CN101941920B - Aromatic ketone oxime photoinitiator compound - Google Patents

Aromatic ketone oxime photoinitiator compound Download PDF

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CN101941920B
CN101941920B CN201010233204.1A CN201010233204A CN101941920B CN 101941920 B CN101941920 B CN 101941920B CN 201010233204 A CN201010233204 A CN 201010233204A CN 101941920 B CN101941920 B CN 101941920B
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CN101941920A (en
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张永波
赵新阳
王衍超
王智刚
宋怀海
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Hubei Youwei New Material Co ltd
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SHENZHEN YOUWEI CHEMICAL TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of compounds with a general formula of I-VIII. The compounds can be singly used as an alkene unsaturated system photopolymerization initiator and also can be combined with another photoinitiator and/or other additives.

Description

Aromatic ketone oxime photoinitiator compound
[technical field]
The present invention relates to some new lists or bifunctional aromatic ketone oxime compounds and this compounds purposes as alkene unsaturated system radical polymerization light trigger.The feature of this compounds be not only in structure containing the crucial group of common C=N-O, and preparation technology uses identical substrate.
[background technology]
Oxime ester compound enlivens as light trigger Recent study, existing more patent literature, such as patent CN1514845A, CN1720245A, CN101014569A, CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A, US3558309, US4255513, US6596445B1, JP2010024296A, and WO2010052882A1, WO2008138733A1, WO0052530A1, WO2007071497A1, WO2009019173A1, WO2009147031A2, WO2009147033A1.But, although oxime ester compound as light trigger last century the seventies have bibliographical information (European Polymer Journal, 1970,6,933), and occurred that business-like product was as Quantacure PDO in early days, really with practical value little, this mainly such compound stability and active over-all properties usually not good enough.Therefore, research and develop and new there is high initiating activity, easily prepare, thermostability and stability in storage good, the particularly with low cost and light trigger of easy handling remains the direction that photopolymerization field is worth exploring.In addition, although oxime ester compound report is more, there is not been reported as novel cpd classification for fragrant ketoxime ether.
[summary of the invention]
The invention discloses the compound that a structural general formula is (I-VIII), this compound can use as light trigger separately, also can be used as the light trigger of the light polymerization of unsaturated allyl compound or the mixture containing unsaturated allyl compound.
The feature of this compounds has list (general formula I and II) or disubstituted fragrant ketoxime ether or ketoxime ester molecular structure (general formula III-VIII), wherein Ar 1and Ar 2a substituted or unsubstituted aromatic group containing 6-32 carbon atom or the aromatic group containing heteroatoms (nitrogen or sulphur) independently of one another; R 1and R 2be the alkyl substituent containing 1-24 carbon atom of hydrogen or straight or branched independently of one another, this substituting group can by 1-6 oxygen, nitrogen, or sulphur atom interval, and this substituting group can contain substituted aryl, or containing having the ring of 3-8 carbon atom; R 1and R 2, or Ar 1and R 1or R 2; Or Ar 2and R 3, or Ar 1and R 1or R 2a ring texture can be formed; Q is a divalence connecting structure containing 1-32 carbon atom.R 3hydrogen, CN, CF 3, CF 2r 1, CFR 1r 2, or Ar 1; R 4hydrogen, CF 3, CF 2h, CFH 2, the straight or branched containing 1-12 carbon atom, ring-type or acyclic alkyl substituting group, or Ar 1; R 5hydrogen, trialkyl or alkoxysilyl group, or the straight or branched containing 1-12 carbon atom, ring-type or acyclic alkyl substituting group; N value 1 or 2, as n=1, X is Ar 1, as n=2, X is Q.
Above-claimed cpd can use as initiator separately, also can be combined with another kind of light trigger and/or with other additive.
The compound that the present invention proposes has high initiating activity as light trigger, easily prepares, thermostability and the good feature of stability in storage, in addition, and easy handling, and with low cost.
