Polymerizable fused tricyclic compounds as UV and visible light absorbers.

Abstract

A polymerizable fused tricyclic compound of formula I, [Formula 1] TIFF2022537849000041.tif36128 formula, R 1 , R 2 , R 3 , m, n, t, and rings B, C, and D are as defined herein. The compounds absorb various wavelengths of ultraviolet and / or visible light (e.g., high-energy visible light) and are suitable for incorporation into various products, such as biomedical and ophthalmic devices.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 16 / 883,199, filed May 26, 2020, and U.S. Provisional Patent Application No. 62 / 867,963, filed June 28, 2019, both of which are incorporated by reference in their entireties.

[0002] FIELD OF THEINVENTION The present invention relates to UV and / or visible light absorbers. More specifically, the present invention relates to compounds having polymerizable functional groups that absorb visible light, such as UV and / or high energy visible light at various wavelengths, and are visually transparent when incorporated into articles. Thus, the compounds can be used in polymeric articles, including biomedical devices, such as ophthalmic devices. [Background technology]

[0003] High energy light from the sun, such as UV light and high energy visible light, is known to be involved in cell damage. Most of the radiation with wavelengths below 280 nm is absorbed by the Earth's atmosphere, but photons with wavelengths in the range of 280-400 nm are associated with degenerative changes in the cornea, as well as several eye disorders, including age-related cataracts and macular degeneration. (See Statement on Ocular Ultraviolet Radiation Hazards in Sunlight, American Optometric Association, November 10, 1993). The human cornea absorbs some radiation up to 320 nm wavelength (30% transmission) (Doutch, JJ, Quantock, AJ, Joyce, NC, Meek, KM, Biophys. J, 2012, 102, 1258-1264), but is inefficient in protecting the back of the eye from radiation in the range of wavelengths from 320 to 400 nm.

[0004] Contact lens standards define the upper ultraviolet wavelength at 380 nm. The current Class I UV absorption standard defined by the American Optometric Association requires that greater than 99% of radiation between 280 and 315 nm (UV B) and greater than 90% of radiation between 316 and 380 nm (UV A) be absorbed by contact lenses. This standard effectively addresses corneal protection (less than 1% UV B transmission), but little attention is paid to lower energy ultraviolet radiation (>380 to <400 nm) which is associated with retinal damage (Ham, WT, Mueller, HA, Sliney, DH Nature 1976;260(5547)153-5) or to high energy visible light.

[0005] High energy-visible (HEV) light can cause visual discomfort or disruption of circadian rhythms. For example, computer and electronic device screens, flat screen televisions, energy-efficient lights, and LED lights are known to emit HEV light. Long-term exposure to such HEV light sources can cause eye strain. Viewing devices that emit HEV light at night is also suspected to disrupt natural circadian rhythms, leading to, for example, lack of sleep.

[0006] Absorption of high energy light rays before they reach the eye continues to be a desirable goal in ophthalmology. However, the degree to which certain wavelength ranges are absorbed is also important. For example, in the UV A and UV B ranges, it may be desirable to absorb as much radiation as possible. On the other hand, since HEV light forms part of the visible spectrum, complete absorption of HEV light may have adverse effects on vision. Therefore, for HEV light, partial absorption may be more desirable. Summary of the Invention [Problem to be solved by the invention]

[0007] There is a need for materials that provide targeted absorption of undesirable wavelengths of high energy radiation and that can be processed into functional products. Compounds that absorb or attenuate high energy radiation, when used in ophthalmic devices, can help protect the cornea, as well as internal cells in the ocular environment, from deterioration, fatigue, and / or disruption of circadian rhythms. [Means for solving the problem]

[0008] The present invention relates to high energy light absorbing compounds that absorb UV and / or high energy visible (HEV) light but substantially transmit (e.g., greater than 80% transmittance) wavelengths longer than about 450 nm. The compounds are therefore effective in providing targeted absorption of high energy light, such as UV (UVA and UVB), low energy UV light (385 nm to 400 nm), or HEV light (e.g., 400 nm to 450 nm).

[0009] The compounds are also polymerizable and generally compatible with the polymerization and processing conditions typically used to make ophthalmic devices such as soft contact lenses, in addition to other raw materials, and therefore can be readily covalently incorporated into final products without the need for significant modifications to existing manufacturing processes and equipment.

[0010] Thus, in one aspect, the present invention provides a fused tricyclic compound of formula I:

[0011] [ka] wherein m, n, and t are independently 0, 1, 2, 3, or 4; R 1 , R 2 , and R 3 is independently at each occurrence H, an optional substituent, or -YP g or two adjacent R 1 , R 2 , or R 3 The groups, together with the atoms to which they are attached, form -YP gand B is O, S, N, or NR 6 R represents an aromatic, saturated, or partially unsaturated 5-, 6-, or 7-membered ring, optionally having up to three heteroatoms independently selected from 6 , H, C 1 ~C 6 Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and one of C and D is O, S, N, or NR 6 and the other of C and D represents an aromatic, saturated or partially unsaturated 5-, 6- or 7-membered ring optionally having up to three heteroatoms independently selected from 6 , SO, or SO 2 and at least one hetero group independently selected from the group consisting of a 6-membered saturated or partially unsaturated heterocycloalkyl ring having at one ring carbon atom a group of the formula =C(EWG)(R 7 ) groups, R 7 EWG or -C(=O)-TYP g and EWG, at each occurrence, is independently an electron withdrawing group; and P g is independently a polymerizable group, Y in each occurrence is independently a linking group, and T in each occurrence is independently a bond, O, or NR 6 and the compound of formula I comprises at least one P g Contains a group.

[0012] In another aspect, the present invention provides an ophthalmic device that is a free radical reaction product of a reactive mixture comprising one or more monomers suitable for making an ophthalmic device and a compound of Formula I described herein.

[0013] In a further aspect, the present invention provides an ophthalmic device comprising a polymer network and a non-reactive polymer comprising repeat units derived from a compound of Formula I described herein. [Brief description of the drawings]

[0014] [Figure 1] 1 shows the UV-VIS transmission spectra of exemplary compounds (A), (C), (D), and (E) in 0.2 mM solutions in methanol. [Diagram 2] 1 shows the UV-VIS transmission spectra of exemplary compounds (E) and (F) in a 0.2 mM solution in methanol. [Diagram 3] 1 shows the UV-VIS transmission spectra of silicone hydrogel contact lenses from Examples 7, 8 and 9. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] It is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description, as the invention is capable of other embodiments and of being practiced or carried out in various ways using the teachings set forth herein.

[0016] As mentioned above, in one aspect, the present invention provides a UV and / or visible light (e.g., HEV) absorbing compound. The compound contains a polymerizable functional group. It has been found that an ophthalmic device that absorbs UV light and / or visible light (e.g., HEV light) can be easily prepared as described herein.

[0017] Thus, the compounds of the present invention are capable of successfully absorbing UV (UVA, UVB) and / or visible light while transmitting other portions of the visible spectrum, making them suitable for incorporation into a variety of products, including biomedical and ophthalmic devices.

[0018] The following definitions are provided for terms used in this disclosure.

[0019] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The definition of polymer is consistent with the definition disclosed in Compendium of Polymer Terminology and Nomenclature, IUPAC Recommendations 2008, edited by: Richard G. Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess, Tatsuki Kitayama, and W. Val Metanomski. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0020] As used herein, the term "(meth)" refers to any methyl substitution. Thus, a term such as "(meth)acrylate" refers to both methacrylate and acrylate.

[0021] Wherever a chemical structure is depicted, it should be understood that the disclosed options for the substituents in the structure may be combined in any combination. * and R ** and each of these contains a list of three possible groups, then nine combinations are disclosed. The same is true for combinations of features.

[0022] General formula [ *** ] n When a subscript, such as "n" in: is used to denote the number of repeating units in a chemical formula for a polymer, the formula should be interpreted as representing the number average molecular weight of the polymer.

[0023] The term "individual" includes humans and vertebrate animals.

[0024] The term "biomedical device" refers to any article designed to be used either in or on mammalian tissue or fluid, preferably in or on human tissue or fluid. Examples of these devices include, but are not limited to, wound dressings, sealants, tissue prostheses, drug delivery systems, coatings, adhesion barriers, catheters, implants, stents, and ophthalmic devices such as intraocular lenses and contact lenses. The biomedical device may be an ophthalmic device, specifically a contact lens, most specifically a contact lens made from silicone hydrogels or conventional hydrogels.

[0025] The term "ocular surface" includes the superficial and glandular epithelium of the cornea, conjunctiva, lacrimal gland, accessory lacrimal gland, nasolacrimal duct, and meibomian gland, as well as their apical and basal matrices, puncta, and adjacent or associated structures including the eyelids, which are connected as a functional system by both the continuity of the epithelium through innervation and by the endocrine and immune systems.

[0026] The term "ophthalmic device" refers to any optical device related to the eye, including any device that resides in or on the eye or any part of the eye (including the surface of the eye). These devices can provide optical correction, appearance enhancement, vision enhancement, therapeutic effects (e.g., as a dressing), or delivery of active ingredients such as pharmaceutical and nutraceutical ingredients, or any combination of the foregoing. Examples of ophthalmic devices include, but are not limited to, lenses, optics, and ocular inserts (including, but not limited to, punctal plugs). "Lens" includes spectacle lenses, sunglass lenses, soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. Ophthalmic devices can include contact lenses.

[0027] The term "contact lens" refers to an ophthalmic device that can be placed on the cornea of ​​an individual's eye. A contact lens can provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of drugs or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet light absorption, reduction of visible light or glare, or any combination thereof. A contact lens can be of any suitable material known in the art and can be a soft lens, a hard lens, or a hybrid lens that contains at least two separate portions with different physical, mechanical, or optical properties, such as elastic modulus, water content, light transmission, or any combination thereof.

[0028] The biomedical devices, ophthalmic devices, and lenses of the present invention may be composed of silicone hydrogels or conventional hydrogels, which typically contain at least one hydrophilic monomer and at least one silicone-containing component covalently bonded to each other in the cured device.

[0029] "Target polymer" refers to a polymer that has been synthesized from a reactive monomer mixture that includes monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.

[0030] The term "polymerizable compound" means a compound that contains one or more polymerizable groups. This term includes, for example, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.

[0031] A "polymerizable group" is a group capable of undergoing free radical and / or cationic polymerization, e.g., chain growth polymerization, such as a carbon-carbon double bond that can polymerize when subjected to radical polymerization initiation conditions. Non-limiting examples of free radical reactive groups include (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, O-vinyl carbamates, O-vinyl carbonates, and other vinyl groups. Preferably, the free radical polymerizable group comprises (meth)acrylates, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, and styryl functional groups, and mixtures of any of the foregoing. More preferably, the free radical polymerizable group comprises (meth)acrylates, (meth)acrylamides, and mixtures thereof. The polymerizable group may be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamides may be bonded to hydrogen, or the hydrogen may be substituted with alkyl or cycloalkyl (which may themselves be further substituted).

[0032] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension, and emulsion, as well as any of the controlled radical polymerization techniques, such as stable free radical polymerization, nitric oxide mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium mediated living radical polymerization, etc.

[0033] A "monomer" is a monofunctional molecule that can undergo chain growth polymerization, particularly free radical polymerization, thereby creating repeating units within the chemical structure of a target macromolecule. Some monomers have difunctional impurities that can act as crosslinkers. A "hydrophilic monomer" is also a monomer that, when mixed with deionized water at a concentration of 5% by weight at 25°C, gives a clear, single-phase solution. A "hydrophilic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that, when mixed with deionized water at a concentration of 5% by weight at 25°C, gives a clear, single-phase solution. A "hydrophobic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that is slightly soluble or insoluble in deionized water at 25°C.

[0034] A "polymer" is an organic compound having a number average molecular weight greater than 1500 and may be reactive or non-reactive.

[0035] A "macromonomer" or "macromer" is a polymer having one group capable of undergoing chain growth polymerization, particularly free radical polymerization, thereby creating a repeat unit within the chemical structure of a target macromolecule. Generally, the chemical structure of a macromer is different from that of the target macromolecule, i.e., the repeat unit of the pendant group of the macromer is different from the repeat unit of the target macromolecule or its backbone. The only difference between a monomer and a macromer is one of the chemical structure of the pendant group, the molecular weight, and the molecular weight distribution. As a result, and as used herein, the patent literature sometimes defines a monomer as a polymerizable compound having a relatively low molecular weight of about 1,500 daltons or less, which essentially includes some macromers. Specifically, monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (mPDMS) and mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (OH-mPDMS) may be referred to as monomers or macromers. Additionally, the patent literature sometimes defines macromers as having one or more polymerizable groups, essentially expanding the general definition of macromer to include prepolymers. As a result, and as used herein, difunctional and multifunctional macromers, prepolymers, and crosslinkers may be used interchangeably.

