CN104327534B - A kind of preparation method of medical polymerizable azo dyes compounds - Google Patents
A kind of preparation method of medical polymerizable azo dyes compounds Download PDFInfo
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- CN104327534B CN104327534B CN201310272554.2A CN201310272554A CN104327534B CN 104327534 B CN104327534 B CN 104327534B CN 201310272554 A CN201310272554 A CN 201310272554A CN 104327534 B CN104327534 B CN 104327534B
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Abstract
The invention discloses the preparation method of a kind of medical polymerizable azo dyes compounds.The preparation method of this medical polymerizable azo dyes compounds comprises the steps: in non-alcohol organic solvent, under the effect of organic base, compound 4 and compound 5 is carried out esterification,.The invention also discloses the application in preparation artificial intraocular lenses of this medical polymerizable azo dyes compounds 1.The simple in construction of the azo dyes compounds of the present invention, and its preparation method reaction condition is gentle, raw material is easy to get, due to its polymerisable response characteristic so that polymer has more preferable lasting effect.
Description
Technical field
The present invention relates to azo dye field, particularly relate to a kind of be suitable to medical polymerizable azo dye
The preparation method of compound.
Background technology
The eyes are the windows of the mind, but along with bad eye custom and the impact of environmental factors so that eye
There are various health problems in eyeball.Therefore, people have to select by means of glasses, contact lens,
The ophthalmic medical equipment such as artificial intraocular lenses, artificial cornea, protective eye lens carry out improving or regulating.But it is as
Growth in the living standard, people are not the most merely requirement can solve eyes problem, but also require attractive in appearance,
Fashion.
In order to meet the demand of people, United States Patent (USP) US5662707, US5470932, US5528322,
US5543502 and Japan Patent JP8503997 all describe multiple Yellow azo dye structure and
Synthetic method, is then used for acrylic monomers copolymerization generates the artificial crystal material of a kind of yellow.Above-mentioned
Dye structure involved by public technology solve only people's demand to yellow artificial crystal material.Mesh
Before, purple artificial crystal material aspect also substantially belongs to blank.So, the need different in order to solve people
Ask, it is necessary to a kind of dye composition that can be used to prepare other color artificial crystal material is provided.
Nowadays, the patent documentation about polymerizable dyes is a lot of both at home and abroad, such as domestic well-known periodical " dye
Material with dye ", " dye chemical industry " and United States Patent (USP) US5367039 all polymerizable dyes is had relevant
Report.Wherein United States Patent (USP) US5367039 describes a kind of anthraquinone type polymerizable dyes, but this patent
The dyestuff introduced simply is applied to the materials such as paint, ink.Above-mentioned patent documentation is also not applied to
Ophthalmic medical equipment artificial intraocular lenses prepares aspect.United States Patent (USP) US5055602 describes a kind of blue anthracene
Quinoid polymerizable dyes, can be applied to lens material as comonomer.It is clear that this patent is simply
Introducing blue colored crystal material, and this patent relates to dyes of anthraquinone, structure is complicated, and instead
Answer material toxicity big, 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
Structure is complicated, reaction raw materials toxicity is big, higher to requirement of shelter, the defect of inadequate environmental protection, it is provided that
Plant medical polymerizable azo dyes compounds and its production and use.The polymerizable purple of the present invention is even
The simple in construction of nitrogen dye composition, and its preparation method reaction condition is gentle, raw material is easy to get, due to it
Polymerisable response characteristic so that polymer has more preferable lasting effect.
The present invention is to solve above-mentioned technical problem by the following technical programs:
The invention provides a kind of medical polymerizable azo dyes compounds 1,
Wherein, R1For nitro or cyano group, R2For halogen, R3、R4And R6Alone for C1-C4Straight chain
Or branched alkyl or hydrogen, R5For C1-C4Straight or branched alkylidene.
In the present invention, alkylidene refers to the non-thiazolinyl group that alkane is formed after sloughing any two hydrogen atom.
Wherein, R2Preferably fluorine, chlorine, bromine or iodine, be more preferably chlorine or bromine.
Wherein, R3Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or the tert-butyl group,
It is more preferably methyl or ethyl.
Wherein, R4Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or the tert-butyl group,
It is more preferably methyl or ethyl.
