Patent DE-102011018815-A1 (DE)
Title: New Substituted terrylene diimide compounds useful e.g. as energy donor groups in bi- and multichromophoric compounds for achieving broadband light absorption and as pigments and dyes for dyeing purposes and decorative and artistic purposes
Inventor: LANGHALS HEINZ
IPC: C09B3/14
Filed: 2011-04-27
Abstract: Substituted terrylene diimide compounds (I), preferably 7,22-bis(tridecan-7-yl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIa) (preferred) or 7,22-bis(4-amino-2,3,5,6-tetramethylphenyl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIb), are new. Substituted terrylene diimide compounds of formula (I), preferably 7,22-bis(tridecan-7-yl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIa) (preferred) or 7,22-bis(4-amino-2,3,5,6-tetramethylphenyl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIb), are new. Either R1-R12 : at least 1-not > 37C linear alkyl (in which 1-10 CH 2groups may be replaced by T, and up to 12 individual H of CH 2groups at same C may be replaced by F, Cl, Br, I, CN or up to 18C linear alkyl (in which 1-6 CH 2groups may be replaced by T, and up to 12 H of CH 2groups of alkyl at same C may be replaced by F, Cl, Br, I, CN, or up to 18C linear alkyl (in which 1-6 CH 2groups may be replaced by T))) or H, where instead of carrying substituents the free valences of the methine groups or the quaternary carbon atoms are linked in pairs to form rings e.g. cyclohexane; or R1-R9 : F, Cl, Br or I; and T : C=O, O, S, Se, Te, cis- or trans-CH=CH- (in which 1 CH unit may be replaced by N), acetylenic CC, phenyl (1,2-, 1,3- or 1,4-disubstituted), pyridinyl (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted), thiophenyl (2,3-, 2,4-, 2,5- or 3,4-disubstituted), naphthalenyl (1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted and 1 or 2 CH groups may be replaced by N), anthracenyl (1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted and 1 or 2 CH groups may be replaced by N). Independent claims are also included for: (1) terrylene tetracarboxylic acid bis-anhydride compounds of formula (II), preferably 7,22-dioxadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIc); (2) preparing (I); (3) preparing (II), comprising reacting (I) with potassium hydroxide in tert-butyl alcohol under harsh reaction conditions, preferably at elevated temperature e.g. the boiling temperature of the reaction solution, preferably 80[deg] C, and for longer time, preferably 12 hours, or reacting (I) with acetic acid at elevated temperatures, preferably boiling temperature of the reaction solution, preferably 90[deg] C and for longer time, preferably 12 hours; and (4) preparing (IIa), comprises condensing (II), preferably (IIc) with primary amines in alkaline media, preferably imidazole (preferred) or quinoline, using condensation auxiliaries e.g. metal salts, preferably zinc acetate (preferred) or lead acetate. [Image] [Image].