Visible light absorbers for ophthalmic lens materials

FIELD: physics, optics.

SUBSTANCE: invention relates to visible light absorbers, particularly novel azo compound monomers, particularly suitable for use in materials for implantable ophthalmic lens materials. The ophthalmic device material includes an azo compound, a device forming acrylic monomer and a cross-linking agent. The ophthalmic device is made from the ophthalmic device material and is in the form of intraocular lenses, contact lenses, keratoprostheses and corneal inlays or rings.

EFFECT: azo compounds are suitable for use as monomers which absorb part of the visible light spectrum (about 380-495 nm).

17 cl, 6 dwg, 3 tbl

 

The technical field to which the invention relates

This invention relates to the absorbers of visible light. In particular, this invention relates to new monomers of azo compounds, particularly applicable for use in materials for implantable ophthalmic lenses.

Background of invention

As ingredients for polymer materials used for the manufacture of ophthalmic lenses, known as UV absorbers and visible light, and such absorbers can be used in combination with each other. Preferably, such absorbers are not only included in this material, and covalently linked to the polymer structure of the lens material in order to prevent their migration, phase separation or leakage of lens material. Such stability is particularly important in the case of implantable ophthalmic lenses, in which the leakage of the absorber can be a Toxicological problem and lead to a loss of activity of blocking UV/visible light in the implant.

Many absorbers contain conventional polymerized olefinic groups such as methacrylate, acrylate, methacrylamide, acrylamide or styrene group. In the copolymerization with other ingredients in the materials for lenses, usually is in the presence of a radical initiator, is the introduction of absorbers in the resulting polymer chain. The inclusion of additional functional groups in the absorber may affect one or more properties of light absorption, solubility or reactivity of the absorber. If the absorber does not have sufficient solubility in the rest of the ingredients material for ophthalmic lenses or polymeric material for lenses, the absorber may coalesce into domains, which could interact with light and lead to reduced optical transparency of the lens.

Examples of absorbers of visible light, suitable for use in intraocular lenses, can be found in U.S. patent No. 5470932. There is a need for additional compounds that absorb visible light, copolymerizing with other ingredients in the materials implantable lenses, relatively inexpensive to obtain, and which are effective in the absorption of light with a wavelength in the range 380-495 nm.

Brief description of the invention

The present invention provides new compounds that satisfy the above-mentioned tasks. These azo compounds are particularly suitable for use as monomers that absorb part of the visible light spectrum (approximately 380-495 nm). These absorbers are suitable for use in ophthalmic lenses, including to the stroke of the lens. They are especially applicable to implantable lenses, such as intraocular lenses (IOL).

Azo compounds of the present invention contain reactive groups that allow absorbers covalently to contact the material of the eye lens. In addition, the absorbers of the present invention can be synthesized in approximately 3-4 stage of readily available, inexpensive starting compounds, eliminating the need for column chromatography.

The present invention also relates to materials for ophthalmic devices containing such compounds.

Brief description of drawings

In figures 1-4 presents the curves of the transparency coefficient for compounds a-C at various concentrations.

The figure 5 presents the curve of the transparency coefficient for the combination of compounds a and UV absorber (UV-1").

The figure 6 presents the results of photostability for the preparation of example 11D after optical exposure, equivalent to 20 years.

Detailed description of the invention

Unless otherwise stated, all amounts of ingredients are expressed in percentages, are presented as % wt./mass.

Azo compounds of the present invention have the structure

,

in which

X1, X2and X3independent means who with N, With1-C6alkyl, C1-C6alkoxy, phenoxy or benzyloxy;

Y denotes H, F, Cl, Br, I or C1-C6alkyl;

W is absent or denotes-O-C(=O)NH-CH2CH2-; and

Z denotes H, CH3With2H5or CH2HE.

Preferred compounds of formula I are compounds in which

X1, X2and X3independently mean H, C1-C4alkyl or C1-C4alkoxy,

Y represents H, Cl or1-C4alkyl;

W is absent, and

Z denotes H or CH3.

More preferred compounds of formula I are the following three compounds: 2-hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzonitrile ("compound A"); 2-hydroxy-5-methyl-3-((3,4,5-trimethoxyphenyl)diazenyl)bezelmaterial ("connection"); and 5-chloro-2-hydroxy-3-((4-methoxyphenyl)diazenyl)bezelmaterial ("connection").

More preferred compounds of formula I are compounds a and B.

