Photochromic benzodioxine fused naphthopyran compounds, compositions and articles containing those naphthopyran compounds
View Patent ↗Benzodioxino-naphtho[1,2-b]pyran compounds having particularly advantageous photochromic properties, such as, high sensitivity/coloration, two distinct absorption bands in the 430-500 nm range and 520-620 nm range of the visible spectrum may be generally described as a naphthopyran having a central nucleus of the formula: wherein F is a 1,4-benzodioxine ring with its 2,3 positions fused to the i, j, or k faces; and 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 1,4-benzodioxine ring having the following graphic formulae:
with its 2,3 positions fused to the i, j, or k side;
R 1 and R 2 are atoms or groups providing photochromic properties to the naphthopyran.
2. The photochromic naphthopyran of claim 1 , characterized in that it has the following structure:
wherein,
R 1 and/or R 2 , independently represent optionally substituted aryl or heteroaryl groups the basic structure of which is selected from those of phenyl, naphthyl, biphenyl, pyridyl, furyl, benzofuryl, dibenzofuryl, N—(C 1 -C 6 )alkylcarbazole, thienyl, benzothienyl, dibenzothienyl, julolidinyl groups; R 1 and/or R 2 representing a para-substituted phenyl group, said substituents of the phenyl group are selected from the group consisting of alkoxy, dialkylamino, diarylamino, or R 1 and R 2 together form an adamantyl group or norbornyl group or anthracenylidene group; either R 1 or R 2 is mono- or di-substituted phenyl which is substituted in the position para to the connection side with -phenyl, —(CH2) p -phenyl or —O—(CH2) p -phenyl substituted, wherein p is an integer from 1 to 6, and the ring of the substituent group forms part of a second photochromic pyran;
R 5 and R 6 are the same or different, and may represent independently
a hydrogen,
a linear or branched alkyl group that comprises 1 to 6 carbon atoms,
a —C(R 14 ) 2 X group, wherein X is hydroxy, alkoxy, benzoyloxy, C 1 -C 6 acyloxy, an amine or amide group: —NH 2 , —NHR 12 , —N(R 12 ) 2 , —CONH 2 , —CONHR 12 , —CON(R 11 ) 2 , R 14 is hydrogen, C 1 -C 6 alkyl, phenyl or naphthyl with C 1 -C 6 alkyl or C 1 -C 6 alkoxy substituents,
an optionally substituted phenyl or benzyl group,
a —COR 15 , or —COOR 15 group, R 15 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms,
or alternatively, R 5 and R 6 may together form a 5- to 7-member optionally substituted carbocyclic or heterocyclic ring comprising a heteroatom selected from oxygen, sulfur, and nitrogen and wherein said substituents are selected from the group consisting of a C1 to C6 alkyl group which is linear or branched, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula
wherein R 12 and R 13 , which are the same or different, independently represent a hydrogen, a linear, branched, or cyclic alkyl group comprising 1 to 6 carbon atoms, an aryl or heteroaryl group consisting of C atoms and a heteroatom selected from the group consisting of N, S or O ring atoms, or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring selected from the group consisting of pyridyl, furyl, benzofuryl, dibenzofuryl, thienyl, and benzothienyl, said nitrogen atom in the 5- to 7-membered ring being optionally substituted with an R 10 group, which R 10 is a linear or branched alkyl group comprising 1 to 6 carbon atoms, a phenyl, a benzyl, or a naphthyl group.
R 7 , and R 8 are independently
a hydrogen,
a linear or branched alkyl group which comprises 1 to 6 carbon atoms,
a cycloalkyl group comprising 3 to 7 carbon atoms,
a linear or branched alkoxy group comprising 1 to 6 carbon atoms,
a haloalkyl, halocycloalkyl, or haloalkoxy group where alkyl groups comprise C 1 -C 6 alkyl groups, C 1 -C 6 haloalkoxy groups above respectively, which are substituted with at least one halogen atom, selected from fluorine, chlorine and bromine,
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, and n is an integer from 0 to 4.
