1. A photochromic compound selected from a spiro(indoline)naphtho(2,1-b) (1,4)oxazine and a spiro(indoline) naphtho(1,2-b)(1,4)oxazine containing a group selected from:
(a) CH2CnF2n1 at the nitrogen atom in the 1-position on the indoline part of the molecule, wherein n is an integer of 1 to 6;
(b) COOR at the 3-position on the indoline part of the molecule, wherein R is (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro; or (iv) aryl;
(c) an OCF3 group on the benzene ring of the indoline part of the molecule;
(d) an aryl(dialkyl)methyl group of the formula C(aryl)(CnH2n1)(CmH2m1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule; and
(e) any combination of (a), (b), (c) andor (d).
2. A spiro(indoline)naphtho(2,1-b) (1,4)oxazine or a spiro(indoline) naphtho(1,2-b)(1,4)oxazine according to claim 1, containing a group CH2CnF2n1 at the nitrogen atom in the 1-position on the indoline part of the molecule, wherein n is an integer of 1 to 4.
3. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 2 having the following formulas Ia and Ib, respectively:
23
wherein
(a) n is an integer from 1 to 6; p is 1 or 2; and q is an integer from 1 to 6;
(b) R2 and R3 represent independently a radical selected from: (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl-; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro; (iv) aryl; (v) alkylcarbonyl; or (vi) one of R2 and R3 is a group COOR wherein R is a radical (i) to (iv) as defined hereinbefore and the other of R2 and R3 is a radical (i) to (iv) as defined hereinbefore; or (vii) R2 and R3 together with the carbon atom at position 3 of the indoline ring form a 3-7 membered saturated ring optionally containing a heteroatom selected from nitrogen, oxygen or sulfur, and
(c) R4 and R5 represent independently (i) hydrogen; (ii) halogen, preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxy optionally substituted by C1-C6 alkyl, C1-C4 alkoxy or amino; (v) C1-C4 alkoxy optionally substituted by halogen, preferably di- and trifluoromethoxy; (vii) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, halogen, preferably trifluoromethyl, C3-C6 cycloalkyl, polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl; (viii) aryl optionally substituted with amino or alkoxy group, preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (CONH2); (x) sulfonamide (SO2NH2); (xi) NR6R7, wherein R6 and R7 are independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferably trifluoromethyl) or R6 and R7 together with the nitrogen atom form a 3-7 membered saturated ring optionally containing a further heteroatom selected from nitrogen, oxygen or sulfur atom, preferably piperidino, piperazino or morpholino; (xii) R4 may further be OCF3, in which case p is 1; and (xiii) R5 may further be an aryl(dialkyl)methyl group of the formula C(aryl)(CnH2n1)(CmH2m1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule, in which case q is an integer from 1 to 5.
4. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine compound according to claim 1, containing at the 3-position on the indoline part of the molecule a group COOR, wherein R is selected from: (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C1-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl; or (iv) aryl.
5. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 4, having the formulas IIa and IIb, respectively:
24
wherein
(a) p is 1 or 2 and q is an integer from 1 to 6;
(b) R1 is a radical selected from: (i) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl, polycycloalkyl, aryl or heterocyclic ring; (ii) C3-C6 cycloalkyl; (iii) polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi) CH2CnF2n1 wherein n is an integer of 1 to 6; or (vii) C2-C6 alkenyl with a terminal double bond;
(c) R3 represents a radical selected from: (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro ; or (iv) aryl; and
(d) R4 and R5 represent independently (i) hydrogen; (ii) halogen, preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxy optionally substituted by C1-C6 alkyl, C1-C4 alkoxy or amino; (v) C1-C4 alkoxy optionally substituted by halogen, preferably di- and trifluoromethoxy; (vii) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, halogen, preferably trifluoromethyl, C3-C6 cycloalkyl, polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl; (viii) aryl optionally substituted with amino or alkoxy group, preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (CONH2); (x) sulfonamide (SO2NH2); (xi) NR6R7, wherein R6 and R7 are independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferably trifluoromethyl) or R6 and R7 together with the nitrogen atom form a 3-7 membered saturated ring optionally containing a further heteroatom selected from nitrogen, oxygen or sulfur atom, preferably piperidino, piperazino or morpholino; (xii) R4 may further be OCF3, in which case p is 1; and (xiii) R5 may further be an aryl(dialkyl)methyl group of the formula C(aryl)(CnH2n1)(CmH2m1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule, in which case q is an integer from 1 to 5.
6. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine and spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 1, having a trifluoromethoxy (OCF3) group on the benzene ring of the indoline part of the molecule.
7. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 6, having the formulas IIIa and IIIb, respectively:
25
(a) q is an integer from 1 to 6;
(b) R1 is a radical selected from: (i) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, C1-C4 alkylcarbonyloxy. C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl, polycycloalkyl, aryl or heterocyclic ring; (ii) C3-C6 cycloalkyl; (iii) polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi) CH2-CnF2n1 wherein n is an integer of 1 to 6; or (vii) C2-C6 alkenyl with a terminal double bond;
(c) R2 and R3 represent independently a radical selected from: (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro; (iv) aryl; or (v) alkylcarbonyl; or (vi) one of R2 and R3 is a group COOR wherein R is a radical (i) to (iv) as defined hereinbefore and the other of R2 and R3 is a radical (i) to (iv) as defined hereinbefore; or (vii) R2 and R3 together with the carbon atom at position 3 of the indoline ring form a 3-7 membered saturated ring optionally containing a heteroatom selected from nitrogen, oxygen or sulfur, and
(d) R4 and R5 represent independently (i) hydrogen; (ii) halogen, preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxy optionally substituted by C1-C6 alkyl, C1-C4 alkoxy or amino; (v) C1-C4 alkoxy optionally substituted by halogen, preferably di- and trifluoromethoxy; (vii) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, halogen, preferably trifluoromethyl, C3-C6 cycloalkyl, polycycloalkyl (such as norbornane or adamantane), aryl or heterocyclyl; (viii) aryl optionally substituted with amino or alkoxy group, preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (CONH2); (x) sulfonamide (SO2NH2); (xi) NR6R7, wherein R6 and R7 are independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferably trifluoromethyl) or R6 and R7 together with the nitrogen atom form a 3-7 membered saturated ring optionally containing a further heteroatom selected from nitrogen, oxygen or sulfur atom, preferably piperidino, piperazino or morpholino; and (xii) R5 may further be an aryl(dialkyl)methyl group of the formula C(aryl)(CnH2n1)(CmH2m1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule, in which case q is an integer from 1 to 5.
8. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 1, having an aryl(dialkyl)methyl group of the formula C(aryl)(CnH2n1)(CmH2m1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule.
9. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 8, having the formulas IVa and IVb, respectively:
26
wherein
(a) p is 1 or 2 and q is an integer from 1 to 5;
(b) R1 is a radical selected from: (i) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl, polycycloalkyl, aryl or heterocyclic ring; (ii) C3-C6 cycloalkyl; (iii) polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi) CH2CnF2n1 wherein n is an integer of 1 to 6; or (vii) C2-C6 alkenyl with a terminal double bond;
(c) R2 and R3 represent independently a radical selected from: (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro; (iv) aryl; or (v) alkylcarbonyl; or (vi) one of R2 and R3 is a group COOR wherein R is a radical (i) to (iv) as defined hereinbefore and the other of R2 and R3 is a radical (i) to (iv) as defined hereinbefore; or (vii) R2 and R3 together with the carbon atom at position 3 of the indoline ring form a 3-7 membered saturated ring optionally containing a heteroatom selected from nitrogen, oxygen or sulfur, and
(d) R4 and R5 represent independently (i) hydrogen; (ii) halogen, preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxy optionally substituted by C1-C6 alkyl, C1-C4 alkoxy or amino; (v) C1-C4 alkoxy optionally substituted by halogen, preferably di- and trifluoromethoxy; (vii) C1-C6 alkyl optionally substituted by C1-C4 alkoxy, halogen, preferably trifluoromethyl, C3-C6 cycloalkyl, polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl; (viii) aryl optionally substituted with amino or alkoxy group, preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (CONH2); (x) sulfonamide (SO2NH2); (xi) NR6R7, )wherein R6 and R7 are independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferably trifluoromethyl) or R6 and R7 together with the nitrogen atom form a 3-7 membered saturated ring optionally containing a further heteroatom selected from nitrogen, oxygen or sulfur atom, preferably piperidino, piperazino or morpholino; and (xii) R4 may further be OCF3, in which case p is 1.
10. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to any one of claims 1 to 9, wherein any alkyl or alkoxy radical is linear or branched; any C2-C4 alkenylcarbonyloxy radical is preferably the radical derived from acrylic (OCOCHCH2) or methacrylic (OCO(CH3)CH2) acid; any C3-C6 cycloalkyl is preferably cyclopentyl or cyclohexyl; the polycycloalkyl may be a C4-C20 bicycloalkyl such as partially or completely saturated naphthyl or a C6-C20 tricycloalkyl such as adamantyl and norbornyl; any C2-C6 alkenyl with a terminal double bond is preferably CH2CHCH2 or CH2(CH2)3CHCH2; preferred radicals CH2CnF2n1 are CH2CF3 and CH2CF2CF3; in the group of the formula C(aryl)(CnH2n1)(CmH2m1), n and m are preferably 1 such that said linking group is preferably tert-propylene (CH3)C(CH3).
11. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine or spiro(indoline)naphtho(1,2-b)(1,4) oxazine according to any one of claims 1 to 10, selected from the compounds:
1,3,3-trimethyl-5-trifluoromethoxy-spiro-(indoline-2,3-(3H)-naphtho2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3,3-dimethyl-5-trifluoromethoxy-6-dimethyl-amino-spiro-(indoline-2,3-(3H)-naphtho2,1-b-(1,4)-oxazine)
1-Propyl-3,3-dimethyl-5-trifluoromethoxy-6-dimethylamino-spiro-(indoline-2,3-(3H)-naphtho2,1-b-(1,4)-oxazine)
1-Propyl-3,3-dimethyl-5-trifluoromethoxy-6-piperidino-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1,3-Dimethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3-methyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho 2,1-b-(1,4)-oxazine
1,3,4,5-Tetramethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1,3,4,5-Tetramethyl-3-carboethoxy-8-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3-(3H)-naphtho2,1-b-(1,4)-oxazine)
1,3-Dimethyl-3-carboethoxy-9-acetyloxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Isobutyl-3-methyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Isobutyl-3,5-dimethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1,3-Dimethyl-3-carboethoxy-8-(1-methyl-1-phenyl)-ethyl-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1,3,5,6-Tetramethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3-methyl-3-carboethoxy-6-dimethylamino-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Propyl-3,5-Dimethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1,3-Dimethyl-3-carboethoxy-6-methoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-(2-Phenylethyl)-3-methyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Ethyl-3,5-dimethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Isobutyl-5-fluoro-3-methyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-(2,2,2-trifluoroethyl)-3,3-dimethyl-6(4-diethylaminophenyl)-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-(2,2,2-Trifluoroethyl)-3,3-dimethyl-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3,3-spiro-(cyclohexyl)-8-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3,3-dimethyl-8-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3,3-dimethyl-6-morpholino-8-(1-methyl-1-phenyl) ethyl-spiro-(indoline-2,3-(3H)-naphtho-2,1-b-(1,4)-oxazine)
1-Cyclohexylmethyl-3,3-dimethyl-6-morpholino-8-(1-methyl-1-phenyl) ethyl-spiro-(indoline-2,3-(3H)-naphtho-1,2-b-(1,4)-oxazine)
1-Propyl-3,5-Dimethyl-3-carboethoxy-spiro-(indoline-2,3-(3H)-naphtho-1,2-b-(1,4)-oxazine)
12. A plastic organic photochromic article comprising a plastic host material containing a photochromic compound as claimed in any one of claims 1 to 11, or a mixture thereof.
13. A photochromic article according to claim 12 containing one or more compounds according to any one of claims 1 to 11 and another photochrome known in the art.
14. A photochromic article according to claim 12 or 13 further containing plasticizers, light stabilizers andor materials for the photochrome microencapsulation.
15. A photochromic article according to any one of claims 12 to 14, said article being a plastic lens.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A stepped riser comprising:
one or more generally horizontal treads; and
one or more generally vertical rises, each of said treads and rises comprising a sandwich structure having upper and lower metal plates and an intermediate layer of a compact polyurethane material bonded to said metal plates so as to transfer shear forces therebetween,
wherein each of said treads extends between adjacent rises and comprises said sandwich structure throughout its extent between said adjacent rises, and
wherein each of said rises extends between adjacent treads and comprises said sandwich structure throughout its extent between said adjacent treads.
2. A stepped riser according to claim 1 wherein said riser is a seating riser.
3. A stepped riser according to claim 2 further comprising mounting details for at least one seat andor railings.
4. A stepped riser according to any one of claims 1 to 3 wherein said riser has a maximum length of from 6 to 20 m.
5. A stepped riser according to any one of claims 1 to 3 wherein said stepped riser has a run of from 600 to 1200 mm.
6. A stepped riser according to any one of claims 1 to 3 wherein said upper and lower metal plates are formed by folding or roll-forming respective flat plates.
7. A stepped riser according to any one of claims 1 to 3 wherein said intermediate layer is thicker in treads of said stepped riser than in rises.
8. A stepped riser according to claim 1 wherein one of said rises joins the front edge of an upper one of said treads to the rear edge of a lower one of said treads and a said second rise extends upwardly from the rear edge of said upper tread, the front edge of said lower tread having a downwardly projection lip portion.
9. A stepped riser according to claim 8 wherein said upper and lower plates are flared in said lip portion to receive an upper edge of an upper rise of a like stepped riser.
10. A stepped riser according to any one of claims 1 to 3 wherein said upper plate is made of a different metal or alloy than said lower plate.
11. A stepped riser according to claim 10 wherein said upper plate is more corrosion resistant than said lower plate.
12. A stepped riser according to any one of claims 1 to 3 wherein said upper plate is thinner than said lower plate.
13. A stepped riser according to any one of claims 1 to 3 wherein said upper plate is provided with a corrosion prevention treatment.
14. A stepped riser according to any one of claims 1 to 3 wherein said upper plate has a thickness in the range of from 2 to 10 mm, said lower plate has a thickness in the range of from 2 to 10 mm and said intermediate layer has a thickness in the range of from 10 to 100 mm.
15. A spectator stand having at least one stepped riser according to any one of claims 1 to 3.