CN101353338B - Osamine modified water-soluble coumarin ketone derivates and preparation thereof - Google Patents

Osamine modified water-soluble coumarin ketone derivates and preparation thereof Download PDF

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CN101353338B
CN101353338B CN2008100404654A CN200810040465A CN101353338B CN 101353338 B CN101353338 B CN 101353338B CN 2008100404654 A CN2008100404654 A CN 2008100404654A CN 200810040465 A CN200810040465 A CN 200810040465A CN 101353338 B CN101353338 B CN 101353338B
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hydrogen
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CN101353338A (en
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姜学松
印杰
村上泰治
锻治诚
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Shanghai Jiaotong University
Showa Denko Materials Co ltd
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Shanghai Jiaotong University
Hitachi Chemical Co Ltd
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Abstract

The invention provides an osamine-modified water-soluble coumarin ketone derivative and a preparation method thereof. In the structural formula of the prepared compound, R1 is selected from hydrogen, halogen, and C1-C22 alkyl or alkoxyl; R2 is selected from substituted or unsubstituted phenyl, halogenated C1-C4 alkyl or C1-C10 alkyl; R3 is selected from the hydrogen or hydroxyl substituted or unsubstituted C1-C10 alkyl; and R4, R5 and R6 are respectively selected from the hydrogen, the C1-C4 alkyl or halogen; A is glycosyl; the substituents are selected from the C1-C4 alkyl, the halogen and C1-C4 alkoxyl; n is an integer between 0 and 4, and m is also an integer between 0 and 4. The derivative prepared by the preparation method of the invention has the original photosensitiveness and biocompatibility of the oil-soluble coumarin ketone photosensitiser, and the can be used for preparing water paint.

Description

Osamine modified water-soluble coumarin ketone derivates and preparation method thereof
Technical field
The present invention relates to a kind of water-soluble coumarin ketone and preparation method thereof, particularly a kind of osamine modified water-soluble coumarin ketone derivates and preparation method thereof.
Background technology
Coumarin ketone is the meta-bolites of a class Plant Secondary Materials, extensively is present in the various leguminous plantss, and this compounds has many important function, and one of them is photosensitizers and the laser dyes that is used for photo chemistry technology.The widespread use of UV-curing technology on industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazing shown bright development prospect.Coumarin ketone is widely used in having extraordinary photosensitive property in various coating, the photosensitive dry film as the important photosensitizers of a class.But commercial a large amount of coumarin ketones (Coumarin 103 etc.) as efficient photosensitizers are not water miscible, and this has limited the application of coumarin ketone in water-soluble system.
Along with the enhancing of people's environmental consciousness, water-soluble photosensitizers is widely used in fields such as water-borne coatingss, is the focus of photosensitizers area research in recent years.For original high-efficiency oil soluble coumarin ketone photosensitizers, how on the basis that does not reduce its photosensitivity and biocompatibility, to develop water miscible coumarin ketone, become the focus of coumarin ketone photosensitizers research.
Chinese invention patent CN1245407C discloses a kind of mixture of gambogic acid compounds.The document is pointed out, because the water solubility of gambogic acid compounds is minimum, has influenced their pharmaceutical use.Therefore, this invention has proposed the mixture of a kind of gambogic acid compounds and glucosamine compounds, and it has better water solubility, thereby has improved the effect of utilizing of gambogic acid compounds.
But, do not report in the prior art and improve the water miscible method of coumarin ketone.Therefore, be badly in need of a kind of coumarin ketone derivates of exploitation in this area, it has better photosensitivity, biocompatibility and water-soluble simultaneously.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of osamine modified water-soluble coumarin ketone derivates and preparation method thereof is provided, the coumarin ketone derivates that makes has good water-solubility, can keep performances such as the original photosensitivity of coumarin ketone simultaneously.
For realizing this purpose, the present invention is incorporated into the osamine group in the coumarin ketone molecule, and the water-soluble coumarin ketone derivates structural formula with osamine group of gained is as shown in the formula shown in (1):
Figure S2008100404654D00021
Formula (1)
Wherein:
R 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group;
R 2Be selected from and replace or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl;
R 3Being selected from hydrogen or hydroxyl replaces or unsubstituted C1-C10 alkyl;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
A is a glycosyl;
Above-mentioned substituting group is selected from alkyl, halogen and the C1-C4 alkoxyl group of C1-C4;
N is the integer between 0 to 4;
M is the integer between 1 to 4.
