3H), 7.82 (d, J = 8.0 Hz, 3H), 7.51-7.36 (m, 6H)。
(2) Synthesis of compound 4 a:
N 2 isoazatriindene (2.90 mmol), potassium hydroxide (14.50 mmol) and 50mL THF were charged to a 100mL three-necked flask under ambient conditions, stirred at room temperature for 30min, bromoethane (29.00 mmol) was added dropwise to the three-necked flask and placed under reflux at 65 ℃ for 24 h. After the reaction, 30 mL dichloromethane was added for dilution, and the pH was adjusted to neutral with 10% hydrochloric acid solution, and the organic phase was washed with saturated brine (10 mL × 3), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, 10 v/v) as an eluent to obtain 4a (yield 80%) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.95 (d, J = 8.0 Hz, 1H), 8.90 (d, J = 8.0 Hz, 1H), 8.41 (d, J = 8.1 Hz, 1H), 7.60-7.51 (m, 3H), 7.40-7.36 (m, 6H), 4.98 (q, J = 8.0 Hz, 2H), 4.72 (q, J = 7.2 Hz, 2H), 4.60 (q, J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H), 1.37 (t, J = 7.2 Hz, 3H), 1.35 (t, J = 7.2 Hz, 3H)。
(3) Synthesis of compound 4 b:
N 2 isoazaterpolyindene (2.90 mmol), potassium hydroxide (14.50 mmol) and 50mL THF were charged to a 100mL three-necked flask under ambient conditions, stirred at room temperature for 30min, bromobutane (29.00 mmol) was added dropwise to the three-necked flask and placed under reflux at 65 ℃ for 24 h. After the reaction was completed, 30 mL dichloromethane was added for dilution, and the pH was adjusted to neutral with 10% hydrochloric acid solution, and then the organic phase was washed with saturated saline (10 mL × 3), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, v/v) as an eluent, to obtain 4b as a yellow solid (yield 90%). 1 H NMR (400 MHz, CDCl 3 ) : δ 8.97 (d, J = 8.0 Hz, 1H), 8.92 (d, J = 8.0 Hz, 1H), 8.43 (d, J = 8.1 Hz, 1H), 7.56-7.48 (m, 3H), 7.38-7.35 (m, 6H), 4.98 (t, J = 8.0 Hz, 2H), 4.72 (t, J = 7.2 Hz, 2H), 4.60 (t, J= 7.2 Hz, 2H), 2.10 (m, 2H), 1.42 (m, 2H), 1.34-1.14 (m, 4H), 0.94 (t, J = 7.2 Hz, 3H), 0.92-0.79 (m, 4H), 0.60 - 0.55 (m, 6H)。
(4) Synthesis of compound 4 c:
N 2 isoazatriindene (2.90 mmol), potassium hydroxide (14.50 mmol) and 50mL THF were charged to a 100mL three-necked flask under ambient conditions, stirred at room temperature for 30min, allyl bromide (29.00 mmol) was added dropwise to the three-necked flask and placed under reflux at 65 ℃ for 24 h. After the reaction was completed, 30 mL dichloromethane was added for dilution, the pH was adjusted to neutral with 10% hydrochloric acid solution, the organic phase was washed with saturated saline (10 mL × 3), dried over anhydrous sodium sulfate, vacuum-dried, and finally purified by column chromatography using ethyl acetate and petroleum ether (DCM: PE = 1:10, v/v) as eluent to obtain 4c as an orange solid (yield 55%). 1 H NMR (400 MHz, CDCl 3 ) δ = 8.98 (d, J = 7.9 Hz, 1H), 8.91 (d, J = 7.8 Hz, 1H), 8.47 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.62 (d, J =7.9 Hz, 2H), 7.55 - 7.39 (m, 5H), 7.35 (t, J = 7.7 Hz, 1H), 6.48 (m, 1H), 6.15 - 5.97 (m, 2H), 5.58 (m, 2H), 5.43 (m, 6H), 5.08 (br, 2H), 4.97 (br, 2H)。
(5) Synthesis of compound 4 d:
