Photochromatic pyrano-1,3-oxazinonaphthalene derivatives

Photochromatic compounds belonging to the groups of chromenes and spiro-pyrans having general formula (I):

• 18
• wherein:
• R represents a linear or branched C1-C10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, aryl groups selected from phenyl, biphenyl and naphthyl, hetero-aromatic groups with 5-10 atoms, heterocyclic groups with 5-6 atoms, hydroxyl groups, carboxyl groups, cyano groups, linear or branched C1-C6 alkoxyl groups, or with a 1,2,2,6,6-pentamethylpiperidine group;
• a vinyl group;
• a (meth)allyl group;
• a linear or branched C2-C6 alkenyl group;
• an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched C1-C6 alkoxyl groups, carboxyl groups, N,N-dialkyl-(C1-C6)-amine groups;
• a COOR′a ester group wherein R′a represents a linear or branched C1-C10 alkyl group;
• a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X′)3 groups wherein X′ is selected from fluorine, chlorine and bromine, linear or branched C1-C10 alkyl groups, linear or branched C1-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 1,2,2,6,6-pentamethylpiperidine group;
• or R represents a linear or branched C1-C10 alkyl group substituted with an ORy group wherein Ry represents a linear or branched hydroxy-(C1-C6)-alkyl group, a (meth)allyl group, a (meth)acrylic group, a linear or branched carboxy-(C1-C6)-alkyl group, an acyloxyl group, a group having general formula (II):
• 19
• wherein
• R′1, R′2 and R′3, the same or different, represent a hydrogen atom;
• a linear or branched C1-C10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, linear or branched C1-C6 alkoxyl groups, carboxyl groups, cyano groups, or with an N,N-dialkyl-(C1-C6)-amine group, or with a cyclic amine;
• a vinyl group;
• a (meth)allyl group;
• a linear or branched C2-C10 alkenyl group;
• a COOR′a ester group wherein R′a represents a linear or branched C1-C10 alkyl group;
• a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X′)3 groups wherein X′ is selected from fluorine, chlorine and bromine, linear or branched C1-C10 alkyl groups, linear or branched C1-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 1,2,2,6,6-pentamethylpiperidine group;
• a linear or branched C1-C6 alkoxyl group;
• an N,N-dialkyl-(C1-C6)-amide group;
• and n is an integer ranging from 0 to 11, extremes included;
• or R represents one of the following groups having general formula (III), (IV) or (V):
• 20
• wherein
• R′4, R′5 and R′6, the same or different, represent a linear or branched C1-C10 alkyl group;
• a linear or branched C1-C6 alkoxyl group;
• a hydroxyl group;
• a tri-alkyl-(C1-C6)-siloxyl group;
• or a group having the formula:
• —O—(CH2)2—O(CH2)2—OCH3;
• m is an integer ranging from 1 to 6, extremes included;
• R1, R2, R3 and R4, the same or different, represent a hydrogen atom;
• a halogen atom selected from fluorine, chlorine, bromine and iodine;
• a linear or branched C1-C10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, linear or branched C1-C6 alkoxyl groups, ORx groups wherein Rx represents a linear or branched hydroxy-(C1-C6)-alkyl group, carboxyl groups, hydroxyl groups, cyano groups, or with a 1,2,2,6,6-pentamethylpiperidine group;
• a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X′)3 groups wherein X′ is selected from fluorine, chlorine and bromine, linear or branched C1-C10 alkyl groups, linear or branched C1-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 1,2,2,6,6-pentamethylpiperidine group;
• a hydroxyl group;
• a hydroxy-(C1-C6)-alkyl group;
• a linear or branched C1-C6 alkoxyl group, said alkoxyl group optionally substituted with hydroxyl groups;
• an N,N-dialkyl-(C1-C6)-amine group;
• a piperidine, piperazine or morpholine group;
• a C1-C6 carboxyalkyl group;
• a C2-C6 carboxyalkenyl group;
• a carboxyamide group;
• an N,N-dialkyl-(C1-C6)-carboxyamide group;
• a cyano group;
• a nitro group;
• a sulfonic group;
• an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl-(C1-C6)-amine groups, linear or branched C1-C6 alkoxyl groups, hydroxyl groups, linear or branched C1-C6 alkyl groups;
• an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type;
• a vinyl group;
• a (meth)allyl group;
• a (meth)acrylic group;
• a heteroallyl group;
• a linear or branched C2-C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl-(C1-C6)-4-aniline groups;