Preparation method with water-soluble coumarin ketone derivates of osamine group provided by the invention may further comprise the steps:
(a) make two phenolic compound and the R shown in the formula (2) 2C (O) CH 2COOCH 2CH 3Reaction forms Hydroxycoumarin ketone,
Figure S2008100404654D00031
Formula (2)
R wherein 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group,
R 2Be selected from replacement or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl,
Above-mentioned substituting group is selected from alkyl, halogen and the C1-C4 alkoxyl group of C1-C4;
(b) with the reaction of the halogenated epoxide shown in step (a) gained Hydroxycoumarin ketone and the following formula (3), form the coumarin ketone that contains epoxide group,
Formula (3)
In the formula: L is selected from halogen;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
N is the integer between 0 to 4;
M is the integer between 1 to 4;
(c) make the coumarin ketone that contains epoxide group that step (b) obtains and the osamine compound reaction of following formula (4) expression, form water-soluble coumarin ketone derivates with osamine group,
ANR 3H (4)
In the formula: A is selected from glycosyl,
R 3Being selected from hydrogen or hydroxyl replaces or unsubstituted C1-C10 alkyl.
The water-soluble coumarin ketone derivates that gained of the present invention has the osamine group has the primary characteristic of oil soluble coumarin ketone photosensitizers, has better photosensitivity and biocompatibility, can be used for preparing water-borne coatings.
Description of drawings
Fig. 1 is the infrared spectra that embodiment 1 gained has the water-soluble coumarin ketone derivates of osamine group.
Fig. 2 is the nucleus magnetic hydrogen spectrum that embodiment 1 gained has the water-soluble coumarin ketone derivates of osamine group.
Embodiment
In the present invention, except as otherwise noted, " alkyl " refer to the replacement of C1-C10 or do not replace, the straight or branched alkyl, better be C1-C8, better have C1-C6, preferably C1-C4 replacement or do not replace, the straight or branched alkyl.
In the present invention, except as otherwise noted, " alkoxyl group " refer to the replacement of C1-C10 or do not replace, the straight or branched alkyl, better be C1-C8, be more preferably C1-C6, preferably C1-C4 replacement or do not replace, the straight or branched alkyl.
In the present invention, except as otherwise noted, " halogen " or " halogen " refers to fluorine, chlorine, bromine and/or iodine.
In the present invention, except as otherwise noted, " halo " expression is replaced by one or more halogen atoms, for example a halo, dihalo, perhalogeno (for example perfluor) etc.
In the present invention, except as otherwise noted, " aromatic base " or " aryl " refers to have the replacement of C6-C20 or substituted aromatic group not, better is C6-C16, is more preferably C6-C14, preferably replacement or the unsubstituted aromatic group of C6-C10.
In the present invention, except as otherwise noted, " glycosyl " expression glycan molecule loses a formed group of hydrogen atom, hydroxyl or aldehyde radical.
In the present invention, except as otherwise noted, " sugar " expression monose and/or polysaccharide, for example disaccharides, trisaccharide etc.
In the present invention, except as otherwise noted, " monose " expression has for example sugar of 3 to 10 carbon atoms, for example triose, pentose and hexose etc.
In the present invention, except as otherwise noted, " substituting group " is selected from alkyl, halogen, alkoxyl group and aryl.
In the present invention, except as otherwise noted, percentage composition and part are all represented weight.
Unless have describedly in addition, all preferred technique schemes of the present invention can make up in any way, and these technical schemes that combine include in the present invention's scope required for protection.
One aspect of the present invention provides a kind of water-soluble coumarin ketone derivates with osamine group, and its structural formula is as shown in the formula shown in (1):
Figure S2008100404654D00051
Formula (1)
Wherein:
R 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group;
R 2Be selected from and replace or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl;
R 3Be selected from hydrogen or hydroxyl and replace or do not replace the C1-C10 alkyl;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
A is a glycosyl;
Above-mentioned substituting group is selected from alkyl, halogen and the C1-C4 alkoxyl group of C1-C4;
N is the integer between 0 to 4;
M is the integer between 1 to 4.
In formula of the present invention (1) compound, R 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group.In a preferred embodiment of the present invention, described halogen is selected from fluorine, chlorine, bromine and iodine.In another preferred embodiment of the present invention, described halogen is selected from fluorine and chlorine.In a preferred embodiment of the present invention, R 1Be selected from C1-C22 alkyl and/or alkoxyl group, better be selected from C1-C16 alkyl and/or alkoxyl group, better be selected from C1-C8 alkyl and/or alkoxyl group, preferably be selected from C1-C4 alkyl and/or alkoxyl group.