A representative synthesis of the azo compounds of the formula I is as follows.

1. At stages 1-2 are salt, page derived 2-nitroaniline, and then injected it into interaction with the required connection phenol, receiving an azo dye.

2. At stage 3 free g is drakelow group of azo dye atrificial, getting the polymerized azo dyes containing (meth)acrylate group. Then this (meth)acrylate group forms a covalent bond when interacting with vinyl monomers, comonomers, macromanage, crosslinking agents and other components that are typically used for obtaining the copolymer substances for ophthalmic devices, in particular, acrylic IOL.

Azo compounds of the present invention suitable for use in materials for ophthalmic devices, in particular IOL. Generally, materials for IOL will contain 0.005 to 0.2% (wt./mass.) the compounds of formula I. Preferably, the materials for IOL will contain from 0.01 to 0.08% (wt./mass.) compounds of the present invention. Most preferably, the materials for IOL will contain from 0.01 to 0.05% (wt./mass.) compounds of the present invention. Materials for such devices is obtained by copolymerization of the compounds of formula I with other ingredients, such as substances forming device, cross-linking agents. Materials for IOL or other ophthalmic devices containing the compounds of formula I, optionally contain UV absorbers and other absorbers of visible light.

In this area there are many substances forming device, and they include, inter alia, as acrylic and is omnistorage monomers. See, for example, U.S. patents№ 7101949, 7067602, 7037954, 6872793, 6852793, 6846897, 6806337, 6528602 and 5693095. In the case of IOL for use in the compositions of the present invention can be any known material for IOL. Preferably, the materials for ophthalmic devices contain acrylic or methacrylic monomer forming device. More preferably, the forming device monomers include a monomer of the formulaII:

,

where in formula II:

And represents N, CH3CH2CH3or CH2IT;

In represents (CH2)mor [O(CH2)2]z;

C represents (CH2)w,

m is 2-6;

z is 1-10;

Y is absent or represents O, S or NR', provided that if Y is O, S or NR', represents (CH2)m;

R' represents H, CH3Cn'H2n'+1(n=1-10), ISO-OS3H7With6H5or CH2With6H5;

w is 0-6, provided that m+w≤8; and

D represents H, C1-C4alkyl, C1-C4alkoxy, C6H5CH2With6H5or halogen.

The preferred monomers of the formulaIIare monomers in which a represents N or CH3In represents (CH2)m, m is 2-5, Y does not is t or represents O, w is 0-1, and D is N. Most preferred are 2-fenilatilmalonamid, 4-fenilmetilketil, 5-perpendicularily, 2-benzyloxyethanol and 3-benzyloxypropionic and their corresponding acrylates.

The monomers of the formulaIIknown and can be obtained by known methods. For example, conjugated alcohol of the desired monomer can be connected in a reaction vessel with methyl methacrylate, tetrabutylammonium (catalyst) and a polymerization inhibitor such as 4-benzyloxyphenol. Then the vessel can be heated to facilitate the reaction and to drive the reaction by-products, in order to bring the reaction to completion. Alternative schemes of synthesis include the addition of methacrylic acid to a paired alcohol and catalysis by carbodiimide or mixing paired alcohol with methacryloylamido and a base, such as pyridine or triethylamine.

Materials for devices usually contain generally at least about 75%, preferably at least about 80%, of the monomers forming the device.

In addition to the absorber of the present invention to provide a device of the monomer materials for devices of the present invention typically include a crosslinking agent. Crosslinking agent used in materials for devices of the present invention, can be any t is Renaldo on unsaturated ethylene type connection, containing more than one unsaturated group. Suitable crosslinking agents include, for example, etilenglikolevykh, detranscendentalized, alismataceae, 1,3-propeciageneric, 2,3-propeciageneric, 1,6-hexaniacinate, 1,4-potentialtheorie, CH2=C(CH3)C(=O)O-(CH2CH2O)p-C(=O)C(CH3)=CH2where p=1-50 and CH2=C(CH3)C(=O)O(CH2)tO-C(=O)C(CH3)=CH2where t=3 to 20 and their corresponding acrylates. Preferred cross-linking monomer is CH2=C(CH3)C(=O)O-(CH2CH2O)p-C(=O)C(CH3)=CH2where R is such that srednekislye molecular weight is about 400, about 600, or about 1000.