[embodiment]
The invention provides some lists or bifunctional fragrance ketoxime ether (I, III, IV) and ketoxime ester (II and V-VIII) compound and contain the light trigger of this compound.These compounds can easily from the industrial hydroxyketone that is easy to get or the preparation of bromo ketone raw material, their feature be not only in structure containing the crucial group of common C=N-O, and preparation technology uses identical substrate.Above-claimed cpd has following general structure (I-VIII):
In these general formulas, Ar 1and Ar 2a substituted or unsubstituted aromatic group or the aromatic group containing heteroatoms (nitrogen or sulphur) independently of one another; As this aromatic group Ar 1or Ar 2when not replaced by extra group, it is preferably as follows structure:
As this aromatic group Ar 1or Ar 2when being replaced by the individual separate extra group Y of 1-6, Y can be F, Cl, Br, I, Ph, CN, NO 2, PPh 2, O=PPh 2, CF 3, CF 2r, CFR 2, R, OR, SR, SOR, SO 2r, NHR, NR 2deng group, R represents the alkyl of a straight or branched containing 1-24 carbon atom here, or R represents a substituted or unsubstituted aromatic ring containing 6-24 carbon atom.
R 1and R 2be the alkyl substituent containing 1-24 carbon atom of hydrogen or straight or branched independently of one another, this substituting group can be 1-6 oxygen, nitrogen, or sulphur atom interval, and this substituting group can contain substituted aryl, or containing having the ring of 3-8 carbon atom; R 1and R 2, or Ar 1and R 1or R 2; Or Ar 2and R 3, or Ar 1and R 1or R 2a ring texture can be formed; Q is a divalence connecting structure containing 1-32 carbon atom, is preferably as follows structure:
R 3hydrogen, CN, CF 3, CF 2r 1, CFR 1r 2, or Ar 1; R 4hydrogen, CF 3, CF 2h, CFH 2, the straight or branched containing 1-12 carbon atom, ring-type or acyclic alkyl substituting group, or Ar 1; R 5hydrogen, trialkyl or alkoxysilyl group, or the straight or branched containing 1-12 carbon atom, ring-type or acyclic alkyl substituting group; N=1 or 2, as n=1, X is Ar 1, as n=2, X is Q.
Above-claimed cpd can be used alone, and also can be combined with another kind of light trigger and/or with other additive.
The compound of diagram I-VIII is because the existence of C=N double bond may produce cis-trans-isomer in preparation process, and they usually can directly use without separation.
The present invention discloses the preparation method of general formula I-VIII compound simultaneously, and these methods depend on some new reaction process, and with regard to each unit process that flow process relates to, then, known by the scientific and technical personnel of this area, can use easily.
The compound of general formula I can generate epoxy intermediate via bromo arone 1 and MeONa reaction, and this intermediate carries out epoxy addition again and obtains under oxime 2 participates in; Effectively more convenient, oxime 2 and sodium hydride can be reacted its sodium salt obtained in advance, this sodium salt reacts with bromo arone 1 and generates target product.
The compound of general formula I I can be converted into acyl chlorides 4 in advance via hydroxyl arone 3, acyl chlorides 4 again with oxime 2 under alkali effect condensation obtain, conventional alkali comprises triethylamine, pyridine, or salt of wormwood.
The compound of general formula III can obtain via the mechanism course similar to compound of Formula I from two bromo arone 5 of difunctionality dough with the oxime 2 of doubling dose.
The compound of general formula I V can obtain via the mechanism course similar to compound of Formula I from the two oxime 6 of the arone of difunctionality dough with the bromo arone 1 of doubling dose.
The compound of general formula V can obtain via the mechanism course similar to Compounds of formula II from the acyl chlorides 7 of difunctionality dough with the oxime 2 of doubling dose.
The compound of general formula VI can obtain via the mechanism course similar to Compounds of formula II from the two oxime 6 of the arone of difunctionality dough with the acyl chlorides 4 of doubling dose.
The compound of general formula VII can replace from hydroxyl or alcoxyl replaces ketone 8 and the leading oximate of oxammonium hydrochloride, then with acyl chlorides R 4c (O) C1 carries out esterification and obtains.
The compound of general formula VIII can directly carry out esterification from benzoyl formyl chloride 9 and oxime 2 and obtain alkali promotes.