In a preferred embodiment of the present invention, R 1Be selected from hydrogen, methyl, ethyl, n-propyl and normal-butyl.In another preferred embodiment of the present invention, R 1Be selected from hydrogen and methyl.
In formula of the present invention (1) compound, R 2Be selected from and replace or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl.In a preferred embodiment of the present invention, described substituted-phenyl is represented the phenyl by one or more substituting groups replacements, better is the phenyl that is replaced by one or two substituting group.In a preferred embodiment of the present invention, R 2Be selected from halo C1-C4 alkyl, better be selected from halogenated methyl.In another preferred embodiment of the present invention, R 2Be selected from the C1-C10 alkyl, better be selected from the C1-C8 alkyl, better be selected from the C1-C6 alkyl, preferably be selected from the C1-C4 alkyl.In a preferred embodiment of the present invention, described halogen is selected from fluorine, chlorine, bromine or iodine.
In a preferred embodiment of the present invention, R 2Be selected from methyl, ethyl, n-propyl, normal-butyl, methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and trichloromethyl.In another preferred embodiment of the present invention, R 2Be selected from methyl and trifluoromethyl.
In formula of the present invention (1) compound, R 3Being selected from hydrogen or hydroxyl replaces or unsubstituted C1-C10 alkyl.In a preferred embodiment of the present invention, R 3Be selected from the C1-C10 alkyl, better be selected from the C1-C8 alkyl, better be selected from the C1-C6 alkyl, preferably be selected from the C1-C4 alkyl.
In a preferred embodiment of the present invention, R 3Be selected from methyl, ethyl, n-propyl and normal-butyl.In another preferred embodiment of the present invention, R 3Be selected from methyl.
In formula of the present invention (1) compound, R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl and halogen separately.In a preferred embodiment of the present invention, R 4, R 5And R 6Each is hydrogen naturally.In another preferred embodiment of the present invention, R 4, R 5And R 6Be selected from methyl, ethyl, n-propyl and normal-butyl separately.In another preferred embodiment of the present invention, R 4, R 5And R 6Be selected from fluorine, chlorine, bromine and iodine separately.
In formula of the present invention (1) compound, A is a glycosyl.In a preferred embodiment of the present invention, A is selected from polysaccharide base and monosaccharide groups.In another preferred embodiment of the present invention, A is selected from diglycosyl, three glycosyls, starch base, cellulose base and chitin base.In another preferred embodiment of the present invention, A is selected from triose base, tetrose base, pentose base, hexose-based and heptose base.In another preferred embodiment of the present invention, A is selected from glucosyl group, galactosyl, mannose group, fructosyl and sorb glycosyl.In another preferred embodiment of the present invention, A is selected from D-glucosyl group, D-galactosyl, D-mannose group, D-fructosyl and D-sorb glycosyl.
In a preferred embodiment of the present invention, A is selected from HOCH 2CH 1OHCH 1OHCH 1OHCH 1OHCH 2-, HOCH 2CH 1OHCH 1OHCH 1OHCH (CHO)-,-CH 2CH 1OHCH 1OHCH 1OHCH 1OHCHO.In another preferred embodiment of the present invention, A is selected from HOCH 2CH 1OHCH 1OHCH 1OHCH 1OHCH 2-.
In formula of the present invention (1) compound, n is 0 to 4 integer, better is 0 to 3 integer, is more preferably 0 to 2 integer, and is preferably zero.
In formula of the present invention (1) compound, m is 1 to 4 integer, better is 1 to 3 integer, is more preferably 1 to 2 integer, preferably 1.
