CN112979649A - Pyridoimidazole derivative and preparation method and application thereof - Google Patents

Pyridoimidazole derivative and preparation method and application thereof Download PDF

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CN112979649A
CN112979649A CN202110282805.XA CN202110282805A CN112979649A CN 112979649 A CN112979649 A CN 112979649A CN 202110282805 A CN202110282805 A CN 202110282805A CN 112979649 A CN112979649 A CN 112979649A
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prepared
pyridoimidazole
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霍延平
温宇东
周路
邱志鹏
向洪平
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Guangdong University of Technology
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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 discloses a pyridino-imidazole derivative and a preparation method and application thereof, wherein the pyridino-imidazole derivative is used as an electron acceptor system, two pyridino-imidazole derivatives with D-pi-A structures are synthesized by means of the electron donating property of phenanthroimidazole/diphenylamine, and can be used as photoinitiators, the two photoinitiators have longer conjugated chain length, the photon absorption cross section of the two photoinitiators is increased, the polymerization reaction can be initiated at the wavelength of 365nm, the polymerization efficiency is higher, and the pyridino-imidazole derivative can be widely applied to the field of ultraviolet light curing.

Description

Pyridoimidazole derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of ultraviolet curing, and particularly relates to a pyridoimidazole derivative and a preparation method and application thereof.
Background
The ultraviolet light curing technology is an environment-friendly green technology in the fields of coatings, printing ink, adhesives and the like, and compared with the traditional solvent-containing system, the ultraviolet light curing technology has the outstanding characteristics of no solvent discharge, high efficiency, energy conservation and the like. The main body of the material generally consists of oligomer, monomer and photoinitiator, and the material is completely cured under the action of enough ultraviolet light, and as the UV light curing material is more and more widely applied, the problem of the migration of the photoinitiator occurs. The problem of mobility of the photoinitiator can be effectively reduced by introducing macromolecular groups, so that the initiator has small residue and no migration problem, and compounds such as OXE-2 are a class of UV photoinitiators which are researched more in recent years. In addition, chinese patent CN106349213A discloses a self-hydrogen-supplying photoinitiator and a preparation method thereof, wherein the photoinitiator introduces photosensitive groups, which can improve the photosensitivity of the initiator, enhance the light absorption capability of the initiator, cause the absorption spectrum of the initiator to generate an obvious red shift, and improve the thermal stability of the initiator. The design and synthesis of novel photoinitiators containing photosensitive groups become one of the hot spots of research in the field of photocuring technology in recent years.
Disclosure of Invention
The invention provides a pyridine imidazole derivative which can be used as a photoinitiator, photosensitive groups are introduced into molecules, the photosensitivity of the initiator is improved, the light absorption capacity of the initiator is enhanced, the polymerization reaction can be initiated at the wavelength of 365nm, and the pyridine imidazole derivative has high polymerization efficiency.
It is still another object of the present invention to provide a process for preparing a pyridoimidazole derivative.
The invention also aims to provide application of the pyridine imidazole derivative.
The above purpose of the invention is realized by the following technical scheme:
a pyridoimidazole derivative has a molecular structure represented by formula (I) and/or formula (II):
Figure BDA0002979252940000011
the invention synthesizes two D-pi-A structural pyridino-imidazole derivatives based on pyridino-imidazole as an electron acceptor system by means of the electron donating property of phenanthrene-imidazole/diphenylamine, can be used as a photoinitiator, has longer conjugated chain length, increases the photon absorption cross section, can initiate polymerization reaction at 365nm wavelength, and has higher polymerization efficiency.
The invention provides a process for the preparation of a compound of formula (I) as defined above, which comprises the steps of:
s1, performing aldol condensation on 4-bromoacetophenone and benzaldehyde to prepare 4-bromochalcone;
s2, adding 2-aminopyridine into the 4-bromochalcone prepared in the step S1, and generating (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone under the catalytic action of iodine simple substance and ammonium acetate;
s3, carrying out Ullmann coupling reaction on the (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone prepared in the step S2 and diphenylamine to prepare the compound shown in the formula (I).