Wherein, R5Preferably methylene, ethylidene, propylidene, isopropylidene, butylidene, sub-different
Butyl or the sub-tert-butyl group, be more preferably methylene or ethylidene.
Wherein, R6Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group
Or hydrogen, it is more preferably methyl or hydrogen.
It is preferred that for compound 1, R in the present invention1=-NO2, R2=Br-, R3=-CH3,
R4=-CH2CH3,R6=-CH3；Or, R1=-NO2, R2=Br-, R3=-CH3,
R4=-CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-, R3=-CH3,
R4=-CH2CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-, R3=-CH3,
R4=-CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3, R4=-CH2CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3, R4=-CH3,
R6=-CH3；Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH2CH3,R6=-CH3；
Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH3,R6=-CH3。
In the present invention ,-Z refers both to Z group, such as-CH3Fingernail base ,-NO2Refer to nitro.
Present invention also offers the preparation method of described medical polymerizable azo dyes compounds 1, its bag
Include following step: in non-alcohol organic solvent, under the effect of organic base, by compound 4 and compound
5 carry out esterification,
Wherein, R1For nitro or cyano group, R2For halogen, R3、R4And R6Alone for C1-C4Straight chain
Or branched alkyl or hydrogen, R5For C1-C4Straight or branched alkylidene.
Wherein, R2Preferably fluorine, chlorine, bromine or iodine, be more preferably chlorine or bromine.
Wherein, R3Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or the tert-butyl group,
It is more preferably methyl or ethyl.
Wherein, R4Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or the tert-butyl group,
It is more preferably methyl or ethyl.
Wherein, R5Preferably methylene, ethylidene, propylidene, isopropylidene, butylidene, sub-different
Butyl or the sub-tert-butyl group, be more preferably methylene or ethylidene.
Wherein, R6Preferably methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group
Or hydrogen, it is more preferably methyl or hydrogen.
It is preferred that for compound 1, R in the present invention1=-NO2, R2=Br-, R3=-CH3,
R4=-CH2CH3,R6=-CH3；Or, R1=-NO2, R2=Br-, R3=-CH3,
R4=-CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-, R3=-CH3,
R4=-CH2CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-, R3=-CH3,
R4=-CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3, R4=-CH2CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3, R4=-CH3,
R6=-CH3；Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH2CH3,R6=-CH3；
Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH3,R6=-CH3。
Wherein, the method for described esterification and condition can be this area this type of reaction conventional method and
Condition, following method specifically preferred according to the invention and condition:
Wherein, described non-alcohol organic solvent is preferably acetone, oxolane and DMF(N, N-
Dimethylformamide) in one or more, be more preferably acetone.Described non-alcohol organic solvent with
The volume mass ratio preferably 1.5～3ml/g of compound 4.
Wherein, described organic base is preferably one or more in triethylamine, pyridine and morpholine, more
Goodly for triethylamine.
Wherein, the mol ratio of described organic base and described compound 4 preferably (1.05:1)～
(1.5:1).
Wherein, the mol ratio preferably (1:1.1) of described compound 4 and described compound 5～
(1:1.5).
Wherein, the temperature of described esterification is preferably 10～50 DEG C, is more preferably 20～40 DEG C,
It is most preferably 30～35 DEG C.
Wherein, the process of described esterification can pass through this area conventional means (such as TLC or HPLC)
Be monitored, typically using compound 4 disappear time as reaction terminal, the time of described esterification
Preferably 20～50 hours.
Wherein, described esterification can also carry out post processing after terminating, and is further purified compound 1.
The mode of described post processing can be the post processing mode that this area is conventional, preferably includes following steps: steam
Removing organic solvent, add absolute methanol, filter, methanol washs, and dries.
In the preparation method of compound 1, described compound 4 can be prepared by following method, and it includes
The following step: under the effect of concentrated sulphuric acid and nitrosyl sulfuric acid, there is diazo-reaction in compound 2, then
Coupling reaction is carried out with compound 3,；
Present invention also offers described medical polymerizable azo dyes compounds 1 in preparation artificial intraocular lenses
Application.
Wherein, described artificial intraocular lenses is preferably contact lens, artificial cornea, cornea internal ring, cornea
Interior lens, Glaucoma Drainage valve, intraocular drug slow-released carrier, glasses, protective eye lens, Medical Equipment lens,
One in telescope and observation mirror.
