DE102010011065A1 - New perylene dye compounds useful e.g. as pigment in e.g. novolacs, as mordant dye to color natural materials e.g. wood, as functional materials in compact disk, and for mass coloring of polymers e.g. polyvinylchloride - Google Patents

Abstract

Perylene dye compounds (VI) are new. Perylene dye compounds of formula (VI) are new. R 1>-R 9>alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl (all optionally substituted), H or halo, where optionally one or more CH 2-units of the alkyl, alkenyl or alkynyl is optionally replaced by O, S, Se, Te, -CH=N-, -N=CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and the alkyl, alkenyl or alkynyl is optionally substituted by halo, CN or oxo; and X : alkylene, alkenylene alkynylene (where one or more CH 2units of the alkylene, alkenylene and alkynylene is optionally replaced by O, S, Se, Te, -CH=N-, -N=CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and the alkylene, alkenylene or alkynylene is optionally substituted by halo, CN or oxo). [Image].

Description

State of the art

strongly Red fluorescent pigment materials are because of their eye-catching Color in technology desires. But it is relative difficult, the strong fluorescence with complete insolubility in the relevant media in which the fluorescent pigments to be applied, especially in organic polymers as the most important application. An insolubility is but u. a. is required for high migration fastness and is also important when using higher temperatures, as they are z. B. occur in the injection molding process. Further important prerequisites for diverse technical Applications are also high light fastness and thermal Resistance. Here would be the perylene dyes [1], perylene-3,4: 9,10-tetracarboxylic bisimides (1), good Provide conditions that fluoresce yellow, so that a bathochromic shift of absorption is required. A such can in principle by a substitution of perylenebisimides in positions 1,6,7 and 12 with donor groups [2]. However, that will be obtained in the synthesis usually difficult separable mixtures and at the vast majority of derivatives is the Perylene nucleus heavily deformed.

strongly red fluorescent and completely insoluble pigments based on Perylenbisimiden would bring a significant Progress.

task

It intended to be red fluorescent pigments of variable particle size be developed on the basis of Perylenbisimiden.

Subject of the invention

• a. Perylene dye of general formula 6:
  
  wherein: R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen optionally having one or more CH ₂ units within the above-mentioned optionally substituted alkyl, the abovementioned optionally substituted alkenyl or the abovementioned optionally substituted alkynyl independently of one another by in each case one replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, Cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforesaid optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ^{3 is} hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen optionally having one or more CH ₂ units within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the above-mentioned optionally substituted alkynyl are independently replaced by a respective substituting radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforesaid optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen optionally with one or more CH ₂ units within the aforementioned optionally substituted alkyl, the abovementioned optionally substituted alkenyl or the abovementioned optionally substituted alkynyl independently of one another by a respective replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen, optionally with one or more CH ₂ units within the aforementioned optionally substituted alkyl, the abovementioned optionally substituted alkenyl or the abovementioned optionally substituted alkynyl independently of one another by a respective replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; X is optionally substituted alkylene, optionally substituted alkenylene or optionally substituted alkynylene, optionally wherein one or more CH ₂ units within the aforesaid optionally substituted alkylene, the aforementioned optionally substituted alkenylene or the aforementioned optionally substituted alkynylene are each independently replaced by one replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkylene, the aforementioned optionally substituted alkenylene or the The above-mentioned optionally substituted alkynyls having one or more substituents independently selected from halogen, cyano or oxo may be substituted.

The perylene dye of the general formula 6 shown above is described in detail below:
Each of R ¹ and R ² independently represents hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen (such as fluorine, chlorine, bromine or iodine) one or more CH ₂ units, preferably 1 to 10 CH ₂ units, more preferably 1 to 3 CH ₂ units, within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the above-mentioned optionally substituted alkynyl independently by one each replacing rest may be replaced.

The aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the aforementioned optionally substituted alkynyl is either unsubstituted or substituted with one or more substituents, preferably having 1 to 12 substituents, more preferably 1 to 6 sub independently selected from halogen (such as fluorine, chlorine, bromine or iodine), cyano (-CN) or oxo (= O). Preferably, the aforementioned radicals are unsubstituted.

The replacing radicals are independently selected from oxygen (-O-), sulfur (-S-), selenium (-Se-), tellurium (-Te-), -CH = N-, -N = CH-, arylene ( preferably C _6-14 -arylene, such as, for example: phenylene, including phen-1,2-diyl, phen-1,3-diyl or phen-1,4-diyl; naphthylene, including naphth-1,2- diyl, naphth-1,3-diyl, naphth-1,4-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, Naphth-2,3-diyl, naphth-2,6-diyl or naphth-2,7-diyl; or anthracenylene, including anthracene-1,2-diyl, anthracene-1,3-diyl, anthracene-1,4- diyl, anthracene-1,5-diyl, anthracene-1,6-diyl, anthracene-1,7-diyl, anthracene-1,8-diyl, anthracene-1,9-diyl, anthracene-1,10-diyl, Anthracene-2,3-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl, anthracene-2,9-diyl, anthracene-2,10-diyl or anthracene-9,10-diyl), heteroarylene (Preferably, heteroaryls having 5 to 14 ring atoms, more preferably heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; such as Pyridinylene, including pyridine-2,3-diyl, pyridine-2,4-diyl, pyridine-2,5-diyl, pyridine-2,6-diyl, pyridine-3,4-diyl or pyridine-3, 5-diyl; Thienylene, including thien-2,3-diyl, thien-2,4-diyl, thien-2,5-diyl or thien-3,4-diyl; Naphthylene having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; Anthracenylene having one or two ring nitrogen atoms in place of CH units; furandiyl; pyrrolediyl; imidazolediyl; pyrazoldiyl; pyrazinediyl; pyrimidinediyl; pyridazinediyl; oxazolediyl; Isoxazoldiyl; or furazanediyl), cycloalkylene (preferably C _3-14 cycloalkylene such as: cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene) or heterocycloalkylene (preferably heterocycloalkylene having 5 to 14 ring atoms, such as the fully saturated analogs of aforementioned heteroarylene radicals).

Preferably, the replacing radicals are independently selected from oxygen; Sulfur; phenylene; naphthylene; antracenylene; Heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; C _5-8 cycloalkylene; or heterocycloalkylene having 5 or 6 ring atoms. It is preferred that no CH ₂ units are replaced.

The aforesaid optionally substituted alkyl is preferably a C _1-90 alkyl, more preferably a C _1-37 alkyl, and even more preferably a C _6-20 alkyl. The aforesaid optionally substituted alkenyl is preferably a C _2-90 alkenyl, more preferably a C _2-37 alkenyl, and more preferably a C _6-20 alkenyl. The aforesaid optionally substituted alkynyl is preferably a C _2-90 alkynyl, more preferably a C _2-37 alkynyl, and even more preferably a C _6-20 alkynyl.

The aforesaid aryl is preferably a C _6-14 aryl, more preferably phenyl, naphthyl or anthracenyl, even more preferably phenyl.

The The aforementioned heteroaryl is preferably a 5 to 5 heteroaryl 14 ring atoms (such as: naphthyl with one or two ring nitrogen atoms instead of CH units, including quinolinediyl, Isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; or anthracenyl with one or two ring nitrogens instead from CH units); more preferably a heteroaryl with 5 or 6 ring atoms, one, two or three of the ring atoms being independent selected from one another from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; even stronger preferably pyridinyl, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, Pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.

The aforesaid cycloalkyl is preferably a C _3-14 cycloalkyl, more preferably a C _5-8 cycloalkyl, even more preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The The aforementioned heterocycloalkyl is preferably a heterocycloalkyl with 5 to 14 ring atoms; more preferably a heterocycloalkyl with 5 or 6 ring atoms, where one, two or three of the ring atoms independently of one another from nitrogen, oxygen or Sulfur selected and the remaining ring atoms Carbon atoms are; even more preferably piperidinyl, Tetrahydrothienyl, tetrahydrofuranyl, pyrrolidinyl, imidazolidinyl, Pyrazolidinyl, piperazinyl, morpholinyl, oxazolidinyl or isoxazolidinyl.

In one embodiment, R ¹ and R ² each independently have the meaning hydrogen, fluorine, chlorine, bromine, iodine or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units may be replaced independently in each case by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups, in which one CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups by Nitrogen atoms, or 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 Anthracenreste in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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-, 2,1 0- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings.

