CN1328273C - Coumarin dyestuff linked by naphthene ketones, method for synthesis and use thereof - Google Patents
Coumarin dyestuff linked by naphthene ketones, method for synthesis and use thereof Download PDFInfo
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- CN1328273C CN1328273C CNB2003101224995A CN200310122499A CN1328273C CN 1328273 C CN1328273 C CN 1328273C CN B2003101224995 A CNB2003101224995 A CN B2003101224995A CN 200310122499 A CN200310122499 A CN 200310122499A CN 1328273 C CN1328273 C CN 1328273C
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Abstract
The present invention belongs to the field of visual light sensitizing dye. The present invention particularly relates to coumarin dye connected by naphthene ketone and a synthetic method and application thereof. Ordinary hydroxyaldehyde condensation reaction is adopted; naphthene ketone, corresponding aldehyde with an A1 base group, etc. are added into one reaction vessel for reaction, which obtains semicyclic naphthene ketone dye with the A1 base group; corresponding coumarin which is substituted by 3-position methyl or 4-position methyl and has an A2 base group, selenious acid, etc. react in the other reaction vessel, which obtains coumarin aldehyde with the A2 base group; the semicyclic naphthene ketone dye with the A1 base group and the coumarin aldehyde with the A2 base group react with the existence of mixed solvent of xylene and ethanol, etc., which obtains the coumarin dye connected by the naphthene ketone. The coumarin dye can be used as a photo sensitizer to form a photosensitized initiation system with other photoinitiator, the photosensitized initiation system is used for photo polymerization of visual light of olefin monomers in solution, or the coumarin dye can be used as photo curing material, laser procss material and holographic memory material.
Description
Invention field
The invention belongs to visible light photoactivated dye field, particularly relate to coumarine dye and preparation method and use thereof that a class connects by cyclanone.
Background technology
The laser of visible wavelength such as Ar in recent years
+(488nm, 514nm), YAG (532nm), He-Ne (633nm) laser be in the widespread use in fields such as holographic recording, directly laser Graphic, photocuring and laser stereolithography, visible light photo sensitized initiation polymerization system becomes the key areas of present photopolymerization research efficiently.No matter be to adopt the mechanism of polymerization starter direct exposure or adopt dye sensitization polymerization starter mechanism, the visible light photoactivated dyestuff of synthesizing efficient is to improve the photopolymerization velocity of initiation, improves the effective way of material property.Coumarine dye is a kind of very fast laser dyes that reacts, 7-amido coumarins dyestuff wherein, as electron donor(ED), can feel visible light effectively, and obtain higher photo sensitized initiation efficient, on " tetrahedron " magazine, report the synthetic of a series of coumarine dyes as nineteen eighty-two Specht Donald P., and them as photosensitizers and light trigger (exercise question: coumarin ketone-novel triplet state photosensitizers, Tetrahedron, vol.38,1203-1211).Wherein absorbing wavelength is 3 of 460nm, 3 '-two (7-N, the N diethylin) coumarin ketone is acknowledged as class visible light triplet state sensitizing dye efficiently over nearly 20 years, and it can form visible light photosensitized initiation system efficiently with salt compounded of iodine, amine, hexa-aryl bi-imidazole etc.; Yet there are shortcomings such as absorbing wavelength is short, the absorption bands coverage is narrower again in it, can not adapt to effective application of multi-wavelength's laser.
Summary of the invention
One of purpose of the present invention is to solve the not available absorption long wavelength laser of common coumarine dye, and the problem of absorption bands coverage broad, provide a class both to have more apneusis receipts wavelength, the wavelength coverage that has broad again, the coumarins dyestuff that is connected with cyclanone that can be complementary with visible light optical maser wavelength commonly used.
A further object of the present invention provides a kind of synthetic method of passing through the efficient coumarine dye of naphthenic hydrocarbon ketone connection.
Another object of the present invention provides the purposes of the coumarins dyestuff that connects with cyclanone.
The coumarins dyestuff that connects with cyclanone of the present invention has following molecular structure:
Wherein: A
1, A
2For containing the group of electron donor(ED) character or electron acceptor(EA) character, as alkyl, alkoxyl group, amido, heterocycle or substituted-phenyl etc.A
1And A
2Can be identical substituting group, also can be substituting group inequality.
Described alkyl is: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms are less than alkyl of 15 etc.
Described alkoxyl group is: methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms are less than alkoxyl group of 15 etc.
Described amido is: methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido, hexichol amido, substituted diphenylamine or quaternary ammonium salt base etc.
Described heterocyclic radical is: pyridine, pyrroles, thiazole, carbazole, cyanines class, coumarins or ammonium salt etc.
