CN104387799A - Polymerisable azo dye compound - Google Patents
Polymerisable azo dye compound Download PDFInfo
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- CN104387799A CN104387799A CN201310264224.9A CN201310264224A CN104387799A CN 104387799 A CN104387799 A CN 104387799A CN 201310264224 A CN201310264224 A CN 201310264224A CN 104387799 A CN104387799 A CN 104387799A
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- Prior art keywords
- compound
- methyl
- polymerisable
- azo dyestuff
- ethyl
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- 0 *C(C(CC1O*N(*)c(cc2)cc(*)c2N=Nc(c(*)c2)c(*)cc2[N+]([O-])=O)C1=O)=C Chemical compound *C(C(CC1O*N(*)c(cc2)cc(*)c2N=Nc(c(*)c2)c(*)cc2[N+]([O-])=O)C1=O)=C 0.000 description 1
Abstract
The invention discloses a polymerisable azo dye compound which is as shown in the formula 1. A preparation method of the polymerisable azo dye compound contains the following step: in a non-alcohol organic solvent, an esterification reaction between a compound 4 and a compound 5 is carried out under the action of organic base. The polymerisable azo dye compound has a simple structure; reaction condition of the preparation method is mild; and raw materials are easily available. Due to the polymerizable reaction characteristic, the polymer has a better persistent effect.
Description
Technical field
The present invention relates to azoic dyestuff field, particularly relate to and be a kind ofly suitable for medical polymerizable azo dyestuff cpds.
Background technology
The eyes are the windows of the mind, but along with the impact of bad eye custom and environmental factors, make eyes occur various health problem.Therefore, people have to select to carry out improving or regulating by means of ophthalmic medical equipment such as glasses, contact lens, artificial lens, artificial cornea, eye-protection glasses.But along with growth in the living standard, people are not only just that requirement can solve eyes problem, but also require attractive in appearance, fashion.
In order to meet the demand of people, US Patent No. 5662707, US5470932, US5528322, US5543502 and Japanese Patent JP8503997 describe structure and the synthetic method of multiple Yellow azo dye, are then used for following Acrylic Acid Monomer copolymerization to generate a kind of artificial crystal material of yellow.Dye structure involved by above-mentioned public technology solve only the demand of people to yellow artificial crystal material.At present, purple artificial crystal material aspect also belongs to blank substantially.So, in order to solve the different demand of people, be necessary to provide a kind of dye composition that can be used for preparing other color artificial crystal material.
Nowadays, the patent documentation both at home and abroad about polymerizable dyes is a lot, as domestic well-known periodical " dyestuff and dyeing ", " dye chemical industry " and US Patent No. 5367039 all have relevant report to polymerizable dyes.Wherein US Patent No. 5367039 describes a kind of anthraquinone type polymerizable dyes, but the dyestuff of this patent Introduction is just applied to the materials such as paint, ink.Also not to be applied to ophthalmic medical equipment artificial lens in above-mentioned patent documentation and to prepare aspect.US Patent No. 5055602 describes a kind of blue anthraquinone type polymerizable dyes, can be used as comonomer and is applied to lens material.Obviously, this patent is just introduced blue colored crystal material, and this patent relates to dyes of anthraquinone, complex structure, and reaction raw materials toxicity is large, higher to requirement of shelter, inadequate environmental protection.
Summary of the invention
Technical problem solved by the invention is to overcome existing polymerizable dyes color single, and complex structure, reaction raw materials toxicity are large, higher to requirement of shelter, the defect of inadequate environmental protection, provides a kind of polymerizable azo dyestuff cpds and its production and use.The structure of polymerizable purple azo dyestuff cpds of the present invention is simple, and its preparation method reaction conditions is gentle, raw material is easy to get, and due to its polymerisable response characteristic, makes polymkeric substance have better long-lasting.
The present invention solves the problems of the technologies described above by the following technical programs:
The invention provides a kind of polymerizable azo dyestuff cpds 1,
Wherein, R
1for nitro or cyano group, R
2for halogen, R
3, R
4and R
6alone be C
1-C
4straight or branched alkyl or hydrogen, R
5for C
1-C
4straight or branched alkylidene group.
In the present invention, alkylidene group refers to the non-thiazolinyl group formed after alkane sloughs any two hydrogen atoms.
Wherein, R
2being preferably fluorine, chlorine, bromine or iodine, is more preferably chlorine or bromine.
Wherein, R
3being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, is more preferably methyl or ethyl.
Wherein, R
4being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, is more preferably methyl or ethyl.
Wherein, R
5being preferably methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene or the sub-tertiary butyl, is more preferably methylene radical or ethylidene.
Wherein, R
6being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or hydrogen, is more preferably methyl or hydrogen.
In the present invention preferably, for compound 1, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3.
