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US-12624214-B2 - Polymerizable absorbers of UV and high energy visible light

US12624214B2US 12624214 B2US12624214 B2US 12624214B2US-12624214-B2

Abstract

Described are polymerizable high energy light absorbing compounds. The compounds absorb various wavelengths of ultraviolet and/or high energy visible light and are suitable for incorporation in various products, such as biomedical devices and ophthalmic devices.

Inventors

  • Shivkumar Mahadevan
  • Dawn D. Wright

Assignees

  • JOHNSON & JOHNSON VISION CARE, INC.

Dates

Publication Date
20260512
Application Date
20231019

Claims (18)

  1. 1 . A compound of formula I: wherein: m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO 2 ; Y is a linking group; P g is a polymerizable group comprising styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or (meth)acrylamide; R at each occurrence is independently H, C 1 -C 6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y-P g ; R 1 and R 2 , when present, are independently at each occurrence 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 3 R 4 , or benzyl, wherein R 3 and R 4 are independently H or C 1 -C 6 alkyl, or two adjacent R 1 or R 2 groups, together with the carbon atoms to which they are attached, combine to form a cycloalkyl or aryl ring; and EWG is an electron withdrawing group.
  2. 2 . The compound of claim 1 wherein m and n are each independently 0 or 1.
  3. 3 . The compound of claim 1 wherein Y at each occurrence is independently alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or combinations thereof.
  4. 4 . The compound of claim 1 wherein X is O.
  5. 5 . The compound of claim 1 wherein X is S.
  6. 6 . The compound of claim 1 wherein EWG is cyano, amide, ester, keto, or aldehyde.
  7. 7 . The compound of claim 1 wherein EWG is cyano.
  8. 8 . The compound of claim 1 that is: 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl acrylate; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl) methacrylamide; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl) acrylamide; 2-(2-cyano-N-methyl-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-cyano-2-(9H-thioxanthen-9-ylidene)-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl acrylate; N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl) methacrylamide; N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl) acrylamide; 2-(2-cyano-N-methyl-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-cyano-N-(2-(N-vinylacetamido)ethyl)-2-(9H-xanthen-9-ylidene) acetamide; 2-(2-(acridin-9 (10H)-ylidene)-2-cyanoacetamido)ethyl acrylate; N-(2-(2-(acridin-9 (10H)-ylidene)-2-cyanoacetamido)ethyl) methacrylamide; N-(2-(2-(acridin-9 (10H)-ylidene)-2-cyanoacetamido)ethyl)acrylamide; 2-(2-(acridin-9 (10H)-ylidene)-2-cyano-N-methylacetamido)ethyl methacrylate; 2-(acridin-9 (10H)-ylidene)-2-cyano-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)-2-methylpropyl methacrylate; 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetoxy)-2-methylpropyl acrylate; (Z)-2-(2-cyano-2-(3-hydroxyacridin-9 (10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(10-methylacridin-9 (10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3,6-dihydroxyacridin-9 (10H)-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-(7H-benzo [c] xanthen-7-ylidene)-2-cyanoacetamido)ethyl methacrylate; (Z)-2-(2-cyano-2-(3-methoxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3,6-dihydroxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2-methyl-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(1-hydroxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2,4-dichloro-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-(2-chloro-9H-thioxanthen-9-ylidene)-2-cyanoacetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(4-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)butanamido)ethyl methacrylate; 2-(3-methoxy-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-amino-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(2-cyano-2-(10, 10-dioxido-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; N-(2-(2-cyano-2-(10-methylacridin-9 (10H) ylidene)acetamido)ethyl) methacrylamide; or 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate.
  9. 9 . An ophthalmic device that is a free radical reaction product of a reactive mixture comprising: one or more monomers suitable for making the ophthalmic device; and a polymerizable high energy light absorbing compound comprising a compound of claim 1 .
  10. 10 . The ophthalmic device of claim 9 further comprising a second polymerizable high energy light absorbing compound.
  11. 11 . The ophthalmic device of claim 10 wherein the second polymerizable high energy light absorbing compound is a UV absorbing compound.
  12. 12 . The ophthalmic device of claim 11 wherein the UV absorbing compound comprises a compound of formula I, a benzophenone, a benzotriazole, a triazine, a substituted acrylonitrile, a salicyclic acid derivative, a benzoic acid derivative, a cinnamic acid derivative, a chalcone derivative, a dypnone derivative, a crotonic acid derivative, or mixtures thereof.
  13. 13 . The ophthalmic device of claim 9 wherein the polymerizable high energy light absorbing compound comprises a mixture of a compound of formula I wherein X is S and a compound of formula I wherein X is O.
  14. 14 . The ophthalmic device of claim 9 wherein the polymerizable high energy light absorbing compound comprises a mixture of a compound of formula I wherein X is S and a benzotriazole UV absorbing compound.
  15. 15 . The ophthalmic device of claim 9 wherein the monomer suitable for making the ophthalmic device comprises a hydrophilic component, a silicone-containing component, or mixtures thereof.
  16. 16 . The ophthalmic device of claim 9 that is a contact lens, a corneal onlay, a corneal inlay, an intraocular lens, or an overlay lens.
  17. 17 . The ophthalmic device of claim 9 that is a hydrogel contact lens.
  18. 18 . A method for making an ophthalmic device, the method comprising: (a) providing a reactive mixture containing a compound according to claim 1 , one or more device forming monomers, and a radical initiator; and (b) polymerizing the reactive mixture to form the ophthalmic device.