Described substituted-phenyl is selected from: adjacent, to, a position itrile group benzene, adjacent, to, a position chlorobenzene, adjacent, to, a position carboxyl benzene, adjacent, to, a position alkylbenzene, adjacent, to, a position alkoxy benzene, adjacent, to, a position amido benzene etc.
The synthetic method of the coumarins dyestuff that connects with cyclanone provided by the invention may further comprise the steps:
(1) has A
1Synthesizing of the semi-ring alkane ketone dyestuff of group
Reaction equation:
Concrete steps:
Adopt common aldol reaction, with naphthenic hydrocarbon ketone, the corresponding described A that has
1The aldehyde cpd of group 1～6: 1 ratio in molar ratio joins in the reaction vessel, and adding mol ratio then is the described A of having
150～500 times of the aldehyde cpds of group and concentration be 20～80% ethanol water mixed solutions, adding mol ratio again is the described A of having
1The basic catalyst that the aldehyde cpd of group is 0.01～0.40 times reacted 5～40 hours under 25 ℃～80 ℃ conditions, and filtering-depositing adopts silicagel column to separate then and obtains corresponding A
1The semi-ring alkane ketone dyestuff of group, standby.
(2) have A
2Synthesizing of the tonka bean camphor aldehyde of group
Reaction equation:
Concrete steps:
Adopt common oxygenant selenous acid methyl oxidation to be become the method for aldehyde.With corresponding 3 methyl substituted or 4 methyl substituted described A
2The tonka bean camphor of group and selenous acid join in another reaction vessel by 1: 1～2 mol ratio, and adding mol ratio then is described A
250～500 times of solvent refluxings of the tonka bean camphor of group 9～30 hours after heat filtering is removed selenium, are separated out after the filtrate cooling and are had A
2The tonka bean camphor aldehyde crystal of group, standby.
(3) the coumarins dyestuff that connects with cyclanone is synthetic
Reaction equation:
Concrete steps:
Have an A with what step (1) made
1The semi-ring alkane ketone dyestuff of group and step (2) make has A
2The tonka bean camphor aldehyde of group carries out condensation reaction and obtains under the effect of basic catalyst.Have an A with what step (1) made
1Group semi-ring alkane ketone dyestuff and step (2) make has A
2The tonka bean camphor aldehyde of group is that 1: 1 ratio joins in the reactor in molar ratio, is to contain A with mol ratio then
2The volume ratio that group tonka bean camphor aldehyde is 100～500 times is 5%～50% dimethylbenzene alcohol mixed solvent, and adding mol ratio again is to have A
1The basic catalyst that group semi-ring alkane ketone is 0.01～0.40 times refluxed 0.5～6 hour, the cooled and filtered precipitation.Precipitation can be obtained coumarins dyestuff with cyclanone connection with the dimethylbenzene recrystallization.
Described basic catalyst is sodium hydroxide, potassium hydroxide, Anhydrous potassium carbonate, anhydrous sodium carbonate, hexahydropyridine or their any mixture etc.
Described solvent comprises dimethylbenzene, ethanol, acetonitrile, 1,4-dioxane solvent or their any mixture.
The coumarins dyestuff that connects with cyclanone of the present invention, they can form photosensitized initiation system efficiently with couplings such as light trigger such as salt compounded of iodine, sulfosalt, hexa-aryl bi-imidazole, benzophenone, ferrocene, thioxanthones, and because its absorption bands is wide, absorbing wavelength is longer, almost can with now all visible light source such as tungsten-iodine lamp, xenon lamp, Ar
+Laser apparatus, YAG (532nm) laser apparatus etc. are complementary.Therefore, the efficient photosensitized initiation system of being made up of as photosensitizers and other light triggers dyestuff of the present invention can be used for the visible light photopolymerization of vinyl monomer in the solution, or as photo-curing material, laser plate-making material, the visible light-sensitive initiator system of holographic storage material etc.
Photosensitizers consumption, configuration and the using method of dyestuff of the present invention during as above purposes is as follows:
A. the coumarine dye that connects with cyclanone is as photosensitizers, component and consumption when causing the photopolymerization of vinyl monomer visible light:
Vinyl monomer 25%～70wt%
Organic solvent 25%～70wt%
Light trigger 0.1%～5wt%
Chain-transfer agent 0.1%～5wt%
Coumarine dye (photosensitizers of the present invention) 0.1%～1wt%
The concrete operations step is as follows:
In reaction vessel, add the organic solvent of 25%～70wt% and the vinyl monomer of 25%～70wt%, logical then nitrogen was removed oxygen in 20～30 minutes, under the lucifuge condition, the coumarine dye that adds 0.1%～1wt%, the chain-transfer agent of 0.1%～5wt% and the light trigger of 0.1%～5wt%, after stirring, at room temperature use 15 centimetres of irradiations of visible light source distance, react and stopped illumination in 0.5～5 hour, use methyl alcohol, normal hexane, or sherwood oil is separated out polymkeric substance, promptly get crude product, handle, can obtain the polymkeric substance of refining vinyl monomer if carry out reprecipitation.
