Photochromic naphthopyran compounds: compositions and articles containing those naphthopyran compounds
View Patent ↗A photochromic naphthopyran displays good color distribution when the naphthopyran has a central nucleus of the formula: wherein F is a 5-member, 6-member, or 7-member heterocyclic ring group having only one heteroatom, the heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen, the 2,3 or 3,2 positions of the heterocyclic ring fused to the g, h, or i side; R 1 and R 2 are the atoms or groups providing photochromic properties to the naphthopyran.
1. A photochromic naphthopyran having a central nucleus of the formula:
wherein F is a dihydrofuran group fused to the g, h, or i side;
R 1 and R 2 are the atoms or groups providing photochromic properties to the naphthopyran.
2. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of aliphatic groups, aromatic groups, and heterocyclic groups.
3. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of alkyl groups, aromatic groups, and heterocyclic groups.
4. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from alkyl groups, phenyl groups, and naphthyl groups.
5. A photochromic naphthopyran having a central nucleus of the formula:
wherein F is a dihydrofuran group fused to the g, h, or i side;
R 1 and R 2 are the atoms or groups providing photochromic properties to the naphthopyran, and the 13-position may be substituted
wherein the 13-position has substituents R 3 and R 4 , wherein R 3 and R 4 individually represent
a hydrogen atom,
a hydroxy group,
a halogen atom,
a linear, branched, or cyclic C1–C6 alkyl, alkenyl, or alkynyl group,
a linear, branched, or cyclic C1–C6 alkoxy or alkenoxy group,
an amino group:
in which R 8 and R 9 , which are the same or different, independently representing a hydrogen, a linear, branched, or cyclic alkyl group comprising 1 to 6 carbon atoms, an aryl or heteroaryl group, or representing (together with the nitrogen atom to which they are bound) a 5- to 7-membered ring which can comprise at least one other heteroatom selected from oxygen, sulfur and nitrogen, said nitrogen being optionally substituted with an R 10 group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, a phenyl, a benzyl, or a naphthyl,
an aryl or heteroaryl group selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, indolyl,
a mono-substituted phenyl having a substituent at the para position that is a linking group, —(CH 2 ) t — or —O—(CH 2 ) t —, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran,
an aralkyl or heteroaralkyl group, the alkyl part of which is linear or branched, comprising 1 to 4 carbon atoms,
a —C(O)R 11 , —OC(O)R 11 , or COOR 11 group, wherein R 11 is hydrogen, hydroxy, linear or branched C1–C6 alkyl, linear or branched C1–C6 alkoxy, phenyl, mono-substituted phenyl, naphthyl, mono-substituted naphthyl, amino, mono(C1–C6) alkylamino or di(C1–C6)alkylamino, e.g., N,N-dimethyl amino, N-methyl-N-propyl amino, morpholino, piperidino or pyrrolidyl, said amino substituents being selected from the group consisting of C1–C6 alkyl, phenyl, benzyl and naphthyl, and said benzyl and phenyl substituents being C1–C6 alkyl or C1–C6 alkoxy,
a group —OR 12 , wherein R 12 is a C1–C6 acyl, an aralkyl or heteroaralkyl group with a C1–C3 alkyl portion, a (C3–C7)cycloalkyl group, a (C2–C4)alkyl group, or R 12 is the group, —CH(R 13 )R 14 , wherein R 13 is hydrogen or C1–C3 alkyl and R 14 is —CN, —CF 3 , or —COOR 15 , wherein R 15 is hydrogen or linear, branched, or cyclic alkyl, aralkyl or heteroaralkyl,
a group —CH(R 16 ) 2 wherein R 16 is —CN or —COOR 15 ,
a group CH(R 15 )R 17 , wherein R 17 is —COOR 11 , —C(O)R 18 or —CH 2 OR 19 , wherein R 18 is hydrogen, linear, branched, or cyclo-alkyl, aryl groups, amino group of formula
R 19 is hydrogen, —C(O)R 11 , alkyl, alkoxyalkyl, phenylalkyl, mono-alkoxy substituted phenyl-alkyl, or aryl groups,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea, polyester residue, or a group ended by a polymerizable residue;
or R 3 and R 4 may together form a 3- to 7-member spiro-cyclic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen.
6. The photochromic naphthopyran of claim 5 wherein, (a) in the 5- and/or 8-position, a group R 6 is present wherein R 6 represents
a hydrogen,
a halogen, a linear or branched alkyl group which comprises 1 to 12 carbon,
a cycloalkyl group comprising 3 to 12 carbon atoms, a linear or branched alkoxy group comprising 1 to 12 carbon atoms,
a haloalkyl, halocycloalkyl, or haloalkoxy group corresponding to the alkyl, cycloalkyl, alkoxy groups above respectively, which are substituted with at least one halogen atom,
a linear or branched alkenyl or alkynyl group comprising 1–12 carbon atoms,
a linear or branched alkenoxy or alkynoxy group comprising 1–12 carbon atoms,
an aryl or heteroaryl group having the same definition as that given above for aryl or heteroaryl groups within the definitions of R 3 , R 4 ,
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the same definitions as those given above for R 3 , R 4 ,
an amine or amide group: —NH 2 , —NHR 8 , —CONH 2 , —CONHR 8 ,
R 8 , and R 9 having their respective definitions given for the amine substituents of the values R 3 , R 4 ,
a —C(R 15 ) 2 R 11, —OCOR 15 , or COOR 15 group, wherein R 11 and R 15 are defined supra in R 3 and R 4 , a methacryloyl group or an acryloyl group,
an epoxy group having the formula,
in which q=1, 2 or 3,
a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue, or a group with polymerizable residue,
(b) in the 9-, 10-, 11-,and 12-positions there are at most 4 R 5 groups, each being the same as R 6 , defined hereinbefore; or
(c) two adjacent R 5 together form a 5- to 7-member aromatic or non-aromatic ring which can comprise at least one heteroatom selected from oxygen, sulfur, and nitrogen, and/or at least one substituent selected from the group consisting of a C1 to C6 alkyl group which is linear, branched, or cyclic, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula —NH 2 , NHR 8 , or
as defined in R 3 and R 4 for amine groups, said aromatic or non-aromatic ring can be optionally annelated with a benzene group.
7. The photochromic naphthopyran of claim 6 wherein R 1 and/or R 2 represent a para-substituted phenyl group, said substituents on the para-substituted phenyl group selected from hydrogen, alkyl, alkoxy, dialkylamino, diarylamino, or R 1 and R 2 together form an adamantyl group or norbornyl group or anthracenylidene group.
8. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 1 .
9. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran comprising 3-phenyl-3-4-methoxyphenyl)-13,13-diethyl-3H-(4,5-dihydrofurano[2,3-b]-indeno[3,2-f]-naphtho)[1,2-b]pyran.
10. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 3 .
11. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 4 .
12. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 5 .
13. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 6 .
14. A photochromic article comprising a polymeric layer containing a photochromic amount of a photochromic naphthopyran according to claim 7 .