In formula of the present invention (1) compound, described water-soluble coumarin ketone derivates with osamine group better is following compound:
Figure DEST_PATH_GSB00000437328500022
Figure DEST_PATH_GSB00000437328500023
The present invention provides a kind of preparation to have the method for the water-soluble coumarin ketone derivates of osamine group on the other hand, said method comprising the steps of:
(a) make two phenolic compound and the R shown in the formula (2) 2C (O) CH 2COOCH 2CH 3Reaction forms Hydroxycoumarin ketone,
Figure S2008100404654D00081
Formula (2)
R wherein 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group,
R 2Be selected from replacement or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl,
Above-mentioned substituting group is selected from alkyl, halogen and the C1-C4 alkoxyl group of C1-C4;
(b) with the reaction of the halogenated epoxide shown in step (a) gained Hydroxycoumarin ketone and the following formula (3), form the coumarin ketone that contains epoxide group,
Figure S2008100404654D00082
Formula (3)
In the formula: L is selected from halogen;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
N is the integer between 0 to 4;
M is the integer between 1 to 4;
(c) make the coumarin ketone that contains epoxide group that step (b) obtains and the osamine compound reaction of following formula (4) expression, form water-soluble coumarin ketone derivates with osamine group,
ANR 3H (4)
In the formula: A is selected from glycosyl,
R 3Being selected from hydrogen or hydroxyl replaces or unsubstituted C1-C10 alkyl.
In the method for the invention, R 1Be selected from hydrogen, halogen, C1-C22 alkyl or alkoxyl group.In preferred embodiment of the present invention, R 1Be selected from C1-C22 alkyl and/or alkoxyl group, better be selected from C1-C16 alkyl and/or alkoxyl group, better be selected from C1-C8 alkyl and/or alkoxyl group, preferably be selected from C1-C4 alkyl and/or alkoxyl group.Described halogen is selected from fluorine, chlorine, bromine and iodine.
In a preferred embodiment of the present invention, R 1Be selected from hydrogen, methyl, ethyl, n-propyl and normal-butyl.
In the method for the invention, two phenolic compound are preferably Resorcinol, pyrocatechol, Resorcinol, methylresorcinol, methyl pyrocatechol, methyl hydroquinone, ethyl resorcinol, ethyl pyrocatechol, ethyl Resorcinol, n-propyl Resorcinol, n-propyl pyrocatechol, n-propyl Resorcinol, n-butyl resorcinol, normal-butyl pyrocatechol and normal-butyl Resorcinol shown in the formula (2).In a preferred embodiment of the present invention, two phenolic compound are Resorcinol and 3 shown in the formula (2), the 5-orcin.
In the method for the invention, R 2Be selected from and replace or unsubstituted phenyl, halo C1-C4 alkyl or C1-C10 alkyl.In a preferred embodiment of the present invention, described substituted-phenyl is represented the phenyl by one or more substituting groups replacements, better is the phenyl that is replaced by one or two substituting group.In a preferred embodiment of the present invention, R 2Be selected from halo C1-C4 alkyl, better be selected from halogenated methyl.In another preferred embodiment of the present invention, R 2Be selected from the C1-C10 alkyl, better be selected from the C1-C8 alkyl, better be selected from the C1-C6 alkyl, preferably be selected from the C1-C4 alkyl.In a preferred embodiment of the present invention, described halogen is selected from fluorine, chlorine, bromine or iodine.
In preferred embodiment of the present invention, R 2Be selected from methyl, ethyl, n-propyl, normal-butyl, methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and trichloromethyl.
In the method for the invention, R 2C (O) CH 2COOCH 2CH 3Be preferably methyl aceto acetate, Propionylacetic acid ethyl ester, ethyl butyrylacetate, valeryl ethyl acetate, an acetyl fluoride ethyl acetate, difluoro methyl aceto acetate, trifluoroacetic ethyl acetoacetate, a chloroacetyl acetacetic ester, two chloroacetyl acetacetic esters and tribromo-acetyl ethyl acetate.
In the method for the invention, the described reaction of step (a) is carried out in organic solvent usually.This organic solvent is conventional in the art, as long as can dissolve described reactant.In preferred embodiment of the present invention, described organic solvent comprises methyl alcohol, ethanol, propyl alcohol, acetone, butanone, pimelinketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene, dimethylbenzene and 1,6-dioxane.
In the method for the invention, two phenolic compound and the R shown in the described formula (2) 2C (O) CH 2COOCH 2CH 3Weight ratio be generally 2: 1-1: 10, be preferably 1: 1-1: 6, more preferably 1: 1-1: 5, be preferably 1: 1-1: 3.
In the method for the invention, the described reaction of step (a) can add catalyzer usually and carries out catalysis.This catalyzer is conventional in the art, and those of ordinary skill in the art can know directly that in conjunction with its expertise which catalyzer can be used among the present invention again according to description of the invention.In preferred embodiment of the present invention, described catalyzer comprises mineral acid and organic acid, specifically comprises sulfuric acid, hydrochloric acid, carbonic acid, nitric acid, acetate, oxalic acid and tartrate.
