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Photochromic materials comprising indeno-fused naphthopyrans having a first electron-withdrawing substituent and, in certain non-limiting embodiments, a second electron-withdrawing substituent are disclosed. The photochromic materials according to the various embodiments may display faster fade rate

Photochromic materials comprising indeno-fused naphthopyrans having a first electron-withdrawing substituent and, in certain non-limiting embodiments, a second electron-withdrawing substituent are disclosed. The photochromic materials according to the various embodiments may display faster fade rates, bathochromic shift, and higher performance ratings compared to comparable indeno-fused naphthopyrans without the electron-withdrawing substituents. Photochromic compositions and articles, such as optical elements, incorporating the photochromic materials are also disclosed.

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We claim: 1. A photochromic material representable by the following structure III: wherein R16 is a first electron withdrawing group having a Hammett σp value of from 0.05 to 0.75; R17 is: hydrogen, or a second electron withdrawing group having a Hammett σp value of from 0.05 to 0.75;

We claim: 1. A photochromic material representable by the following structure III: wherein R16 is a first electron withdrawing group having a Hammett σp value of from 0.05 to 0.75; R17 is: hydrogen, or a second electron withdrawing group having a Hammett σp value of from 0.05 to 0.75; q is the integer 0, and s is the integer 0; R19 and R20 are each independently: hydrogen; C1-C6 alkyl; C3-C7 cycloalkyl; allyl; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chloro; fluoro; the group--C(═O)W, wherein W is hydrogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, the unsubstituted, mono-or disubstituted aryl groups phenyl or naphthyl, phenoxy, mono-or di-(C1-C6)alkoxy substituted phenoxy, mono-or di-(C1-C6)alkoxy substituted phenoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, phenylamino, mono-or di-(C1-C6)alkyl substituted phenylamino, or mono-or di-(C1-C6)alkoxy substituted phenylamino; or R19 and R20 together form 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 spirocarbon atom, said spiro-carbocyclic and spiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings, provided that substitution at the carbon to which R19 and R20 are attached does not comprise hydroxyl; and B and B' are each independently an unsubstituted, or substituted aryl group that has at least one pi-bond capable of being in conjugation with the pi-system of the open form of the core indeno-fused naphthopyran structure, provided that substitution at the 13-position of the indeno-fused naphthopyran does not comprise hydroxyl. 2. The photochromic material of claim 1, wherein the first electron withdrawing group R16 is fluoro, chloro, bromo, perfluoroalkyl, perfluoroalkoxy, cyano,--OC(═O)R0, or--C(═O)--X, wherein X is hydrogen, C1-C6 alkyl,--OR1 or--NR2R3, wherein R0 , R1 , R2 and R3 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl, disubstituted phenyl, alkylene glycol, or polyalkylene glycol, wherein said mono-and disubstituted phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy. 3. The photochromic material of claim 1, wherein the second electron withdrawing group R17 is fluoro, chloro, bromo, perfluoroalkyl, perfluoroalkoxy, cyano,--OC(═O)R4, or--C(═O)--X, wherein X is hydrogen, C1-C6 alkyl,--OR5 or--NR6R7, wherein R4, R5, R6 and R7 are each independently hydrogen, C1-C6 alkyl, C1-C7 cycloalkyl, phenyl, mono-substituted phenyl, disubstituted phenyl, alkylene glycol or polyalkylene glycol, wherein said mono-or di-substituted phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy. 4. The photochromic material of claim 1, wherein the first electron withdrawing group R16 and the second electron withdrawing group R17 are each independently fluoro, chloro, bromo, cyano, or--C(═O)--OR8, wherein 8 is C1-C6 alkyl, alkylene glycol or polyalkylene glycol. 5. The photochromic material of claim 4, wherein the first electron-withdrawing group R16 is a fluoro group and the second electron-withdrawing group R17 is a fluoro group. 