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WO2010053917A1 - Uv/visible light absorbers for ophthalmic lens materials - Google Patents

Uv/visible light absorbers for ophthalmic lens materials

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Publication number
WO2010053917A1
WO2010053917A1 PCT/US2009/063120 US2009063120W WO2010053917A1 WO 2010053917 A1 WO2010053917 A1 WO 2010053917A1 US 2009063120 W US2009063120 W US 2009063120W WO 2010053917 A1 WO2010053917 A1 WO 2010053917A1
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ml
mixture
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water
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PCT/US2009/063120
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French (fr)
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Walter R. Laredo
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Alcon, Inc.
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D249/00Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18Benzotriazoles

Abstract

Benzotriazole UV/Visible light-absorbing monomers are disclosed. The UV/Vis absorbers are particularly suitable for use in intraocular lens materials.

Description

UV/VISIBLE LIGHT ABSORBERS FOR OPHTHALMIC LENS MATERIALS

Field of the Invention

This invention is directed to ultraviolet/visible light absorbers. In particular, this invention relates to novel benzotriazole monomers especially suitable for use in implantable ophthalmic lens materials.

Background of the Invention

Many ultraviolet and visible light absorbers are known as ingredients for polymeric materials used to make ophthalmic lenses. Such absorbers are preferably covalently bound to the polymeric network of the lens material instead of simply physically entrapped in the material to prevent them from migrating, phase separating or leaching out of the lens material. Such stability is particularly important for implantable ophthalmic lenses where the leaching of the absorber may present both toxicological issues and lead to the loss of UV/visible blocking activity in the implant.

Numerous copolymerizable benzatriazole, benzophenone and triazine absorbers are known. Most of these compounds are known as UV absorbers, though some may be known to also absorb some portion of visible light. Many absorbers contain conventional olefinic polymerizable groups, such as methacrylate, acrylate, methacrylamide, acrylamide or styrene groups. Copolymerization with other ingredients in the lens materials, typically with a radical initiator, incorporates the absorbers into the resulting polymer chain. Incorporation of additional functional groups on an absorber may influence one or more of the absorber's light-absorbing properties, solubility or reactivity. If the absorber does not have sufficient solubility in the remainder of the ophthalmic lens material ingredients or polymeric lens material, the absorber may coalesce into domains that could interact with light and result in decreased optical clarity of the lens. Examples of polymeric ophthalmic lens materials that incorporate UV absorbers can be found in U.S. Patent Nos. 5,290,892; 5,331 ,073 and 5,693,095.

Summary of the Invention

The present invention provides benzotriazole light absorbing monomers that absorb both ultraviolet light and a portion of visible light ("UVA/is absorbers"). These absorbers are suitable for use in ophthalmic lenses, including contact lenses. They are particularly useful in implantable lenses, such as intraocular lenses (1OLs).

The absorber compounds of the present invention absorb wavelengths of light between 400 - 450 nm in addition to higher energy UVA rays between

400 - 320 nm, UVB rays between 320 - 280 nm, and UVC rays below 280 nm. They contain reactive groups, which allow for covalent attachment of the absorbers to ocular lens materials. Additionally, the absorbers of the present invention can be synthesized in approximately 5 steps from readily available starting materials.

Brief Description of the Drawings

Figure 1 shows percent transmittance curves for UVA/is absorber compounds WL-1 - WL-7.

Figures 2A - 2J show percent transmittance curves for IOL materials containing UVA/is absorber compounds WL-1 - WL-4 that were subjected to photostability testing producing the equivalent of 10 or 20 years of light exposure. Detailed Description of the Invention

Unless indicated otherwise, all ingredient amounts expressed in percentage terms are presented as % w/w.

The UV/Vis absorbers of the present invention are represented by the formula

wherein

R1 = H, CH3, CH2CH3, or CH2OH; R2 = C1-C4 alkyl or C1-C4 alkoxy; and R3 = H, CH3, CH3O, F, Cl1 Br, I, or CF3.

Preferred UV/Vis absorbers of the present invention are those wherein R1 = H or CH3; R2 = C1-C4 alkoxy; and R3 = H, CH3, CH3O, F, Cl, or CF3.

More preferred absorbers of the present invention are selected from the group consisting of: 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2- yl)benzyl methacrylate;

3-(5-fluoro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate;

3-(2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate; 3-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate;

2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate; 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate; and

2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate.

Most preferred UV/Vis absorbers of the present invention are 2- hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate and 3-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5- methoxybenzyl methacrylate.

The synthesis of the UV/Vis absorbers of the present invention is described below.

Step 1 : Phenol derivative 1 is synthesized via the hydroxymethylation of p- methoxyphenol as shown below.

In steps 2 and 3, the diazonium salt of a 2-nitroaniline derivative is synthesized and subsequently reacted with 1 to form an azo dye.

Diazonium salt

Step 2

NaOH(aq) pH= 10-12

Azo dye

In step 4, the azo dye is treated with a reducing agent, such as formamidinesulfinic acid, to form the corresponding benzotriazole compound. The purity of the isolated benzotriazole compound can be enhanced by techniques known in the art, including filtration of excess reducing agent and reducing agent byproducts before addition of protic acids and column chromatography.

Formamidinesulfinic acid, NaOH H,O+

Ethanol/water, 800C, 2 hours

Benzotriazole

In step 5, the benzotriazole from step 4 is esterified to form a "reactive" compound which contains a vinyl group. By "reactive" it is understood that the vinyl group can polymerize to form covalent bonds when reacted with vinyl monomers, co-monomers, macromers, crosslinking agents, and other components typically used in making polymer-based ocular materials, particularly acrylics. The reactive groups are preferably acrylate or methacrylate groups.

Compound WH Step 5

The UV/Vis absorbers of the present invention are particularly suitable for use in 1OLs. IOL materials will generally contain from 0.1 to 3 % (w/w) of a UV/Vis absorber of the present invention. Preferably, IOL materials will contain from 0.2 to 2.5 % (w/w) of an absorber of the present invention. Most preferably, IOL materials will contain from 0.3 to 2 % (w/w) of an absorber of the present invention. Such device materials are prepared by copolymerizing the absorbers of the present invention with other ingredients, such as device- forming materials, cross-linking agents, and optionally blue-light blocking chromophores.

Many device-forming monomers are known in the art and include both acrylic and silicone-containing monomers among others. See, for example, U.S. Nos. 7,101 ,949; 7,067,602; 7,037,954; 6,872,793 6,852,793; 6,846,897; 6,806,337; 6,528,602; and 5,693,095. In the case of lOLs, any known IOL device material is suitable for use in the compositions of the present invention. Preferably, the ophthalmic device materials comprise an acrylic or methacrylic device-forming monomer. More preferably, the device-forming monomers comprise a monomer of formula IV:

IV where in formula IV: A iS H1 CH31 CH2CH31 Or CH2OH;

B is (CH2)m or [O(CH2)2]Z; C is (CH2)W; m is 2 - 6; z is 1 - 10; Y is nothing, O1 S1 or NR', provided that if Y is O1 S, or NR', then

B is (CH2)m;

R1 is H, CH3, Cn'H2n'+i (n'=1 -10), iso-OC3H7, C6H5, or CH2C6H5; w is O - 6, provided that m + w <8; and D is H, C1 - C4 alkyl, C1 - C4 alkoxy, C6H5, CH2C6H5 or halogen.

Preferred monomers of formula IV are those wherein A is H or CH3, B is (CH2)m, m is 2 - 5, Y is nothing or O, w is O - 1 , and D is H. Most preferred are 2-phenylethyl methacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate;and their corresponding acrylates.

Monomers of formula IV are known and can be made by known methods. For example, the conjugate alcohol of the desired monomer can be combined in a reaction vessel with methyl methacrylate, tetrabutyl titanate (catalyst), and a polymerization inhibitor such as 4-benzyloxy phenol. The vessel can then be heated to facilitate the reaction and distill off the reaction by-products to drive the reaction to completion. Alternative synthesis schemes involve adding methacrylic acid to the conjugate alcohol and catalyzing with a carbodiimide or mixing the conjugate alcohol with methacryloyl chloride and a base such as pyridine or triethylamine.

5 Device materials generally comprise a total of at least about 75%, preferably at least about 80%, of device-forming monomers.

In addition to an absorber of the present invention and a device- forming monomer, the device materials of the present invention generally io comprise a cross-linking agent. The cross-linking agent used in the device materials of this invention may be any terminally ethylenically unsaturated compound having more than one unsaturated group. Suitable cross-linking agents include, for example: ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; allyl methacrylate; 1 ,3-propanediol dimethacrylate; 2,3- i5 propanediol dimethacrylate; 1 ,6-hexanediol dimethacrylate; 1 ,4-butanediol dimethacrylate; CH2=C(CH3)C(=O)O-(CH2CH2O)p-C(=O)C(CH3)=CH2 where p = 1 - 50; and CH2=C(CH3)C(=O)O(CH2)tO-C(=O)C(CH3)=CH2 where t = 3 - 20; and their corresponding acrylates. A preferred cross-linking monomer is CH2=C(CH3)C(=O)O-(CH2CH2θ)p-C(=O)C(CH3)=CH2 where p is such that the 0 number-average molecular weight is about 400, about 600, or about 1000.