In General, the total number of cross-linking component is at least 0.1% wt., and, depending on the identity and concentration of other components and the desired physical properties may vary up to about 20% of the mass. The preferred range of concentration of crosslinking component is 1-5% for small hydrophobic compounds with molecular masses that make up typically less than 500 daltons, and 5-17% (wt./mass.) for large hydrophilic compounds with molecular weights generally in the range of 500-5000 daltons.

Suitable polymerization initiators for materials, devices containing the UV absorber/the ID. the present invention, include thermal initiators and photoinitiators. Preferred thermal initiators include peroxide free radical initiators such as tert-butyl(peroxy-2-ethyl)hexanoate and di(tert-butylcyclohexyl)PEROXYDICARBONATE (commercially available in the form of Perkadox® 16 from Akzo Chemicals Inc. Chicago, Illinois). Usually the initiators are present in an amount of from about 5% (wt./mass)or less. Because of free radical initiators chemically not become part of the resulting polymer, the total amount of initiator is usually not included in the determination of the number of other ingredients.

Materials for devices containing uzasadnienie the present invention also optionally include a UV absorber and/or other absorber of visible light. There are many reactive (copolymerizing) UV absorbers that are suitable for use in implantable ophthalmic lenses and devices. Preferred UV absorbers include absorbers described in one of two jointly transferred to, provisional patent application U.S. serial number 61/111204, simultaneously pending before the patent office, filed November 4, 2008. The UV absorbers are usually present in the materials for intraocular lenses.

In addition to azo compounds of the formulaIforming device is in monomer, cross-linking agent, and, optionally, a UV absorber and/or other absorber of visible light, the materials of the present invention may also include other ingredients to reduce the stickiness and reflections. Examples of agents for reducing the stickiness agents are described in the publication U.S. No. 2009/0132039 A1 and 2009/0137745 A1. Examples of agents for reducing reflections are the agents described in the publication U.S. No. 2009/0093604 A1 and 2009/0088544 A1.

IOL created from the materials of the present invention may have any structure that can be collapsed or folded to a small cross-section, which will be held in a relatively smaller incision. For example, the IOL may constitute what is known as a gooseneck or polyblock design, and include optical and tactile components. Optics is that part, which serves as a lens. Tactile components associated with optics and hold the optics in the eye at the proper place. Optical and tactile(e) components can be from the same or from different material. Polyblock lenses are so named because the optical and tactile(e) the components are manufactured separately, and then tactile components associated with optical. In the one-piece lenses optical and tactile components obtained from one piece of material. Depending on the material, tactil the major components are then cut off, or grind material, receiving the IOL.

In addition to the IOL, the materials of the present invention are also suitable for use in other ophthalmic devices such as contact lenses, keratoplasty and corneal implants or rings.

Hereinafter the invention will be illustrated by the following examples, which are intended to illustrate, but not limit.

Example 1

Synthesis of 2-(hydroxymethyl)-4-methyl-6-((3,4,5-trimethoxyphenyl)diazenyl)phenol. In a round bottom flask of 250 ml, equipped with a magnetic stirrer, were placed 9,06 g (49.4 mmol) of 3,4,5-trimethoxyaniline (Aldrich, Milwaukee, WI), 21 ml of concentrated HCl (aq.) (J. T. Baker), 100 ml of absolute ethanol and 100 ml of deionized water. Within 30 minutes was added dropwise sodium nitrite (3,63 g, for 52.6 mmol, Sigma-Aldrich) in 30 ml of water, maintaining the temperature of the reaction mixture at -10°C. the Reaction mixture was stirred for 1 hour. Was added sulfamic acid (300 mg, Aldrich) and the mixture was stirred for another 20 minutes. The solid was filtered, and the cold filtrate was left. (2-Hydroxy-5-methyl-1,3-phenylene)dimethanol was dissolved in 100 ml of deionized water. To a solution of (2-hydroxy-5-methyl-1,3-phenylene)dimethanol was added approximately one-fourth volume of a solution containing 10.0 g (250 mmol) of NaOH in water, and cool the mixture to 0°C. for 30-60 minutes to a mixture of (2-Ki-the Roxy-5-methyl-1,3-phenylene)dimethanol simultaneously added a mixture of the page and the remaining NaOH solution, and then was stirred for 1 hour at 0°C and for 4 hours at ambient temperature. The mixture was poured into 3 l of deionized water and acidified to pH 4 1N HCl. The solid was filtered and washed with several liters of water and dried in vacuum at 50°C, obtaining a solid dark color.

lH NMR (CDCl3) Delta: 13,21 (s, 1H, Ar-OH), 7,71 (s, 1H, Ar-H), 7,21 (s, 1H, Ar-H), to 7.15 (s, 2H, Ar-OH), 4,78 (s, 2H, Ar-CH2), of 3.96 (s, 6H, Ar-OCH3), of 3.94 (s, 3H, Ar-OCH3), 2,39 (s, 3H, Ar-CH3).