Concrete reaction equation is as follows:
The oxime ether represented as above-mentioned general formula I-VIII and the preferred example of oxime ester compound, following compound structure can be listed, but, following exemplary construction is only the representative oxime ester compound of aid illustration, the compound that the present invention is contained is as the criterion with claims, and not by any restriction of these exemplary construction.
There is the compound of general formula I including, but not limited to following example arrangement:
There is the compound of general formula I I including, but not limited to following example arrangement:
There is the compound of general formula III including, but not limited to following example arrangement:
There is the compound of general formula I V including, but not limited to following example arrangement:
There is the compound of general formula V including, but not limited to following example arrangement:
There is the compound of general formula VI including, but not limited to following example arrangement:
There is the compound of general formula VII including, but not limited to following example arrangement:
As n=1:
As n=2:
There is the compound of general formula VII including, but not limited to following example arrangement:
As n=1:
As n=2:
Illustrate concrete preparation method and the photocuring application of above-claimed cpd below.
Embodiment one: (E)-2-methyl isophthalic acid-phenyl-2-(((1-phenylethyl alkene) amine) oxygen)-propane-1-ketone:
Under nitrogen protection; 7.3 grams of (E)-acetophenone oximes are placed in 120 milliliters of dry DMSO; be cooled to zero degree; slowly 2.6 grams of NaH (powder of 60% mineral oil dispersion) are added under stirring; after half an hour; add 14.6 grams of 2-bromo-2-methyl isophthalic acid-phenyl-propane-1-ketone in batches, finish stirring reaction 1 hour, be warming up to room temperature and react 2 hours again.Reaction solution pours in 300 ml waters slowly, equal-volume extraction into ethyl acetate 2 times, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filter, steaming desolventizes, resistates on silica gel column chromatography with pure hexane for eluent obtains target compound (12.6 grams, 83% yield), pale yellow oily liquid body, slowly solidifies in placement.
In this compound, C=N double bond cis-trans-isomer ratio is (Z): (E)=1: 4.
Proton nmr spectra 1h NMR (CDCl 3):
8.27(d，2H)，7.50-7.31(m，3H)，7.30-7.22(5H)，2.33(s，3H)，1.77ppm(s，6H)；
Carbon-13 nmr spectra 13c NMR (CDCl 3):
202.0，154.5，136.2，135.5，131.9，129.9，129.6，129.0，128.1，127.9，125.9，87.1，25.1，12.6ppm；
Ultimate analysis (molecular formula C 18h 19nO 2):
Theoretical value: carbon, 76.84%; Hydrogen, 6.81%; Nitrogen, 4.98%;
Measured value: carbon, 76.93%; Hydrogen, 6.96%; Nitrogen, 5.03%.
Embodiment two: (E)-2-methyl isophthalic acid-phenyl-2-(((((1-phenylethyl alkene) amine) oxygen) carbonyl) oxygen)-propane-1-ketone:
Under nitrogen protection, by 11.3 grams of Irgacure, 1173,15 milliliters of dry pyridines, and 130 milliliters of chloroform mixing, be cooled to zero degree, slowly add 29.1 grams of (Cl 3cO) 2c=O, finishes stirring reaction half an hour, is warming up to room temperature and reacts 2 hours again.In this system, add 11.2 grams of (E)-acetophenone oximes in batches, add 9 milliliters of pyridines, continue reaction 8 hours, with thin-layer chromatography tracking monitor reaction end.Reaction solution pours in 250 ml waters slowly, with 80 milliliters of chloroform dilutions, jolting is separated organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filters, steaming desolventizes, resistates on silica gel column chromatography with 9:1 hexane/ethyl acetate for eluent obtains target compound (14.1 grams, 63% yield), pale yellow oily liquid body.
In this compound, C=N double bond cis-trans-isomer ratio is (Z): (E)=1: 9.
Proton nmr spectra 1h NMR (CDCl 3):
8.05(d，2H)，7.60-7.26(m，8H)，2.31(s，3H)，1.66ppm(s，6H)；
Ultimate analysis (molecular formula C 19h 19nO 4):
Theoretical value: carbon, 70.14%; Hydrogen, 5.89%; Nitrogen, 4.31%;
Measured value: carbon, 70.26%; Hydrogen, 5.99%; Nitrogen, 4.43%.
