CN102618062B - Polymerizable yellow azo dye - Google Patents
Polymerizable yellow azo dye Download PDFInfo
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- CN102618062B CN102618062B CN201110039936.1A CN201110039936A CN102618062B CN 102618062 B CN102618062 B CN 102618062B CN 201110039936 A CN201110039936 A CN 201110039936A CN 102618062 B CN102618062 B CN 102618062B
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- YTDOXMXXFDOISW-MRCUWXFGSA-N CCc1cc(/N=N\c(cc2)ccc2NC(C(C)=C)=O)ccc1O Chemical compound CCc1cc(/N=N\c(cc2)ccc2NC(C(C)=C)=O)ccc1O YTDOXMXXFDOISW-MRCUWXFGSA-N 0.000 description 1
Abstract
The invention relates to a polymerizable yellow azo dye shown in a formula (I), the maximum absorption wavelength is about 365nm. Because a structure of the polymerizable yellow azo dye contains an acrylamide unsaturated group, can be copolymerized with other monomers, and can reach the effect for absorbing the ultraviolet rays.
Description
Technical field
The present invention relates to the compound of polymerizable Yellow azo dye, its maximum absorption wavelength is in 365nm left and right.Owing to containing acrylamide unsaturated group in structure, can follow other monomer copolymerization, and can reach the ultraviolet effect of effective absorption.
Background technology
The solar radiation in the earth atmosphere upper bound, nearly 50% solar radiation energy is at visible spectrum (wavelength 400～760nm), 7% in UV spectrum district (wavelength < 400nm), 43% in infrared spectral region (wavelength > 760nm), and the UV-light that arrives ground by atmospheric layer is little.But this part UV-light is still very harmful to the mankind's eyesight.
In order to reach the requirement of above-mentioned characteristic, United States Patent (USP) 5662707, United States Patent (USP) 5470932, United States Patent (USP) 5528322, United States Patent (USP) 5543502 and Japanese Patent 8503997 have all been reported structure and the synthetic method of two kinds of Yellow azo dyes, then it is used for Acrylic Acid Monomer copolymerization, it is the artificial crystal material of " anti-blue light " that generation one is known as.Although the related dye structure of above-mentioned public technology also can be followed other monomer copolymerization, maximum absorption wavelength is in 410nm left and right.Can be with the problem of other monomer copolymerization in order to solve this dye structure, this area needs can be with the dye composition of other monomer copolymerization.
The yellow azoic dyestuff maximum absorption wavelength of the artificial crystal of the present invention, in 365nm left and right, contains vinylformic acid reactive group, can follow other monomer copolymerization, for example, for glasses lens, can effectively stop ultraviolet ray, reaches the object of vision protection.
Summary of the invention
The dyestuff that theme of the present invention relates to, has wherein introduced acrylamido, and the synthetic method of this dye composition is provided, and has reaction conditions gentleness, simple possible, all high features of yield and content.
Owing to having introduced acrylamide unsaturated group in this dye structure, for polymer materials processing and use procedure, can make to have polymerization between active group and polymeric substrate, due to its polymerisable response characteristic, make polymkeric substance there is better long-lasting; Due to the existence of acrylamide unsaturated group, also make dye composition structure and polymeric substrate have certain consistency in addition.
The present invention has general formula (I) structure for the compound of dyestuff:
General formula (I)
R
1', R
2', R
3', R
4', R
5' and R
6', identical or different, represent independently respectively hydrogen, hydroxyl, halogen, replacement or unsubstituted, C1-30 alkyl, C1-30 alkoxyl group, C1-30 hydroxyalkyl, C3-30 cycloalkyl, C5-30 aryl, C1-30 alkylaryl, C1-30 miscellaneous alkyl aryl, C1-30 alkyl heterocyclic, C1-30 alkylidene group oxygen base alkyl, C1-30 alkylidene group oxygen Ji Fangji, C1-30 alkylidene group oxygen base heteroaryl or C1-30 alkylidene group oxygen base heterocyclic radical
Prerequisite is to work as R
2' be-when OH: R
1', R
3', R
4', R
5' and R
6' different times table-H.