Present invention also offers the preparation method of above-mentioned artificial intraocular lenses, it comprises the steps: described
Medical polymerizable azo dyes compounds 1 and comonomer polymerization forming.Described polymerization can be this
The polymerization that field is conventional, such as radical polymerization, anionic polymerisation, cationic polymerization, activity are gathered
Conjunction, polymerisation in solution, polymerisation in bulk, emulsion polymerization, suspension polymerisation etc..
It is preferred that described medical polymerizable azo dyes compounds 1 mix with comonomer after through stirring
Form homogeneous solution, the most in a mold by radical polymerization synthesis type.Described radical polymerization is permissible
Select thermal initiator or light trigger.If use thermal initiator, polymerization temperature is generally located in
50-100 DEG C, preferably 60-90 DEG C.Polymerization process can select multiple temperature, and preferably 60 DEG C are polymerized 10～25h,
80 DEG C of polymerizations 10～25h again.If use light trigger, polyreaction is at ultraviolet light or radiation of visible light
Under carry out.
Wherein, described comonomer is preferably EMA(ethyl methacrylate) and PEA(2-
Styrene acrylate).
Wherein, in radical polymerization process, it is also possible to add cross-linking agent and ultraviolet absorber, described
Cross-linking agent is preferably Ethylene glycol dimethacrylate, and described ultraviolet absorber is preferably 2-propylene
Acyloxy-5-methylphenyl BTA.
Wherein, the most double (4-tert-butylcyclohexyl) peroxy dicarbonate of described thermal initiator
(perkadox16)；Described light trigger is preferably 2-methyl-2-(4-morpholinyl)-1-[4-(methyl mercapto)
Phenyl]-1-acetone and/or 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.
In the present invention, the described material after polymerization forming can be required shape, as board-like, column,
Disc-shaped etc..In polymer, monomer or the oligomer of remaining can pass through vacuum draw or solvent-extracted side
Formula removes.The material of molding is again by working procedure processing such as cutting, polishings.
The material prepared through said process has the characteristic needed for following artificial intraocular lenses: refraction index is the lowest
In 1.52, Abbe number is not less than 42, and glass transition temperature is between 5-20 DEG C.Wherein, these materials
The characteristic of material measures by the following method: refraction index and Abbe number are to be existed by refractive index equipment
Measure under 25 DEG C of temperature environments；Glass transition temperature is at 10 DEG C every point by differential scanning calorimeter
Measure under clock Elevated Temperature Conditions.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can combination in any, obtain this
Invent each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is: the simple in construction of the azo dyes compounds of the present invention, and
Its preparation method reaction condition is gentle, raw material is easy to get, due to its polymerisable response characteristic so that polymerization
Thing has more preferable lasting effect.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
Embodiment 1～8
Compound 4-1(R1For nitro, R2For bromine, R3For methyl, R4For ethyl, R5For ethylidene)
Preparation
Accurately weigh 10g98% sulphuric acid, three mouthfuls of burnings that 13.34g40% nitrosyl sulfuric acid is dried in 100ml
In Ping, stirring, ice-water bath cools to less than 15 DEG C, controls system temperature and is not higher than 15 DEG C, slow
Slowly add about 10.48g2,4-dinitro-6-bromaniline, about add 1～1.5h, be warmed up to 20～23 DEG C the most slowly,
It is incubated 4h at this temperature.Then in 1h, drip 7.53g N-ethyl-N hydroxyethyl meta-aminotoluene carry out
Coupling reaction, by control reaction temperature 0 on the rocks～5 DEG C in course of reaction, 0～5 DEG C of guarantor after dripping
Temperature 2h completes coupling reaction, and stirring is to room temperature naturally, filters, and washing is dried, obtained compound 4-1
(R1For nitro, R2For bromine, R3For methyl, R4For ethyl, R5For ethylidene) disperse dyes filter
Cake 17.5g, yield 96.74%, HPLC purity 97.8%, LC-MS measures the result of compound 4-1