Embodiment three: (E)-1,1 '-(sulphur two (4,1-phenyl alkene)) two (2-methyl-2-(((E)-(1-phenylethyl alkene) amine) oxygen) propane-1-ketone:
Under nitrogen protection; 10.1 grams of (E)-acetophenone oximes are placed in 180 milliliters of dry DMSO; be cooled to zero degree; slowly add 3.6 grams of NaH (powder of 60% mineral oil dispersion) under stirring, after 1 hour, add 18.1 gram 1 in batches; 1 '-(sulphur two (4; 1-phenyl alkene)) two (the bromo-2-methylpropane of 2--1-ketone), finish stirring reaction 2 hours, be warming up to room temperature and react 4 hours again.Reaction solution pours in 500 ml waters slowly, equal-volume extraction into ethyl acetate 2 times, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filter, steaming desolventizes, and resistates is that eluent obtains target compound (11.7 grams, 53% yield) with 12: 1 hexane/ethyl acetate on silica gel column chromatography, yellow oily liquid, slow paste solidification in placement.
What be separated in this compound is pure C=N double bond trans-isomer(ide).
Proton nmr spectra 1h NMR (d 6-DMSO):
8.01-7.52(m，10H)，7.79(d，4H)，7.52(d，4H)，2.80(s，6H)，1.53ppm(s，6H)；
Ultimate analysis (molecular formula C 36h 36n 2sO 4):
Theoretical value: carbon, 72.95%; Hydrogen, 6.12%; Nitrogen, 4.73%;
Measured value: carbon, 73.07%; Hydrogen, 6.38%; Nitrogen, 4.78%.
Embodiment four: 2,2 '-(((1E, 1 ' E)-((sulphur two (4,1-phenyl alkene)) two (ethane-1-base-1-base alkene)) two (azepine base alkene)) two (oxygen)) two (2-methyl isophthalic acid-phenyl-propane-1-ketone):
Under nitrogen protection; two for 5.8 grams of diphenyl sulfides acetophenone oxime is placed in 90 milliliters of dry DMSO; be cooled to zero degree; slowly 1.9 grams of NaH (powder of 60% mineral oil dispersion) are added under stirring; after half an hour; add 9.6 grams of 2-bromo-2-methyl isophthalic acid-phenyl-propane-1-ketone in batches, finish stirring reaction 1 hour, be warming up to room temperature and react 2 hours again.Reaction solution pours in 300 ml waters slowly, equal-volume extraction into ethyl acetate 2 times, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filters, steaming desolventizes, resistates on silica gel column chromatography with pure hexane for eluent obtains target compound (7.0 grams, 61% yield), yellow blocks of solid.
What be separated in this compound is pure C=N double bond trans-isomer(ide).
Ultimate analysis (molecular formula C 36h 36n 2sO 4):
Theoretical value: carbon, 72.95%; Hydrogen, 6.12%; Nitrogen, 4.73%;
Measured value: carbon, 73.01%; Hydrogen, 6.47%; Nitrogen, 4.89%.
Embodiment five: (E)-1,1 '-(methyl alkene two (4,1-phenyl alkene)) two (2-methyl-2-(((((E)-(1-phenylethyl alkene) amine) oxygen) carbonyl) oxygen)-propane-1-ketone):
Under nitrogen protection, by 28.1 grams of Irgacure, 127,18 milliliters of dry pyridines, and 340 milliliters of chloroform mixing, be cooled to zero degree, slowly add 36.2 grams of (Cl 3cO) 2c=O, finishes stirring reaction 1 hour, is warming up to room temperature and reacts 4 hours again.In this system, add 14.6 grams of (E)-acetophenone oximes in batches, add 11 milliliters of pyridines, continue reaction 14 hours, with thin-layer chromatography tracking monitor reaction end.Reaction solution pours in 800 ml waters slowly, with 150 milliliters of chloroform dilutions, jolting is separated organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filters, steaming desolventizes, resistates is that eluent obtains target compound (31.2 grams, 57% yield), pale yellow oily liquid body with 9: 1 hexane/ethyl acetate on silica gel column chromatography.