The embodiment of a modification according to the present invention, R in the compounds of this invention
1', R
2', R
3', R
4', R
5' and R
6', identical or different, represent independently that respectively hydrogen, hydroxyl, halogen are as fluorine, chlorine, bromine or iodine, replacement or unsubstituted, C1-30 alkyl, C1-30 hydroxyalkyl or C1-30 alkoxyl group.
The embodiment of another modification according to the present invention, in the compounds of this invention, alkyl is selected from, and replaces or unsubstituted methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, hendecane base, 12 carbon alkyl, n-tridecane base, n-tetradecane base, pentadecane base, hexadecane base, heptadecane base, octadecyl, nonadecane base and petrosilane base.
The embodiment of another modification according to the present invention, in the compounds of this invention, hydroxyalkyl is selected from, and replaces or unsubstituted methylol, hydroxyethyl, hydroxypropyl, hydroxyl sec.-propyl, hydroxyl normal-butyl, hydroxyl sec-butyl, hydroxyl isobutyl-, the hydroxyl tertiary butyl, hydroxyl amyl group, hydroxyl hexyl, hydroxyl heptyl, hydroxyl octyl group, hydroxyl nonyl, hydroxy decyl.
The embodiment of another modification according to the present invention, in the compounds of this invention, alkoxyl group is selected from, replace or unsubstituted methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, hendecane oxygen base, 12 carbon alkoxyl groups, n-tridecane oxygen base, n-tetradecane oxygen base, pentadecane oxygen base, hexadecane oxygen base, heptadecane oxygen base, octodecane oxygen base, nonadecane oxygen base and petrosilane oxygen base.
The embodiment of another modification according to the present invention, R in the compounds of this invention
1', R
2', R
3', R
4', R
5' and R
6', identical or different, represent independently respectively hydrogen, hydroxyl, halogen is as fluorine, chlorine, bromine or iodine, replacement or unsubstituted, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base or the last of the ten Heavenly stems oxygen base, methylol, hydroxyethyl, hydroxypropyl, hydroxyl sec.-propyl, hydroxyl normal-butyl, hydroxyl sec-butyl, hydroxyl isobutyl-, the hydroxyl tertiary butyl, hydroxyl amyl group, hydroxyl hexyl, hydroxyl heptyl, hydroxyl octyl group, hydroxyl nonyl or hydroxy decyl.
The embodiment of another modification according to the present invention, R in the compounds of this invention
1' be-when OH: R
2', R
3', R
4', identical or different, representative-H ,-CH3 ,-CH3O; R
5' representative-H or-CH3.
The embodiment of another modification according to the present invention, R in the compounds of this invention
2' be-when OH: R
1', R
3', R
4', identical or different, representative-H ,-CH3 ,-CH3O; R
5' representative-H or-CH3.
The embodiment of another modification according to the present invention, the present invention has general formula (II) structure for the compound of dyestuff:
General formula (II)
R
1', R
2', R
3', R
4' and R
6' define as described in general formula (I),
Prerequisite is to work as R
2' be-when OH: R
1', R
3', R
4' and R
6' different times table-H.
The embodiment of another modification according to the present invention, the present invention has general formula (III) structure for the compound of dyestuff:
General formula (III)
R
1', R
2', R
3' and R
4' define as described in general formula (I),
Prerequisite is to work as R
2' be-when OH: R
1', R
3', R
4' different times table-H.
The embodiment of another modification according to the present invention, the compounds of this invention is:
The embodiment of another modification according to the present invention, particularly preferably general formula (I) compound is as follows:
The present invention also provides the process program of efficient stable to synthesize general formula (I) compound, and its technological design is as follows.
Preparation scheme:
1. general formula (IV) compound replacing by amino
General formula (IV)
With acrylic anhydride class
Formula (V)
Carry out acylation reaction and prepare general formula (I) compound:
General formula (I)
In above-mentioned formula, R
1', R
2', R
3', R
4', R
5' and R
6' definition with the definition in above-mentioned general formula (I).