[0036] A "silicone-containing component" is a monomer, macromer, prepolymer, crosslinker, initiator, additive, or polymer in the reactive mixture that has at least one silicon-oxygen bond, usually in the form of a siloxy group, a siloxane group, a carbosiloxane group, and mixtures thereof.

[0037] Examples of silicone-containing components useful in the present invention are disclosed in U.S. Pat. Nos. 3,808,178, 4,120,570, 4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, 5,96 No. 2,548, No. 5,965,631, No. 5,998,498, No. 6,367,929, No. 6,822,016, No. 6,943,203, No. 6,951,894, No. 7,052,131, No. No. 7,247,692, No. 7,396,890, No. 7,461,937, No. 7,468,398, No. 7,538,146, No. 7,553,880, No. 7,572,841, No. 7,666,921 , No. 7,691,916, No. 7,786,185, No. 7,825,170, No. 7,915,323, No. 7,994,356, No. 8,022,158, No. 8,163,206, No. 8,273, No. 802, No. 8,399,538, No. 8,415,404, No. 8,420,711, No. 8,450,387, No. 8,487,058, No. 8,568,626, No. 8,937,110, No. 8,9 37,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825, 9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544, 9,297,928, 9,297,929, and European Patent No. 080539. These patents are incorporated herein by reference in their entirety.

[0038] A "polymer" is a target macromolecule made up of repeating units of the monomers used during polymerization.

[0039] A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of compositionally distinct blocks or segments. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb or graft copolymer" is made from at least one macromer.

[0040] A "repeating unit" is the smallest group within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0041] An "initiator" is a molecule that is decomposable into radicals that can subsequently react with monomers to initiate a free radical polymerization reaction. Thermal initiators decompose at a specific rate depending on the temperature, and typical examples are azo compounds such as 1,1'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid), peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide, peracids such as peracetic acid and potassium persulfate, and various redox systems. Photoinitiators decompose by a photochemical process, and typical examples are derivatives of benzil, benzoin, acetophenone, benzophenone, camphorquinone, and mixtures thereof, as well as various monoacyl and bisacylphosphine oxides, and combinations thereof.

[0042] A "crosslinker" is a di- or polyfunctional monomer or macromer that can undergo free radical polymerization at two or more positions on the molecule, thereby creating branch points and polymer networks. Common examples are ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, etc.

[0043] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can be further reacted to form a polymer.

[0044] A "polymer network" is a cross-linked macromolecule that can swell but cannot be dissolved in a solvent. A "hydrogel" is a polymer network that swells in water or an aqueous solution, typically absorbing at least 10% by weight of water. A "silicone hydrogel" is a hydrogel made from at least one silicone-containing component together with at least one hydrophilic component. The hydrophilic component may also include a non-reactive polymer.

[0045] "Conventional hydrogel" refers to a polymer network made from components that do not have any siloxy, siloxane, or carbosiloxane groups. Conventional hydrogels are prepared from reactive mixtures that contain hydrophilic monomers. Examples include 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone (NVP), N,N-dimethylacrylamide (DMA), or vinyl acetate. U.S. Patent Nos. 4,436,887, 4,495,313, 4,889,664, 5,006,622, 5,039459, 5,236,969, 5,270,418, 5,298,533, 5,824,719, 6,420,453, 6,423,761, 6,767,979, 7,934,830, 8,138,290, and 8,389,597 disclose the formation of conventional hydrogels. Commercially available conventional hydrogels include, but are not limited to, etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymacon, and vifilcon (including all variations thereof).

[0046] "Silicone hydrogel" refers to a polymer network made from at least one hydrophilic component and at least one silicone-containing component. Examples of silicone hydrogels include acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, and nafilcon. In addition to arafilcon, riofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon (including all variations thereof), U.S. Pat. Nos. 4,659,782, 4,659,783, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998,498, 6,087,4 No. 15, No. 5,760,100, No. 5,776,999, No. 5,789,461, No. 5,849,811, No. No. 5,965,631, No. 6,367,929, No. 6,822,016, No. 6,867,245, No. 6,943, No. 203, No. 7,247,692, No. 7,249,848, No. 7,553,880, No. 7,666,921, No. No. 7,786,185, No. 7,956,131, No. 8,022,158, No. 8,273,802, No. 8,399, 538, 8,470,906, 8,450,387, 8,487,058, 8,507,577, No. 8,637,621, No. 8,703,891, No. 8,937,110, No. 8,937,111, No. 8,940 , No. 812, No. 9,056,878, No. 9,057,821, No. 9,125,808, No. 9,140,825, No. 9156,934, No. 9,170,349, No. 9,244,196, No. 9,244,197, No. 9,260,544, 9,297,928, 9,297,929, and silicone hydrogels such as those prepared in WO 03 / 22321, WO 2008 / 061992, and U.S. Patent Application Publication No. 2010 / 0048847, which are incorporated herein by reference in their entireties.

[0047] An "interpenetrating polymer network" includes two or more networks that are at least partially entangled on a molecular scale, but are not covalently bonded to each other and cannot be separated without a blocking chemical bond. A "semi-penetrating polymer network" includes one or more networks and one or more polymers that are characterized by some intermixing at the molecular level between at least one network and at least one polymer. A mixture of different polymers is a "polymer blend." Although semi-penetrating networks are technically polymer blends, in some cases the polymers are entangled in such a way that they cannot be easily removed.

[0048] "Reactive components" are the polymerizable compounds (such as monomers, macromers, oligomers, prepolymers, and crosslinkers) in the reactive mixture (as defined below), as well as any other components in the reactive mixture that are intended to remain substantially in the resulting polymer network after polymerization and all work-up steps (such as extraction steps) and packaging steps are complete. The reactive components may be retained in the polymer network by covalent bonds, hydrogen bonds, electrostatic interactions, the formation of an interpenetrating polymer network, or any other means. Components that are intended to be released from the polymer network during use are still considered "reactive components". For example, a pharmaceutical or nutraceutical component in a contact lens that is intended to be released during wear is considered a "reactive component". Components that are intended to be removed from the polymer network during the manufacturing process (e.g., by extraction), such as diluents, are not "reactive components".

[0049] The terms "reactive mixture" and "reactive monomer mixture" refer to a mixture of components that, when mixed together and subjected to polymerization conditions, result in the formation of polymer networks (such as conventional or silicone hydrogels) and biomedical devices, ophthalmic devices, and contact lenses made therefrom. The reactive monomer mixture may include reactive components such as monomers, macromers, prepolymers, crosslinkers, and initiators, wetting agents, polymers, light absorbing compounds such as dyes, UV absorbers, pigments, dyes, and photochromic compounds, and additives such as pharmaceutical and nutraceutical compounds, all of which may be polymerizable or non-polymerizable but are capable of being retained in the resulting biomedical device (e.g., contact lens). The reactive mixture may also contain other components that are intended to be removed from the device before use, such as diluents. It is understood that a wide range of additives may be added depending on the lens to be produced and the intended application. The concentrations of the components of the reactive mixture are therefore expressed as a weight percentage of all components in the reactive mixture, excluding the diluent. When diluents are used, their concentrations are expressed as weight percentages based on the amounts of all components in the reactive mixture (including the diluent).

[0050] The term "silicone hydrogel contact lenses" refers to hydrogel contact lenses made from at least one silicone-containing component. Silicone hydrogel contact lenses typically have increased oxygen permeability compared to traditional hydrogels. Silicone hydrogel contact lenses utilize both their water content and polymer content to deliver oxygen to the eye.

[0051] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0052] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0053] "Alkyl" refers to an optionally substituted straight or branched chain alkyl group containing the specified number of carbon atoms. If no number is specified, the alkyl (including the optional substituents on the alkyl) may contain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examples of substituents on alkyl include one, two, or three groups independently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "Alkylene" refers to a -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 - and -CH 2 CH 2 CH 2 CH 2 - means a divalent alkyl group such as -.

[0054] "Haloalkyl" refers to an alkyl group as defined above substituted with one or more halogen atoms, each halogen being independently F, Cl, Br, or I. A preferred halogen is F. Preferred haloalkyl groups contain 1 to 6 carbons, more preferably 1 to 4 carbons, and even more preferably 1 to 2 carbons. "Haloalkyl" refers to -CF 3 -or-CF 2 CF 3 -. "Haloalkylene" includes perhaloalkyl groups such as -CH 2 CF 2 - means a divalent haloalkyl group such as -.

[0055] "Cycloalkyl" refers to an optionally substituted cyclic hydrocarbon containing the specified number of ring carbon atoms. If no number is specified, the cycloalkyl may contain from 3 to 12 ring carbon atoms. Preferably, C 3 ~C 8 Cycloalkyl groups, C 3 ~C 7 Cycloalkyl, more preferably C 4 ~C 7 Cycloalkyl, even more preferably C 5 ~C 6 Cycloalkyl. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on cycloalkyl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, thioalkyl, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Cycloalkylene" refers to a divalent cycloalkyl group, such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

[0056] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system as defined above in which at least one ring carbon is replaced with a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring is optionally fused or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or phenyl rings. Preferred heterocycloalkyl groups have 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members. Heterocycloalkylene refers to a divalent heterocycloalkyl group.

[0057] "Aryl" refers to an optionally substituted aromatic hydrocarbon ring system containing at least one aromatic ring. The aryl group contains the indicated number of ring carbon atoms. If no number is indicated, the aryl may contain 6 to 14 ring carbon atoms. The aromatic ring may be optionally fused or otherwise attached to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl. Examples of substituents on an aryl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Arylene" refers to a divalent aryl group, such as 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0058] "Heteroaryl" refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom is replaced with a heteroatom selected from nitrogen, oxygen, and sulfur. The heteroaryl ring may be fused or otherwise bonded to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, and thienyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0059] "Alkoxy" refers to an alkyl group attached to the parent molecular moiety through an oxygen bridge. Examples of alkoxy groups include, for example, methoxy, ethoxy, propoxy, and isopropoxy. "Thioalkyl" refers to an alkyl group attached to the parent molecular moiety through a sulfur bridge. Examples of thioalkyl groups include, for example, methylthio, ethylthio, n-propylthio, and isopropylthio. "Aryloxy" refers to an aryl group attached to the parent molecular moiety through an oxygen bridge. Examples include phenoxy. "Cyclic alkoxy" refers to a cycloalkyl group attached to the parent moiety through an oxygen bridge.

[0060] "Alkylamine" refers to an alkyl group attached to the parent molecular moiety through an -NH bridge. Alkyleneamines are those that are linked to the parent molecular moiety through a -CH 2 CH 2 It means a divalent alkylamine group such as NH-.

[0061] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Thus, for example, a siloxanyl group refers to a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanyl compound refers to a compound having at least one Si-O-Si group. "Siloxanyl" refers to monomeric (e.g., Si-O-Si) as well as oligomeric / polymeric structures (e.g., -[Si-O] n - (where n is 2 or 3 or more). Each silicon atom in the siloxanyl group is independently selected to complete their valence. A Group (where R A is replaced by (as defined in options (b) to (i) of Formula A).

[0062] "Cyril" is a compound of the formula R 3 "Siloxy" refers to the structure of Si-, 3 The structure refers to Si-O-, where each R in silyl or siloxy is trimethylsiloxy, C 1 ~C 8 Alkyl (preferably C 1 ~C3 alkyl, more preferably ethyl or methyl), and C 3 ~C 8 cycloalkyl.

[0063] "Alkyleneoxy" refers to a group having the general formula -(alkylene-O-) p -or-(O-alkylene) p -, where alkylene is as defined above, p is 1 to 200, or 1 to 100, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 10, and each alkylene is independently optionally substituted with one or more groups independently selected from hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl, carboxyl, and combinations thereof. When p is greater than 1, each alkylene may be the same or different, and the alkyleneoxy may be in a block or random configuration. When the alkyleneoxy forms a terminal group in a molecule, the terminus of the alkyleneoxy may be, for example, hydroxy or alkoxy (e.g., HO-[CH 2 CH 2 O] p - or CH 3 O-[CH 2 CH 2 O] p Examples of alkyleneoxy include polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0064] "Oxaalkylene" refers to one or more non-adjacent CH 2 The group is -CH 2 CH 2 OCH(CH 3 )CH 2 -, or an oxygen atom. "Thiaalkylene" refers to an alkylene group as defined above that is substituted with one or more non-adjacent CH 2 The group is -CH 2 CH 2 SCH(CH 3 )CH 2- refers to an alkylene group as defined above that is substituted with a sulfur atom, such as -.