This compound (and other compounds described below) can be functionalitywith side (meth)acrylate groups (according to the formula (I) using different methods of esterification. For example, this compound is dissolved in anhydrous tetrahydrofuran, or methylene chloride containing MEHQ as inhibitor and pyridine as HCl acceptor. Was added dropwise approximately 1-1,5 molar equivalent of methacryloylamido at -20 to 0°C. during the addition of methacryloylamido the cooling bath is removed and leave the reaction mixture is mixed at ambient temperature for 20 hours. Salt secrete HCl by filtration, and the organic layer washed with 0.5 to 1N HCl, dried over MgSO4or Na2SO4and then concentrated under reduced pressure to give crude product, which perakis alsovisit from methanol or ethanol, receiving the desired product. Other standard methods of esterification, which are known to specialists in this area include methods using methacrylic anhydride and methyl methacrylate.

Example 2

Synthesis of 2-(hydroxymethyl)-6-((4-methoxyphenyl)diazenyl)-4-METHYLPHENOL. In a round bottom flask of 250 ml, equipped with a magnetic stirrer, were placed 8,91 g (to 72.4 mmol) of p-anisidine (Aldrich), 30 ml of concentrated HCl (aq.) (J. T. Baker), 150 ml of absolute ethanol and 150 ml of deionized water. Within 30 minutes was added dropwise sodium nitrite (are 5.36 g, and 77.6 mmol)in 30 ml of water, maintaining the temperature of the reaction mixture at -10°C. the Reaction mixture was stirred for 1 hour. Was added 300 mg of sulfamic acid, and then stirred for another 20 minutes. The solid was filtered, and the cold solution, page left. (2-Hydroxy-5-methyl-1,3-phenylene)dimethanol was dissolved in 100 ml of deionized water. To a solution of (2-hydroxy-5-methyl-1,3-phenylene)dimethanol was added approximately one-fourth volume of a solution containing of 14.7 g (367 mmol) NaOH in water, and cool the mixture to 0°C. for 30-60 minutes to a mixture of (2-hydroxy-5-methyl-1,3-phenylene)dimethanol simultaneously added a mixture of the page and the remaining NaOH solution, and then stirred for 1 hour at 0°C and for 4 hours at the temperature of the environment is s. The mixture was poured into 3 l of deionized water and acidified to pH 4 1N HCl. The solid was filtered and washed with several liters of water and dried in vacuum at 50°C receives 15.9 g (81%) solid orange color.

1H NMR (CDCl3) Delta: 13,22 (s, 1H, Ar-OH), a 7.85 (m, 2H, Ar-H), 7,66 (s, 1H, Ar-H), 7,17 (s, 1H, Ar-H), 7,03 (m, 2H, Ar-H), of 4.77 (s, 2H, Ar-CH2), the 3.89 (s, 3H, CH3O-Ar), is 2.37 (s, 3H, Ar-CH3).

Example 3

Synthesis of 2-methoxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzonitrile ("Compound A"). In a round bottom flask of 500 ml, equipped with a magnetic stirrer and the input of nitrogen, dissolved rate of 8.75 g (32.1 mmol) of 2-(hydroxymethyl)-6-((4-methoxyphenyl)diazenyl)-4-METHYLPHENOL in 300 ml of anhydrous THF. Added ~50 mg of 4-methoxyphenol (MEHQ), then 16.5 g (209 mmol) of anhydrous pyridine. The reaction mixture was cooled to -20°C and added dropwise 4,91 g (47,0 mmol) methacryloylamido. The reaction mixture was stirred for 1 hour at -20°C and then for 20 hours at ambient temperature. The precipitate was filtered and was added to the filtrate diethyl ether (200 ml) and ethyl acetate (200 ml). The organic layer was washed with 0.5 N HCl, and then dried over magnesium sulfate. The solvent was removed under reduced pressure and the crude product is recrystallized from methanol, getting a solid orange color that washed oldnum ethanol, and then dried for 20 hours under vacuum (0.1 mm, RT. Art.) at room temperature, receiving 7.0 g (64%).