Preferably, R ¹ and R ² each independently represent hydrogen, optionally substituted C _6-20 alkyl, optionally substituted C _6-20 alkenyl or optionally substituted C _6-20 alkynyl, more preferably unsubstituted C _6-20 alkyl , Preferably, at least one of the two radicals R ¹ and R ^{2 is} an optionally substituted C _6-20 alkyl, an optionally substituted C _6-20 alkenyl or an optionally substituted C _6-20 alkynyl; More preferably, both R ¹ and R ^{2 are} each an optionally substituted C _6-20 alkyl, an optionally substituted C _6-20 alkenyl, or an optionally substituted C _6-20 alkynyl.

R ³ has the meaning of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen (such as fluorine, chlorine, bromine or iodine), where one or more CH ₂ - Units, preferably 1 to 10 CH ₂ units, more preferably 1 to 3 CH ₂ units, within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be replaced independently of one another by a respective substituting radical.

The aforesaid optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl is either unsubstituted or substituted with one or more substituents, preferably having 1 to 12 substituents, more preferably having 1 to 6 substituents, independently selected from halogen (such as fluorine, chlorine, Bromine or iodine), cyano (-CN) or oxo (= O). Preferably, the said radicals unsubstituted.

The replacing radicals are independently selected from oxygen (-O-), sulfur (-S-), selenium (-Se-), tellurium (-Te-), -CH = N-, -N = CH-, arylene ( preferably C _6-14 -arylene, such as, for example: phenylene, including phen-1,2-diyl, phen-1,3-diyl or phen-1,4-diyl; naphthylene, including naphth-1,2- diyl, naphth-1,3-diyl, naphth-1,4-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, Naphth-2,3-diyl, naphth-2,6-diyl or naphth-2,7-diyl; or anthracenylene, including anthracene-1,2-diyl, anthracene-1,3-diyl, anthracene-1,4- diyl, anthracene-1,5-diyl, anthracene-1,6-diyl, anthracene-1,7-diyl, anthracene-1,8-diyl, anthracene-1,9-diyl, anthracene-1,10-diyl, Anthracene-2,3-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl, anthracene-2,9-diyl, anthracene-2,10-diyl or anthracene-9,10-diyl), heteroarylene (Preferably, heteroaryls having 5 to 14 ring atoms, more preferably heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; such as Pyridinylene, including pyridine-2,3-diyl, pyridine-2,4-diyl, pyridine-2,5-diyl, pyridine-2,6-diyl, pyridine-3,4-diyl or pyridine-3, 5-diyl; Thienylene, including thien-2,3-diyl, thien-2,4-diyl, thien-2,5-diyl or thien-3,4-diyl; Naphthylene having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl, or benzopyrazinediyl; Anthracenylene having one or two ring nitrogen atoms in place of CH units; furandiyl; pyrrolediyl; imidazolediyl; pyrazoldiyl; pyrazinediyl; pyrimidinediyl; pyridazinediyl; oxazolediyl; Isoxazoldiyl; or furazanediyl), cycloalkylene (preferably C _3-14 cycloalkylene such as: cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene) or heterocycloalkylene (preferably heterocycloalkylene having 5 to 14 ring atoms, such as the fully saturated analogs of the above heteroarylene radicals mentioned).

Preferably, the replacing radicals are independently selected from arylene or heteroarylene, more preferably from C _6-14 arylene or heteroarylene having from 5 to 14 ring atoms; even more preferably from phenylene, naphthylene, anthracenylene or heteroarylene having 5 or 6 ring atoms wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms.

The aforesaid optionally substituted alkyl is preferably a C _1-90 alkyl, more preferably a C _1-37 alkyl, even more preferably a C _1-10 alkyl, and even more preferably methyl. The aforesaid optionally substituted alkenyl is preferably a C _2-90 alkenyl, more preferably a C _2-37 alkenyl, and even more preferably a C _2-10 alkenyl. The aforesaid optionally substituted alkynyl is preferably a C _2-90 alkynyl, more preferably a C _2-37 alkynyl, and even more preferably a C _2-10 alkynyl.

The aforesaid aryl is preferably a C _6-14 aryl, more preferably phenyl, naphthyl or anthracenyl, even more preferably phenyl.

The The aforementioned heteroaryl is preferably a 5 to 5 heteroaryl 14 ring atoms (such as: naphthyl with one or two ring nitrogen atoms instead of CH units, including quinolinediyl, Isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; or anthracenyl with one or two ring nitrogens instead of CH units); more preferably a heteroaryl with 5 or 6 ring atoms, one, two or three of the ring atoms being independent selected from one another from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; even stronger preferably pyridinyl, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, Pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.

The aforesaid cycloalkyl is preferably a C _3-14 cycloalkyl, more preferably a C _5-8 cycloalkyl, even more preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The The aforementioned heterocycloalkyl is preferably a heterocycloalkyl with 5 to 14 ring atoms; more preferably a heterocycloalkyl with 5 or 6 ring atoms, where one, two or three of the ring atoms independently of one another from nitrogen, oxygen or Sulfur selected and the remaining ring atoms Carbon atoms are; even more preferably piperidinyl, Tetrahydrothienyl, tetrahydrofuranyl, pyrrolidinyl, imidazolidinyl, Pyrazolidinyl, piperazinyl, morpholinyl, oxazolidinyl or isoxazolidinyl.

In one embodiment, R ^{3 has} the meaning hydrogen, fluorine, chlorine, bromine, iodine or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, Sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2-, 1,3- or 1, 4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two CH groups are substituted by nitrogen atoms e can be replaces. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two Koh may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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-, 2,1 0- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings.

Preferably, R ^{3 has} the meaning C _6-14 aryl or heteroaryl having 5 to 14 ring atoms. More preferably, R ^{3 is} phenyl, naphthyl, anthracenyl or heteroaryl having 5 or 6 ring atoms wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms. Even more preferably, R ^{3 is} phenyl.

R ⁴ , R ⁵ and R ⁶ each independently of one another have the meaning of hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen (such as, for example, fluorine, chlorine, bromine or iodine ), wherein one or more CH ₂ units, preferably 1 to 10 CH ₂ units, more preferably 1 to 3 CH ₂ units, within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the aforementioned optionally substituted alkynyl independently can be replaced by one replacement each.

The aforesaid optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl is either unsubstituted or substituted with one or more substituents, preferably having 1 to 12 substituents, more preferably having 1 to 6 substituents, independently selected from halogen (such as fluorine, chlorine, Bromine or iodine), cyano (-CN) or oxo (= O). Preferably, the said radicals unsubstituted.

The replacing radicals are independently selected from oxygen (-O-), sulfur (-S-), selenium (-Se-), tellurium (-Te-), -CH = N-, -N = CH-, arylene ( preferably C _6-14 -arylene, such as, for example: phenylene, including phen-1,2-diyl, phen-1,3-diyl or phen-1,4-diyl; naphthylene, including naphth-1,2- diyl, naphth-1,3-diyl, naphth-1,4-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, Naphth-2,3-diyl, naphth-2,6-diyl or naphth-2,7-diyl; or anthracenylene, including anthracene-1,2-diyl, anthracene-1,3-diyl, anthracene-1,4- diyl, anthracene-1,5-diyl, anthracene-1,6-diyl, anthracene-1,7-diyl, anthracene-1,8-diyl, anthracene-1,9-diyl, anthracene-1,10-diyl, Anthracene-2,3-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl, anthracene-2,9-diyl, anthracene-2,10-diyl or anthracene-9,10-diyl), heteroarylene (Preferably, heteroaryls having 5 to 14 ring atoms, more preferably heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; such as Pyridinylene, including pyridine-2,3-diyl, pyridine-2,4-diyl, pyridine-2,5-diyl, pyridine-2,6-diyl, pyridine-3,4-diyl or pyridine-3, 5-diyl; Thienylene, including thien-2,3-diyl, thien-2,4-diyl, thien-2,5-diyl or thien-3,4-diyl; Naphthylene having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; Anthracenylene having one or two ring nitrogen atoms in place of CH units; furandiyl; pyrrolediyl; imidazolediyl; pyrazoldiyl; pyrazinediyl; pyrimidinediyl; pyridazinediyl; oxazolediyl; Isoxazoldiyl; or furazanediyl), cycloalkylene (preferably C _3-14 cycloalkylene such as: cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene) or heterocycloalkylene (preferably heterocycloalkylene having 5 to 14 ring atoms, such as the fully saturated analogs of the above heteroarylene radicals mentioned).

Preferably, the replacing radicals are independently selected from oxygen; Sulfur; phenylene; naphthylene; antracenylene; Heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; C _5-8 cycloalkylene; or heterocycloalkylene having 5 or 6 ring atoms. It is preferred that no CH ₂ units are replaced.