The preparation embodiment of a modification according to the present invention,
2. general formula (VI) compound replacing by nitro
General formula (VI)
Carry out reduction reaction with Na2S and prepare general formula (IV) compound
General formula (IV)
Then, with acrylic anhydride class
Formula (V)
Carry out acylation reaction and prepare general formula (I) compound:
General formula (I)
In above-mentioned formula, R
1', R
2', R
3', R
4', R
5' and R
6' definition with the definition in above-mentioned general formula (I).
The preparation embodiment of another modification according to the present invention,
3. pass through p-Nitroaniline
Formula (VII)
After diazotization and general formula (VIII)
General formula (VIII)
Carry out coupled reaction and prepare general formula (I) compound
General formula (I)
In above-mentioned formula, R
1', R
2', R
3', R
4', R
5' and R
6' definition with the definition in above-mentioned general formula (I).
The invention still further relates to above-claimed cpd in the purposes of preparing in ophthalmic medical equipment, for example this compound is for the preparation of ring, intracorneal lens, glaucoma drain valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, medical supply lens, visual telescope, surveillance mirror in artificial lens, recessive glasse, artificial cornea, cornea.
The invention still further relates to medical device, it comprises above-claimed cpd, for example medical device comprises ophthalmic medical equipment, as ring, intracorneal lens, glaucoma drain valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, medical supply lens, visual telescope, surveillance mirror in artificial lens, recessive glasse, artificial cornea, cornea.
The example that is used for the alkyl of the compounds of this invention includes but not limited to, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, nonyl, decyl, hendecane base, 12 carbon alkyl, n-tridecane base, n-tetradecane base, pentadecane base, hexadecane base, heptadecane base, octadecyl, nonadecane base and petrosilane base, methylol, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, 2-dihydroxy ethyl, 1, 3-dihydroxyl sec.-propyl, 2, 3-dihydroxyl-tertiary butyl, 1, 2, 3-trihydroxy-propyl group, chloromethyl, 1-chloroethyl, 2-chloroethyl, 2-chlorine isobutyl-, 1, 2-Dichloroethyl, 1, 3-bis-chloro isopropyls, 2, the chloro-tertiary butyl of 3-bis-, 1, 2, 3-tri-chloropropyls, brooethyl, 1-bromotrifluoromethane, 2-bromotrifluoromethane, 2-bromine isobutyl-, 1, 2-bis-bromotrifluoromethanes, 1, 3-dibromo sec.-propyl, 2, the bromo-tertiary butyl of 3-bis-, 1, 2, 3-tri-bromopropyls, one iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1, 2-diiodo-ethyl, 1, 3-diiodo-sec.-propyl, 2, the iodo-tertiary butyl of 3-bis-, 1, 2, 3-triiodo propyl group, one amino methyl, 1-amino-ethyl, 2-amino-ethyl, 2-aminoisobutyric base, 1, 2-diamino ethyl, 1, 3-diamino sec.-propyl, 2, 3-diamino-tertiary butyl, 1, 2, 3-triamino propyl group, cyano methyl, 1-cyano ethyl, 2-cyano ethyl, 2-cyano group isobutyl-, 1, 2-dicyano ethyl, 1, 3-dicyano sec.-propyl, 2, 3-dicyano-tertiary butyl, 1, 2, 3-tricyano propyl group, nitro methyl, 1-nitro-ethyl, 2-nitro-ethyl, 2-nitro isobutyl-, 1, 2-dinitrobenzene ethyl, 1, 3-dinitrobenzene sec.-propyl, 2, 3-dinitrobenzene-tertiary butyl, with 1, 2, 3-trinitro-propyl group.
In the present invention described in another in compound embodiment, alkoxyl group is selected from, replace or unsubstituted methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, hendecane oxygen base, 12 carbon alkoxyl groups, n-tridecane oxygen base, n-tetradecane oxygen base, pentadecane oxygen base, hexadecane oxygen base, heptadecane oxygen base, octodecane oxygen base, nonadecane oxygen base and petrosilane oxygen base.