Description

RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 17/110,443, filed Dec. 3, 2020, which is a continuation of U.S. patent application Ser. No. 16/268,897, filed Feb. 6, 2019, now U.S. Pat. No. 10,935,695, which claims priority to U.S. Provisional Patent Application Ser. No. 62/691,112, filed Jun. 28, 2018, and U.S. Provisional Patent Application Ser. No. 62/637,505, filed Mar. 2, 2018, each of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION The invention relates to UV and high energy visible light absorbers. More particularly, the invention relates to compounds with polymerizable functionality that absorb various wavelengths of UV and/or high energy visible light, and yet are visibly transparent when incorporated in an article. Thus, the compounds may be used in polymeric articles, including biomedical devices, such as ophthalmic devices. BACKGROUND OF THE INVENTION High energy light from the sun, such as UV light and high-energy visible light, is known to be responsible for cellular damage. While most of the radiation below 280 nm in wavelength is absorbed by the earth's atmosphere, photons possessing wavelengths ranging between 280 and 400 nm have been associated with several ocular disorders including corneal degenerative changes, and age-related cataract and macular degeneration. (See Statement on Ocular Ultraviolet Radiation Hazards in Sunlight, American Optometric Association, Nov. 10, 1993). The human cornea absorbs some radiation up to 320 nm in wavelength (30% transmission) (Doutch, J. J., Quantock, A. J., Joyce, N. C., Meek, K. M, Biophys. J, 2012, 102, 1258-1264), but is inefficient in protecting the back of the eye from radiation ranging from 320 to 400 nm in wavelength. Contact lens standards define the upper UV radiation wavelength at 380 nm. The current Class I UV absorbing criteria defined by the American Optometric Association require >99% of the radiation between 280 and 315 nm (UV B) and >90% of the 316 to 380 nm (UV A) radiation to be absorbed by the contact lens. While the criteria effectively address protection of the cornea (<1% UV B transmittance), there is little attention paid to the lower energy UV radiation (>380<400 nm) associated with retinal damage (Ham, W. T, Mueller, H. A., Sliney, D. H. Nature 1976; 260(5547):153-5) or to high energy visible radiation. High energy-visible (HEV) radiation may cause visual discomfort or circadian rhythm disruption. For example, computer and electronic device screens, flat screen televisions, energy efficient lights, and LED lights are known to generate HEV light. Prolonged exposure to such sources of HEV light may cause eye strain. Viewing HEV light emitting devices at night is also postulated to disrupt the natural circadian rhythm leading, for example, to inadequate sleep. Absorption of high energy light radiation before it reaches the eye continues to be a desirable goal in the ophthalmics field. However, the extent to which a particular wavelength range is absorbed is also important. For instance, 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 a part of the visible spectrum, complete absorption of HEV light may negatively affect vision. With HEV light, therefore, partial absorption may be more desirable. There is a need for materials that provide targeted absorption of undesirable wavelengths of high energy radiation, and that are processable into functional products. Compounds that absorb or attenuate high energy radiation, when used in ophthalmic devices, can help protect the cornea, as well as the interior cells in the ocular environment, from degradation, strain, and/or circadian rhythm disruption. SUMMARY OF THE INVENTION The invention relates to high energy light absorbing compounds that absorb UV and/or high energy visible (HEV) light while substantially transmitting (e.g., greater than 80% transmission) at wavelengths longer than about 450 nm. The compounds are therefore effective at 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 to 450 nm). The compounds are also polymerizable and are generally compatible with other raw materials, as well as the polymerization and processing conditions that are typically used for making ophthalmic devices such as soft contact lenses. The compounds can therefore be readily covalently incorporated into the final product without the need for significant modification of existing manufacturing processes and equipment. Accordingly, in one aspect the invention provides a compound of formula I: wherein: m and n are independently 0, 1, 2, 3, or 4;T is a bond, O, or NR;X is O, S, NR, SO, or SO2;Y is a linking group;Pg is a polymerizable group;R at each occurrence is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y—Pg;R1 and