The aforementioned optionally substituted alkyl is preferably a C _1-90 alkyl, more preferably a C _1-37 alkyl, and even more preferably a C _1-20 alkyl. The aforesaid optionally substituted alkenyl is preferably a C _2-90 alkenyl, more preferably a C _2-37 alkenyl, and more preferably a C _2-20 alkenyl. The aforesaid optionally substituted alkynyl is preferably a C _2-90 alkynyl, more preferably a C _2-37 alkynyl, and even more preferably a C _2-20 alkynyl.

The aforesaid aryl is preferably a C _6-14 aryl, more preferably phenyl, naphthyl or anthracenyl, even more preferably phenyl.

The The aforementioned heteroaryl is preferably a 5 to 5 heteroaryl 14 ring atoms (such as: naphthyl with one or two ring nitrogen atoms instead of CH units, including quinolinediyl, Isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; or anthracenyl with one or two ring nitrogens instead from CH units); more preferably a heteroaryl with 5 or 6 ring atoms, one, two or three of the ring atoms being independent selected from one another from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; even stronger preferably pyridinyl, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, Pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.

The aforesaid cycloalkyl is preferably a C _3-14 cycloalkyl, more preferably a C _5-8 cycloalkyl, even more preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The The aforementioned heterocycloalkyl is preferably a heterocycloalkyl with 5 to 14 ring atoms; more preferably a heterocycloalkyl with 5 or 6 ring atoms, where one, two or three of the ring atoms independently of one another from nitrogen, oxygen or Sulfur selected and the remaining ring atoms Carbon atoms are; even more preferably piperidinyl, Tetrahydrothienyl, tetrahydrofuranyl, pyrrolidinyl, imidazolidinyl, Pyrazolidinyl, piperazinyl, morpholinyl, oxazolidinyl or isoxazolidinyl.

In one embodiment, R ⁴ , R ⁵ and R ⁶ each independently have the meaning hydrogen, fluorine, chlorine, bromine, iodine or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units independently may be replaced by in each case carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2 , 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3- , 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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-, 2,1 0- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings.

Preferably, R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, optionally substituted C _1-20 alkyl, optionally substituted C _2-20 alkenyl, optionally substituted C _2-20 alkynyl or halogen, more preferably hydrogen or unsubstituted C _1-20 alkyl, even more preferably hydrogen.

R ⁷ , R ⁸ and R ⁹ each independently represent hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen (such as fluorine, chlorine, bromine or iodine ), wherein one or more CH ₂ units, preferably 1 to 10 CH ₂ units, more preferably 1 to 3 CH ₂ units, within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the aforementioned optionally substituted alkynyl independently can be replaced by one replacement each.

The aforesaid optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl is either unsubstituted or substituted with one or more substituents, preferably having 1 to 12 substituents, more preferably having 1 to 6 substituents, independently selected from halogen (such as fluorine, chlorine, Bromine or iodine), cyano (-CN) or oxo (= O). Preferably, the said radicals unsubstituted.

The replacing radicals are independently selected from oxygen (-O-), sulfur (-S-), selenium (-Se-), tellurium (-Te-), -CH = N-, -N = CH-, arylene ( preferably C _6-14 -arylene, such as, for example: phenylene, including phen-1,2-diyl, phen-1,3-diyl or phen-1,4-diyl; naphthylene, including naphth-1,2- diyl, naphth-1,3-diyl, naphth-1,4-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, Naphth-2,3-diyl, naphth-2,6-diyl or naphth-2,7-diyl; or anthracenylene, including anthracene-1,2-diyl, anthracene-1,3-diyl, anthracene-1,4- diyl, anthracene-1,5-diyl, anthracene-1,6-diyl, anthracene-1,7-diyl, anthracene-1,8-diyl, anthracene-1,9-diyl, anthracene-1,10-diyl, Anthracene-2,3-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl, anthracene-2,9-diyl, anthracene-2,10-diyl or anthracene-9,10-diyl), heteroarylene (Preferably, heteroaryls having 5 to 14 ring atoms, more preferably heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; such as Pyridinylene, including pyridine-2,3-diyl, pyridine-2,4-diyl, pyridine-2,5-diyl, pyridine-2,6-diyl, pyridine-3,4-diyl or pyridine-3, 5-diyl; Thienylene, including thien-2,3-diyl, thien-2,4-diyl, thien-2,5-diyl or thien-3,4-diyl; Naphthylene having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; Anthracenylene having one or two ring nitrogen atoms in place of CH units; furandiyl; pyrrolediyl; imidazolediyl; pyrazoldiyl; pyrazinediyl; pyrimidinediyl; pyridazinediyl; oxazolediyl; Isoxazoldiyl; or furazanediyl), cycloalkylene (preferably C _3-14 cycloalkylene such as: cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene) or heterocycloalkylene (preferably heterocycloalkylene having 5 to 14 ring atoms, such as the fully saturated analogs of the above heteroarylene radicals mentioned).

Preferably, the replacing radicals are independently selected from oxygen; Sulfur; phenylene; naphthylene; antracenylene; Heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; C _5-8 cycloalkylene; or heterocycloalkylene having 5 or 6 ring atoms. It is preferred that no CH ₂ units are replaced.

The aforesaid optionally substituted alkyl is preferably a C _1-90 alkyl, more preferably a C _1-37 alkyl, even more preferably a C _1-12 alkyl, even more preferably a C _1-6 alkyl, even more preferably a C _1-4 alkyl, and most preferably methyl. The aforesaid optionally substituted alkenyl is preferably a C _2-90 alkenyl, more preferably a C _2-37 alkenyl, even more preferably a C _2-12 alkenyl, even more preferably a C _2-6 alkenyl, and most preferably a C _1-4 alkenyl. The aforesaid optionally substituted alkynyl is preferably a C _2-90 alkynyl, more preferably a C _2-37 alkynyl, even more preferably a C _2-12 alkynyl, even more preferably a C _2-6 alkynyl, and most preferably a C _1-4 alkynyl.

The aforesaid aryl is preferably a C _6-14 aryl, more preferably phenyl, naphthyl or anthracenyl, even more preferably phenyl.

The aforesaid heteroaryl is preferably a heteroaryl having 5 to 14 ring atoms (such as: naphthyl having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isochi nolindiyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; or anthracenyl having one or two ring nitrogen atoms in place of CH units); more preferably a heteroaryl having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; even more preferably pyridinyl, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl or furazanyl.

The aforesaid cycloalkyl is preferably a C _3-14 cycloalkyl, more preferably a C _5-8 cycloalkyl, even more preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The The aforementioned heterocycloalkyl is preferably a heterocycloalkyl with 5 to 14 ring atoms; more preferably a heterocycloalkyl with 5 or 6 ring atoms, where one, two or three of the ring atoms independently of one another from nitrogen, oxygen or Sulfur selected and the remaining ring atoms Carbon atoms are; even more preferably piperidinyl, Tetrahydrothienyl, tetrahydrofuranyl, pyrrolidinyl, imidazolidinyl, Pyrazolidinyl, piperazinyl, morpholinyl, oxazolidinyl or isoxazolidinyl.

In one embodiment, R ⁷ , R ⁸ and R ⁹ each independently have the meaning hydrogen, fluorine, chlorine, bromine, iodine or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units independently may be replaced by in each case carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2 , 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3- , 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1, 8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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-, 2,1 0- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings.

Preferably R ⁷ , R ⁸ and R ⁹ each independently have the meaning C _1-12 -alkyl, C _2-12 -alkenyl or C _2-12 -alkynyl, more preferably C _1-6 -alkyl or C _2-6 - Alkenyl, even more preferably C _1-4 alkyl, and most preferably methyl.

X has the meaning optionally substituted alkylene, optionally substituted alkenylene or optionally substituted alkynylene, wherein one or more CH ₂ units, preferably 1 to 10 CH ₂ units, more preferably 1 to 3 CH ₂ units, within the aforementioned optionally substituted alkylene , of the abovementioned optionally substituted alkenylene or of the abovementioned optionally substituted alkynylene, may be replaced independently of one another by a respective substituting radical.

The aforementioned optionally substituted alkylene, the aforementioned optionally substituted Alkenylene or the aforementioned optionally substituted alkynylene is either unsubstituted or substituted with one or more substituents, preferably having 1 to 12 substituents, more preferably having 1 to 6 substituents independently selected from halogen (such as fluorine, chlorine, bromine or Iodine), cyano (-CN) or oxo (= O). Preferably, the aforementioned radicals are unsubstituted.