For [M+H]+453.2, [M+Na]+475.1。
Prepare compound 4-2～4-8, relevant experimental data and Structural Identification data according to the method described above to be shown in Table
1。
The experimental data of table 1 compound 4-1～4-8 and Structural Identification data
Embodiment 9～16
Compound 1-1(R1For nitro, R2For bromine, R3For methyl, R4For ethyl, R5For ethylidene,
R6For methyl) preparation
Accurately Weigh Compound 4-1 dry product 13.57g is in 100ml there-necked flask, is subsequently adding about 30ml
Anhydrous propanone, stirs under room temperature, is warming up to 30-35 DEG C the most slowly, in batches add triethylamine 3ml,
Methacrylic anhydride 3ml, insulation reaction under this temperature conditions, TLC or HPLC monitors reaction, directly
To compound 4-1 reaction completely.React distillation and steamed major part acetone, be subsequently adding absolute methanol
30ml, stirs and is cooled to room temperature, filters, washes with a small amount of methanol, be washed with water to filtrate basic
Without color.Obtain compound 1-1 filter cake.30 DEG C of drying, yield 75.72%, HPLC purity 94.3%,
It is [M+H] that LC-MS measures the result of compound 1-1+521.4, [M+Na]+543.3。
Compound 1-2(R1For nitro, R2For bromine, R3For methyl, R4For methyl, R5For ethylidene,
R6For methyl) preparation
Accurately Weigh Compound 4-2 dry product 13.15g is in 100ml there-necked flask, is subsequently adding about 30ml
DMF (DMF), stirs under room temperature, is warming up to 30-35 DEG C the most slowly, in batches
Secondary addition pyridine 3ml, methacrylic anhydride 3ml, insulation reaction under this temperature conditions, TLC or HPLC
Monitoring reaction, until compound 4-2 reaction is completely.After having reacted, decompression distillation steams major part DMF,
It is subsequently adding absolute methanol about 30ml, stirs and be cooled to room temperature, filter, wash with a small amount of methanol,
It is washed with water to filtrate substantially without color.Obtain compound 1-2 filter cake.30 DEG C of drying, yield 74.8%,
HPLC purity 93.9%, it is [M+H] that LC-MS measures the result of compound 1-2+507.3,
[M+Na]+529.4。
Compound 1-3(R1For nitro, R2For chlorine, R3For methyl, R4For ethyl, R5For ethylidene,
R6For methyl) preparation
Accurately Weigh Compound 4-3 dry product 12.23g is in 100ml there-necked flask, is subsequently adding about 30ml
Anhydrous tetrahydro furan, stirs under room temperature, is warming up to 30-35 DEG C the most slowly, adds morpholine in batches
About 3ml, methacrylic anhydride about 3ml, insulation reaction under this temperature conditions, TLC or HPLC supervises
Control reaction, until compound 4-3 reaction is completely.Steam major part oxolane after having reacted, then add
Enter absolute methanol about 30ml, stir and be cooled to room temperature, filter, wash with a small amount of methanol, then use
It is washed to filtrate substantially without color.Obtain compound 1-3 filter cake.30 DEG C of drying, yield 73.2%, HPLC
Purity 94.5%, it is [M+H] that LC-MS measures the result of compound 1-3+476.9, [M+Na]+498.8。
Prepare compound 1-4～1-8, relevant experimental data and Structural Identification data according to the method described above to be shown 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 ethyl methacrylate, 58g2-acrylic acid benzene second
Alkene ester, 3.5g Ethylene glycol dimethacrylate, 0.02g compound 1-1,0.35g2-acryloxy-5-
Methylphenyl BTA, double (4-tert-butylcyclohexyl) peroxidating two carbon of 0.15g perkadox16(
Acid esters), it is mixed and stirred for uniformly, being passed through nitrogen 10 minutes, then transferring the solution into one by two-layer
In the mould of one silica gel pad composition of glass plate holder.The mould filling solution is put into the baking oven of 80 DEG C
After polymerization 24h, obtain the elastomeric material that a purple is transparent.In polymer, monomer and the oligomer of residual are used
Methanol removes by the way of soxhlet extraction method.Material after extraction is dried at the vacuum drying oven of 60 DEG C,
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 purple
The elastomeric material that color is transparent, measures every character further, and related data is shown in Table 3.