Ultimate analysis (molecular formula C 39h 38n 2o 8):
Theoretical value: carbon, 70.68%; Hydrogen, 5.78%; Nitrogen, 4.23%;
Measured value: carbon, 70.90%; Hydrogen, 5.93%; Nitrogen, 4.55%.
Embodiment six: (E)-1,1 '-(methyl alkene two (4,1-phenyl alkene)) two (2-methyl-2-(((((E)-(1-(4-((4-nitrophenyl) sulphur) phenyl) ethyl alkene) amine) oxygen) carbonyl) oxygen)-propane-1-ketone):
The first step: p-nitro-to ' synthesis of-ethanoyl-diphenyl sulfide: under nitrogen protection; by 23.3 grams of p-nitro-diphenyl sulfides and 130 milliliters of dry dithiocarbonic anhydride mixing; add 8.6 grams of Acetyl Chloride 98Min.s; under mixture of ice and water cooling; slowly add 40 grams of aluminum trichloride (anhydrous) powder; system was progressively warmed up to backflow in 2 hours, kept back flow reaction to spend the night.Reaction solution is cooled to room temperature, pours in the mixture of frozen water and 1N dilute hydrochloric acid, is separated dithiocarbonic anhydride phase, anhydrous magnesium sulfate drying, steams the residue from ethanol recrystallization desolventized and obtains solid product 7.3 grams for 2 times, fusing point 116-117 DEG C.
Second step: the synthesis to (p-nitro-diphenyl sulfide) acetophenone oxime: adopt common oximation reaction condition; get 6.8 grams of above-mentioned p-nitros-to ' oxammonium hydrochloride of-ethanoyl-diphenyl sulfide sterling and 1.2 equivalents reacts in ethanol; purify with ethyl alcohol recrystallization; obtain 5.6 grams to (p-nitro-diphenyl sulfide) acetophenone oxime solid product, fusing point 167-169 DEG C.
3rd step: with reference to the reaction conditions of embodiment five, obtains 3.7 grams, the yellow solid product of 41% yield by above-mentioned 5.4 grams to (p-nitro-diphenyl sulfide) acetophenone oxime substrate and the derivative acyl chlorides condensation of 3.2 grams of Irgacure 127.
Ultimate analysis (molecular formula C 51h 44n 4o 12s 2):
Theoretical value: carbon, 63.21%; Hydrogen, 4.58%; Nitrogen, 5.78%;
Measured value: carbon, 63.72%; Hydrogen, 4.77%; Nitrogen, 5.95%.
Embodiment seven: 2,2 '-(((((1E, 1 ' E)-((methyl alkene two (4,1-phenyl alkene)) two (ethane-1-base-1-base alkene)) two (azepine base alkene)) two (oxygen)) two (carbonyl)) two (oxygen)) two (1-(4-p-methoxy-phenyl)-2-methylpropane-1-ketone):
Under nitrogen protection, by 27.1 grams of Irgacure, 1173,33 milliliters of dry pyridines, and 400 milliliters of chloroform mixing, be cooled to zero degree, slowly add 62.4 grams of (Cl 3cO) 2c=O, finishes stirring reaction 1 hour, is warming up to room temperature and reacts 3 hours again.In this system, add 23.4 gram 4, the two acetophenone oxime of 4 '-ditane, adds 16 milliliters of pyridines, continues stirring reaction and spends the night in batches.Reaction solution pours in 700 ml waters slowly, with 150 milliliters of chloroform dilutions, jolting is separated organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filters, steaming desolventizes, resistates obtains target compound (35.4 grams, 51% yield) with hexane and 9: 1 hexane/ethyl acetate tonsure drip washing on silica gel column chromatography, faint yellow cream solid.
High resolution mass spectrum HRMS (molecular formula+H=C 41h 43n 2o 10):
Theoretical value: 723.2918; Measured value: 723.2937.
