HK1150075B - Ophthalmic devices comprising photochromic materials with reactive substituents - Google Patents

Description

Ophthalmic devices comprising photochromic materials having reactive substituents

The present application is a divisional application of the following applications: application date 2006, 4/3, application No. 200680020553.7(PCT/US2006/013005), titled "ophthalmic device comprising photochromic material having reactive substituent".

Technical Field

Various non-limiting embodiments disclosed herein relate to ophthalmic devices comprising photochromic materials comprising reactive substituents. Other non-limiting embodiments disclosed herein relate to photochromic ophthalmic devices, and methods of making photochromic ophthalmic devices, wherein the photochromic ophthalmic devices comprise the photochromic materials described herein.

Background

Many commonly used photochromic materials, such as photochromic naphthopyrans, can transition from one state to another in response to the absorption of electromagnetic radiation. For example, many commonly used photochromic materials are capable of transitioning from a first "clear" or "bleached" ground state to a second "colored" activated state in response to the absorption of electromagnetic radiation (or "actinic radiation") of a particular wavelength. As used herein, the term "actinic radiation" refers to electromagnetic radiation that is capable of transforming a photochromic material from one form or state to another. In the absence of actinic radiation, the photochromic material can revert back to a clear ground state in response to thermal energy. Photochromic compositions and articles comprising one or more photochromic materials, such as photochromic lenses for wearing on the eye, typically exhibit clear and colored states, which correspond to the photochromic materials they comprise. Thus, for example, ophthalmic lenses comprising photochromic materials can transition from a clear state to a colored state when exposed to actinic radiation, such as certain wavelengths found in sunlight, and can revert back to the clear state in the absence of such radiation.

When used in photochromic articles and compositions, the conventional photochromic materials are typically incorporated into the host polymer matrix by absorption, mixing, and/or bonding. For example, one or more photochromic materials can be mixed with the polymeric material or precursor thereof, and the photochromic composition can then be formed into a photochromic article or, alternatively, the photochromic composition can be applied as a film or coating to the surface of the optical element. As used herein, the term "photochromic composition" refers to a combination of a photochromic material and one or more other materials, which may or may not be photochromic materials. Alternatively, the photochromic material may be impregnated into a preformed article or coating.

In certain circumstances, it is desirable to modify the compatibility of the photochromic material with the host polymer into which it is incorporated. For example, by making the photochromic material more compatible with the host polymer, clouding (cloudiness) or clouding turbidity (haze) caused by phase separation or migration of the photochromic material in the host polymer is less likely to occur in combination. In addition, compatible photochromic materials can be more soluble in the host polymer and/or more uniformly distributed in the polymer matrix. Moreover, by modifying the compatibility of the photochromic material and the host polymer, other properties of the photochromic composition can also be affected, such as, but not limited to, fade and/or activation rate, saturated optical density, molar absorptivity or molar extinction coefficient, and activated color. These properties are modified, for example, to match the same properties of an otherwise complementary photochromic material, or to enable the use of these compounds in hydrophilic or hydrophobic coating compositions, films or rigid to flexible plastic matrices.

One method of modifying the compatibility of the photochromic material with the host polymer is to attach a polymerizable moiety to the photochromic material through a polyalkoxylated linking group, such as a polyethylene glycol, polypropylene glycol, and/or polybutylene glycol linking group. The purity of the final photochromic material that is readily available is a potential limitation to the use of polyalkoxylated linking groups. For example, commercially available polyethylene glycols that can incorporate linking groups of these photochromic materials can comprise a mixture of ethylene glycol chains having different numbers of ethylene glycol units between each of the chains. Incorporation of these commercially available polyethylene glycols into photochromic materials can produce a mixture of compounds that differ in chain length and molecular weight. This can cause purification difficulties because it is not easy to isolate the desired photochromic materials in these mixtures.

Furthermore, the polyalkoxylated linking group can comprise a long chain containing a polyether oxide functionality that is itself hydrophilic. While certain desirable characteristics may arise with respect to compatibility with the host polymer, linking groups of differing hydrophilicity, including linking groups that may be hydrophobic or, alternatively, shorter linking groups, may provide for different interactions with the host polymer and the resulting photochromic article.

Accordingly, for some applications, it may be desirable to develop photochromic materials that can incorporate a variety of host polymers, wherein the host polymers may contain one or more reactive substituents that are polar (i.e., hydrophilic or lipophilic), which can be more closely matched to the polarity of the host polymer. In other applications, it may be desirable to develop a composition that includes one or more reactive substituents that have a polarity that does not match the polarity of the host polymer. Furthermore, it may be advantageous to develop photochromic materials comprising reactive substituents of uniform composition/molecular weight that can be readily purified, for example by crystallization, chromatography or other purification methods known to those skilled in the art.

Disclosure of Invention

Various non-limiting embodiments disclosed herein relate to ophthalmic devices comprising photochromic materials. In one non-limiting embodiment, the photochromic material comprises a photochromic naphthopyran and at least one reactive substituent bonded to the photochromic naphthopyran, wherein each reactive substituent is independently represented by one of the following groups:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J；

wherein: (i) each-a-is independently-C (═ O) -, -OC (═ O) -, -NHC (═ O) -, or-CH₂-; (ii) each-D-is independently: (a) a diamine residue or a derivative thereof, said diamine residue being an aliphatic diamine residue, a cyclic aliphatic diamine residue, a diazacycloalkane residue, an azacycloaliphatic amine residue, a diazacrown ether residue or an aromatic diamine residue, wherein a first amine nitrogen of said diamine residue is bonded to-a-or photochromic naphthopyran and a second amine nitrogen of said diamine residue is bonded to-E-, -G-or-J; or (b) an amino alcohol residue or a derivative thereof, said amino alcohol residue being an aliphatic amino alcohol residue, a cyclic aliphatic amino alcohol residue, an azacyclic aliphatic alcohol residue, a diazacycloaliphatic alcohol residue or an aromatic amino alcohol residue, wherein the amine nitrogen of said amino alcohol residue is bonded to-a-or photochromic naphthopyran and the alcohol oxygen of said amino alcohol residue is bonded to-E-, -G-or-J, or alternatively, the amine nitrogen of said amino alcohol residue is bonded to-E-, -G-or-J and the alcohol oxygen of said amino alcohol residue is bonded to-a-or photochromic naphthopyran; (iii) each-E-is independently a dicarboxylic acid residue or a derivative thereof, said dicarboxylic acid residue being an aliphatic dicarboxylic acid residue, a cyclic aliphatic dicarboxylic acid residue, or an aromatic dicarboxylic acid residue, wherein a first carbonyl group of said dicarboxylic acid residue is bonded to-G-or-D-and a second carbonyl group of said dicarboxylic acid residue is bonded to-G-; (iv) each-G-is independently:(a)-[(OC₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x, y and z are each independently a number from 0 to 50, and the sum of x, y and z is in the range from 1 to 50; or (b) a polyol residue or a derivative thereof, the polyol residue being an aliphatic polyol residue, a cyclic aliphatic polyol residue or an aromatic polyol residue, wherein a first polyol oxygen of the polyol residue is bonded to-E-, -D-, or photochromic naphthopyran, and a second polyol oxygen of the polyol residue is bonded to-E-or-J; and (v) each-J is independently a group comprising a reactive moiety or residue thereof, or-J is hydrogen, with the proviso that if-J is hydrogen then-J is bonded to the oxygen of a-D-or-G-group to form a reactive moiety.

Another non-limiting embodiment includes an ophthalmic device comprising a compound represented by the formula PC R]_rThe photochromic material of (a), wherein (a) PC comprises a photochromic naphthopyran, wherein said photochromic naphthopyran is 2H-naphtho [1, 2-b ]]Pyran, 3H-naphtho [2, 1-b ]]Pyran, indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyran or indeno [1 ', 2': 4,3]Naphtho [2, 1-b ]]A pyran or mixtures thereof; (b) r is an integer from 1 to 4; and (c) each R is a reactive substituent independently represented by one of the following groups:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J；

wherein: (i) each-a-is independently-C (═ O) -, -OC (═ O) -, -NHC (═ O) -, or-CH₂-; (ii) each-D-is independently: (a) a diamine residue or a derivative thereof, the diamine residue being an aliphatic diamine residue, a cyclic aliphatic diamine residue, a diazacycloalkane residue, an azacyclylaliphatic amine residue, a diazacycloether residue, or an aromaticAn aromatic diamine residue, wherein a first amine nitrogen of said diamine residue is bonded to-A-or PC and a second amine nitrogen of said diamine residue is bonded to-E-, -G-, or-J; or (b) an aminoalcohol residue or a derivative thereof, the aminoalcohol residue being an aliphatic aminoalcohol residue, a cyclic aliphatic aminoalcohol residue, an azacyclic aliphatic alcohol residue, a diazacyclic aliphatic alcohol residue or an aromatic aminoalcohol residue, wherein the amine nitrogen of the aminoalcohol residue is bonded to-A-or PC and the alcohol oxygen of the aminoalcohol residue is bonded to-E-, -G-or-J, or the amine nitrogen of the aminoalcohol residue is bonded to-E-, -G-or-J and the alcohol oxygen of the aminoalcohol residue is bonded to-A-or PC; (iii) each-E-is independently a dicarboxylic acid residue or a derivative thereof, said dicarboxylic acid residue being an aliphatic dicarboxylic acid residue, a cyclic aliphatic dicarboxylic acid residue, or an aromatic dicarboxylic acid residue, wherein a first carbonyl group of said dicarboxylic acid residue is bonded to-G-or-D-and a second carbonyl group of said dicarboxylic acid residue is bonded to-G-; (iv) each-G-is independently: (a) - [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x, y and z are each independently a number between 0 and 50, and the sum of x, y and z is in the range of 1 to 50; or (b) a polyol residue or a derivative thereof, the polyol residue being an aliphatic polyol residue, a cyclic aliphatic polyol residue or an aromatic polyol residue, wherein a first polyol oxygen of the polyol residue is bonded to-E-, -D-or PC, and a second polyol oxygen of the polyol residue is bonded to-E-or-J; and (v) each-J is an independent group comprising acryloyl, crotonyl (crotyl), methacryloyl, 2- (methacryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chloroethenyl or epoxy; or-J is hydrogen, with the proviso that if-J is hydrogen then-J is bonded to the oxygen of the group-D-or-G-.

Further non-limiting embodiments include ophthalmic devices comprising photochromic materials represented by one or a mixture of structures I through IV described below.

Wherein the content of the first and second substances,

(a)R₁the method comprises the following steps: a reactive substituent R, wherein said reactive substituent R is represented by one of the following groups:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J；

wherein

-a-is-C (═ O) -, -OC (═ O) -, -NHC (═ O) -, or-CH₂-；

-D-is: a diamine residue or a derivative thereof, said diamine residue being an aliphatic diamine residue, a cyclic aliphatic diamine residue, a diazacycloalkane residue, an azacycloaliphatic amine residue, a diazacroyl ether residue or an aromatic diamine residue, wherein a first amine nitrogen of said diamine residue is bonded to-a-, structure I, structure II, structure III or structure IV and a second amine nitrogen of said diamine residue is bonded to-E-, -G-or-J; or an aminoalcohol residue or derivative thereof, the aminoalcohol residue being an aliphatic aminoalcohol residue, a cyclic aliphatic aminoalcohol residue, an azacyclic aliphatic alcohol residue, a diazacyclic aliphatic alcohol residue or an aromatic aminoalcohol residue, wherein the amine nitrogen of the aminoalcohol residue is bonded to-a-, structure I, structure II, structure III or structure IV and the alcohol oxygen of the aminoalcohol residue is bonded to-E-, -G-or-J, or the amine nitrogen of the aminoalcohol residue is bonded to-E-, -G-or-J and the alcohol oxygen of the aminoalcohol residue is bonded to-a-, structure I, structure II, structure III or structure IV;

-E-is a dicarboxylic acid residue or a derivative thereof, said dicarboxylic acid residue being an aliphatic dicarboxylic acid residue, a cyclic aliphatic dicarboxylic acid residue or an aromatic dicarboxylic acid residue, wherein a first carbonyl group of said dicarboxylic acid residue is bonded to-G-or-D-and a second carbonyl group of said dicarboxylic acid residue is bonded to-G-;

each-G-is independently: - [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x, y and z are each independently a number between 0 and 50, and the sum of x, y and z is in the range of 1 to 50; or a polyol residue or a derivative thereof, said polyol residue being an aliphatic, cyclic aliphatic or aromatic polyol residue, wherein a first polyol oxygen of said polyol residue is bonded to-E-, -D-, structure I, structure II, structure III or structure IV, and a second polyol oxygen of said polyol residue is bonded to-E-or-J; and

-J is a group comprising acryloyl, methacryloyl, crotonyl, 2- (methacryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chloroethenyl or epoxy, or-J is hydrogen, with the proviso that if-J is hydrogen then-J is bonded to the oxygen of the group-D-or-G-;

or R₁Is hydrogen; a hydroxyl group; c₁-C₃An alkyl group; OR a group-C (═ O) W, wherein W is-OR₇，-N(R₈)R₉Piperidino or morpholino wherein R₇Is alkyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C6) alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆A haloalkyl group; r₈And R₉Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, and the halogen substituent is chloro or fluoro;

(b)R₁' is: a reactive substituent R; hydrogen; a hydroxyl group; c₁-C₃An alkyl group; OR a group-C (═ O) W, wherein W is-OR₇，-N(R₈)R₉Piperidino or morpholino wherein R₇Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆A haloalkyl group; and R₈And R₉Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein said phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, and the halogen substituent is chloro or fluoro;

(c)R₂is a reactive substituent R; hydrogen; c₁-C₆An alkyl group; c₃-C₇Cycloalkyl, substituted or unsubstituted phenyl; OR-OR₁₀(ii) a or-OC (═ O) R₁₀Wherein R is₁₀Is hydrogen; c₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) An alkyl group, a carboxyl group,C₃-C₇cycloalkyl radicals, or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, and the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

(d) n is an integer of 0 to 4, each R₃And R₄Independently in each case: a reactive substituent R; hydrogen; fluorine, chlorine, C₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substituted or unsubstituted phenyl; -OR₁₀or-OC (═ O) R₁₀Wherein R is₁₀Is hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, and the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group; mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_tOr- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material; -N (R)₁₁)R₁₂Wherein R is₁₁And R₁₂Each independently of the other being hydrogen, C₁-C₈Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈Alkylaryl group, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl in which the aryl radical is phenyl or naphthyl, or R₁₁And R₁₂Together with nitrogen atoms to form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A hetero-tricycloalkyl ring; the nitrogen-containing ring is represented by the following graphic formula VA:

wherein each-Y-is independently selected at each occurrence from-CH₂-，-CH(R₁₃)-，-C(R₁₃)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃) (aryl) -, Z is-Y-, -O-, -S (O) -, -SO₂-，-NH-，-N(R₁₃) -or-N (aryl) -, wherein each R is₁₃Independently is C₁-C₆Alkyl, each aryl is independently phenyl or naphthyl, m is an integer of 1, 2 or 3, p is an integer of 0,1, 2 or 3, and when p is 0, Z is-Y-; a group represented by one of the following structural formulae VB or VC:

wherein R is₁₅、R₁₆And R₁₇Each independently of the other being hydrogen, C₁-C₆Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms, each R₁₄Independently at each occurrence selected from C₁-C₆Alkyl radical, C₁-C₆Alkoxy, fluorine or chlorine, p is the integer 0,1, 2 or 3; and unsubstituted, mono-or di-substituted C₄-C₁₈Spirobicyclic amines, or unsubstituted, mono-or di-substituted C₄-C₁₈Spirotricyclic amine wherein said substituents are independently aryl, C₁-C₆An alkyl group, a carboxyl group,C₁-C₆alkoxy, or phenyl (C)₁-C₆) An alkyl group; or