Generally, the total amount of the cross-linking component is at least 0.1 % by weight and, depending on the identity and concentration of the remaining components and the desired physical properties, can range to 5 about 20% by weight. The preferred concentration range for the cross-linking component is 1 - 5 % for small, hydrophobic compounds with molecular weights typically less than 500 Daltons, and 5 - 17% (w/w) for larger, hydrophilic compounds with molecular weights typically between 500 - 5000 Daltons. 0

Suitable polymerization initiators for device materials containing a UV/Vis absorber of the present invention include thermal initiators and photoinitiators. Preferred thermal initiators include peroxy free-radical initiators, such as t-butyl (peroxy-2-ethyl)hexanoate and di-(tert-butylcyclohexyl) peroxydicarbonate (commercially available as Perkadox® 16 from Akzo Chemicals Inc., Chicago, Illinois). Initiators are typically present in an amount of about 5% (w/w) or less. Because free-radical initiators do not become chemically a part of the polymers formed, the total amount of initiator is customarily not included when determining the amounts of other ingredients.

The device materials containing a UV/Vis absorber of the present invention optionally also contain a reactive colorant. Suitable reactive blue-light absorbing compounds include those described in U.S. Patent No. 5,470,932.

Blue-light absorbers are typically present in an amount from about 0.01 - 0.5 %

(weight).

IOLs constructed of the materials of the present invention can be of any design capable of being rolled or folded into a small cross section that can fit through a relatively smaller incision. For example, the IOLs can be of what is known as a one piece or multipiece design, and comprise optic and haptic components. The optic is that portion which serves as the lens. The haptics are attached to the optic and hold the optic in its proper place in the eye. The optic and haptic(s) can be of the same or different material. A multipiece lens is so called because the optic and the haptic(s) are made separately and then the haptics are attached to the optic. In a single piece lens, the optic and the haptics are formed out of one piece of material. Depending on the material, the haptics are then cut, or lathed, out of the material to produce the 1OL.

In addition to IOLs, the materials of the present invention are also suitable for use in other ophthalmic devices, such as contact lenses, keratoprostheses, and corneal inlays or rings. The invention will be further illustrated by the following examples, which are intended to be illustrative, but not limiting.

EXAMPLE 1

Synthesis of (2-hydroxy-5-methoxy-1,3-phenylene)-dimethanol. In a 2 liter reaction flask equipped with magnetic stirrer was suspended 200 g p- methoxyphenol in 1300 ml water. Formaldehyde solution (335 ml, 37% in water) was added to the stirring solution followed by 55.8 g calcium oxide. The reaction mixture was covered in aluminum foil and allowed to stand at ambient temperature for 10 days. The solid was filtered and then suspended in 1 L deionized water. 130 ml glacial acetic acid was added to the stirring suspension at ambient temperature. The off-white solid was filtered, rinsed with hexane, and then dried under high vacuum for 72 hours to afford 118.9 g (37.8 %). 1H NMR (DMF-dy) delta: 3.75 (s, 3H, OCH3), 4.73 (s, 4H, CH2O), 5.39 (bs, 2H, CH2OH), 6.85 (s, 2H, Ar-H). 13C NMR (DMF-d7) delta: 55.12 (1C, OCH3), 59.84 (2C1 CH2OH), 111.18 (2C1 Ar-CH), 129.51 (2C1 Ar-CCH2), 146.30 (1 C, Ar-COH)1 152.95 (1 C, Ar-COCH3).

EXAMPLE 2

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-((2-nitro-4-(trifluoro- methyl)-phenyl)diazenyl)-phenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 19.9 g 2-nitro-4-(trifluoromethyl)-aniline (96.5 mmol) (Aldrich, Milwaukee, Wl), 41 ml concentrated HCI (aq), 100 ml deionized water, 100 ml ethanol, and 80 ml THF. The suspension was stirred for 30 minutes and 7.07 g sodium nitrite (102 mmol) in 30 ml water was added dropwise over 60 minutes while keeping the reaction mixture at 0 0C. The reaction mixture was stirred for an additional 1 hour. 300 mg Sulfamic acid was added to destroy excess nitrite. The mixture was filtered to remove undissolved solids. The filtered diazonium mixture along with a solution of sodium hydroxide (15.1 g in 100 ml water) were added dropwise to a solution containing 19.7 g (2-hydroxy-5-methoxy-1 ,3-phenylene)dimethanol (107 mmol), 4.3 sodium hydroxide, 200 ml deionized water, and 50 ml THF at 0 °C.

The reaction mixture was allowed to stir at 0 °C for 1 hour and room temperature for 4 hours. The mixture was poured into 3 liters water. The mixture was acidified to pH 3-4. The dark crude product was filtered and washed with several liters of water to generate a dark solid which was dried under high vacuum at 55 0C for 72 hours to give 15.2 g (42 % yield) product.

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-(5-(trifluoromethyl)- 2H-benzo[d][1 ,2,3]triazol-2-yl)phenol. In a 250 ml round bottom flask equipped with a magnetic stirrer was added 7.70 g (20.7 mmol) 2- (hydroxymethyl)-4-methoxy-6-((2-nitro-4-(trifluoromethyl)phenyl)diazenyl)- phenol from Example 2 part 1 , 25 ml deionized water, 1.85 g sodium hydroxide, and 80 ml 1-propanol. The mixture was heated to 80 °C and 6.55 g (60.6 mmol) formamidine sulfinic acid (Aldrich) was added slowly and concurrently with a solution of 3.0 g NaOH in 50 ml deionized water. The reaction mixture was heated at 80 °C for 2 hours. The reaction mixture was cooled at -20 0C for 2 hours and filtered. The solid was dissolved in 2.5 L deionized water containing 4 grams NaOH. The pH was adjusted to 2.0 using 1 N HCI. The resultant solid was filtered, washed with ample amounts of deionized water, filtered and dried to give 2.2 g (31 %) of a yellow solid. 1H NMR (CDCI3) delta: 11.03 (s, 1 H, Ar-OH), 8.30 (s, 1 H, Ar-H benzotriazole A- position), 8.07 (d, 1 H, Ar-H benzotriazole 6-position), 7.88 (s, 1 H, Ar-H phenol), 7.69 (d, 1 H, Ar-H benzotriazole), 7.08 (s, 1 H, Ar-H phenol), 4.84 (s, 2H, Ar-CH2), 3.90 (s, 3H, Ar-OCH3).

EXAMPLE 3 (Compound WL-1)

Synthesis of 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H- benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate. In a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 1.15 g (3.39 mmol) 2-(hydroxymethyl)-4-methoxy-6-(5-(trifluoromethyl)-2H- benzo[d][1 ,2,3]triazol-2-yl)phenol from Example 3 in 50 ml anhydrous THF containing BHT inhibitor (Aldrich). Triethylamine (1.4 ml, 11 mmol) was added and the mixture was cooled to -10 0C. Methacryloyl chloride (0.436 g, 4.17 mmol) was added dropwise and the mixture was stirred for 1 hr at -10 °C followed by 20 hours at ambient temperature. The solid was filtered and rinsed with 100 ml diethyl ether. The filtrate was poured into 100 ml diethyl ether and washed with 0.5 N HCI and water. The organic layer was dried with magnesium sulfate, filtered, and then concentrated via rotary evaporation to give the desired product as a dark yellow oil which was recrystallized in methanol to give 0.35 g product (25 %). [M+H+] = 408.1. 1H NMR (CDCI3) delta: 10.97 (s, 1 H, Ar-OH), 8.30 (s, 1 H, Ar-H benzotriazole), 8.07 (d, 1 H, Ar- H benzotriazole), 7.91 (s, 1H, Ar-H phenol), 7.69 (d, 1 H, Ar-H benzotriazole), 7.10 (s, 1 H, Ar-H phenol), 6.21 (s, 1 H, C=C-H trans), 5.62 (s, 1 H, C=C-H cis), 5.40 (s, 2H1 Ar-CH2), 3.90 (s, 3H, Ar-OCH3), 2.01 (s, 3H, C=C-CH3). Elemental analysis: calculated %C (56.02), %H (3.96), %N (10.32), %F (13.99); found %C (56.11), %H (3.96), %N (10.24), %F (14.37).