6. The photochromic material of claim 4 wherein R19 and R20 are geminal C1-C6 dialkyl, wherein the B group is 4-fluorophenyl and the B' group comprises a 4-substituted phenyl, wherein the substituent on the 4-position is--NR10R11, wherein R10 and R11 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein said mono-or di-substituted phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy; or R10 and R11 come together with the nitrogen atom to form a nitrogen containing ring represented by the following graphic formula: wherein each--Y--is independently chosen for each occurrence from--CH2--,--CH(R15)--,--C(R15)2--,--CH(aryl)-,--C(aryl)2-, and--C(R15)(aryl)-, and Z is--Y--,--O--,--S--,--S(O)--,--SO2--,--NH--,--N(R15)--, or--N(aryl)-, wherein each R15 is independently C1-Calkyl or hydroxy(C1-C6)alkyl, each aryl is independently phenyl or naphthyl, m is the integer 1,2 or 3, and p is the integer 0, 1,2,or 3,provided that when p is 0, Z is--Y--. 7. The photochromic material of claim 1, wherein the groups B and B' are each independently phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituents are independently an electron-donating group or a third electron withdrawing group. 8. The photochromic material of claim 7, wherein the groups B and B' are each independently phenyl or 4-substituted phenyl, wherein the substituent on the 4-position of the phenyl is an electron-donating group or a third electron-withdrawing group. 9. The photochromic material of claim 7, wherein at least one of the groups B and B' is a 4-substituted phenyl, wherein the substituent on the 4-position of the phenyl is fluoro or an electron-donating group chosen from C1-C6 alkyl,--OR9 and--NR10R11, wherein R9, R10 and R11 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein said mono-or di-substituted phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy. 10. The photochromic material of claim 8, wherein the substituent on the 4-position of the phenyl is a third electron withdrawing group selected from chloro, bromo, perfluoroalkyl, perfluoroalkoxy, cyano,--OC(═))(═O)Z', or--C(═O)--X', where Z' and X' are each independently hydrogen, C1-C6 alkyl,--OR12 or--NR13, R14 wherein R12, R13, and R14 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl, alkylene glycol or polyalkylene glycol, wherein said mono-and di-substituted phenyl substituents are C1-C6 alkyl or alkoxy. 11. The photochromic material of claim 8, wherein the B group is 4-fluorophenyl and the B' group comprises a 4-substituted phenyl, wherein the substituent on the 4-position is--NR10R11, wherein R10 and R11 are each independently hydrogen, C1-C6 alkyl, C5-C7, cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein said mono-or di-substituted phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy; or R10 and R11 come together with the nitrogen atom to form a nitrogen containing ring represented by the following graphic formula: wherein each--Y--is independently chosen for each occurrence from--CH2--,--C(R15)--,--C(R15)2--,--CH(aryl)-,--C(aryl)2-, and--C(R15)(aryl)-, and Z is--Y--,--O--,--S--,--S(O)--,--SO2--,--NH--,--N(R15)--, or--N(aryl)-, wherein each R15 is independently C1-C6 alkyl or hydroxy(C1-C6)alkyl, each aryl is independently phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, Z is--Y--. 12. The photochromic material of claim 11, wherein B' comprises 4-morpholinophenyl, 4-piperidinophenyl, 4(substituted piperidino)phenyl, 4-pyrrolidinophenyl, 4-(substituted pyrrolidino)phenyl, 4-piperazinophenyl, or 4-(substituted piperazino)phenyl, wherein the substitution may comprise hydroxy(C1-C6)alkyl. 13. The photochromic material of claim 1, further comprising a geminal C1-C6 dialkyl substitution at the 13-position of the indeno-fused naphthopyran. 14. A photochromic article comprising: a substrate; and the photochromic material according to claim 1 connected to at least a portion of the substrate. 15. The photochromic article of claim 14, wherein the substrate comprises a polymeric material and the photochromic material is incorporated into at least a portion of the polymeric material by at least one method of blending the photochromic material with at least a portion of the polymeric material, bonding the photochromic material to at least a portion of the polymeric material, and imbibing the photochromic material into at least a portion of the polymeric material. 