Embodiment eight: 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone-O-acetyl oxime:
Under nitrogen protection, by 9.3 grams of Irgacure1173,15.6 grams of Anhydrous potassium carbonates, 5.2 grams of oxammonium hydrochlorides are mixed in 250 milliliters of absolute ethanol, back flow reaction 12 hours.After ethanol is concentrated, reaction system is cooled to room temperature, pour in 300 ml waters, with equal-volume extraction into ethyl acetate 3 times, combining extraction liquid, saturated common salt water washing once, anhydrous sodium sulfate drying, filter, decompression is spin-dried for solvent, vacuum-drying gained solid directly and 3.6 grams of Acetyl Chloride 98Min.s 150 milliliters of dry ethylene dichloride mixing, add 5 milliliters of dry pyridines, first react 1 hour in stirring at room temperature, faint back flow reaction 1 hour, be cooled to room temperature, use semi-saturation brine It, anhydrous magnesium sulfate drying, filter, be spin-dried for solvent, resistates obtains target compound (4.6 grams with 6: 1 hexane/ethyl acetate tonsure drip washing on silica gel column chromatography, 37% yield), faint yellow mucus.
Proton nmr spectra 1h NMR (CDCl 3, ppm):
7.41-7.39(m，3H)，7.17-7.14(m，2H)，3.68(br，1H)，1.92(s，3H)，1.46(s，6H)。
Carbon-13 nmr spectra 13c NMR (CDCl 3, ppm):
171.6，168.4，131.7，128.7，128.0，126.9，73.3，28.1，19.3。
High resolution mass spectrum HRMS (molecular formula+H=C 12h 16nO 3):
Theoretical value: 222.1130; Measured value: 222.1146.
Embodiment nine: 2-butoxy-1-(4-p-methoxy-phenyl)-2-methylpropane-1-ketone-O-acetyl oxime:
The first step: the synthesis of 2-butoxy-1-(4-p-methoxy-phenyl)-2-methylpropane-1-ketone: under nitrogen protection; 8.8 grams of 2-hydroxyl-1-(4-p-methoxy-phenyl)-2-methylpropane-1-ketone are placed in 120 milliliters of dry DMF; be cooled to zero degree; slowly add 2.2 grams of NaH (powder of 60% mineral oil dispersion); after half an hour; drip 6.8 grams of 1-n-butyl bromide, finish stirring reaction 1 hour, be warming up to room temperature and react 1 hour again.Reaction solution pours in 300 ml waters slowly, equal-volume extraction into ethyl acetate 2 times, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filter, steaming desolventizes, resistates obtains target compound (9.4 grams, 83% yield) with pure hexane and 8: 1 hexane/ethyl acetate tonsure drip washing on silica gel column chromatography.
Be worth it is specifically intended that this butoxy ether ketone intermediate self is also effective Photoepolymerizationinitiater initiater.
Second step: with reference to the reaction conditions of embodiment eight, get above-mentioned 8.5 grams of obtained 2-butoxy-1-(4-p-methoxy-phenyl)-2-methylpropane-1-ketone and 9.4 grams of Anhydrous potassium carbonates, 3.1 grams of oxammonium hydrochlorides are mixed in 200 milliliters of absolute ethanol and react, oxime intermediate again with the 2.2 grams of Acetyl Chloride 98Min.s generated and 3.5 milliliters of dry pyridines react in 120 milliliters of dry ethylene dichloride, obtain product 4.5 grams, 43% yield.
High resolution mass spectrum HRMS (molecular formula+H=C 17h 26nO 4):
Theoretical value: 308.1862; Measured value: 308.1877.
Embodiment ten: (E)-1-phenyl-2-(((1-phenylethyl alkene) amido) oxygen) ethane-1,2-diketone:
Under nitrogen protection, by 2.8 grams of acetophenone oximes and 120 milliliters of dry methylene dichloride mixing, at room temperature another 3.8 grams of benzoyl formyl chlorides are added dropwise to said mixture with after 15 milliliters of dchloromethane, after stirring reaction spends the night, reaction solution pours in 200 ml waters slowly, be separated organic phase, aqueous phase uses equal-volume dichloromethane extraction 2 times again, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filter, steaming desolventizes, resistates obtains target compound (4.1 grams with pure hexane and 10: 1 hexane/ethyl acetate gradient elutions on silica gel column chromatography, 74% yield).