The replacing radicals are independently selected from oxygen (-O-), sulfur (-S-), selenium (-Se-), tellurium (-Te-), -CH = N-, -N = CH-, arylene ( preferably C _6-14 -arylene, such as, for example: phenylene, including phen-1,2-diyl, phen-1,3-diyl or phen-1,4-diyl; naphthylene, including naphth-1,2- diyl, naphth-1,3-diyl, naphth-1,4-diyl, naphth-1,5-diyl, naphth-1,6-diyl, naphth-1,7-diyl, naphth-1,8-diyl, Naphth-2,3-diyl, naphth-2,6-diyl or naphth-2,7-diyl; or anthracenylene, including anthracene-1,2-diyl, anthracene-1,3-diyl, anthracene-1,4- diyl, anthracene-1,5-diyl, anthracene-1,6-diyl, anthracene-1,7-diyl, anthracene-1,8-diyl, anthracene-1,9-diyl, anthracene-1,10-diyl, Anthracene-2,3-diyl, anthracene-2,6-diyl, anthracene-2,7-diyl, anthracene-2,9-diyl, anthracene-2,10-diyl or anthracene-9,10-diyl), heteroarylene (Preferably, heteroaryls having 5 to 14 ring atoms, more preferably heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; such as Pyridinylene, including pyridine-2,3-diyl, pyridine-2,4-diyl, pyridine-2,5-diyl, pyridine-2,6-diyl, pyridine-3,4-diyl or pyridine-3, 5-diyl; Thienylene, including thien-2,3-diyl, thien-2,4-diyl, thien-2,5-diyl or thien-3,4-diyl; Naphthylene having one or two ring nitrogen atoms in place of CH units, including quinolinediyl, isoquinolinediyl, benzopyridazinediyl, benzopyrimidinediyl or benzopyrazinediyl; Anthracenylene having one or two ring nitrogen atoms in place of CH units; furandiyl; pyrrolediyl; imidazolediyl; pyrazoldiyl; pyrazinediyl; pyrimidinediyl; pyridazinediyl; oxazolediyl; Isoxazoldiyl; or furazanediyl), cycloalkylene (preferably C _3-14 cycloalkylene such as: cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene) or heterocycloalkylene (preferably heterocycloalkylene having 5 to 14 ring atoms, such as the fully saturated analogs of the above heteroarylene radicals mentioned).

Preferably, the replacing radicals are independently selected from oxygen; Sulfur; phenylene; naphthylene; antracenylene; Heteroaryls having 5 or 6 ring atoms, wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms; C _5-8 cycloalkylene; or heterocycloalkylene having 5 or 6 ring atoms. It is preferred that no CH ₂ units are replaced.

The aforesaid optionally substituted alkylene is preferably a C _1-90 alkylene, more preferably a C _1-37 alkylene, even more preferably a C _1-20 alkylene, even more preferably a C _1-12 alkylene, and most preferably a C _1-4 alkylene. The aforesaid optionally substituted alkenylene is preferably a C _2-90 alkenylene, more preferably a C _2-37 alkenylene, even more preferably a C _2-20 alkenylene, even more preferably a C _2-12 alkenylene, and most preferably a C _2-4 alkenylene. The aforesaid optionally substituted alkynylene is preferably a C _2-90 alkynylene, more preferably a C _2-37 alkynylene, even more preferably a C _2-20 alkynylene, even more preferably a C _2-12 alkynylene, and most preferably a C _2-4 alkynylene.

In one embodiment, X has the meaning linear alkyl radical having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans- CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2 , 4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1, 2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6 or 2,7-disubstituted naphthalene radicals, in which one or two CH groups may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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 anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. To to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals may each be replaced independently of the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a bis 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C≡C Groups, 1,2-, 1,3- or 1,4-disubstituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted Pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1 , 7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, or 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 r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings.

Preferably X is unsubstituted or substituted C _1-12 -alkylene, optionally substituted C _2-12 -alkenylene or optionally substituted C _2-12 -alkynylene. More preferably X is an unsubstituted C _1-4 alkylene, such as. As methylene, ethylene, propylene or butylene.

• b. Perylenfarbstoff gemäß a), wobei der Perylenfarbstoff ein Perylentetracarbonsäurebisimid der Formel 4 ist:
  