More preferably, the process for the preparation of said compound of formula (i) comprises the steps of:
s1, performing aldol condensation on 4-bromoacetophenone and benzaldehyde in an alcoholic solution of sodium hydroxide to obtain 4-bromochalcone; the reaction equation is as follows:
Figure BDA0002979252940000021
s2, obtaining a target product by catalyzing the 4-bromochalcone and the diaminopyridine obtained in the step S1 with a simple substance of iodine and ammonium acetate; the reaction equation is as follows:
Figure BDA0002979252940000022
s3, preparing (4 '- (1-phenyl-1H-phenanthrene [9, 10-d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) (3-phenylimidazo [1,2-a ] pyridine-2-yl) ketone (i.e. a compound I) from (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridine-2-yl) ketone and diphenylamine obtained in S2 under the catalysis of palladium acetate and sodium tert-butyl alkoxide and tri-tert-butylphosphine; the reaction equation is as follows:
Figure BDA0002979252940000023
preferably, the molar ratio of 4-bromoacetophenone to benzaldehyde in step S1 is 1-2: 1 to 2.
More preferably, the molar ratio of 4-bromoacetophenone to benzaldehyde in step S1 is 1:1.
preferably, the solvent of the aldol condensation in step S1 is ethanol.
Preferably, the aldol condensation of step S1 is catalyzed with a strong base; the strong base is sodium hydroxide.
Preferably, the aldol condensation reaction temperature of step S1 is 25 ℃; the reaction time was 3 hours.
Preferably, the aldol condensation in step S1 further comprises washing. The resulting mixture was washed in a buchner funnel and the solid was taken from the filter paper.
Preferably, the molar ratio of the 4-bromochalcone to the 2-aminopyridine in the step S2 is 1-1.2: 2 to 2.5.
More preferably; in the step S2, the molar ratio of 4-bromochalcone diaminopyridine is 1: 1.2.
preferably, in the step S2, the molar ratio of the iodine to the amine acetate is 1: 2.
preferably, the reaction solvent described in step S2 is chloroform.
Preferably, the reaction temperature of step S2 is 75 ℃; the reaction time was 12 h.
Preferably, step S2 further includes post-treatment of filtering, washing, drying, concentrating, separating.
More preferably, step S2 further includes adding sodium thiosulfate to remove iodine after the reaction is completed, performing suction filtration and washing with dichloromethane to obtain an organic phase, adding anhydrous sodium sulfate to the organic phase for drying, and concentrating the organic phase under reduced pressure to obtain a crude product; finally, the (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluent.
Preferably, the molar ratio of the (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone to the diphenylamine in step S3 is 1-2: 2-2.5.
More preferably, the molar ratio of (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone to diphenylamine in step S3 is 1: 1.2.
Preferably, the solvent for the Ullmann coupling reaction in step S3 is anhydrous toluene.
Preferably, the reaction in step S3 is catalyzed with palladium acetate.
Preferably, the reaction condition in step S3 is heating reflux under the protection of inert gas.
Preferably, the inert gas in step S3 is nitrogen, argon or helium.
More preferably, the inert gas in step S3 is nitrogen.
Preferably, the reaction temperature is 110-120 ℃; the reaction time was 12 h.
More preferably, the temperature of the reaction is 120 ℃; the reaction time was 12 h.
Preferably, step S3 further includes post-treatments of cooling, extraction, drying, concentration, separation.
More preferably, step S3 further comprises, after the reacted solution is cooled to room temperature, extracting the obtained mixture with dichloromethane three times, and combining the organic phases obtained by the three extractions; then drying the mixture by using anhydrous sodium sulfate, and then concentrating an organic phase under reduced pressure to obtain a crude product; finally, the (4- (diphenylamino) phenyl) (3-phenyl-2, 3-dihydroimidazo [1,2-a ] pyridin-2-yl) methanone is separated by silica gel column chromatography using ethyl acetate and petroleum ether as eluent.
The invention protects a preparation method of the compound shown in the formula (II), which comprises the following steps:
s1, carrying out condensation reaction on aniline, 4-bromobenzaldehyde and 9, 10-phenanthrenequinone to obtain 4-bromopyridine imidazole chalcone;
s2, introducing pinacol diboron into the 4-bromopyridine imidazole chalcone prepared in the step S1 to perform a boric acid reaction to prepare 4-boranophenamidezoimidazole;
s3, carrying out Ullmann coupling reaction on the 4-bromopyridine imidazole chalcone prepared in the step S1 and the 4-boranophenamidazole prepared in the step S2 to obtain the compound shown in the formula (II).