In the above-mentioned prescription, described vinyl monomer comprises esters of acrylic acid, acrylic amide, vinyl cyanide, styrenic, vinyl-acetic ester or vinyl pyrrole ketone or their any mixture.
Described organic solvent comprises aromatic hydrocarbons, halogenated hydrocarbon, ethers, acetonitrile, dimethyl sulfoxide (DMSO) or their any mixture.
Described aromatic hydrocarbons comprises benzene, toluene or their any mixture.
Described halohydrocarbon comprises methylene dichloride, trichloromethane, chlorobenzene or their any mixture.
Described ether is ethylene glycol monomethyl ether etc.
Described light trigger is that salt compounds, two imidazoles, organometallic compound, organoboron compound, Benzophenones, various alkyl replace thia and fear ketone, acetophenone derivs, amine or their any mixture.
Described salt compounds is salt compounded of iodine, sulfosalt or their any mixture etc.
Described pair of imidazoles is hexa-aryl bi-imidazole etc.
Described organometallic compound is ferrocene compounds, ferrocene salt, aluminate complex compound or their any mixture etc.
Described organoboron compound is a butyl triphenyl borate etc.
Described acetophenone derivs is Alpha-hydroxy-phenylcyclohexane ethyl ketone etc.
Described chain-transfer agent is a sulfur alcohol compound etc., as lauryl mercaptan.
Component and consumption when B. the coumarine dye that connects with cyclanone is as the photosensitizers of photo-curing material:
Light reactive resin 40%～70wt%
Multi-functional acrylate's linking agent 10%～30wt%
Simple function group acrylate reactive thinner 5%～15wt%
Organic solvent 5%～10wt%
Light trigger 2%～12wt%
Coumarine dye (photosensitizers of the present invention) 1%～3wt%
The concrete operations step is as follows:
In the container of whipping device is housed, add the light reactive resin of 40%～70wt% and multi-functional acrylate's linking agent of 10%～30wt%, under 40 ℃～50 ℃, stirring makes it to mix, and gets B
1Component.
In another container, add reactive thinner, the coumarine dye of 1%～3wt%, the light trigger of 2%～12wt% and the organic solvent of 5%～10wt% of 5%～15wt%, stir, dissolve B
2Component.
At the following B of lucifuge condition
2Component is added to B
1In the component, mix, after coating on the dacron chip base, with visible light source irradiation 1～10 minute, can obtain the light solidifying coating material under the room temperature.
Light reactive resin described in the above-mentioned prescription is epoxy acrylate, polyester acrylate or unsaturated polyester and their mixture etc.
Described multi-functional acrylate's linking agent is Viscoat 295, dipentaerythritol triacrylate, tetramethylolmethane five acrylate, propylene glycol double methacrylate or tirethylene glycol double methacrylate and their mixture etc.
Described reactive thinner is the simple function group acrylate, as vinylformic acid tetrahydrofuran ester or hydroxyalkyl acrylates and their mixture etc.
Described hydroxyalkyl acrylates is Hydroxyethyl acrylate, Propylene glycol monoacrylate or hydroxyethyl methylacrylate and their mixture etc.
Described light trigger is that salt compounds, two imidazoles, organometallic compound, organoboron compound, Benzophenones, various alkyl replace thia and fear ketone, acetophenone derivs, amine or their any mixture.
Described salt compounds is salt compounded of iodine, sulfosalt or their any mixture etc.
Described pair of imidazoles is hexa-aryl bi-imidazole etc.
Described organometallic compound is ferrocene compounds, ferrocene salt, aluminate complex compound or their any mixture etc.
Described organoboron compound is a butyl triphenyl borate etc.
Described acetophenone derivs is Alpha-hydroxy-phenylcyclohexane ethyl ketone etc.
Described organic solvent is aromatic hydrocarbons, halogenated hydrocarbon, ethers, acetonitrile, dimethyl sulfoxide (DMSO) or their any mixture.
Described aromatic hydrocarbons comprises benzene, toluene or their any mixture.
Described halohydrocarbon comprises methylene dichloride, trichloromethane, chlorobenzene or their any mixture.