3. A photochromic naphthopyran having a central nucleus of the formula
wherein F is a 1,4-benzodioxine ring having the following graphic formulae:
with its 2,3 positions fused to the i, j, or k side;
R 1 and R 2 are atoms or groups providing photochromic properties to the naphthopyran, and F, with its 2,3 positions, is fused to the g, h, i, n, o, or p side.
4. The photochromic naphthopyran of claim 3 , characterized in that it has the following structure
wherein,
R 7 , and R 8 are independently
a hydrogen,
a linear or branched alkyl group which comprises 1 to 6 carbon atoms,
a cycloalkyl group comprising 3 to 7 carbon atoms,
a linear or branched alkoxy group comprising 1 to 6 carbon atoms,
a haloalkyl, halocycloalkyl, or haloalkoxy group where alkyl groups comprise C 1 -C 6 alkyl groups, C 1 -C 6 haloalkoxy groups above respectively, which are substituted with at least one halogen atom, notably selected from fluorine, chlorine and bromine,
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, and
n is an integer from 0 to 4,
R 9 independently represents groups as defined for R 8 ;
k is an integer from 0 to 2;
R 3 and R 4 are the same or different, and may represent independently
a hydrogen, a hydroxy, a halogen,
a linear, branched, or cyclic alkyl group that comprises 1 to 6 carbon atoms,
a —OR 20 group, wherein R 20 is (C1-C3)alkyl, phenyl(C1-C3)alkyl, mono(C1-C3)alkylphenyl(C1-C3)alkyl, mono(C1-C3)alkoxyphenyl(C1-C3)alkyl, (C1-C3)alkoxy, (C2-C4)alkyl, fluoro(C1-C3)alkyl, chloro(C1-C3)alkyl, or optionally substituted phenyl groups,
an optionally substituted aryl group, said substituents being mono, di-, or tri-, and selected from group R 20 , and OR 20 ,
a —C(R 14 ) 2 X group, wherein X is hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, an ester group: —COOR 11 , an amine or amide group: —NH 2 , —NHR 12 , —N(R 12 ) 2 , —CONH 2 , —CONHR 12 , —CON(R 12 ) 2 , R 14 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
a polyether or polyurea residue,
or R 3 and R 4 together form a 5- to 7-member optionally substituted spiro-cyclic ring comprising a heteroatom selected from oxygen, sulfur, and nitrogen, and which spirocyclic ring may be annelated with one or two benzene groups, the substituents on said 5- to 7-member ring being selected from the group consisting of a C1 to C6 alkyl group which is linear or branched, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula
wherein R 12 and R 13 are selected from the group consisting of hydrogen, a linear, branched, or cyclic alkyl group comprising 1 to 6 carbon atoms, an aryl or heteroaryl group consisting of C atoms and a N, S or O ring atom, or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring selected from the group consisting of pyridyl, furyl, benzofuryl, dibenzofuryl, thienyl, and benzothienyl.
5. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 1 .
6. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 2 .
7. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 3 .
8. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 4 .
9. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of hydrogen atoms, halogen atoms, and organic groups.
10. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of hydrogen atoms and organic groups.
11. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of hydrogen atoms, aliphatic groups, aryl groups, and heterocyclic groups.
12. The photochromic naphthopyran of claim 1 wherein R 1 and R 2 are selected from the group consisting of a) hydrogen atoms, b) a linear or branched alkyl group of 1 to 12 carbon atoms, c) a cycloalkyl group of 3 to 12 carbon atoms, d) an aryl group of 6 to 24 ring carbon atoms, e) a heteroaryl group of 4 to 24 carbon atoms and at least one hetero ring atom selected from sulfur, oxygen and nitrogen; and f) wherein R 1 and R 2 together form a heterocyclic ring.