• c. Unter Verwendung der Substanzen von a) oder b) oberflächlich mit Perylenfarbstoffen silylierte feste Dinge, bevorzugt aus Siliciumdioxid, Glas, Aluminiumoxid, Titandioxid, Zinkoxid, Indiumzinnoxid (ITO) und Glimmer. Am stärksten bevorzugt wird Siliciumdioxid.
• d. Unter Verwendung der Substanzen von a) oder b) oberflächlich mit Perylenfarbstoffen silylierte Pigmente, wie Pigmente aus Siliciumdioxid, Aluminiumoxid, Titandioxid, Zinkoxid oder Glimmer, bevorzugt aus Siliciumdioxid.
• e. Unter Verwendung der Substanzen von a) oder b) oberflächlich mit Perylenfarbstoffen silylierte Nanopartikel wie z. B. Nanopartikel aus Siliciumdioxid oder Titandioxid, bevorzugt Nanopartikel aus Siliciumdioxid, am stärksten bevorzugt wird hoch disperse Kieselsäure (HDK).
• f. Verfahren dadurch gekennzeichnet, dass die Perylenderivate nach a) oder b) in lipophilen Medien wie z. B. Chloroform, Toluol oder Ethylacetat auf Oberflächen von Pigmentteilchen oder Nanopartikeln gebracht werden und diese Pigmentteilchen oder Nanopartikel in polaren Medien wie z. B. Wasser, Ethanol, Methanol, iso-Propylalkohol oder tert-Butylalkohol re-dispergiert werden.
• g. Verfahren zur Herstellung der Perylenderivate nach a) oder b), umfassend einen Schritt des Hydrosilylierens von Olefinen. Bevorzugte Katalysatoren für die Hydrosilylierung sind Platinverbindungen und von diesen bevorzugt der Karstedt-Katalysator.
• h. Verfahren dadurch gekennzeichnet, dass für die Hydrosilylierung nach g) flüssige Reaktionsmedien verwendet werden, wie z. B. Chloroform, Dichlormethan oder andere chlorierte Alkane, bevorzugt wird Chloroform.
• i. Verwendung der Substanzen nach a) bis e) als Pigmente für Leimfarben und verwandten Farben wie z. B. Aquarell-Farben und Wasserfarben und Farben für Tintenstrahldrucker, Papierfarben, Druckfarben, Tinten und Tuschen und andere Farben für Mal- und Schreib-Zwecke und in Anstrichstoffen.
• j. Verwendung der Substanzen nach a) bis e) als Pigmente in Lacken. Bevorzugte Lacke sind Kunstharz Lacke wie z. B. Acryl- oder Vinyl-Harze, Polyesterlacke, Novolacke, Nitrocellulose-Lacke (Nitrolacke) oder auch Naturstoffe wie Zaponlack, Schellack oder Qi-Lack (Japanlack bzw. Chinalack oder ostasiatischer Lack).
• k. Verwendung der Farbstoffe nach a) bis e) in Datenspeichern, bevorzugt in optischen Speichern. Beispiele sind Systeme wie die CD- oder DVD-Platten.
• l. Verwendung der Substanzen nach a) bis e) als Fluoreszenzfarbstoffe.
• m. Verwendung der Substanzen nach a) bis e) in OLEDS (organischen Leuchtdioden).
• n. Verwendung der Substanzen nach a) bis e) in photovoltaischen Anlagen.
• o. Anwendung der Farbstoffe von a) bis e) zur Masse-Färbung von Polymeren. Beispiele sind Materialien aus Polyvinylchlorid, Polyvinylidenchlorid, Polyacrylsäure, Polyacrylamid, Polyvinylbutyral, Polyvinylpyridin, Celluloseacetat, Nitrocellulose, Polycarbonaten, Polyamiden, Polyurethanen, Polyimiden, Polybenzimidazolen, Melaminharzen, Silikonen wie z. B. Polydimethylsiloxan, Polyester, Polyethern, Polystyrol, Polydivinylbenzol, Polyvinyltoluol, Polyvinylbenzylchlorid, Polymethylmethacrylat, Polyethylen, Polypropylen, Polyvinylacetat, Polyacrylnitril, Polyacrolein, Polybutadien, Polychlorbutadien oder Polyisopren bzw. die Copolymeren der genannten Monomeren.
• p. Anwendung der Farbstoffe von a) bis e) zur Färbung von Naturstoffen. Beispiele sind Papier, Holz, Stroh, oder natürliche Fasermaterialien wie Baumwolle, Jute, Sisal, Hanf, Flachs, Seide, Tierhaare, menschliche Haare oder deren Umwandlungsprodukte wie z. B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon).
• q. Anwendung der Farbstoffe von a) bis e) als Beizenfarbstoffe, z. B. zur Färbung von Naturstoffen. Beispiele sind Papier, Holz, Stroh, oder natürliche Fasermaterialien wie Baumwolle, Jute, Sisal, Hanf, Flachs, Seide, Tierhaare, menschliche Haare oder deren Umwandlungsprodukte wie z. B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon). Bevorzugte Salze zum Beizen sind Aluminium-, Chrom- und Eisensalze.
• r. Anwendung der Farbstoffe von a) bis e) als Farbmittel, z. B. zur Färbung von Farben, Lacken und anderen Anstrichsstoffen, Papierfarben, Druckfarben, Tinten und andere Farben für Mal- und Schreib-Zwecke.
• s. Anwendung der Farbstoffe von a) bis e) als Pigmente in der Elektrophotographie: z. B. für Trockenkopiersysteme (Xerox-Verfahren) und Laserdrucker (”Non-Impact-Printing”).
• t. Anwendung der Farbstoffe von a) bis e) für Sicherheitsmarkierungs-Zwecke, wobei die große chemische und photochemische Beständigkeit und ggf. auch die Fluoreszenz der Substanzen von Bedeutung ist. Bevorzugt ist dies für Schecks, Scheckkarten, Geldscheine, Coupons, Dokumente, Ausweispapiere und dergleichen, bei denen ein besonderer, unverkennbarer Farbeindruck erzielt werden soll.
• u. Anwendung der Farbstoffe von a) bis e) als Zusatz zu anderen Farben, bei denen eine bestimmte Farbnuance erzielt werden soll, bevorzugt sind besonders leuchtende Farbtöne.
• v. Anwendung der Farbstoffe von a) bis e) zum Markieren von Gegenständen zum maschinellen Erkennen dieser Gegenstände über die Fluoreszenz, bevorzugt ist die maschinelle Erkennung von Gegenständen zum Sortieren, z. B. auch für das Recycling von Kunststoffen.
• w. Anwendung der Farbstoffe von a) bis e) als Fluoreszenzfarbstoffe für maschinenlesbare Markierungen, bevorzugt sind alphanumerische Aufdrucke oder Barcodes.
• x. Anwendung der Farbstoffe von a) bis e) zur Frequenzumsetzung von Licht, z. B. um aus kurzwelligem Licht längerwelliges, sichtbares Licht zu machen.
• y. Anwendung der Farbstoffe von a) bis e) in Anzeigeelementen für vielerlei Anzeige-, Hinweis- und Markierungszwecke, z. B. passive Anzeigeelemente, Hinweis- und Verkehrszeichen, wie Ampeln.
• z. Anwendung der Farbstoffe von a) bis e) in Tintenstrahldruckern in homogener Lösung als fluoreszierende Tinte.
• aa. Anwendung der Farbstoffe von a) bis e) als Ausgangsmaterial für supraleitende organische Materialien.
• bb. Anwendung der Farbstoffe von a) bis e) für Feststoff-Fluoreszenz-Markierungen.
• cc. Anwendung der Farbstoffe von a) bis e) für dekorative Zwecke.
• dd. Anwendung der Farbstoffe von a) bis e) für künstlerische Zwecke.
• ee. Anwendung der Farbstoffe von a) bis e) zu Tracer-Zwecken, z. B. in der Biochemie, Medizin, Technik und Naturwissenschaft. Hierbei können die Farbstoffe kovalent mit Substraten verknüpft sein oder über Nebenvalenzen wie Wasserstoffbrückenbindungen oder hydrophobe Wechselwirkungen (Adsorption).
• ff. Anwendung der Farbstoffe von a) bis e) als Fluoreszenzfarbstoffe in hochempfindlichen Nachweisverfahren.
• gg. Anwendung der Farbstoffe von a) bis e) als Fluoreszenzfarbstoffe in Szintillatoren.
• hh. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in optischen Lichtsammelsystemen.
• ii. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Fluoreszenz-Solarkollektoren.
• jj. Anwendung der Farbstoffe von a) bis e) in Flüssigkristallen zum Umlenken von Licht.
• kk. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Fluoreszenz-aktivierten Displays.
• ll. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Kaltlichtquellen zur lichtinduzierten Polymerisation zur Darstellung von Kunststoffen.
• mm. Anwenung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe zur Materialprüfung, z. B. bei der Herstellung von Halbleiterschaltungen.
• nn. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe zur Untersuchung von Mikrostrukturen von integrierten Halbleiterbauteilen.
• oo. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Photoleitern.
• pp. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in fotografischen Verfahren.
• qq. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Anzeige-, Beleuchtungs- oder Bildwandlersystemen, bei denen die Anregung durch Elektronen, Ionen oder UV-Strahlung erfolgt, z. B. in Fluoreszenzanzeigen, Braunscheu Röhren oder in Leuchtstoffröhren.
• rr. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe als Teil einer integrierten Halbleiterschaltung, die Farbstoffe als solche oder in Verbindung mit anderen Halbleitern z. B. in Form einer Epitaxie.
• ss. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Chemilumineszenzsystemen, z. B. in Chemilumineszenz-Leuchtstäben, in Lumineszenzimmunoassays oder anderen Lumineszenznachweisverfahren.
• tt. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe als Signalfarben, bevorzugt zum optischen Hervorheben von Schriftzügen und Zeichnungen oder anderen graphischen Produkten, zum Kennzeichnen von Schildern und anderen Gegenständen, bei denen ein besonderer optischer Farbeindruck erreicht werden soll.
• uu. Anwendung der Farbstoffe von a) bis e) als Farbstoffe oder Fluoreszenzfarbstoffe in Farbstoff-Lasern, bevorzugt als Fluoreszenzfarbstoffe zur Erzeugung von Laserstrahlen.
• vv. Anwendung der Farbstoffe von a) bis e) als Farbstoffe in Farbstoff-Lasern als Q-Switch Schalter.
• ww. Anwendung der Farbstoffe von a) bis e) als aktive Substanzen für eine nichtlineare Optik, z. B. für die Frequenzverdopplung und die Frequenzverdreifachung von Laserlicht.
• xx. Anwendung der Farbstoffe von a) bis e) als Rheologieverbesserer.
• yy. Anwendung der Farbstoffe von a) bis e) zur Dichtigkeitsprüfung geschlossener Systeme.

For the purposes of the present invention, the CH ₂ unit within a methyl group (-CH ₃ ) may also be replaced by one of the replacing radicals described herein.

• b. A perylene dye according to a), wherein the perylene dye is a perylenetetracarboxylic bisimide of the formula 4:
  