R in the 6-position₃Radicals and R in the 7-position₃The groups together form a group represented by one of VD and VE:

wherein T and T' are each independently oxygen or a group-NR₁₁-, wherein R₁₁、R₁₅And R₁₆As described above;

(e)R₅and R₆Each independently is: a reactive substituent R; hydrogen; a hydroxyl group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; an allyl group; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chlorine; fluorine; -C (═ O) W ', where W' is hydrogen, hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aromatic phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino; -OR₁₈Wherein R is₁₈Is C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl radical, C₁-C₆Chloroalkyl, C₁-C₆Fluoroalkyl, allyl, or a radical-CH (R)₁₉) Y', wherein R₁₉Is hydrogen or C₁-C₃Alkyl, Y' is CN, CF₃Or COOR₂₀Wherein R is₂₀Is hydrogen or C₁-C₃Alkyl or R₁₈Is a group-C (═ O) W 'wherein W' is hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aromatic phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkyl-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino, in which each of the phenyl, benzyl or aryl substituents is independently C₁-C₆Alkyl or C₁-C₆An alkoxy group; or mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_tOr- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material; or R₅And R₆Together form an oxo group, a spirocarbocyclic group containing from 3 to 6 carbon atoms, or a spiroheterocyclic group containing from 1 to 2 oxygen atoms and from 3 to 6 carbon atoms including the spirocarbon atom, said spirocarbocyclic and spiroheterocyclic groups being annelated with 0,1 or 2 benzene rings (annelate); and

(f) b and B' are each independently: substituted phenyl; a substituted aryl group; substituted 9-jullolinyl; substituted heteroaromatic radical selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuranPyran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl, and fluorenyl, wherein phenyl, aryl, 9-juliondinyl, or heteroaromatic substituent is a reactive substituent R; unsubstituted, mono-, di-or tri-substituted phenyl or aryl; 9-julolidinyl (juliolinyl); and an unsubstituted, mono-or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein each phenyl, aryl and heteroaromatic substituent is independently: hydroxy, group-C (═ O) R₂₁Wherein R is₂₁is-0R₂₂，-N(R₂₃)R₂₄Piperidino or morpholino, wherein R₂₂Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆A haloalkyl group; r₂₃And R₂₄Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C₁-C₆Alkyl or C₁-C₆Alkoxy, said halogen substituents being chloro or fluoro, aryl, mono (C)₁-C₁₂) Alkoxyaryl, di (C)₁-C₁₂) Alkoxyaryl, mono (C)₁-C₁₂) Alkylaryl, di (C)₁-C₁₂-) alkylaryl, haloaryl, C₃-C₇Cycloalkyl-aryl radical, C₃-C₇Cycloalkyl radical, C₃-C₇Cycloalkoxy, C₃-C₇Cycloalkoxy radical(C₁-C₁₂) Alkyl radical, C₃-C₇Cycloalkoxy (C)₁-C₁₂) Alkoxy, aryl (C)₁-C₁₂) Alkyl, aryl (C)₁-C₁₂) Alkoxy, aryloxy (C)₁-C₁₂) Alkyl, aryloxy (C)₁-C₁₂) Alkoxy, mono-or di (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkoxy, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkoxy, amino, mono-or di- (C)₁-C₁₂) Alkylamino, diarylamino, piperazine, N- (C)₁-C₁₂) Alkylpiperazino, N-arylpiperazino, aziridino (aziridino), indolino (indolino), piperidino, morpholino, thiomorpholino, tetrahydroquinolino (tetrahydroquinolino), tetrahydroisoquinolino (tetrahydroquinolino), pyrrolidinyl, C₁-C₁₂Alkyl radical, C₁-C₁₂Haloalkyl, C₁-C₁₂Alkoxy, mono (C)₁-C₁₂) Alkoxy (C)₁-C₁₂) Alkyl, acryloxy, methacryloxy or halogen; the unsubstituted or mono-substituted radical being selected from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, thiophenylOxazinyl, phenazinyl and acridinyl, each of said substituents being C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, phenyl or halogen; mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_tOr- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material; a group represented by one of the following structures:

and

wherein each K is-CH₂-or-O-M is-O-or substituted nitrogen, with the proviso that when M is substituted nitrogen, K is-CH₂-, the substituted nitrogen substituent being hydrogen, C₁-C₁₂Alkyl or C₁-C₁₂Acyl radical, each R₂₅In each case independently of one another from C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, hydroxy and halogen, R₂₆And R₂₇Each independently is hydrogen or C₁-C₁₂Alkyl, u is an integer from 0 to 2; or a group represented by the following structure:

wherein R is₂₈Is hydrogen or C₁-C₁₂Alkyl radical, R₂₉Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl, wherein the substituent is C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy or halogen; or B and B' together form a fluoren-9-ylidene, mono-or di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene substituents being independently selected from C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy and halogen; with the proviso that the photochromic material comprises at least one reactive substituent R.

Another non-limiting embodiment relates to an ophthalmic device comprising the photochromic composition, and methods of making the same, wherein the ophthalmic device comprises the photochromic material according to various non-limiting embodiments disclosed herein.

Drawings

The various non-limiting embodiments disclosed herein can be better understood when read in conjunction with the appended drawings, in which: fig. 1 and 2 are schematic illustrations of reaction schemes for synthesizing photochromic materials of various non-limiting embodiments disclosed herein.

Detailed Description

The articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

Moreover, for the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other properties or parameters used in the specification are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, it is understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Further, while the numerical ranges and parameters setting forth the broad scope of the invention are approximations discussed above, the numerical values set forth in the examples section are to be understood as being as precise as possible. It should be understood, however, that the numerical values themselves contain certain errors due to the measurement equipment and/or measurement techniques.

As used herein, the terms "lens" and "ophthalmic device" refer to devices that are located in or on the eye. These devices may provide optical correction, wound care, drug delivery, diagnostic functions, cosmetic enhancements or effects, or a combination of these properties. The terms lens and ophthalmic device include, but are not limited to, soft contact lenses, hard contact lenses, intraocular lenses, overlay lenses, ophthalmic inserts, and optical inserts.

Various non-limiting embodiments of the photochromic materials of the present invention will now be discussed. As used herein, the term "photochromic" means having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Furthermore, as used herein, the term "photochromic material" means any substance suitable for exhibiting photochromic properties, i.e., suitable for having an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation.

One non-limiting embodiment provides a photochromic material comprising a photochromically naphthopyran and a reactive substituent bonded to the photochromically naphthopyran, wherein the reactive substituent is represented by one of the following groups:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J。

non-limiting examples of the structure of-a-according to various non-limiting embodiments of the present invention include-C (═ O) -, -OC (═ O) -, -NHC (═ O) -, and-CH —₂-。

Non-limiting examples of structures of-D-include diamine residues or derivatives thereof according to various non-limiting embodiments of the present invention, wherein the first amine nitrogen of the diamine residue forms a bond with-A-or photochromic naphthopyrans, and the second amine nitrogen of said diamine residue is bonded to-E-, -G-or-J and an amino alcohol residue or a derivative thereof, wherein the amine nitrogen of the amino alcohol residue forms a bond with-A-or a photochromic naphthopyran, and the alcohol oxygen of the amino alcohol residue forms a bond with-E-, -G-or-J, or alternatively, the amine nitrogen of the amino alcohol residue is bonded to-E-, -G-or-J, and the alcohol oxygen of the amino alcohol residue forms a bond with-A-or a photochromic naphthopyran.

In certain non-limiting embodiments, wherein-D-is a diamine residue or derivative thereof, non-limiting examples of said diamine residue include aliphatic diamine residues, cyclic aliphatic diamine residues, diazacycloalkane residues, azacyclicaliphatic amine residues, diazacrown ether residues, and aromatic diamine residues. Non-limiting examples of-D-alternative diamine residues include diamine residues represented by any one of the following structures:

in other non-limiting embodiments, wherein-D-is an amino alcohol residue or derivative thereof, non-limiting examples of said amino alcohol residue include aliphatic amino alcohol residues, cyclic aliphatic amino alcohol residues, azacyclic aliphatic alcohol residues, diazacycloaliphatic alcohol residues and aromatic amino alcohol residues. Non-limiting examples of-D-alternative amino alcohol residues include any amino alcohol residue represented by the following structure:

according to various non-limiting embodiments of the present invention, non-limiting examples of the structure of-E-include dicarboxylic acid residues or derivatives thereof, wherein a first carbonyl group of the dicarboxylic acid residue is bonded to-G-or-D-and a second carbonyl group of the dicarboxylic acid residue is bonded to-G-. Non-limiting examples of suitable dicarboxylic acid residues include aliphatic dicarboxylic acid residues, cyclic aliphatic dicarboxylic acid residues, and aromatic dicarboxylic acid residues. Non-limiting examples of-E-alternative dicarboxylic acid residues include any of the dicarboxylic acid residues represented by the following structures:

according to various non-limiting embodiments of the present invention, non-limiting examples of the structure of-E-include polyolefin diol residues and polyol residues and derivatives thereof, wherein a first polyol oxygen of the polyol residue is bonded to-E-, -D-, or photochromic naphthopyran, and a second polyol oxygen of the polyol residue is bonded to-E-or-J. Non-limiting examples of suitable polyolefin diol residues include the structures: - [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x, y and z are each independently a number between 0 and 50, and the sum of x, y and z is in the range of 1 to 50. Non-limiting examples of suitable polyol residues include aliphatic polyol residues, cyclic aliphatic polyol residues, and aromatic polyol residues.

As noted above, -G-may be a polyol residue, which definition herein includes hydroxyl-containing carbohydrates, such as those listed in U.S. Pat. No. 6,555,028, column 7, line 56 to column 8, line 17, the disclosure of which is hereby expressly incorporated herein by reference. For example, and without limitation, polyol residues can be formed by reacting one or more of the hydroxyl groups of the polyol with a precursor of-E-or-D-, such as a carboxylic acid or methylene halide, a precursor of a polyalkoxylated group, such as a polyalkylene glycol, or a hydroxyl substituent of an indeno-fused naphthopyran. The polyol can be U- (OH)_aThe residue of the polyhydric alcohol can be represented by the formula-O-U- (OH)_a-1Wherein U is the backbone or main chain of the polyol and "a" is at least 2.

Examples of polyols that can form-G-include polyols having at least 2 hydroxyl groups such as (a) low molecular weight polyols having an average molecular weight of less than 500, for example, but not limited to, those listed in U.S. patent No. 6,555,028 at column 4, lines 48-50, and column 4, line 55 through column 6, line 5, the disclosures of which are hereby expressly incorporated herein by reference; (b) polyester polyols such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 5, lines 7-33, the disclosure of which is hereby expressly incorporated herein by reference; (c) polyether polyols such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 5, lines 34-50, the disclosure of which is hereby expressly incorporated herein by reference; (d) amide-containing polyols such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 5, lines 51-62, the disclosure of which is hereby expressly incorporated herein by reference; (e) epoxy polyols such as, but not limited to, those listed at column 5, line 63 to column 6, line 3 of U.S. Pat. No. 6,555,028, the disclosure of which is hereby expressly incorporated herein by reference; (f) polyhydroxy polyvinyl alcohols, such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 6, lines 4-12, the disclosure of which is hereby expressly incorporated herein by reference; (g) urethane polyols such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 6, lines 13-43, the disclosure of which is hereby expressly incorporated herein by reference; (h) polyacrylic polyols, such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 6, line 43 to column 7, line 40, the disclosure of which is hereby expressly incorporated herein by reference; (i) polycarbonate polyols such as, but not limited to, those listed in U.S. Pat. No. 6,555,028 at column 7, lines 41-55, the disclosure of which is hereby expressly incorporated herein by reference; and (j) mixtures of these polyols.

In various non-limiting embodiments of the invention, -J is a group comprising a reactive moiety or residue thereof, or-J is hydrogen, with the proviso that if-J is hydrogen then-J bonds to the oxygen of a-D-or-G-group to form a reactive moiety.

The term "photochromic naphthopyran" as used herein is defined as a photochromic compound having a core naphthopyran structure that exhibits photochromic properties. For example, according to various non-limiting embodiments, photochromic naphthopyrans are capable of converting between a first "closed" form and a second "open" form in response to absorption of actinic radiation. An example of a core naphthopyran structure is represented by the following structure:

according to various non-limiting embodiments disclosed herein, the groups B and B' (as shown above) are part of the photochromic naphthopyran core structure. Without intending to be limited by any particular theory, it is believed that the B and B' groups may help stabilize the open form of the core naphthopyran structure by binding to the π system of the open form of the core naphthopyran structure. Suitable structures for B and/or B' are any structures having at least one pi bond in combination with the pi system of the open form of the core naphthopyran structure, such as, but not limited to, substituted or unsubstituted aromatic ring (e.g., substituted or unsubstituted benzene or naphthalene ring), and substituted or unsubstituted heteroaromatic ring structures. Various non-limiting examples for structures B and/or B' are discussed in detail below.

Photochromic naphthopyrans suitable for use in combination with the various non-limiting embodiments disclosed herein include, but are not limited to, substituted 2H-naphtho [1, 2-b ] pyrans, substituted 3H-naphtho [2, 1-b ] pyrans, substituted indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans, substituted indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyrans, and mixtures thereof. Photochromic naphthopyrans having these structures are shown in the following structures 1 to 4, respectively.

As noted above, according to various non-limiting embodiments disclosed herein, the photochromic materials, such as photochromic naphthopyrans, comprise reactive substituents. As used herein, the term "reactive substituent" refers to an arrangement of atoms, some of which comprise a reactive moiety or residue thereof. According to various non-limiting embodiments disclosed herein, the reactive substituent further comprises a linking group that links the reactive moiety to the photochromic naphthopyran. As used herein, the term "moiety" means a portion or section of an organic molecule having a characteristic chemical form. As used herein, the term "reactive moiety" means a portion or segment of an organic molecule that can react with an intermediate in a polymerization reaction, or with a polymer into which it has been incorporated, to form one or more covalent bonds. As used herein, the phrase "intermediate in a polymerization reaction" refers to any combination of two or more host monomeric units that is capable of reacting to form one or more bonds to additional monomeric units such that the polymerization reaction continues or, alternatively, reacts with a reactive moiety of a reactive substituent on the photochromic material. For example, in one non-limiting embodiment, the reactive moiety may be used as a comonomer reaction in a polymer reaction. Alternatively, but not limited to, the reactive moiety may be reacted with the intermediate as a nucleophile or electrophile. As used herein, the term "host monomer or oligomer" refers to a monomeric or oligomeric material that can be incorporated into the photochromic materials of the present invention. As used herein, the term "oligomer" or "oligomeric material" refers to a combination of two or more monomeric units capable of reacting with additional monomeric units. As used herein, the term "linking group" refers to one or more groups or chains of atoms that link the reactive moiety to the photochromic naphthopyran. As used herein, the term "residue of a reactive moiety" refers to a group that remains after the reactive moiety has been reacted with a protecting group or intermediate in a polymerization reaction. As used herein, the term "protecting group" refers to a group that is removably bonded to a reactive moiety, preventing the reactive moiety from participating in a reaction until the group is removed.