Compound WL-I

WL-1 EXAMPLE 4

Synthesis of 2-((4-fluoro-2-nitrophenyl)diazenyl)-6- (hydroxymethyl)-4-methoxyphenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 25.1 g (161 mmol) 4-fluoro-2- nitroaniline (Aldrich), HCI(aq) (JT. Baker), 100 ml deionized water, and 100 ml absolute ethanol. The suspension was cooled to 0 0C. 11.8 g (171 mmol) Sodium nitrite (Sigma-Aldrich) in 50 ml water was added dropwise over 60 minutes while keeping the reaction mixture at 0 0C. The reaction mixture was stirred for an additional 1 hour. 420 mg sulfamic acid (Aldrich) was added and the reaction mixture was stirred for an additional 30 minutes and then filtered. In a 1 liter round bottom flask was combined 32.5 g (176 mmol) (2- hydroxy-5-methoxy-1 ,3-phenylene)dimethanol, 200 ml deionized water, and 200 ml ethanol. 32.3 g (807 mmol) NaOH (Aldrich) was dissolved in 100 ml water and approximately one-fourth of this was added to the solution containing the phenol derivative at 0 °C. The diazonium salt solution and remaining sodium hydroxide solution were added dropwise to the reaction mixture at 0 °C over a 1 hour period and then allowed to stir for an additional 1 hour at 0 0C and 3 hours at ambient temperature. The reaction mixture was poured into 3 liters water and the pH was adjusted to 4 using 1 N HCI. The solid was collected by filtration, washed with several liters of water, and vacuum dried (0.1 mm Hg) at 55 0C for 72 hours using P2O5 as drying agent to afford 29.9 g (68 %) of a dark solid which was used in the next step without further purification.

Synthesis of 2-(5-fluoro-2H-benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxy- methyl)-4-methoxyphenol. In a 500 ml round bottom flask equipped with a magnetic stirrer, liquid addition funnel, powder addition funnel, and nitrogen inlet was added 2-((4-fluoro-2-nitrophenyl)diazenyl)-6-(hydroxymethyl)-4- methoxyphenol from Example 5 part I and 200 ml ethanol. NaOH (21.7 g, 542 mmol) pellets (97+%, A.C.S. reagent, Aldrich) were dissolved in 100 ml deionized water and approximately one-fourth of the solution was added dropwise to the reaction mixture. The mixture was subsequently heated to 80 0C and 29.3 g (271 mmol) formamidinesulfinic acid (Aldrich) and the remaining sodium hydroxide solution were concurrently added to the reaction mixture over 30 minutes. The mixture was stirred at 80 0C for 3 hours and the contents were then poured into 3L deionized water and acidified to pH 4 using 1 N HCI. The solid was collected by filtration, suspended in 300 ml methanol, and stirred for 30 minutes while cooling to below - 20 0C. The solid was collected by filtration and then suspended in 300 ml ethanol, cooled again to below - 20 0C, filtered, and then dried to afford 7.8 g (30 %) of a yellow solid, which was used in the next esterification step.

EXAMPLE 5 (Compound WL-2)

Synthesis of 3-(5-fluoro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy- 5-methoxybenzyl methacrylate. The esterification was carried out using the product from Example 5. In a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 5.06 g (17.5 mmol) 2-(5- fluoro-2H-benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol in 60 ml anhydrous THF. Triethylamine (8.7 ml, 62 mmol)) was added and the mixture was cooled to -10 - 0 0C. Methacryloyl chloride (2.26 g, 21.6 mmol) was added dropwise and the mixture was stirred for 1 hr at -10 °C followed by 20 hours at ambient temperature. The salts were filtered and rinsed with 100 ml THF (>99.9 %, anhydrous containing inhibitor, Aldrich). Diethyl ether (100 ml) was added to the filtrate, which was washed with 1 N HCI and water, dried over magnesium sulfate, filtered, and concentrated by rotary evaporation to give the desired product, which was recrystallized in ethanol to give 2.5 g (40 %) of a yellow solid. 1H NMR (CDCI3) delta: 11.03 (s, 1 H, phenol OH), 7.94 (m, 1 H, Ar-H benzotriazole ring), 7.87 (s, 1 H, Ar-H phenol ring), 7.53 (m, 1 H, Ar-H benzotriazole ring), 7.29 (m, 1 H, Ar-H benzotriazole ring), 7.05 (s, 1 H, Ar-H phenol ring), 6.21 (s, 1H, C=C-H trans), 5.61 (s, 1H, C=C-H cis), 5.39 (s, 2H, Ar-CH2), 3.89 (s, 3H, Ar-OCH3), 2.01 (s, 3H, C=C-CH3).

WL-2

EXAMPLE 6

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-((2-nitrophenyl)- diazenyl)-phenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 19.9 g (144 mmol) 2-nitroaniline (Aldrich), HCI(aq), 100 ml deionized water, and 100 ml EtOH. The mixture was cooled to 0 °C and 10.6 g (153 mmol) sodium nitrite in 50 ml water was added dropwise over 60 minutes while keeping the reaction mixture between -10 - 0 0C. The reaction mixture was stirred for an additional 1 hour. 300 mg sulfamic acid was added to destroy excess nitrite and the mixture was stirred for an additional 20 minutes. The solids were filtered and the filtrate containing the diazonium salt was set aside and kept cold at -10 0C. NaOH (29.3 g, 731 mmol) was dissolved in 100 ml water and approximately one-fourth was added to a solution of (2-hydroxy-5-methoxy-1 ,3-phenylene)dimethanol in 100 ml deionized water and 200 ml ethanol. The diazonium salt mixture and remaining sodium hydroxide solution were added to the reaction mixture containing the phenol derivative over a 1 hour period at 0 °C. The reaction mixture was allowed to stir at 0 0C for 1 hour and ambient temperature for 3 hours. The contents were poured into 3 liters water and the pH was adjusted to 6 using 1 N HCI. The resultant solid was washed with several liters of water and then dried at 55 0C for 40 hours using P2O5 as drying agent to afford 24.4 g (55.8 %) of a dark solid which was used in the next step without further purification.

Synthesis of 2-(2H-benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxymethyl)-4- methoxyphenol. In a 500 ml round bottom flask equipped with a magnetic stirrer, regular addition funnel, powder addition funnel, and nitrogen inlet was added 23.6 g (77.7 mmol) 2-(hydroxymethyl)-4-methoxy-6-((2- nitrophenyl)diazenyl)phenol and 200 ml ethanol. NaOH (18.8 g, 470 mmol) was dissolved in 100 ml deionized water and approximately one-fourth was added dropwise to the reaction mixture. The mixture was heated to 80 0C and 25.1 g (232 mmol) formamidine sulfinic acid and the remaining sodium hydroxide solution were concurrently added dropwise to the reaction mixture over 30 minutes. The mixture was stirred at 80 0C for 3 hours, poured into

3.5 L water, and then acidified to pH 4 using 1 N HCI. The resultant solid was collected by filtration and worked up as in Example 5 to give a light yellow solid (4.3 g, 20.5 %).

EXAMPLE 7 (Compound WL-3)

Synthesis of 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5- methoxybenzyl methacrylate. In a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 4.03 g (14.9 mmol) 2-(2H- benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol from Example 7 in 50 ml anhydrous THF. Triethylamine (7.4 ml, 53 mmol) was added and the mixture was cooled to -10 °C. Methacryloyl chloride (1.99 g, 19.0 mmol) was added dropwise and the mixture was stirred for 1 hr at 0 °C followed by 6 hours at ambient temperature. The mixture was poured into 200 ml diethyl ether and washed with 0.5 N HCI and water. The organic layer was dried with magnesium sulfate, filtered, and concentrated via rotary evaporation to give the desired product as a dark yellow oil which was recrystallized in methanol to give 1.73 g of a light yellow solid (34%). 1H NMR (CDCI3) delta: 11.26 (s, 1 H, Ar-OH), 7.92 (d, 2H, Ar-H benzotriazole), 7.91 (s, 1 H, Ar-H meta to phenol), 7.49 (d, 2H, Ar-H benzotriazole, 5,6-position), 7.05 (s, 1 H, Ar-H meta to phenol), 6.21 (s, 1 H, C=C-H trans), 5.61 (s, 1 H, C=C-H cis), 5.40 (s, 2H, Ar-CH2), 3.90 (s, 3H, Ar-OCH3), 2.01 (s, 3H, C=C-CH3).

WL-3

EXAMPLE 8

Synthesis of 2-((5-chloro-2-nitrophenyl)diazenyl)-6-

(hydroxymethyl)-4-methoxyphenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 30.0 g (174 mmol) 5-chloro-2- nitroaniline (Aldrich), cone. HCI(aq) (JT. Baker), 100 ml deionized water and 100 ml absolute ethanol. The suspension was cooled to 0 0C and 12.7 g (184 mmol) sodium nitrite in 50 ml water was added dropwise over 30 minutes while keeping the reaction mixture at 0 0C. The reaction mixture was stirred for an additional 1 hour. Sulfamic acid (430 mg) was added to destroy excess nitrite and the reaction mixture was stirred for an additional 20 minutes. The solids were filtered and the filtrate containing the diazonium salt was set aside and kept cold at -10 0C. NaOH (34.9 g, 873 mmol) was dissolved in 100 ml water and approximately one-fourth was added to a solution of (2-hydroxy-5- methoxy-1 ,3-phenylene)dimethanol in 100 ml deionized water and 200 ml ethanol. The diazonium salt mixture and remaining sodium hydroxide solution were added to the reaction mixture containing the phenol derivative over a 1 hour period at 0 °C. The reaction mixture was allowed to stir at 0 0C for 1 hour and ambient temperature for 2hours. The contents were poured into 3 liters water and the pH was adjusted to 5 using 1 N HCI. The resultant solid was washed with several liters of water and then vacuum dried (0.1 mm Hg) at 55 °C for 40 hours using P2O5 as drying agent to afford 28.0 g (48 %) of a dark solid which was used in the next step without further purification.

