CN1634909A - 3- or 4- carbonyl substituted coumarin connected with naphthenones and its synthesis method and use - Google Patents
3- or 4- carbonyl substituted coumarin connected with naphthenones and its synthesis method and use Download PDFInfo
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- CN1634909A CN1634909A CNA2003101224980A CN200310122498A CN1634909A CN 1634909 A CN1634909 A CN 1634909A CN A2003101224980 A CNA2003101224980 A CN A2003101224980A CN 200310122498 A CN200310122498 A CN 200310122498A CN 1634909 A CN1634909 A CN 1634909A
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Abstract
The invention relates to a process for synthesizing 3- or 4- carbonyl substituted coumarin connected by naphthenones and its use. The preparation process using general aldol condensation reaction comprises cyclanone and its corresponding aldehyde compounds with A1 group are added in reactor to produce semi-cyclanone with A1 group; 3- or 4- acetyl substituted coumarin with A2 group and selenious acid are added in another reactor to produce coumarin aldehyde with A2 group; said semi-cyclanone with A1 group dye reacts with coumarin aldehyde with A2 group in the presence of xylene and ethanol mixed solvent to form 3- or 4- carbonyl substituted coumarin connected by naphthenones. The product can be used for visible light polymerization of olefine monomer in photosensitized initiation system and used as photo curing materials, etc.
Description
Invention field
The invention belongs to visible light photoactivated dye field, particularly relate to the preparation method and use of a class by the coumarin ketone of 3 or 4 carbonyl substituted of cyclanone connection.
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 coumarin ketone dyestuff, 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 coumarin ketone dyestuff that can be complementary with visible light optical maser wavelength commonly used.
A further object of the present invention provides the coumarin ketone of 3 or 4 carbonyl substituted that connect with cyclanone.Another object of the present invention provides a kind of synthetic method of coumarin ketone of 3 or 4 carbonyl substituted that connect by naphthenic hydrocarbon ketone.
The present invention goes back the purposes that a purpose provides the coumarin ketone of 3 or 4 carbonyl substituted that connect with cyclanone.
The coumarin ketone of 3 or 4 carbonyl substituted that connect 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 or neighbour, to, a position amido benzene etc.
Be the structure of naphthenic hydrocarbon ketone, described naphthenic hydrocarbon ketone comprises cyclopentanone, pimelinketone, suberone or cyclooctanone etc.
The synthetic method of the coumarin ketone dyestuff of 3 or 4 carbonyl substituted that connect with cyclanone provided by the invention may further comprise the steps:
(1) has A
1Synthesizing of group semi-ring alkane ketone dyestuff
Reaction equation:
Concrete steps:
Adopt common aldol reaction, with naphthenic hydrocarbon ketone, the corresponding described A that has
1The compound of group aldehyde 1～6: 1 ratio in molar ratio joins in the reaction vessel, and adding mol ratio then is the described A of containing
150～500 times in aldehyde of group and concentration are the ethanol water mixed solution of 20～80wt%, and adding mol ratio again is the described A of containing
1The basic catalyst that the aldehyde 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 had A accordingly
1The semi-ring alkane ketone dyestuff of group, standby.
(2) have A
2Synthesizing of group tonka bean camphor keto-aldehyde
Reaction equation:
Concrete steps:
Adopt common oxygenant selenous acid methyl oxidation to be become the method for aldehyde.The A that has with corresponding 3 ethanoyl replacement or 4 ethanoyl replacements
2The coumarin ketone compound of group and selenous acid join in another reaction vessel by 1: 1～2 mol ratio, and adding mol ratio then is the described A of having
2The solvent that the group coumarin ketone is 50～500 times refluxed 9～30 hours, after heat filtering is removed selenium, separated out A after the filtrate cooling
2The crystal of tonka bean camphor keto-aldehyde, standby.