Described ether is ethylene glycol monomethyl ether etc.
Component and consumption when C. the coumarine dye that connects with cyclanone is as the photosensitizers of holographic storage material and laser plate-making material:
Organic solvent 60%～85wt%
Vinyl monomer 4%～15wt%
Binding agent 5%～25wt%
Light trigger 0.1%～3wt%
Chain-transfer agent 0.1%～1wt%
Coumarine dye (photosensitizers of the present invention) 0.1%～1wt%
Auxiliary agent 0.1%～1wt%
The concrete operations step is as follows:
In container with the binding agent dissolving of the organic solvent of 60%～85wt% with 5%～25wt%, the vinyl monomer that adds 4%～15wt% then, lucifuge adds light trigger, the chain-transfer agent of 0.1%～1wt%, the coumarine dye photosensitizers of 0.1%～1wt% and the auxiliary agent of 0.1%～1wt% of 0.1%～3wt% behind the mixing, obtains liquid visible light polymerized sensitization material after the dissolving fully.
This liquid visible light polymerized sensitization material is coated on sheet glass or the mylar, in 40 ℃ of vacuum drying ovens, promptly obtains can be used for the visible light photopolymerization sensitized material of laser hologram storage after dry 24 hours.If be applied on the aluminium plate of electrolysis, oxidation, be coated with the polyvinyl alcohol solution of 1wt% again, promptly obtain can be used for the visible light photopolymerization sensitized material of laser system PS version after the oven dry.
In the above-mentioned prescription, described vinyl monomer is esters of acrylic acid, acrylic amide, vinyl cyanide, styrenic, N-vinylcarbazole and contains carbon-to-carbon double bond and addition polymerization polymeric monomer can take place or their mixture etc.
Described light trigger is salt compounds, two imidazoles, organometallic compound, organoboron compound, Benzophenones, various alkyl replacement thioxanthone, acetophenone derivs, st-yrax ethers, amine or their any mixture.
Described salt compounds is salt compounded of iodine, sulfosalt or their any mixture etc.
Described pair of imidazoles is hexa-aryl bi-imidazole etc.
Described organometallic compound is ferrocene compounds, ferrocene salt, aluminate complex compound or their any mixture etc.
Described organoboron compound is a butyl triphenyl borate etc.
Described acetophenone derivs is Alpha-hydroxy-phenylcyclohexane ethyl ketone etc.
Described chain-transfer agent is a sulfur alcohol compound etc., as lauryl mercaptan.
Described organic solvent is aromatic hydrocarbons, halogenated hydrocarbon, ethers or their any mixture.
Described aromatic hydrocarbons comprises benzene, toluene or their any mixture.
Described halohydrocarbon comprises methylene dichloride, trichloromethane, chlorobenzene or their any mixture.
Described ether is ethylene glycol monomethyl ether etc.
Described binding agent is polymethylmethacrylate, polyvinyl acetate (PVA), Mierocrystalline cellulose and derivative thereof, acrylate and vinyl acetate copolymer, modification mandelic resin or their mixture etc.
Described auxiliary agent is a flow agent, the moral modest 435,455 of producing as the modest company of moral or 466 etc.
The radiation source of above-mentioned materials adopts visible light source, as xenon lamp, incandescent light or tungsten-iodine lamp etc., also can adopt LASER Light Source such as argon laser or YAG532 LASER Light Source.
Of the present invention have:
(1) the synthetic and separation of coumarins dyestuff of the present invention is fairly simple, and raw material sources conveniently are easy to get, and wherein contain A
2The tonka bean camphor aldehyde of group with contain A
1The semi-ring alkane ketone of group all can be synthetic by ordinary method, only needs then to contain A accordingly
1Group with contain A
2The condensation under alkaline condition of group aldehyde ketone just can make dyestuff of the present invention, and productive rate is higher.
(2) absorption bands of dyestuff of the present invention covers broad, and by changing A
1Group or A
2The molecular structure of group can be adjusted the maximum absorption wavelength of dyestuff easily, almost can mate all visible light sources now.
(3) dyestuff of the present invention is a triplet state sensitizing dye efficiently, it can with multiple initiator coupling, form visible light initiated polymerization system efficiently.
(4) contain the higher photoreduction coumarins species of efficiency of initiation in the dye structure of the present invention, contain triplet state naphthenic hydrocarbon ketone efficiently again simultaneously, so dyestuff itself has initiated polymerization efficient efficiently.
