Disubstituted diaryloxybenzoheterodiazole compounds

Process for the preparation of a disubstituted diaryloxybenzoheterodiazole compound of general formula (I):

• in which Z represents a sulfur atom, an oxygen atom, a selenium atom;
• or an NR5 group in which R5 is selected from linear or branched C1-C20 alkyl groups, or from optionally substituted aryl groups;
• R1, R2 and R3, which are the same or different, represent a hydrogen atom;
• or are selected from linear or branched C1-C20 alkyl groups;
• linear or branched C1-C20 alkyl groups containing heteroatoms;
• optionally substituted cycloalkyl groups;
• optionally substituted aryl groups;
• optionally substituted linear or branched C1-C20 alkoxyl groups;
• optionally substituted phenoxyl groups, or —OCOR6 groups in which R6 is selected from linear or branched C1-C20 alkyl groups, or is a cyano group;
• wherein said optionally substituted aryl group of R1 is selected from optionally substituted phenyl, naphthyl, phenyl naphthyl, phenanthrene or anthracene;
• or R1 and R2, can optionally be linked together so as to form, together with the carbon atoms to which they are linked, a saturated, unsaturated or aromatic cyclic ring or a polycyclic system containing from 3 to 14 carbon atoms, optionally containing one or more heteroatoms;
• or R2 and R3 can optionally be linked together so as to form, together with the carbon atoms to which they are linked, a saturated, unsaturated or aromatic cyclic ring or a polycyclic system containing from 3 to 14 carbon atoms, optionally containing one or more heteroatoms;
• R4, which are the same or different, are selected from optionally substituted aryl groups;
• in which at least one of R1, R2 and R3 is/are different from hydrogen, comprising the following steps:
• (a) reacting at least one disubstituted diaryloxybenzoheterodiazole compound of general formula (Ia1):
• in which Z, R2, R3 and R4, have the same meanings as described above, with at least one N-haloimides compound selected from N-bromosuccinimide, N-bromophthalimide, N-iodosuccinimide, or N-iodophthalimide, obtaining a disubstituted halogenated diaryloxybenzoheterodiazole compound of general formula (IV):
• in which Z, R2, R3 and R4, have the same meanings as described above and X is a halogen atom selected from bromine or iodine;
• said disubstituted diaryloxybenzoheterodiazole compound of general formula (Ia1) and said N-haloimides compound being used in molar ratios ranging from 1:2 to 1:3;
• (b) reacting the disubstituted halogenated diaryloxybenzoheterodiazole compound of general formula (IV) obtained in step (a) with:
• (i) at least one aryl-boron compound of general formula (V):
• in which R1 has the same meanings as described above, provided that the R1 substituent does not represent a hydrogen atom, and the R7 substituents represent a hydrogen atom, or can be selected from linear or branched C1-C10 alkyl groups or optionally substituted cycloalkyl groups, or the two R7 substituents can optionally be linked together so as to form, together with other atoms to which they are linked, a cyclic ring selected from pinacol esters of boronic acid or 1,3-propanodiol esters of boronic acid;
• or
• (ii) with at least one aryl-stannylated compound of general formula (VI):
• in which R1 has the same meanings as described above, provided that the R1 substituent does not represent a hydrogen atom, and the R8 substituents can be selected from linear or branched C1-C8 alkyl groups;
• said disubstituted halogenated diaryloxybenzoheterodiazole compound of general formula (IV) and said aryl-boron compound of general formula (V), or said aryl-stannylated compound of general formula (VI) being used in molar ratios ranging from 1:2 to 1:5.