13. The photochromic naphthopyran of claim 9 wherein the heterocyclic ring formed from R 1 and R 2 is selected from the group consisting of an adamantyl, norbornyl, fluorenylidene, di(C 1 -C 6 )alkylanthracenylidene and spiro(C 5 -C 6 )cycloalkylanthracenylidene group.
14. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 9 .
15. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 10 .
16. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 11 .
17. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 12 .
18. A photochromic article comprising a light permeable matrix having applied thereto or dispersed or diffused therein a photochromic amount of a photochromic naphthopyran according to claim 13 .
19. A photochromic naphthopyran having a central nucleus of the formula:
wherein F is a 1,4-benzodioxine ring having the following graphic formulae:
with its 2,3 positions fused to the i, j, or k side;
R 1 and R 2 are selected from the group consisting of phenyl and substituted phenyl.
20. A photochromic naphthopyran having a central nucleus of the formula
wherein F is a 1,4-benzodioxine ring having the following graphic formulae:
with its 2,3 positions fused to the i, j, or k side; and
R 1 and R 2 are phenyl groups providing photochromic properties to the naphthopyran, and F, with its 2,3 positions, is fused to the g, h, i, n, o, or p side.
21. The photochromic naphthopyran of claim 20 , characterized in that it has the following structure
wherein,
R 7 , and R 8 are independently
a hydrogen,
a linear or branched alkyl group which comprises 1 to 6 carbon atoms,
a cycloalkyl group comprising 3 to 7 carbon atoms,
a linear or branched alkoxy group comprising 1 to 6 carbon atoms,
a haloalkyl, halocycloalkyl, or haloalkoxy group where alkyl groups comprise C 1 -C 6 alkyl groups, C 1 -C 6 haloalkoxy groups above respectively, which are substituted with at least one halogen atom selected from fluorine, chlorine and bromine,
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, and n is an integer from 0 to 4,
R 9 independently represents groups as defined for R 8 ;
k is an integer from 0 to 2;
R 3 and R 4 are the same or different, and may represent independently
a hydrogen, a hydroxy, a halogen,
a linear, branched, or cyclic alkyl group that comprises 1 to 6 carbon atoms,
a —OR 20 group, wherein R 20 is (C1-C3)alkyl, phenyl(C1-C3)alkyl, mono(C1-C3)alkylphenyl(C1-C3)alkyl, mono(C1-C3)alkoxyphenyl(C1-C3)alkyl, (C1-C3)alkoxy, (C2-C4)alkyl, fluoro(C1-C3)alkyl, chloro(C1-C3)alkyl, or optionally substituted phenyl groups,
an optionally substituted aryl group, said substituents being mono, di-, or tri-, and selected from group R 20 , and OR 20 ,
a —C(R 14 ) 2 X group, wherein X is hydroxy, alkoxy, benzoyloxy, C1-C6 acyloxy, an ester group: —COOR 11 , an amine or amide group: —NH 2 , —NHR 12 , —N(R 12 ) 2 , —CONH 2 , —CONHR 12 , —CON(R 12 ) 2 , R 14 is hydrogen, C1-C6 alkyl, phenyl or naphthyl with C1-C6 alkyl or C1-C6 alkoxy substituents,
a polyether or polyurea residue,
or R 3 and R 4 together form a 5- to 7-member optionally substituted spiro-cyclic ring which comprising one heteroatom selected from oxygen, sulfur, and nitrogen, and which spirocyclic ring may be annelated with one or two benzene groups, the substituents on said 5- to 7-member ring being selected from the group consisting of a C1 to C6 alkyl group which is linear or branched, a C1 to C6 alkoxy group which is linear or branched, and an amine group of formula
wherein R 12 and R 13 are selected from the group consisting of hydrogen, a linear, branched, or cyclic alkyl group comprising 1 to 6 carbon atoms, an aryl or heteroaryl group consisting of C atoms and one N, S or O ring atoms, or representing, together with the nitrogen atom to which they are bound, a 5- to 7-membered ring selected from the group consisting of pyridyl, furyl, benzofuryl, dibenzofuryl, thienyl, and benzothienyl.