Synthesis of 2-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxy- methyl)-4-methoxyphenol. In a 500 ml round bottom flask equipped with a magnetic stirrer, addition funnel, powder addition funnel, and nitrogen inlet was added 27.4 g (81.0 mmol) 2-((5-chloro-2-nitrophenyl)diazenyl)-6- (hydroxymethyl)-4-methoxyphenol and 200 ml ethanol. NaOH (19.7 g, 493 mmol) was dissolved in 100 ml deionized water and approximately one-fourth was added dropwise to the reaction mixture. The mixture was heated to 80 °C and 26.5 g (245 mmol) formamidine sulfinic acid and the remaining sodium hydroxide solution were concurrently added dropwise to the reaction mixture. The mixture was stirred at 80 °C for 2 hours and then poured into 3L deionized water. The mixture was acidified to pH 3 using 1 N HCI and the solid was collected by filtration, rinsed with ample amounts of water, and then worked up as in Example 5 to afford 7.4 g (30 %) solid which was used in the next esterification step.

EXAMPLE 9 (Compound WL-4)

Synthesis of 3-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy- 5-methoxybenzyl methacrylate. In a 250 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 3.98 g (13.0 mmol) 2- (5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-6-(hydroxymethyl)-4-methoxyphenol in 60 ml anhydrous THF. Triethylamine (6.4 ml) was added and the mixture was cooled to -10 - 0 °C. Methacryloyl chloride (1.62 g, 15.5 mmol) was added dropwise and the mixture was stirred for 1 hr at -10 - 0 0C followed by 20 hours at ambient temperature. The solid was filtered and rinsed with 100 ml diethyl ether. The organic layer was washed with 1 N HCI and water, dried with magnesium sulfate, filtered, and concentrated via rotary evaporation to yield a yellow oil which was recrystallized in ethanol to give 1.73 g (34 %) of a light yellow solid. 1H NMR (CDCI3) delta: 11.00 (s, 1 H, Ar-OH), 7.92 (s, 1 H, Ar-H benzotriazole), 7.88 (s, 1 H, Ar-H phenol), 7.87 (d, 1 H, Ar-H benzotriazole), 7.45 (d, 1 H, Ar-H benzotriazole), 7.06 (s, 1 H, Ar-H phenol), 6.21 (S, 1 H, C=C-H trans), 5.62 (s, 1 H, C=C-H cis), 5.38 (s, 2H, Ar-CH2), 3.89 (s, 3H, Ar-OCH3), 2.01 (s, 3H, C=C-CH3).

WL-4

EXAMPLE 10

Synthesis of 2-(2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H- benzo[d][1,2,3]triazol-2-yl)phenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 24.8 g (148 mmol) 4-methoxy-2-nitroaniline (Aldrich), cone. HCI(aq) (J.T. Baker), 150 ml water, and 150 ml absolute ethanol. The mixture was cooled to -20 °C and a solution comprised of 10.8 (156 mmol) sodium nitrite in 40 ml water was added dropwise over 30 minutes. The reaction mixture was stirred for an additional 1 hour and then sulfamic acid (315 mg) was added to destroy excess nitrite. The undissolved solids were filtered and the filtrate containing the diazonium salt was set aside and kept cold at -10 0C. NaOH (29.5 g, 739 mmol) was dissolved in 100 ml water and approximately one-fourth was added to a solution comprised of (2- hydroxy-5-methoxy-1 ,3-phenylene)dimethanol in 100 ml deionized water and 200 ml ethanol. The diazonium salt mixture and remaining sodium hydroxide solution were added to the reaction mixture containing the phenol derivative over a 1 hour period at 0 °C. The reaction mixture was allowed to stir at 0 0C for 1 hour and ambient temperature for 3 hours. The contents were poured into 3 liters water and the pH was adjusted to 4.5 using 1 N HCI. The resultant solid was filtered, washed with several liters of water, and then vacuum dried (0.1 mm Hg) at 65 °C for 20 hours using P2O5 as drying agent to afford 33.5 g (68 %) of a dark solid which was used in the next step without further purification.

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H- benzo[d][1 ,2,3]triazol-2-yl)phenol. In a 500 ml round bottom 3-neck flask equipped with a magnetic stirrer, addition funnel, powder addition funnel, and nitrogen inlet was added 2-(hydroxymethyl)-4-methoxy-6-((4-methoxy-2- nitrophenyl)diazenyl)phenol from Example 11 and 200 ml absolute ethanol

(Pharmco Products, Brookfield, CT). NaOH pellets, 97% (Aldrich, 16.8 g, 420 mmol) were dissolved in 80 ml deionized water and approximately one-fourth of the solution was added dropwise to the azo mixture. The reaction mixture was heated to 80 0C and 22.6 g (209 mmol) formamidinesulfinic acid (Aldrich) and the remaining NaOH solution were added concurrently to the azo mixture over 0.5 hr. The mixture was heated at 80 °C for 3 hours, poured into 3.5 L water, and acidified to pH 4-5 with cone. HCI (JT. Baker). The crude product was recrystallizsed from ethanol and then collected and vacuum dried (0.1 mm Hg) at 50 0C for 72 hours to give 7 g (27 %) of a light yellow solid.

EXAMPLE 11 (Compound WL-5)

Synthesis of 2-hydroxy-5-methoxy-3-(5-methoxy-2H- benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate. The esterification was carried out using the product from Example 11. In a 100 ml round bottom 3- neck flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 3.24 g (10.8 mmol) 2-(hydroxymethyl)-4-methoxy-6-(5-methoxy-2H- benzo[d][1 ,2,3]triazol-2-yl)phenol in 60 ml anhydrous THF. Triethylamine (1.2 ml) was added and the mixture was cooled to -10 - 0 0C. Methacryloyl chloride (1.40 g, 13.4 mmol) was added dropwise and the mixture was stirred for 2 hr at 0 °C followed by 20 hours at ambient temperature. The salts were filtered off and the filtrate was poured into 100 ml diethyl ether and washed with 0.5 N HCI and water. The organic layer was dried with magnesium sulfate, filtered, and concentrated via rotary evaporation to give the desired product as a dark yellow oil which was recrystallized in ethanol to give a light yellow solid. 1H NMR (CDCI3) delta: 11.20 (s, 1 H, phenol OH), 7.80 (m, 1 H, Ar-H benzotriazole), 7.77 (s, 1 H, Ar-H phenol), 7.17 (m, 1 H, Ar-H benzotriazole), 7.14 (s, 1 H, Ar-H phenol), 7.10 (m, 1 H, Ar-H benzotriazole), 6.21 (s, 1 H1 C=C-H trans), 5.61 (s, 1 H, C=C-H cis), 5.38 (s, 2H, Ar-CH2), 3.92 (s, 3H1 Ar-OCH3, phenol), 3.88 (s, 3H, Ar-OCH3, benzotriazole), 2.01 (s, 3H, C=C-CH3).

WL-5

EXAMPLE 12

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-((4-methyl-2- nitrophenyl)-diazenyl)phenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was added 24.3 g (160 mmol) 4-methyl-2-nitroaniline, 98% (Aldrich), 67 ml cone. HCI(aq), 100 ml water, and 100 ml absolute ethanol. The mixture was cooled to -10 - 0 0C and 11.6 g (169 mmol) sodium nitrite in 40 ml water was added dropwise over 30 minutes at - 10 - 0 °C. The reaction mixture was stirred for an additional 1 hour and 315 mg sulfamic acid was added to destroy excess nitrite. After an additional 20 minutes of stirring the reaction mixture was filtered and the cold filtrate was set aside. In a 1 L flask was suspended (2-hydroxy-5-methoxy-1 ,3-phenylene)dimethanol in 200 ml deionized water and 100 ml ethanol. A solution of 32.2 g (805 mmol) sodium hydroxide was prepared and approximately one-fourth was added to the phenol derivative. The phenol derivative was cooled to 0 °C and the diazonium salt mixture and remaining sodium hydroxide solution were added concurrently to the phenol derivative over 1 hour at 0 0C. The reaction mixture was stirred at 0 °C for 1 hour and ambient temperature for 3 hours. The mixture was poured into 3 liters water and the pH was adjusted to 4.5 using 1 N HCI. The crude product was dried at 65 0C for 20 hours under high vacuum (0.1 mm Hg) using P2O5 as drying agent to afford 30.8 g (61 %). The product was used in the next step without further purification.