Preferably, the preparation method of the compound of formula (ii) comprises the following steps:
s1, 4-bromobenzaldehyde, aniline and 9, 10-phenanthrenequinone are subjected to the action of ammonium acetate to obtain 4-bromophenanthroimidazole;
the reaction equation is as follows:
Figure BDA0002979252940000041
s2, preparing 4-alkyl boron phenanthroimidazole through suzuki reaction of 4-bromo phenanthroimidazole and pinacol bisborate under the action of a catalyst [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex;
the reaction equation is as follows:
Figure BDA0002979252940000042
s3, obtaining (4 '- (1-phenyl-1H-phenanthrene [9, 10-d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) (3-phenylimidazo [1,2-a ] pyridine-2-yl) ketone by catalyzing 4-boranyl phenanthroimidazole and 4-bromopyridine imidazole chalcone with palladium acetate, sodium tert-butoxide and tri-tert-butylphosphine;
the reaction equation is as follows:
Figure BDA0002979252940000051
preferably, the molar ratio of 4-bromobenzone to aniline to 9, 10-phenanthrenequinone in step S1 is 1-2: 1-2: 1 to 2.
More preferably, the molar ratio of 4-bromobenzone, aniline and 9, 10-phenanthrenequinone in step S1 is 1: 1:1.
preferably, the solvent for the reaction of step S1 is glacial acetic acid.
Preferably, the reaction condition in step S1 is heating reflux under the protection of inert gas.
Preferably, the inert gas in step S1 is nitrogen, argon or helium.
More preferably, the inert gas in step S1 is nitrogen.
Preferably, the reaction temperature is 110-120 ℃; the reaction time was 2 h.
More preferably, the temperature of the reaction is 120 ℃; the reaction time was 2 h.
Preferably, the treatment in step S1 is cooling, washing, concentrating, separating. After the solution after the reaction was cooled to room temperature, the resulting mixture was washed with methanol and filtered to separate the crude product, and (4- (diphenylamino) phenyl) (3-phenyl-2, 3-dihydroimidazo [1,2-a ] pyridin-2-yl) methanone was separated by silica gel column chromatography using silica gel powder as a stationary phase and ethyl acetate and petroleum ether as eluents.
Preferably, the molar ratio of the 4-bromophenanthroimidazole to the pinacol diboron in the step S2 is 1-1.2: 2-2.5.
More preferably, the molar ratio of 4-bromophenanthroimidazole to pinacol diboron in step S2 is 1: 2.
Preferably, the solvent for the reaction described in step S2 is 1, 4-dioxahexane.
Preferably, the inert gas in step S2 is nitrogen, argon or helium.
More preferably, the inert gas in step S2 is nitrogen.
Preferably, the reaction temperature of the step S2 is 80-90 ℃; the reaction time is 6-12 h.
More preferably, the temperature of the reaction of step S2 is 85 ℃; the reaction time was 8 h.
Preferably, the treatment in step S2 is extraction, washing, drying, concentration, separation. After the reaction is finished, extracting with dichloromethane for three times, combining organic phases obtained by three times of extraction, drying the organic phases with anhydrous magnesium sulfate, and then concentrating the organic phases under reduced pressure to obtain a crude product; and finally, separating the 4-boranophenamidazole by silica gel column chromatography by using ethyl acetate and petroleum ether as eluent.
Preferably, the molar ratio of the 4-boranophenamidzole to the (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone in step S3 is 1-2: 1 to 2.
More preferably, the molar ratio of 4-boranophenamidzole and (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone in step S3 is 1: 1.2.
preferably, the solvent for the reaction described in step S3 is anhydrous toluene. Preferably, the inert gas in step S6 is nitrogen, argon or helium.
More preferably, the inert gas in step S3 is nitrogen. Preferably, the reaction temperature of the step S2 is 110-120 ℃; the reaction time is 12-14 h.
Preferably, the temperature of the reaction of step S3 is 120 ℃; the reaction time was 12 h.
Preferably, the treatment in step S3 is extraction, washing, drying, concentration, separation. After the reaction is finished, extracting with dichloromethane for three times, combining organic phases obtained by three times of extraction, drying the organic phases with anhydrous magnesium sulfate, and then concentrating the organic phases under reduced pressure to obtain a crude product; finally, the (4 '- (1-phenyl-1H-phenanthrene [9, 10-d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone is separated by silica gel column chromatography using dichloromethane and petroleum ether as eluent.
The invention also protects the application of the pyridine imidazole derivative as an ultraviolet curing photoinitiator.
The invention also provides an ultraviolet curing photoinitiator which is prepared from the pyridine imidazole derivative.