N 2 isoazatruxene (0.58 mmol), potassium hydroxide (8.7 mmol) and 50mL THF were added to a 100mL three-necked flask under ambient conditions, stirred at room temperature for 30min, tert-butyl bromoacetate (17.40 mmol) was added dropwise to the three-necked flask and placed at 65 ℃ for reflux reaction 24 h. After the reaction, 30 mL dichloromethane was added for dilution, and Ph was adjusted to neutral with 10% hydrochloric acid solution, and the organic phase was washed with saturated brine (10 mL × 3), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, 3, v/v) as an eluent to obtain 4d as a yellow solid (yield 21%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.96 – 8.92 (m, 1H), 8.87 (d, J = 7.8 Hz, 1H), 8.24 (d, J = 8.1Hz, 1H), 7.55 – 7.43 (m, 8H), 7.37 (m, 1H), 5.42 (s, 2H), 5.15 (s, 2H), 5.04 (s, 2H), 1.49 (s, 9H), 1.38 (s, 9H), 1.26 (s, 9H)。
(6) Synthesis of Compound 4e
Isoazatruxene (6.75 mmol), di-tert-butyl dicarbonate (33.73 mmol), DMAP (6.75 mmol) and 30 mL acetonitrile were added to a 100mL eggplant-shaped bottle at room temperature, stirred overnight and filtered to give 4e as a white solid (53% yield). 1 H NMR (400 MHz, CDCl 3 ) : δ 8.98 (d, J = 8.0 Hz, 1H), 8.93 (d, J = 8.0 Hz, 1H), 8.42 (d, J = 8.1 Hz, 1H), 7.55 – 7.47 (m, 3H), 7.38 -7.35 (m, 6H), 1.72 (s, 9H), 1.57 (m, 18H)。
Example 2
An organic photocatalyst based on an isoazatruxene skeleton, which comprises the following synthetic process and a specific preparation method:
Figure DEST_PATH_IMAGE007
(1) Synthesis of compound 4 f:
N 2 the compound 3a (2.90 mmol) obtained in example 1 and potassium carbonate K were reacted under an atmosphere 2 CO 3 (11.60 mmol) and quinoline (20 mL) were added to a 50mL three-necked flask and stirred at room temperature for 30 min. Additional reactants, iodobenzene (17.40 mmol) and cuprous iodide (11.60 mmol) were added. The three-neck flask is placed in a 180 ℃ oil bath to react with 72 h, and the reaction result is detected by TLC. After the reaction was completed, it was filtered, and the precipitate was washed with ethyl acetate. The pH of the system is then adjusted to a strongly acidic pH with a 10% hydrochloric acid solution<1). Finally, the aqueous phase was extracted with ethyl acetate (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, and after concentration by a rotary evaporator, column chromatography was performed using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, 10, v/v) as an eluent to obtain 4f (yield 59%) as a pale yellow solid. 1 H NMR (400 MHz, DMSO) δ 9.03 (m, 2H), 7.80-7.68 (m, 5H), 7.52 (m, 4H), 7.44 (m, 2H), 7.25-7.11 (m, 8H), 6.71 (m, 5H), 6.08 (d, J = 8.3 Hz, 1H)。
(2) Synthesis of Compound 4 g:
N 2 the compound 3a (2.90 mmol) obtained in example 1 and potassium carbonate K were reacted under an atmosphere 2 CO 3 (11.60 mmol) and quinoline (20 mL) were added to a 50mL three-necked flask and stirred at room temperature for 30 min. Additional reactants were added p-fluoroiodobenzene (17.40 mmol) and cuprous iodide (11.60 mmol). The three-neck flask is placed in a 180 ℃ oil bath to react with 72 h, and the reaction result is detected by TLC. After the reaction was completed, it was filtered, and the precipitate was washed with ethyl acetate. The pH of the system is then adjusted to a strongly acidic pH (pH) with a 10% hydrochloric acid solution<1). Finally, the aqueous phase was extracted with ethyl acetate (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, and after concentration by a rotary evaporator, column chromatography was performed using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, 10, v/v) as an eluent to obtain 4g of a pale yellow solid (yield 59%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.05 (m, 2H), 7.71- 7.66 (m, 2H), 7.53 – 7.33 (m, 8H), 7.24 -7.16 (m, 2H), 6.93- 6.86 (m, 5H), 6.76 (m, 4H), 6.23 (d, J = 8.2 Hz, 1H)。
(3) Synthesis of compound 4 h:
N 2 the compound 3a (2.90 mmol) obtained in example 1 and potassium carbonate K were mixed under an atmosphere 2 CO 3 (11.60 mmol) and quinoline (20 mL) were added to a 50mL three-necked flask and stirred at room temperature for 30 min. Additional reactants were added p-trifluoromethyliodobenzene (17.40 mmol) and cuprous iodide (11.60 mmol). The three-neck flask is placed in a 180 ℃ oil bath to react with 72 h, and the reaction result is detected by TLC. After the reaction was completed, it was filtered, and the precipitate was washed with ethyl acetate. The pH of the system is then adjusted to a strongly acidic pH (pH) with a 10% hydrochloric acid solution<1). Finally the aqueous phase was extracted with ethyl acetate (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, concentrated by rotary evaporator and column chromatographed using dichloromethane and petroleum ether mixed solvent (DCM: PE = 1, 10, v/v) as eluent to give a light yellow solid 4h (yield 59%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.11- 9.03 (m, 2H), 7.94 (d, J = 8.3 Hz, 2H), 7.84 (d, J = 8.2 Hz, 2H), 7.64 (m, 1H), 7.60 – 7.51 (m, 3H), 7.47 (m, 2H), 7.42 (d, J = 8.3 Hz, 4H), 7.27 (d, J = 8.1 Hz, 1H), 7.23 -7.18 (m, 1H), 6.91 – 6.81 (m, 5H), 6.13 (d, J = 8.4 Hz, 1H)。
(4) Synthesis of compound 4 i:
N 2 compound 3a (2.9 mmol) obtained in example 1, potassium carbonate (13 mmol) and DMSO (8 mL) were charged into a three-necked flask under an atmosphere, stirred at room temperature for 20 min, p-fluoronitrobenzene (10.1 mmol) was added, heated at 110 ℃ under reflux, and the reaction results were checked by TLC. After the reaction, water was added to the reaction system, and the mixture was filtered to obtain an orange solid. Under ice-bath conditions, the orange solid (4.2 mmol), ammonium chloride (0.17 mmol), water (10 mL), methanol (12 mL), and tetrahydrofuran (24 mL) were added to a 250 mL eggplant-shaped bottle, and zinc powder (0.28 mmol) was added in small amounts several times during stirring, and the reaction results were checked by TLC. After the reaction was complete, the solid was filtered through celite, the solution was collected by washing with dichloromethane (5 mL × 3), the layers were separated, the organic phase was collected and spin dried to give a brown solid. The brown solid (2.75 mmol), trifluoroacetic anhydride (14 mmol), triethylamine (14 mmol), DMAP (30 mg) and tetrahydrofuran (20 mL) were added to a 250 mL eggplant-shaped bottle under ice-bath conditions, stirred overnight and the reaction results were checked by TLC. After the reaction, the reaction system was diluted with water (10 mL) and dichloromethane (10 mL), washed with saturated brine (10 mL × 3), separated, the organic phases combined, concentrated, and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate (PE: EA = 8, 1, v/v) as an eluent to obtain a light green solid 4i (yield 57%). 1 H NMR (400 MHz, DMSO-d 6 ) δ 11.68 (s, 1H), 11.40 (br, 2H), 9.06-9.00 (m, 2H), 8.05 (d, J = 8.9 Hz, 2H), 7.83 (d, J = 8.8 Hz, 2H), 7.61 – 7.43 (m, 10H), 7.31 – 7.17 (m, 2H), 6.82 (m, 5H), 6.27 (d, J = 8.0 Hz, 1H)。
Example 3
An organic photocatalyst based on an isoazatruxene skeleton, which comprises the following synthetic process and a specific preparation method:
Figure 740872DEST_PATH_IMAGE008
(1) Synthesis of compound 4 k:
acetyl chloride (2.1 mmol) and aluminum trichloride (2.1 mmol) were added to a 100mL eggplant-shaped bottle under ice bath conditions, and the compound 4f (0.6 mmol) obtained in example 2 was dissolved in 5mL dichloromethane, and slowly added to the above system, and the reaction result was checked by TLC. After the reaction was completed, the reaction was quenched by adding ice water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give 4k as a yellow solid (yield 90%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.82 (s, 1H), 9.78 (s, 1H), 8.09 (m, 2H), 7.86 (m, 1H), 7.76 – 7.64 (m, 5H), 7.58 (d, J = 8.7 Hz, 1H), 7.46 (d, J = 8.7 Hz, 1H), 7.28 – 7.11 (m, 8H), 6.81 – 6.72 (m, 4H), 2.90 (s, 3H), 2.87 (s, 3H), 2.28 (s, 3H)。
(2) Synthesis of compound 4 j:
under ice-bath conditions, liquid bromine (4.81 mmol) was added dropwise to sodium hydroxide solution (16.72 mmol,10 mL) and stirred for 30min to give sodium hypobromite solution. Compound 4k (0.44 mmol) was dissolved in 1,4-dioxane (10 mL), and the above sodium hypobromite solution was added thereto, heated under reflux at 90 ℃ and the reaction result was checked by TLC. After the reaction is finished, reducing the pressure to remove most of 1,4-dioxane, dripping hydroxylamine hydrochloride into the reaction system until no bubbles are generated, and then adding hydrochloric acid to adjust the pH value<1, separating out a precipitate. Filtration, washing with water and drying gave 4j as a yellow solid (68% yield). 1 H NMR (400 MHz, DMSO-d 6 ) δ = 12.77 (br, 3H), 9.74 (m, 2H), 8.17 (m, 1H), 8.10 (m, 1H), 7.85-7.78 (m, 4H), 7.73 (t, J = 7.6 Hz, 2H), 7.70 -7.60 (m, 2H), 7.52 (d, J = 8.7 Hz, 1H), 7.30 – 7.21 (m, 7H), 6.78 (m, 4H)。
Example 4
An organic photocatalyst based on an isoazatruxene skeleton, which comprises the following synthetic process and a specific preparation method:
Figure DEST_PATH_IMAGE009
1) Synthesis of compound 5 a:
DMF (14.79 mmol) was added dropwise to the POCl in ice bath 3 (12.62 mmol) in a flask and stirred at this temperature for 10 min. Then, the temperature was raised to 35 ℃ and the compound 4b (0.87 mmol) obtained in example 1 was added to react at 90 ℃ to give 48 h, and the reaction result was checked by TLC. After the reaction, ice water was added to quench, the pH was adjusted to neutral with sodium hydroxide solution, the aqueous phase was extracted with dichloromethane (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate and concentrated under reduced pressure, and column chromatography was performed using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1:3,v/v) as an eluent to obtain 5a (yield 52%) as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ 10.31 (s, 1 H), 10.29 (s, 1 H),10.21 (s, 1 H), 9.49 (s, 1 H), 9.43 (s, 1 H), 8.96 (s, 1 H), 8.20 – 8.07 (m, 3 H), 7.86 – 7.76 (m, 3H), 5.11 – 5.02 (t, J = 7.2 Hz , 2H), 4.81 (t, J = 7.2 Hz, 2H), 4.71 (t, J = 7.2 Hz, 2H), 2.22 (m, 2H), 1.61 (m, 2H), 1.36 (m, 4H), 1.02 (t, J = 4 Hz, 3H), 0.82 (m, 4H), 0.60 (m, 6H)。
2) Synthesis of compound 5 b:
under ice-bath condition, acetyl chloride (2.1 mmol) and AlCl are added 3 (2.1 mmol) and methylene chloride (10 mL) were added to a 100mL eggplant-shaped bottle. The compound 4b (0.6 mmol) obtained in example 1 was dissolved in 10 mL dichloromethane and added dropwise to an eggplant-shaped bottle, and the reaction result was checked by TLC. After the reaction is finished, adding ice water to quench, transferring the liquid in the eggplant-shaped bottle into a separating funnel, and adding saturated Na 2 CO 3 The solution was washed, separated, the aqueous phase was extracted with dichloromethane (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give 5b as a yellow solid (yield 99.0%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.78 (s, 1H), 9.74 (s, 1H), 9.17 (s, 1H), 8.30-8.15 (m, 3H), 7.76 -7.69 (m, 3H), 5.08 (t, J = 7.2 Hz, 2H), 4.78 (t, J = 7.2 Hz, 2H), 4.68 (t, J = 7.2 Hz, 2H), 2.99 (s, 3H), 2.95 (s, 3H), 2.80 (s, 3H), 2.17 (m, 2H), 1.38 -1.25 (m, 6H), 0.97 (t, J = 7.2 Hz, 3H), 0.77 (m, 4H), 0.58 (m, 6H)。