(3) coumarin ketone of 3 or 4 carbonyl substituted that connect with cyclanone is synthetic
Reaction equation:
Concrete steps:
Have an A with what step (1) made
1Group semi-ring alkane ketone dyestuff and step (2) make has A
2Group tonka bean camphor keto-aldehyde 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
2Group tonka bean camphor keto-aldehyde is that 1: 1 ratio joins in the reactor in molar ratio, is to have A with mol ratio then
1The volume ratio that group semi-ring alkane ketone is 100～500 times is that 5%～50% dimethylbenzene/ethanol mixed solvent is dissolved it, and adding mol ratio 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 coumarin ketone with 3 or 4 carbonyl substituted of 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 coumarin ketone of 3 or 4 carbonyl substituted that connect 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 trigger 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 coumarin ketone dyestuff of 3 or 4 carbonyl substituted that connect with cyclanone is a 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%
Coumarin ketone dyestuff (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 coumarin ketone dyestuff 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 are 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, 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 salt compounds, two imidazoles, organometallic compound, organoboron compound, Benzophenones, various alkyl replacement thioxanthone, 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 coumarin ketone dyestuff of 3 or 4 carbonyl substituted that connect 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%
Coumarin ketone dyestuff (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 coumarin ketone dyestuff 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 salt compounds, two imidazoles, organometallic compound, organoboron compound, Benzophenones, various alkyl replacement thioxanthone, 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 coumarin ketone dyestuff of 3 or 4 carbonyl substituted that connect 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%
Coumarin ketone dyestuff (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 coumarin ketone dyestuff 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 concentration 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) synthetic method of the coumarin ketone dyestuff of 3 or 4 carbonyl substituted that connect with cyclanone of the present invention and separate fairly simplely, raw material sources conveniently are easy to get, and wherein have A
2The tonka bean camphor keto-aldehyde of group with have an A
1The semi-ring alkane ketone of group all can be synthetic by ordinary method, only needs then to have A
1With A
2Corresponding aldehyde ketone condensation under alkaline condition of group just can make new dye of the present invention, and productive rate is higher.
(2) the present invention covers broad with the absorption bands of the coumarin ketone dyestuff of 3 or 4 carbonyl substituted of cyclanone connection, 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) the coumarin ketone dyestuff of 3 or 4 carbonyl substituted connecting with cyclanone of the present invention is triplet state sensitizing dyves efficiently, it can with multiple initiator coupling, form visible light initiated polymerization system efficiently.
(4) contain the higher photoreduction coumarin ketone species of efficiency of initiation in the coumarin ketone dye structure of the present invention with 3 or 4 carbonyl substituted of cyclanone connection, simultaneously contain triplet state naphthenic hydrocarbon ketone efficiently again, so dyestuff itself has initiated polymerization efficient efficiently.
Embodiment
Embodiment 1
The coumarin ketone (CP-KETOCOU) of 3 or 4 carbonyl substituted that connect 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 hexahydropyridine, 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-ethanoyl-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 red needle-like crystal; filter and promptly obtain pure product 4-ketaldonyl 5-pyrryl tonka bean camphor, productive rate 70%.
(3) the half 4-ketaldonyl 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 sodium hydroxide ethanolic soln 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 coumarin ketone dyestuff CP-KETOCOU that pure product connect with cyclopentanone, productive rate 45% with the dimethylbenzene recrystallization.
Embodiment 2
The coumarin ketone (CHE-KETOCOU) of 3 or 4 carbonyl substituted that connect 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 10wt%NaOH aqueous solution, 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-ethanoyl-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-ketaldonyl-ayapanin, productive rate 84%.
(3) the half 2-ethyl cyclohexanone dyestuff of above-mentioned synthetic 1 mmole and the 3-ketaldonyl-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 coumarin ketone dyestuff CHE-KETOCOU that pure product connect with pimelinketone, productive rate 42% with the dimethylbenzene recrystallization.
Embodiment 3
The coumarin ketone (CHP-KETOCOU) of 3 or 4 carbonyl substituted that connect 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 milliliter 1,4-dioxane heating for dissolving, back flow reaction 24 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out red crystals, filter and promptly obtain pure product 3-ketaldonyl-6-phenyl tonka bean camphor, productive rate 80%.