In the present invention described in another in compound embodiment, hydroxyalkyl is selected from, replace or unsubstituted methylol, hydroxyethyl, hydroxypropyl, hydroxyl sec.-propyl, hydroxyl normal-butyl, hydroxyl sec-butyl, hydroxyl isobutyl-, the hydroxyl tertiary butyl, hydroxyl amyl group, hydroxyl hexyl, hydroxyl heptyl, hydroxyl octyl group, hydroxyl nonyl, hydroxy decyl, hydroxyl hendecane base, hydroxyl 12 carbon alkyl, hydroxyl n-tridecane base, hydroxyl n-tetradecane base, hydroxyl pentadecane base, hydroxyl hexadecane base, hydroxyl heptadecane base, hydroxyl octadecyl, hydroxyl nonadecane base and hydroxyl petrosilane base.
In the present invention, described in another in compound embodiment, heterocyclic radical is selected from, and replaces or unsubstituted thiophene, furans, pyrans, fen
thiophene, pyrroles, imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, indoles, pseudoindoyl, indazole, purine, quinolizine, quinoline, phthalazines, naphthyridines, quinoxaline, pteridine, carbazole, carboline, phenanthridines, phenanthroline, acridine, azophenlyene, thiazole, thiodiphenylamine,
azoles, fen
piperazine,
azoles base,
di azoly, furazan base, two Thienopyrroles, three thiophthenes, benzo
azoles base, benzimidazolyl-, thionaphthene, benzothiazolyl, thionaphthene, cumarone, chromene, benzo fen
thiophene, benzopyrrole, benzoglyoxaline, benzopyrazoles, benzo pyridine, benzopyrazines, benzo pyrimidine, benzo pyridazine, benzo indolizine, benzindole, benzo indazole, benzo purine, benzoquinolizine, benzoquinoline, benzo phthalazines, benzo naphthyridines, Benzoquinoxalines, benzo pteridine, benzo carbazole, benzo carboline, benzo phenanthridines, benzo phenanthroline, benzacridine, phenonaphthazine, benzothiazole, benzo thiodiphenylamine, benzo
azoles, benzo fen
the ring of the ring of piperazine or above-mentioned group and the claims 2 aryl that defines condenses derivative group, or the combination of above-mentioned group.Each in these substituting groups can be substituted in addition.
In the present invention described in another in compound embodiment, alkylidene group is selected from, and replaces or unsubstituted methylene radical, ethylidene, propylidene, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene, the sub-tertiary butyl, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-hendecane base, sub-12 carbon alkyl, sub-n-tridecane base, sub-n-tetradecane base, sub-pentadecane base, sub-hexadecane base, sub-heptadecane base, sub-octadecyl, sub-nonadecane base and sub-petrosilane base.
In the present invention described in another in compound embodiment, cycloalkyl is selected from, and replaces or unsubstituted cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ten carbocyclic ring alkyl, 12 carbocyclic ring alkyl, 13 carbocyclic ring alkyl, 14 carbocyclic ring alkyl, ten five-carbon ring naphthene bases, ten hydrogenation of six carbocyclic alkyl, 17 carbocyclic ring alkyl, ten eight ring carbon alkyl, 19 carbocyclic ring alkyl and 20 carbocyclic ring alkyl.
In the present invention described in another in compound embodiment, heteroaryl is selected from, replacement or unsubstituted, pyrryl, pyrazinyl, pyridyl, indyl, pseudoindoyl, furyl, benzofuryl,, isobenzofuran-base, quinolyl, 1-isoquinolyl, quinoxalinyl, carbazyl, phenanthridinyl, acridyl, phenanthrolene base, phenazinyl, phenothiazinyl, phenothiazinyl, fen
piperazine base,
azoles base, furan Xanthones base, thienyl.
The example that is used for the aryl of the compounds of this invention includes but not limited to phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pentacenyl, hexacenyl, pyrenyl, indenyl, xenyl, o-tolyl, m-tolyl, p-tolyl, p-tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl, 4 "-tertiary butyl-p-terphenyl-4-base, 9, 9-dimethyl fluorene-1-base, 9, 9-dimethyl fluorene-2-base, 9, 9-dimethyl fluorene-3-base, with 9, 9-dimethyl fluorene-4-base.Other example comprises and belongs to phenyl, phenylene, and the substituting group of the binding substances of naphthyl and naphthylidene (as phenyl napthyl, naphthyl phenyl, naphthyl naphthyl, naphthyl naphthyl naphthyl, phenyl naphthyl, naphthyl naphthyl phenyl, naphthyl phenyl napthyl, naphthyl phenyl, phenyl napthyl naphthyl, and phenyl napthyl phenyl).From there is the replacement of 6-8 carbon atom or be not substituted aryl form group be preferred.Especially, phenyl, naphthyl and phenanthryl are preferred.