3) Synthesis of compound 5 c: :
benzoyl chloride (4.68 mmol), dichloromethane (20 mL) and AlCl were mixed under ice-bath conditions 3 (4.68 mmol) was added to a 250 mL eggplant-shaped bottle. The compound 4b (0.78 mmol) obtained in example 1 was dissolved in 20 mL dichloromethane, and dropped into an eggplant-shaped bottle, and the reaction result was checked by TLC. After the reaction is finished, ice water is added for quenching, the liquid in the eggplant-shaped bottle is transferred into a separating funnel, and saturated Na is added 2 CO 3 The solution was washed, separated, the aqueous phase was extracted with dichloromethane (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate (PE: EA = 5, 1, v/v) as an eluent, to obtain 5c as a yellow solid (yield 72%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.22 (m, 2H), 8.98 (s, 1H), 8.10 – 8.03 (m, 2H), 8.00 – 7.93 (m, 3H), 7.86 – 7.72 (m, 6H), 7.68 – 7.55 (m, 4H), 7.46 – 7.35 (m, 6H), 4.96 – 4.65 (m, 6H), 1.39 – 1.21 (m, 6H), 0.88 – 0.78 (m, 9H), 0.64 – 0.59 (m, 6H)。
4) Synthesis of compound 5 d: :
liquid bromine (7.26 mmol) was added dropwise to sodium hydroxide solution (25.08 mmol,10 mL) under ice bath and stirred for 30min to obtain sodium hypobromite solution. Compound 5b (0.66 mmol) was dissolved in 1,4-dioxane (10 mL), and the above sodium hypobromite solution was added thereto, heated under reflux at 90 ℃ and the reaction result was checked by TLC. After the reaction is finished, hydroxylamine hydrochloride is dripped into the reaction system until no bubbles are generated, and hydrochloric acid is added to adjust the pH value<1, precipitate was precipitated, filtered, washed with water, and dried to obtain yellow solid 5d (yield 59%). 1 H NMR (400 MHz, DMSO-d 6 ) δ = 12.19 (m, 3H), 9.66 – 9.48 (m, 2H), 9.10 (s, 1H), 8.27 – 7.86 (m, 6H), 5.14 – 4.73 (m, 6H), 2.05 (m, 2H), 1.38 – 1.21 (m, 6H), 0.94 – 0.85 (m, 3H), 0.62 (m, 4H), 0.52 – 0.42 (m, 6H)。
Example 5
An organic photocatalyst based on an isoazatruxene skeleton, which comprises the following synthetic process and a specific preparation method:
Figure 414298DEST_PATH_IMAGE010
1) Synthesis of compound 8 a:
the reactants 5-bromoindole 6 (78.00 mmol) and chloroacetic acid (78.00 mmol) were weighed into a 100mL round bottom flask, followed by 30 mL dichloromethane to dissolve the indole completely. Nitrosobenzene (78.00 mmol) was weighed, dissolved in 30 mL in dichloromethane and placed in a constant pressure dropping funnel. Dropwise adding a dichloromethane solution of nitrosobenzene into a round-bottom flask filled with indole at a controlled dropping speed of 5s, and continuously stirring during the dropping process. After reaction at 12 h, it was isolated by filtration to give solid 7. Solid 7 (3.79 mmol) is weighed and placed in a 100mL round-bottom flask, then reactants phenylhydrazine (4.32 mmol) and 25 mL acetonitrile are weighed and mixed, then phenylhydrazine solution in acetonitrile is dropwise added into the round-bottom flask containing the solid 7, the dropping speed is controlled to be 5s per drop, and stirring is carried out continuously during the dropping process. After reaction 2 h the reaction was isolated by filtration and washed with acetonitrile and dried to yield compound 8a as a white solid (40% yield). 1 H NMR (400 MHz, DMSO) δ 12.21 (s, 1 H), 11.73 (s, 1 H), 11.65 (s, 1 H), 9.04 (s, 1 H), 8.70 (s, 1 H), 8.63 (s, 1 H), 7.83 (t, J = 8.9 Hz, 2 H), 7.75 (d, J = 8.5 Hz, 1 H), 7.61 (m, 3 H)。