In one non-limiting embodiment, the reactive moiety comprises a polymerizable moiety. As used herein, the term "polymerizable moiety" refers to a portion or segment of an organic molecule that can participate as a comonomer in the polymerization of a host monomer or oligomer. In another non-limiting embodiment, the reactive moiety comprises a nucleophilic moiety that reacts to form a bond with an electrophilic moiety on an intermediate in the polymerization reaction or on the host polymer. Alternatively, in another non-limiting embodiment, the reactive moiety comprises an electrophilic moiety that reacts to form a bond with a nucleophilic moiety on an intermediate in the polymerization reaction or on the host polymer. As used herein, the term "nucleophilic moiety" refers to an electron-rich atom or group of atoms. As used herein, the term "electrophilic moiety" refers to an atom or group of atoms that lacks electrons. It will be appreciated by those skilled in the art that nucleophilic moieties may react with electrophilic moieties, for example to form covalent bonds.

As noted above, in one non-limiting embodiment, the ophthalmic devices of the present invention comprise a photochromic naphthopyran and a reactive substituent bonded to the photochromic naphthopyran. The reactive substituent may be bonded to the photochromic naphthopyran at a variety of positions on the photochromic naphthopyran. With reference to the numbering schemes associated with structures 1, 2, 3, and 4 above, according to certain non-limiting embodiments, the reactive substituent may be attached to the naphthopyran as follows. For structures 1 or 2, the reactive substituent can be bonded to the naphthopyran at any position from 5 to 10. For structures 3 or 4, the reactive substituent can be bonded to the indeno-fused naphthopyran at any position from 5 to 13. Further, for structures 1, 2, 3, and 4, the reactive substituent may additionally or alternatively be bonded to group B and/or group B'.

For example, according to various non-limiting embodiments disclosed herein, wherein the photochromic naphthopyran comprises a 2H-naphtho [1, 2-b ] pyran or a 3H-naphtho [2, 1-b ] pyran of structures 1 or 2, respectively, the reactive substituent may be bonded to the photochromic naphthopyran by replacing a hydrogen on a ring of a naphtho portion of the photochromic naphthopyran with the reactive substituent. Alternatively or additionally, the reactive substituent may be bonded to the photochromic naphthopyran 1 or 2 by replacing a hydrogen on the B and/or B' group of the photochromic naphthopyran with a reactive substituent. According to other non-limiting embodiments, wherein the photochromic naphthopyran comprises an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran or indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyrans, the reactive substituent being bonded to the photochromic naphthopyran by replacing a hydrogen on a ring of the indeno-fused naphthopyran moiety of the photochromic naphthopyran with the reactive substituent. Alternatively or in addition, the reactive substituent may be bonded to the photochromic naphthopyran 3 or 4 by replacing the hydrogen on the photochromic naphthopyran B and/or B' group with a reactive substituent.

As noted above, according to various non-limiting embodiments disclosed herein, the reactive substituent may be represented by one of the following structural groups:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J；

wherein the groups-A-, -D-, -E-and-G-are as described above, -J is a group comprising a reactive moiety or a residue of a reactive moiety; or-J is hydrogen, provided that if-J is hydrogen, then-J bonds to the oxygen of the-D-or-G-group to form a reactive moiety. the-J group may comprise any moiety capable of reacting with an intermediate or host monomer in a polymerization reaction. For example, in one non-limiting embodiment, the-J group comprises a polymerizable moiety that can be used as a comonomer in an additive polymerization or a condensation polymerization of a host monomer to yield a copolymer of the photochromic material and the host polymer. As used herein, the term "addition polymerization" refers to a polymerization reaction in which the resulting polymer contains all of the atoms originally present in the monomer unit. As used herein, the term "condensation-type polymerization" refers to a polymerization in which the resulting polymer does not contain all of the atoms originally present in the monomer unit. As used herein, the term "host polymer" refers to a polymer obtained by polymerizing host monomers. For example, in certain non-limiting embodiments, the host polymer may include a polymer comprising functional groups that may bond with reactive substituents of the photochromic material. In other non-limiting embodiments, the host polymer may be one in which the photochromic material is incorporated, copolymerized with, or bonded to. In another non-limiting embodiment, the-J group comprises a nucleophilic moiety or electrophilic moiety that can react with an electrophilic moiety or nucleophilic moiety on an intermediate in the polymerization reaction or on the host polymer, respectively. In another non-limiting embodiment, -J comprises hydrogen, with the proviso that if-J is hydrogen then-J bonds to the oxygen of the group-D-or-G-to form a reactive moiety, i.e., a hydroxyl group.

Reactive moieties suitable for various non-limiting embodiments of the present invention include, but are not limited to, acryloyl, methacryloyl, crotonyl, 2- (methacryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chloroethenyl, and epoxy when-J is bonded to oxygen or nitrogen. The structures corresponding to these reactive moieties are shown below:

alternatively, -J can be hydrogen, provided that if-J is hydrogen, then-J is bonded to oxygen such that the linkage is terminated by a reactive hydroxyl group, wherein the hydroxyl group comprises a reactive moiety.

As indicated above, the reactive substituent according to the various non-limiting embodiments disclosed herein may comprise one or more groups-A-, -D-, -E-, and-G-, which groups link the group-J to the photochromic naphthopyran. As used herein, a linking group, as defined above, may contain one or more groups-A-, -D-, -E-and-G-. That is, various combinations of the groups-A-, -D-, -E-, and-G-may form part of the linking group of the reactive substituent. As defined herein, the term "group" or "groups" refers to an arrangement of one or more atoms.

The structure of the linking group of various non-limiting embodiments will be discussed in detail below. As noted above, the linking group portion of the reactive substituent includes various combinations of the groups-A-, -D-, -E-, and-G-. For example, in certain non-limiting embodiments, the linking group moiety of the reactive substituent comprises: -A-D-E-G-, -G-E-G-, -D-E-G-, -A-D-, -D-G-, or-D-, wherein the first group of the linking group is bonded to the photochromic naphthopyran at the position as set forth above, as discussed in detail below, and the first group of the linking group is bonded to the-J group. It will be understood by those skilled in the art that linking groups comprising various combinations of groups-A-, -D-, -E-, and-G-can be synthesized by a variety of methods, and that the linkages discussed below are for illustration purposes only and by no means imply a synthetic method particularly desirable or preferred for the preparation of reactive substituents.

The linkages between the various groups, i.e., -A-, -D-, -E-, and-G-, according to various non-limiting embodiments will now be discussed. In one non-limiting embodiment, the-A-group is bonded to the photochromic naphthopyran and to the-D-group. According to this non-limiting embodiment, the A-D bond may be a covalent bond between the carbonyl or methylene carbon of the-A-group and the nitrogen or oxygen of the diamine residue or amino alcohol residue of the-D-group. For example, according to various non-limiting embodiments, when-a-comprises a carbonyl carbon, the a-D bond can be an amide or ester bond. In another-non-limiting embodiment, when-A-comprises a methylene carbon, the A-D bond may be an amine or an ether linkage. As used herein, the term "methylene" refers to a group having a-CH₂Of structure (a)An organic group.

In other non-limiting embodiments, the-D-group is bonded to the-A-group (as described above) or to the photochromic naphthopyran and to the-E-or-G-group. According to one non-limiting embodiment, the D-E bond may be a covalent bond between the nitrogen or oxygen of the diamine residue or amino alcohol residue of the-D-group and the carbonyl carbon of one of the carboxylic acid residues of the-E-group, thereby forming an amide or ester bond therebetween. According to another non-limiting embodiment, the D-G bond may be a covalent bond, wherein the nitrogen or oxygen of the diamine residue or amino alcohol residue of the-D-group replaces the terminal oxygen residue on the polyol residue or polyolefin diol residue of the G-group, thereby forming an amine or ether linkage.

In other non-limiting embodiments, the-E-group is bonded to a-D-group (as described above) or a first-G-group, and to a second-G-group. According to these non-limiting embodiments, the E-G bond may be a covalent bond between the terminal oxygen residue on the-G-group polyol residue or the polyolefin diol residue and the carbonyl carbon of one of the carboxylic acid residues of the-E-group, forming an ester bond therebetween.

As previously discussed, the physical and chemical properties of the linking group can affect the overall properties of the photochromic material. For example, in one non-limiting embodiment, the linking group of the reactive substituent may have hydrophilic properties to make the photochromic material more readily soluble in hydrophilic and polar host monomers. In another non-limiting embodiment, the linking group of the reactive substituent may be lipophilic to render the photochromic material more readily soluble in the lipophilic or non-polar host monomer.

The linking groups according to certain non-limiting embodiments of the present disclosure can also be of the same length and/or composition, such that the resulting photochromic material can be more easily purified compared to photochromic materials having non-uniform length linking groups. For example, in certain non-limiting embodiments, wherein the linking groups are of the same length and/or composition, the resulting photochromic material can be crystallized and thus can be purified by recrystallization. In other non-limiting embodiments, where the linking groups are of the same length and/or composition, the resulting photochromic material can be readily purified by chromatographic methods or other purification methods known to those skilled in the art. For example, in one non-limiting embodiment set forth in example 3, the photochromic material (i.e., 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran) comprises a photochromic naphthopyran having a reactive substituent corresponding to-D-J. According to this non-limiting embodiment, the photochromic material can be purified to give a purple-colored crystal by crystallization using an ethyl acetate/hexane mixture. In another non-limiting embodiment set forth in example 5, the photochromic material (i.e., 3-phenyl-3- (4- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) phenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran) comprises a photochromic naphthopyran having a reactive substituent corresponding to-D-J. According to this non-limiting embodiment, the photochromic material can be purified by silica gel chromatography to give a green expanded foam solid. In other non-limiting embodiments, intermediates in the synthesis of photochromic materials can be readily purified by recrystallization methods, chromatographic methods, or other purification methods known to those skilled in the art.

The bonding between the various linking groups and the group-J will now be discussed. According to various non-limiting embodiments disclosed herein, the group-J may be bonded to the linking group via a G-J bond or a D-J bond. In certain non-limiting embodiments, wherein the reactive moiety-J is bonded to the linking group via a G-J bond, the G-J bond can have many possible structures. For example, when-J is acryloyl, methacryloyl or crotonyl, the G-J bond may be an ester bond, i.e., the terminal oxygen residue of the-G-group is bonded to the carbonyl group of the-J group. Alternatively, when-J is a 2- (methacryloyloxy) ethylcarbamoyl group or a 2- (methacryloyloxy) ethoxycarbonyl group, the G-J bond can be a carbamate and carbonate bond, respectively, wherein the terminal oxygen residue of the-G-group is bonded to the carbonyl group of the-J group ethylcarbamoyl or ethoxycarbonyl moiety. Further, when-J is a 4-vinylphenyl group, a vinyl group, a 1-chloroethenyl group or an epoxy group, the G-J bond may be an ether bond between the terminal oxygen residue of the-G-group and the carbon of the-J group. In certain non-limiting embodiments, the-J group can be hydrogen, such that the G-J bond is an oxygen-hydrogen bond resulting in a reactive moiety, i.e., a hydroxyl group, on the linking group.

In other non-limiting embodiments, wherein the reactive moiety-J is bonded to the linking group via a D-J bond, the D-J bond can have a variety of possible structures. For example, when-J is acryloyl, methacryloyl or crotonyl, the D-J bond may be an ester or amide bond, i.e., the alcohol oxygen or amine nitrogen on the amino alcohol residue or diamine residue of the-D-group is bonded to the carbonyl group of the-J group. Alternatively, when-J is a 2- (methacryloyloxy) ethylcarbamoyl group or a 2- (methacryloyloxy) ethoxycarbonyl group, the D-J bond may be a urea, urethane or carbonate bond, wherein the diamine residue of the-D-group or the amine nitrogen of the amino alcohol residue, or the alcohol oxygen of the amino alcohol residue is bonded to the carbonyl group of the ethylcarbamoyl or ethoxycarbonyl moiety of the-J-group. Further, when-J is 4-vinylphenyl, vinyl, 1-chloroethenyl or epoxy, D-J may be an amine or ether linkage between the amine nitrogen or alcohol oxygen of the-D-group and the carbon of the-J group. In certain non-limiting embodiments, when-D-is an amino alcohol, the-J group may be hydrogen bonded to the oxygen of the amino alcohol residue such that the D-J bond is an oxygen-hydrogen bond, resulting in a reactive moiety, i.e., a hydroxyl group, on the linking group.

According to various non-limiting embodiments disclosed herein, wherein-J is acryloyl, methacryloyl, 2- (methacryloyloxy) ethylcarbamoyl, or epoxy, -J can be attached to a-D-or-G-group of the linking group by condensation of-D-or-G-with acryloyl chloride, methacryloyl chloride, 2-isocyanatoethyl methacrylate, or epichlorohydrin, respectively.

Another non-limiting embodiment provides a photochromic material represented by the formula:

PC-[R]_r

wherein: (a) the PC comprises a photochromic naphthopyran, which can be, for example and without limitation, a 2H-naphtho [1, 2-b ] pyran, a 3H-naphtho [2, 1-b ] pyran, an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran, indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyran, or mixtures thereof; (b) r is an integer from 1 to 4; and (c) R is a reactive substituent represented by one of the following formulae:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J；

wherein the groups-A-, -D-, -E-, and-G-are as set forth above, -J is a group comprising a reactive moiety or a residue thereof, or-J is hydrogen, with the proviso that if-J is hydrogen, then-J is bonded to the oxygen of the-D-or-G-group to form a reactive moiety. According to certain non-limiting embodiments, non-limiting examples of-J include acryloyl, crotonyl, methacryloyl, 2- (methacryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chloroethenyl, and epoxy.

As discussed with respect to the various non-limiting embodiments listed above, according to this non-limiting embodiment, the reactive substituent R can be bonded to the photochromic naphthopyran PC at a variety of positions. For example, when PC is 2H-naphtho [1, 2-b ] pyran or 3H-naphtho [2, 1-b ] pyran, the reactive substituent R may be bonded at any position from 5 to 10 of the above structure 1 or 2. When PC is indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran or indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyran, the reactive substituent R is bonded at any position of 5 to 13 in the above-mentioned structure 3 or 4. Additionally or alternatively, when PC is 2H-naphtho [1, 2-b ] pyran, 3H-naphtho [2, 1-b ] pyran naphthopyran, indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran or indeno [1 ', 2': 4, 3] naphtho [2, 1-B ] pyran, the reactive substituent R may be bonded to the group B and/or the group B'.

Further, as indicated above, the photochromic materials according to the various non-limiting embodiments disclosed herein may comprise one reactive substituent R or may comprise a plurality of reactive substituents R, each of which may be the same or different. For example, according to one non-limiting embodiment, where R is 2, the photochromic material comprises two reactive substituents R, where the two reactive substituents R may be the same or different and may be bonded to the photochromic naphthopyran PC at two of the positions listed above, at one of the positions listed, at one of the B or B 'groups, or both R substituents may be bonded to the photochromic naphthopyran PC at the B and/or B' groups.