In the present invention ,-Z all refers to Z group, such as-CH
3nail base ,-NO
2refer to nitro.
Present invention also offers the preparation method of described polymerizable azo dyestuff cpds 1, it comprises the steps: in non-alcohol organic solvent, under the effect of organic bases, compound 4 and compound 5 is carried out esterification,
Wherein, R
1for nitro or cyano group, R
2for halogen, R
3, R
4and R
6alone be C
1-C
4straight or branched alkyl or hydrogen, R
5for C
1-C
4straight or branched alkylidene group.
Wherein, R
2being preferably fluorine, chlorine, bromine or iodine, is more preferably chlorine or bromine.
Wherein, R
3being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, is more preferably methyl or ethyl.
Wherein, R
4being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, is more preferably methyl or ethyl.
Wherein, R
5being preferably methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene or the sub-tertiary butyl, is more preferably methylene radical or ethylidene.
Wherein, R
6being preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or hydrogen, is more preferably methyl or hydrogen.
In the present invention preferably, for compound 1, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3.
Wherein, the method for described esterification and condition can be ordinary method and the condition of this type of reaction of this area, and the present invention is following method and condition particularly preferably:
Wherein, described non-alcohol organic solvent is preferably acetone, tetrahydrofuran (THF) and DMF(N, dinethylformamide) in one or more, be more preferably acetone.The volume mass of described non-alcohol organic solvent and compound 4 is 1.5 ~ 3ml/g than preferably.
Wherein, described organic bases is preferably one or more in triethylamine, pyridine and morpholine, is more preferably triethylamine.
Wherein, the mol ratio of described organic bases and described compound 4 is preferably (1.05:1) ~ (1.5:1).
Wherein, described compound 4 is preferably (1:1.1) ~ (1:1.5) with the mol ratio of described compound 5.
Wherein, the temperature of described esterification is preferably 10 ~ 50 DEG C, is more preferably 20 ~ 40 DEG C, is 30 ~ 35 DEG C best.
Wherein, the process of described esterification is monitored by this area conventional means (as TLC or HPLC), and as the terminal of reaction when generally disappearing using compound 4, the time of described esterification is preferably 20 ~ 50 hours.
Wherein, can also aftertreatment be carried out after described esterification terminates, be further purified compound 1.The mode of described aftertreatment can be the post processing mode of this area routine, preferably includes following steps: boil off organic solvent, add anhydrous methanol, and filter, methanol wash, dries.
In the preparation method of compound 1, described compound 4 can be obtained by following method, and it comprises the following steps: that diazotization reaction occurs compound 2, then carries out coupled reaction with compound 3 under the effect of the vitriol oil and nitrosyl sulfuric acid;
Present invention also offers described polymerizable azo dyestuff cpds 1 and prepare the application in artificial lens.
Wherein, described artificial lens is preferably the one in contact lens, artificial cornea, cornea inner ring, intracorneal lens, Glaucoma Drainage valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, medical supply lens, visual telescope and surveillance mirror.
Present invention also offers the preparation method of above-mentioned artificial lens, it comprises the steps: shaping with copolymerization monomer polymerization for described polymerizable azo dyestuff cpds 1.Described polymerization can be the polymerization process of this area routine, such as radical polymerization, anionoid polymerization, cationoid polymerisation, living polymerization, solution polymerization, mass polymerization, letex polymerization, suspension polymerization etc.
Preferably, after described polymerizable azo dyestuff cpds 1 mixes with comonomer, form homogeneous solution through stirring, then in a mold by radical polymerization synthesis type.Described radical polymerization can select thermal initiator or light trigger.If use thermal initiator, polymerization temperature is generally located at 50-100 DEG C, preferred 60-90 DEG C.Polymerization process can select multiple temperature, preferably 60 DEG C of polymerization 10 ~ 25h, then 80 DEG C of polymerization 10 ~ 25h.If use light trigger, polyreaction is carried out under UV-light or radiation of visible light.
Wherein, described comonomer is preferably EMA(β-dimethyl-aminoethylmethacrylate) and PEA(2-styrene acrylate).
Wherein, in radical polymerization process, can also add linking agent and uv-absorbing agent, described linking agent is preferably Ethylene glycol dimethacrylate, and described uv-absorbing agent is preferably 2-acryloxy-5-methylphenyl benzotriazole.
Wherein, described thermal initiator is preferably two (4-tert-butylcyclohexyl) peroxy dicarbonates (perkadox16); Described light trigger is preferably 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone and/or 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.
In the present invention, the material after described polymerization forming can be required shape, as board-like, column, disc-shaped etc.Monomer remaining in polymkeric substance or oligopolymer can be removed by vacuum take-off or solvent-extracted mode.Shaping material is processed by operations such as cutting, polishings again.