2) Synthesis of compound 9 a:
N 2 compound 8a (2.30 mmol), potassium hydroxide (11.50 mmol) and 50mL tetrahydrofuran were added to a 100mL three-necked flask under ambient conditions, stirred at room temperature for 30min, bromobutane (23.00 mmol) was added dropwise to the three-necked flask and placed under reflux at 65 ℃ for 24 h. After the reaction is finished, adding 30 mL dichloromethane for dilution, adjusting the pH to be neutral by using 10% hydrochloric acid solution, washing an organic phase by using saturated saline (10 mL X3), drying the organic phase by using anhydrous sodium sulfate, concentrating the organic phase under reduced pressure, and finally mixing ethyl acetate and petroleum ether with a mixed solventColumn chromatography purification was performed (DCM: PE = 1. 1 H NMR (400 MHz, CDCl 3 ) δ 8.92 (s, 1H), 8.85 (s, 1H), 8.48 (s, 1H), 7.65-7.48 (m, 6H), 4.82 (t, J = 8 Hz, 2H), 4.66 (t, J = 8 Hz, 2H), 4.55 (t, J = 8 Hz, 2H), 2.20-2.09 (m, 2H), 1.52 (m, 2H), 1.31-1.23 (m, 4H), 1.01 (t, J = 7.4 Hz, 3H), 0.75 (m, 4H), 0.56 (m, 6H)。
3) Synthesis of compound 9 b:
compound 8a (2.15 mmol), di-tert-butyl dicarbonate (10.77 mmol), DMAP (2.15 mmol) and 30 mL acetonitrile were charged into a 100mL eggplant-shaped bottle at room temperature and stirred overnight. After the reaction was complete, white solid 9b was obtained by filtration (yield 60%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.78 (m, 2H), 8.38 (d, J = 8.9 Hz, 1H), 8.29 (d, J = 8.8 Hz, 1H), 8.20 (d, J = 8.8 Hz, 1H), 7.97 (d, J = 1.9 Hz, 1H), 7.75 – 7.56 (m, 3H), 1.71 (s, 9H), 1.56 (m, 18H)。
4) Synthesis of compound 10 a:
N 2 compound 9a (1.64 mmol) and copper iodide CuI (4.90 mmol) were added to a 50mL three-necked flask under ambient atmosphere, followed by addition of 10 mL of N, N-Dimethylformamide (DMF), stirring at room temperature for 30min, addition of a mixed solution of sodium methoxide (6.00 g) and methanol (20 mL), reaction at 120 ℃ for 48 h, and detection of the reaction result by TLC. After the reaction was complete, water was added and filtered, the filtrate was washed with dichloromethane and the aqueous phase was extracted with dichloromethane (10 mL × 3). The organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1) as an eluent, to obtain an orange solid 10a (yield 80%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (s, 2H), 7.91 (s, 1H), 7.51-7.49 (m, 3H), 7.17 – 7.08 (m, 3H), 5.15 – 4.70 (m, 6H), 4.05 (m, 6H), 3.90 (m, 3H), 2.00 – 1.92 (m, 2H), 1.29 – 1.21 (m, 6H), 0.84 (m, 7H), 0.53 (m, 6H)。
5) Synthesis of compound 10 b:
N 2 will combine together under the atmosphereThe product 10a (0.30 mmol) and dichloromethane (10 mL) were charged into a 50mL two-neck flask, cooled in an ice bath, and then boron tribromide (9.90 mmol) was slowly added, followed by warming to room temperature, stirring the reaction 24h at room temperature, and checking the reaction result by TLC. After the reaction was completed, water was added to quench, the aqueous phase was extracted with dichloromethane (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1, 3, v/v) as an eluent, to obtain a green solid 10b (yield 50%). 1 H NMR (400 MHz, CDCl 3 ) δ 10.66 (s, 1H), 10.59 (s, 1H), 10.36 (s, 1H), 8.39 (s, 1H), 8.30 (s, 1H), 7.96 (s, 1H), 7.55 – 7.50 (m, 3H), 7.20 – 7.10 (m, 3H), 4.93 (t, J = 6.8 Hz, 2H), 4.84 (t, J = 6.8 Hz, 2H), 4.68 (t, J = 6.8 Hz, 2H), 1.71 (m, 2H), 1.24 (m, 6H), 0.84-0.57 (m, 7H), 0.50-0.45 (m, 6H)。