Embodiment
Embodiment 1
The coumarins dyestuff (CP-COU) that connects with cyclopentanone synthetic
(1) with the cyclopentanone of 40 mmoles and 10 mmoles the dimethylin phenyl aldehyde is inserted in the flask, add 7 milliliters dehydrated alcohol and 10 milliliters water, drip 0.5 milliliter of 10wt%NaOH aqueous solution, 25 ℃ of reactions of room temperature 5 hours, filter orange precipitation, carry out column chromatography with 0.2wt% ethanol/chloroform and separate, get half dimethylin benzal cyclopentanone dyestuff, productive rate 85%.
(2) (3014 pages of synthetic method reference literature " pharmaceutical chemistry journal " nineteen eighty-threes 31 volumes, ChemPharm Bull, 1983,31,3014) 4-methyl-5-pyrryl tonka bean camphor, the 12 mmole selenous acid with 10 mmoles place flask, add 50 milliliters of dimethylbenzene heating for dissolving, back flow reaction 10 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out yellow needle-like crystal, filter and promptly obtain pure product 4-aldehyde radical 5-pyrryl tonka bean camphor, productive rate 82%.
(3) the half 4-aldehyde radical 5-pyrryl tonka bean camphor to dimethylin benzal cyclopentanone dyestuff and 1 mmole with above-mentioned synthetic 1 mmole places flask, add 15 milliliters of ethanol, 4 milliliters of dimethylbenzene, drip 0.1 milliliter of 1 mol potassium hydroxide-ethanol solution after being heated to reactants dissolved, have the dark red precipitation to produce at once, refluxed 1 hour, leave standstill cooling, filtering-depositing can get the coumarine dye CP-COU that pure product connect with cyclopentanone, productive rate 50% with the dimethylbenzene recrystallization.
Embodiment 2
The coumarins dyestuff (CHE-COU) that connects with pimelinketone synthetic
(1) pimelinketone of 30 mmoles and the acetaldehyde of 10 mmoles are inserted in the flask, add 20 milliliters dehydrated alcohol and 5 milliliters water, drip 2 milliliters of hexahydropyridines, 60 ℃ were reacted 24 hours, filter orange precipitation, carry out column chromatography with 0.2wt% ethanol/chloroform and separate, get half 2-ethyl cyclohexanone dyestuff, productive rate 75%.
(2) (3014 pages of synthetic method reference literature " pharmaceutical chemistry journal " nineteen eighty-threes 31 volumes, ChemPharm Bull, 1983,31,3014) 3-methyl-ayapanin, the 15 mmole selenous acid with 10 mmoles place flask, add 60 milliliters of ethanol heating for dissolving, back flow reaction 15 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out yellow needle-like crystal, filter and promptly obtain pure product 3-aldehyde radical-ayapanin, productive rate 93%.
(3) the half 2-ethyl cyclohexanone dyestuff of above-mentioned synthetic 1 mmole and the 3-aldehyde radical-ayapanin of 1 mmole are placed flask, add 20 milliliters of ethanol, 2 milliliters of dimethylbenzene, drip the 0.02g Anhydrous potassium carbonate after being heated to reactants dissolved, have the dark red precipitation to produce at once, refluxed 4 hours, leave standstill cooling, filtering-depositing can get the coumarine dye CHE-COU that pure product connect with pimelinketone, productive rate 45% with the dimethylbenzene recrystallization.
Embodiment 3
The coumarins dyestuff (CHP-COU) that connects with suberone synthetic
(1) suberone of 20 mmoles and the phenyl aldehyde of 10 mmoles are inserted in the flask, add 20 milliliters dehydrated alcohol and 2 milliliters water, drip 3 milliliters of 10wt%KOH aqueous solution, 65 ℃ were reacted 36 hours, filter orange precipitation, carry out column chromatography with 0.2wt% ethanol/chloroform and separate, get half benzal suberone dyestuff, productive rate 65%.
(2) (3014 pages of synthetic method reference literature " pharmaceutical chemistry journal " nineteen eighty-threes 31 volumes, ChemPharm Bull, 1983,31,3014) 3-methyl-6-phenyl tonka bean camphor, the 18 mmole selenous acid with 10 mmoles place flask, add 70 milliliters of acetonitrile heating for dissolving, back flow reaction 24 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out yellow needle-like crystal, filter and promptly obtain pure product 3-aldehyde radical-6-phenyl tonka bean camphor, productive rate 90%.
(3) the half 3-aldehyde radical-6-phenyl tonka bean camphor to methyl suberone dyestuff and 1 mmole with above-mentioned synthetic 1 mmole places flask, add 25 milliliters of ethanol, 3 milliliters of dimethylbenzene, drip 2 milliliters of 1 mol sodium hydroxide ethanolic solns after being heated to reactants dissolved, have the dark red precipitation to produce at once, refluxed 6 hours, leave standstill cooling, filtering-depositing can get the coumarine dye CHP-COU that pure product connect with suberone, productive rate 50% with the dimethylbenzene recrystallization.