According to other non-limiting embodiments disclosed herein, the photochromic material comprises at least one reactive substituent or mixture thereof that may be represented by the following structures I through IV:

with reference to Structure II above, the group R, according to various non-limiting embodiments of the present disclosure₁Non-limiting examples of structures include: a reactive substituent R; hydrogen, hydroxy, C₁-C₃An alkyl group; and a group-C (═ O) W, wherein W is-OR₇，-N(R₈)R₉Piperidino or morpholino wherein R₇Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy radicalSubstituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆Haloalkyl, R₈And R₉Each independently selected from C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, and di-substituted phenyl, said phenyl substituent being C₁-C₆Alkyl or C₁-C₆Alkoxy, said halogen substituent being chloro or fluoro.

Referring now to structure I above, in accordance with various non-limiting embodiments of the present disclosure, the group R₁Non-limiting examples of' structures include: a reactive substituent R; hydrogen; a hydroxyl group; c₁-C₃An alkyl group; and a group-C (═ O) W, wherein W is-OR₇，-N(R₈)R₉Piperidino or morpholino wherein R₇Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆Haloalkyl, R₈And R₉Each independently selected from C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, and di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, said halogen substituent being chloro or fluoro.

Referring now to structures I and II above, the group R according to various non-limiting embodiments of the present disclosure₂Non-limiting examples of structures include: a reactive substituent R; hydrogen; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substitutionOr unsubstituted phenyl; and-OR₁₀(ii) a or-OC (═ O) R₁₀Wherein R is₁₀Is hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C3) alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, the phenyl substituent being C₁-C₆Alkyl or C₁-C₆An alkoxy group.

Referring now to structures I, II, III and IV above, in various non-limiting embodiments of the present disclosure, each R is₃And each R₄Non-limiting examples of structures independently include: a reactive substituent R; hydrogen; fluorine; chlorine; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substituted or unsubstituted phenyl; -OR₁₀(ii) a or-OC (═ O) R₁₀Wherein R is₁₀Is hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, the phenyl substituent being C₁-C₆Alkyl or C₁-C₆An alkoxy group; mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_tOr- [ O- (CH)₂)_t]_k-, where t is an integer 2, 3, 4,5 or 6, k is1 to 50, and the substituent is attached to an aryl group on the other photochromic material. For structures I, II, III and IV, n is an integer from 1 to 4.

Each R₃And each R₄Other non-limiting examples of structures include nitrogen-containing groups, wherein the nitrogen-containing group can be-N (R)₁₁)R₁₂Wherein R is₁₁And R₁₂Each independently of the other being hydrogen, C₁-C₈Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈Alkylaryl group, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl in which the aryl radical is phenyl or naphthyl, or R₁₁And R₁₂Together with nitrogen atoms to form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A hetero-tricycloalkyl ring; the nitrogen-containing ring is represented by the following graphic formula VA:

wherein each Y is independently in each occurrence-CH₂-，-CH(R₁₃)-，-C(R₁₃)₂-, -CH (aryl) -, -C (aryl)₂-or-C (R)₁₃) (aryl) -, Z is-Y-, -O-, -S (O) -, -SO₂-，-NH-，-N(R₁₃) -or-N (aryl) -, wherein each R is₁₃Independently is C₁-C₆Alkyl, each aryl is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer 0,1, 2 or 3 and when p is 0, Z is Y; a group represented by one of the following graphic formulae VB or VC:

wherein R is₁₅，R₁₆And R₁₇Each independently of the other being hydrogen, C₁-C₆Alkyl, phenyl or naphthyl, or R₁₅And R₁₆Taken together may form a ring of 5 to 8 carbon atoms, each R₁₄In each case independently C₁-C₆Alkyl radical, C₁-C₆Alkoxy, fluorine or chlorine, p is the integer 0,1, 2 or 3; unsubstituted, mono-or di-substituted C₄-C₁₈A spiro bicyclic amine; and unsubstituted, mono-or di-substituted C₄-C₁₈A spirotricyclic amine; wherein said spirobicyclic and spirotricyclic amine substituents are independently at each occurrence aryl, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or phenyl (C)₁-C₆) An alkyl group.

Alternatively, R at position 6 according to various non-limiting embodiments disclosed herein₃Radical and R in position 7₃Groups, according to the numbering set forth in structures 1, 2, 3 and 4 above, together form a group represented by structure VD or VE:

wherein T and T' are each independently oxygen or a group-NR₁₁-, wherein R₁₁，R₁₅And R₁₆As described above.

Referring now to structures III and IV above, each R, according to various non-limiting embodiments of the present disclosure₅And R₆Non-limiting examples of group structures may independently include: a reactive substituent R; hydrogen; a hydroxyl group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; an allyl group; a phenyl group; mono-substituted phenyl; a benzyl group; mono-substituted benzyl; chlorine; fluorine; a radical-C (═ O) W ', where W'Is hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, phenyl, mono-substituted phenyl, amino, mono (C)₁-C₆) Alkylamino or di (C)₁-C₆) An alkylamino group; -OR₁₈Wherein R is₁₈Is C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl radical, C₁-C₆Chloroalkyl, C₁-C₆Fluoroalkyl, allyl, or a group, -CH (R)₁₉) Y', wherein R₁₉Is hydrogen or C₁-C₃Alkyl, Y' is CN, CF₃Or COOR₂₀Wherein R is₂₀Is hydrogen or C₁-C₃Alkyl, or R₁₈Is a group-C (═ O) W 'wherein W' is hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aromatic phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkyl-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino wherein each of the phenyl, benzyl or aryl substituents is independently C₁-C₆Alkyl or C₁-C₆An alkoxy group; mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-or- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material.

Alternatively, in certain non-limiting embodiments, R₅And R₆Together may form an oxo group, a spiro carbocyclic group containing 3 to 6 carbon atoms, or a spiro heterocyclic group containing 1 to 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom, which rings are augmented with 0,1 or 2 benzene rings.

Referring again to structures I, II, III and IV above, according to various non-limiting embodiments, non-limiting examples of the structures of groups B and B' each independently include: substituted phenyl; a substituted aryl group; substituted 9-jullolinyl; substituted heteroaromatic groups, such as pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl or fluorenyl, wherein one or more of the phenyl, aryl, 9-juliondinyl or heteroaromatic substituents is a reactive substituent R; unsubstituted, mono-, di-or tri-substituted phenyl or aryl; 9-julolidinyl; or an unsubstituted, mono-or di-substituted heteroaromatic group; such as pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl or fluorenyl, wherein the phenyl, aryl and heteroaromatic substituents are each independently selected from the group consisting of: hydroxy, group-C (═ O) R₂₁Wherein R is₂₁is-OR₂₂，-N(R₂₃)R₂₄Piperidino or morpholino wherein R₂₂Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl-substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl substitutedPhenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C₁-C₆Haloalkyl, R₂₃And R₂₄Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl or substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, said halogen substituents being chloro or fluoro, aryl, mono (C)₁-C₁₂) Alkoxyaryl, di (C)₁-C₁₂) Alkoxyaryl, mono (C)₁-C₁₂) Alkylaryl, di (C)₁-C₁₂) Alkylaryl, haloaryl, C₃-C₇Cycloalkyl-aryl radical, C₃-C₇Cycloalkyl radical, C₃-C₇Cycloalkoxy, C₃-C₇Cycloalkoxy (C)₁-C₁₂) Alkyl radical, C₃-C₇Cycloalkoxy (C)₁-C₁₂) Alkoxy, aryl (C)₁-C₁₂) Alkyl, aryl (C)₁-C₁₂) Alkoxy, aryloxy (C)₁-C₁₂) Alkyl, aryloxy (C)₁-C₁₂) Alkoxy, mono-or di (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkoxy, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkoxy, amino, mono-or di- (C)₁-C₁₂) Alkylamino, diarylamino, piperazino, N- (C)₁-C₁₂) Alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidinyl, C₁-C₁₂Alkyl radical, C₁-C₁₂Haloalkyl, C₁-C₁₂Alkoxy, mono (C)₁-C₁₂) Alkoxy (C)₁-C₁₂) Alkyl, acryloxy, methacryloxy and halogen; unsubstituted or mono-unsubstituted radicals, e.g. pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, thiophenylAn oxazinyl, phenazinyl or acridinyl group, wherein each said substituent is independently C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, phenyl or halogen; mono-substituted phenyl, said phenyl having a substituent in the para position, wherein the substituents are: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-or- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material; a group represented by one of the following structures:

and

wherein K is-CH₂-or-O-M is-O-or substituted nitrogen, with the proviso that when M is substituted nitrogen, K is-CH₂-, unsubstituted nitrogen substituents being hydrogen, C₁-C₁₂Alkyl or C₁-C₁₂Acyl radical, each R₂₅In each case independently C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, hydroxy or halogen, R₂₆And R₂₇Each independently is hydrogen or C₁-C₁₂An alkyl group; u is an integer 0,1 or 2; or a group represented by the following structure:

wherein R is₂₈Is hydrogen or C₁-C₁₂Alkyl radical, R₂₉Is an unsubstituted, mono-or di-substituted radical, e.g. naphthyl, phenyl, furyl or thienyl, wherein the substituents are independently C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, or halogen.

Alternatively according to certain non-limiting embodiments, B and B' together form an unsubstituted mono-or di-substituted fluoren-9-ylidene group, each of said fluoren-9-ylidene group substituents independently being C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, or halogen.

For each group R discussed above₁，R₁′，R₂，R₃，R₄，R₅，R₆And B', wherein the group comprises a reactive substituent R, each of the reactive substituents R may be independently selected from groups represented by one of the following structures:

-A-D-E-G-J；

-G-E-G-J；

-D-E-G-J；

-A-D-J；

-D-G-J; and

-D-J

non-limiting examples of structure-a-according to various non-limiting embodiments of the present disclosure include-C (═ O) -, -OC (═ O) -, -NHC (═ O) -, and-CH₂-。

Non-limiting examples of structure-D-according to various non-limiting embodiments of the present disclosure include diamine residues or derivatives thereof, and amino alcohol residues or derivatives thereof, as listed above.

In certain non-limiting embodiments, wherein-D-is a diamine residue or derivative thereof, a first amine nitrogen of the diamine residue may be bonded to-A-, structure I, structure II, structure III, or structure IV, and a second amine nitrogen of the diamine residue may be bonded to-E-, -G-, or-J. In other non-limiting embodiments, wherein-D-is an amino alcohol residue or a derivative thereof, the amine nitrogen of the amino alcohol residue can be bonded to-A-, structure I, structure II, structure III, or structure IV, and the alcohol oxygen of the amino alcohol residue can be bonded to-E-, -G-, or-J; or the amine nitrogen of the amino alcohol residue may be bonded to-E-, -G-, or-J and the alcohol oxygen of the amino alcohol residue may be bonded to-A-, structure I, structure II, structure III, or structure IV.

Non-limiting examples of structure-E-according to various non-limiting embodiments of the present disclosure include dicarboxylic acid residues or derivatives thereof, as listed above. In certain non-limiting embodiments of-E-, a first carbonyl group of the dicarboxylic acid residue may be bonded to-G-or-D-, and a second carbonyl group of the dicarboxylic acid residue may be bonded to-G-.

Non-limiting examples of structure-G-according to various non-limiting embodiments of the present disclosure include polyolefin diol residues and polyol residues and derivatives thereof, as listed above. In certain non-limiting embodiments, wherein-G-is a polyolefin diol residue, non-limiting examples of the polyolefin diol include the structure:

-[(OC₂H₄)_x(OC₃H₆)_y(OC₄H₈)₂]-O-，

wherein x, y and z are each integers between 0 and 50, and the sum of x, y and z is from 1 to 50. In other non-limiting embodiments, where-G-is a polyol residue or derivative thereof, a first polyol oxygen of the polyol residue may be bonded to-E-, -D-, structure I, structure II, structure III, or structure IV, and a second polyol oxygen of the polyol may be bonded to-E-or-J.

According to various non-limiting embodiments disclosed herein, -J comprises a reactive moiety or residue thereof; or alternatively, -J is hydrogen, with the proviso that if-J is hydrogen then-J bonds to the oxygen of the-D-or-G-group to form a reactive moiety. Non-limiting embodiments of the reactive moiety are discussed above.

Further, according to various non-limiting embodiments disclosed herein, R on each of structures I, II, III, and IV₁，R₁′，R₂，R₃，R₄，R₅，R₆One of the groups B and B' comprises a reactive substituent R. In another non-limiting embodiment, R on each of structures I, II, III and IV₁，R₁′，R₂，R₃，R₄，R₅，R₆Two of the groups B and B' may contain a reactive substituent R, wherein the reactive substituents R may be the same or different. In another non-limiting embodiment, R on each of structures I, II, III and IV₁，R₁′，R₂，R₃，R₄，R₅，R₆From 1 to 4 of the radicals B and B' may contain reactive substituents R, where the reactive substituents R may be identical or different.

Non-limiting examples of photochromic materials comprising naphthopyrans containing a reactive substituent R according to various non-limiting embodiments of the present disclosure include:

(i)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (3- (2-methacryloyloxyethyl) carbamoyloxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(ii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2-methacryloyloxyethyl) carbamoyloxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2- ] pyrane;

(iii) 3-phenyl-3- (4- (4-phenylpiperazino) phenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(iv)3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(v)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(vi) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(vii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(viii) 3-phenyl-3- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethoxy) phenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(ix) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(x) 3-phenyl-3- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethoxy) phenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xi) 3-phenyl-3- (4- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) phenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xii) 3-phenyl-3- (4- (2-methacryloyloxyethyl) carbamoyloxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xiii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xiv) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (3- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xv) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xvi) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xvii) 3-phenyl-3- (4- (2- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxyethoxy) phenyl) -6-methoxy-7-morpholino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xviii) 3-phenyl-3- (4- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethyl) piperazin-1-yl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

and mixtures thereof.

In accordance with non-limiting embodiments of the photochromic materials comprising reactive substituents disclosed herein, non-limiting methods for synthesizing the reactive substituent R on the photochromic naphthopyrans are discussed below with reference to the reaction schemes shown in FIGS. 1 and 2. FIG. 1 depicts a cross-sectional view of a polymer in an indeno [2 ', 3': various non-limiting methods for synthesizing a reactive substituent at the 7-position of 3, 4] naphtho [1, 2-b ] pyran. FIG. 2 depicts a cross-sectional view of a polymer in an indeno [2 ', 3': one non-limiting method of synthesizing the reactive substituent R on the B group of 3, 4] naphtho [1, 2-B ] pyran. It will be appreciated by those skilled in the art that there are a variety of methods for synthesizing the reactive substituents on the photochromic naphthopyrans, and therefore, it will be understood that these reaction schemes are illustrative only and not intended to be limiting.

Referring now to fig. 1, 2, 3-dimethoxy-7, 7-dimethyl-7H-benzo [ C ] fluoren-5-ol 5 can be reacted with a substituted 2-propyn-1-ol to form an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran 6. Non-limiting methods for synthesizing 7H-benzo [ C ] fluoren-5-ol, suitable for use in the synthesis of the various non-limiting embodiments disclosed herein, are disclosed in U.S. Pat. No. 6,296,785, column 11, line 6 through column 28, line 35, the disclosures of which are incorporated herein by reference in their entirety. Non-limiting methods of synthesizing substituted 2-propyn-1-ols, suitable for use in the synthesis of the various non-limiting embodiments disclosed herein, are disclosed in U.S. patent No. 5,458,814, column 4, line 11 to column 5, line 9, step 1 of examples 1, 4-6, 11, 12 and 3, and column 5, line 12 to column 6, line 30 of 5,645,767, the entire contents of which are incorporated herein by reference. The indeno-fused naphthopyran 6 may then be reacted with a diamine or an amino alcohol. For example, 6 can be reacted with a diamine, such as piperazine, to give 6-methoxy-7- (piperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran 7. The piperazine moiety of 7 can be condensed with 2-isocyanatoethyl methacrylate to give photochromic naphthopyrans 8 having an R substituent comprising-D-J, as defined above, wherein-D-is a diamine residue. Alternatively, the indeno-fused naphthopyran 6 may be reacted with an aminoalcohol, such as 3-piperidinemethanol, to provide a 6-methoxy-7- (3-hydroxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran 9. The hydroxyl moiety of 9 can be condensed with 2-isocyanatoethyl methacrylate to provide photochromic naphthopyrans 10 having an R substituent containing-D-J, as defined above, wherein-D-is the residue of an amino alcohol.