Further being substituted in the substituent example of each group in each the compounds of this invention comprises: alkyl (has preferred 1-30, more preferably 1-20, as methyl, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl or Octadecane base); Cycloalkyl (there is preferred 3-30, more preferably 3-20, or 3-10 carbon atom particularly preferably, as cyclopropyl, cyclopentyl, or cyclohexyl); Alkenyl (there is preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, as vinyl, allyl group, crotyl, or 3-pentenyl); Alkynyl (has preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, as propargyl or 3-pentynyl), aryl (has preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, as phenyl, p-aminomethyl phenyl, naphthyl or anthryl); Amino (there is preferred 0-30, more preferably 0-20, or 0-10 carbon atom particularly preferably, as amino, methylamino, dimethylamino, diethylamino, dibenzyl amino, diphenyl amino, or xylyl amino); Alkoxyl group (there is preferred 1-30, more preferably 1-20, or 1-10 carbon atom particularly preferably, as methoxyl group, oxyethyl group, butoxy or 2-ethyl hexyl oxy); Aryloxy (there is preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, as phenyl oxygen base, 1-naphthyloxy, or 2-naphthyloxy); Heteroaryloxy (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as pyridyl oxygen base, pyrazoloxy, pyrimidyl oxygen base or quinolyl oxygen base); Acyl group (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as ethanoyl, benzoyl, formyl radical or valeryl); Alkoxy carbonyl (there is preferred 2-30, more preferably 2-20, or 2-12 carbon atom particularly preferably, as methoxycarbonyl or ethoxy carbonyl); Aryloxycarbonyl (there is preferred 7-30, more preferably 7-20, or 7-12 carbon atom particularly preferably, as phenyl oxygen base carbonyl); Acyloxy (there is preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, as acetoxyl group or benzoyloxy); Amide group (there is preferred 2-30, more preferably 2-20, or 2-10 carbon atom particularly preferably, as kharophen or benzoyl-amido); Alkoxycarbonyl amino (there is preferred 2-30, more preferably 2-20, or 2-12 carbon atom particularly preferably, as methoxycarbonyl amino); Aryloxy oxygen base amino (there is preferred 7-30, more preferably 7-20, or 7-12 carbon atom particularly preferably, as phenyl oxygen base carbonylamino); Sulfuryl amino (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as methane sulfonyl amido or benzenesulfonyl amino); Sulfamyl (there is preferred 0-30, more preferably 0-20, or 0-12 carbon atom particularly preferably, as amino-sulfonyl, methylamino alkylsulfonyl, dimethylamino-sulfonyl, or phenyl amino alkylsulfonyl); Formamyl (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as formamyl, methylamino formyl radical, diethylamino formyl radical, or phenyl amino formyl radical); Alkylthio (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as methylthio group or ethylmercapto group); Arylthio (there is preferred 6-30, more preferably 6-20, or 6-12 carbon atom particularly preferably, as thiophenyl); Heteroaryl sulfenyl (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as pyridyl sulfenyl, 2-benzimidazolyl-sulfenyl, 2-benzo
azoles base sulfenyl, or 2-[4-morpholinodithio base sulfenyl); Alkylsulfonyl (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as methylsulfonyl or tosyl group); Sulfinyl (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as methylsulfinyl or benzenesulfinyl); Urea groups (there is preferred 1-30, more preferably 1-20, or 1-12 carbon atom particularly preferably, as urea groups, methyl urea groups or phenyl urea groups); Phosphoamide base (have preferred 1-30, more preferably 1-20 or 1-12 carbon atom particularly preferably, as diethyl phosphoamide or phenyl phosphamide); Hydroxyl; Sulfydryl; Halogen atom (as fluorine atom, chlorine atom, bromine atoms, or iodine atom); Cyano group; Sulfo group; Carboxyl; Nitro; Hydroxamic acid group; Sulfino; Diazanyl; Imino-; Heterocyclic group (have preferred 1-30 or preferred 1-12 carbon atom containing as heteroatomic for example nitrogen-atoms, Sauerstoffatom or sulphur atom, and specifically example comprises imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzo
azoles base, benzimidazolyl-, and benzothiazolyl); And silyl (there is preferred 3-40, more preferably 3-30, or 3-24 carbon atom particularly preferably, as trimethyl silyl or triphenyl silyl).Each in these substituting groups can be substituted in addition.
