Naphthopyrans annelated in C5-C6, their preparation and compositions and (co)polymer matrices containing them

Compounds of the following formula (I):

• in which:
• a R1 and R2 are identical or different and independently represent:
• hydrogen,
• a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
• a cycloalkyl group which comprises 3 to 12 carbon atoms,
• an aryl or heteroaryl group which comprises in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulphur, oxygen, and nitrogen;
• said basic structure being optionally substituted with at least one substituent selected from the group consisting of:
• a halogen,
• a hydroxy group,
• a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
• a linear or branched alkoxy group which comprises 1 to 12 carbon atoms,
• a haloalkyl or haloalkoxy group corresponding respectively to the (C1-C12) alkyl or alkoxy groups above which are substituted with at least one halogen atom,
• a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
• a linear or branched alkenyl group which comprises 2 to 12 carbon atoms,
• an —NH2 group,
• an —NHR group, R representing a linear or branched alkyl group which comprises 1 to 6 carbon atoms,
• a group having the formula:
• where R′ and R″, which are identical or different, independently representing a linear or branched alkyl group which comprises 1 to 6 carbon atoms, a phenyl group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms, 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, sulphur and nitrogen, said nitrogen being optionally substituted with an R″′ group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms, and
• a methacryloyl group or an acryloyl group, or
• 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 definitions given above, or
• said two said two substituents R1 and R2 together form an adamantyl, norbornyl, fluorenylidene, di(C1-C6)alkylanthracenylidene, or spiro (C5-C6)cycloalkylanthracen-ylidene group;
• said group being optionally substituted with at least one of the substituents listed above for R1, R2 corresponding to an aryl or heteroaryl group;
• R3, which are identical or different, represent, independently:
• a halogen,
• a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
• a cycloalkyl group which comprises 3 to 12 carbon atoms,
• a linear or branched alkoxy group which comprises 1 to 12 carbon atoms,
• a haloalkyl, halocycloalkyl, haloalkoxy group corresponding respectively to the alkyl, cycloalkyl, alkoxy groups above, which are substituted with at least one halogen atom,
• an aryl or heteroaryl group having the same definition as that given supra for R1, R2,
• 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 supra for R1, R2,
• a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
• an amine or amide group:
• —NH2, —NHR, —CONH2, —CONHR,
• R, R′, R″ having their respective definitions given supra for the amine substituents of the values R1, R2:
• aryl or heteroaryl,
• an —OCOR8 or —COOR8 group, R8 representing a straight or branched alkyl group comprising 1 to 6 carbon atoms or a cycloalkyl group comprising 3 to 6 carbon atoms or a phenyl group which is optionally substituted with at least one of the substituents listed above for the values of R1, R2:
• aryl or heteroaryl;
• or
• at least two adjacent R3 groups together form at least one aromatic or non-aromatic cyclic group having a single king or two annelated rings, optionally comprising at least one heteroatom selected from the group comprising:
• oxygen, sulphur and nitrogen, this or these annelated rings being optionally substituted with at least one substituent selected from those having the definition given above for the aryl or heteroaryl groups which can form R1 and/or R2;
• m is an integer of 0 to 4;
• A represents:
• wherein, in this annelated ring (A4)
• the dashed line represents the carbon C5 carbon C6 bond of the naphthopyran ring of formula (I);
• the α bond of the annelated ring (A4) can be linked indifferently to carbon C5 or to carbon C6 of the naphthopyran ring of formula (I);
• R4, which are identical or different, represent, independently, an OH, an alkyl or alkoxy group which is linear or branched and which comprises 1 to 6 carbon atoms or two of the R4 form a carbonyl (CO);
• R5 represents:
• a halogen,
• a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
• a haloalkyl group corresponding to the linear or branched above alkyl group, which is substituted with at least one halogen atom;
• a cycloalkyl group which comprises 3 to 12 carbon atoms,
• a linear or branched alkoxy group which comprises 1 to 6 carbon atoms,
• a phenyl or benzyl group, optionally substituted with at least one of the substituents listed above in the definitions of the radicals R1, R2 of formula (I) in the case in which the radicals independently correspond to an aryl or heteroaryl group,
• a —NH2, —NHR, or amino group having the formula:
• R, R′, R″ having their respective definitions given supra for the amine substituents of the values R1, R2:
• aryl or heteroaryl,
• a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
• a —COR9, —COOR9, or —CONHR, group, R9 representing a linear or branched alkyl group comprising 1 to 6 carbon atoms or a cycloalkyl group comprising 3 to 6 carbon atoms or a phenyl or benzyl group which is optionally substituted with at least one of the substituents listed above in the definitions of the radicals R1, R2 of formula (I) in the case in which the radicals independently correspond to an aryl or heteroaryl group, and
• wherein two adjacent R5 groups, taken together, optionally form a 5- to 6-membered aromatic or non-aromatic ring which can comprise at least one heteroatom selected from the group comprising:
• oxygen, sulphur, and nitrogen;
• n is an integer of 0 to 4 and p is an integer of 0 to 4.