Still referring to FIG. 1, the hydroxyl moiety of 9 may optionally be reacted with a cyclic anhydride, such as succinic anhydride, to give 6-methoxy-7- (3- (2-hydroxycarbonylethylcarboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran 11. esterification of the carboxylic acid of 11 with polyethylene glycol methacrylate affords photochromic naphthopyrans 12 having an R substituent containing-D-E-G-J, as defined above.

Referring now to FIG. 2, 7, 7-dimethyl-7H-benzo [ C ] fluoren-5-ol (13) can be reacted with 1-phenyl-1- (4- (4- (2-hydroxyethyl) piperazin-1-yl) phenyl-2-propyn-1-ol to form indeno [2 ', 3': 3, 4] naphtho [1, 2-B ] pyran 14.14 the hydroxyl moiety of which can be condensed with 2-isocyanatoethyl methacrylate to give photochromic naphthopyrans 15 having an R substituent on the B group, wherein the reactive substituent R comprises-D-J, as defined above, wherein-D-is an amino alcohol residue.

Photochromic materials, such as photochromic materials comprising a photochromic naphthopyran and a reactive substituent bonded to the photochromic naphthopyran, wherein the reactive substituent has the structure set forth herein, are useful in ophthalmic devices.

In certain non-limiting embodiments, the photochromic materials disclosed herein can be used in soft contact lenses, hard contact lenses, intraocular lenses, overlay lenses, ocular inserts, and optical inserts.

Photochromic materials according to various non-limiting embodiments disclosed herein can incorporate organic materials, such as polymeric, oligomeric, or monomeric materials, which can be used, for example and without limitation, to form ophthalmic devices. The term "incorporated" as used herein refers to being physically and/or chemically bound thereto. Accordingly, ophthalmic devices according to various non-limiting embodiments disclosed herein can be formed from photochromic materials physically and/or chemically combined with at least a portion of an organic material. The terms "polymer" and "polymeric material" as used herein refer to homopolymers and copolymers (e.g., random, block, and alternating copolymers), as well as blends and other combinations. Further, it should be noted that photochromic materials according to various non-limiting embodiments disclosed herein can be used alone, in combination with other photochromic materials according to various non-limiting embodiments disclosed herein, or in combination with other suitable conventional photochromic materials. For example, photochromic materials according to various non-limiting embodiments disclosed herein can be used in combination with other complementary conventional photochromic materials having an activated absorption maximum in the range of 300 to 1000 nanometers. The complementary conventional photochromic materials can include other polymerizable or compatible photochromic materials.

The present disclosure also contemplates ophthalmic devices formed from photochromic compositions comprising a polymeric material and a photochromic material according to various non-limiting embodiments discussed herein. As used herein, the term "photochromic composition" refers to a combination of a photochromic material and another material, which may or may not be a photochromic material. In certain non-limiting examples of the photochromic compositions according to various non-limiting embodiments of the present disclosure, the photochromic material is incorporated into at least a portion of the polymeric material. For example, and without limitation, the photochromic materials disclosed herein can be incorporated into a portion of the polymeric material, such as by bonding to a portion of the polymeric material, such as by copolymerizing the photochromic material with a portion of the polymeric material; or mixed with a polymeric material. As used herein, the term "blended" or "mixing" refers to the photochromic material being mixed or blended with at least a portion of the organic material, e.g., polymeric material, rather than being bonded to the organic material. As used herein, the term "bonded" or "bonding" refers to the attachment of a photochromic material to a portion of an organic material, such as a polymeric material, or a precursor thereof. For example, in certain non-limiting embodiments, the photochromic material may be bonded to a portion of the organic material through a reactive substituent (such as, but not limited to, the reactive substituents discussed above).

According to one non-limiting embodiment, photochromic materials can be incorporated into at least partially polymeric materials or at least partially monomeric or oligomeric materials to form ophthalmic devices. For example, photochromic materials having reactive substituents according to various non-limiting embodiments disclosed herein can be bonded to organic materials, such as monomers, oligomers, or polymers, that have groups that can react with the reactive moieties or in which the reactive moieties can react as comonomers in a polymerization reaction to form the organic material, e.g., in a copolymerization process. As used herein, the term "and.. copolymerize" means that the photochromic material is used as a comonomer in a host monomer polymerization reaction to link with a portion of the polymeric material to produce a polymeric material. For example, the photochromic materials of the various non-limiting embodiments herein have reactive substituents with polymerizable moieties that can be used as comonomer reactions during polymerization of the host monomer.

Polymeric materials suitable for use in the various non-limiting embodiments of the present disclosure include those suitable for the manufacture of ophthalmic devices.

Further, according to various non-limiting embodiments, at least a portion of the ophthalmic device is transparent. For example, according to various non-limiting embodiments, an ophthalmic device can be formed from an optically clear polymeric material. According to a specific non-limiting embodiment, the polymeric material is comprised of a mixture including polymerizable and optionally non-polymerizable ophthalmic device-forming ingredients known in the art to be useful in forming ophthalmic devices, such as contact lenses. More particularly, suitable ingredients include polymerizable monomers, prepolymers and macromers, humectants, UV absorbing compounds, compatibilizing components, colorants and colorants, mold release agents, processing aids, mixtures thereof, and the like.

According to a specific non-limiting embodiment, the components forming the ophthalmic device preferably form a hydrogel by polymerization and hydration. Hydrogels are aqueous, crosslinked polymer systems that contain water in an equilibrium state. Hydrogels are generally oxygen permeable and biocompatible, making them the preferred material for the preparation of ophthalmic devices, particularly contact lenses and intraocular lenses.

Components for forming ophthalmic devices are known in the art and include polymerized monomers, prepolymers, and macromers that contain polymerizable groups and performance groups that provide the desired properties to the final polymer. Suitable performance groups include, but are not limited to, hydrophilic groups, groups that increase oxygen permeability, UV or visible light absorbing groups, combinations thereof, and the like.

The term "monomer" as used herein refers to a low molecular weight compound (i.e., generally having a number average molecular weight of less than about 700). The prepolymer is a vehicle to a high molecular weight compound or polymer (having repeating structural units and a number average molecular weight greater than about 700) containing functional groups capable of further polymerization. Macromers are non-crosslinked polymers that can be crosslinked or further polymerized.

One suitable type of component for forming an ophthalmic device includes a hydrophilic component that, when combined with the remaining components, is capable of providing a final lens with a water content of at least about 20% and preferably at least about 25%. Hydrophilic components useful in preparing the polymers of the present invention are monomers having at least one polymerizable double bond and at least one hydrophilic functional group. Examples of polymerizable double bonds include acrylic, methacrylic, acrylamide, methacrylamide, fumaric, maleic, styrene, isopropenylphenyl, O-vinyl carbonate, O-vinyl carbamate, allyl, O-vinyl acetyl and N-vinyl lactam and N-vinyl amide double bonds. Non-limiting examples of hydrophilic monomers having acrylic and methacrylic polymerizable double bonds include N, N-Dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, and mixtures thereof.

Non-limiting examples of hydrophilic monomers having N-vinyl lactam and N-vinyl amide polymerizable double bonds include N-vinyl pyrrolidone (NVP), N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-2-hydroxyethyl vinyl carbamate, N-carboxy- β -alanine N-vinyl ester, with NVP and N-vinyl-N-methyl acetamide being preferred. Polymers formed from these monomers may also be included.

Other hydrophilic monomers that can be used in the present invention include polyoxyethylene polyols having one or more terminal hydroxyl groups substituted with a functional group containing a polymerizable double bond.

Still further examples are hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215, and hydrophilic vinyl carbonates or vinyl carbamates disclosed in U.S. Pat. No. 4,190,277An oxazolone monomer. Other suitable hydrophilic monomers will be apparent to those skilled in the art.

Preferred hydrophilic monomers that can be incorporated into the polymerizable mixture of the present invention include hydrophilic monomers such as N, N-Dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinyl pyrrolidone (NVP), N-vinyl-N-methylacetamide, polyethylene glycol monomethacrylate, and mixtures thereof.

Most preferred hydrophilic monomers include HEMA, DMA, NVP, N-vinyl-N-methylacetamide and mixtures thereof.

The hydrophilic monomers referenced above are suitable for preparing conventional contact lenses, such as those made from etafilcon, polymacon, vifilcon, genfilcon A and lenefilcon A, among others. For conventional contact lenses, the amount of hydrophilic monomer incorporated into the polymerizable mixture is at least about 70 weight percent, preferably at least about 80 weight percent, based on the weight of all components in the polymerizable mixture.

In another non-limiting embodiment, suitable contact lenses may be made from polymeric materials having increased oxygen permeability to oxygen, such as galyfilcon A, senofilcon A, balafilcon, lotrafilcon A and B, and the like. The polymerizable mixture used to form these and other materials having increased permeability to oxygen typically includes one or more of the hydrophilic monomers listed above, with at least one silicone-containing component.

The silicone-containing component is a component that contains at least one [ -Si-O-Si ] group in a monomer, macromer or prepolymer. Preferably, Si and attached O are present in the silicone-containing component in an amount greater than 20 wt.%, more preferably greater than 30 wt.%, based on the total molecular weight of the silicone-containing component. Useful silicone-containing components preferably contain polymerizable functional groups such as acrylate, methacrylate, acrylamide, methacrylamide, N-vinyl lactam, N-vinyl amide, and styryl functional groups. Examples of silicone-containing components useful in the present invention can be found in U.S. Pat. nos. 3,808,178; 4,120,570, respectively; 4,136,250; 4,153,641; 4,740,533, respectively; nos. 5,034,461 and 5,070,215, and EP 080539. All patents cited herein are incorporated herein by reference in their entirety. These references disclose a number of examples of olefinic silicone-containing components.

Further examples of suitable silicone-containing monomers are polysiloxane-based (meth) acrylic monomers represented by the formula:

formula VI

Wherein: r³⁰Represents H or lower alkyl; x represents O or NR³⁴(ii) a Each R³⁴Independently represents hydrogen or a methyl group, or a salt thereof,

each R³¹-R³³Independently represents lower alkyl or phenyl, and n is 1 or 3 to 10.

Examples of these polysiloxanylalkyl (meth) acrylic acid monomers include methacryloxypropyltris (trimethylsiloxy) silane, methacryloxymethylpentamethyldisiloxane, methacryloxypropylpentamethyldisiloxane, methyldi (trimethylsiloxy) methacryloxypropylsilane, and methyldi (trimethylsiloxy) methacryloxymethylsilane. Methacryloxypropyltris (trimethylsiloxy) silane is most preferred.

One preferred class of silicone-containing components is poly (organosiloxane) prepolymers represented by formula VII:

formula VII

Wherein each a independently represents an activated unsaturated group, such as an ester or amide of acrylic or methacrylic acid or an alkyl or aryl group (provided that at least one a comprises an activated unsaturated group capable of undergoing free radical polymerization); each R³⁵，R³⁶，R³⁷And R³⁸Independently selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms or halogen-substituted monovalent hydrocarbon groups which may have ether linkages between carbon atoms;

R³⁹denotes a compound having 1 to 22 carbon atomsDivalent hydrocarbon group of the subgroup, and m is 0 or an integer of 1 or more, preferably 5 to 400, most preferably 10 to 300. A specific example is α, ω -bis-methacryloxypropyl poly-dimethylsiloxane. Another preferred example is mPDMS (mono-n-butyl terminated polydimethylsiloxane terminated with monomethacryloxypropyl).

Another useful class of silicone-containing components includes silicone-containing vinyl carbonate or vinyl carbamate monomers of the formula:

of the formula VIII

Wherein: y represents O, S or NH; r' represents a silicone-containing organic group; r⁴⁰Represents hydrogen or methyl; d is 1, 2, 3 or 4; and q is 0 or 1. Suitable silicone-containing organic radicals R^SiComprising the following:

-(CH₂)_q.Si[(CH₂)_sCH₃]₃

-(CH₂)_q.Si[OSi(CH₂)_sCH₃]₃

wherein:

q represents

Wherein p is 1 to 6; r⁴¹Represents an alkyl or fluoroalkyl group having 1 to 6 carbon atoms; e is1 to 200; q' is 1, 2, 3 or 4; and s is 0,1, 2, 3, 4 or 5.

The silicone-containing vinyl carbonate or vinyl carbamate monomers specifically include: 1, 3-bis [4- (vinyloxycarbonyloxy) but-1-yl ] tetramethyl-disiloxane; 3- (vinyloxycarbonylthio) propyl- [ tris (trimethylsiloxy) silane ]; 3- [ tris (trimethylsiloxy) silyl ] propylallylcarbamate; 3- [ tris (trimethylsiloxy) silyl ] propylvinylcarbamate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate, and

the above description of silicone-containing components is not an exhaustive list. Any other silicone component known in the art may be used. Further examples include, but are not limited to, macromers prepared using group transfer polymerization, such as those disclosed in U.S. Pat. No. 6,367,929, silicone-containing polyurethane compounds, such as those disclosed in U.S. Pat. No. 6,858,218, silicone-containing macromers, such as those disclosed in U.S. Pat. No. 5,760,100 as materials A-D; macromonomeric-containing polysiloxanes, polyalkylene ethers, diisocyanates, polyfluorinated hydrocarbons, polyfluorinated ethers and polysaccharide groups, such as those disclosed in WO 96/31792; polysiloxanes having polar fluorinated grafts or side chains having a hydrogen atom attached to a terminally difluoro-substituted carbon atom, such as disclosed in U.S. patent nos. 5,321,108; 5,387,662 and 5,539,016; hydrophilic siloxane-based methacrylate monomers and polysiloxane-dimethacrylate macromonomers such as those disclosed in US 2004/0192872; combinations thereof, and the like.

The polymerizable mixture may contain additional components such as, but not limited to, wetting agents such as those disclosed in US6,822,016, US serial No. 11/057,363 (VTN5045), US series No. 10/954,560, US series No. 10/954,559 and US series No. 955,214; compatible components such as those disclosed in US6,822,016 and WO 03/022322; UV absorbers, medicaments, antimicrobial compounds, reactive dyes (reactive tints), pigments, copolymerizable and non-polymerizable dyes, release agents and combinations thereof.

Also contemplated are copolymers of the above monomers, combinations, and blends of the above monomers, as well as copolymers with other polymers, for example to form interpenetrating network products.