Brief description of the drawings
Figure mono-exemplary illustration embodiment mono-high-efficient liquid phase chromatogram (area normalization method), wherein this test result is Aglient 1200 high performance liquid chromatographs (outfit diode-array detectors).
The absorption curve of figure bis-to figure five exemplary illustration embodiment mono-in different organic solvents, wherein this test result is 723 type visible spectrophotometer test results.Figure bis-is that embodiment mono-makes solvent absorbing graphic representation (λ max=370nm) with methyl acrylate; Figure tri-is that embodiment mono-makes solvent absorbing graphic representation (λ max=370nm) with acetone; Figure tetra-is that embodiment mono-makes solvent absorbing graphic representation (λ max=370nm) with DMF; Figure five is that embodiment mono-makes solvent absorbing graphic representation (λ max=370nm) with tetrahydrofuran (THF).
The liquid chromatogram (area normalization method) of figure six exemplary illustration embodiment bis-, wherein this test result is Aglient 1200 high performance liquid chromatographs (outfit diode-array detectors).
Figure seven and the absorption curve of figure eight exemplary illustration embodiment bis-in organic solvent, wherein this test result is the U-3900H of Hitachi ultraviolet spectrometry spectrograph test result.Figure seven is that embodiment bis-makes solvent absorbing graphic representation (λ max=365nm) with acetonitrile; Figure eight is that embodiment bis-makes solvent absorbing graphic representation (λ max=365nm) with DMF.
Embodiment
Preparation Example one:
Take 12.17g (0.12mol) 36% hydrochloric acid in 100ml there-necked flask, add 20ml water, add 4.14g (0.03mol) p-Nitroaniline, be dissolved as transparent liquid, cool to 0-5 DEG C, drip 2.07g (0.03mol) sodium nitrite solution, 1h is stand-by in insulation; In 1000ml beaker, take 3.4g (0.03mol) meta-cresol, add 100ml water, add 1.2g (0.03mol) dissolution of sodium hydroxide.Above-mentioned diazo liquid is slowly added dropwise to beaker and completes coupling.Filter, washing, dries.
Take above-mentioned dyestuff 2.7g (0.01mol) in 100ml there-necked flask, add 40ml water, add 2.6g (0.02mol) sodium sulfide solution, after adding, be warmed up to 94-95 DEG C, be incubated about 1h reaction and finish.Regulating ph with 36% hydrochloric acid is that slant acidity has solid to separate out, and filters, and washing, dries, and yield is more than 95%, and HPLC content is more than 95%.
Take above-mentioned dry reduzate 2.39g (0.01mol) in dry there-necked flask, add 10ml anhydrous propanone, then slowly add 1.64g (0.01mol) methacrylic anhydride, under room temperature, stir the reaction of having spent the night.Yield 97%, content is more than 95%.
Preparation Example two:
Take 12.17g (0.12mol) 36% hydrochloric acid in 100ml there-necked flask, add 20ml water, add 4.14g (0.03mol) p-Nitroaniline, be dissolved as transparent liquid, cool to 0-5 DEG C, drip 2.07g (0.03mol) sodium nitrite solution, 1h is stand-by in insulation; In 1000ml beaker, take 3.4g (0.03mol) meta-cresol, add 100ml water, add 1.2g (0.03mol) dissolution of sodium hydroxide.Above-mentioned diazo liquid is slowly added dropwise to beaker and completes coupling.Filter, washing, dries.
Take above-mentioned dyestuff 2.56g (0.01mol) in 100ml there-necked flask, add 40ml water, add 2.6g (0.02mol) sodium sulfide solution, after adding, be warmed up to 94-95 DEG C, be incubated about 1h reaction and finish.Regulating ph with 36% hydrochloric acid is that slant acidity has solid to separate out, and filters, and washing, dries, and yield is more than 95%, and HPLC content is more than 95%.