Compared with the prior art, the invention has the beneficial effects that:
the invention synthesizes two D-pi-A pyridine imidazole derivatives based on pyridine imidazole as an electron acceptor system by means of the electron donating property of phenanthroimidazole/diphenylamine, can be further used as a photoinitiator, introduces the photoinitiator in an ultraviolet curing system, can increase the photon absorption cross section of the photoinitiator due to the longer conjugated chain length of the photoinitiator, can initiate polymerization reaction at the wavelength of 365nm, has higher polymerization efficiency, and can be widely applied to the field of ultraviolet curing.
Drawings
FIG. 1 shows (4- (diphenylamino) phenyl) (3-phenyl-2, 3-Dihydroimidazo [1,2-a ] compounds]Process for preparing pyridin-2-yl) methanones1HMNR graph.
FIG. 2 shows (4' - (1-phenyl-1H-phenanthrene [9, 10-d ] obtained in example 2]Imidazol-2-yl) - [1,1' -biphenyl]-4-yl) (3-phenylimidazo [1, 2-a)]Pyridin-2-yl) methanones1HMNR graph.
FIG. 3 is an absorption diagram of the compound prepared in example 1 in a dichloromethane solution.
FIG. 4 is an absorption diagram of the compound prepared in example 2 in a dichloromethane solution.
FIG. 5 is a graph showing the double bond conversion of the novel photoinitiator prepared in example 1.
FIG. 6 is the double bond conversion of the novel photoinitiator prepared in example 2.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A pyridoimidazole derivative, the chemical name of which is (4- (diphenylamino) phenyl) (3-phenyl-2, 3-dihydroimidazo [1,2-a ] pyridin-2-yl) methanone, has a molecular structure shown as the formula (I):
Figure BDA0002979252940000071
a process for the preparation of a compound of formula (i) as hereinbefore defined comprising the steps of:
s1 preparation of (E) -1- (4-bromophenyl) -3-phenylprop-2-en-1-one (i.e. Compound 1):
4-bromoacetophenone (1.83g, 10mmol) and benzaldehyde (1.06g, 10mmol) were sequentially added to a 250ml round-bottom flask, and 45ml of a 0.1g/ml potassium hydroxide solution was added, and the mixture was stirred at ordinary temperature for 3 hours to obtain a yellow mixture. The mixture was placed in a buchner funnel with filter paper and washed with dichloromethane to give a yellowish powder (yield 80%); the reaction equation is as follows:
Figure BDA0002979252940000072
preparation of (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone (i.e., compound 2) S2:
the 4-bromochalcone (2.87g, 10mmol) obtained in S1, diaminopyridine (1.16g, 12mmol), iodine (2.53g, 10mmol) and ammonium acetate (1.44g, 20mmol) were added in this order to a 250ml two-necked flask, and 20ml of chloroform was added to give a mixture, and the mixture was stirred at 75 ℃ for 12 hours, whereupon the solution became dark brown. Three spoons of sodium thiosulfate were added to the two-necked flask, and after stirring at room temperature for 20min, the mixture was filtered and washed with dichloromethane, and then dried in vacuo. The product was purified using silica gel powder as stationary phase and petroleum ether and ethyl acetate as eluent (petroleum ether: ethyl acetate ═ 5: 1) to give a yellow-green powder (yield 65%); the reaction equation is as follows:
Figure BDA0002979252940000081
preparation of (4- (diphenylamino) phenyl) (3-phenyl-2, 3-dihydroimidazo [1,2-a ] pyridin-2-yl) methanone:
the product from S2 (1.85g, 5mmol), diphenylamine (1.01g, 6mmol), palladium acetate (22.4mg, 0.1mmol), sodium tert-butoxide (0.72g, 7.5mmol), tri-tert-butylphosphine (20.23mg, 0.1mmol) were added sequentially to a 250ml two-necked flask and 20ml of anhydrous toluene to give a mixture which, after stirring at 120 ℃ for 12 hours, gave a dark brown suspension, which was extracted with saturated brine and dichloromethane and distilled under reduced pressure to give a brown solid which was purified using silica gel powder as the stationary phase and petroleum ether and ethyl acetate as the eluents (petroleum ether: ethyl acetate ═ 5: 1) to give a yellow powder (I) (yield 50%), the reaction equation is as follows:
Figure BDA0002979252940000082
the nuclear magnetic spectrum of compound M1 is shown in FIG. 1.As can be seen from FIG. 1, the characteristic wave number (ppm) is1H NMR。
Example 2
A pyridylimidazole derivative, which has a chemical name of (4 '- (1-phenyl-1H-phenanthrene [9, 10-d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone and has a molecular structure shown as a formula (II):
Figure BDA0002979252940000083
a process for the preparation of a compound of formula (ii) as described above comprising the steps of:
s1.preparation of 4-Bromophenanthrolimidazole (i.e. Compound 1):
4-bromobenzaldehyde (1.86g, 10mmol), aniline (1.49g,10mmol), 9, 10-phenanthrenequinone (2.08g,10mmol), ammonium acetate (4.62 g, 60mmol) were added successively to a 250ml two-necked flask and 60ml of glacial acetic acid were added to give a dark brown suspension, the mixture was stirred at 120 ℃ for two hours, the solution changed from dark brown to black in color, and the reaction mixture was stirred at ambient temperature overnight (12 hours), washed with methanol and filtered to isolate the crude product, which was then dried again in vacuo. Using silica gel powder as stationary phase and petroleum ether and dichloromethane as eluent (petroleum ether: CH)2Cl21: 2) purifying the product to obtain a white powder; the reaction equation is as follows:
Figure BDA0002979252940000091
s2.preparation of 4-Boroalkylphenanthroimidazole (i.e., Compound 2):
4-Bromophenanthrolimidazole (2.02g, 4mmol) and pinacol ester boronate (1.06g, 4.2mmol) were added to a solution of DMF (60ml) and 60ml of deionized water to give a dark brown suspension. Stirring and reacting at 85 ℃ for 16 hours, extracting with saturated saline and dichloromethane, distilling under reduced pressure to obtain black solid, purifying the product by using silica gel powder as a stationary phase and petroleum ether and ethyl acetate as eluent (petroleum ether: ethyl acetate: 8: 1) to obtain white powder; the reaction equation is as follows:
Figure BDA0002979252940000092
preparation of (4 '- (1-phenyl-1H-phenanthro [9, 10-d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone:
s6: 4-Borophenanthoimidazole (492mg, 1mmol) and 4-bromopyridine imidazole chalcone (452.4mg, 1.2mmol), palladium acetate (22.4mg, 0.1mmol), sodium tert-butoxide (0.72g, 7.5mmol), tri-tert-butylphosphine (20.23mg, 0.1mmol) were added successively to a 250ml two-necked flask, and 20ml of anhydrous toluene was added to give a mixture. After stirring and reacting for 12 hours at 120 ℃, extracting with saturated saline and dichloromethane, distilling under reduced pressure to obtain a coffee solid, purifying the product by using silica gel powder as a stationary phase and petroleum ether and ethyl acetate as eluent (the petroleum ether: ethyl acetate: 5: 1) to obtain yellow-green powder (i.e. compound II); the reaction equation is as follows:
Figure BDA0002979252940000101
example 3 structural characterization and Performance testing
As can be seen from FIG. 1, the compounds of formula (I) are characterized by a wave number (ppm) of1H NMR (400MHz, DMSO-d6) δ 8.32(d, J ═ 7.7Hz,1H),8.19(d, J ═ 7.6Hz,1H),8.14 to 8.03(m,2H),7.93(d, J ═ 7.6Hz,2H),7.67(d, J ═ 9.2Hz,1H),7.57 to 7.45(m,5H),7.43 to 7.28(m,8H),7.26 to 7.16(m,3H),6.83(d, J ═ 7.6Hz,2H),6.71(d, J ═ 7.6Hz,1H),6.53(s,1H), peaks can correspond one-to one, and are reasonable in number, to the hydrogen atoms on the ring of pyridoimidazole, triphenylamine. The compound shown in the formula (I) has a single structure and high purity.
As can be seen from fig. 2, the compound of formula (ii) has characteristic wave numbers (ppm) of 1H NMR (400MHz, Chloroform-d) δ 8.92(dd, J ═ 20.5,8.4Hz,2H),8.73(dd, J ═ 8.0,1.5Hz,1H),8.25 to 8.19(m,3H),7.90 to 7.84(m,2H),7.83 to 7.67(m,12H),7.62 to 7.50(m,6H),7.45(ddd, J ═ 9.2,6.6,1.2Hz,1H),7.38 to 7.30(m,1H),7.13 to 7.00(m,2H). peaks can correspond to the hydrogen atoms on the aromatic rings of phenanthroimidazole, biphenyl, and pyridoimidazole, in a reasonable number. The compound shown in the formula (II) has a single structure and high purity.