[0065] The term "linking group" refers to a moiety that connects a polymerizable group to a parent molecule. A linking group can be any moiety that is compatible with the compound of which it is a part, does not undesirably interfere with the polymerization of the compound, and is stable under the conditions of polymerization as well as the conditions of processing and storage of the final product. For example, a linking group can be a bond or can be one or more of alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester (-CO 2 -), arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or more halo groups, e.g., -OCF 2 -, -OCF 2 CF 2 -, -OCF 2 CH 2 -), siloxanyl, alkylenesiloxanyl, or combinations thereof. The linking group may be optionally substituted with one or more substituents. Suitable substituents may include those independently selected from alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy- (wherein more than one alkyleneoxy group may be present, and each methylene in the alkylene and alkyleneoxy is independently optionally substituted with hydroxyl), ether, amine, carbonyl, carbamate, and combinations thereof. The linking group may also be substituted with a polymerizable group such as (meth)acrylate (in addition to the polymerizable group to which it is attached).

[0066] Preferred linking groups include C 1 ~C 8 Alkylene (preferably C 2 ~C 6 alkylene) and C 1 ~C 8Oxaalkylene (preferably C 2 ~C 6 oxaalkylene), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Preferred linking groups also include carboxylate, amide, C 1 ~C 8 Alkylene-carboxylate-C 1 ~C 8 Alkylene or C 1 ~C 8 Alkylene Amide C 1 ~C 8 Alkylene is an example.

[0067] When the linking group is composed of a combination of moieties as described above (e.g., alkylene and cycloalkylene), the moieties may be present in any order. For example, in the following formula A, when L is shown to be -alkylene-cycloalkylene-, Rg-L may be either Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Regardless, the order listed represents the preferred order in which the moieties appear in the compound, starting from the terminal polymerizable group (Rg or Pg) to which the linking group is attached. For example, in the following formula A, when L is shown to be -alkylene-cycloalkylene-, Rg-L is preferably Rg-alkylene-cycloalkylene-.

[0068] The term "electron withdrawing group" (EWG) refers to a chemical group that withdraws electron density from the atom or group of atoms to which it is bonded. Examples of EWGs include, but are not limited to, cyano, amide, ester, keto, or aldehyde. A preferred EWG is cyano (CN).

[0069] The term "light absorbing compound" refers to a chemical that absorbs light within the visible spectrum (e.g., in the range of 380-780 nm). A "high energy absorber", "UV / HEV absorber" or "high energy light absorbing compound" is a chemical that absorbs various wavelengths of ultraviolet light, high energy visible light, or both. The ability of a material to absorb light of a particular wavelength can be determined by measuring its UV / Vis transmission spectrum. A compound that exhibits no absorption at a particular wavelength exhibits substantially 100 percent transmission at that wavelength. Conversely, a compound that is completely absorbing at a particular wavelength exhibits substantially 0% transmission at that wavelength. When the transmission of a material is given as a percentage for a particular wavelength range, it is understood that the material exhibits transmission at all wavelengths within that range.

[0070] When the compounds described herein contain olefinic double bonds or other centers of geometric asymmetry, unless otherwise specified, the compounds are intended to include the cis, trans, Z-, and E-configurations, as well as all tautomers and salt forms.

[0071] The term "optional substituent" means that an underlying hydrogen atom is optionally replaced by a substituent. Any substituent that is sterically practical at the substitution site and synthetically feasible may be used. Identification of suitable optional substituents is within the ability of one of ordinary skill in the art. Examples of "optional substituents" include, but are not limited to, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Thioalkyl, C 3 ~C 7 Cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5 , Benzyl, SO 3 H or SO 3 Na, wherein R 4 and R 5 are independently H or C 1 ~C6 The aforementioned substituents may be optionally substituted with optional substituents (preferably not further substituted unless otherwise indicated). For example, alkyl may be substituted with halo (e.g., CF 3 ).

[0072] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0073] Unless otherwise stated, a numerical range such as, for example, "2 to 10" is inclusive of the numbers defining the range (eg, 2 and 10).

[0074] As noted above, in one aspect, the present invention provides tricyclic compounds of formula I:

[0075] [ka] wherein m, n, and t are independently 0, 1, 2, 3, or 4; R 1 , R 2 , and R 3 is independently at each occurrence H, an optional substituent, or -YP g or two adjacent R 1 , R 2 , or R 3 The groups, together with the atoms to which they are attached, form -YP g and B is O, S, N, or NR 6 R represents an aromatic, saturated, or partially unsaturated 5-, 6-, or 7-membered ring, optionally having up to three heteroatoms independently selected from 6 , H, C 1 ~C 6 Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and one of C and D is O, S, N, or NR 6and the other of C and D represents an aromatic, saturated or partially unsaturated 5-, 6- or 7-membered ring optionally having up to three heteroatoms independently selected from 6 , SO, or SO 2 and at least one hetero group independently selected from the group consisting of a 6-membered saturated or partially unsaturated heterocycloalkyl ring having at one ring carbon atom a group of the formula =C(EWG)(R 7 ) groups, R 7 EWG or -C(=O)-TYP g and EWG, at each occurrence, is independently an electron withdrawing group; and P g is independently a polymerizable group, Y in each occurrence is independently a linking group, and T in each occurrence is independently a bond, O, or NR 6 and the compound of formula I comprises at least one P g Contains a group.

[0076] Formula I-1. Compounds of formula I may include compounds of formula I-1, which are compounds of formula I where the heteroatom in the 6-membered saturated or partially unsaturated heterocycloalkyl ring of C or D is S.

[0077] I-2. Compounds of formula I may include compounds of formula I-2, which are compounds of formula I where the heteroatom in the 6-membered saturated or partially unsaturated heterocycloalkyl ring of C or D is O.

[0078] I-3. Compounds of formula I are those in which the heteroatom in the 6-membered saturated or partially unsaturated heterocycloalkyl ring of C or D is NR 6 , preferably NH or N-alkyl, which is a compound of formula I-3.

[0079] I-4. Compounds of formula I may include compounds of formula I-4, which are compounds of formula I where the heteroatom in the 6-membered saturated or partially unsaturated heterocycloalkyl ring of C or D is SO.

[0080] I-5. Compounds of formula I are those in which the heteroatom in the 6-membered saturated or partially unsaturated heterocycloalkyl ring of C or D is SO 2 Compounds of formula I may include compounds of formula I-5, which are compounds of formula I,

[0081] I-6. Compounds of formula I, I-1, I-2, I-3, I-4, and I-5 may include compounds of formula I-6, which is a compound of formula I, I-1, I-2, I-3, I-4, or I-5, where m, n, and t are independently 0 or 1, or each is 0.

[0082] I-7. Compounds of formula I, I-1, I-2, I-3, I-4, and I-5 are R 1 But, H, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Thioalkyl, C 3 ~C 7 Cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5 , Benzyl, SO 3 H or SO 3 Na and R 4 and R 5 are independently H or C 1 ~C 6 The compounds may include compounds of formula I-7, which are compounds of formula I, I-1, I-2, I-3, I-4, or I-5, which are alkyl.

[0083] I-8. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, and I-7 are R 2 and R 3 However, independently, H, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Thioalkyl, C 3 ~C 7 Cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5, Benzyl, SO 3 H or SO 3 Na and R 4 and R 5 are independently H or C 1 ~C 6 The compounds may include compounds of formula I-8, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, or I-7, which are alkyl.

[0084] I-9. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, and I-8 are R 6 But H or C 1 ~C 6 Preferably, R in the group T is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, or I-8, which is an alkyl group. 6 is H.

[0085] I-10. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, and I-9 are P g The compounds of formula I-10 may include those compounds of formula I-10, where (polymerizable group) is independently at each occurrence a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, or I-9, which includes styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacted with monomers, crosslinkers, and other components used in the fabrication of polymeric devices. The compatibility of the compounds with the reactive mixture can be controlled by the selection of the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. More preferred polymerizable groups are methacrylates.

[0086] I-11. The compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, and I-10 may include compounds of formula I-11, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, or I-10, in which Y (the linking group) is an alkylene, a cycloalkylene, a heterocycloalkylene, an arylene (e.g., phenylene), a heteroarylene, an oxaalkylene, an alkylene-amide-alkylene, an alkylene-amine-alkylene, or any combination of these groups. Preferred linking groups include C 1 ~C 8 Alkylene (e.g., ethylene or propylene), C 1 ~C 8 Oxaalkylene, C 1 ~C 8 Alkylene-amide-C 1 ~C 8 Alkylene, and C 1 ~C 8 Alkylene-amine-C 1 ~C 8 Particularly preferred are C 1 ~C 8 Alkylene, especially ethylene (-CH 2 CH 2 -).

[0087] I-12. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, and I-11 are compounds in which T is a bond or NR 6 (preferably NH) which is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, or I-11.

[0088] I-13. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, and I-12 can include compounds of formula I-13, which is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, or I-12, where EWG, at each occurrence, is independently cyano, amide, ester, keto, or aldehyde.

[0089] I-14. The compounds of formulae I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, and I-13 may include compounds of formula I-14, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, or I-13, where B represents a 6-membered aromatic ring, optionally having one heteroatom selected from O, S, and N.

[0090] I-15. Compounds of formulae I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, and I-14 may include compounds of formula I-15, which is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, or I-14, wherein D represents a 6-membered aromatic ring, optionally having one heteroatom selected from O, S, and N.

[0091] I-16. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, and I-15 are those in which ring C is a ring carbon atom and a ring atom selected from the group consisting of O, S, NR 6 , SO, or SO 2 and wherein the heterocycloalkyl ring is a 6-membered saturated heterocycloalkyl ring having at one ring carbon atom a hetero group selected from the formula =C(EWG)(R 7) groups.

[0092] I-17. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, and I-16 are R 7 is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, or I-16, wherein I-17 is an EWG.

[0093] I-18. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, and I-16 are R 7 But -C(=O)-TYP g The compound may include a compound of formula I-18, which is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, or I-16,

[0094] I-19. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, and I-18 are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, and I-18, which are g The compounds of formula I-19 may be compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, or I-18, which contain a group.

[0095] I-20. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, and I-18 are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, and I-18, g The compounds of formula I-20 may include compounds of formula I-21, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, or I-18 containing a group.

[0096] Compounds of formula Iz may be excluded from compounds of formula I.

[0097] [ka] In the formula, X is O, S, NR 6 , SO, or SO 2 where R 1 , R 2 ,n,m,E.W.G.,T,Y,P. g and R 6 is as defined above for compounds of formula I.

[0098] Compounds of formula I and subformulas thereof (I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, and I-20) may include compounds shown in Table A, which are compounds of formula I or any of its subformulas, having the following structure:

[0099] [Table 1]

[0100] In the structures shown in Table A, X is independently O, S, NR 6 , SO, or SO 2 and Z is independently O, S, or NR 6 It is.

[0101] Specific examples of compounds of Formula I include, but are not limited to, the compounds shown in Table B.

[0102] [Table 2-1]

[0103] [Table 2-2]

[0104] [Table 2-3]

[0105] [Table 2-4]

[0106] [Table 2-5]

[0107] The compound of formula I can be used in combination with other light absorbing compounds to provide desirable absorption properties. For example, a preferred composition may include a compound of formula I and a UV absorbing compound. The UV absorbing compound may be, for example, a compound of formula I that absorbs in the UV region, or may be another UV absorbing compound. Suitable UV absorbing compounds other than formula I are known in the art and are classified into several classes, including, but not limited to, benzophenones, benzotriazoles, triazines, substituted acrylonitriles, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, dipnone derivatives, crotonic acid derivatives, or any mixture thereof. A preferred class of UV absorbing compounds is benzotriazoles, such as Norbloc (2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole).

[0108] Compounds of formula I can be prepared by those skilled in the art using literature methods. For example, various compounds of formula I in which EWG is cyano can be prepared as shown in Scheme 1 and the associated description. Exemplary reagents and procedures for these reactions are shown in the Examples.

[0109] [ka]

[0110] Scheme 1 shows a method for preparing exemplary compounds of the present invention. Thus, the carbonyl moiety of the starting material is converted to a reactive dihalide intermediate, which is further reacted with an active methylene compound without further purification or separation. The reactive mixture is protected from air and moisture until the reaction with the cyanomethylamide derivative is completed. Other compounds of the present invention can be prepared by those skilled in the art using procedures similar to those shown in Scheme 1 with appropriate substitution of reagents.

[0111] Other compounds of formula I can be prepared by one skilled in the art by using or adapting the general strategy depicted in Scheme 2.

[0112] [ka]

[0113] The compound of formula I can be included in a reactive mixture to form a variety of products, including biomedical and ophthalmic devices. In general, the compound of formula I can be present in any amount up to its solubility limit. For example, the compound can be present in a concentration of at least 0.1 percent, or at least 2 percent, and up to 10 percent, or up to 5 percent, based on the weight percent of all components in the reactive mixture excluding the diluent. Typical concentrations can range from 1 to 5%. The upper limit is typically determined by the solubility of the compound with other comonomers and / or diluents in the reactive monomer mixture.

[0114] Preferably, the compound of formula I is included in an ophthalmic device.Various ophthalmic devices can be prepared, including hard contact lenses, soft contact lenses, corneal onlays, corneal inlays, intraocular lenses, or overlay lenses.Preferably, the ophthalmic device is an intraocular lens or a soft contact lens.Soft contact lenses may be made from conventional (non-silicone) hydrogels or silicone hydrogels.