• c. Using the substances of a) or b) superficially silylated with perylene dyes, solid matters, preferably of silica, glass, alumina, titania, zinc oxide, indium tin oxide (ITO) and mica. Most preferred is silica.
• d. Using the substances of a) or b) superficially with perylene dyes silylated pigments, such as pigments of silica, alumina, titania, zinc oxide or mica, preferably of silica.
• e. Using the substances of a) or b) superficially with perylene dyes silylated nanoparticles such. B. Nanoparticles of silica or titanium dioxide, preferably nanoparticles of silica, most preferred is highly disperse silica (HDK).
• f. A process characterized in that the perylene derivatives according to a) or b) in lipophilic media such. As chloroform, toluene or ethyl acetate are brought to surfaces of pigment particles or nanoparticles and these pigment particles or nanoparticles in polar media such. For example, water, ethanol, methanol, iso-propyl alcohol or tert-butyl alcohol re-dispersed.
• G. A process for the preparation of the perylene derivatives of a) or b), comprising a step of hydrosilylating olefins. Preferred catalysts for the hydrosilylation are platinum compounds and of these preferably the Karstedt catalyst.
• H. Process characterized in that for the hydrosilylation according to g) liquid reaction media are used, such as. As chloroform, dichloromethane or other chlorinated alkanes, chloroform is preferred.
• i. Use of the substances according to a) to e) as pigments for glues and related colors such. For example, watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints.
• j. Use of the substances according to a) to e) as pigments in paints. Preferred paints are synthetic resin paints such. As acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as Zaponlack, shellac or Qi-lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer).
• k. Use of the dyes according to a) to e) in data memories, preferably in optical memories. Examples are systems such as the CD or DVD disks.
• l. Use of the substances according to a) to e) as fluorescent dyes.
• m. Use of the substances according to a) to e) in OLEDS (organic light-emitting diodes).
• n. Use of the substances according to a) to e) in photovoltaic systems.
• o. Application of the dyes of a) to e) for mass-dyeing of polymers. Examples are materials of polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinyl butyral, polyvinyl pyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such. Polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, polyacrylonitrile, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers.
• p. Application of the dyes from a) to e) for coloring natural products. Examples are paper, wood, straw, or natural fiber materials such as cotton, jute, sisal, hemp, flax, silk, animal hair, human hair or their transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon).
• q. Application of the dyes of a) to e) as mordant dyes, z. B. for coloring natural products. Examples are paper, wood, straw, or natural fiber materials such as cotton, jute, sisal, hemp, flax, silk, animal hair, human hair or their transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon). Preferred salts for pickling are aluminum, chromium and iron salts.
• r. Application of the dyes of a) to e) as a colorant, z. For example, for coloring paints, varnishes and other paints, paper inks, inks, inks and other colors for painting and writing purposes.
• s. Application of the dyes of a) to e) as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing").
• t. Application of the dyes of a) to e) for security marking purposes, wherein the high chemical and photochemical stability and possibly also the fluorescence of the substances is of importance. This is preferred for checks, check cards, banknotes, coupons, documents, identification documents and the like, in which a special, unmistakable color impression is to be achieved.
• u. Use of the dyes of a) to e) as an additive to other colors in which a certain shade of shade is to be achieved, preferred are particularly bright shades.
• v. Application of the dyes of a) to e) for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. B. also for the recycling of plastics.
• w. Application of the dyes of a) to e) as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes.
• x. Application of the dyes of a) to e) for the frequency conversion of light, z. B. to make shortwave light longer-wavelength, visible light.
• y. Application of the dyes of a) to e) in display elements for a variety of display, reference and marking purposes, eg. B. passive display elements, information and traffic signs, such as traffic lights.
• z. Application of the dyes of a) to e) in ink jet printers in homogeneous solution as a fluorescent ink.
• aa. Application of the dyes from a) to e) as starting material for superconducting organic materials.
• bb. Application of the dyes from a) to e) for solid fluorescence labels.
• cc. Application of the dyes from a) to e) for decorative purposes.
• dd. Application of the dyes from a) to e) for artistic purposes.
• ee. Application of the dyes of a) to e) for tracer purposes, eg. B. in biochemistry, medicine, technology and science. In this case, the dyes may be covalently linked to substrates or via secondary valences such as hydrogen bonds or hydrophobic interactions (adsorption).
• ff. Application of the dyes from a) to e) as fluorescent dyes in highly sensitive detection methods.
• gg. Application of the dyes of a) to e) as fluorescent dyes in scintillators.
• hh. Application of the dyes of a) to e) as dyes or fluorescent dyes in optical light-harvesting systems.
• ii. Application of the dyes from a) to e) as dyes or fluorescent dyes in fluorescence solar collectors.
• jj. Application of the dyes from a) to e) in liquid crystals for deflecting light.
• kk. Application of the dyes of a) to e) as dyes or fluorescent dyes in fluorescence akti fourth displays.
• ll. Application of the dyes from a) to e) as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics.
• mm. Application of the dyes of a) to e) as dyes or fluorescent dyes for material testing, eg. B. in the manufacture of semiconductor circuits.
• nn. Application of the dyes of a) to e) as dyes or fluorescent dyes for the investigation of microstructures of integrated semiconductor devices.
• oo. Application of the dyes from a) to e) as dyes or fluorescent dyes in photoconductors.
• pp. Application of the dyes of a) to e) as dyes or fluorescent dyes in photographic processes.
• qq. Use of the dyes of a) to e) as dyes or fluorescent dyes in display, illumination or image converter systems, in which the excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braunscheu tubes or in fluorescent tubes.
• rr. Application of the dyes of a) to e) as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in combination with other semiconductors z. In the form of an epitaxy.
• ss. Application of the dyes of a) to e) as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method.
• tt. Use of the dyes of a) to e) as dyes or fluorescent dyes as signal colors, preferably for the visual highlighting of lettering and drawings or other graphic products, for marking signs and other objects in which a particular optical color impression is to be achieved.
• uu. Application of the dyes of a) to e) as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for the production of laser beams.
• vv. Application of the dyes from a) to e) as dyes in dye lasers as Q-switch switches.
• ww. Application of the dyes of a) to e) as active substances for nonlinear optics, eg. B. for the frequency doubling and frequency tripling of laser light.
• xx. Application of the dyes from a) to e) as rheology improver.
• yy. Application of the dyes from a) to e) for leak testing of closed systems.

description

We have started with perylenetetracarboxylic bisimide 1a (R = 1-hexylheptyl), in which the long-chain sec-alkyl radicals mediate light solubility in organic media, [3] and have investigated the extent to which nuclear substitution with the highly nucleophilic amide anion is possible. When the dipolar aprotic solvent benzonitrile is used, not only is the core substitution of 1a, but also an extension of the aromatic system involving the solvent. ¹ H NMR spectroscopy revealed three vicinal HH couplings of perylene core signals consistent with only a five-ring extension. Compound 2 was alkylated with allyl bromide to yield the strongly red fluorescent 3 (see 1 ). In the case of the alkylation product, ¹ H NMR spectroscopy shows no NOE effect between the allylic CH ₂ group and protons of the perylene core. Thus, the regio-orientation of the alkylation according to the structure 3 is given preference. 3 was hydrosilated to 4 using trimethoxysilane using the Karstedt catalyst [4], which is a universal material for "grafting". The reaction with silica derivatives is of particular interest because of the structure 5 (see 2 ) the silica network structure blends harmoniously into a silicone structure that eventually bears the strongly fluorescent chromophore of 4.

We have first implemented Kieselgel 60 with 4 and thereby amazing Smooth get a strong red fluorescent pigment, because of of its silica backbone in all organic compounds studied Media such as chloroform or ethyl acetate is insoluble. Herewith are given ideal properties as a fluorescent pigment. The covalent Linkage of the chromophore with the silica structure can prove that it is with the usual Solvents such as chloroform or ethyl acetate fail to produce the chromophore again to remove from the silica material. About that In addition, the material is amazingly lightfast; even after several months When exposed to sunlight, the color remains unchanged.

We have also studied the combination of 4 with smaller silica structures, and the nanoparticles Cabosil ^® M-5 and the pyrogenic silica (fumed silica) HDK T40 therefor used. Coating in polar media such as ethanol resulted in inadequate reaction, while surprisingly strong coatings came in chloroform. By centrifuging and redispersing in Etha Nol dispersions were prepared in ethanol. The particle size was determined by the DLS method, and it was found for both the Cabosil ^® M-5 as well as nanoparticles for the highly disperse silica HDK T40 a similar particle size distribution with a frequency maximum at about 150 nm; please refer 3 , When redispersed in water, the distribution becomes inhomogeneous, with levels well below 100 nm. The distribution can be further controlled by the composition of the solvent. Thus, a mixture of methanol / water 1: 1 gives a frequency maximum at about 40 nm; However, the exact location depends on the preparation. The particle size distribution can be further influenced by filtration techniques cf. also ref. [5]. Filtration of the aqueous dispersion by "Blue Band ^®" paper filter (porosity ≤ 450 nm, Schleicher & Schuell) shifts the maximum of the distribution towards smaller particle sizes of about 70 nm; please refer 4 , Even smaller dimensions are obtained (200 nm porosity) by filtration through a Millex ^® filter with which the particle size can be up to 50 nm well reduced. These filtered nanodispersions show no tendency to form larger aggregates. Obviously, individual surface structures are responsible for the formation of aggregates, so that dispersions with smaller particles are obtained when the respective fractions are filtered off.

In 5 the UV / Vis spectra of the nanoparticles are shown. The fluorescence excitation spectrum of the coated Cabosil ^® M-5 nanoparticles in ethanol is very similar to the spectrum of the dye in the homogeneous 3, lipophilic solution in chloroform. It can therefore be assumed that the chromophores on the surface of the particles are freely movable and absorb light in isolation from each other (no exciton effects).

The nanoparticle composites fluoresce strongly - fluorescence quantum yields close to 100% were found. The fluorescence spectra of the nanoparticles of Cabosil M-5 ^® and HDK T40 resemble each other very strong; second line from below and almost congruent line in 5 , right. However, the long-wavelength region of the spectrum is more pronounced than in the spectrum of dye 3 in chloroform. This is an indication of the occurrence of excimers. This is interesting for a practical use of the substances because the effective Stokes shift is increased and thus re-absorption of fluorescent light is reduced. Stronger effects occur in the nanoparticles in water and finally in the coated silica gel T60 (next lines from bottom to top).

Because of the extremely fine distribution, the nanoparticles be used in many ways, such. B. for the Homogeneous coloring of polymer materials in which the strong red fluorescence is attractive. The nanocomposites can be left beyond that also with all established applications of pigments.

Of the Dye 4 also reacted with γ-alumina surprisingly, this was not only possible with basic, but also with acid; you get highly fluorescent Solids. Even more surprising is the easy mounting from 4 to titanium dioxide pigment that causes a red coloration leads, but with weaker fluorescence than the other described support materials; also Here, the dye is no longer with solvents remove. The titanium dioxide is particularly interesting because it is in the Grätzel cell used for the production of solar energy and here the linkage with the sensitizing dyes an essential element for the function of these solar cells represents.