Synthesis of 2-(hydroxymethyl)-4-methoxy-6-(5-methyl-2H- benzo[d][1,2,3]triazol-2-yl)phenol. In a 500 ml round bottom 3-neck flask equipped with a magnetic stirrer, regular addition funnel, powder addition funnel, and nitrogen inlet was added 30.0 g (94.6 mmol) of the azo compound from part 1 and 200 ml ethanol. NaOH (22.9 g, 573 mmol) was dissolved in 100 ml deionized water and approximately one-fourth of the solution was added dropwise to the reaction mixture. The reaction mixture was heated to 80 0C. Formamidinesulfinic acid (30.7 g, 284 mmol) and the remaining sodium hydroxide solution were added concurrently to the azo mixture over 30 minutes. The mixture was heated at 80 °C for 3 hours. The reaction mixture was poured into 3 L water and then acidified to pH 4-5 with 1 N HCI. The solid was filtered and then dissolved in 3L water containing 5 grams NaOH and acidified to pH 2 with 1 N HCI. The solid was filtered again and then dried at 55 °C under high vacuum (0.1 mm Hg) for 40 hours to afford 20 g (74 %) which was used in the next step without further purification. EXAMPLE 13 (Compound WL-6)

Synthesis of 2-hydroxy-5-methoxy-3-(5-methyl-2H- benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate. In a 100 ml round bottom 3-neck flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 19.5 g (68.3 mmol) 2-(hydroxymethyl)-4-methoxy-6-(5-methyl-2H- benzo[d][1 ,2,3]triazol-2-yl)phenol in 200 ml anhydrous THF. Triethylamine (34 ml, 240 mmol) was added and the mixture was cooled to -10 0C. Methacryloyl chloride (8.55 g , 81.8 mmol) was added dropwise and the mixture was stirred for 2 hr at 0 °C followed by 20 hours at ambient temperature. The solid was filtered and rinsed with diethyl ether and the filtrate was poured into 100 ml diethyl ether and washed with 0.5 N HCI and water. The organic layer was dried with magnesium sulfate, filtered, and concentrated via rotary evaporation. The crude product was recrystallized in ethanol to give 7.2 g (30 %) of a light yellow solid. 1H NMR (CDCI3) delta: 11.28 (s, 1 H, Ar-OH), 7.89 (s, 1 H, Ar-H benzotriazole 4-position), 7.79 (d, 1 H, Ar-H benzotriazole 6-position), 7.66 (s, 1 H, Ar-H phenol 6-position), 7.26 (d, 1 H, Ar-H benzotriazole 7-position), 7.03 (s, 1 H, Ar-H phenol 4-position), 6.21 (s, 1 H, C=C-H trans), 5.61 (s, 1 H, C=C-H cis), 5.39 (s, 2H, Ar-CH2), 3.89 (s, 3H, Ar-OCH3), 2.54 (s, 3H, Ar-CH3), 2.01 (s, 3H, C=C-CH3).

WL-6 EXAMPLE 14

Synthesis of 2-(hydroxymethyl)-4-methyl-6-((2-nitro-4-

(trifluoromethyl)-phenyl)-diazenyl)phenol. In a 500 ml round bottom flask equipped with a magnetic stirrer was combined 26.0 g (126 mmol) 2-nitro-4- (trifluoromethyl)-aniline, 53 ml cone. HCI, 100 ml deionized water, and 150 ml ethanol. The mixture was cooled to 0 °C and sodium nitrite in 30 ml water was added dropwise over 60 minutes. The reaction mixture was stirred for an additional 1 hour and 300 mg sulfamic acid was added to destroy the excess nitrite. The solids were filtered and the cold filtrate was set aside. In a 1 liter flask was suspended (2-hydroxy-5-methoxy-1 ,3-phenylene)dimethanol in 200 ml deionized water and 100 ml ethanol. Approximately one-fourth of a solution of sodium hydroxide (25.4 g, 635 mmol) in 100 ml water was added to the phenolic mixture at 0 °C. The diazonium salt mixture and remaining sodium hydroxide solution were added concurrently to the phenolic mixture over 1 hour. The reaction mixture was allowed to stir at 0 0C for 1 hour and room temperature for 4 hours. The mixture was poured in 3 liters water and the pH adjusted to 3-4 using 1 N HCI. The solid was filtered and washed with ample amounts of water and then vacuum dried (0.1 mm Hg) at 55 °C for 40 hours to give 27.4 g (76 %) of a red solid.

Synthesis of 2-(hydroxymethyl)-4-methyl-6-(5-(trifluoromethyl)-2H- benzo[d][1,2,3]triazol-2-yl)phenol. In a 1 L round bottom flask equipped with a magnetic stirrer, addition funnel, powder addition funnel, and nitrogen inlet was added 26.0 g (73.2 mmol) 2-(hydroxymethyl)-4-methyl-6-((2-nitro-4- (trifluoromethyl)phenyl)-diazenyl)phenol and 300 ml ethanol. Sodium hydroxide (17.6 g, 441 mmol) was dissolved in 100 ml deionized water and approximately one fourth was added dropwise to the azo mixture. The reaction mixture was heated to 80 0C and 23.9 g (221 mmol) formamidinesulfinic acid and the remaining sodium hydroxide solution were added to the azo mixture over 30 minutes. The reaction mixture was heated at 80 0C for 3 hours, poured in 3 L deionized water, and acidified to pH 4 using 1 N HCI. The solid was collected by vacuum filtration, washed with ample amounts of water, and then dried for 20 hours under vacuum (0.1 mm Hg) at 42 °C to give 18.6 g (79 %) of an off white solid.

EXAMPLE 15 (Compound WL-7)

Synthesis of 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H- benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate. In a 100 ml round bottom 3-neck flask equipped with a magnetic stirrer and nitrogen inlet was dissolved 3.58 g (11.1 mmol) 2-(hydroxymethyl)-4-methyl-6-(5-(trifluoromethyl)-2H- benzo[d][1 ,2,3]triazol-2-yl)phenol in 60 ml anhydrous THF. Triethylamine (5.6 ml, 40 mmol) was added and the mixture was cooled to -10 0C. Methacryloyl chloride (1.373 g, 13.1 mmol) was added dropwise and the mixture was stirred for 1 hour at -10 0C followed by 20 hours at ambient temperature. The solid was filtered off and rinsed with diethyl ether and the resultant filtrate was poured into 100 ml diethyl ether and washed with 0.5 N HCI and water. The organic layer was dried with magnesium sulfate, filtered, and recrystallized with diethyl ether to give 1.90 g (44 %) of a white solid. 1H NMR (CDCI3) delta: 11.17 (s, 1 H, Ar-OH), 8.29 (s, 1 H, Ar-H benzotriazole 4-position), 8.21 (s, 1 H, Ar-H phenol 6-position), 8.06 (d, 1 H, Ar-H benzotriazole 6-position), 7.69 (d, 1 H, Ar-H benzotriazole 7-position), 7.29 (s, 1 H, Ar-H phenol 4- position), 6.20 (s, 1 H, C=C-H trans), 5.61 (s, 1 H, C=C-H cis), 5.39 (s, 2H, Ar- CH2), 2.42 (s, 3H, Ar-CH3), 2.00 (s, 3H, C=C-CH3).

WL-7 EXAMPLE 16

Transmittance curves for Compounds WL-1 through WL-7 were generated by UV/Vis spectroscopy. Each compound was dissolved in chloroform and evaluated in a PerkinElmer Lambda 35 UVΛ/is spectrometer. The results are shown in Figure 1 and the 1% T and 10% T results are shown in Table 1.