In the method for the invention, the temperature of reaction for step (a) does not specifically limit.But in order to accelerate reaction process, the described reaction of step (a) is carried out under the condition of heating usually.Usually, described temperature of reaction is 40-150 ℃, is preferably 50-100 ℃, more preferably 50-90 ℃, is preferably 50-80 ℃.
In the method for the invention, the described reaction of step (a) time of carrying out does not have concrete regulation.Generally speaking, long more productive rate is high more the reaction times.But the described reaction times is generally 1-24 hour, is preferably 2-20 hour, more preferably 4-10 hour, is preferably 6 hours.
In the method for the invention, R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl and halogen separately.In a preferred embodiment of the present invention, R 4, R 5And R 6Each is hydrogen naturally.In another preferred embodiment of the present invention, R 4, R 5And R 6Be selected from methyl, ethyl, n-propyl and normal-butyl separately.In another preferred embodiment of the present invention, R 4, R 5And R 6Be selected from fluorine, chlorine, bromine and iodine separately.
In the method for the invention, n is 0 to 4 integer, better is 0 to 3 integer, is more preferably 0 to 2 integer, and is preferably zero.
In the method for the invention, m is 1 to 4 integer, better is 1 to 3 integer, is more preferably 1 to 2 integer, preferably 1.
In the step (b) of the inventive method, described formula (3) compound better is 1,2-epoxy chloropropane, 1,2-epoxy fluoro-propane, 1,2-epoxy bromopropane, 1,2-epoxy iodopropane, 1,2-epoxy n-butyl bromide, 1,2-epoxy chlorobutane, 1,2-epoxy butyl iodide, 1,2-epoxy fluorine butane, 1,3-epoxy iodopropane, 1,3-epoxy n-butyl bromide, 1,3-epoxy chlorobutane, 1,3-epoxy butyl iodide, 1,3-epoxy fluorine butane.
In the method for the invention, the described reaction of step (b) is carried out in organic solvent.Described solvent is conventional, and which organic solvent those of ordinary skill in the art can directly obtain in conjunction with its expertise again at the specification sheets of reading the application can be used for the present invention.In preferred embodiment of the present invention, described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, acetone, butanone, pimelinketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene or dimethylbenzene.
In the method for the invention, the weight ratio of formula (3) compound and Hydroxycoumarin ketone is 1: 0.25-1: 20, be preferably 1: 0.5-1: 15, more preferably 1: 0.5-1: and 10, be preferably 1: 0.5-1: 5.
In the method for the invention, the temperature of reaction for step (b) does not specifically limit.But in order to accelerate reaction process, step (b) is generally carried out under the condition of heating.Usually, temperature of reaction is 40-200 ℃, is preferably 50-150 ℃, more preferably 60-100 ℃.
In the method for the invention, not concrete restriction of the carrying out time of the described reaction of step (b).Generally speaking, the reaction times is long more, and productive rate is high more.But the described reaction times is generally 1-48 hour, is preferably 2-36 hour, more preferably 2-24 hour, is preferably 4-12 hour.
In the method for the invention, A is a glycosyl.In a preferred embodiment of the present invention, A is selected from polysaccharide base and monosaccharide groups.In another preferred embodiment of the present invention, A is selected from diglycosyl, three glycosyls, starch base, cellulose base and chitin base.In another preferred embodiment of the present invention, A is selected from triose base, tetrose base, pentose base, hexose-based and heptose base.In another preferred embodiment of the present invention, A is selected from glucosyl group, galactosyl, mannose group, fructosyl and sorb glycosyl.In another preferred embodiment of the present invention, A is selected from D-glucosyl group, D-galactosyl, D-mannose group, D-fructosyl and D-sorb glycosyl.
In preferred embodiment of the present invention, A is selected from HOCH 2CH 1OHCH 1OHCH 1OHCH 1OHCH 2-, HOCH 2CH 1OHCH 1OHCH 1OHCH (CHO)-,-CH 2CH 1OHCH 1OHCH 1OHCH 1OHCHO.
In the method for the invention, R 3Being selected from hydrogen or hydroxyl replaces or unsubstituted C1-C10 alkyl.In preferred embodiment of the present invention, R 3Be selected from the C1-C10 alkyl, better be selected from the C1-C8 alkyl, better be selected from the C1-C6 alkyl, preferably be selected from the C1-C4 alkyl.