The new pigments and nanoparticles can be extremely versatile be used and are characterized by their utter Insolubility in organic media at the same time high Fluorescence quantum yields. The light fastness of the materials is significant because no degradation has been observed so far when the Substances have been exposed to sunlight for a longer period of time. The coated silica gel is initially as a fluorescent pigment for decorative purposes or even for warning and Signs of interest and for much more. The In addition, smaller nanoparticles may be due to their small dimensions for applications such as detection used by cracks or even the marking of organic structures, so z. Inside living cells.

General Procedure for Dye Coating of Silica Particles: The silica particles used were heated at 80 ° C. for one hour under a fine vacuum prior to the coating reaction in order to remove superficially bound water. 100 mg of the respective silica particles (Cabosil ^® M-5 and HDK T 40) were dissolved in chloroform (8 mL) for 16 h dispersed at room temperature, treated dropwise with the dye solution by dye 2,11-Bis (1-hexylheptyl) -4 - (3-trimethoxysilylpropyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3, 10,12 (2H, 11H) -tetraone 1,3,9,11 (2H, 5H, 9H, 11H) -tetraon (0.5 mL), boiled under reflux for 5 h, stirred for 16 h at room temperature, repeatedly centrifuged (min 15 min at 19,000 rpm) and in chloroform by stirring (at least 30 min.) At room temperature redispersed until the supernatant was colorless and then redispersed in ethanol. As needed, ethanol was removed by centrifugation and redispersion to water or other media, and then the nanodispersions were further filtered through Blauband filters (pore size ≤ 450 nm, Schleicher and Schuell)) or Millex filter (porosity 220 nm).

Illustrations - list of reference numerals

1 Synthesis of Trimethoxysilyl Imidazole Perylene Dye 4.

2 Linkage of Dye 4 to Reactive Surfaces.

3 Particle sizes of the 4-coated nanoparticles in ethanol determined by the DLS method. Right Carbosil M5 ^® and further left highly disperse silica HDK T40, HDK T40 in methanol / water 1: 1 far left and further to the right Cabosil ^® M5 in water.

4 , The influence of a nanofiltration of coated highly disperse silica HDK T40. From right to left: HDK T40 in ethanol in water after filtration with ^® Blue Band ^® filters and after filtration with Millex filters.

5 , UV / Vis absorption (left) and fluorescence spectra (right). Left: thick line: Absorption spectrum of 3 in chloroform, thin line fluorescence excitation spectrum of 4 coated nanoparticles Cabosil M5 ^® in ethanol. Right at 650 nm from bottom to top: 3 in chloroform, coated nanoparticles Cabosil M5 ^® and thin, almost congruent line HDK T40 in ethanol, nanoparticles Cabosil M5 ^® in water and silica gel T60 in chloroform.

Experimental part

General. IR Spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000; UV / Vis spectra: Varian Cary 5000 and Bruins Omega 20; Fluorescence spectra: Perkin Elmer FS 3000 (fully corrected); NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95.

2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e'f '] diisochinolin- 1,3,10,12 (2H, 11H) -tetraone (2a): 2,9-bis (1-hexylheptyl) anthra [2,1,9-def: 6,5,10-d'e'f diisoquinoline-1,3,8,10 (2H, 9H) -tetraone (1a, 1.00 g, 1.32 mmol) and NaNH ₂ (1.00 g, 25.6 mmol) were suspended in benzonitrile (250 mL), 165 h for 3 h ° C (blue color), allowed to cool and shaken with a 1: 1 mixture of 2N HCl and CHCl ₃ (300 mL). The organic phase was dried (MgSO ₄ ), evaporated to dryness in vacuo (remove excess benzonitrile), taken up in CHCl ₃ , filtered and purified by column chromatography (silica gel, CHCl ₃ ). There was obtained a single adduct and a double adduct of benzonitrile. 1st fraction: double adduct. Yield: 40 mg (4%) black dye, mp> 300 ° C, R _f (silica gel, chloroform) = 0.88, IR (ATR): v ~ = 3316.7 m, 2950.3 m, 2920.1 s, 2852.0 m, 1672.9 s, 1616.9 s, 1586.9 s, 1532.3 w, 1487.0 w, 1453.1 w, 1436.5 w, 1401.4 w, 1339.6 m, 1332.0 s, 1299.4 w, 1267.0 w, 1232.4 w, 1184.3 w, 1109.1 w, 1058.6 m, 1000.6 m, 955.5 w, 895.7 w, 867.9 w, 815.0 w, 779.6 w, 758.2 m, 731.6 w, 687.6 w cm ^-1 . ¹ H-NMR (600 MHz, _CDCl3, 25 ° C), δ = 0.82-0.89 (m, 12H, CH _3), 1:26 to 1:47 (m, 32H, CH _2), 1.91-2.06 (dm, 4H, β-CH ₂ ), 2.28-2.43 (m, 4H, β-CH ₂ ), 5.22-5.36 (m, 2H, CH-N), 7.65-7.67 (m, 3H, CH _aromat. ), 8.33-8.38 ( m, 2H, CH _aromat. ), 8.72-8.85 (m, 6H, H _perylene ), 10.95 (d, 1H, ³ J = 8.0 Hz), 11.55 ppm (s, 1H, NH). ¹³ C-NMR (151 MHz, CDCl _3, 25 ° C): δ = 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.6, 104.8, 121.2, 122.7, 123.5, 126.5, 126.6, 127.7, 128.1, 129.1, 129.4, 130.4, 130.6, 131.1, 132.2, 134.7, 134.9, 135.2, 135.2, 138.7, 39.0, 139.2, 143.9, 157.3, 163.9, 166.9, 165.7 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 388.6 (0.07), 413.0 (12:12), 452.6 (12:14), 481.0 (0.15) 514.4 (12:14), 547.2 (12:11), 589.6 (12:42) 640.6 (1.00). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 650.8 (1.00), 712.3 nm. (0.32). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 472 nm, E ₄₇₂ nm = 0.149 cm ^-1 , reference: S13 at 1.00): 1.00, MS (DEI ⁺ / 70 eV): m / z (%) = 990 (25) [M ⁺ + 4H], 989 (63) [M ⁺ + 3H], 988 (91) [M ⁺ + 4H], 806 (19), 805 (20), 624 (21), 623 (66), 622 (100 ), 55 (11), HMRS (C ₆₄ H ₇₁ N ₆ O ₄ ): Ber. m / z: 987,554; Gef. M / z: 987,552, Δ = -2 mmu.

2nd Fraction: Ausb. 409 mg (36%) of 2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e 'f'] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (2a) as shiny metallic violet dye, mp> 300 ° C, R _f (silica gel, chloroform) = 0.85, IR (ATR ): v ~ = 3411.7 m, 2954.8 m, 2923.5 s, 2855.2 m, 1689.1 s, 1656.0 s, 1640.3 s, 1623.0 s, 1591.7 s, 1534.8 w, 1486.6 w, 1455.4 w, 1432.6 w, 1396.1 w, 1375.6 w, 1342.4 s, 1332.0 s, 1305.6 m, 1257.4 m, 1219.9 w, 1179.1 w, 1090.9 m, 1054.9 m, 1016.0 m, 871.0 w, 807.6 m, 796.5 m, 748.1 m, 727.0 w, 684.0 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.81-0.85 (m, 12H, CH _3), 1:23 to 1:40 (m, 32H, CH _2), 1.86-1.97 (m, 4H, β-CH ₂ ), 2.24-2.37 (m, 4H, β-CH ₂ ), 5.18-5.30 (m, 2H, CH-N), 7.67-7.69 (m, 3H, CH _aromat. ), 8.33-8.35 ( m, 2H, CH _aromat. ), 8.56-8.77 (m, 6H, H _perylene ), 10.74 (d, 1H, ³ J = 8.2 Hz), 11.52 ppm (s, 1H, NH). ¹³ C-NMR (151 MHz, CDCl _3, 25 ° C): δ = 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.6, 104.8, 121.2, 122.7, 123.5, 126.5, 126.6, 127.7, 128.1, 129.1, 129.4, 130.4, 130.6, 131.1, 132.2, 134.7, 134.9, 135.2, 135.2, 138.7, 39.0, 139.2, 143.9, 157.3, 163.9, 166.9, 165.7 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 378.6 (9020) 396.9 (9210) 439.4 (13400), 463.6 (14700), 504.6 (15900), 541.9 (48100), 586.6 nm (92000) , Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 599.3 (1.00), 651.5 (0.43). Fluoreszenzquantenausb. _(CHCl3, λ _exc = 541 nm, E541 nm = 0.322 cm ^-1 Reference: 1a with Φ = 1.00): 1.00. HMRS (C ₅₇ H ₆₇ N ₄ O ₄ ): Ber. m / z: 871,516; M / z: 871,517, Δ = 1 mmu, C ₅₇ H ₆₆ N ₄ O ₄ (871.2): Ber. C 78.59%, H 7.64, N 6.43%; Gef. C 78.49, H 7.78, N 6.55%.