6) Synthesis of compound 10 c:
compound 8a (1.00 mmol), cuprous cyanide (4.5 mmol) and 20 mL of DMF were added to a 100mL eggplant-shaped flask, and the reaction was checked by TLC under reflux at 148 ℃. After the reaction is finished, adding concentrated ammonia water for quenching, filtering, washing filter residues by EA, collecting filtrate, extracting water phase by ethyl acetate (5 mL multiplied by 3), combining organic phases, drying by anhydrous sodium sulfate, concentrating under reduced pressure, and performing column chromatography purification by using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1:8,v/v) as an eluent to obtain solid 10c (34% yield). 1 H NMR (400 MHz, DMSO-d 6 ) δ = 12.57 (d, J = 3.6 Hz, 1H), 12.10 (s, 1H), 11.79 (s, 1H), 9.31 (s, 1H), 9.09 (s, 1H), 7.95 (s, 1H), 7.61 – 7.53 (m, 3H), 7.36 -7.27 (m, 3H)。
7) Synthesis of compound 11 a:
DMF (16.56 mmol) was added dropwise to the POCl charge in ice bath 3 (8.28 mmol) in a flask and stirred at this temperature for 10 min. The temperature was then raised to 35 ℃ and the reaction mixture 10a (1.66 mmol) was added and reacted at 90 ℃ for 48 h and the reaction was checked by TLC. After the reaction, adding ice water to quench, adjusting pH to neutral with sodium hydroxide solution, extracting water phase with dichloromethane (10 mL X3), and collectingThe organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1, 8,v/v) as an eluent, to obtain 11a (yield 36%) as a red solid. 1 H NMR (400 MHz, CDCl 3 ) δ 10.69 (s, 1H), 10.67 (s, 2H), 8.36 (s, 1H), 8.27 (s, 1H), 8.21-8.16 (m, 3H), 7.89 (s, 1H), 4.95 (t, J = 8 Hz, 2H), 4.71 (t, J = 8 Hz, 2H), 4.59 (t, J = 8 Hz, 2H), 1.97-1.91 (m, 2H), 1.38-1.25 (m, 6H), 0.83-0.75 (m, 7H), 0.57 (m, 6H)。
8) Synthesis of compound 11 b:
N 2 the reaction product 11a (0.30 mmol) and dichloromethane (10 mL) were added to a 50mL two-neck flask under an atmosphere, cooled in an ice bath, and then boron tribromide (9.90 mmol) was slowly added, followed by warming to room temperature, stirring the reaction product 24h at room temperature, and the reaction results were checked by TLC. After the reaction, water quenching was performed, the aqueous phase was extracted with dichloromethane (10 mL × 3), the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography using a mixed solvent of ethyl acetate and petroleum ether (EA: PE = 1:3,v/v) as an eluent, to obtain a red solid 11b (yield 38%). 1 H NMR (400 MHz, DMSO) δ 10.73 (s, 1H), 10.70 (s, 1H), 10.59 (s, 1H), 10.45 (s, 1H), 10.43 (s, 1H), 10.36 (s, 1H), 8.34 (s, 1H), 8.23 (m, 4H), 7.96 (s, 1H), 4.97 (t, J = 6.8 Hz, 2H), 4.85 (t, J = 6.8 Hz, 2H), 4.65 (t, J = 6.8 Hz, 2H), 1.71 (m, 2H), 1.24 (m, 5H), 0.96 (m, 2H), 0.83 – 0.59 (m, 6H), 0.50 – 0.45 (m, 6H)。
Application example 1: carbonyl reduction coupling reaction catalyzed by visible light
Figure DEST_PATH_IMAGE011
The different compounds prepared in the example are used as photocatalyst (5 mol%), p-chlorobenzaldehyde (0.2 mmol), DIPEA (0.4 mmol) and acetonitrile (2 mL) are respectively added into a sealed tube of 5mL, after 3 times of refrigeration cycle degassing, stirring is carried out for 24 hours under the irradiation of a 465 nm blue LED lamp, the reaction is monitored through thin layer chromatography, dibromomethane (0.2 mmol) is added into the reaction mixture after the reaction is finished, and the nuclear magnetic yield is obtained through calibration calculation of coarse nuclear magnetic, and the result is shown in table 1.