(3) the half 3-ketaldonyl-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 coumarin ketone CHP-KETOCOU that pure product connect with suberone, productive rate 35% with the dimethylbenzene recrystallization.
Embodiment 4
The coumarin ketone (COC-KETOCOU) of 3 or 4 carbonyl substituted that connect 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-ethanoyl-8-phenoxy group tonka bean camphor, the 20 mmole selenous acid with 10 mmoles place flask; add 80 milliliters of acetonitrile heating for dissolving; back flow reaction 28 hours, heat filtering is removed the selenium of grey black, filtrate is left standstill cooling separate out red needle-like crystal; filter and promptly obtain pure product 4-ketaldonyl 8-phenoxy group tonka bean camphor, productive rate 72%.
(3) the semibenzene benzothiazolyl cyclooctanone dyestuff of above-mentioned synthetic 1 mmole and the 4-ketaldonyl 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 novel coumarin dyestuff COC-KETOCOU that pure product connect with cyclooctanone, productive rate 30% with the dimethylbenzene recrystallization.
Embodiment 5
Tonka bean camphor ketone 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 coumarin ketone CP-KETOCOU0.1 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
Tonka bean camphor ketone 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 coumarin ketone CHE-KETOCOU, 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
Tonka bean camphor ketone 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 coumarin ketone dyestuff CHP-KETOCOU and 0.2g lauryl mercaptans, 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 tonka bean camphor ketone dyestuff in laser PS version
Hexa-aryl bi-imidazole 0.3 gram, lauryl mercaptan 0.4 gram, embodiment 4 synthetic coumarin ketone dyestuff COC-KETOCOU 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 1wt% 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, the PS version after the exposure is immersed in the alkaline developer of 5wt%, developed 30 seconds, can get visual.
Claims (8)
1. the coumarin ketone of 3 or 4 carbonyl substituted that connect with cyclanone, it is characterized in that: the molecular structure of described coumarin ketone is:
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: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms are less than 15 alkyl;
Described alkoxyl group is: methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms are 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, hexichol amido, substituted diphenylamine or quaternary ammonium salt base;
Described heterocyclic radical is: pyridine, pyrroles, thiazole, carbazole, cyanines class, coumarins or ammonium salt;
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 or neighbour, to, a position amido benzene;
2. the synthetic method of a coumarin ketone 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
With naphthenic hydrocarbon ketone, the corresponding 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 described A
1The ethanol water mixed solution that the aldehyde of group is 50～500 times, adding mol ratio again is described A
1The basic catalyst that group aldehyde 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, standby;
(2) have A
2Synthesizing of group tonka bean camphor keto-aldehyde
The A that has with corresponding 3 ethanoyl replacement or 4 ethanoyl replacements
2Group coumarin ketone and selenous acid join in another reaction vessel by 1: 1～2 mol ratio, and adding mol ratio then is described A
2The solvent refluxing that the group coumarin ketone is 50～500 times, remove by filter selenium after, separate out after the filtrate cooling and have A
2The crystal of group tonka bean camphor keto-aldehyde, standby;
(3) coumarin ketone of 3 or 4 carbonyl substituted that connect with cyclanone is synthetic
Have an A with what step (1) made
1The semi-ring alkane ketone dyestuff of group and step (2) make has A
2Group tonka bean camphor keto-aldehyde is that 1: 1 ratio joins in the reactor in molar ratio, is described A with mol ratio then
1The volume ratio that group semi-ring alkane ketone is 100～500 times is that 5%～50% dimethylbenzene/ethanol mixed solvent is dissolved it, and adding mol ratio is to have A
1The basic catalyst that group semi-ring alkane ketone is 0.01～0.40 times refluxes, the cooled and filtered precipitation; Precipitation can be obtained coumarin ketone with 3 or 4 carbonyl substituted of cyclanone connection 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: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms are less than 15 alkyl;
Described alkoxyl group is: methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms are 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, hexichol amido, substituted diphenylamine or quaternary ammonium salt base;
Described heterocyclic radical is: pyridine, pyrroles, thiazole, carbazole, cyanines class, coumarins or ammonium salt;
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 or neighbour, to, a position amido benzene;
3. the method for claim 1, it is characterized in that: described basic catalyst is sodium hydroxide, potassium hydroxide, Anhydrous potassium carbonate, anhydrous sodium carbonate, hexahydropyridine or their any mixture.