The polymerizable mixture may optionally further comprise a diluent. Suitable diluents for the polymerizable mixture are well known in the art. Non-limiting examples of polymerizable mixtures for hydrophilic soft contact lenses include organic solvents or water or mixtures thereof. Preferred organic solvents include alcohols, diols, triols, polyols and polyalkylene alcohols. Examples include, but are not limited to, glycerol, glycols such as ethylene glycol or diethylene glycol; borate esters of polyols are disclosed, for example, in U.S. Pat. nos. 4,680,336; those of nos. 4,889,664 and 5,039,459; polyvinylpyrrolidone; ethoxylated alkyl glucosides; ethoxylated bisphenol a; polyethylene glycol; a mixture of propoxylated and ethoxylated alkyl glucosides; ethoxylated or propoxylated alkyl glucosides and C_2-12A single phase mixture of dihydric alcohols; 8-caprolactone with C_2-6Adducts of alkane diols and triols; ethoxylation C_3-6An alkane triol; and mixtures thereof, such as US5,457,140; 5,490,059, 5,490,960; 5,498,379, respectively; 5,594,043, respectively; 5,684,058, respectively; 5,736,409, respectively; 5,910,519, respectively. The diluent may also be selected from the group having a combination of defined viscosity and Hanson cohesion parameters as described in U.S. patent 4,680,336.

Non-limiting examples of diluents suitable for use in the polymerizable mixture of silicone hydrogel soft contact lenses include alcohols such as those disclosed in US6,020,445 and US series No. 10/794,399 for silicone hydrogel soft contact lenses. The disclosures of these and all other documents cited in this application are hereby incorporated by reference. Many other suitable examples are known to those skilled in the art and are included within the scope of the present invention.

Hard contact lenses are made from polymers including, but not limited to, polymers of poly (methyl) methacrylate, silicon acrylate, fluoroacrylate, fluoroether, polyacetylene, and polyimide, typical examples of which can be made as described in U.S. patent 4,540,761; 4,508,884, respectively; 4,433,125 and 4,330,383. The intraocular lens of the present invention may be formed of known materials. For example, the lens may be made of a hard material, including, but not limited to, polymethyl methacrylate, polystyrene or polycarbonate, and the like, and combinations thereof. Additionally, flexible materials may also be used, including, but not limited to, hydrogels, silicone materials, acrylic materials, fluorocarbon materials, and the like, or combinations thereof. Typical intraocular lenses are described in WO0026698, WO0022460, WO9929750, WO9927978, WO 0022459. Other ophthalmic devices, such as punctal plugs, can be prepared from collagen and silicone elastomers.

Various non-limiting embodiments disclosed herein provide photochromic ophthalmic devices that include the photochromic material of any of the non-limiting embodiments discussed above, associated with a portion of the ophthalmic device. The term "coupled to" as used herein means directly or indirectly coupled through another material or structure.

For example and without limitation, the photochromic materials disclosed herein can be associated with at least a portion of an ophthalmic device, such as by bonding the photochromic material to at least a portion of the material from which the ophthalmic device is made, such as by copolymerizing or otherwise bonding the photochromic material to the ophthalmic device material; mixing a photochromic material and an ophthalmic device material; or coated with a photochromic material on at least a portion of the surface of the ophthalmic device. Alternatively, the photochromic material can be attached to at least a portion of the ophthalmic device, such as through an intermediate coating, film, or layer.

According to various non-limiting embodiments disclosed herein, photochromic materials can be associated with at least a portion of an ophthalmic device by incorporating the photochromic materials into at least a portion of the ophthalmic device polymeric materials, or into at least a portion of the oligomeric or monomeric materials forming the ophthalmic device. For example, according to one non-limiting embodiment, photochromic materials can be incorporated into the polymeric material of an ophthalmic device by cast-in-place. Additionally or alternatively, the photochromic material can be coupled to at least a portion of the polymeric material of the ophthalmic device by an imbibition process. The infiltration method and the in-situ casting method will be discussed below.

For example, according to one non-limiting embodiment, an ophthalmic device includes a polymeric material and a photochromic material associated with at least a portion of the polymeric material. According to another non-limiting embodiment, an ophthalmic device includes a polymeric material and a photochromic material mixed with at least a portion of the polymeric material. According to another non-limiting embodiment, an ophthalmic device comprises a polymeric material and a photochromic material copolymerized with at least a portion of the polymeric material. Non-limiting examples of polymeric materials that can be used to form the substrate according to various non-limiting embodiments disclosed herein are set forth in detail above.

According to other non-limiting embodiments, the photochromic material can be associated with an ophthalmic device of the at least partially photochromic article as part of at least one partial coating associated with the at least partially ophthalmic device. Further, the photochromic material can be incorporated into at least a portion of the coating composition prior to application of the coating composition to the ophthalmic device, or alternatively, the coating composition can be applied to the substrate for at least partial disposal (set), after which the photochromic material can be impregnated into at least a portion of the coating layer. As used herein, the terms "disposing (set)" and "disposing" include, but are not limited to, curing, polymerizing, crosslinking, cooling, and drying.

For example, in one non-limiting embodiment of the present disclosure, an ophthalmic device can comprise an at least partial coating of a polymeric material attached to at least a portion of its surface. According to this non-limiting embodiment, the photochromic material can be mixed with or bonded to the at least partially polymeric material of the at least partially coating layer. According to a specific, non-limiting embodiment, the photochromic material may be polymerized with the at least partially polymeric material of the at least partial coating.

At least a partial coating containing a photochromic material can be directly associated with an ophthalmic device, for example, by directly applying a coating composition comprising a photochromic material to at least a portion of the surface of the ophthalmic device and at least partially treating the coating composition. Additionally or alternatively, at least a partial coating comprising a photochromic material may be attached to the ophthalmic device, for example, by one or more additional coatings. For example, and without limitation, according to various non-limiting embodiments, an additional coating composition may be applied to at least a portion of the surface of the ophthalmic device, at least partially disposed, after which a coating composition comprising a photochromic material may be applied over the additional coating and at least partially disposed.

Non-limiting examples of additional coatings and films that can be used in connection with the ophthalmic devices disclosed herein include commonly used photochromic coatings and films; ophthalmically compatible coatings include clearcoats, hydrophilic coatings, combinations thereof; and the like.

Non-limiting examples of commonly used photochromic coatings and films include, but are not limited to, coatings and films comprising commonly used photochromic materials.

The present disclosure also contemplates various methods of making ophthalmic devices comprising photochromic materials attached to at least a portion of an ophthalmic device, according to various non-limiting embodiments disclosed herein. For example, in one non-limiting embodiment, associating the photochromic material with at least a portion of the ophthalmic device can include mixing the photochromic material with at least a portion of the polymeric material used to form the ophthalmic device. In another non-limiting embodiment, coupling the photochromic material to at least a portion of the ophthalmic device can include bonding the photochromic material to at least a portion of the polymeric material of the ophthalmic device. For example, in one non-limiting embodiment, associating the photochromic material with at least a portion of the ophthalmic device can include copolymerizing the photochromic material with at least a portion of the polymeric material used to form the ophthalmic device. Non-limiting methods of coupling the photochromic material to the polymeric material include, for example, mixing the photochromic material into a solution or melt of the polymeric, oligomeric, or monomeric material, followed by at least partial disposal of the polymeric, oligomeric, or monomeric material. It will be appreciated by those skilled in the art that, according to this non-limiting embodiment, the photochromic materials can be mixed with (i.e., mixed rather than bonded to) or bonded to the polymeric materials in the resulting photochromic composition. For example, if the photochromic material comprises polymerizable groups, i.e., is compatible with polymeric, oligomeric, or monomeric materials, then upon disposal of the organic material, the photochromic material may at least partially react therewith, thereby bonding to the photochromic material.

In another non-limiting embodiment, associating the photochromic material with at least a portion of the ophthalmic device can include impregnating the photochromic material with at least a portion of the polymeric material of the ophthalmic device. According to this non-limiting embodiment, the photochromic material can be dispersed in the polymeric material, for example, by dipping the ophthalmic device comprising the polymeric material in a solution comprising the photochromic material, with or without heating. In another non-limiting embodiment, associating the photochromic material with at least a portion of the ophthalmic device can include a combination of two or more of mixing, bonding (e.g., copolymerizing), and impregnating the photochromic material into/with the polymeric material of at least a portion of the ophthalmic device.

According to one non-limiting embodiment of the method of the present invention, wherein the substrate comprises a polymeric material, and mixing the photochromic material with at least a portion of the substrate comprises an in-situ casting process. According to this non-limiting embodiment, the photochromic materials can be mixed with a polymeric solution or melt, or other oligomeric and/or monomeric solution or mixture, and these are then placed into a mold having the desired shape, at least partially disposed of, to form the ophthalmic device. Further, according to this non-limiting embodiment, the photochromic material may be bonded to the polymeric material, although this is not required.

According to another non-limiting embodiment of the method of the present invention, wherein the ophthalmic device comprises a polymeric material, and attaching the photochromic material to at least a portion of the ophthalmic device comprises in-mold casting. According to this non-limiting embodiment, a coating composition comprising a photochromic material (which may be a liquid coating composition) is applied to the surface of the mold and at least partially disposed. Thereafter, a polymer solution or melt, or an oligomeric or monomeric solution or mixture is cast over the coating and at least partially disposed of. After disposal, the coated ophthalmic device is removed from the mold.

According to another non-limiting embodiment of the method of the present invention, associating the photochromic material with at least a portion of the ophthalmic device comprises applying at least a partial coating comprising the photochromic material to at least a portion of the ophthalmic device. Non-limiting examples of suitable coating methods include dip coating, spin coating, spray coating (e.g., using a liquid coating), curtain coating, roll coating, spin and spray coating, over-molding, and the like. For example, according to one non-limiting embodiment, the photochromic material can be attached to the ophthalmic device by overmolding. According to this non-limiting embodiment, a coating composition comprising a photochromic material (which may be a liquid coating composition) is applied to a mold, and then an ophthalmic device is placed into the mold such that the ophthalmic device contacts the coating, causing the coating to coat at least a portion of the surface of the ophthalmic device. Thereafter, the coating composition is at least partially disposed of and the coated ophthalmic device is removed from the mold. Alternatively, the overmolding may be accomplished by placing the ophthalmic device into a mold such that an open area exists between the ophthalmic device and the mold, and then injecting a coating composition comprising a photochromic material into the open area. Thereafter, the coating composition can be at least partially disposed of and the coated ophthalmic device removed from the mold.

Further, it will be appreciated by those skilled in the art that photochromic compositions, photochromic ophthalmic devices, and photochromic coating compositions prepared according to the various non-limiting embodiments disclosed herein may further comprise other additives that aid in processing and/or performance of the compositions. Such additives are for example, but not limited to, supplemental photochromic materials, photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, for example Hindered Amine Light Stabilizers (HALS)), thermal stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), radical scavengers or adhesion promoters (such as hexanediol diacrylate and coupling agents).

Each photochromic material disclosed herein can be used in an amount (or ratio) such that the ophthalmic device or polymeric material associated with (i.e., mixed, copolymerized, or otherwise bonded and/or impregnated with) the photochromic material exhibits a desired final color, e.g., substantially clear and colorless when the photochromic material is in a closed form and substantially colored when activated by actinic radiation and the photochromic material is in an open form.

The amount of the photochromic naphthopyrans of the present invention associated with or incorporated into the coating composition, polymeric material, ophthalmic device and/or photochromic composition is not critical, provided that a sufficient amount is used to produce the desired effect. Generally, this amount can be described as a "photochromic amount". The specific amount of photochromic material used depends on many factors such as the absorption characteristics of the photochromic material used, the intensity of the color desired by the radiation, and the method used to incorporate or apply the photochromic material.

The relative amounts of the foregoing photochromic materials used in the non-limiting embodiments of the various methods disclosed herein will vary depending in part on and in accordance with the following factors: the relative intensity of the color of the activated species of these materials, the desired final color, the molar absorption coefficient ("extinction coefficient") of the actinic radiation, and the method of application to the polymeric material or substrate. In general, the total amount of photochromic material incorporated into or associated with the polymeric material or ophthalmic device can be from about 0.05 to about 5.0 milligrams per square centimeter of surface into which the photochromic material is incorporated or associated. The amount of photochromic material incorporated into or associated with the coating composition can range from 0.1 to 40 weight percent based on the weight of the liquid coating composition. The amount of photochromic material incorporated, i.e., mixed, copolymerized or bonded with the host polymer photochromic composition or photochromic ophthalmic device, for example by a cast-in-place type process, can be from 0.01 to 40 percent by weight based on the weight of the polymeric composition or photochromic ophthalmic device.

Examples

The following examples illustrate various non-limiting embodiments of the compositions and methods in the present disclosure, but do not limit the invention to that described herein.

Example 1:

step 1

2, 3-dimethoxy-7, 7-dimethyl-7H-benzo [ C ] fluoren-5-ol (10g), 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol (13g), dodecylbenzenesulfonic acid (10 drops), and chloroform (400mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 3 hours and concentrated. Acetone was added to the residue and the slurry was filtered to give 18g of an off-white solid.

Step 2

The 3-phenyl-3- (4-morpholinophenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (20g), 3-piperidinomethane (7.6g) and tetrahydrofuran (250mL) were combined in a dry reaction flask cooled in an ice bath. A solution of butyllithium in hexane (2.5M, 50mL) was added dropwise to the reaction mixture with stirring. After addition the ice bath was removed and the flask was allowed to warm to room temperature. The dark solution was poured into ice water (400mL) and the mixture was extracted with ethyl acetate (twice each 400 mL). The organic layer was washed with saturated aqueous sodium chloride (200mL), dried over sodium sulfate and concentrated. The residue was chromatographed on silica gel (ethyl acetate/hexane (v/v): 1/1.5). The product obtained was an expanded brownish foam (17 g).

Step 3

3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3-hydroxymethylpiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (9g), isocyanatoethyl 2-methacrylate (3mL), dibutyltin laurate (5 drops) and ethyl acetate (200mL) were combined in a reaction flask with a condenser open to the air. The mixture was heated under reflux for 30 minutes. Methanol (15mL) was added to the mixture to quench the excess of isocyanatoethyl 2-methacrylate. The reaction mixture was concentrated, and the residue was purified by silica gel chromatography (ethyl acetate/hexane (v/v): 1/1). The product obtained was an expanded purple foam (11 g). Nuclear magnetic resonance spectroscopy ("NMR") supported a mixture of 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2-methacryloyloxyethyl) carbamoyloxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 2:

step 1

The procedure is followed in step 2 of example 1, except that 4-hydroxypiperidine is used instead of 3-piperidinomethanol. The product obtained is an off-white crystal.

Step 2

The procedure is followed in step 3 of example 1, except that the mixture is purified by eluting 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4-hydroxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 1) in place of 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3-hydroxymethylpiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained is purplish crystals. Mass spectrometry supports a mixture of 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': molecular weight of 3, 4] naphtho [1, 2-b ] pyran.

Example 3:

step 1

The procedure is followed in step 2 of example 1, except that piperazine is used instead of 3-piperidinomethane. The product obtained is purplish crystals.

Step 2

Reacting the 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4-piperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (10g), isocyanatoethyl 2-methacrylate (3mL) and ethyl acetate (150mL) were combined in a dry reaction flask open to the air. The mixture was stirred at room temperature for 20 minutes. Methanol (5mL) was added to the mixture to quench the excess of isocyanatoethyl 2-methacrylate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexane (v/v): 1/1). After chromatography, the product was crystallized from ethyl acetate/hexane (v/v: 1/1) and filtered to give purple crystals (10 g). Mass spectrometry supports that 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': molecular weight of 3, 4] naphtho [1, 2-b ] pyran.