16. The photochromic article of claim 14, wherein the photochromic article comprises an at least partial coating connected to at least a portion of the substrates the at least partial coating comprising the photochromic material. 17. A photochromic material representable by the following structure III: wherein R16 is a first electron withdrawing group chosen from fluoro, chloro, bromo, perfluoroalkyl, perfluoroalkoxy, cyano,--OC(═O)R21, or--C(═O)--X, wherein X is hydrogen, C1-C6 alkyl,--OR22, or--NR23R24, wherein R21, R22, R23 and R24 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl, alkylene glycol or polyalkylene glycol, wherein said phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy; R17 is hydrogen, or a second electron withdrawing group chosen from fluoro, chloro, bromo, perfluoroalkyl, perfluoroalkoxy, cyano,--OC(═O)R25 or--C(═O)--X, wherein X is hydrogen, C1-C6 alkyl,--OR26 or--NR27R28, wherein R25, R26, R27 and R28 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl, alkylene glycol or polyalkylene glycol, wherein said phenyl substituents are C1-C6 alkyl or C1-C6 alkoxy; q is the integer 0, and s is the integer 0; R19 and R20 are each independently: hydrogen; C1-C6 alkyl; C3-C7 cycloalkyl; allyl; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chloro; fluoro; the group--C(═O)W, wherein W is hydrogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, the unsubstituted, mono-or di-substituted aryl groups phenyl or naphthyl, phenoxy, mono-or di-(C1-C6) alkoxy substituted phenoxy, amino, mono(C1-C6) alkylamino, di(C1-C6)alkylamino, phenyl amino, mono-or di (C1 -C6)alkyl substituted phenylamino or mono-or di-( C1C6)alkoxy substituted phenylamino; or R19 and R20 together form 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 spirocarbon atom, said spiro-carbocyclic and spiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings, provided that substitution at the carbon to which R19 and R20 are attached does not comprise hydroxyl; and B and B' are each independently: an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9-julolidinyl; or an unsubstituted, mono-or di-substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and fluorenyl, wherein each of the phenyl, aryl and heteroaromatic substituents are each independently: hydroxyl, a group--C(═O)R40, wherein R40 is--OR41,--N(R42)R43, piperidino, or morpholino, wherein R"is allyl, C1-C6 alkyl, phenyl, mono(C1-C6)alkyl substituted phenyl, mono(C1-C6)alkoxy substituted phenyl, phenyl(C1-C3)alkyl, mono(C1-C6)alkyl substituted phenyl(C1-C3)alkyl, mono(C1-C6)alkoxy substituted phenyl(C1-C3)alkyl, C1-C6 alkoxy(C2-C4alkyl or C1-C6 haloalkyl, said halo substituent being chloro or fluoro, R42 and R43 are each independently C1-C6 alkyl, C5-C7 cycloalkyl, phenyl or substituted phenyl, the phenyl substituents being C1-C6 alkyl or C1-C6 alkoxy; an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, each of said substituents being C1-C12 alkyl, C1-C12 alkoxy, phenyl, or halogen; a mono-substituted phenyl, said phenyl having a substituent located at the para position, wherein the substituent is: 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)t--, or--[O--(CH2)t]k--, wherein t is the integer 2, 3, 4, 5 or 6 and k is an integer from 1 to 50, the substituent being connected to an aryl group on another photochromic material; a group represented by one of: wherein K is--CH2--or--O--, and M is--O--or substituted nitrogen, provided that when M is substituted nitrogen, K is--CH2--, the substituted nitrogen substituents being hydrogen, C1-C12 alkyl, or C1-C12 acyl, each R44 being independently chosen for each occurrence from C1-C12 alkyl, C1-C12 alkoxy, hydroxy, and halogen, R45 and R46 each being independently hydrogen or C1-C12 alkyl, and u is an integer ranging from 0 to 2; or B and B' taken together form one of a fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene substituents being independently chosen from C1-C12 alkyl, C1-C12 alkoxy, and halogen, provided that substitution at the 13-position of the indeno-fused naphthopyran does not comprise hydroxyl. 