The material prepared through said process has the characteristic needed for following artificial lens: refractive index is not less than 1.52, and Abbe number is not less than 42, and second-order transition temperature is between 5-20 DEG C.Wherein, these properties of materials measure by the following method: refractive index and Abbe number are measured under 25 DEG C of temperature environments by refractive index equipment; Second-order transition temperature is measured under 10 DEG C of per minute Elevated Temperature Conditions by differential scanning calorimeter.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: the structure of azo dyestuff cpds of the present invention is simple, and its preparation method reaction conditions is gentle, raw material is easy to get, and due to its polymerisable response characteristic, makes polymkeric substance have better long-lasting.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
Embodiment 1 ~ 8
Compound 4-1(R
1for nitro, R
2for bromine, R
3for methyl, R
4for ethyl, R
5for ethylidene) preparation
Accurately take 10g98% sulfuric acid, 13.34g40% nitrosyl sulfuric acid in the there-necked flask of 100ml drying, stir, ice-water bath cools to less than 15 DEG C, hierarchy of control temperature is not higher than 15 DEG C, slowly add about 10.48g2,4-dinitrobenzene-6-bromaniline, about add 1 ~ 1.5h, then be warmed up to 20 ~ 23 DEG C slowly, be incubated 4h at this temperature.Then in 1h, drip 7.53g N-ethyl-N hydroxyethyl meta-aminotoluene carry out coupled reaction, by control temperature of reaction on the rocks 0 ~ 5 DEG C in reaction process, after dripping, complete coupled reaction at 0 ~ 5 DEG C of insulation 2h, naturally be stirred to room temperature, filter, washing, dry, obtain compound 4-1(R
1for nitro, R
2for bromine, R
3for methyl, R
4for ethyl, R
5for ethylidene) dispersed dye filter cake 17.5g, the result that yield 96.74%, HPLC purity 97.8%, LC-MS measures compound 4-1 is [M+H]
+453.2, [M+Na]
+475.1.
Prepare compound 4-2 ~ 4-8 according to the method described above, relevant experimental data and Structural Identification data are in table 1.
The experimental data of table 1 compound 4-1 ~ 4-8 and Structural Identification data
Embodiment 9 ~ 16
Compound 1-1(R
1for nitro, R
2for bromine, R
3for methyl, R
4for ethyl, R
5for ethylidene, R
6for methyl) preparation
Accurate Weigh Compound 4-1 dry product 13.57g is in 100ml there-necked flask, then about 30ml anhydrous propanone is added, stirred at ambient temperature is even, then 30-35 DEG C is warming up to slowly, add triethylamine 3ml, methacrylic anhydride 3ml in batches, insulation reaction under this temperature condition, TLC or HPLC monitors reaction, until compound 4-1 reacts completely.React distillation and steamed most of acetone, then added anhydrous methanol 30ml, stirred and be cooled to room temperature, filtered, use a small amount of methanol wash column, then wash with water to filtrate substantially without color.Obtain compound 1-1 filter cake.30 DEG C of oven dry, the result that yield 75.72%, HPLC purity 94.3%, LC-MS measures compound 1-1 is [M+H]
+521.4, [M+Na]
+543.3.
Compound 1-2(R
1for nitro, R
2for bromine, R
3for methyl, R
4for methyl, R
5for ethylidene, R
6for methyl) preparation
Accurate Weigh Compound 4-2 dry product 13.15g is in 100ml there-necked flask, then about 30mlDMF (N is added, dinethylformamide), stirred at ambient temperature is even, then be warming up to 30-35 DEG C slowly, add pyridine 3ml, methacrylic anhydride 3ml in batches, insulation reaction under this temperature condition, TLC or HPLC monitors reaction, until compound 4-2 reacts completely.React rear underpressure distillation and steamed most of DMF, then added anhydrous methanol and be about 30ml, stirred and be cooled to room temperature, filtered, use a small amount of methanol wash column, then wash with water to filtrate substantially without color.Obtain compound 1-2 filter cake.30 DEG C of oven dry, the result that yield 74.8%, HPLC purity 93.9%, LC-MS measures compound 1-2 is [M+H]
+507.3, [M+Na]
+529.4.
Compound 1-3(R
1for nitro, R
2for chlorine, R
3for methyl, R
4for ethyl, R
5for ethylidene, R
6for methyl) preparation
Accurate Weigh Compound 4-3 dry product 12.23g is in 100ml there-necked flask, then about 30ml anhydrous tetrahydro furan is added, stirred at ambient temperature is even, then 30-35 DEG C is warming up to slowly, add that morpholine is about 3ml, methacrylic anhydride is about 3ml in batches, insulation reaction under this temperature condition, TLC or HPLC monitors reaction, until compound 4-3 reacts completely.Steam most of tetrahydrofuran (THF) after having reacted, then add anhydrous methanol and be about 30ml, stir and be cooled to room temperature, filter, use a small amount of methanol wash column, then wash with water to filtrate substantially without color.Obtain compound 1-3 filter cake.30 DEG C of oven dry, the result that yield 73.2%, HPLC purity 94.5%, LC-MS measures compound 1-3 is [M+H]
+476.9, [M+Na]
+498.8.