Example 4:

step 1

4-hydroxybenzophenone (100g), 2-chloroethanol (50g), sodium hydroxide (20g) and water (500mL) were combined in a reaction flask. The mixture was heated under reflux for 6 hours. The oil layer was separated, crystallized by cooling, washed with aqueous sodium hydroxide followed by water, and dried to yield 85g of an off-white solid. The product was used without further purification.

Step 2

The 4- (2-hydroxyethoxy) benzophenone obtained in step 1 (30g) was dissolved in anhydrous dimethylformamide (250mL) in a reaction flask with overhead stirring. A slurry of sodium acetylene in toluene (15g) was added to the reaction flask with vigorous stirring. After completion of the reaction, the mixture was added to water (500mL), and the solution was extracted with ether (twice each with 500 mL). The organic layers were combined, washed with saturated aqueous sodium chloride solution and dried over sodium sulfate. The solution was then filtered and concentrated, and the dark residue was purified by chromatography on silica gel (ethyl acetate/hexane (v/v): 1/1). The product was obtained as a white solid (33 g).

Step 3

The procedure of step 1 of example 1 was followed, except that 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol (from step 2) was used in place of 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol. After chromatography, the product was precipitated from ethyl acetate/hexane (v/v: 1/1) and filtered to give a yellowish solid.

Step 4

The procedure of step 2 of example 1 was followed except that the mixture was purified by distillation using 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 3) instead of 3-phenyl-3- (4-morpholinophenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran, and piperidine instead of 3-piperidinomethane. The product obtained was a dark green expanded foam.

Step 5

The procedure of step 3 of example 1 was followed except that the mixture was purified by washing with 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 4) in place of 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3-hydroxymethylpiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained was a yellowish expanded foam. Mass spectrometry supported that 3-phenyl-3- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethoxy) phenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': molecular weight of 3, 4] naphtho [1, 2-b ] pyran.

Example 5:

step 1

4-Fluorobenzophenone (30g), piperazine (23g), triethylamine (23mL), potassium carbonate (22g) and dimethylsulfoxide (50mL) were combined in a reaction flask, and the mixture was heated under reflux conditions for 20 hours. After this time, the mixture was cooled and poured into water, the slurry was extracted with chloroform, the chloroform phase was washed twice with water and dried over sodium sulfate. The solution was concentrated to 45g of orange solid. The product was used without further purification.

The 4-piperazinobenzophenone obtained in step 1 was dissolved in dimethylformamide (50mL) in a reaction flask, and an excess of sodium acetylene (9% by weight in toluene) was added in portions. After completion of the reaction, the mixture was poured into water, and then the mixture was extracted with ethyl acetate, and the organic layer was dried over sodium sulfate. The solution was filtered and concentrated. The residue was chromatographed on silica gel (ethyl acetate/methanol (v/v): 1/1) to give 17g of a yellow solid.

Step 3

The procedure of step 1 of example 1 was followed, except for using 3, 9-dimethoxy-7, 7-dimethyl-7H-benzo [ C ] -fluoren-5-ol in place of 2, 3-dimethoxy-7, 7-dimethyl-7H-benzo [ C ] -fluoren-5-ol and 1-phenyl-1- (4-piperazinophenyl) -2-propyn-1-ol in place of 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol. After chromatography, the product was precipitated from acetone/methanol (v/v: 1/1) and filtered as a greenish solid.

Step 4

Reacting the phenyl-3- (4-piperazinophenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (1g), isocyanatoethyl 2-methacrylate (1.5mL) and ethyl acetate (30mL) were combined in a dry reaction flask. The mixture was stirred at room temperature for 1 hour. Methanol (5mL) was added to quench the excess of isocyanatoethyl 2-methacrylate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexane (v/v): 1/1). The product was obtained as a green expanded foam. Mass spectrometry supported that 3-phenyl-3- (4- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) phenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': molecular weight of 3, 4] naphtho [1, 2-b ] pyran.

Example 6:

step 1

4-Fluorobenzophenone (20g) and 1- (2-hydroxyethyl) piperazine (40g) were heated in 200ml DMSO to 160 ℃ for 3 hours. The mixture was poured into water (1L) and the solid collected by filtration. The solid was washed with water, dried, slurried in hexane and dried again. An off-white solid (25g) was used without further purification.

Step 2

The 4- (4- (2-hydroxyethyl) piperazin-1-yl) -benzophenone (25g) obtained in step 1 was dissolved in dimethylformamide (50mL) in a reaction flask and an excess of sodium acetylene (9 wt% solution in toluene) was added in portions. After completion of the reaction, the mixture was poured into water and 20g of white solid was filtered off.

Step 3

The procedure is followed as in step 2 of example 1, except that 7, 7-dimethyl-7H-benzo [ C ] fluoren-5-ol is replaced with 7, 7-dimethyl-7H-benzo [ C ] fluoren-5-ol, and 1-phenyl-1- (4- (4- (2-hydroxyethylpiperazin-1-yl) phenyl) -2-propyn-1-ol (from step 2) was used instead of 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol the product was isolated by column chromatography, diluted with ethyl acetate/methanol 80/20(v/v) and crystallized from methanol to give an off-white solid.

Step 4

The procedure of step 3 of example 1 was followed except that the mixture was purified by eluting 3-phenyl-3- (4- (4- (2-hydroxyethyl) piperazin-1-yl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 3) in place of 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3-hydroxymethylpiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. Continuous chromatography with chloroform/methanol 90/10(v/v), and with ethyl acetate/methanol 95/5(v/v) gave pure oil which was isolated as a purple-colored expanded foam. Mass spectrometry supported that 3-phenyl-3- (4- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethyl) piperazin-1-yl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': molecular weight of 3, 4] naphtho [1, 2-b ] pyran.

Example 7:

step 1

The procedure of step 1 of example 1 was followed, except that 1-phenyl-1- (4-morpholinophenyl) -2-propyn-1-ol was replaced with 1-phenyl-1- (4-methoxyphenyl) -2-propyn-1-ol. The product obtained is an off-white crystal.

Step 2

The procedure is followed in step 2 of example 1, except that 3-phenyl-3- (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 1) instead of 3-phenyl-3- (4-morpholinophenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran, and 4-hydroxypiperidine instead of 3-piperidinemethanol. After chromatography, the product was crystallized from ether/methanol/hexane (1/1/1) to give yellowish crystals.

Step 3

Reacting the 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4-hydroxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (1g), succinic anhydride (0.3g), triethylamine (0.5mL) and toluene (20mL) were combined in a dry reaction flask. The mixture was heated under reflux for 7 hours. Water (50mL) was added to the solution and the mixture was partitioned. The toluene layer was washed with a saturated aqueous sodium chloride solution and dried over sodium sulfate. The solution was concentrated and the residue purified by silica gel chromatography (ethyl acetate/hexane (v/v): 2/1) to give 1.2g of an expanded yellowish foam.

Reacting the 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-hydroxycarbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (1.2g), polyethylene glycol methacrylate (average molecular weight 360, 1mL), dicyclohexylcarbodiimide (0.7g), 4- (dimethylamino) -pyridine (0.4g), and methylene chloride (10mL) were combined in a dry reaction flask. The mixture was heated under reflux for 5 hours and filtered. The solution was concentrated, and the residue was purified by silica gel chromatography (ethyl acetate/hexane (v/v): 1/1) to give 1.8g of an oily mixture. MS indicates that the major component has 5 to 8 ethoxy groups in the polyethylene glycol chain, including the compound 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2- (2- (2- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 8:

step 1

The procedure is followed in step 3 of example 7, except that the mixture is purified by washing with 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (3-hydroxymethylmethylpiperidin) -1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (step 2 from example 1) instead of 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4-hydroxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained was an expanded foam with a purple color.

Step 2

The procedure of step 4 of example 7 was followed except that the mixture was purified by eluting 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-hydroxycarbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 1) instead of 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-hydroxycarbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained was an oily mixture. Mass spectrometry showed that the major component had 5 to 8 ethoxy groups in the ethylene glycol chain, including 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2- (2- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 9:

step 1

The procedure is as in step 4 of example 4, except that morpholine is used instead of 3-piperidine. After chromatography, the product was recrystallized from t-butyl methyl ether/hexane (2/1) to give off-white crystals.

Step 2

The procedure of step 3 of example 7 was followed except that the mixture was purified by eluting 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-7-morpholino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 1) in place of 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4-hydroxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained was a brown expanded foam.

Step 3

The procedure of step 4 of example 7 was followed except that the mixture was purified by distillation using 3-phenyl-3- (4- (2- (2-hydroxycarbonylethyl) carboxy) phenyl) -6-methoxy-7-morpholino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran (from step 2) instead of 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-hydroxycarbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans. The product obtained was an oily mixture. Mass spectrometry showed that the major component had 5 to 8 ethoxy groups in the ethylene glycol chain, including 3-phenyl-3- (4- (2- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxyethoxy) phenyl) -6-methoxy-7-morpholino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 10:synthesis of photochromic Polymer test squares and photochromic Performance testing

Photochromic Performance test

The photochromic materials of examples 1-9 were tested for photochromic performance as follows.

Will be calculated to yield 1.5 × 10^-3A quantity of the photochromic material to be tested in a molar solution was added to a flask containing 4 parts of ethoxylated bisphenol a dimethacrylate (BPA2EO DMA), 1 part of poly (ethylene glycol) 600 dimethacrylate, and 0.033 weight percent of a 50 gram monomer mixture of 2, 2' -azobis (2-methylpropanenitrile) (AIBN). The photochromic material is dissolved into the monomer mixture by stirring and gentle heating. After a clear solution was obtained, it was poured into a flat bed mold having internal dimensions of 2.2mm by 6 inches (15.24 Cm). Sealing the mold, placing it in a horizontal air stream, and programming the oven to raise the temperature from 40 ℃ to 95 ℃ over a 5 hour interval, maintaining the temperature at 95 ℃ for 3 hoursAnd then cooled to 60 ℃ for at least 2 hours. After this time, the photochromic dye having a methacrylic acid end is copolymerized into a flake. After opening the mold, the polymer sheet was cut into 2 inch (5.1Cm) test squares with a diamond plate saw.

Photochromic test squares prepared as described above were tested for photochromic response to optical bench (optical bench). The photochromic test squares were exposed to 365nm uv light for about 15 minutes to convert the photochromic material from the unactivated (or bleached) state to the activated (or colored) state prior to testing on the optical bench and then placed in the oven at 76 c for about 15 minutes to allow the photochromic material to return to the bleached state. The test squares were then cooled to room temperature, exposed to fluorescent room illumination for at least 2 hours, and then left covered (that is, in a dark environment) for at least 2 hours before being tested on an optical bench maintained at 24 ℃. The optical bench was equipped with a 300-watt xenon arc lamp, a remote control shutter, a KG-2 filter, which served as a heat sink for the arc lamp, and a medium density filter. The sample holder with the dice to be tested inserted therein was placed in a water bath maintained at 23 ℃. The collimated beam of light from the tungsten lamp passes through the block at a small angle (about 30) normal to the block. After passing through the dice, the light from the tungsten lamp is directed to a collection sphere (collection sphere) to avoid collecting the scattered light and remixing the beam. Light is directed from the collection sphere through a fiber optic cable to an Ocean Optics S2000 spectrometer, the resulting spectrum being measured at the maximum visible lambda ("lambda") of the photochromic material to be tested_max-vis") measurement. Lambda [ alpha ]_max-visIs the wavelength in the visible spectrum where the absorption maximum of the activated (colored) form of the photochromic compound in the test square occurs. λ is measured by testing the photochromic test squares in a Variancary4000 UV-visible spectrophotometer_max-visWavelength. The output signal from the detector is processed with a radiometer.

The saturated optical density ("Sat'd OD") of each test square was tested by opening the shutter from the xenon lamp and measuring the transmittance after exposing the test sheet to UV radiation for 30 minutes. To test thisType of dye to set the xenon radiation to 1W/m²However, in some cases, 3W/m is also used²Power setting of (1). The irradiance is adjusted by changing the neutral color filter at the light source and by adjusting the lamp output. First fade half life ("T)_1/2") is the time interval in seconds at room temperature (24 ℃) at which the activated form of the photochromic material in the test square reaches an absorbance of one-half the Sat'd OD absorbance value after removal of the activating light source. The results of the photochromic materials tested are listed in table 1 below.

Table 1: photochromic test data

Testing under 3W radiation

Example 11

Under nitrogen atmosphere, about 100mg of the following mixture: 91% (wt) 2-hydroxyethyl methacrylate, 2.2% methacrylic acid, 0.83% ethylene glycol dimethacrylate, 0.1% trimethylolpropane trimethacrylate, 0.55% 2, 2' -azobisisobutyronitrile and 0.5% CGI819 (bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide photoinitiator, commercially available from Ciba specialty Chemicals), and 5.25% of the photochromic compound prepared in example 2, combined with Glucam E-20 diluent (poly (oxy-1, 2-ethanediyl), alpha-hydro-omega-hydroxy-, ether, and methyl D-glucopyranoside, average MW1074 g/mole, commercially available from chemron corporation, at a ratio of 50 parts by weight) to give 50 parts by weight of reactive monomer, and placed in the mold for each positive curve. The back curve mold was placed on the front curve mold and the lens was formed by curing the mixture under visible light from a fluorescent light bulb (Philips TLK03/40W) at about 50 ℃ for about 20 minutes. The mold was removed from the light and placed in an oven heated to 70 ℃ for about 3 hours. Removing from ovenThe mold, while still hot, opens quickly. By impregnating the lenses with 0.16% by weight disodium EDTA and 0.02% by weight at about 70 ℃80 (polyoxyethylene (20) sorbitan monooleate, commercially available from aldrich chemicals) for about 30 minutes in water to remove the lens from the mold. The lenses were rinsed in borate buffered saline. The final lens shape is uniform.

It is to be understood that this description illustrates only some aspects of the invention relevant to a clear understanding of the invention. Certain aspects that would be apparent to those of ordinary skill in the art, and that, therefore, would not facilitate a better understanding of the invention, have not been presented in order to simplify the present description. While the invention has been described in connection with certain embodiments, the invention is not to be limited to the specific embodiments disclosed, and it is intended to cover modifications within the spirit and scope of the invention, as defined by the appended claims.

Claims (22)

1. A photochromic ophthalmic device comprising a photochromic material, the photochromic material comprising: photochromic naphthopyrans; and at least one reactive substituent bonded to the photochromic naphthopyran, wherein each reactive substituent is independently represented by-D-E-G-J,

wherein:

(i) each-D-is independentlyWherein the nitrogen of the piperidine ring in each D group is substituted withPhotochromic naphthopyrans are bonded and the oxygen of each D group is bonded to-E-or-G-, or the nitrogen of the piperidine ring in each D group is bonded to-E-or-G-, and the oxygen of each D group is bonded to photochromic naphthopyrans;

(ii) each-E-is independentlyWherein the first carbonyl group of each E group is bonded to-D-and the second carbonyl group of each E group is bonded to-G-;

(iii) each-G-is independently- [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x =4-8, y =0 and z =0, wherein the first polyol oxygen of each G group is bonded to-E-or-D-and the second polyol oxygen of each G group is bonded to-J; and

(iv) each-J is independently acryloyl, crotonyl, methacryloyl, 2- (methacryloyloxy) ethylcarbamoyl, or 2- (methacryloyloxy) ethoxycarbonyl.