Embodiment 4
The coumarins dyestuff (COC-COU) that connects with cyclooctanone synthetic
(1) cyclooctanone of 10 mmoles and the 2-aldehyde radical benzothiazole of 10 mmoles are inserted in the flask, add 10 milliliters dehydrated alcohol and 1 milliliter water, drip 1 milliliter of 10wt%KOH aqueous solution, 80 ℃ were reacted 36 hours, filter yellow mercury oxide, carry out column chromatography with 0.2wt% ethanol/chloroform and separate, get semibenzene benzothiazolyl cyclooctanone dyestuff, productive rate 55%.
(2) (3014 pages of synthetic method reference literature " pharmaceutical chemistry journal " nineteen eighty-threes 31 volumes, ChemPharm Bull, 1983,31,3014) 4-methyl-8-phenoxy group tonka bean camphor, the 20 mmole selenous acid with 10 mmoles place flask, add 80 milliliter 1,4-dioxane heating for dissolving, back flow reaction 28 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out yellow needle-like crystal, filter and promptly obtain pure product 4-aldehyde radical 8-phenoxy group tonka bean camphor, productive rate 82%.
(3) the semibenzene benzothiazolyl cyclooctanone dyestuff of above-mentioned synthetic 1 mmole and the 4-aldehyde radical 8-phenoxy group tonka bean camphor of 1 mmole are placed flask, add 25 milliliters of ethanol, 4 milliliters of dimethylbenzene, drip 2 milliliters of 1 mol potassium hydroxide-ethanol solutions after being heated to reactants dissolved, have the dark red precipitation to produce at once, refluxed 1 hour, leave standstill cooling, filtering-depositing can get the coumarine dye COC-COU that pure product connect with cyclooctanone, productive rate 52% with the dimethylbenzene recrystallization.
Embodiment 5
The coumarins dyestuff is as vinyl monomer visible light polymeric photosensitizers
In reaction vessel, add 2g chloroform and 8g methyl methacrylate, logical nitrogen 20 minutes, add 0.2 gram lauryl mercaptan under the lucifuge condition, 0.3 gram hexa-aryl bi-imidazole and embodiment 1 synthetic new dye CP-COU 0.1 gram are after treating to dissolve fully, place illumination under the tungsten-iodine lamp of 1KW under the room temperature, after 2 hours, the reactant methanol extraction can obtain white polymerisate polymethylmethacrylate.
Embodiment 6
The coumarins dyestuff is as the photosensitizers in the light solidifying coating material initiator system
In Glass Containers, add 60g epoxy acrylate and 20g Viscoat 295, under 40 ℃, mix, get B
1Component.Under the lucifuge condition, adding 2g chloroform, 10g Hydroxyethyl acrylate, 0.2g embodiment 2 synthetic new dye CHE-COU, 0.5g hexa-aryl bi-imidazole, 0.6g lauryl mercaptan stirring and dissolving get B in another container
2Component.Under the lucifuge condition with B
2Component adds B
1In the component, mix.Then the solution for preparing is applied on the dacron chip base, the lucifuge seasoning vapors away solvent, places under the xenon lamp of 1KW illumination 1 minute, the photocuring film.
Embodiment 7
The coumarins dyestuff is as the photosensitizers of laser hologram storage initiator system
Under the lucifuge condition in the container of 100ml, add 40g trichloromethane and 5g polymethylmethacrylate, the 2g hydroxyethyl methylacrylate, 0.2g embodiment 3 synthetic new dye CHP-COU and 0.2g lauryl mercaptan, fully after the mixing dissolving, add the 0.5g hexa-aryl bi-imidazole, all the dissolving back is coated on the glass baseplate by the blade coating mode, vacuum drying oven dries by the fire 24 hours film forming for 30 ℃～40 ℃, promptly obtains carrying out the photochromics of Hologram Storage.The Argon ion laser that utilizes the 514nm wavelength is as light source, the about 5mW/cm of reference light intensity
2, the about 2.4mW/cm of the largest light intensity in the thing light
2, the angle of reference light and thing light is 30 degree, by angular multiplexed technology, can carry out the Hologram Storage of picture information at same position.