[0115] The ophthalmic devices of the present invention may comprise the free radical reaction product of a reactive mixture containing one or more monomers suitable for making the desired ophthalmic device (also referred to herein as device-forming monomers or hydrogel-forming monomers) and optional ingredients. Upon polymerization, the reactive mixture results in the formation of a polymer network in which the ophthalmic device may be included. The polymer network may be, for example, a hydrogel (e.g., a conventional hydrogel or a silicone hydrogel).

[0116] The compounds of formula I may be copolymerized with other components in a reactive mixture, in which case the reactive mixture may contain one or more compounds of formula I in addition to one or more monomers suitable for making the desired ophthalmic device (and any optional components).

[0117] Alternatively, or in addition, the compound of formula I may be incorporated into the polymer network as a preformed non-reactive polymer. The non-reactive polymer may be included in the reactive mixture, or may be incorporated into the polymer network after the polymer network has already been formed from the reactive mixture (e.g., as a coating or by heating a mixture of the polymer network and the non-reactive polymer).

[0118] The non-reactive polymer may include repeat units derived from a compound of formula I. The non-reactive polymer may include repeat units derived from other compounds, such as amide monomers or monofunctional polyalkylene glycols, or combinations thereof, in addition to repeat units derived from a compound of formula I. The non-reactive polymer may contain at least 0.1 mole percent repeat units derived from a compound of formula I, alternatively at least 1 mole percent, alternatively at least 10 mole percent, alternatively at least 20 mole percent repeat units derived from a compound of formula I. The non-reactive polymer may include 100 mole percent, alternatively up to 80 mole percent, alternatively up to 50 mole percent, alternatively up to 20 mole percent, alternatively up to 5 mole percent repeat units derived from a compound of formula I.

[0119] Exemplary monofunctional polyalkylene glycols that may be used to form the non-reactive polymer are monofunctional polyethylene glycols having a weight average molecular weight of about 200 to about 10,000 g / mole, e.g., about 200 to about 2,000 g / mole. Monofunctional polyethylene glycols contain only one polymerizable group and may be mono-ether terminated, mono-(meth)acrylate or (meth)acrylamide terminated polyethylene glycols. Examples of mono-ether end groups include, but are not limited to, C1-C6 alkoxy groups, such as methoxy and ethoxy groups or alkoxy groups containing up to 8 carbons. Examples of such mono-ether terminated, mono-methacrylate terminated polyethylene glycols include, but are not limited to, mPEG 475 (Polyethylene glycol (475 Mw) monomethyl ether monomethacrylate) available from Sigma-Aldrich (St. Louis, MO USA) ("mPEG 475").

[0120] Examples of amide monomers that can be used to form the non-reactive polymer include acyclic amides of formula H1 or H2, cyclic amides of formula H3, or combinations thereof:

[0121] [ka] In the formula, R 45 is H or methyl, and V is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is C 1 ~C 3 is alkyl, R 40 is H or C 1 ~C 4 is alkyl, R 41 , H, C 1 ~C 4 alkyl, amino having up to 2 carbon atoms, amido having up to 4 carbon atoms, and alkoxy having up to 2 carbon groups; R 42 , H, C 1 ~C 4 an alkyl group, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R 43 , H, C 1 ~C 4 alkyl, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R 40 and R 41 The total number of carbon atoms in R is 8 or less. 42 and R 43 The total number of carbon atoms is 8 or less, and f is a number from 1 to 10. Exemplary optional substituents on the foregoing groups include amine, amide, ether, hydroxyl, carbonyl, or carboxy groups, or combinations thereof.

[0122] Non-limiting examples of polymer networks into which a compound of Formula I may be incorporated (e.g., as a monomer or non-reactive polymer in the reactive mixture or by subsequent addition) are described above and include, for example, etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymafilcon, bifilcon, aquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, funfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, lyofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon, including all variations thereof.

[0123] As a further example, the polymer network may be made from a reactive mixture that includes one or more of a hydrophilic component, a hydrophobic component, a silicone-containing component, a wetting agent such as a polyamide, a crosslinker, and additional components such as a diluent and an initiator. As mentioned above, the reactive mixture may also contain one or more compounds of formula I and / or a non-reactive polymer that includes repeat units derived from one or more compounds of formula I, or the non-reactive polymer may be added after formation of the polymer network.

[0124] hydrophilic component Examples of suitable families of hydrophilic monomers that may be present in the reactive mixture include (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, N-vinyl imides, N-vinyl ureas, O-vinyl carbamates, O-vinyl carbonates, other hydrophilic vinyl compounds, and mixtures thereof.

[0125] Non-limiting examples of hydrophilic (meth)acrylate and (meth)acrylamide monomers include acrylamide, N-isopropylacrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl)(meth)acrylamide, N-(3 ... N-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, 2-aminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 2-aminopropyl(meth)acrylate, N-2-aminoethyl(meth)acrylamide), N-3-aminopropyl(meth)acrylamide, N-2-aminopropyl(meth)acrylamide, N,N-bis-2-aminoethyl(meth)acrylamide, N,N-bis-3-aminopropyl(meth)acrylamide), N,N-bis-2-aminopropyl(meth)acrylamide, glycerol methacrylate, polyethylene glycol monomethacrylate, (meth)acrylic acid, vinyl acetate, acrylonitrile, and mixtures thereof.

[0126] The hydrophilic monomers may also be ionic, such as anionic, cationic, zwitterionic, betaine, and mixtures thereof. Non-limiting examples of such charged monomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine (VINAL), 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopropanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 1-propanaminium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, inner salt (CBT), 1-propanaminium, N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt (SBT), 3,5-dioxa- 8-Aza-4-phosphanedec-10-ene-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT), 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS), and methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

[0127] Non-limiting examples of hydrophilic N-vinyl lactam and N-vinyl amide monomers include N-vinyl pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl acetamide (NVA), N-vinyl-N-methyl acetamide (VMA), N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl-N-methyl propionamide, N-vinyl-N-methyl-2-methyl propionamide, N-vinyl ... N-methylpropionamide, N-vinyl-N,N'-dimethylurea, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-N-propyl-3-methylene-2-pyrrolidone, 1-N-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-vinylisopropylamide, N-vinylcaprolactam, N-vinylimidazole, and mixtures thereof.

[0128] Non-limiting examples of hydrophilic O-vinyl carbamate and O-vinyl carbonate monomers include N-2-hydroxyethyl vinyl carbamate and N-carboxy-β-alanine N-vinyl ester. Further examples of hydrophilic vinyl carbonate or vinyl carbamate monomers are disclosed in U.S. Patent No. 5,070,215. Hydrophilic oxazolone monomers are disclosed in U.S. Patent No. 4,910,277.

[0129] Other hydrophilic vinyl compounds include ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and 2-ethyloxazoline.

[0130] The hydrophilic monomer may also be a macromer or prepolymer of linear or branched poly(ethylene glycol), poly(propylene glycol), or statistical random or block copolymers of ethylene oxide and propylene oxide, having polymerizable moieties such as (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl amides, etc. Macromers of these polyethers have one polymerizable group and prepolymers may have two or more polymerizable groups.

[0131] Preferred hydrophilic monomers of the present invention are DMA, NVP, HEMA, VMA, NVA, and mixtures thereof. Preferred hydrophilic monomers include mixtures of DMA and HEMA. Other suitable hydrophilic monomers will be apparent to those skilled in the art.

[0132] Generally, there is no particular restriction as to the amount of hydrophilic monomer present in the reactive monomer mixture. The amount of hydrophilic monomer can be selected based on the desired properties of the resulting hydrogel, including water content, transparency, wettability, protein uptake, and the like. Wettability can be measured by contact angle, with desirable contact angles being less than about 100°, less than about 80°, and less than about 60°. The hydrophilic monomer can be present in an amount ranging from about 0.1 to about 100 weight percent, alternatively from about 1 to about 80 weight percent, alternatively from about 5 to about 65 weight percent, alternatively from about 40 to about 60 weight percent, alternatively from about 55 to about 60 weight percent, based on the total weight of the reactive components in the reactive monomer mixture.

[0133] Silicone-containing ingredients Silicone-containing components suitable for use in the present invention include one or more polymerizable compounds, each compound independently including at least one polymerizable group, at least one siloxane group, and one or more linking groups connecting the polymerizable group(s) to the siloxane group(s). The silicone-containing component may contain, for example, 1 to 220 siloxane repeating units, such as the groups defined below. The silicone-containing component may also contain at least one fluorine atom.

[0134] The silicone-containing component may comprise one or more polymerizable groups as defined above, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units. The silicone-containing component may comprise one or more polymerizable groups, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units, which are independently (meth)acrylate, styryl, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, vinyl groups, or mixtures thereof.

[0135] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styryl, or mixtures of the foregoing, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0136] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, or a mixture of the foregoing, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0137] The silicone-containing component may include one or more polymerizable compounds of formula A:

[0138] [ka] During the ceremony, At least one R A is the formula R g -L group, where R g is a polymerizable group, L is a linking group, and the remaining R A are each independently (a)R g -L-, (b) C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 1 ~C 16 Alkyl, (c) C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 3 ~C 12 Cycloalkyl, (d) C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 6 ~C 14 Aryl groups, (e) halo, (f) alkoxy, cyclic alkoxy, or aryloxy, (g) siloxy, (h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl); or (i) a monovalent siloxane chain comprising 1 to 100 siloxane repeat units optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amido, carbamate, halo, or combinations thereof; n is 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20, and when n is other than 0, it is understood that n is a distribution having a mode equivalent to the indicated value. When n is 2 or more, the SiO units may be the same or different R A may carry substituents, different R A When substituents are present, the n groups may be in a random or block configuration.

[0139] In formula A, three R A may each contain a polymerizable group, alternatively two R A may each contain a polymerizable group, or alternatively one R A may contain a polymerizable group.

[0140] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in Table C. When a compound in Table C contains a polysiloxane group, the number of SiO repeat units in such compound is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0141] [Table 3-1]

[0142] [Table 3-2]

[0143] Further non-limiting examples of suitable silicone-containing components are listed in Table D. Unless otherwise specified, where applicable, j2 is preferably 1-100, more preferably 3-40, or even more preferably 3-15. In compounds containing j1 or j2, the sum of j1 and j2 is preferably 2-100, more preferably 3-40, or even more preferably 3-15.

[0144] [Table 4-1]

[0145] [Table 4-2]

[0146] Mixtures of silicone-containing components may also be used.For example, suitable mixtures may include, but are not limited to, mixtures of mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (OH-MPDMS) with different molecular weights, such as mixtures of OH-mPDMS containing 4 and 15 repeating SiO units; mixtures of OH-mPDMS with different molecular weights (e.g., containing 4 and 15 repeating SiO units) and silicone-based crosslinkers, such as bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes (ac-PDMS); mixtures of 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA) and mono-methacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (mPDMS), such as mPDMS1000.

[0147] The silicone-containing component used in the present invention can have an average molecular weight of from about 400 to about 4000 Daltons.

[0148] The silicone-containing component(s) may be present in an amount up to about 95%, or from about 10 to about 80%, or from about 20 to about 70% by weight of the reactive mixture (excluding diluent), based on all reactive components.

[0149] polyamide The reactive mixture may include at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers that include repeating units that contain amide groups. The polyamide may include cyclic amide groups, non-cyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Non-cyclic polyamides include pendant non-cyclic amide groups and are capable of association with hydroxyl groups. Cyclic polyamides include cyclic amide groups and are capable of association with hydroxyl groups.

[0150] Examples of suitable acyclic polyamides include polymers and copolymers comprising repeat units of formulae G1 and G2,

[0151] [ka] In the formula, X is a direct bond, -(CO)-, or -(CONHR 44 )-, wherein R 44 is C 1 ~C 3 is an alkyl group, R 40 is H, linear or branched, substituted or unsubstituted C 1 ~C 4 alkyl groups; R 41 is H, linear or branched, substituted or unsubstituted C 1 ~C 4 R is selected from an alkyl group, an amino group having up to 2 carbon atoms, an amide group having up to 4 carbon atoms, and an alkoxy group having up to 2 carbon atoms; 42 is H, linear or branched, substituted or unsubstituted C 1 ~C 4 R is selected from alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl; 43is H, linear or branched, substituted or unsubstituted C 1 ~C 4 R is selected from alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl; 40 and R 41 the total number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or fewer; 42 and R 43 The total number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or fewer. 40 and R 41 The total number of carbon atoms in R may be 6 or less, or 4 or less. 42 and R 43 may have a total of up to 6 carbon atoms. As used herein, a substituted alkyl group includes an alkyl group substituted with an amine group, an amide group, an ether group, a hydroxyl group, a carbonyl group, or a carboxyl group, or combinations thereof.