1C TABLE 1

EXAMPLE 17

I5

Acrylic IOL Formulations

Compounds WL-1 - WL-4 were formulated in IOL materials as shown in Tables 2 - 6. All components were vortex mixed in a 30 ml glass vial,

20 degassed with nitrogen, and then syringe filtered using a 0.2 micron Teflon filter into ~1 mm deep rectangular polypropylene molds. Samples were thermally cured at 70 0C for 1 hour and 110 °C for 2 hours and then extracted in acetone at 50 °C for 6 hours with fresh solvent replacement every 90 minutes. 5 TABLE 2

Example

(% w/w)

Component 17A 17B

Compound WL-1 1.81 1 .81

(Example 3)

N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)- ethylmethylacrylamide

PEA 48.8 —

PEMA 42.9 —

BzA — 79.7

BzMA — 12.0

Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester

BDDA 1.50 1.51

AIBN 0.56 0.59

PEA = 2-phenylethyl acrylate

PEMA = 2-phenylethyl methacrylate

BzA = benzyl acrylate

BzMA = benzyl methacrylate

BDDA = 1 ,4-butanediol diacrylate Secondary alcohol ethoxylate, methacrylic acid ester = methacrylic acid ester of Tergitol™ 15-S-30 surfactant (Dow/Union Carbide)

AIBN = 2,2'-Azobis(2-methylpropionitrile)

TABLE 3

Example

(% w/w)

Component 17C 17D

Compound WL-2 1.81 1.81

(Example 5)

N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)- ethylmethylacrylamide

PEA 48.8 —

PEMA 42.9 —

BzA — 79.7

BzMA — 12.0

Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester

BDDA 1.50 1.51

AIBN 0.55 0.53

TABLE 4

Example

(% w/w)

Component 17E 17F

Compound WL-3 1.80 1.82

(Example 7)

N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)- ethylmethylacrylamide

PEA 48.8 —

PEMA 42.9 —

BzA — 79.7

BzMA — 12.0

Secondary alcohol 5.01 5.00 ethoxylate, methacrylic acid ester

BDDA 1.50 1.51

AIBN 0.50 0.52 TABLE 5

Example

(% w/w)

Component 17G 17H

Compound WL-4 1.80 1.80

(Example 9)

N-2-(3-(2- 0.021 0.021 methylphenylazo)-4- hydroxy-phenyl)- ethylmethylacrylamide

PEA 48.8 —

PEMA 42.9 —

BzA — 79.7

BzMA — 12.0

Secondary alcohol 5.00 5.00 ethoxylate, methacrylic acid ester

BDDA 1.50 1.50

AIBN 0.50 0.51

TABLE 6

Example

(% w/w)

Component 171 17J

Compound WL-1 1.67 —

(Example 3)

Compound WL-4 — 1.53

(Example 9)

BzA 83.7 83.9

BzMA 10.0 10.0

PoIyPEGMA 3.02 3.03

BDDA 1.58 1.53

AIBN 0.50 0.51

PoIyPEGMA = Macromonomer of poly(ethylene glycol) monomethyl ether methacrylate (MW = 550), Mn (SEC): 4100 Daltons, Mn (NMR): 3200 Daltons, PDI = 1.50. EXAMPLE 18 Photostability

Samples of Formulations 17A, 17B, 17C, 17D, 17E, 17F, 17G, 17H, 171, and 17J were subject to UV radiation from 300 to 800 nm using an Atlas Suntest CPS+ test chamber (Atlas Electric Devices Company, Chicago, Illinois) utilizing a xenon arc lamp with light intensity of approximately 8 - 10 mW/cm2 at the height of the test sample. The temperature of the PBS medium was 35 0C. UVA/is spectra from 0.9 mm thick sample sections were collected using a PerkinElmer Lambda 35 UVA/is spectrometer. Results from light exposure equivalent to 20 years (Examples 17A - 17H) or 10 years (Examples 171 and 17J) are shown in Figures 2A - 2J.

This invention has been described by reference to certain preferred embodiments; however, it should be understood that it may be embodied in other specific forms or variations thereof without departing from its special or essential characteristics. The embodiments described above are therefore considered to be illustrative in all respects and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description.

Claims

We claim:
1. A benzotriazole compound of the formula
wherein
R1 = H, CH3, CH2CH3, or CH2OH; R2 = CrC4 alkyl or d-C4 alkoxy; and R3 = H, CH3, CH3O, F, Cl, Br, I1 or CF3.
2. A benzotriazole compound of Claim 1 wherein R1 = H or CH3;
R2 = CrC4 alkoxy; and R3 S H1 CH31 CH3O1 F1 CI1 Or CF3.
3. A benzotriazole compound of Claim 2 wherein the compound is selected from the group consisting of:
2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2- yl)benzyl methacrylate; 3-(5-fluoro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate;
3-(2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate;
3-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate;
2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1 ,2,3]triazol-2- yl)benzyl methacrylate; 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate; and
2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2- yl)benzyl methacrylate.
4. A benzotriazole compound of Claim 3 wherein the compound is 2- hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1 ,2,3]triazol-2-yl)benzyl methacrylate.
5. A benzotriazole compound of Claim 3 wherein the compound is 3-(5-chloro-2H-benzo[d][1 ,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate.
6. An ophthalmic device material comprising a benzotriazole compound of Claim 1 and a device-forming monomer selected from the group consisting of acrylic monomers and silicone-containing monomers.
7. An ophthalmic device material of Claim 6 wherein the ophthalmic device material comprises from 0.1 to 3 % (w/w) of a benzotriazole compound of Claim 1.
8. An ophthalmic device material of Claim 7 wherein the ophthalmic device material comprises from 0.2 to 2.5 % (w/w) of a benzotriazole compound of Claim 1.
9. An ophthalmic device material of Claim 8 wherein the ophthalmic device material comprises from 0.3 to 2 % (w/w) of a benzotriazole compound of Claim 1.
10. An ophthalmic device material of Claim 6 wherein the ophthalmic device material comprises a device-forming monomer of formula [IV]:
[IV]
where in formula [IV]:
A is H, CH3, CH2CH3, or CH2OH; B is (CH2)m or [O(CH2)2]Z;
C is (CH2)W; m is 2 - 6; z is 1 - 10;
Y is nothing, O, S, or NR', provided that if Y is O, S, or NR', then B is (CH2)m;
R' is H, CH3, Cn'H2n'+i (n'=1-10), iso-OC3H7, C6H5, or CH2C6H5; w is 0 - 6, provided that m + w <8; and
D is H, C1 - C4 alkyl, C1 - C4 alkoxy, C6H5, CH2C6H5 or halogen.
11. An ophthalmic device material of Claim 10 wherein in formula [IV]:
A is H Or CH3; B is (CH2)m; m is 2 - 5; Y is nothing or O; w is 0 - 1 ; and D is H.
12. An ophthalmic device material of Claim 11 wherein the ophthalmic device material comprises a monomer selected from the group consisting of:
2-phenylethyl methacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate; and their corresponding acrylates.
13. An ophthalmic device material of Claim 6 wherein the ophthalmic device material comprises a cross-linking agent.
14. An ophthalmic device material of Claim 6 wherein the ophthalmic device material comprises a reactive blue-light absorbing compound.
15. An intraocular lens comprising a benzotriazole compound of Claim 1.
16. An intraocular lens comprising a benzotriazole compound of Claim 2.
17. An intraocular lens comprising a benzotriazole compound of Claim 3.
18. An ophthalmic device comprising the ophthalmic device material of Claim 6.
19. The ophthalmic device of Claim 18 wherein the ophthalmic device is selected from the group consisting of an intraocular lens; a contact lens; a keratoprosthesis; and a corneal inlay or ring.
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WO2011137142A1 (en) * 2010-04-29 2011-11-03 Novartis Ag Intraocular lenses with combinations of uv absorbers and blue light chromophores
WO2012163936A1 (en) * 2011-05-31 2012-12-06 Dsm Ip Assets B.V. Process for the synthesis of benzotriazoles useful as uv-filters
EP2941419A4 (en) * 2013-11-14 2015-11-11 Novartis Ag Uv-absorbers for ophthalmic lens materials

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RU2503667C2 (en) * 2008-11-04 2014-01-10 Алькон, Инк. Uv/visible light absorbers for ophthalmic lens materials
CN102510860B (en) * 2009-07-06 2014-07-02 诺瓦提斯公司 UV/visible light absorbers for ophthalmic lens materials
EP2451875B1 (en) * 2009-07-06 2013-08-28 Novartis AG Visible light absorbers for ophthalmic lens materials
RU2571085C2 (en) 2010-01-18 2015-12-20 Новартис Аг Visible radiation absorbers for ophthalmic lenses materials
WO2013025671A1 (en) 2011-08-15 2013-02-21 Novartis Ag Uv-absorbers for ophthalmic lens materials
JP6105589B2 (en) * 2011-09-16 2017-03-29 ベンズ リサーチ アンド ディベロップメント コーポレーション Ultraviolet light absorbing material and the use thereof for intraocular lenses
US8585938B1 (en) 2012-03-30 2013-11-19 Novartis Ag UV-absorbers for ophthalmic lens materials
EP2857459B1 (en) * 2012-04-27 2017-12-27 Kowa Company, Ltd. Stable polymerizable uv-absorbing colorant for intraocular lens
CN105579480A (en) 2013-09-30 2016-05-11 诺华股份有限公司 Method for making UV-absorbing ophthalmic lenses
US9568645B2 (en) 2013-09-30 2017-02-14 Novartis Ag Silicone hydrogel lenses with relatively-long thermal stability
CN105683313A (en) * 2013-10-29 2016-06-15 巴斯夫欧洲公司 The use of 2-(2-hydroxyphenyl)benzotriazole compounds as an UV absorbing agent in coatings
JPWO2015064675A1 (en) * 2013-10-30 2017-03-09 興和株式会社 The method of manufacturing polymerizable ultraviolet absorbing dye
WO2015064674A1 (en) * 2013-10-30 2015-05-07 興和株式会社 Method for manufacturing polymerizable uv-absorbing dye
CA2928011A1 (en) 2013-12-04 2015-06-11 Novartis Ag Soft acrylic materials comprising a poly(phenylether)-containing monomer having a high refractive index and minimized glistening
WO2015170278A1 (en) 2014-05-07 2015-11-12 Tubitak A formulation and lens manufacturing process for the production of intraocular lens (iol)
CN106999628A (en) 2014-12-16 2017-08-01 诺华股份有限公司 Hydrophobic acrylate-acrylamide copolymers for ophthalmic devices
EP3200840A1 (en) 2014-12-16 2017-08-09 Novartis AG Low-water content acrylate-acrylamide copolymers for ophthalmic devices
JP2018506348A (en) 2015-02-16 2018-03-08 ノバルティス アーゲー Wet packs intraocular lens material having a high refractive index
US20170242275A1 (en) 2016-02-22 2017-08-24 Novartis Ag Uv-absorbing vinylic monomers and uses thereof
WO2017145022A1 (en) 2016-02-22 2017-08-31 Novartis Ag Uv/visible-absorbing vinylic monomers and uses thereof
EP3236296A1 (en) 2016-04-21 2017-10-25 ESSILOR INTERNATIONAL (Compagnie Générale d'Optique) Optical material comprising a red-shifted benzotriazole uv absorber