1H NMR (CDCl3) Delta: 13,12 (s, 1H, Ar-OH), to 7.84 (m, 2H, Ar-H), 7,68 (s, 1H, Ar-H), of 7.23 (s, 1H, Ar-H), 7,02 (m, 2H, Ar-H), 6,16 (s, 1H, vinyl-H), to 5.58 (s, 1H, vinyl-H), 5,31 (s, 2H, Ar-CH2), the 3.89 (s, 3H, CH3O-Ar), of 2.38 (s, 3H, Ar-CH3), to 1.98 (s, 3H, C=C-CH3).

Example 4

Synthesis of (5-chloro-2-hydroxy-1,3-phenylene)dimethanol.In a 1 litre graduated flask, equipped with magnetic stirrer, suspended to 100.4 g (781 mmol) of 4-chlorophenol (99+%, Aldrich) in 500 ml of water. To the reaction mixture was added dropwise a solution containing of 38.9 g (973 mmol) NaOH in 100 ml, which had resulted in the suspension became transparent. Added 168 grams (2,07 mol) of formaldehyde solution (37% in water, Aldrich) and covered the reaction mixture with aluminum foil and left to mix for 10 days at ambient temperature and for another 3 days without stirring. The mixture was cooled to 0°C and filtered. Sediment suspended in ~800 ml of water and acidified with 70 ml of glacial acetic acid. The mixture was cooled to 0°C., was filtered and suspended sediment in 500 ml of water, cooled to 0°C and filtered. The solid is nearly white was dried in vacuum, obtaining 43,8 g (30%).

1H NMR (DMF-d7) Delta: to 7.35 (s, 2H, Ar-N), a 4.86 (s, 4H, Ar-CH2).

Example 5

Synthesis of 4-chloro-2-(hydroxymethyl)-6-((4-methoxyphenyl)diazenyl)phenol.In a round bottom flask of 250 ml, equipped with a magnetic stirrer, was placed of 7.60 g (of 61.7 mmol) p-anisidine, 26 ml of concentrated HCl (aq.), 150 ml of absolute ethanol and 150 ml of deionized water. Within 30 minutes was added dropwise sodium nitrite (4,58 g, to 66.3 mmol) in 30 ml of water, maintaining the temperature of the reaction mixture at -10°C. the Reaction mixture was stirred for 1 hour. Was added 300 mg of sulfamic acid, and then stirred for another 20 minutes. The solid was filtered, and the cold solution, page left. (5-Chloro-2-hydroxy-1,3-phenylene)dimethanol from example 3 was dissolved in 100 ml of deionized water. To a solution of (5-chloro-2-hydroxy-1,3-phenylene)dimethanol was added approximately one-fourth volume of a solution containing 12.7 g (318 mmol) of NaOH in water, and cooled the reaction mixture to 0°C. for 30-60 minutes to a mixture of (5-chloro-2-hydroxy-1,3-phenylene)dimethanol simultaneously added a mixture of the page and the remaining NaOH solution. The reaction mixture was stirred at room temperature for 16 hours. The mixture was poured into 3 l of deionized water and acidified to pH 4 1N HCl. The solid was filtered and washed with several liters of water and dried in vacuum at 50°C, getting a solid dark color.

This connection can be atrificial in accordance with known methods (see above, example 1).

Example 6

Synthesis of (5-bromo-2-hydroxy-1,3-phenylene)dimethanol.In the 2-litre graduated flask, equipped with magnetic stirrer, suspended 101 g (585 mmol) of 4-bromophenol in 500 ml of water. To the reaction mixture were added at once a solution containing of 28.9 g (723 mmol) of NaOH in 100 ml. was Then added 128 g (1,58 mol) of formaldehyde solution (Aldrich, 37% in water) and covered the reaction mixture with aluminum foil and left to stand for 45 days at ambient temperature. For planting precipitation was added glacial acetic acid (60 ml, 1.0 mol). This precipitate was washed ampoule quantities of water, and then dried under high vacuum (0.1 mm, RT.CT.) for 20 hours at 50°C, getting to 101.2 g (74%) solid light orange color.

1H NMR (DMF-d7) Delta: 8,21 (s, 1H, phenolic-OH), 7,56 (s, 2H, Ar-H), 5,70 (s, 2H, OH), the 4.90 (s, 4H, CH2).