Embodiment 8
The purposes of coumarins dyestuff in laser PS version
Hexa-aryl bi-imidazole 0.3 gram, lauryl mercaptan 0.4 gram, embodiment 4 synthetic novel coumarin dyestuff COC-COU 0.08g, modification mandelic resin 5 grams, hydroxyethyl methylacrylate 2 grams, double pentaerythritol C5 methacrylate 1.2 grams are dissolved in the 50 gram ethylene glycol monomethyl ethers, after the dissolving liquid is applied to 2cm * 2cm on the aluminium base version of electrolysis, oxide treatment, be coated with 1% polyvinyl alcohol water solution oxygen barrier again, 30 ℃～40 ℃ bakings of vacuum drying oven 24 hours can be prepared laser PS version photochromics.As light source, do mask with signal strips, light intensity 5mW/cm with the Argon ion laser of 514nm wavelength
2, shone 60 seconds, in the alkaline developer with the immersion of the PS version after the exposure 5%, developed 30 seconds, can get visual.
Claims (10)
1. coumarins dyestuff that connects with cyclanone is characterized in that: the molecular structure that described coumarins dyestuff has:
Wherein: A
1, A
2Be alkyl, alkoxyl group, amido, heterocycle or substituted-phenyl; A
1And A
2It is substituting group identical or inequality;
Described alkyl is a carbonatoms less than 15 alkyl;
Described alkoxyl group is a carbonatoms less than 15 alkoxyl group;
Described amido is: methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido or hexichol amido;
Described heterocyclic radical is: pyridine, pyrroles, thiazole or carbazole;
Described substituted-phenyl is selected from: adjacent, to, a position itrile group benzene, adjacent, to, a position chlorobenzene, adjacent, to, a position carboxyl benzene, adjacent, to, a position alkylbenzene, adjacent, to, a position alkoxy benzene, adjacent, to, a position amido benzene;
2. coumarins dyestuff as claimed in claim 1 is characterized in that: described carbonatoms is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or amyl group less than 15 alkyl; Described carbonatoms is methoxyl group, oxyethyl group, propoxy-, butoxy or pentyloxy less than 15 alkoxyl group.
3. the synthetic method of a coumarins dyestuff as claimed in claim 1, it is characterized in that: described method may further comprise the steps:
(1) has A
1Synthesizing of group semi-ring alkane ketone dyestuff
Reaction equation:
With naphthenic hydrocarbon ketone, the corresponding A that contains
1The aldehyde of group 1～6: 1 ratio in molar ratio joins in the reaction vessel, and adding mol ratio then is to have A
150～500 times of ethanol water mixed solutions of the aldehyde of group, adding mol ratio again is to have A
1The basic catalyst that the aldehyde of group is 0.01～0.40 times, the precipitation behind the filtering reaction adopts silicagel column to separate then and obtains corresponding A
1Semi-ring alkane ketone dyestuff;
(2) have A
2Synthesizing of group tonka bean camphor aldehyde
Reaction equation:
With corresponding 3 methyl substituted or 4 methyl substituted A that contain
2The tonka bean camphor of group and selenous acid join in another reaction vessel by 1: 1～2 mol ratio, and adding mol ratio then is to contain A
250～500 times of solvent refluxings of group tonka bean camphor after heat filtering is removed selenium, are separated out after the filtrate cooling and are contained A
2The crystal of group tonka bean camphor aldehyde;
(3) the coumarins dyestuff that connects with cyclanone is synthetic
Reaction equation:
Contain A with what step (1) made
1The semi-ring alkane ketone dyestuff of group and step (2) make contains A
2The tonka bean camphor aldehyde of group is that 1: 1 ratio joins in the reactor in molar ratio, is to have A with mol ratio then
2The volume ratio that the tonka bean camphor aldehyde of group is 100～500 times is that 5%～50% dimethylbenzene alcohol mixed solvent dissolves it, and adding mol ratio is to have A
1Reflux behind the basic catalyst that the semi-ring alkane ketone of group is 0.01～0.40 times, cooled and filtered precipitates, and precipitation can be obtained the coumarins dyestuff that connects with cyclanone with the dimethylbenzene recrystallization;
Wherein: A
1, A
2Be alkyl, alkoxyl group, amido, heterocycle or substituted-phenyl; A
1And A
2It is substituting group identical or inequality;
Described alkyl is a carbonatoms less than 15 alkyl;
Described alkoxyl group is a carbonatoms less than 15 alkoxyl group;
Described amido is: methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido or hexichol amido;
Described heterocyclic radical is: pyridine, pyrroles, thiazole or carbazole;
Described substituted-phenyl is selected from: adjacent, to, a position itrile group benzene, adjacent, to, a position chlorobenzene, adjacent, to, a position carboxyl benzene, adjacent, to, a position alkylbenzene, adjacent, to, a position alkoxy benzene, adjacent, to, a position amido benzene;
Be the structure of naphthenic hydrocarbon ketone, described naphthenic hydrocarbon ketone is selected from cyclopentanone, pimelinketone, suberone or cyclooctanone.