In preferred embodiment of the present invention, R 3Be selected from methyl, ethyl, n-propyl and normal-butyl.
In the method for the invention, described formula (4) compound better is meglumine, Portugal's ethamine, Portugal's propylamine, Portugal's butylamine, alpha-D-glucose amine and α-D-galactosamine.In a preferred embodiment of the present invention, described formula (4) compound is methyl glucoside amine (meglumine).
In the method for the invention, described step (c) is normally carried out in organic solvent.Described organic solvent is conventional, and those of ordinary skill in the art can know directly that in conjunction with its expertise which organic solvent can be used among the present invention again according to the description of present specification.In preferred embodiment of the present invention, described organic solvent comprises methyl alcohol, ethanol, propyl alcohol, acetone, butanone, pimelinketone, chloroform, benzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, toluene or dimethylbenzene.
In the method for the invention, contain the coumarin ketone of epoxide group and the weight ratio of formula (4) compound in the described step (c) and be generally 1: 0.5-1: 20, be preferably 1: 1-1: 15, more preferably 1: 1-1: 10, be preferably 1: 1-1: 5.
In the method for the invention, not concrete qualification of the described reaction of step (c) time of carrying out.Generally speaking, the reaction times is long more, and productive rate is high more.But the described reaction times is generally 0.5-48 hour, is preferably 1-36 hour, more preferably 1-20 hour, is preferably 1-12 hour.
In the method for the invention, the temperature of reaction for step (c) does not specifically limit.But in order to accelerate reaction process, step (c) is generally carried out under the condition of heating.Usually, temperature of reaction is 40-200 ℃, is preferably 50-150 ℃, more preferably 60-100 ℃.
The entire reaction equation of prepared product of the present invention can followingly be represented:
Figure S2008100404654D00131
Another aspect of the present invention provides a kind of photo curable composition, and described composition comprises the water-soluble coumarin ketone derivates with osamine group of the present invention.
In the present invention, described Photocurable composition also can comprise photo curable monomer.Described photo curable monomer is conventional, and which photocurable monomer those of ordinary skill in the art can directly obtain according to description of the invention can be used among the present invention.In a preferred embodiment of the present invention, described photocurable monomer comprises water miscible photocurable monomer.In another preferred embodiment of the present invention, described photocurable monomer comprises water-soluble photo curable unsaturated monomer, for example (methyl) acrylamide, methyl bisacrylamide and waterborne polyester, polyacrylic ester and polyurethane high molecule matrix.
In Photocurable composition of the present invention, can also comprise other components as known in the art, for example coinitiator, chain-transfer agent, stopper or the like.
The present invention also provides the purposes of water-soluble coumarin ketone derivates in water-borne coatings with osamine group of the present invention.
Gained of the present invention has the water-soluble coumarin ketone derivates of osamine group, owing to contain the water soluble group glucosamine, makes coumarin ketone have good water-solubility, has expanded coumarin ketone as the application of photosensitizers in water-based system.
Describe the present invention in detail below in conjunction with embodiment, these embodiment are presented for purposes of illustration, do not limit the scope of the invention.
Embodiment 1
11g (0.1mol) Resorcinol is dissolved in 1 of 20ml, in the 4-dioxane, in gained solution, adds 2ml sulfuric acid then.Then, in above-mentioned solution, splash into 13g (0.1mol) methyl aceto acetate, after dropwising reaction mixture is warmed up to 60 ℃, and reacted 6 hours.After reaction was finished, reaction mixture was separated out white precipitate, filtering-depositing then, and with water/washing with alcohol filter cake of 1: 1, again with the cold water washing several.With gained filter cake recrystallization in ethanol, obtain 4-methyl-umbelliferone ketone, productive rate is 85%.
1.8g (0.01mol) 4-methyl-umbelliferone ketone is dissolved in the pimelinketone of 20ml, in gained solution, adds 4g Anhydrous potassium carbonate and 10ml epoxy chloropropane then.Then, make the gained reaction mixture, refluxed 6 hours at 135 ℃ then 80 ℃ of reactions 4 hours.After reaction finishes, wash organic phase with water and use the Calcium Chloride Powder Anhydrous drying, drain organic phase then.With residue obtained in ethanol recrystallization, obtain containing the coumarin ketone of epoxide group, productive rate is 50%.Then the coumarin ketone that contains epoxide group of 2.3g (0.01mol) and the methyl glucoside amine of 3g (0.015mol) are dissolved in the methyl alcohol of 100ml, after 12 hours, drain solvent in 80 ℃ of reactions.With residue obtained in ethanol recrystallization obtain the water miscible coumarin ketone that contains the glucosamine group, productive rate is 80%.