Proton nmr spectra 1h NMR (d 6-DMSO):
7.88-7.35(m，10H)，2.97(s，3H)ppm；
Carbon-13 nmr spectra 13c NMR ((d 6-DMSO):
185.6，162.3，159.4，135.6，133.9，132.8，132.2，129.6，129.1，128.4，121.6，26.8ppm；
High resolution mass spectrum HRMS (molecular formula+H=C 17h 26nO 4):
Theoretical value: 268.0974; Measured value: 268.0986.
Embodiment 11: (E)-2,2 '-(methylene-bis (4,1-phenyl alkene)) two (1-(((E)-(1-1-phenylethyl alkene) amido) oxygen) ethane-1,2-diketone:
Under nitrogen protection, by 2.8 grams of acetophenone oximes and 120 milliliters of dry methylene dichloride mixing, at room temperature another by (initial via diacetyl-SeO from ditane for 14.2 grams of ditane formyl formyl chlorides 2oxidation-SOCl 2prepared by chloride, Bioorganic and Medicinal Chemistry Letters, 2003, 13, 3133) said mixture is added dropwise to after 120 milliliters of dchloromethane, after stirring reaction spends the night, reaction solution pours in 400 ml waters slowly, be separated organic phase, aqueous phase uses equal-volume dichloromethane extraction 2 times again, merge organic phase, saturated common salt water washing 2 times, anhydrous sodium sulfate drying, filter, steaming desolventizes, resistates obtains target compound (3.4 grams with pure hexane and the gradient elution of 9:1 hexane/ethyl acetate on silica gel column chromatography, 61% yield).
Ultimate analysis (molecular formula C 33h 26n 2o 6):
Theoretical value: carbon, 72.52%; Hydrogen, 4.79%; Nitrogen, 5.13%;
Measured value: carbon, 72.64%; Hydrogen, 4.84%; Nitrogen, 5.37%.
High resolution mass spectrum HRMS (molecular formula+H=C 33h 27n 2o 6):
Theoretical value: 547.1869; Measured value: 547.1874.
Photopolymerizable reactive and room temperature stability evaluation:
By 20 weight percents (lower same) methacrylic acid, 15 parts of hydroxyethyl methacrylate, 10 parts of methyl methacrylates, and 55 parts of butyl methacrylate and the mixing of 300 parts of ethyl cellosolves, add 1 part of AIBN 70 degrees Celsius of reactions 5 hours, obtain the multipolymer of aforesaid propylene acid system.Next step, get 65 parts of these acrylic copolymers and 15 parts of propoxylated glycerol triacrylates and 20 parts of hexanediyl esters and mix.In this mixture, at room temperature add the light trigger of 4 parts, stirring and dissolving, get a little this sample application (45 microns) on card board kai, with medium pressure mercury lamp (80W/cm) for radiation of light source initiated polymerization, the length of having solidified in record unit time.With finger-press method (namely thumb platen wiping coating is repeatedly not damaged), curing efficiency judges that photocuring completes.Room temperature stability nuclear magnetic resonance method (the CDCl of compound 3or d 6-DMSO solution, concentration 10 mg/ml) interval tracking in three days, NMR hydrogen spectrum signal is unchanged is stable.The measurement result of some light triggers is as follows:

Claims (5)

1. a structural general formula is the compound of (II):
Wherein Ar 1and Ar 2a unsubstituted aromatic group containing 6 carbon atoms independently of one another; R 1and R 2hydrogen or methyl independently of one another; R 3it is methyl.
2. general structure according to claim 1 is the compound of (II), Ar 1and Ar 2be preferably as follows structure:
3. compound, is selected from following structure:
4. a class is containing the light trigger of the compound according to any one of claim 1-3.
5. the compound according to any one of claim 1-3 is as the purposes of light trigger.
CN201010233204.1A 2010-07-21 2010-07-21 Aromatic ketone oxime photoinitiator compound Expired - Fee Related CN101941920B (en)

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CN103044581B (en) * 2012-04-05 2014-10-29 常州强力电子新材料股份有限公司 Macromolecular photoinitiator as well as preparation method and application thereof
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CN109666088A (en) 2017-10-16 2019-04-23 北京英力科技发展有限公司 A kind of diketone oxime ester compound and its manufacturing method and application
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