Prepare compound 1-4 ~ 1-8 according to the method described above, relevant experimental data and Structural Identification data are in table 2.
The experimental data of table 2 compound 1-1 ~ 1-8 and Structural Identification data
Application Example 17 ~ 24
In the beaker of a 250ml, add 38g β-dimethyl-aminoethylmethacrylate, 58g2-styrene acrylate, 3.5g Ethylene glycol dimethacrylate, 0.02g compound 1-1,0.35g2-acryloxy-5-methylphenyl benzotriazole, two (4-tert-butylcyclohexyl) peroxy dicarbonate of 0.15g perkadox16(), mix and stir, passing into nitrogen 10 minutes, then solution being transferred in a mould be made up of layer glass plate holder silica gel pad.After the baking oven mould filling solution being put into 80 DEG C is polymerized 24h, obtain the resilient material that a purple is transparent.Monomer residual in polymkeric substance and oligopolymer methyl alcohol are removed by the mode of soxhlet extraction method.Material after extraction is after the vacuum drying oven drying of 60 DEG C, and the every character measuring material is as shown in table 3.
According to the method described above, compound 1-2 ~ 1-8 all can carry out being polymerized with comonomer thus obtain the transparent resilient material of purple, and measure every character further, related data is in table 3.
The every character related data of table 3 embodiment 17 ~ 24
Compared with the artificial crystal material invented in other patent of prior art (US Patent No. 4834750, US Patent No. 5290892), in table 3, the material of embodiment 17-24 has high refractive index, high Abbe number and suitable second-order transition temperature concurrently, meets artificial lens industry standard YY0290-1997 series completely.The present invention obtains above-mentioned resilient material and is not only suitable for manufacturing slim artificial lens, as medical supply lens such as contact lens, artificial cornea, cornea inner ring, intracorneal lens, Glaucoma Drainage valve, intraocular drug slow-released carrier, glasses, eye-protection glasses, surveillance mirrors, and prepared little, the good visual effect of equipment artificial lens dispersion difference.In addition, the material of embodiment 17 ~ 24 is all purple, while solution eyes problem, and attractive in appearance, fashion, solve people to the demand of purple artificial crystal material.
Claims (7)
1. a polymerizable azo dyestuff cpds 1,
Wherein, R
1for nitro or cyano group, R
2for halogen, R
3, R
4and R
6be C independently of one another
1-C
4straight or branched alkyl or hydrogen, R
5for C
1-C
4straight or branched alkylidene group.
2. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, described R
2for fluorine, chlorine, bromine or iodine.
3. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, described R
3for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.
4. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, described R
4for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.
5. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, described R
5for methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene or the sub-tertiary butyl.
6. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, described R
6for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or hydrogen.
7. polymerizable azo dyestuff cpds 1 as claimed in claim 1, is characterized in that, for compound 1, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-NO
2, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Br-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
2cH
3,
r
6=-CH
3; Or, R
1=-CN, R
2=Cl-, R
3=-CH
3, R
4=-CH
3,
r
6=-CH
3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018036543A1 (en) * | 2016-08-25 | 2018-03-01 | 广东东阳光药业有限公司 | Azo compound, polymer, preparation method and use |
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| WO1995011279A1 (en) * | 1993-10-18 | 1995-04-27 | Alcon Laboratories, Inc. | Polymerisable yellow dyes and their use in ophthalmic lenses |
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2013
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|---|---|---|---|---|
| WO1995011279A1 (en) * | 1993-10-18 | 1995-04-27 | Alcon Laboratories, Inc. | Polymerisable yellow dyes and their use in ophthalmic lenses |
| CN1849375A (en) * | 2003-09-08 | 2006-10-18 | 博士伦公司 | Novel reactive yellow dyes useful for ocular devices |
| CN101368002A (en) * | 2008-06-02 | 2009-02-18 | 上海大学 | Azo dye acrylic ester, its copolymerization latex coating dyeing watersoluble adhesive agent and method of producing the same |
| CN102471597A (en) * | 2009-07-06 | 2012-05-23 | 诺瓦提斯公司 | Visible light absorbers for ophthalmic lens materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018036543A1 (en) * | 2016-08-25 | 2018-03-01 | 广东东阳光药业有限公司 | Azo compound, polymer, preparation method and use |
| CN109641832A (en) * | 2016-08-25 | 2019-04-16 | 广东东阳光药业有限公司 | Azo-compound, polymer and Preparation method and use |
| 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 | Publication date |
|---|---|
| CN104387799B (en) | 2016-09-07 |
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