[0152] R 40 and R 41 are independently H, substituted or unsubstituted C 1 ~C 2 X may be a direct bond, R 40 and R 41 are independently H, substituted or unsubstituted C 1 ~C 2 R may be selected from alkyl groups. 42 and R 43 are independently H, substituted or unsubstituted C 1 ~C 2 The alkyl groups may be selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0153] The acyclic polyamides of the invention may comprise a majority of repeat units of formula LV or formula LVI, or the acyclic polyamides may comprise at least 50 mol % of repeat units of formula G or formula G1, such as at least about 70 mol %, and at least 80 mol %. Specific examples of repeat units of formula G and formula G1 include N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, N-vinyl-2-methyl-propionamide, N-vinyl-N,N'-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and repeat units derived from the acyclic amides of formula G2 and G3.

[0154] [ka]

[0155] Examples of suitable cyclic amides that can be used to form the cyclic polyamides include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. Examples of suitable cyclic polyamides include polymers and copolymers comprising repeating units of formula G4:

[0156] [ka] In the formula, R 45 is a hydrogen atom or a methyl group, f is a number from 1 to 10, and X is a direct bond, -(CO)-, or -(CONHR 46 )-, where R 46 is C 1 ~C 3is an alkyl group. In formula LIX, f can be 8 or less, including 7, 6, 5, 4, 3, 2, or 1. In formula G4, f can be 6 or less, including 5, 4, 3, 2, or 1. In formula G4, f can be 2 to 8, including 2, 3, 4, 5, 6, 7, or 8. In formula LIX, f can be 2 or 3. When X is a direct bond, f can be 2. In such cases, the cyclic polyamide can be polyvinylpyrrolidone (PVP).

[0157] The cyclic polyamides of the present invention may comprise 50 mol % or more of repeat units of formula G4, or the cyclic polyamides may comprise at least 50 mol % of repeat units of formula G4, such as at least 70 mol %, and at least 80 mol %.

[0158] Polyamides may also be copolymers that contain both cyclic and non-cyclic amide repeat units. The additional repeat units may be formed from monomers selected from hydroxyalkyl (meth)acrylates, alkyl (meth)acrylates, other hydrophilic monomers, and siloxane-substituted (meth)acrylates. Any of the monomers listed as suitable hydrophilic monomers may be used as comonomers to form the additional repeat units. Specific examples of additional monomers that may be used to form polyamides include 2-hydroxyethyl (meth)acrylate, vinyl acetate, acrylonitrile, hydroxypropyl (meth)acrylate, methyl (meth)acrylate and hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like, and mixtures thereof. Ionic monomers may also be included.Examples of ionic monomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine (VINAL, CAS#148969-96-4), 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 1-propanaminium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, inner salt (CBT, carboxybetaine, CAS 79704-35-1), 1-propanaminium, N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt (SBT, sulfobetaine, CAS 80293-60-3), 3,5-dioxa-8-aza-4-phosphanundeca-10-ene-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT, phosphobetaine, CAS 163674-35-9, 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS), methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

[0159] The reactive monomer mixture may include both acyclic and cyclic polyamides or copolymers thereof. The acyclic polyamide may be any of the acyclic polyamides or copolymers thereof described herein, and the cyclic polyamide may be any of the cyclic polyamides or copolymers thereof described herein. The polyamide may be selected from the group of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamide may be a combination of PVP (e.g., PVP K90) and PVMA (e.g., PVMA with an M of about 570 KDa). w The mixture may be

[0160] The total amount of all polyamides in the reactive mixture can be in the range of 1% to about 35% by weight, such as in the range of 1% to about 15% by weight, and such as in the range of about 5% to about 15% by weight, in all cases based on the total weight of the reactive components of the reactive monomer mixture.

[0161] Without being bound by theory, when used with silicone hydrogels, polyamides function as internal wetting agents. The polyamides of the present invention may be non-polymeric, in which case they are incorporated into the silicone hydrogel as a semi-interpenetrating network. The polyamides are encapsulated or physically held within the silicone hydrogel. Alternatively, the polyamides of the present invention may be polymeric, for example as polyamide macromers or prepolymers, in which case they are covalently incorporated into the silicone hydrogel. Mixtures of polymeric and non-polymeric polyamides may also be used.

[0162] When a polyamide is incorporated within the reactive monomer mixture, the polyamide may have a weight average molecular weight of at least 100,000 Daltons, greater than about 150,000, from about 150,000 to about 2,000,000 Daltons, from about 300,000 Daltons to about 1,800,000 Daltons. Higher molecular weight polyamides can be used if compatible with the reactive monomer mixture.

[0163] Crosslinking Agent It is generally desirable to add one or more crosslinking agents, also referred to as crosslinking monomers, multifunctional macromers, and prepolymers, to the reactive mixture. The crosslinking agents may be selected from difunctional crosslinkers, trifunctional crosslinkers, tetrafunctional crosslinkers, and mixtures thereof, including silicone-containing and non-silicone-containing crosslinkers. Non-silicone-containing crosslinkers include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glycerol trimethacrylate, methacryloxyethyl vinyl carbonate (HEMAVc), allyl methacrylate, methylene bisacrylamide (MBA), and polyethylene glycol dimethacrylate, where the polyethylene glycol has a molecular weight of up to about 5000 Daltons. The crosslinking agents are used in the reactive mixture in conventional amounts, for example, from about 0.000415 to about 0.0156 moles per 100 grams of reactive formulation. Alternatively, if the hydrophilic monomer and / or silicone-containing component is multifunctional due to molecular design or impurities, the addition of a crosslinking agent to the reactive mixture is optional. Examples of hydrophilic monomers and macromers that can act as crosslinking agents and do not require the addition of additional crosslinking agents to the reactive mixture when present include polyethers end-capped with (meth)acrylates and (meth)acrylamides. Other crosslinking agents will be known to those skilled in the art and can be used to make the silicone hydrogel of the present invention.

[0164] It may be desirable to select a crosslinker that has a similar reactivity to one or more of the other reactive components in the formulation. In some cases, it may be desirable to select a mixture of crosslinkers with different reactivities to control some physical, mechanical, or biological properties of the resulting silicone hydrogel. The structure and morphology of the silicone hydrogel may also be affected by the diluent(s) and curing conditions used.

[0165] Multifunctional silicone-containing components, including macromers, crosslinkers, and prepolymers, may also be included to further increase modulus and maintain tensile strength. Silicone-containing crosslinkers may be used alone or in combination with other crosslinkers. An example of a silicone-containing component that can act as a crosslinker and does not require the addition of a crosslinking monomer to the reactive mixture when present includes α,ω-bismethacryloylpropyl polydimethylsiloxane. Another example is bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (ac-PDMS).

[0166] Crosslinkers with hard chemical structures and polymerizable groups that undergo free radical polymerization may also be used. Non-limiting examples of suitable hard structures include crosslinkers containing phenyl and benzyl rings, such as 1,4-phenylenediacrylate, 1,4-phenylenedimethacrylate, 2,2-bis(4-methacryloxyphenyl)-propane, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, and 4-vinylbenzyl methacrylate, and combinations thereof. Hard crosslinkers may be included in an amount of about 0.5 to about 15, or about 2 to 10, 3 to 7, based on the total weight of all reactive components. The physical and mechanical properties of the silicone hydrogels of the present invention may be optimized for a particular application by adjusting the components in the reactive mixture.

[0167] Non-limiting examples of silicone crosslinkers also include the multifunctional silicone-containing components set forth in Table D above.

[0168] Further components The reactive mixture may contain additional components such as, but not limited to, diluents, initiators, UV absorbers, visible light absorbers, photochromic compounds, pharmaceuticals, nutritional supplements, antimicrobial substances, colorants, pigments, copolymeric dyes, non-polymeric dyes, release agents, and combinations thereof.

[0169] Suitable types of diluents for the silicone hydrogel reactive mixture include alcohols having 2 to 20 carbon atoms, amides derived from primary amines having 10 to 20 carbon atoms, and carboxylic acids having 8 to 20 carbon atoms. The diluents can be primary, secondary, and tertiary alcohols.

[0170] Generally, the reactive components are mixed in a diluent to form a reactive mixture. Suitable diluents are known in the art. For silicone hydrogels, suitable diluents are disclosed in WO 03 / 022321 and U.S. Pat. No. 6,020,445, the disclosures of which are incorporated herein by reference. Suitable diluent types for silicone hydrogel reactive mixtures include alcohols having 2-20 carbons, amides having 10-20 carbon atoms derived from primary amines, and carboxylic acids having 8-20 carbon atoms. Primary and tertiary alcohols may be used. Preferred types include alcohols having 5-20 carbons and carboxylic acids having 10-20 carbon atoms. Specific diluents that may be used include 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol, 3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, tert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2 ... Examples of diluents include ethanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol, (3-acetoxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy)methylsilane, 1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2-(diisopropylamino)ethanol, mixtures thereof, and the like. Examples of amide diluents include N,N-dimethylpropionamide and dimethylacetamide.

[0171] Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, mixtures thereof, and the like.

[0172] More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 1-dodecanol, 3-methyl-3-pentanol, 1-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, mixtures thereof, and the like. When a diluent is present, there is generally no particular restriction as to the amount of diluent present. When a diluent is used, the diluent may be present in an amount ranging from about 2 to about 70 percent by weight, such as from about 5 to about 50 percent by weight and from about 15 to about 40 percent by weight, based on the total weight of the reactive mixture (including reactive and non-reactive formulations). Mixtures of diluents may also be used.

[0173] A polymerization initiator may be used in the reactive mixture. The polymerization initiator may include at least one of those that generate free radicals at moderately high temperatures, such as lauryl peroxide, benzoyl peroxide, iso-propyl percarbonate, azobisisobutyronitrile, and photoinitiator systems, such as aromatic α-hydroxyketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides, and tertiary amines + diketones, mixtures thereof. Specific examples of photoinitiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,4,6-trimethylbenzyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ester, and a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.

[0174] Commercially available (from IGM Resins BV, The Netherlands) visible light initiator systems include Irgacure® 819, Irgacure® 1700, Irgacure® 1800, Irgacure® 819, Irgacure® 1850, and Lucrin® TPO initiators. Commercially available (from IGM Resins BV) UV photoinitiators include Darocur® 1173 and Darocur® 2959. These and other photoinitiators that may be used are disclosed in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by JV Crivello & K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998. The initiator is used in the reactive mixture in an amount effective to initiate photopolymerization of the reactive mixture, for example, from about 0.1 to about 2 parts by weight per 100 parts of the reactive monomer mixture. Polymerization of the reactive mixture can be initiated using heat or visible or ultraviolet light or other means, appropriately selected depending on the polymerization initiator used. Alternatively, initiation can be carried out using an electron beam without a photoinitiator. However, when a photoinitiator is used, the preferred initiator is a bisacylphosphine oxide, such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure® 819), or a combination of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO).

[0175] The reactive mixtures for making the ophthalmic devices of the present invention may include, in addition to the compound of Formula I, any of the polymerizable compounds and optional ingredients described above.

[0176] The reactive mixture can include a compound of Formula I and a hydrophilic monomer.

[0177] A preferred reactive mixture may comprise a compound of formula I and a hydrophilic component selected from DMA, NVP, HEMA, VMA, NVA, methacrylic acid, and mixtures thereof. A mixture of HEMA and methacrylic acid is preferred.

[0178] The reactive mixture can include a compound of Formula I, a hydrophilic component, and a silicone-containing component.

[0179] The reactive mixture may comprise a compound of formula I, a hydrophilic component selected from DMA, HEMA and mixtures thereof, a silicone-containing component selected from 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA), mono-methacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane (mPDMS), mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated mono-n-butyl terminated polydimethylsiloxane (OH-mPDMS) and mixtures thereof, and a wetting agent (preferably PVP or PVMA). For the hydrophilic component, a mixture of DMA and HEMA is preferred. For the silicone-containing component, a mixture of SiMAA and mPDMS is preferred.

[0180] The reactive mixture may include a hydrophilic component comprising a mixture of a compound of formula I, DMA and HEMA, and a silicone-containing component comprising a mixture of OH-mPDMS having 2-20 repeat units, preferably a mixture of 4 and 15 repeat units. Preferably, the reactive mixture further comprises a silicone-containing crosslinker, such as ac-PDMS. Also preferably, the reactive mixture contains a wetting agent, preferably DMA, PVP, PVMA, or a mixture thereof.

[0181] The reactive mixture comprises a compound of Formula I, from about 1 to about 15 weight percent of at least one polyamide (e.g., acyclic polyamide, cyclic polyamide, or mixtures thereof), at least one first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeat units (e.g., OH-mPDMS, where n is 4 to 8, preferably n is 4), and at least one second hydroxyl-substituted poly(disubstituted siloxane) that is a monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200, or 10 to 100, or 10 to 50, or 10 to 20 siloxane repeat units (e.g., OH-mPDMS, where n is 10 to 200, or 10 to 10). 0, or 10-50, or 10-20, preferably n is 15), about 5 to about 35 weight percent of at least one hydrophilic monomer, and optionally a multifunctional hydroxyl-substituted poly(disubstituted siloxane) (e.g., ac-PDMS) having 10-200 or 10-100 siloxane repeat units. Preferably, the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) and the second hydroxyl-substituted poly(disubstituted siloxane) are present in concentrations to provide a ratio of the weight percent of the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) to the weight percent of the second hydroxyl-substituted poly(disubstituted siloxane) of 0.4 to 1.3, or 0.4 to 1.0.