• an N-2,3-dihydroindoline group;
• a linear or branched C1-C6 thioether group;
• two consecutive substituents between R1, R2, R3 and R4 can represent the condensation points with other aromatic, heterocyclic or quinonic rings;
• P represents one of the following groups having general formula (VI) or (VII):
• 21
• wherein
• R5, R6, R7, R8, R9, R10, R11 and R12, the same or different, have the same meanings as the R1-R4 substituents described above;
• two consecutive substituents between R5 and R12 can represent the condensation points with other aromatic, heterocyclic or quinonic rings;
• Ra represents a methylene group;
• a vinylene group;
• a carbon-carbon bond;
• q is 0, 1 or 2;
• B and B1 are selected from the following groups:
• (i) aryl, phenyl and naphthalene groups, said aryl, phenyl and naphthalene groups optionally mono-, di- or tri-substituted;
• (ii) heterocyclic aromatic groups such as, for example, pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, said heterocyclic aromatic groups optionally mono-, or di-substituted;
• said aryl, phenyl, naphthalene and heterocyclic aromatic groups optionally being substituted with hydroxyl groups, piperidine groups, morpholine groups, pyrrole groups, linear or branched C1-C6 alkyl groups, linear or branched C1-C6 chloro-alkyl groups, linear or branched C1-C6 fluoro-alkyl groups, linear or branched C1-C6 alkoxyl groups optionally substituted with hydroxyl groups, linear or branched C1-C4 alkyl groups substituted with hydroxyl groups, linear or branched C1-C6 alkoxyl groups, acryloxyl groups, methacryloxyl groups, halogen atoms selected from chlorine and fluorine;
• (iii) groups represented by the following general formulae (VIII) or (IX):
• 22
• wherein
• E represents a carbon atom or an oxygen atom;
• D represents an oxygen atom or a substituted nitrogen atom, on the condition that, when D represents a substituted nitrogen atom, E represents a carbon atom, said nitrogen atom being substituted with linear or branched C1-C6 alkyl groups, or with C2-C6 acyl groups;
• R13 represents a linear or branched C1-C6 alkyl group, a linear or branched C1-C6 alkoxyl group, a hydroxyl group, a halogen atom selected from chlorine and fluorine;
• R14 and R15 each independently represent a hydrogen atom, a linear or branched C1-C6 alkyl group;
• p′ is 0, 1 or 2;
• (iv) linear or branched C1-C6 alkyl groups, linear or branched C1-C6 chloro-alkyl groups, linear or branched C1-C6 fluoro-alkyl groups, linear or branched C1-C4 alkyl groups substituted with linear or branched C1-C6 alkoxyl groups, C3-C6 cycloalkyl groups optionally mono-substituted with a linear or branched C1-C6 alkoxyl group or with a linear or branched C1-C6 alkyl group, or with a halogen atom selected from chlorine and fluorine;
• (v) a group having general formula (X):
• 23
• wherein
• F represents a hydrogen atom, a linear or branched C1-C4 alkyl group;
• and Z is selected from the following groups:
• naphthyl, phenyl, furanyl, thienyl, said naphthyl, phenyl, furanyl and thienyl groups, optionally mono- or di-substituted with linear or branched C1-C4 alkyl groups, linear or branched Cl-C4 alkoxyl groups, halogen atoms selected from fluorine and chlorine;
• (vi) or, B and B1 considered jointly, represent a fluoren-9-ylidene group, said fluoren-9-ylidene group optionally mono- or di-substituted with linear or branched C1-C4 alkyl groups optionally substituted with hydroxyl groups, linear or branched C1-C4 alkoxyl groups optionally substituted with hydroxyl groups, hydroxyl groups, halogen atoms selected from fluorine and chlorine, or they represent a group selected from spiro-monocyclic C3-C12 saturated hydrocarbon rings such as, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclo-octylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cyclododecylidene;
• spiro-bicyclic C7-C12 saturated hydrocarbon rings such as, for example, bicyclo[2.2.1]heptylidene (norbornylidene), 1,7,7,-trimethyl-bicyclo[2.2.1]heptylidene (bornylidene), bicyclo[3.2.1]octylidene, bicyclo[3.3.1]nonan-9-ylidene, bicyclo[4.3.2]undecane;
• spiro-tricyclic C7-C12 saturated hydrocarbon rings such as, for example, tricyclo-[2.2.1.02,6]heptylidene, tricyclo[3.3.1.13,7]decylidene (adamantylidene), tricyclo[5.3.1.1.12,6]dodecylidene.