Take above-mentioned dry reduzate 2.24g (0.01mol) in dry there-necked flask, add 10ml anhydrous propanone, then slowly add 1.64g (0.01mol) methacrylic anhydride, under room temperature, stir the reaction of having spent the night.Yield 97%, content is more than 95%.
Preparation Example three:
Take 12.17g (0.12mol) 36% hydrochloric acid in 100ml there-necked flask, add 20ml water, add 4.14g (0.03mol) p-Nitroaniline, be dissolved as transparent liquid, cool to 0-5 DEG C, drip 2.07g (0.03mol) sodium nitrite solution, 1h is stand-by in insulation; In 1000ml beaker, take 3.4g (0.03mol) meta-cresol, add 100ml water, add 1.2g (0.03mol) dissolution of sodium hydroxide.Above-mentioned diazo liquid is slowly added dropwise to beaker and completes coupling.Filter, washing, dries.
Take above-mentioned dyestuff 2.87g (0.01mol) in 100ml there-necked flask, add 40ml water, add 2.6g (0.02mol) sodium sulfide solution, after adding, be warmed up to 94-95 DEG C, be incubated about 1h reaction and finish.Regulating ph with 36% hydrochloric acid is that slant acidity has solid to separate out, and filters, and washing, dries, and yield is more than 95%, and HPLC content is more than 95%.
Take above-mentioned dry reduzate 2.56g (0.01mol) in dry there-necked flask, add 10ml anhydrous propanone, then slowly add 1.64g (0.01mol) methacrylic anhydride, under room temperature, stir the reaction of having spent the night.Yield 97%, content is more than 95%.
Preparation Example four:
Take 12.17g (0.12mol) 36% hydrochloric acid in 100ml there-necked flask, add 20ml water, add 4.14g (0.03mol) p-Nitroaniline, be dissolved as transparent liquid, cool to 0-5 DEG C, drip 2.07g (0.03mol) sodium nitrite solution, 1h is stand-by in insulation; In 1000ml beaker, take 3.4g (0.03mol) meta-cresol, add 100ml water, add 1.2g (0.03mol) dissolution of sodium hydroxide.Above-mentioned diazo liquid is slowly added dropwise to beaker and completes coupling.Filter, washing, dries.
Take above-mentioned dyestuff 2.87g (0.01mol) in 100ml there-necked flask, add 40ml water, add 2.6g (0.02mol) sodium sulfide solution, after adding, be warmed up to 94-95 DEG C, be incubated about lh reaction and finish.Regulating ph with 36% hydrochloric acid is that slant acidity has solid to separate out, and filters, and washing, dries, and yield is more than 95%, and HPLC content is more than 95%.
Take above-mentioned dry reduzate 2.56g (0.01mol) in dry there-necked flask, add 10ml anhydrous propanone, then slowly add 1.64g (0.01mol) methacrylic anhydride, under room temperature, stir the reaction of having spent the night.Yield 97%, content is more than 95%.
Preparation Example five:
Take 12.17g (0.12mol) 36% hydrochloric acid in 100ml there-necked flask, add 20ml water, add 4.14g (0.03mol) p-Nitroaniline, be dissolved as transparent liquid, cool to 0-5 DEG C, drip 2.07g (0.03mol) sodium nitrite solution, 1h is stand-by in insulation; In 1000ml beaker, take 3.4g (0.03mol) meta-cresol, add 100ml water, add 1.2g (0.03mol) dissolution of sodium hydroxide.Above-mentioned diazo liquid is slowly added dropwise to beaker and completes coupling.Filter, washing, dries.
Take above-mentioned dyestuff 2.85g (0.01mol) in 100ml there-necked flask, add 40ml water, add 2.6g (0.02mol) sodium sulfide solution, after adding, be warmed up to 94-95 DEG C, be incubated about 1h reaction and finish.Regulating ph with 36% hydrochloric acid is that slant acidity has solid to separate out, and filters, and washing, dries, and yield is more than 95%, and HPLC content is more than 95%.