[0182] The aforementioned reactive mixture may contain optional ingredients such as, but not limited to, one or more initiators, internal wetting agents, crosslinkers, other UV or HEV absorbers, and diluents.

[0183] When the monomer suitable for making the above-described ophthalmic devices is a combination of a hydrophilic component and a silicone-containing component, the reaction product preferably contains a repeat unit derived from a compound of formula I other than a compound of formula Iz.

[0184] [ka]

[0185] It should be noted that compounds of formula Iz may still be present in the reaction product, but other compounds of formula I may also be present.

[0186] Curing of Hydrogels and Lens Fabrication The reactive mixture may be formed by any method known in the art, such as shaking or stirring, and used to form a polymeric article or device by known methods. The reactive components are mixed together, either with or without a diluent, to form the reactive mixture.

[0187] For example, an ophthalmic device can be prepared by mixing the reactive components and optionally a diluent(s) with a polymerization initiator and curing under appropriate conditions to form a product that can later be molded into a suitable shape by lathing, cutting, etc. Alternatively, the reactive mixture can be placed in a mold and then cured into a suitable article.

[0188] A method of making a molded ophthalmic device such as a silicone hydrogel contact lens may include preparing a reactive monomer mixture, transferring the reactive monomer mixture to a first mold, placing a second mold over the first mold filled with the reactive monomer mixture, and curing the reactive monomer mixture by free radical copolymerization to form a silicone hydrogel in the shape of a contact lens.

[0189] The reactive mixture may be cured through any known process for shaping the reactive mixture in making contact lenses, including rotational molding and static molding. Rotational molding methods are disclosed in U.S. Patents 3,408,429 and 3,660,545, and static molding methods are disclosed in U.S. Patents 4,113,224 and 4,197,266. The contact lenses of the present invention may be formed by direct molding of silicone hydrogels, which is economical and allows precise control of the final shape of the hydrated lens. In this method, the reactive mixture is placed into a mold having the shape of the desired final silicone hydrogel, and the reactive mixture is subjected to conditions that polymerize the monomers, thereby producing a polymer of the approximate shape of the desired final product.

[0190] After curing, the lens may be subjected to extraction to remove unreacted components and to remove the lens from the lens mold. Extraction may be performed using conventional extraction fluids, such as organic solvents, such as alcohols, or may be extracted using aqueous solutions.

[0191] An aqueous solution is a solution that contains water. The aqueous solution of the present invention may contain at least about 20% water by weight, or at least about 50% water by weight, or at least about 70% water by weight, or at least about 95% water by weight. The aqueous solution may also contain additional water-soluble preparations, such as inorganic salts or release agents, wetting agents, slip agents, pharmaceutical ingredients and nutritional supplements, combinations thereof. A release agent is a compound or mixture of compounds that, when combined with water, reduces the time required to remove a contact lens from a mold when compared to the time required to remove a contact lens using an aqueous solution that does not contain a release agent. The aqueous solution may not require special handling, such as purification, recycling, or special waste disposal.

[0192] Extraction can occur, for example, via immersion of the lens in an aqueous solution or exposure to a stream of an aqueous solution. Extraction can also include, for example, one or more of heating the aqueous solution, agitating the aqueous solution, increasing the concentration of a release agent in the aqueous solution to a level sufficient to cause release of the lens, mechanical or ultrasonic agitation of the lens, and incorporating at least one filter aid or extraction aid into the aqueous solution to a sufficient concentration to facilitate adequate removal of unreacted components from the lens. The foregoing, with or without the addition of heat, vibration, or both, can be performed in a batch or continuous process.

[0193] To facilitate leaching and demolding, it may be desirable to apply physical agitation. For example, the lens mold part to which the lens is attached can be vibrated or moved back and forth in the aqueous solution. Other methods may include passing ultrasound through the aqueous solution.

[0194] The lenses may be sterilized by known means, such as, but not limited to, high pressure steam treatment.

[0195] As mentioned above, the preferred ophthalmic device is a contact lens, more preferably a soft hydrogel contact lens. The transmission wavelengths and percentages described herein can be measured on lenses of various thicknesses, for example, using the methods described in the Examples. By way of example, a preferred center thickness for measuring the transmission spectrum in a soft contact lens can be 80-100 micrometers, or 90-100 micrometers, or 90-95 micrometers. Typically, measurements can be made at the center of the lens, for example, using an instrument slit width of 4 nm. Various concentrations of one or more polymerizable high-energy light absorbing compounds can be used to achieve the above transmission characteristics. For example, the concentrations can range from at least 1 percent, or at least 2 percent, and up to 10 percent or up to 5 percent, based on the weight percent of all components in the reactive mixture excluding the diluent. Typical concentrations can range from 3-5%.

[0196] Silicone hydrogel ophthalmic devices (e.g., contact lenses) according to the present invention preferably exhibit the following properties. All values ​​are preceded by "about" and the device can have any combination of the listed properties. Properties can be determined by methods known to those of skill in the art, for example, as described in U.S. Pregrant Publication No. 20180037690, which is incorporated herein by reference.

[0197] Water concentration %: at least 20%, or at least 25% and at most 80%, or at most 70% Haze: 30% or less, or 10% or less Advancing dynamic contact angle (Wilhelmy plate method): 100° or less, or 80° or less, or 50° or less Tensile modulus (psi): 120 or less, or 80-120 Oxygen permeability (Dk, Barrer): at least 80, or at least 100, or at least 150, or at least 200 Elongation at break: at least 100

[0198] With respect to ionic silicone hydrogels, the following properties may also be preferred (in addition to those mentioned above): Lysozyme uptake (μg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 or less Some embodiments of the present invention will now be described in detail in the following examples. EXAMPLES

[0199] Test Method The ultraviolet-visible spectra of the compounds in solution were measured on a Perkin Elmer Lambda 45 or Agilent Cary 6000i, or Ocean Optics QE65 PRO (DH-2000-BAL light source) UV / VIS scanning spectrometer. Prior to use, the instruments were thermally equilibrated for at least 30 min. For the Perkin Elmer instruments, the scan range was 200-800 nm, the scan speed was 960 nm per minute, the slit width was 4 nm, the mode was set to transmission or absorbance, and baseline correction was selected. For the Cary instruments, the scan range was 200-800 nm, the scan speed was 600 nm / min, the slit width was 2 nm, the mode was transmission or absorbance, and baseline correction was selected. For the Ocean Optics instruments, the scan range was 200-800 nm, the slit width was 10 μm, the mode was transmission or absorbance, and baseline correction was selected. Baseline correction was performed before analyzing the samples using the autozero function.

[0200] The UV-visible spectra of contact lenses partially formed from the claimed compositions were measured using packing solutions on a Perkin Elmer Lambda 45 UV / VIS, Agilent Cary 6000i, or Ocean Optics UV / VIS scanning spectrometer. The instruments were thermally equilibrated for at least 30 minutes prior to use. Baseline correction was performed using plastic two-piece lens holders and cuvettes containing the same solvent. These two-piece contact lens holders were designed to hold the samples in the quartz cuvette at the location traversed by the incident light beam. A reference cuvette also housed the two-piece holder. All lenses were made using the same mold to ensure consistent sample thickness. The center thickness of the contact lenses was measured using an electronic thickness gauge. The reported center thickness and transmission spectra are obtained by averaging three individual lens data.

[0201] It is important to ensure that the exterior surface of the cuvette is completely clean and dry and that there are no air bubbles within the cuvette. Measurement reproducibility is improved when the reference cuvette and its lens holder remain constant and all samples use the same sample cuvette and its lens holder, ensuring that both cuvettes are properly inserted into the instrument.

[0202] The following abbreviations are used throughout the examples and figures and have the following meanings: L: Liter (multiple) mL: milliliter(s) Equiv. or eq.: equivalent kg: kilogram(s) g: grams (multiple) mg: milligram(s) mol: mole(s) mmol: millimolar(s) Da: Daltons or g / mol kDa: kilodalton, or atomic mass unit equal to 1,000 daltons min:minutes μm: micrometer(s) nm: nanometer 1 N NMR: Proton nuclear magnetic resonance spectroscopy UV-VIS: Ultraviolet-visible spectroscopy TLC: Thin Layer Chromatography BC: Back or base curve plastic mold FC: Front curve plastic mold PP: Polypropylene, a homopolymer of propylene TT: Tuftec (Asahi Kasei Chemicals), a hydrogenated styrene butadiene block copolymer Z: Zeonor (Nippon Zeon Co Ltd), a polycycloolefin thermoplastic polymer DMA: N,N-dimethylacrylamide (Jarchem) HEMA: 2-hydroxyethyl methacrylate (Bimax) PVP K90: Poly(N-vinylpyrrolidone) (ISP Ashland) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Irgacure or Omnirad 1870: A blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone (IGM Resins or BASF or Ciba Specialty Chemicals) mPDMS: mono-n-butyl terminated, monomethacryloxypropyl terminated polydimethylsiloxane (M n =800~1500 Daltons) (Gelest) SiMAA: 2-Propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (Toray), or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate Norbloc: 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) RB247: 1,4-Bis[2-methacryloxyethylamino]-9,10-anthraquinone TL03 Light: Phillips TLK 40W / 03 bulb LED: Light Emitting Diode D3O: 3,7-dimethyl-3-octanol (Vigon) DIW: Deionized water MeOH: Methanol IPA: Isopropyl alcohol DMF: N,N-dimethylformamide DMSO: Dimethyl sulfoxide DCM or CH 2 Cl 2 :Dichloromethane or methylene chloride DCE: 1,2-dichloroethane CDCl 3: Deuterated chloroform PhOH: Phenol H 2 SO 4 :Sulfuric acid HCl: Hydrochloric acid pTsOH: p-toluenesulfonic acid Ac 2 O: Acetic anhydride Cs 2 CO 3 : Cesium carbonate SOCl 2 : Thionyl chloride NaH: Sodium hydride CPTP: 2-(3-chloropropoxy)tetrahydro-2H-pyran NaI: Sodium iodide Borate Buffer Packing Solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in enough deionized water to fill a 2 liter volumetric flask.

[0203] Preparation 1: Synthesis of 2-(2-cyanoacetamido)ethyl methacrylate Methyl cyanoacetate (40 grams, 0.4037 moles) and 25 mL of dichloromethane were stirred in a three-necked 500 mL round bottom flask equipped with a reflux condenser under a nitrogen environment. After 2-aminoethanol (23.8 grams, 0.3897 moles, approximately 0.97 equivalents) was added to the solution via an addition funnel, the temperature rose and the methylene chloride began to reflux. After the exotherm ceased, external heat was applied to continue the gentle reflux for a total of 2 hours after which no ethanolamine was observed by thin layer chromatography.

[0204] The reaction may also be carried out at room temperature and is complete within a few hours. The mixture was cooled to room temperature and all methylene chloride was evaporated under reduced pressure. The residual oil was washed with 50 mL of ethyl acetate three times to remove unreacted starting material and non-polar impurities. The residual ethyl acetate was then removed under reduced pressure and the resulting oil was used for acylation without further purification.

[0205] The crude N-2-hydroxyethylacetamide derivative was dissolved in 150 mL of dichloromethane containing 40 grams of pyridine (about 0.5 moles) in a three-necked round-bottom flask equipped with a reflux condenser, an addition funnel, and a magnetic stir bar. The flask was immersed in an ice bath and cooled to about 0° C. Methacryloyl chloride (45.76 g, about 0.44 moles) was added dropwise through the addition funnel, and the resulting reactive mixture was allowed to warm to room temperature while the system was constantly stirred. Methanol (20 mL) was added to the flask to quench any unreacted methacryloyl chloride. The volatile components were removed by rotary evaporation under reduced pressure, and the crude product was dissolved in 800 mL of dilute aqueous HCl. The resulting aqueous solution was extracted three times with 100 mL of hexane in a separatory funnel to remove any non-polar impurities. The organic layer was discarded. Sodium chloride was added to the aqueous layer, which was then extracted three times with 300 mL of ethyl acetate. Approximately 50 milligrams of BHT was added as an inhibitor to the combined organic fractions and the ethyl acetate was removed by rotary evaporation under reduced pressure. The crude product crystallized out of solution during solvent removal. When approximately 100 mL of ethyl acetate remained in the flask, 250 mL of hexane was added and the crude product was isolated by vacuum filtration using a fritted glass funnel. Thin layer chromatography indicated the presence of a single compound. The filter cake was washed twice with 150 mL of hexane and then dried under vacuum at 40° C. to give 53 grams (approximately 70% yield) of 2-(2-cyanoacetamido)ethyl methacrylate. 1 H NMR (500 MHz, CDCl 3 )δ 1.93(3H,s,CH3),3.36(2H,s,CNCH 2 ), 3.60(2H,dd,CH 2 NH), 4.26(2H,t,CH 2 OC=O), 5.59(1H,m,vinylic),6.11(1H,bs,vinylic),6.52(1H,bs,NH).