4. method as claimed in claim 3 is characterized in that: described carbonatoms is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or amyl group less than 15 alkyl; Described carbonatoms is methoxyl group, oxyethyl group, propoxy-, butoxy or pentyloxy less than 15 alkoxyl group.
5. method as claimed in claim 3 is characterized in that: described basic catalyst is sodium hydroxide, potassium hydroxide, Anhydrous potassium carbonate, anhydrous sodium carbonate, hexahydropyridine or their any mixture.
6. method as claimed in claim 3 is characterized in that: described step (1) ethanol water mixed solution concentration is 20～80wt%.
7. method as claimed in claim 3 is characterized in that: described step (1) temperature of reaction is 25 ℃～80 ℃.
8. method as claimed in claim 3 is characterized in that: described step (2) return time is 9～30 hours.
9. method as claimed in claim 3 is characterized in that: the described solvent of described step (2) is selected from dimethylbenzene, ethanol, acetonitrile, 1,4 one dioxane solvent or their any mixture.
10. purposes as each described coumarine dye of claim 1～2, it is characterized in that: form the visible light photopolymerization that photosensitized initiation system is used for the solution vinyl monomer as photosensitizers and other light trigger, or as photo-curing material, laser plate-making material and holographic storage material.
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| CNB2003101224995A CN1328273C (en) | 2003-12-26 | 2003-12-26 | Coumarin dyestuff linked by naphthene ketones, method for synthesis and use thereof |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469841C (en) * | 2005-12-27 | 2009-03-18 | 中国科学院理化技术研究所 | Coumarin dye connected by diphenyl ethylene and its synthesis method and use |
| CN101759815B (en) * | 2008-12-25 | 2011-12-28 | 中国科学院理化技术研究所 | Application of coumarin/or benzal naphthenic hydrocarbon ketone dyes in preparation of two-photon polymerized resin |
| CN102766349B (en) * | 2011-05-05 | 2013-11-20 | 中国科学院理化技术研究所 | Lipid-water amphiphilic coumarin dye, preparation method thereof and application in preparation of photodynamic therapy photosensitive drug |
| CN103232462B (en) * | 2013-05-13 | 2016-03-02 | 湖北科技学院 | The synthetic method of coumarin-pyrrole compound |
| CN103408554B (en) * | 2013-07-31 | 2015-07-08 | 西安交通大学 | Hypertensive activity reducing pyrrole coumarins compound and preparation method thereof |
| CN107200694B (en) * | 2016-03-16 | 2019-08-16 | 中国科学院理化技术研究所 | A kind of water soluble anion benzal cycloalkane ketone photosensitizer, preparation method and the application in light power anti-microbial infection |
| CN110078693B (en) * | 2019-04-30 | 2023-06-02 | 同济大学 | Alpha-hydroxy ketone compound containing coumarin and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0527383A2 (en) * | 1991-08-08 | 1993-02-17 | Bayer Ag | Mass dyeing of synthetic material |
| CN1105360A (en) * | 1993-11-02 | 1995-07-19 | 杜菲尔国际开发有限公司 | 1-[2H-1-benzopyran-2-one-8yl]-piperazin derivative |
| CN1138041A (en) * | 1995-02-21 | 1996-12-18 | 拜尔公司 | Coumarin derivatives, method of preparing them and their use as intermediates |
| CN1258698A (en) * | 2000-01-21 | 2000-07-05 | 大连理工大学 | Fluorescent coumarin dye |
| JP2002080822A (en) * | 2000-07-04 | 2002-03-22 | Hayashibara Biochem Lab Inc | Photofunctional material |
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- 2003-12-26 CN CNB2003101224995A patent/CN1328273C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0527383A2 (en) * | 1991-08-08 | 1993-02-17 | Bayer Ag | Mass dyeing of synthetic material |
| CN1105360A (en) * | 1993-11-02 | 1995-07-19 | 杜菲尔国际开发有限公司 | 1-[2H-1-benzopyran-2-one-8yl]-piperazin derivative |
| CN1138041A (en) * | 1995-02-21 | 1996-12-18 | 拜尔公司 | Coumarin derivatives, method of preparing them and their use as intermediates |
| CN1258698A (en) * | 2000-01-21 | 2000-07-05 | 大连理工大学 | Fluorescent coumarin dye |
| JP2002080822A (en) * | 2000-07-04 | 2002-03-22 | Hayashibara Biochem Lab Inc | Photofunctional material |
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