The every character related data of table 3 embodiment 17～24
With in other patent of prior art (United States Patent (USP) US4834750, United States Patent (USP) US5290892)
The artificial crystal material invented is compared, and in table 3, the material of embodiment 17-24 has high index of refraction, height concurrently
Abbe number and suitable glass transition temperature, comply fully with artificial intraocular lenses's industry standard
YY0290-1997 series.The present invention obtains above-mentioned elastomeric material and is not only suitable for manufacturing slim artificial crystalline substance
Body, such as contact lens, artificial cornea, cornea internal ring, intracorneal lens, Glaucoma Drainage valve, ophthalmic
The Medical Equipment lens such as slow releasing carrier of medication, glasses, protective eye lens, observation mirror, and prepared equipment
Artificial intraocular lenses's dispersion differs little, good visual effect.It addition, the material of embodiment 17～24 is all purple,
While solving eyes problem, and attractive in appearance, fashion, solve people to purple artificial crystal material
Demand.
Claims (7)
1. the preparation method of a medical polymerizable azo dyes compounds 1, it is characterised in that its bag
Include following step: in non-alcohol organic solvent, under the effect of organic base, by compound 4 and compound
5 carry out esterification,
Wherein, R1For nitro or cyano group, R2For halogen, R3、R4And R6It is each independently C1-C4
Straight or branched alkyl or hydrogen, R5For C1-C4Straight or branched alkylidene；
Described compound 1 is not
2. preparation method as claimed in claim 1, it is characterised in that described R2For fluorine, chlorine,
Bromine or iodine；And/or, described R3For methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or
The tert-butyl group；And/or, described R4For methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group or
The tert-butyl group；And/or, described R5For methylene, ethylidene, propylidene, isopropylidene, butylidene,
Isobutylidene or the sub-tert-butyl group；And/or, described R6For methyl, ethyl, propyl group, isopropyl, fourth
Base, isobutyl group, the tert-butyl group or hydrogen.
3. preparation method as claimed in claim 1, it is characterised in that for compound 1, R1=-NO2,
R2=Br-, R3=-CH3, R4=-CH2CH3,R6=-CH3；Or, R1=-NO2,
R2=Br-, R3=-CH3, R4=-CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-,
R3=-CH3, R4=-CH2CH3,R6=-CH3；Or, R1=-NO2, R2=Cl-,
R3=-CH3, R4=-CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3,
R4=-CH2CH3,R6=-CH3；Or, R1=-CN, R2=Br-, R3=-CH3, R4=-CH3,R6=-CH3；Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH2CH3,R6=-CH3；Or, R1=-CN, R2=Cl-, R3=-CH3, R4=-CH3,
R6=-CH3。
4. preparation method as claimed in claim 1, it is characterised in that described non-alcohols is organic molten
Agent is one or more in acetone, oxolane and DMF.
5. preparation method as claimed in claim 1, it is characterised in that described organic base is three second
The mol ratio of one or more in amine, pyridine and morpholine, described organic base and described compound 4
For 1.05:1～1.5:1.
6. preparation method as claimed in claim 1, it is characterised in that described compound 4 and institute
The mol ratio of the compound 5 stated is 1:1.1～1:1.5.
7. preparation method as claimed in claim 1, it is characterised in that the temperature of described esterification
Degree is 10～50 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821194A (en) * | 1966-12-27 | 1974-06-28 | Ciba Geigy Ag | Water-insoluble monoazo dyestufs |
| US5662707A (en) * | 1993-10-18 | 1997-09-02 | Alcon Laboratories, Inc. | Polymerizable yellow dyes and their use in ophthalmic lenses |
| 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 |
| CN102618062A (en) * | 2011-02-01 | 2012-08-01 | 上海安诺其纺织化工股份有限公司 | Polymerizable yellow azo dye |
-
2013
- 2013-06-27 CN CN201310272554.2A patent/CN104327534B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3821194A (en) * | 1966-12-27 | 1974-06-28 | Ciba Geigy Ag | Water-insoluble monoazo dyestufs |
| US5662707A (en) * | 1993-10-18 | 1997-09-02 | Alcon Laboratories, Inc. | Polymerizable yellow dyes and their use in ophthalmic lenses |
| 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 |
| CN102618062A (en) * | 2011-02-01 | 2012-08-01 | 上海安诺其纺织化工股份有限公司 | Polymerizable yellow azo dye |
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