18. The photochromic material of claim 17 that is chosen from: (a) 3,3-di(4-methoxyphenyl)-6,11-difluoro-13,13-dimethyl-3H,13H-indeno[2',3': 3,4]naphtho[1,2-b]pyran; (b) 3-(4-fluorophenyl)-3-(4-methoxyphenyl)-6,11-difluoro-13,13-dimethyl-3H, 13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (c) 3-(4-fluorophenyl)-3-(4-piperidinophenyl)-6,11-difluoro-13,13-dimethyl-3H, 13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (d) 3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,11-difluoro-13, 13-dimethyl-3H-13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (e) 3-(4-fluorophenyl)-3-(4-morpholinophenyl)-6,11-difluoro-13, 13-dimethyl-3H-13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (f) 3-(4-methylphenyl)-3-(4-morpholinophenyl)-6,11-difluoro-13, 13-dimethyl-3H-13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (g) 3-phenyl-3-(4-piperidinophenyl)-6,11-difluoro-13,13-dimethyl-3H,13H-indeno [2',3':3,4]naphthol[1,2-b]pyran; (h) 3-(4-morpholinophenyl)-3-phenyl-6,11-difluoro-13,13-dimethyl-3H,13H-indeno [2',3':3,4]naphtho[1,2-b]pyran; (i) 3-(4-fluorophenyl)-3-(4-methoxyphenyl-6,11-dichloro-13,13-dimethyl-3H, 13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (j) 3,3-di(4-fluorophenyl)-6,11-dichloro-13,13-dimethyl-3H,13H-indeno[2',3':3, 4]naphtho[1,2-b]pyran; (k) 3-phenyl-3-(4-piperidinophenyl)-6,11-dichloro-13,13-dimethyl-3H,13H-indeno [2',3:3,4]naphtho[1,2b]pyran; (l) 3-(4-methoxyphenyl)-3-(5-methylthiophen-2-yl)-6,11-dichloro-13, 13-dimethyl-3H-13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (m) 3,3-di(4-methoxyphenyl)-6,11-dichioro-13,13dimethyl-3H,13H-indeno[2',3':3, 4]naphtho[1,2-b]pyran; (n) 3,3-di(4-fluorophenyl)-6-cyano-13,13-dimethyl-3H,13H-indeno[2',3':3,4] naphtho[1,2b]pyran; (o) 3,3-di(4-fluorophenyl)-6,11-dicyano-13,13-dimethyl-3H,13H-indeno[2',3':3, 4]naphtho[1,2-b]pyran; (p) 3,3-diphenyl-6,11-dicyano-13,13-dimethyl-3H,13H-indeno[2',3':3,4]naphtho1, 2-b]pyran; (q) 3,3-di(4-fluorophenyl)-6-methoxycarbonyl-13,13-dimethyl-3H,13H-indeno[2', 3':3,4]naphtho[1,2-b]pyran; (r) 3,3-di(4-fluorophenyl)-6,11-di(methoxycarbonyl)-13,13-dimethyl-3H, 13H-indeno[2',3':3,4]naphtho[1,2b]pyran; (s) 3,3-di(4-methoxyphenyl)-6,11-di(methoxycarbonyl)-13,13-dimethyl-3H, 13H-indeno[2',3':3,4]naphtho[1,2-b]pyran; (t) 3-(4-morpholinophenyl)-3-phenyl-6-bromo-13,13-dimethyl-3H,13H-indeno[2', 3':3,4] naphtho[1,2b]pyran; (u) 3-(4-methoxyphenyl)-3-phenyl-6-bromo-13,13-dimethyl-3H,13H-indeno[2',3':3, 4] naphtho[1,2-b]pyran; and (v) 3,3-di(4-fluorophenyl)-6,11-difluoro-13,13-dimethyl-3H,13H-indeno[2',3':3, 4]naphtho[1,2-b]pyran. 19. The photochromic material of claim 17, wherein the first electron withdrawing group and the second electron withdrawing group are each independently fluoro, chloro, bromo, cyano, or--C(═O)--OR8, wherein R8 is C1-C6 alkyl, alkylene glycol or polyalkylene glycol. 20. The photochromic material of claim 19, wherein R16 is fluoro; R17 is hydrogen or fluoro; and R19 and R20 are each independently C1-C6 alkyl. 21. The photochromic material of claim 19, wherein the groups B and B' are each independently phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the substituents on the phenyl are independently an electron-donating group or a third electron withdrawing group. 22. The photochromic material of claim 21, wherein the B group is a 4-fluorophenyl and the B' group comprises a 4-Substituted phenyl, wherein the substituent in the 4-position is--NR10R11, wherein R10 and R11 are each independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-Substituted phenyl or di-substituted phenyl, wherein said mono-and di-substituted phenyl substituents are C1-C6alkyl or C1-C6 alkoxy, or R10 and R11 come together with the nitrogen atom to form a nitrogen containing ring represented by the following graphic formula: wherein each--Y--is independently chosen for each occurrence from--CH2--,--CH(R15)--,--C(R15)2--,--CH(aryl)-,--C(aryl)2--, and--C(R15)(aryl)-, and Z is--Y--,--O--,--S--,--S(O)--,--SO2--,--NH--,--N(R15)--, or--N(aryl)-, wherein each R15 is independently C1-C6 alkyl or hydroxy(C1-C6)alkyl, each aryl is independently phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3, provided that when p is 0, Z is--Y--. 23. The photochromic material of claim 22, wherein B' comprises 4-morpholinophenyl, 4-piperidinophenyl, 4-(substituted piperidino)phenyl, 4-pyrrolidinophenyl, 4-(substituted pyrrolidino)phenyl, 4-piperazinophenyl or 4-(substituted piperazino)phenyl, wherein the substitution may comprise hydroxy(C1-C6)alkyl. 24. The photochromic material of claim 22 wherein R19 and R20 are geminal C1-C6 dialkyl substituents. 25. The photochromic material of claim 24, wherein R19 and R2 are methyl.