4. the method for claim 1, it is characterized in that: described step (1) ethanol water mixed solution concentration is 20～80wt%.
5. the method for claim 1, it is characterized in that: described step (1) temperature of reaction is 25 ℃～80 ℃.
6. the method for claim 1, it is characterized in that: described step (2) return time is 9～30 hours.
7. the method for claim 1, it is characterized in that: the described solvent of described step (2) comprises dimethylbenzene, ethanol, acetonitrile, 1,4-dioxane solvent or their any mixture.
8. the purposes of a coumarin ketone dyestuff as claimed in claim 1, 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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Cited By (8)
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| 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 |
| CN101368003B (en) * | 2007-08-15 | 2011-09-14 | 中国科学院理化技术研究所 | Pyrazoline pyridine-fluorescent coumarin dye derivant, synthesis and uses thereof |
| 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 |
| CN102344504A (en) * | 2011-07-29 | 2012-02-08 | 华中科技大学 | Visible light photoinitiation system for preparing high diffraction efficiency holographic photopolymer material |
| CN101525497B (en) * | 2008-03-06 | 2012-07-04 | 中国科学院理化技术研究所 | Pyrazoline naphthyridine benzocoumarin fluorescent dye derivatives, synthesis method of same, and application of same |
| CN104877057A (en) * | 2014-12-04 | 2015-09-02 | 重庆大学 | Coumarin fragment-containing benzotriazole photosensitizer and its synthesis and use |
| CN107200694A (en) * | 2016-03-16 | 2017-09-26 | 中国科学院理化技术研究所 | A kind of water soluble anion benzal cycloalkane ketone sensitising agent, preparation method and the application in light power anti-microbial infection |
| CN111601795A (en) * | 2017-12-14 | 2020-08-28 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketones |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1111190C (en) * | 2000-01-21 | 2003-06-11 | 大连理工大学 | Fluorescent coumarin dye |
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| 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 |
| CN101368003B (en) * | 2007-08-15 | 2011-09-14 | 中国科学院理化技术研究所 | Pyrazoline pyridine-fluorescent coumarin dye derivant, synthesis and uses thereof |
| CN101525497B (en) * | 2008-03-06 | 2012-07-04 | 中国科学院理化技术研究所 | Pyrazoline naphthyridine benzocoumarin fluorescent dye derivatives, synthesis method of same, and application of same |
| 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 |
| CN102344504A (en) * | 2011-07-29 | 2012-02-08 | 华中科技大学 | Visible light photoinitiation system for preparing high diffraction efficiency holographic photopolymer material |
| CN102344504B (en) * | 2011-07-29 | 2013-03-13 | 华中科技大学 | Visible light photoinitiation system for preparing high diffraction efficiency holographic photopolymer material |
| CN104877057A (en) * | 2014-12-04 | 2015-09-02 | 重庆大学 | Coumarin fragment-containing benzotriazole photosensitizer and its synthesis and use |
| CN107200694A (en) * | 2016-03-16 | 2017-09-26 | 中国科学院理化技术研究所 | A kind of water soluble anion benzal cycloalkane ketone sensitising agent, preparation method and the application in light power anti-microbial infection |
| 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 |
| CN111601795A (en) * | 2017-12-14 | 2020-08-28 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketones |
| CN111601795B (en) * | 2017-12-14 | 2024-03-19 | 意大利艾坚蒙树脂有限公司 | Water-soluble 3-coumarin ketone |
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