TABLE 1
Figure 800543DEST_PATH_IMAGE012
As can be seen from Table 1, the reaction proceeded smoothly by using the obtained different compounds as the photocatalyst, and the yield was between 30% and 89%.
Application example 2: visible light catalyzed dearomatization reaction in indole molecule
Figure DEST_PATH_IMAGE013
The different compounds prepared in the example as photocatalyst (5 mol%) were added to a sealed tube of 5mL together with indole derivative (0.1 mmol), DIPEA (0.2 mmol), HEH (0.15 mmol) and acetonitrile (2 mL), degassed by 3 times of freezing cycle, stirred for 24h under the irradiation of 465 nm blue LED lamp, the reaction was monitored by thin layer chromatography, dibromomethane (0.2 mmol) was added thereto after the reaction was completed, and the nuclear magnetic yield was calculated by crude nuclear magnetic calibration, the results are shown in Table 2.
TABLE 2
Figure 661051DEST_PATH_IMAGE014
As can be seen from Table 2, the reaction proceeded smoothly by using the obtained different compounds as organic photocatalysts, and the yield was between 30% and 89%.
The foregoing is illustrative and explanatory of the present invention, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made without inventive faculty.

Claims (5)

1. An organic photocatalyst based on an isoazatruxene skeleton is characterized in that the structural general formula of the organic photocatalyst is as follows:
Figure DEST_PATH_IMAGE002
，
wherein R is 1 Is H, substituted or unsubstituted C 1 -C 30 Alkyl, substituted or unsubstituted C 3 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Alkynyl, substituted or unsubstituted C 1 -C 30 Alkoxy, substituted or unsubstituted C 3 -C 12 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Heterocycloalkyl, substituted or unsubstituted C 3 -C 12 Cycloalkenyl, substituted or unsubstituted C 1 -C 10 Heterocycloalkenyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 1 -C 30 Heteroaryl, acyl, or ester groups; r is 2 Is H, acetyl, hydroxyl, methoxyl, formyl, carboxyl, cyano, ester group, halogen, substituted or unsubstituted aryl; r 3 Is H, formyl, carboxyl, ester group or halogen.
2. The organic photocatalyst based on an isoindoline skeleton according to claim 1, wherein the specific structural formula of the organic photocatalyst is as follows:
Figure DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE006
。
3. the preparation method of the organic catalyst based on the isoindole skeleton as claimed in claim 1, wherein indole is used as a reaction raw material, the indole and chloroacetic acid are added into dichloromethane to completely dissolve the indole, nitrosobenzene dissolved in the dichloromethane is added dropwise, stirring is continuously carried out during the dropwise addition, the obtained compound is dissolved into acetonitrile after filtration and separation, an acetonitrile solution of phenylhydrazine is slowly added dropwise, and after filtration and separation, the obtained reaction intermediate is subjected to N-terminal substitution reaction and N-terminal para-aromatic electrophilic substitution reaction sequentially to obtain a corresponding product;
or 5-bromoindole is taken as a reaction raw material, the reaction raw material and chloroacetic acid are added into dichloromethane to completely dissolve indole, then nitrosobenzene dissolved in dichloromethane is dropwise added, stirring is continuously carried out during the dropwise adding process, the obtained compound is dissolved into acetonitrile after filtering and separation, acetonitrile solution of phenylhydrazine is slowly dropwise added, and after filtering and separation, the obtained reaction intermediate is subjected to N-terminal substitution reaction, metal organic reaction and ortho-position aromatic electrophilic substitution reaction in sequence to obtain a corresponding product.
4. Use of an organic photocatalyst based on an isoindoline skeleton according to claim 1 for visible-light-catalyzed organic reactions.
5. Use according to claim 4, characterized in that the visible photocatalytic organic reaction comprises in particular carbonyl reduction coupling and intramolecular dearomatization of the indole.
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JP2003272865A (en) * 2002-03-19 2003-09-26 Mitsubishi Rayon Co Ltd Organic electroluminescent element
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CN110350109A (en) * 2018-04-02 2019-10-18 三星Sdi株式会社 Composition, organic photoelectric device and display device
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