[0206] Example 1: Synthesis of mixed isomers of (E and Z)-2-(2-cyano-2-(9H-thieno[3,2-b]thiochromen-9-ylidene)acetamide)ethyl methacrylate and (E and Z)-2-cyano-N-(2-((3-methylbut-1,3-dien-2-yl)oxy)ethyl)-2-(4H-thieno[2,3-b]thiochromen-4-ylidene)acetamide (Compound A) as shown in Scheme 1.

[0207] [ka]

[0208] Under a nitrogen atmosphere, oxalyl chloride (25 grams, approximately 3 equivalents) was added dropwise over 5 minutes to a stirred suspension of 7.0 grams of 9H-thieno[3,2-b]thiochromen-9-one and 4H-thieno[2,3-b]thiochromen-4-one (0.032 moles) in 40 mL of anhydrous 1,2-dichloroethane. The mixture quickly darkened and a mild exotherm was observed. Once the exotherm had ceased, the mixture was heated at 55° C. for 6 hours. The system was then cooled to room temperature and the volatiles were evaporated under reduced pressure to obtain a solid. Under a nitrogen atmosphere, a solution of 7.0 grams of 2-(2-cyanoacetamido)ethyl methacrylate (approximately 0.036 moles) and 5.0 grams of triethylamine (excess) in 50 mL of anhydrous dichloromethane was added to the solid. The mixture was stirred at room temperature for 20 minutes and then heated to reflux for 6 hours. The mixture was cooled to room temperature and the volatiles were evaporated under reduced pressure. The crude product was dissolved in warm ethyl acetate and filtered. The filtrate was concentrated. After purification on a silica gel column, a mixture of the target molecules was isolated (mixture shown as Compound A). Mixture of isomers - Compound A (Mixture of isomers) 1 H NMR (CDCl 3 ) δ1.85-1.94(3H,m,CH 3 ), 3.51-3.69 (2H, multiple signals, CH 2 ), 4.10-4.29 (2H, multiple signals, CH 2), 5.54-5.58(1H, multiple signals, vinylic), 6.00-6.12(1H, multiple signals, vinylic), 6.10-6.49(1H, multiple signals, NH), 6.89-8.54(6H, multiple signals, ArH)

[0209] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound A is shown in FIG.

[0210] Example 3: Synthesis of mixed isomers of (E)-2-(2-cyano-2-(2-propoxy-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and (Z)-2-(2-cyano-2-(2-propoxy-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate as shown in Scheme 3.

[0211] [ka]

[0212] To a stirred suspension of 2.28 grams of 2-hydroxythioxanthenone (0.01 moles) and 5.0 grams of cesium carbonate in anhydrous DMSO under a nitrogen atmosphere was added 1.5 grams of 1-bromopropane (approximately 1.25 equivalents) and the resulting mixture was heated at 60° C. overnight. The reaction mixture was cooled and poured into 300 mL of ethyl acetate. The organics were extracted three times with 300 mL of 1% aqueous sodium chloride solution. The volatiles were removed under reduced pressure and the crude material was used "as is" in the next step.

[0213] Thionyl chloride (10 grams, 0.085 moles) was added to the crude propyl ether under nitrogen atmosphere and the mixture was stirred at reflux for 1 hour. The mixture was cooled to room temperature and the volatiles were evaporated under reduced pressure. The system was returned to nitrogen atmosphere and a solution of 2-(2-cyanoacetamido)ethyl methacrylate (3.0 g, approximately 1.5 equivalents) and 5.0 grams of pyridine (excess) in 30 mL of anhydrous dichloromethane was added. The mixture was stirred at gentle reflux for an additional 3 hours. The system was cooled to room temperature and the volatiles were evaporated under reduced pressure. The crude product was redissolved in ethyl acetate and extracted with dilute aqueous HCl. The organic layer was concentrated and the product mixture was isolated by chromatography through a silica gel plug (mixture designated as Compound C). Compound C (mixture of isomers) - 1 H NMR(CDCl3)-δ0.99(3H,m,CH 3 ), 1.57-1.85(2H,m,CH 2 and 3H,m,CH 3 ), 3.48(2H,m,CH 2 ),3.84(1H,t,J=6Hz),3.98(1H,t,J=6Hz),4.0(2H,m,CH 2 ), 5,54 (1H,m,vinylic), 5.85 (1H,m,NH), 5.96 and 5.97 (1H,bs(2 signals),NH), 6.78-8.14 (6H,Ar).

[0214] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound C is shown in FIG.

[0215] Example 4: Synthesis of 3-(9-(dicyanomethylene)acridin-10(9H)-yl)propyl methacrylate (Compound D) as shown in Scheme 4

[0216] [ka]

[0217] A suspension of acridone (3.92 grams, 0.02 moles) and 0.8 grams of 60% by weight sodium hydride in mineral oil (0.02 moles) was stirred in 20 mL of anhydrous N,N-dimethylformamide under a nitrogen atmosphere. Once hydrogen gas evolution ceased, 3.9 grams of 2-(3-chloropropoxy)tetrahydro-2H-pyran (approximately 1.1 equivalents) was added to the flask, followed by 250 mg of sodium iodide, and the mixture was heated overnight in a mantle set at 90°C. The system was cooled to room temperature, and the mixture was poured into water and stirred for 15 minutes. The resulting solid was filtered, and the filter cake was washed with dichloromethane to remove most of the unreacted acridone. The filtrate was concentrated under reduced pressure. The residue was dissolved in 200 mL of methanol, 200 mg of p-toluenesulfonic acid was added, and the resulting mixture was stirred at room temperature. After stirring overnight, the deprotection appeared to be complete by TLC. Then, after adding 2 grams of sodium carbonate, the mixture was stirred at room temperature for 30 minutes. The suspension was filtered and the volatiles were evaporated under reduced pressure. The resulting solid was stirred in 100 mL of cold methanol and filtered. The insoluble material was a mixture of unreacted acridone and the desired product, but was nevertheless used directly in the next step.

[0218] A mixture of 10-(3-hydroxypropyl)acridin-9(10H)-one and acridine-9(10H)-one (1.6 grams, <6.28 mmol starting material) and 3 grams of triethylamine (approximately 30 mmol) was stirred in 70 mL of chilled methylene chloride. Methacryloyl chloride (1.0 grams, 9.6 mmol) was added dropwise to the mixture and the system was then allowed to warm to room temperature. Once the acylation appeared complete, the volatile components were removed under reduced pressure and the product was isolated after filtration through a short silica gel plug as a 6:1 mixture with the N-acylated (methacrylamido)acridone derivative.

[0219] Malononitrile (1 gram, 0.015 moles) and 0.5 grams (<1.56 mmol) of a mixture of 3-(9-oxoacridin-10(9H)-yl)propyl methacrylate and 10-methacryloylacridin-9(10H)-one were heated to 130° C. in approximately 10 mL of acetic anhydride and the reaction was monitored by TLC. The reaction appeared to be complete after 6 hours as a bright orange non-polar spot was observed as the major product from the reaction. The mixture was cooled to room temperature and then water was added with continuous stirring for an additional 30 minutes. A precipitate formed which was separated by filtration and the filter cake was then washed several times with water on a fritted glass funnel. The organics were dissolved in dichloromethane, filtered and the product was purified after silica gel chromatography using a mixture of ethyl acetate and dichloromethane (Compound D). Compound D 1 H NMR(CDCl3)-δ2.00(3H,bs,CH 3 ), 2.34(2H,m,CH 2 ),4.36(2H,t,J=6Hz),4.45(2H,m),5.66(1H,m,vinylic),6.17(1H,m,vinylic),7.31(2H,ddd,J=8.5,7.0,1 .5Hz,ArH),7.48(2H,d,8.5Hz,ArH),7.67(2H,ddd,J=7.5,7.0,1.5Hz,ArH),8.51(2H,dd,J=8.5,1.5Hz,ArH).

[0220] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound D is shown in FIG.

[0221] Example 5: Synthesis of 2-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)ethyl methacrylate (Compound E) as shown in Scheme 5

[0222] [ka]

[0223] 3-Hydroxy-9H-xanthen-9-one (4.24 grams, 0.02 moles) in 40 mL of anhydrous DMSO, 7.0 grams of Cs 2 CO 3 A suspension of hydroxyxanthenone (0.07 mol) and 3.0 grams of 2-chloroethyl methacrylate (0.02 mol) was heated at 60° C. overnight. Monitoring by TLC showed complete consumption of hydroxyxanthenone with formation of less polar derivatives. The reaction mixture was cooled to room temperature and diluted with 500 mL of ethyl acetate. After the organics were washed three times with 300 mL of 2 wt % aqueous sodium chloride, they were concentrated under reduced pressure. The resulting solid was washed with hexane on a fritted glass funnel to give a white powder of 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl methacrylate.

[0224] 3-((9-oxo-9H-xanthen-3-yl)oxy)propyl methacrylate (1.0 gram, 3.08 mmol) and 10 grams of thionyl chloride were heated to reflux under nitrogen atmosphere for 4 hours. The system was cooled to room temperature and excess thionyl chloride was evaporated under reduced pressure. A solution of 1 gram of malononitrile (about 15.15 mmol) in 20 mL of dichloromethane was added to the flask under nitrogen atmosphere and the mixture was heated to gentle reflux for another 2 hours. The mixture was cooled to room temperature and the desired product was isolated after purification on a silica gel column (Compound E). Compound E 1 The H NMR spectrum is shown in Figure 8. Compound E 1 H NMR(CDCl3)-δ1.93(3H,t,J=0.75Hz,CH 3 ), 4.33(2H,t,J=4.5Hz,CH 2 ), 4.53(2H,m,CH 2),5.59(1H,m,vinylic),6.12(1H,bs,vinylic),6.90(1H,d,J=3.0Hz,ArH),6.97(1H,dd,J=9.5,3.0Hz,ArH),7.37(1H,ddd,J=8.5,7.0,1. 5Hz,ArH), 7.42(1H,dd,J=8.5,1.5Hz),7.65(1H,ddd,J=8.5,7.0,1.5Hz,ArH),8.47(1H,d,J=9.5Hz,ArH),8.53(1H,dd,J=8.5,1.5Hz,ArH).

[0225] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound E is shown in FIG. 1 and FIG.

[0226] Example 6: Synthesis of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (Compound F) as shown in Scheme 6

[0227] [ka]

[0228] A mixture of 9H-thioxanthen-9-one (2.12 grams, 0.01 mole) and thionyl chloride (5 mL, 8.2 grams, ca. 0.07 mole) was refluxed in a 50 mL round bottom flask under constant stirring under a nitrogen atmosphere. After 2 hours, the red solution was evaporated to dryness to ensure that all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (2.3 grams, 0.0117 mole, ca. 1.17 equiv.) and 15 mL of dichloromethane were added and the resulting reactive mixture was heated to reflux under a nitrogen blanket. The reaction was monitored by thin layer chromatography. After 2 hours, no change was observed in the chromatogram so the reactive mixture was cooled to room temperature. A short silica gel column (CH 2 Cl 2 , followed by C.H. 2 Cl 2After passing through elution with 8 wt % EtOAc in hexane, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate was isolated as yellow crystals (3.2 grams, 82% yield). 1 H NMR (500 MHz, CDCl 3 ) δ 1.84(3H,s,CH 3 ), 3.47(2H,m,CH 2 NH), 4.01(2H,t,CH 2 OC=O), 5.55 (1H,m,vinylic), 5.91 (1H,bs,NH), 5.98 (1H,bs,vinylic), 7.24 (1H,t,Ar-H), 7.31 (1H,t,Ar-H), 7.39 (2H,m,Ar-H), 7.49 (1H,d,Ar-H), 7.55 (1H,m,Ar-H), 7.61 (1H,d,Ar-H), 8.04 (1H,m,Ar-H). The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound F is shown in Figure 2.

[0229] Examples 7 to 9 Reactive monomer mixtures were prepared consisting of 77 weight percent of the formulation listed in Table 1 and 23 weight percent of diluent D3O. The reactive monomer mixtures were individually filtered under pressure through 3 μm filters using stainless steel syringes.