Example 7

Synthesis of 4-bromo-2-(hydroxymethyl)-6-(p-tridiagonal)phenol. In a round bottom flask of 500 ml, equipped with a magnetic stirrer, were placed 10.6 g (the 98.9 mmol) of p-toluidine (Aldrich), 42 ml of concentrated HCl (aq.) (J. T. Baker), deionized water (100 ml) and ethanol (100 ml) and cooled the reaction mixture to 0°C. for 30 minutes was added p the drops of sodium nitrite (7,21 g, 104 mmol) in 50 ml of water, maintaining the temperature of the reaction mixture at 0°C. the Reaction mixture was stirred for 1 hour. Was added 300 mg of sulfamic acid to decompose the excess of nitrite and the mixture was stirred for another 20 minutes. (5-Bromo-2-hydroxy-1,3-phenylene)dimethanol from example 6 was dissolved in 400 ml of a mixture of 50/50 ethanol/deionized water. To a solution of (5-bromo-2-hydroxy-1,3-phenylene)dimethanol was added at 0°C for approximately one-quarter of the volume of the solution containing 21,3 g (533 mmol) NaOH in 100 ml water. Within 60 minutes to a mixture of (5-bromo-2-hydroxy-1,3-phenylene)dimethanol simultaneously added a mixture of the page and the remaining NaOH solution. The reaction mixture was stirred for 20 hours at ambient temperature and then poured into 3.5 l of deionized water and acidified to pH 4-5 1N HCl. The solid was filtered, washed ampoule quantities of water and dried in vacuum (0.1 mm, RT.cent.), getting 16,64 g (52%) solid dark color.

As in the case of example 6, this connection can be atrificial in accordance with known methods (see above, example 1).

Example 8

Synthesis of 2-(hydroxymethyl)-4-methyl-6-(p-tridiagonal)phenol. In a round bottom flask of 500 ml, equipped with a magnetic stirrer, were placed 10.6 g (the 98.9 mmol) of p-toluidine (99%, Aldrich), 42 ml (500 mm is l) of concentrated HCl (aq.) (J. T. Baker), deionized water (100 ml) and ethanol (100 ml) and cooled the reaction mixture to 0°C. for 20 minutes was added at 0°C dropwise sodium nitrite (7,21 g, 105 mmol) (Sigma-Aldrich) in 50 ml of water. The reaction mixture was stirred for 1 hour. Was added 300 mg of sulfamic acid (Aldrich) to decompose the excess of nitrite and the mixture was stirred for another 20 minutes. (2-Hydroxy-5-methyl-1,3-phenylene)dimethanol (95%, Aldrich) was dissolved in 400 ml of a mixture of 50/50 ethanol/deionized water. To a solution of (2-hydroxy-5-methyl-1,3-phenylene)dimethanol was added approximately one-fourth the volume of aqueous sodium hydroxide solution (>97%, Aldrich) (21,34 g/100 ml) and cooled to 0°C. over 60 minutes to a mixture of (2-hydroxy-5-methyl-1,3-phenylene)dimethanol simultaneously added a mixture of the page and the remaining NaOH solution. The reaction mixture was stirred for 20 hours at room temperature, and then poured into 3.5 l of deionized water and acidified to pH 4-5 1N HCl. The solid was filtered and dried in high vacuum to a constant weight, getting 17.8 g (70%) solid orange color.

1H NMR (CDCl3) Delta: 13,28 (s, 1H, Ar-OH), 7,76 (d, 2H, Ar-H), 7,68 (s, 1H, Ar-H), 7,31 (d, 2H, Ar-H), 7,19 (s, 1H, Ar-H), of 4.77 (s, 2H, CH2), is 2.44 (s, 3H, Ar-CH3), of 2.38 (s, 3H, Ar-CH3).

As in the case of example 6, this connection can be atrificial in accordance the with known methods (see the above example 1).

Example 9

Synthesis of 2-((2-hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzoate)carbylamine)ethyl methacrylate,. A 3-necked round bottom flask of 500 ml, equipped with a magnetic stirrer and the input of nitrogen, dissolved 5,01 g (18.4 mmol) of 2-(hydroxymethyl)-6-((4-methoxyphenyl)diazenyl)-4-METHYLPHENOL from example 2 in 300 ml of anhydrous THF. Were added octoate tin (50 mg, Pfaltz &Bauer), then 2-isocyanatoacetate (3,14 g, a 20.2 mmol). MEHQ was added (100 mg). The reaction mixture was stirred for 20 h at 60°C and then poured into 200 ml of diethyl ether and washed with 0.5 N HCl and water. The organic layer was dried over magnesium sulfate, filtered and evaporated on a rotary evaporator, obtaining the desired product, which was recrystallized from ethanol, receiving 6.0 g (76%) solid orange color.