The photophysical properties of the test objects, which were the compounds of formula (i) and the compounds of formula (ii) prepared in examples 1 and 2, were measured for uv absorption wavelength and the test results are shown in fig. 3 to 4. The maximum absorption wavelength of the formula (I) is 375 nm; the maximum absorption wavelength of the compound of formula (II) is 350nm, and thus, the two compounds of formula (I) and the compound of formula (II) having long wavelengths can be used as photoinitiators, so that the requirement of mercury lamps can be reduced, and the problem of environmental pollution caused by mercury lamps can be reduced.
The prepared compound of the formula (I) or the formula (II) is used as a novel photoinitiator to initiate 5 wt% of a propane trimethanol triacrylate monomer to carry out polymerization reaction under a 365nm wavelength UV light source, and as a result, as shown in figures 5 and 6, the double bond conversion rate of the compound of the formula (I) within 150s is 37.73%; the double bond conversion of the compound of formula (II) was 22.92%; the double bond conversion of the commercial photoinitiator 184 was 26.54%. Compared with the traditional commercial photoinitiator 184, the compound shown in the formula (I) has higher double bond conversion rate, higher polymerization efficiency and certain application value, although the compound shown in the formula (II) is lower than the photoinitiator 184, the double bond conversion rate of the compound with the structure is proved to be close to the double bond conversion rate of the commercial photoinitiator, and the compound shown in the formula (II) can overcome the defects of the photoinitiator 184, such as high mobility, high volatility and the like, and also has certain application value. The imidazopyridine derivative prepared by the invention can be widely applied to the field of ultraviolet curing.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A pyridoimidazole derivative having a molecular structure represented by formula (I) and/or formula (II):
Figure FDA0002979252930000011
2. a process for the preparation of a pyridoimidazole derivative according to claim 1, wherein the compound of formula (i) is prepared by a process comprising the steps of:
s1, performing aldol condensation on 4-bromoacetophenone and benzaldehyde to prepare 4-bromochalcone;
s2, adding 2-aminopyridine into the 4-bromochalcone prepared in the step S1, and generating (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone under the catalytic action of iodine simple substance and ammonium acetate;
s3, carrying out Ullmann coupling reaction on the (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone prepared in the step S2 and diphenylamine to prepare the compound shown in the formula (I).
3. A process for the preparation of a pyridoimidazole derivative according to claim 1, wherein the compound of formula (ii) is prepared by a process comprising the steps of:
s1, carrying out condensation reaction on aniline, 4-bromobenzaldehyde and 9, 10-phenanthrenequinone to obtain 4-bromopyridine imidazole chalcone;
s2, introducing pinacol diboron into the 4-bromopyridine imidazole chalcone prepared in the step S1 to perform a boric acid reaction to prepare 4-boranophenamidezoimidazole;
s3, carrying out Ullmann coupling reaction on the 4-bromopyridine imidazole chalcone prepared in the step S1 and the 4-boranophenamidazole prepared in the step S2 to obtain the compound shown in the formula (II).
4. The pyridoimidazole derivative according to claim 2, wherein the molar ratio of 4-bromoacetophenone to benzaldehyde in step S1 is 1-2: 1 to 2.
5. The pyridoimidazole derivative according to claim 2, wherein the molar ratio of 4-bromochalcone to 2-aminopyridine in step S2 is 1 to 1.2: 2 to 2.5.
6. The pyridoimidazole derivative according to claim 2, wherein the molar ratio of (4-bromophenyl) (3-phenylimidazo [1,2-a ] pyridin-2-yl) methanone to diphenylamine in step S3 is 1-2: 2-2.5.
7. The pyridoimidazole derivative according to claim 3, wherein the molar ratio of 4-bromobenzophenone, aniline and 9, 10-phenanthrenequinone in step S1 is 1-2: 1-2: 1 to 2.
8. The pyridoimidazole derivative according to claim 3, wherein the molar ratio of 4-bromophenanthroimidazole to pinacol diboron at step S2 is 1-1.2: 2-2.5.
9. Use of the pyridoimidazole derivatives according to any one of claims 1 to 8 as uv-curing photoinitiators.
10. An ultraviolet-curable photoinitiator, which is prepared from the pyridoimidazole derivative according to any one of claims 1 to 8.
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CN101812142B (en) * 2010-02-05 2012-12-26 深圳市有为化学技术有限公司 Double functionalized aromatic ketone compounds and photoinitiator containing same
CN111875602B (en) * 2020-07-15 2022-10-21 广东工业大学 Cyano-modified pyridino-imidazole derivative and preparation method and application thereof
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