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4528311A (en) * 1983-07-11 1985-07-09 Iolab Corporation Ultraviolet absorbing polymers comprising 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazoles
JPH08208628A (en) * 1995-01-31 1996-08-13 Osaka Seika Kogyo Kk Benzotriazole and production thereof
CN1727338A (en) * 2004-12-27 2006-02-01 常州华钛化学有限公司 Compound in benzotriazole category possessing alkenyl ester type structure, and preparation method

Family Cites Families (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1287494A (en) * 1969-08-28 1972-08-31 Gaf Corp Improvements in or relating to triazole derivatives
GB1356434A (en) 1970-06-17 1974-06-12 Gaf Corp Triazole compounds and cosmetic compositions containing them
US4390676A (en) * 1976-11-15 1983-06-28 Schering Corporation Ultraviolet absorbing lenses
US4310650A (en) * 1980-03-03 1982-01-12 California Institute Of Technology Ultraviolet absorbing copolymers
US4611061A (en) * 1984-03-26 1986-09-09 Iolab Corporation 2'-hydroxy-5'-(hydroxyalkyl)phenyl-2H-benzotriazoles
JPH0452799B2 (en) 1984-08-27 1992-08-24 Konishiroku Photo Ind
US4795461A (en) * 1985-07-19 1989-01-03 Pharmacia Ab UV absorbing lens material
US4716234A (en) * 1986-12-01 1987-12-29 Iolab Corporation Ultraviolet absorbing polymers comprising 2-(2'-hydroxy-5'-acryloyloxyalkoxyphenyl)-2H-benzotriazole
JPH0480033B2 (en) 1987-01-30 1992-12-17 Dainichiseika Color Chem
JP2683007B2 (en) 1987-03-03 1997-11-26 アイオーラブ・コーポレーシヨン Benzotriazole compounds, their copolymers and UV-absorbing composition
US4803254A (en) * 1987-03-11 1989-02-07 Iolab Corporation Vinylsilylalkoxy arylbenzotriazole compounds and UV absorbing compositions made therefrom
JPH0621233B2 (en) 1987-03-25 1994-03-23 大日精化工業株式会社 Pigment composition and a method of manufacturing the same
JPH01250944A (en) 1988-03-30 1989-10-05 Konica Corp Silver halide color photographic sensitive material
JP2604799B2 (en) 1988-05-27 1997-04-30 株式会社メニコン Intraocular lens material
DE3837884A1 (en) * 1988-11-08 1990-05-10 Mutzhas Maximilian F Light filters for improvement of Seeing
JP2864256B2 (en) 1989-11-10 1999-03-03 セーレン株式会社 Fiber structure and a manufacturing method thereof comprising the elastic yarn is excellent in durability
US5145790A (en) 1990-05-04 1992-09-08 Abbott Laboratories Reagents and method for detecting polychlorinated biphenyls
US5290892A (en) * 1990-11-07 1994-03-01 Nestle S.A. Flexible intraocular lenses made from high refractive index polymers
JP2685980B2 (en) * 1990-11-26 1997-12-08 株式会社メニコン UV absorbing intraocular lens
JP2858940B2 (en) 1990-11-26 1999-02-17 シプロ化成株式会社 Method for producing a novel benzotriazole compounds
JP3486909B2 (en) 1992-09-09 2004-01-13 東レ株式会社 Contact lenses and intraocular lens
JP3477723B2 (en) 1992-09-09 2003-12-10 東レ株式会社 Ultraviolet absorbers and ultraviolet absorbing composition containing the same
US5331073A (en) * 1992-11-09 1994-07-19 Allergan, Inc. Polymeric compositions and intraocular lenses made from same
US5487885A (en) 1992-12-21 1996-01-30 Biophysica, Inc. Sunblocking polymers and their formulation
JP2858953B2 (en) * 1993-04-22 1999-02-17 ウェズリー ジェッセン コーポレイション uv absorbing benzotriazole having a styrene group
US5470932A (en) * 1993-10-18 1995-11-28 Alcon Laboratories, Inc. Polymerizable yellow dyes and their use in opthalmic lenses
JP3152271B2 (en) 1993-12-17 2001-04-03 日産自動車株式会社 Door structure for a vehicle
JPH08176139A (en) 1994-12-20 1996-07-09 Tokuyama Corp Chromene compound
WO1996040303A1 (en) * 1995-06-07 1996-12-19 Alcon Laboratories, Inc. Improved high refractive index ophthalmic lens materials
US6166218A (en) * 1996-11-07 2000-12-26 Ciba Specialty Chemicals Corporation Benzotriazole UV absorbers having enhanced durability
US6710051B1 (en) 1997-01-06 2004-03-23 Klaus Trier Aps Screening method
US6320008B2 (en) * 1999-02-17 2001-11-20 Menicon Co., Ltd. Polymeric colorant and colored material for ocular lens using the colorant
JP3805853B2 (en) * 1997-03-13 2006-08-09 株式会社メニコン Polymerizable dyes and colorings ocular lens material using the
US6326448B1 (en) * 1997-08-20 2001-12-04 Menicon Co., Ltd. Soft intraocular lens material
JPH11130744A (en) 1997-10-29 1999-05-18 Menicon Co Ltd Crosslinkabke compound and optical material using the same
US5914355A (en) * 1998-05-15 1999-06-22 Bausch & Lomb Incorporated Method for making contact lenses having UV absorbing properties
US6244707B1 (en) * 1998-07-21 2001-06-12 Wesley Jessen Corporation UV blocking lenses and material containing benzotriazoles and benzophenones
EP0989124B1 (en) 1998-09-25 2002-08-14 Daicel Chemical Industries, Ltd. New polyester compounds having a benzotriazole group and a preparation method thereof
US6329485B1 (en) 1998-12-11 2001-12-11 Bausch & Lomb Incorporated High refractive index hydrogel compositions for ophthalmic implants
JP4149068B2 (en) 1999-03-02 2008-09-10 株式会社メニコン Lens material for the eye
JP3449406B2 (en) * 1999-04-07 2003-09-22 Hoyaヘルスケア株式会社 Novel pyrazolone compounds and ophthalmic plastic lens using it
EP1210380B1 (en) * 1999-09-07 2005-03-16 Alcon Inc. Foldable ophthalmic and otorhinolaryngological device materials
US20020042653A1 (en) * 1999-11-23 2002-04-11 Copeland Victor L. Blue blocking intraocular lens implant
JP3494946B2 (en) 2000-03-09 2004-02-09 株式会社メニコン Tackiness is reduced soft intraocular lenses and their preparation
JP3850729B2 (en) * 2000-03-22 2006-11-29 株式会社メニコン Lens material for the eye
JP2002046358A (en) 2000-08-03 2002-02-12 Fuji Photo Film Co Ltd Image recording medium including leuco coloring matter
US6703466B1 (en) * 2001-06-18 2004-03-09 Alcon, Inc. Foldable intraocular lens optics having a glassy surface
JP4210719B2 (en) * 2001-09-14 2009-01-21 スター・ジャパン株式会社 Ophthalmic lens
US6908978B2 (en) * 2001-11-02 2005-06-21 Bausch & Lomb Incorporated High refractive index polymeric siloxysilane compositions
US6762271B2 (en) * 2001-11-02 2004-07-13 Bausch & Lomb Incorporated High refractive index aromatic-based silyl monomers
US6794514B2 (en) 2002-04-12 2004-09-21 Symyx Technologies, Inc. Ethylene-styrene copolymers and phenol-triazole type complexes, catalysts, and processes for polymerizing
EP1495059B1 (en) 2002-04-12 2006-05-24 Dow Global Technologies Inc Low molecular weight copolymer of ethylene and vinyl aromatic monomer and uses thereof
DK2226316T3 (en) * 2002-05-30 2016-04-11 Scripps Research Inst Copper catalyzed ligation of azides and acetylenes
US20030223954A1 (en) * 2002-05-31 2003-12-04 Ruscio Dominic V. Polymeric materials for use as photoablatable inlays
US6852793B2 (en) * 2002-06-19 2005-02-08 Bausch & Lomb Incorporated Low water content, high refractive index, flexible, polymeric compositions
CA2491319C (en) * 2002-07-16 2010-02-16 Alcon, Inc. Ophthalmic and otorhinolaryngological device materials
JP2004137395A (en) 2002-10-18 2004-05-13 Fuji Photo Film Co Ltd Cellulose acylate film, its manufacturing method, and optical film, liquid crystal display, and silver halide photographic material made by using the film
DE60306203D1 (en) * 2003-01-09 2006-07-27 Alcon Inc lentils dual function UV absorber materials for ophthalmic