1H NMR (CDCl3) Delta: 13,22 (c, 1H, Ar-OH), a 7.85 (m, 2H, Ar-H), of 7.69 (s, 1H, Ar-H), of 7.23 (s, 1H, Ar-HI), 7,03 (m, 2H, Ar-H), 6,09 (s, 1H, vinyl-H), to 5.57 (s, 1H, vinyl-H), of 5.24 (s, 2H, Ar-CH2), 5,02 (s, 1H, CONH), 4,24 (m, 2H, CH2OCO), 3,90 (s, 3H, Ar-OCH3), 3,53 (m, 2H, OCNHCH2), of 2.38 (s, 3H, Ar-CH3), with 1.92 (s, 3H, CH3-C=C).

Example 10

Curves transparency for compounds a-C were obtained using a UV/view. spectroscopy. Each compound was dissolved in chloroform at a specified concentration and conducted its evaluation by the JV is ChromaTRU PerkinElmer Lambda 35 UV/Vis. The results are shown in figures 1-4. In addition, the curve of transparency for a combination of compounds a and UV absorber 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazole-2-yl)benzylmalonate ("UV-1"below) was obtained by a similar method. The results for this combination is shown in figure 5.

Example 11

Drugs acrylic IOL

Of the compounds of the formulaIit is possible to obtain a composition for the material for the IOL, as shown in the following tables 1-3. All components were mixed while rotating in a glass vessel of 30 ml was degirolami nitrogen and then filtered using a syringe with the use of 0.2 micron Teflon filter in a polypropylene matrix. The samples were subjected to heat treatment at 70°C for 1 hour and at 110°C for 2 hours, and then were extracted with acetone at 50°C for 6 hours when replacing the solvent in fresh every 90 minutes.

Table 1
Example
% (wt./mass.)
Component11A11B11S/td> 11D
Connection And
UV-1
0,0208
1,48
0,0200
1,49
0,0200
1,50
0,024
1,52
REA73,173,9073,6
REMUS20,920,0019,3
BzA0094,00
The ethylate secondary alcohol, methacrylic acid3,003,033,003,00
BDDA1,531,491,501,53
PSMA0001,00
Perkadox 16S00,991,0 1,01
AIBN0,50000
REA = 2-phenylethylamine
REM = 2-fenilatilmalonamid
BzA = benzoylacrylate
BDDA = 1,4-potentialtarget
The ethylate secondary alcohol, methacrylic acid = methacrylic acid and surfactant Tergitol™ NP-70 (Dow/Union Carbide)
AIBN = 2,2'-azobis(2-methylpropionitrile)
Perkadox 16S = di(4-tert-butylcyclohexyl)PEROXYDICARBONATE (AlzoNobel)
PSMA = solution of polystyrene terminated with methacrylate (Aldrich, Mn~12000) (33% of the mass. in cyclohexane), filtered and precipitated.

Table 2
Example
(% wt./mass.)
Component11D11E11F
Connection And
UV-1
0,0300
1,51
0,0202
1,46
0,025
1,50
REA73,1 073,6
REMUS20,9019,3
BzA094,10
polyPEGMA3,003,003,01
BDDA1,531,451,53
PSMA001,00
Perkadox 16S01,040,99
AIBN0,5000
PolyPEGMA = macromonomer methacrylate nanometrology ether poly(ethylene glycol) (M=550), Mn (SEC): 4100 Dalton, Mn (NMR): 3200 Dalton, PDI=1,50.

Table 3
Example
% (wt./mass.)
Component11G11H11I11J
Connection And
UV-1
0.02
1,12
0.02
1,12
0.02
1,12
0.02
1,12
REA074,173,374,3
REMUS0to 19.920,020,0
BzA94,3000
polyPEGMA0003,00
polyPEGMA-23,023,253,060
BDDA1,531,541,501,52
PSMA
Perkaox 16S
0
0
0
0
1,00
1,25
0
0
AIBN0,500,5000,50
PolyPEGMA-2 = macromonomer methacrylate nanometrology ether poly(ethylene glycol) (M=475), Mn (SEC): 11000 Dalton, PDI=1,2.