2. The ophthalmic device of claim 1 wherein the photochromic naphthopyran is a 2H-naphtho [1, 2-b ] pyran, a 3H-naphtho [2, 1-b ] pyran, an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran, indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyran or mixtures thereof.

3. The ophthalmic device of claim 1 wherein the photochromic material is purified by recrystallization.

4. An ophthalmic device comprising at least one photochromic material represented by the formula:

PC-[R]_r

wherein

(a) The PC comprises a photochromic naphthopyran, wherein said photochromic naphthopyran is a 2H-naphtho [1, 2-b ] pyran, a 3H-naphtho [2, 1-b ] pyran, an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran, indeno [1 ', 2': 4, 3] naphtho [2, 1-b ] pyran, or mixtures thereof;

(b) r is an integer from 1 to 4; and

(c) each R group is a reactive substituent independently represented by-D-E-G-J,

wherein:

(i) each-D-is independentlyWherein the nitrogen of the piperidine ring in each D group is bonded to the photochromic naphthopyran and the oxygen of each D group is bonded to-E-or-G-or the nitrogen of the piperidine ring in each D group is bonded to-E-or-G-and the oxygen of each D group is bonded to the photochromic naphthopyran;

(ii) each-E-is independentlyWherein the first carbonyl group of each E group is bonded to-D-and the second carbonyl group of each E group is bonded to-G-;

(iii) each-G-is independently- [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x =4-8, y =0 and z =0, wherein the first polyol oxygen of each G group is bonded to-E-or-D-and the second polyol oxygen of each G group is bonded to-J; and

(iv) each-J is independently acryloyl, crotonyl, methacryloyl, 2- (methacryloyloxy) ethylcarbamoyl, or 2- (methacryloyloxy) ethoxycarbonyl.

5. The ophthalmic device of claim 4, wherein r is 1 or 2.

6. An ophthalmic device comprising at least one photochromic material represented by the formula:

or a mixture thereof, wherein,

(a)R₁the method comprises the following steps: a reactive substituent R, wherein the reactive substituent R is represented by-D-E-G-J,

wherein-D-, -E-and-G-are each as defined in claim 1; and is

-J is acryloyl, methacryloyl, crotonyl, 2- (methacryloyloxy) ethylcarbamoyl or 2- (methacryloyloxy) ethoxycarbonyl;

or R₁Is hydrogen; a hydroxyl group; c₁-C₃An alkyl group; OR a group-C (= O) W, wherein W is-OR₇、-N(R₈)R₉Piperidino or morpholino wherein R₇Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C substituted by chlorine or fluorine₁-C₆An alkyl group; r₈And R₉Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

(b)R₁' is: a reactive substituent R; hydrogen; a hydroxyl group; c₁-C₃An alkyl group; OR a group-C (= O) W, wherein W is-OR₇、-N(R₈)R₉Piperidino or morpholino wherein R₇Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl group (C₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C substituted by chlorine or fluorine₁-C₆An alkyl group; and R is₈And R₉Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein said phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

(c)R₂is a reactive substituent R; hydrogen; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substituted or unsubstituted phenyl; OR-OR₁₀(ii) a or-OC (= O) R₁₀Wherein R is₁₀Is hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl, (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, and the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

(d) n is an integer of 0 to 4, wherein R₃And R₄Independently in each case:

a reactive substituent R;

hydrogen;

fluorine;

chlorine;

C₁-C₆an alkyl group;

C₃-C₇a cycloalkyl group;

substituted or unsubstituted phenyl;

-OR₁₀(ii) a or-OC (= O) R₁₀，

Wherein R is₁₀Is hydrogen, C₁-C₆Alkyl, benzeneRadical (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl, (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, and the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group;

a mono-substituted phenyl group, which is substituted,

the phenyl group has a substituent at the para-position, wherein the substituent is: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-、-(CH₂)_t-or- [ O- (CH)₂)_t]_k-, where t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material;

-N(R₁₁)R₁₂，

wherein R is₁₁And R₁₂Each independently is hydrogen, C₁-C₈Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈Alkylaryl group, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl in which the aryl radical is phenyl or naphthyl, or

R₁₁And R₁₂Together with nitrogen atoms to form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A hetero-tricycloalkyl ring;

a nitrogen-containing ring represented by the following structural formula VA:

wherein each-Y-is independently selected at each occurrence from-CH₂-、-CH(R₁₃)-、-C(R₁₃)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃) (aryl) -, Z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃) -or-N (aryl) -, wherein each R is₁₃Independently is C₁-C₆Alkyl, each aryl is independently phenyl or naphthyl, m is an integer of 1, 2 or 3, p is an integer of 0,1, 2 or 3, and when p is 0, Z is-Y-;

a group represented by one of the following structural formulae VB or VC:

wherein R is₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₆Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms,

each R₁₄In each case independently C₁-C₆Alkyl radical, C₁-C₆Alkoxy, fluorine or chlorine, p is the integer 0,1, 2 or 3; and

unsubstituted, mono-or di-substituted C₄-C₁₈Spirobicyclic amines, or unsubstituted, mono-or di-substituted C₄-C₁₈(ii) a spirotricyclic amine,

wherein said substituents are independently aryl, C₁-C₆Alkyl radical, C₁-C₆Alkoxy or phenyl (C)₁-C₆) An alkyl group; or

R in the 6-position₃Radicals and R in the 7-position₃The groups together form a group represented by one of VD and VE:

wherein T and T' are each independently oxygen or a group-NR₁₁-, wherein R₁₁、R₁₅And R₁₆As described above;

(e)R₅and R₆Each independently is:

a reactive substituent R;

hydrogen;

a hydroxyl group;

C₁-C₆an alkyl group;

C₃-C₇a cycloalkyl group;

an allyl group;

substituted or unsubstituted phenyl;

substituted or unsubstituted benzyl;

chlorine;

fluorine;

-C(=O)W′，

wherein W' is hydrogen, hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aromatic phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino radical, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino;

-OR₁₈，

wherein R is₁₈Is C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl, mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl radical, C₁-C₆Chloroalkyl, C₁-C₆Fluoroalkyl, allyl, or the radical-CH (R)₁₉)Y′，

Wherein R is₁₉Is hydrogen or C₁-C₃Alkyl, and Y' is CN, CF₃Or COOR₂₀，

Wherein R is₂₀Is hydrogen or C₁-C₃Alkyl or

R₁₈Is a group-C (= O) W ",

wherein W' is hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aromatic phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkyl-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino radical, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino, in which the phenyl, benzyl or aryl substituents are each independently

C₁-C₆Alkyl or C₁-C₆An alkoxy group; or

Mono-substituted phenyl having a substituent in the para position selected from the group consisting of a dicarboxylic acid residue or derivative thereof, a diamine residue or derivative thereof, an amino alcohol residue or derivative thereof, a polyol residue or derivative thereof, -CH₂-、-(CH₂)_tOr- [ O- (CH)₂)_t]_k-，

Wherein t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material; or R₅And R₆Together form an oxo group, a spirocarbocyclic group containing 3 to 6 carbon atoms, or a spiroheterocyclic group containing 1 to 2 oxygen atoms and 3 to 6 carbon atoms including a spirocarbon atom, said spirocarbocyclic and spiroheterocyclic groups being annelated with 0,1 or 2 benzene rings; and

(f) b and B' are each independently:

a substituted aryl group;

a substituted heteroaromatic group selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl,

wherein the aryl or heteroaromatic substituent is a reactive substituent R; unsubstituted, mono-, di-or tri-substituted aryl; 9-julolidinyl; or an unsubstituted, mono-or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl,

wherein each substituent on the mono-, di-or tri-substituted aryl group and each of the mono-or di-substituted heteroaromatic substituents is independently:

hydroxy, group-C (= O) R₂₁Wherein R is₂₁is-OR₂₂、-N(R₂₃)R₂₄A piperidino group or a morpholino group,

wherein R is₂₂Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl or C substituted by chlorine or fluorine₁-C₆An alkyl group, a carboxyl group,

R₂₃and R₂₄Each independently is

C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl or substituted phenyl,

the phenyl substituent being C₁-C₆Alkyl or C₁-C₆Alkoxy, arylBase, mono (C)₁-C₁₂) Alkoxyaryl, di (C)₁-C₁₂) Alkoxyaryl, mono (C)₁-C₁₂) Alkylaryl, di (C)₁-C₁₂) Alkylaryl, aryl substituted by chlorine or fluorine, C₃-C₇Cycloalkyl aryl, C₃-C₇Cycloalkyl radical, C₃-C₇Cycloalkoxy, C₃-C₇Cycloalkoxy (C)₁-C₁₂) Alkyl radical, C₃-C₇Cycloalkoxy (C)₁-C₁₂) Alkoxy, aryl (C)₁-C₁₂) Alkyl, aryl (C)₁-C₁₂) Alkoxy, aryloxy (C)₁-C₁₂) Alkyl, aryloxy (C)₁-C₁₂) Alkoxy, mono-or di (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkyl, mono-or di- (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) Alkoxy, mono-or di- (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) Alkoxy, amino, mono-or di- (C)₁-C₁₂) Alkylamino, diarylamino, piperazino, N- (C)₁-C₁₂) Alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidinyl, C₁-C₁₂Alkyl, C substituted by chlorine or fluorine₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, mono (C)₁-C₁₂) Alkoxy (C)₁-C₁₂) Alkyl, acryloxy, methacryloxy or halogen;

unsubstituted or mono-substituted radical selected from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, thiophenylAn oxazinyl group, a phenazinyl group and an acridinyl group,

each said substituent on said mono-substituted group being C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, phenyl or halogen; mono-substituted phenyl having a substituent at the para position selected from the group consisting of: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-、-(CH₂)_tOr- [ O- (CH)₂)_t]_k-，

Wherein t is an integer of 2, 3, 4,5 or 6, k is an integer of 1 to 50, and the substituent is attached to an aryl group on another photochromic material;

a group represented by one of the following structures:

wherein K is-CH₂-or-O-,

m is-O-or substituted nitrogen, with the proviso that when M is substituted nitrogen, K is-CH₂-，

The substituent of the substituted nitrogen being hydrogen, C₁-C₁₂Alkyl or C₁-C₁₂The acyl group,

each R₂₅Independently at each occurrence selected from C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, hydroxy and halogen, and a pharmaceutically acceptable salt thereof,

R₂₆and R₂₇Each independently is hydrogen or C₁-C₁₂Alkyl, u is an integer from 0 to 2; or a group represented by the following structure:

wherein R is₂₈Is hydrogen or C₁-C₁₂Alkyl radical, R₂₉Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl, wherein the substituent is C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy or halogen; or

B and B' together form a fluoren-9-ylidene, mono-or di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene substituents being independently selected from C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy and halogen;

provided that the photochromic material comprises at least one reactive substituent R.

7. The ophthalmic device of claim 6 wherein the photochromic material comprises two reactive substituents R.

8. The ophthalmic device of claim 6, wherein each R is₃Independently a substituent at the 6-or 7-position on formula III or formula IV, said substituents at the 6-and 7-positions each independently being a reactive substituent R; -OR₁₀Wherein R is₁₀Is hydrogen; c₁-C₆An alkyl group; or a nitrogen-containing group, wherein the nitrogen-containing group is:

(i)-N(R₁₁)R₁₂wherein R is₁₁And R₁₂Each independently is hydrogen, C₁-C₈Alkyl, phenyl or C₁-C₂₀Alkoxyalkyl, or

(ii) A nitrogen-containing ring represented by the following structural formula VA:

wherein each Y is independently selected at each occurrence from-CH₂-、-CH(R₁₃)-、-C(R₁₃)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃) (aryl) -, and Z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃) -or-N (aryl) -, wherein each R is₁₃Independently is C₁-C₆Alkyl, each aryl is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer0.1, 2 or 3, and when p is 0, Z is Y.

9. The ophthalmic device of claim 6, wherein R₅And R₆Each independently is a reactive substituent R; c₁-C₆An alkyl group; a hydroxyl group; OR-OR₁₈Wherein R is₁₈Is C₁-C₆An alkyl group.

10. The ophthalmic device of claim 1, wherein said device is formed from at least one polymeric material comprising said photochromic material incorporated into at least a portion of the polymeric material.

11. The ophthalmic device of claim 10, wherein the polymeric material is formed from components comprising a hydrophilic monomer, a hydrophilic polymer, and a silicone component.

12. The ophthalmic device of claim 10 wherein the ophthalmic device is a contact lens and the polymeric material comprises a hydrogel.

13. The ophthalmic device of claim 1, wherein the ophthalmic device is selected from the group consisting of soft contact lenses, hard contact lenses, intraocular lenses, overlay lenses, ocular inserts, and optical inserts.

14. The ophthalmic device of claim 1, wherein the ophthalmic device is a soft contact lens.

15. The ophthalmic device of claim 1, wherein the ophthalmic device comprises a polymeric material and the photochromic material is at least one of: mixed with and bonded to the at least partially polymeric material.

16. The ophthalmic device of claim 15, wherein the photochromic material is bonded to the at least partially polymeric material by copolymerization.

17. An ophthalmic device comprising at least one photochromic material selected from the group consisting of:

(i)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (3- (2-methacryloyloxyethyl) carbamoyloxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(ii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2-methacryloyloxyethyl) carbamoyloxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(iii) 3-phenyl-3- (4- (4-phenylpiperazino) phenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(iv)3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(v)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(vi) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoyloxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(vii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(viii) 3-phenyl-3- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethoxy) phenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(ix) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(x) 3-phenyl-3- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethoxy) phenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xi) 3-phenyl-3- (4- (4- (2-methacryloyloxyethyl) carbamoylpiperazin-1-yl) phenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xii) 3-phenyl-3- (4- (2-methacryloyloxyethyl) carbamoyloxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xiii) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (3- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xiv) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (3- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxymethylenepiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xv) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- (4- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xvi) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- (4- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxypiperidin-1-yl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xvii) 3-phenyl-3- (4- (2- (2- (2- (2- (2-methacryloyloxyethoxy) ethoxy) carbonylethyl) carboxyethoxy) phenyl) -6-methoxy-7-morpholino-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(xviii) 3-phenyl-3- (4- (4- (2- (2-methacryloyloxyethyl) carbamoyloxyethyl) piperazin-1-yl) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

and combinations thereof.

18. The ophthalmic device of claim 10, wherein the ophthalmic device comprises at least one supplemental photochromic material, photoinitiator, thermal initiator, polymerization inhibitor, solvent, light stabilizer, heat stabilizer, mold release agent, rheology control agent, leveling agent, free radical scavenger, adhesion promoter, wetting agent, pharmaceutical agent, antimicrobial compound, reactive colorant, and mixtures thereof.

19. The ophthalmic device of claim 10, wherein the ophthalmic device comprises at least one pigment and a copolymerizable and non-polymerizable dye.

20. The ophthalmic device of claim 1, wherein the ophthalmic device comprises at least one supplemental photochromic material, photoinitiator, thermal initiator, polymerization inhibitor, solvent, light stabilizer, heat stabilizer, mold release agent, rheology control agent, leveling agent, free radical scavenger, adhesion promoter, wetting agent, pharmaceutical agent, antimicrobial compound, reactive colorant, and mixtures thereof.

21. The ophthalmic device of claim 1, wherein the ophthalmic device comprises at least one pigment and a copolymerized and non-polymerizable dye.

22. The ophthalmic device of claim 1, wherein the device is coated with a coating composition comprising a photochromic material.