Take above-mentioned dry reduzate 2.54g (0.01mol) in dry there-necked flask, add 10ml anhydrous propanone, then slowly add 1.64g (0.01mol) methacrylic anhydride, under room temperature, stir the reaction of having spent the night.Yield 97%, content is more than 95%.
Preparation Example six:
The dyestuff finished product of embodiment 1-2 is dissolved with acetone, tetrahydrofuran (THF), DMF, methyl acrylate respectively, on UV, visible light sub-ray spectrometer, test absorption curve, and definite maximum absorption wavelength position.
Through the test of UV, visible light sub-ray spectrometer, with two kinds that mention in United States Patent (USP) 5662707, United States Patent (USP) 5470932, United States Patent (USP) 5528322, United States Patent (USP) 5543502 and Japanese Patent 8503997
Yellow azo dye is compared, and the dye structure maximum absorption wavelength the present invention relates to, in 365nm left and right, exists acrylamide unsaturated group in structure, can be used on glasses lens to reach the object of vision protection with other monomer copolymerization.Test result is in table one:
The maximum absorption wavelength of table one: embodiment under different solvents
Claims (8)
1. there is the compound shown in following structural formula,
。
According to claim 1 compound in the purposes of preparing in ophthalmic medical equipment.
3. purposes according to claim 2, wherein this compound is for the preparation of ring, intracorneal lens, glaucoma drain valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, medical supply lens, visual telescope, surveillance mirror in artificial lens, artificial cornea, cornea.
4. purposes according to claim 3, wherein glasses are recessive glasse.
5. medical device, it comprises compound claimed in claim 1.
6. according to the medical device of claim 5, wherein medical device comprises ophthalmic medical equipment.
7. according to the medical device of claim 6, wherein said ophthalmic medical equipment is ring, intracorneal lens, glaucoma drain valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, medical supply lens, visual telescope, surveillance mirror in artificial lens, artificial cornea, cornea.
8. according to the medical device of claim 7, wherein glasses are recessive glasse.
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| CN104327534B (en) * | 2013-06-27 | 2016-12-28 | 上海安诺其集团股份有限公司 | A kind of preparation method of medical polymerizable azo dyes compounds |
| CN104312208B (en) * | 2013-06-27 | 2016-04-06 | 上海安诺其集团股份有限公司 | A kind of polymerizable azo dyestuff cpds is preparing the application in artificial lens |
| CN104387799B (en) * | 2013-06-27 | 2016-09-07 | 上海安诺其集团股份有限公司 | A kind of polymerizable azo dyes compounds |
| CN109641832B (en) * | 2016-08-25 | 2021-06-08 | 东莞东阳光医疗智能器件研发有限公司 | Azo compounds, polymers, and methods of preparation and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2604799B2 (en) * | 1988-05-27 | 1997-04-30 | 株式会社メニコン | Intraocular lens material |
| CA2147856C (en) * | 1993-10-18 | 1999-04-27 | David L. Jinkerson | Polymerizable yellow dyes and their use in ophthalmic lenses |
| CN101051090A (en) * | 2006-04-03 | 2007-10-10 | 苏州六六明人工晶体有限公司 | Color changeable transparent ophthalmolgical lens material and its use |
| WO2010089060A2 (en) * | 2009-02-09 | 2010-08-12 | Merck Patent Gmbh | Particles for electrophoretic displays |
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| MX2009003813A (en) * | 2006-10-13 | 2009-05-12 | Alcon Inc | Intraocular lenses with unique blue-violet cutoff and blue light transmission characteristics. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2604799B2 (en) * | 1988-05-27 | 1997-04-30 | 株式会社メニコン | Intraocular lens material |
| CA2147856C (en) * | 1993-10-18 | 1999-04-27 | David L. Jinkerson | Polymerizable yellow dyes and their use in ophthalmic lenses |
| CN101051090A (en) * | 2006-04-03 | 2007-10-10 | 苏州六六明人工晶体有限公司 | Color changeable transparent ophthalmolgical lens material and its use |
| WO2010089060A2 (en) * | 2009-02-09 | 2010-08-12 | Merck Patent Gmbh | Particles for electrophoretic displays |
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