[0230] [Table 5]

[0231] These reactive monomer mixtures were degassed at ambient temperature by applying a vacuum (about 40 torr) for at least about 20 minutes. About 75 μL of the reactive mixture was then dispensed onto the FC made with the 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box with a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas. The BC made with the 90:10 (w / w) Z:TT blend was then placed onto the FC. The molds were equilibrated in the glove box for a minimum of 12 hours prior to pouring. The pallets, each containing eight mold assemblies, were transferred to an adjacent glove box maintained at 65° C. and an intensity of about 1.5 mW / cm was applied. 2 A 435 nm LED light having a power of about 2.5 mW / cm was used for 3 minutes. 2 An intensity of 1000 nm was used for 7 minutes to cure the lenses from the top and bottom.

[0232] With most of the lenses attached to the FC, the lenses were removed from the molds by hand and detached by floating the lenses in about 1 liter of 70 percent IPA for about 1 hour, followed by immersion in fresh 70 percent IPA for 30 minutes twice, then fresh DIW for 15 minutes twice, then packing solution for 30 minutes twice. The lenses were equilibrated and stored in the borate buffered packing solution. Those skilled in the art will appreciate that the exact lens demolding process can vary depending on the lens formulation and mold material in terms of the concentration of the aqueous isopropanol, the number of washes with each solvent, and the duration of each step. The objective of the lens demolding process is to demold all of the lenses without damage and to transition from a diluent swollen network to a packing solution swollen hydrogel. The average center thickness of each lens set was measured. Example 7=88 microns, Example 8=91 microns, Example 9=90 microns.

[0233] 3 shows the UV-VIS spectra of the lenses made in Examples 7-9, which show that the mixture of compounds E and F can provide nearly complete absorption from 300 nm to 400 nm, as well as significant absorption in the high energy visible region from 400 nm to 450 nm. Similar mixtures in combination with other UV-VIS blockers such as benzotriazole (Norbloc) and / or at different concentrations can provide complete absorption from 300 nm to 400 nm, as well as significant absorption in the high energy visible region from 400 nm to 500 nm.

[0234] [Embodiment] (1) A fused tricyclic compound of formula I,

[0235] [ka] During the ceremony, m, n, and t are independently 0, 1, 2, 3, or 4; R 1 , R 2 , and R 3 is independently at each occurrence H, an optional substituent, or -YP g or two adjacent R 1 , R 2 , or R 3 The groups, together with the atoms to which they are attached, form -YP g forming a cycloalkyl or aryl ring optionally substituted with B is O, S, N, and NR 6 R represents an aromatic, saturated, or partially unsaturated 5-, 6-, or 7-membered ring, optionally having up to three heteroatoms independently selected from 6 , H, C 1 ~C 6 Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and One of C and D is O, S, N, and NR 6and the other of C and D represents an aromatic, saturated or partially unsaturated 5-, 6- or 7-membered ring optionally having up to three heteroatoms independently selected from 6 , SO, or SO 2 and at least one hetero group independently selected from the group consisting of a 6-membered saturated or partially unsaturated heterocycloalkyl ring having at one ring carbon atom a group of the formula =C(EWG)(R 7 ) groups, R 7 EWG or -C(=O)-TYP g and EWG, independently at each occurrence, is an electron-withdrawing group; At each occurrence, P g is independently a polymerizable group, Y in each occurrence is independently a linking group; T in each occurrence is independently a bond, O, or NR 6 and The compound of formula I has at least one P g A compound containing a group. (2) The compound of embodiment 1, wherein m, n, and t are independently 0 or 1. (3) R 1 But, H, C 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Thioalkyl, C 3 ~C 7 Cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5 , Benzyl, SO 3 H or SO 3 Na and R 4 and R 5 are independently H or C 1 ~C 6 The compound according to embodiment 1 or 2, wherein R is alkyl. (4) R 2 and R 3 However, independently, H, C1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Thioalkyl, C 3 ~C 7 Cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5 , Benzyl, SO 3 H or SO 3 Na and R 4 and R 5 are independently H or C 1 ~C 6 The compound according to any one of embodiments 1 to 3, wherein R is alkyl. (5) R 6 But H or C 1 ~C 6 The compound according to any one of embodiments 1 to 4, wherein R is alkyl.

[0236] (6) At each occurrence, P g The compound of any one of embodiments 1-5, wherein independently comprises styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. (7) The compound of any one of embodiments 1-6, wherein Y at each occurrence is independently alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of the foregoing groups. (8) T is a bond or NR 6 The compound according to any one of embodiments 1 to 7, wherein (9) The compound of any one of embodiments 1-8, wherein EWG at each occurrence is independently cyano, amide, ester, keto, or aldehyde. (10) The compound according to any one of embodiments 1 to 9, wherein B represents a 6-membered aromatic ring optionally having one heteroatom selected from O, S, and N.

[0237] (11) The compound according to any one of embodiments 1 to 10, wherein D represents a 6-membered aromatic ring optionally having one heteroatom selected from O, S, and N. (12) C is at least one ring carbon atom and O, S, NR 6 , SO, or SO 2 and wherein the heterocycloalkyl ring is a 6-membered saturated heterocycloalkyl ring having at one ring carbon atom a hetero group selected from the formula =C(EWG)(R 7 12. The compound according to any one of embodiments 1 to 11, substituted with a group: (13) R 7 is EWG. (14) R 7 But -C(=O)-TYP g 13. The compound according to any one of embodiments 1 to 12, wherein (15) The compound is one YP g The compound according to any one of embodiments 1 to 14, comprising a group.

[0238] (16) Having a structure selected from the following:

[0239] [ka]

[0240] [ka] In the formula, X is O, S, NR 6 , SO, or SO 2 and Z is independently O, S, or NR 6 16. The compound according to any one of embodiments 1 to 15, wherein (17) 2-(2-cyano-2-(phenanthridin-6(5H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(phenanthridin-6(5H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(1,9-phenanthroline-2(1H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(1,9-phenanthroline-2(1H)-ylidene)acetamido)ethyl methacrylate, 2-(2-(benzo[c][2,6]naphthyridin-5(6H)-ylidene)-2-cyanoacetamido)ethyl methacrylate, 2-(2-(benzo[c][2,6]naphthyridin-5(6H)-ylidene)-2-cyanoacetamido)ethyl methacrylate, 2-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)ethyl methacrylate, 3-(9-(dicyanomethylene)acridin-10(9H)-yl)propyl methacrylate, 2-(2-cyano-2-(4H-thieno[2,3-b]thiochromen-4-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-thieno[3,2-b]thiochromen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(4H-thieno[2,3-b]thiochromen-4-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-thieno[3,2-b]thiochromen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(10,10-dioxido-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)methacrylamide, N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide, N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl)acrylamide, 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate, 2-(2-cyano-2-(2-propoxy-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, 2-(2-cyano-2-(2-propoxy-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate, or The compound according to embodiment 1, which is 2-(9-(dicyanomethylene)acridin-10(9H)-yl)ethyl methacrylate. (18) is not a compound of formula Iz,

[0241] [ka] In the formula, X is O, S, NR 6 , SO, or SO 2 17. The compound according to any one of embodiments 1 to 16, wherein (19) An ophthalmic device that is a polymerization reaction product of a reactive mixture comprising: (a) a monomer suitable for making the ophthalmic device; and (b) a compound according to any one of embodiments 1 to 17. (20) The ophthalmic device of embodiment 19, wherein the monomers suitable for preparing the device are selected from a hydrophilic component, a hydrophobic component, a silicone-containing component, or a mixture of two or more thereof.

[0242] (21) The ophthalmic device of embodiment 19 or 20, which is a conventional (non-silicone) hydrogel or a silicone hydrogel. (22) The ophthalmic device according to any one of embodiments 19 to 21, which is an intraocular lens or a soft contact lens. (23) When the monomer suitable for making the device is a combination of a hydrophilic component and a silicone-containing component, the reaction product comprises a repeat unit derived from a compound of formula I other than a compound of formula Iz;

[0243] [ka] In the formula, X is O, S, NR 6 , SO, or SO 2 23. The ophthalmic device according to any one of embodiments 19 to 22, (24) An ophthalmic device comprising a polymer network and a non-reactive polymer comprising a repeating unit derived from a compound according to any one of embodiments 1 to 17. (25) The ophthalmic device of embodiment 24, wherein the non-reactive polymer further comprises a repeating unit derived from an amide monomer, a monofunctional polyalkylene glycol, or a combination thereof.

[0244] (26) The amide monomer is a non-cyclic amide of formula H1 or H2, a cyclic amide of formula H3, or a combination thereof;

[0245] [ka] In the formula, R 45 is H or methyl, and V is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is C 1 ~C 3 is alkyl, R 40 is H or C 1 ~C 4 is alkyl, R 41 , H, C 1 ~C 4 alkyl, amino having up to 2 carbon atoms, amido having up to 4 carbon atoms, and alkoxy having up to 2 carbon groups; R 42 , H, C 1 ~C 4an alkyl group, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R 43 , H, C 1 ~C 4 alkyl, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R 40 and R 41 The total number of carbon atoms in R is 8 or less. 42 and R 43 The ophthalmic device of embodiment 25, wherein the total number of carbon atoms is 8 or less, and f is a number from 1 to 10. (27) An ophthalmic device described in any one of embodiments 19 to 26, which is imported into a country. (28) The ophthalmic device of embodiment 27, wherein the country is the United States of America.

Claims

1. Compounds of formula III: 【Chemistry 1】 During the ceremony, X is O; m and n are independently 0, 1, 2, 3, or 4; R １ and R2, in each occurrence, is independently -Y-P ｇ or C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 thioalkyl, halo, hydroxy, amino, NR 4 R 5 , benzyl, SO 3 H, or SO 3 Na, where R 4 and R 5 are independently H or C 1 -C 6 alkyl; EWG is cyano; At each occurrence, P ｇ is independently a polymerizable group, Y in each occurrence is independently a linking group; The compound of formula III has at least one P ｇ A compound containing a group.

2. 2. The compound of claim 1, wherein m and n are independently 0 or 1.

3. The compound is one Y-P ｇ 3. The compound according to claim 1 or 2, which contains a group.

4. At each occurrence, P ｇ The compound of any one of claims 1 to 3, wherein independently comprises a styryl, a vinyl carbonate, a vinyl ether, a vinyl carbamate, an N-vinyl lactam, an N-vinyl amide, a (meth)acrylate, or a (meth)acrylamide.

5. 5. The compound of any one of claims 1 to 4, wherein Y at each occurrence is independently alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of the foregoing groups.

6. m is 0, n is 1, R ２ Ga-Y-P ｇ The compound according to any one of claims 1 to 5,

7. m is 0, n is 1, R ２ is -Y-P ｇ and EWG is cyano; P ｇ is a (meth)acrylate or a (meth)acrylamide, The compound according to any one of claims 1 to 6, wherein Y are, independently of each other, alkylene, oxaalkylene, or any combination of the foregoing groups.

8. The compound according to claim 7, wherein P g is a (meth)acrylate.

9. The compound according to claim 7 or 8, wherein P g is methacrylate.

10. The compound of claim 1 which is 2-((9-(dicyanomethylene)-9H-xanthen-3-yl)oxy)ethyl methacrylate.

11. An ophthalmic device that is a polymerization reaction product of a reactive mixture, the reactive mixture comprising: (a) monomers suitable for making the ophthalmic device; and (b) a compound according to any one of claims 1 to 10.

12. The ophthalmic device of claim 11 , wherein the monomers suitable for making the ophthalmic device are selected from hydrophilic components, hydrophobic components, silicone-containing components, or mixtures of two or more thereof.

13. 13. The ophthalmic device of claim 11 or 12, which is a (non-silicone) hydrogel or a silicone hydrogel.

14. The ophthalmic device according to any one of claims 11 to 13, which is an intraocular lens or a soft contact lens.

15. An ophthalmic device comprising a polymer network and a non-reactive polymer comprising repeat units derived from a compound according to any one of claims 1 to 10.

16. The ophthalmic device of claim 15 , wherein the non-reactive polymer further comprises repeat units derived from an amide monomer, a monofunctional polyalkylene glycol, or a combination thereof.

17. the amide monomer is a non-cyclic amide of formula H1 or H2, a cyclic amide of formula H3, or a combination thereof; 【Chemistry 2】 In the formula, R ４５ is H or methyl, and V is a direct bond, -(CO)-, or -(CONHR ４４ )-, and R ４４ is C １ ~C ３ alkyl, R ４０ is H or C １ ~C ４ alkyl, R ４１ is H, C １ ~C ４ alkyl, amino having up to 2 carbon atoms, amido having up to 4 carbon atoms, and alkoxy having up to 2 carbon groups; R ４２ is H, C １ ~C ４ an alkyl group, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R ４３ is H, C １ ~C ４ alkyl, or methoxy, ethoxy, hydroxyethyl, or hydroxymethyl; R ４０ and R ４１ The total number of carbon atoms in R is 8 or less. ４２ and R ４３ The ophthalmic device of claim 16 , wherein the number of carbon atoms combined is 8 or less, and f is a number from 1 to 10.

18. 18. An ophthalmic device according to any one of claims 11 to 17, which is imported into the United States of America.

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