US20040186241A1 (en) * 2003-03-20 2004-09-23 Gemert Barry Van Photochromic ocular devices
JP2005053058A (en) 2003-08-04 2005-03-03 Fuji Photo Film Co Ltd Optical information recording medium and information recording method
US6872793B1 (en) * 2003-08-07 2005-03-29 Alcon, Inc. Ophthalmic and otorhinolaryngological device materials
US7098283B2 (en) * 2003-09-08 2006-08-29 Bausch & Lomb Incorporated Reactive yellow dyes useful for ocular devices
US20050055091A1 (en) * 2003-09-08 2005-03-10 Yu-Chin Lai Process for making silicone intraocular lens with blue light absorption properties
US7276544B2 (en) * 2003-09-08 2007-10-02 Bausch & Lomb Incorporated Process for manufacturing intraocular lenses with blue light absorption characteristics
US6918931B2 (en) * 2003-09-08 2005-07-19 Bausch & Lomb Incorporated Prepolymers with yellow dye moiety
EP1694721B1 (en) * 2003-11-05 2013-10-09 Benz Research and Development Corporation Materials for making hydrophobic intraocular lens
EP1699385B1 (en) * 2003-12-29 2012-10-24 Abbott Medical Optics Inc. Intraocular lenses having a visible light-selective-transmissive-region
CA2564921C (en) * 2004-04-30 2015-03-24 Advanced Medical Optics, Inc. Ophthalmic devices having a highly selective violet light transmissive filter and related methods
US20070159594A9 (en) 2004-05-13 2007-07-12 Jani Dharmendra M Photochromic blue light filtering materials and ophthalmic devices
US8133274B2 (en) * 2004-06-18 2012-03-13 Medennium, Inc. Photochromic intraocular lenses and methods of making the same
US7381762B2 (en) * 2004-08-20 2008-06-03 Milliken & Company Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds
JP4532243B2 (en) * 2004-11-10 2010-08-25 株式会社ニデック Lens colorant for ocular and coloring ocular lens material using the colorant
JP4896036B2 (en) * 2004-11-22 2012-03-14 アボット・メディカル・オプティクス・インコーポレイテッドAbbott Medical Optics Inc. Copolymerizable azo compound and articles containing it
WO2006057824A3 (en) 2004-11-22 2006-10-05 Advanced Medical Optics Inc Copolymerizable methine and anthraquinone compounds and articles containing them
DE602006020839D1 (en) * 2005-02-02 2011-05-05 Basf Se Long wavelength shifted benzotriazole uv absorber and their use
US20060197067A1 (en) * 2005-03-04 2006-09-07 Erning Xia Radiation-absorbing materials, ophthalmic compositions containing same, and method of treating ophthalmic devices
US20060252850A1 (en) 2005-05-04 2006-11-09 Bausch & Lomb Incorporated Radiation-absorbing polymeric materials and ophthalmic devices comprising same
WO2006121876A3 (en) 2005-05-05 2009-04-23 Key Medical Technologies Inc Lenses with chromophore gradient
US7842367B2 (en) * 2005-05-05 2010-11-30 Key Medical Technologies, Inc. Ultra violet, violet, and blue light filtering polymers for ophthalmic applications
US20070092830A1 (en) * 2005-10-24 2007-04-26 Bausch & Lomb Incorporated Polymeric radiation-absorbing materials and ophthalmic devices comprising same
US20070092831A1 (en) 2005-10-24 2007-04-26 Bausch & Lomb Incorporated Radiation-absorbing polymeric materials and ophthalmic devices comprising same
JP4193869B2 (en) 2006-05-09 2008-12-10 三菱自動車工業株式会社 Deterioration diagnosis device for an exhaust gas purifying catalyst
DE102006028507A1 (en) 2006-06-21 2007-12-27 *Acri.Tec AG Gesellschaft für ophthalmologische Produkte Ophthalmic composition and its use
EP2081612B1 (en) * 2006-10-13 2012-11-21 Novartis AG Intraocular lenses with unique blue-violet cutoff and blue light transmission characteristics
WO2008103798A3 (en) * 2007-02-21 2009-09-11 Powervision, Inc. Polymeric materials suitable for ophthalmic devices and methods of manufacture
EP2130071A2 (en) 2007-03-05 2009-12-09 Benz Research and Development Corporation Light filters comprising a naturally occurring chromophore and derivatives thereof
ES2349182T3 (en) * 2007-04-30 2010-12-28 Alcon, Inc. UV absorbers for ophthalmic lens materials.
JP2009013148A (en) 2007-07-03 2009-01-22 Shipro Kasei Kaisha Ltd Chemical modification to bis type structure by adipoyl dichloride, isophthaloyl dichloride or terephthaloyl dichloride of benzotriazole-based ultraviolet light absorbent having hydroxymethyl group
US7728051B2 (en) * 2007-08-09 2010-06-01 Alcon, Inc. Ophthalmic lens materials containing chromophores that absorb both UV and short wavelength visible light
JP2010535906A (en) * 2007-08-09 2010-11-25 アルコン,インコーポレイテッド Ocular lens material comprising a chromophore that absorbs both the Uv light and short wavelength visible light
CN101727338B (en) 2008-08-15 2012-12-26 北京北大众志微系统科技有限责任公司 Parallel upgrade method and application system for network computer
RU2503667C2 (en) * 2008-11-04 2014-01-10 Алькон, Инк. Uv/visible light absorbers for ophthalmic lens materials
CN102510860B (en) 2009-07-06 2014-07-02 诺瓦提斯公司 UV/visible light absorbers for ophthalmic lens materials
EP2564245A1 (en) 2010-04-29 2013-03-06 Novartis AG Intraocular lenses with combinations of uv absorbers and blue light chromophores
US9265455B2 (en) 2012-11-13 2016-02-23 Medtronic Minimed, Inc. Methods and systems for optimizing sensor function by the application of voltage
JP6088065B2 (en) 2012-12-07 2017-03-01 ヴォッベン プロパティーズ ゲーエムベーハーWobben Properties Gmbh Rotor blade rearward edge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4528311A (en) * 1983-07-11 1985-07-09 Iolab Corporation Ultraviolet absorbing polymers comprising 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazoles
JPH08208628A (en) * 1995-01-31 1996-08-13 Osaka Seika Kogyo Kk Benzotriazole and production thereof
CN1727338A (en) * 2004-12-27 2006-02-01 常州华钛化学有限公司 Compound in benzotriazole category possessing alkenyl ester type structure, and preparation method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011086127A1 (en) * 2010-01-15 2011-07-21 Dsm Ip Assets B.V. Process to make uv radiation absorbing 2 - phenyl - 1, 2, 3 - benzotriazoles
WO2011086124A1 (en) * 2010-01-15 2011-07-21 Dsm Ip Assets B.V. 2 - phenyl - 1, 2, 3 - benzotriazoles for uv radiation absorbance
US8895754B2 (en) 2010-01-15 2014-11-25 Dsm Ip Assets B.V. Process to make UV radiation absorbing 2-phenyl-1,2,3,-benzotriazoles
JP2013517250A (en) * 2010-01-15 2013-05-16 ディーエスエム アイピー アセッツ ビー.ブイ. 2-phenyl-1,2,3-benzotriazole for ultraviolet absorption
US8883829B2 (en) 2010-01-15 2014-11-11 Dsm Ip Assets B.V. 2-phenyl-1,2,3-benzotriazoles for UV radiation absorbance
US8262948B2 (en) 2010-04-29 2012-09-11 Novartis Ag Intraocular lenses with combinations of UV absorbers and blue light chromophores
JP2013526925A (en) * 2010-04-29 2013-06-27 ノバルティス アーゲー Intraocular lenses having a combination of Uv absorbers and blue light chromophore
WO2011137142A1 (en) * 2010-04-29 2011-11-03 Novartis Ag Intraocular lenses with combinations of uv absorbers and blue light chromophores
WO2012163936A1 (en) * 2011-05-31 2012-12-06 Dsm Ip Assets B.V. Process for the synthesis of benzotriazoles useful as uv-filters
EP2941419A4 (en) * 2013-11-14 2015-11-11 Novartis Ag Uv-absorbers for ophthalmic lens materials

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