Example 12

The photostability

Sample preparation 11D were subjected to UV irradiation with a wavelength of from 300 to 800 nm using a camera for testing Atlas Suntest CPS+ (Atlas Electric Devices Company, Chicago, Illinois) using a xenon arc lamp with a light intensity of approximately 8-10 mV/cm2at the top of the test specimen. Temperature PBS was 35°C. the Spectra UV/view. slices of the sample with a thickness of 0.9 mm was obtained using a spectrometer PerkinElmer Lambda 35 UV/Vis. The results of optical exposure, equivalent to 20 years (example 11D, N=3), shown in figure 6.

This invention has been described with reference to some preferred embodiments of, but it should be understood that it may be embodied in other specific forms or modifications within the scope of his specific or essential characteristics. So the above options is sushestvennee in all respects be deemed illustrative and not restrictive, while the scope of this invention is indicated above claims, and not the previous description.

1. Uzasadnienie formula

where X1X2and X3independently represent H, C1-C6alkyl, C1-C6alkoxy, phenoxy
or benzyloxy;
Y represents H, F, Cl, Br, I or C1-C6alkyl;
W is absent or represents-O-C(=O)NH-CH2CH2-; and
Z represents N, CH3C2H5or CH2OH.

2. Uzasadnienie under item 1, where
X1X2and X3independently represent H, C1-C4alkyl or C1-C4alkoxy,
Y represents H, Cl or C1-C4alkyl;
W is absent, and
Z represents N or CH3.

3. Uzasadnienie under item 2, where the compound is chosen from the group consisting of 2-hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzonitrile, 2-hydroxy-5-methyl-3-((3,4,5-trimethoxyphenyl)diazenyl)benzylmalonate and 5-chloro-2-hydroxy-3-((4-methoxyphenyl)diazenyl)benzylmalonate.

4. Uzasadnienie under item 3, where the compound is 2-hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzonitrile.

5. Material for ophthalmic devices, including uzasadnienie on p. 1 forming device acrylic monomer and a crosslinking agent.

6. Material for ophthalmic devices under item 5, containing 0.005 to 0.2% (wt./mass.) azo compounds under item 1.

7. Material for ophthalmic devices by p. 6, containing from 0.01 to 0.08% (wt./mass.) azo compounds under item 1.

8. Material for ophthalmic devices under item 7, containing from 0.01 to 0.05% (wt./mass.) azo compounds under item 1.

9. Material for ophthalmic devices under item 5, containing forming device monomer of the formula [II]:

where in the formula [II]:
And represents N, CH3CH2CH3or CH2HE;
In represents (CH2)mor [O(CH2)2]z;
With represents (CH2)w,
m is 2-6;
z is 1-10;
Y is absent or represents O, S or NR', provided that if Y is O, S or NR', represents (CH2)m;
R' represents H, CH3Cn'H2n'+1(n=1-10), ISO-OS3H7C6H5or CH2With6H5;
w is 0-6, provided that m+w≤8; and
D represents H, C1-C4alkyl, C1-C4alkoxy, C6H5CH2C6H5or halogen.

10. Material for ophthalmic devices by p. 9, where in the formula [II]:
And represents N or CH3;
In represents (CH2 )m;
m is 2-5;
Y is absent or represents O;
w is 0-1; and
D represents N.

11. Material for ophthalmic devices by p. 10 containing monomer selected from the group consisting of 2-generateelectricity, 4-phenylbutyrate, 5-perpendicularity, 2-benzyloxyacetaldehyde and 3-benzyloxypropionic and their corresponding acrylates.

12. Material for ophthalmic devices by p. 6 containing reactive compound, absorbing UV rays.

13. Intraocular lens obtained from the material for ophthalmic device according to any one of paragraphs.5-12 containing uzasadnienie under item 1.

14. Intraocular lens obtained from the material for ophthalmic device according to any one of paragraphs.5-12 containing uzasadnienie under item 2.

15. Intraocular lens obtained from the material for ophthalmic device according to any one of paragraphs.5-12 containing uzasadnienie under item 3.

16. Ophthalmological device, obtained from the material for ophthalmic devices under item 5.

17. Ophthalmological device according to p. 16, selected from the group including intraocular lenses, contact lenses, keratoplasty and corneal implant, or ring.



 

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[=F=CH-C6H40-CH2-C6H40-CH=n,

where n= 6-9,

< / BR>
The claimed connection most effectively can be used as fluorescent additives in liquid and solid scintillators as active element in laser technology

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