1H NMR ([d6] DMSO, 400MHz): δ=6.2-7.7 (phenyl ring), 4.82 (OH), 4.10-3.30 (OCH2 ,-OCH), 2.62-2.41 (NCH3 ,-CH3), specifically referring to Fig. 2.
FT-IR (KBr): 3400 (O-H), 2931 (C-H), 1708cm-1 (C=O) is specifically referring to Fig. 1.
Embodiment 2
11g (0.1mol) Resorcinol is dissolved in 1 of 20ml, in the 4-dioxane, in gained solution, is adding 2ml sulfuric acid then.Then, in above-mentioned solution, splash into the trifluoroacetic ethyl acetoacetate of 18.4g (0.1mol), after dropwising reaction mixture is warmed up to 60 ℃, and reacted 6 hours.After reaction was finished, reaction mixture was separated out white precipitate, filtering-depositing, and with water/washing with alcohol filter cake of 1: 1, again with the cold water washing several.With gained filter cake recrystallization in ethanol, obtain 4-trifluoromethyl-umbelliferone ketone, productive rate is 86%.
2.4g (0.01mol) 4-trifluoromethyl-umbelliferone ketone is dissolved in the pimelinketone of 20ml, in gained solution, adds 4g Anhydrous potassium carbonate and 10ml epoxy chloropropane then.Then, the gained reaction mixture was reacted 2 hours at 80 ℃ down, refluxed 6 hours down at 135 ℃ then.After reaction finishes, wash organic phase with water and use the Calcium Chloride Powder Anhydrous drying, drain organic phase then.With residue obtained in ethanol recrystallization, obtain containing the coumarin ketone of epoxide group, productive rate is 48%.Then the coumarin ketone that contains epoxide group of 2.8g (0.01mol) and the methyl glucoside amine of 3g (0.015mol) are dissolved in the methyl alcohol of 100ml, after 12 hours, drain solvent in 80 ℃ of reactions.With residue obtained in ethanol recrystallization obtain the water miscible coumarin ketone that contains the glucosamine group, productive rate is 82%.
1H NMR ([d6] DMSO, 400MHz): δ=6.2-7.7 (phenyl ring), 4.82 (OH), 4.10-3.30 (OCH2 ,-OCH), 2.62-2.41 is (NCH3).
FT-IR(KBr)：3400(O-H)，2931(C-H)，1708cm-1(C＝O)。
Embodiment 3
With 12g (0.1mol) 3, the 5-orcin is being dissolved in 1 of 20ml, in the 4-dioxane, adds 2ml sulfuric acid then in gained solution.Then, in above-mentioned solution, splash into the methyl aceto acetate of 13g (0.1mol), after dropwising reaction mixture is warmed up to 60 ℃, and reacted 6 hours.After reaction was finished, reaction mixture was separated out white precipitate, filtering-depositing then, and with water/washing with alcohol of 1: 1, again with the cold water washing several.With gained filter cake recrystallization in ethanol, obtain 4,5-dimethyl-umbelliferone ketone, productive rate are 86%.
With 1.9g (0.01mol) 4,5-dimethyl-umbelliferone ketone is dissolved in the pimelinketone of 20ml, adds 4g Anhydrous potassium carbonate and 10ml epoxy chloropropane then in gained solution.Then, make the gained reaction mixture, refluxed 6 hours down at 135 ℃ then 80 ℃ of reactions 2 hours.After reaction finishes, wash organic phase with water and use the Calcium Chloride Powder Anhydrous drying, drain organic phase.With residue obtained in ethanol recrystallization, obtain containing the coumarin ketone of epoxide group, productive rate is 50%.Then the coumarin ketone that contains epoxide group of 2.4g (0.01mol) and the methyl glucoside amine of 3g (0.015mol) are dissolved in the methyl alcohol of 100ml, after 12 hours, drain solvent in 80 ℃ of reactions.With residue obtained in ethanol recrystallization obtain the water miscible coumarin ketone that contains the glucosamine group, productive rate is 80%.
1H NMR ([d6] DMSO, 400MHz): δ=6.2-7.7 (phenyl ring), 4.82 (OH), 4.10-3.30 (OCH2 ,-OCH), 2.62-2.41 is (NCH3).
FT-IR(KBr)：3400(O-H)，2931(C-H)，1708cm-1(C＝O)。
Embodiment 4 water-soluble mensuration
The solubleness of the coumarin ketone derivates of embodiment 1 gained in water (pH value 4.0-7.0) is 0.001-0.05g.
Embodiment 5 light-initiated water-soluble monomer velocity determinations
Test formulations:
The aqueous solution of acrylamide: 2.0mol/L
Coinitiator methyldiethanolamine: 2 * 10 -3Mol/L
Photosensitizers is the coumarin ketone among the embodiment 1: 2 * 10 -3Mol/L
Test condition: get the 5mg sample and place crucible, adopt photo-DSC (DSC6200, SeikoInstument Inc) to test, high voltage mercury lamp is a light source, and light intensity is 50mW/cm 2In illumination polymeric process, the heat that is discharged is directly proportional with the monomer of conversion, so the heat that level of response or transformation efficiency can pass through to be discharged determines, is expressed from the next:
C = Δ H t / Δ H 0 theor
Δ H wherein tBe the heat that reaction times t discharges, Δ H 0 TheorThe total heat that is discharged when reacting completely.Speed of response can draw by the derivative of transformation efficiency to the time, as shown in the formula
R p = dC / dt = ( dH / dt ) / Δ H 0 theor
Test result: maximum reaction velocity is 0.003S -1
Embodiment 6 light-initiated water-soluble monomer velocity determinations
Test formulations:
The aqueous solution of acrylamide: 2.0mol/L
Coinitiator methyldiethanolamine: 2 * 10 -3Mol/L
Photosensitizers is the coumarin ketone among the embodiment 2: 2 * 10 -3Mol/L
Test condition: with embodiment 5
Test result: maximum reaction velocity is 0.0035S -1
Embodiment 7 light-initiated water-soluble monomer velocity determinations
Test formulations:
The aqueous solution of acrylamide: 2.0mol/L
Coinitiator methyldiethanolamine: 2 * 10 -3Mol/L
Photosensitizers is the coumarin ketone among the embodiment 3: 2 * 10 -3Mol/L
Test condition: with embodiment 5
Test result: maximum reaction velocity is 0.0028S -1

Claims (3)

1. water-soluble coumarin ketone derivates with osamine group is characterized in that structural formula is:
Figure FSB00000437328400011
In the formula:
R 1Be selected from hydrogen, halogen, C1-C4 alkyl or alkoxyl group;
R 2Be selected from phenyl, fluoro C1-C4 alkyl or C1-C4 alkyl;
R 3Be selected from hydrogen or C1-C4 alkyl;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
A is selected from HOCH 2CH 1OHCH 1OHCH 1OHCH 1OHCH 2-;
N is the integer between 0 to 4;
M is the integer between 1 to 4.
2. coumarin ketone derivates as claimed in claim 1 is characterized in that its structural formula is:
Figure FSB00000437328400012
Figure FSB00000437328400013
Figure FSB00000437328400021
3. method for preparing the described water-soluble coumarin ketone derivates of claim 1 is characterized in that may further comprise the steps:
(a) make two phenolic compound and the R shown in the following formula 2C (O) CH 2COOCH 2CH 3Reaction forms Hydroxycoumarin ketone,
Figure FSB00000437328400022
Wherein: R 1Be selected from hydrogen, halogen, C1-C4 alkyl or alkoxyl group,
R 2Be selected from phenyl, fluoro C1-C4 alkyl or C1-C4 alkyl;
(b) with the reaction of the halogenated epoxide shown in step (a) gained Hydroxycoumarin ketone and the following formula, form the coumarin ketone that contains epoxide group,
Figure FSB00000437328400023
In the formula: L is selected from halogen;
R 4, R 5And R 6Be selected from hydrogen, C1-C4 alkyl or halogen separately;
N is the integer between 0 to 4;
M is the integer between 1 to 4;
(c) make the coumarin ketone that contains epoxide group that step (b) obtains and use ANR 3The osamine compound reaction that H represents forms the water-soluble coumarin ketone derivates with osamine group,
Wherein: A is selected from HOCH 2CH 1OHCH 1OHCH 1OHCH 1OHCH 2-,
R 3Be selected from hydrogen or C1-C4 alkyl.
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