4-allyl-2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (3a): 2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4,5': 3,4] anthra [2 , 1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (2a, 100 mg, 0.115 mmol), allyl bromide (624 mg , 3.45 mmol) and potassium carbonate (300 mg, 2.17 mmol) were suspended in DMPU (5 mL), heated to 65 ° C for 24 h, while still lukewarm with aqueous HCl (2 N, 50 mL), filtered, dried, in a little Chloroform taken and purified by column chromatography to remove unreacted allyl bromide (silica gel, chloroform / iso-hexane 2: 1). Y. 87 mg (83%), mp> 250 ° C. R _f (silica gel, chloroform): 0.52. ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, ³ J = 7.0 Hz, 12H, CH ₃ ), 1.16-1.40 (m, 32H, CH ₂ ), 1.82-1.92 ( m, 4H, β-CH), 2.20-2.34 (m, 4H, β-CH), 4.44-4.64 (br, 1H, CH _allyl ), 4.81-4.88 (br, 1H, CH _allyl ), 5.15-5.22 ( m, 2H, N-CH ₂ ), 5.42-5.60 (br, 3H, N-CH + CH _allyl ), 7.64-7.68 (m, 3H, CH _aromat. ), 7.95-8.00 (m, 2H, CH _aromat. ), 8.60-8.79 (m, 5H, CH _perylene ), 10.75 ppm (d, ³ J = 8.1 Hz, 1H, CH _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.3, 22.8, 22.8, 27.2, 27.3, 29.5, 29.5, 32.0, 32.1, 32.7, 51.3, 54.9, 55.3, 121.5, 122.8, 123.9, 125.6, 127.0, 127.3, 129.3, 129.9, 130.4, 130.4, 131.5, 132.5, 135.0, 139.6, 144.8, 163.4, 164.1, 165.1 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 376.0 (8067), 395.4 (8978), 500.3 (14530), 536.9 (43870), 581.3 nm (82740). Fluorescence (CHCl ₃ ): λ _max (I _rel ) 594.6 (1.00), 644.2 nm (0.32). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 537.5 nm, E _537.5 nm = 0.01405 cm ^-1 , reference: 1a with Φ = 1.00): 1.00. HRMS (C ₆₀ H ₇₀ N ₄ O _4): Calcd. m / z = 910.5397, Gef. m / z = 910.5379, Δ = -0.0018. C ₆₀ H ₇₀ N ₄ O ₄ (911.2): Calcd. C 79.09, H 7.74, N 6.15; Gen. C 78.87, H 7.71, N 5.83.

2,11-bis (1-hexylheptyl) -4- (3-trimethoxysilylpropyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d 'e'f'] diisoquinoline-1,3,10,12 (2H, 11H) -tetrazone 1,3,9,11 (2H, 5H, 9H, 11H) -tetraone (4a): In a heated and argon flooded Schlenk flask was reacted at room temperature with 4-allyl-2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10- d'e'f '] diisoquinoline-1,3,10,12 (2H, 11H) -tetraone (3a, 50 mg, 54 μmol) was dissolved in dry chloroform (7 mL), carefully treated with trimethoxysilane (1.2 mL) via a septum , 9.84 mmol) and platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt catalyst, 40 mg, 3.75 mol% in vinyl-terminated polydimethylsilicone). Stirred for 6 h at room temperature (the solution can be stored under argon at room temperature) and then used under an argon atmosphere without further purification for the grafting reactions. Upon contact with Kieselgel 60, immobilization took place in a few minutes. Chromatographic purification was accomplished using a rotary chromatograph (Chromatotron) with gypsum-hardened silica gel plates and chloroform for elution. Y. 20 mg (36%) violet solid, mp 230 ° C. R _f value (CHCl ₃ ) = 0.42. IR (ATR): v ~ = 2954.9 (w), 2925.0 (m), 2856.6 (w), 1685.0 (s), 1644.5 (s), 1592.0 (m), 1528.8 (w), 1484.4 (w), 1457.4 ( w), 1424.7 (m), 1407.8 (w), 1379.3 (w), 1362.9 (w), 1333.1 (vs), 1256.4 (s), 1185.5 (m), 1081.4 (vs), 1014.9 (s), 933.9 ( w), 872.6 (w), 808.0 (vs), 799.8 (vs), 772.8 (s), 751.6 (s), 738.6 (s), 721.7 (m), 701.9 cm ^-1 (s). ¹ H-NMR (400 MHz, CDCl ₃ , 25 ° C, TMS): δ = -0.05-0.03 (m, 2H, Si-CH ₂ ), 0.80-0.84 (m, 12H, 4 x CH ₃ ), 1.20 -1.40 (m, 32H, 16 x CH ₂ ), 1.43-1.51 (m, 2H, Si-CH ₂ -C H₂ ), 1.82-1.96 (m, 4H, 2 x β-CH ₂ ), 2.22-2.34 ( m, 4H, 2 x β-CH ₂ ), 3.22 (s, 9H, Si (OCH ₃ ) ₃ ), 4.95 (t, ³ J (H, H) = 6.8Hz, 2H, N-CH ₂ ), 5.16 -5.28 (m, 2H, 2 x N-CH), 7.67-7.69 (m, 3H, 3 x CH _aromat. ), 8.00-8.03 (m, 2H, 2 x CH _aroma ), 8.64-8.00 (m, 5H, 5 x CH _perylene ), 10.79-10.83 ppm (d, J = 8.2 Hz, 1H, CH _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C, TMS): δ = 5.4, 14.1, 22.1, 22.6, 26.9, 27.0, 29.2, 29.3, 31.8, 32.4, 50.3, 51.3, 54.6, 54.8, 121.2, 122.6, 123.6, 126.8, 127.1, 129.1, 129.9, 130.3, 131.1, 131.3, 134.9, 144.8, 163.9 ppm. ²⁹ Si-NMR (80 MHz, CDCl _3, 22 ° C): δ = -43.3 ppm. UV / VIS (CHCl ₃ ): λ _max (E) = 502.4 (0.18), 539.2 (0.53), 583.7 nm (1.00). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 596.4 (1.00), 648.9 (0.46). Fluorescence quantum yield (CHCl ₃ , λ _exc = 539 nm, E ₅₃₉ nm = 0.0105 cm ^-1 , reference: 1a with Φ = 1.00): 1.00. MS (DEP / EI): m / z (%): 1034.6 (32) [M ⁺ + 2H], 1033.6 (73) [M ⁺ + H], 1032.6 (100) [M ⁺ ], 851.4 (12), 850.4 (10), 507.1 (20), 506.1 (31), 121.0 (23). HRMS (C ₆₃ H ₈₀ N ₄ O ₇ Si): Mf: 1032.5796; Gef .: 1032.5799, Δ = + 0.0003.

• [1] [a] Review: H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343 , [B] Review: H. Langhals, Heterocycles 1995, 40, 477-500 , [C] H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 ,
• [2] [a] R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Federal Minister. Research. Technol., Tech nol. Research. Develop. 1984, BMFT-FB-T 84-164; Chem. Abstr. 1985, 102, 150903 , [B] H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380 , [C] MI Rudkevich, TA Korotenko, Vestn. Khar'kov. Politekh. Inst. 1969, 41, 21-26; Chem. Abstr. 1971, 75, 7375 , [D] Y. Zhao, WMR Wasielewski, Tetrahedron Lett. 1999, 40, 7047-7050 ,
• [3] [a] S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230 , [B] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748 ,
• D. Karstedt, Ger. [4] a) B. Open. DE 2307085 ( 08/23/1973 ); Chem. Abstr. D. Karstedt, Ger. 1974, 80, 16134. b) B. Open. DE 1941411 ( 23/12/1970 ); Chem. Abstr. 1971, 74, 100519. c) M. Lautens (ed.), M. Science of Synthesis, Houben-Weyl Methods of Molecular Transformations; Organometallics: Compounds with Transition Metal-Carbon π-Bonds and Compounds of Groups 10-8 (Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) 2002, vol. 1, 1112 pp., Georg Thieme Verlag, Stuttgart (Germany); Chem. Abstr. 2002, 139, 22333 , d) A. Behr, F. Naendrup, D. Obst, Adv. Synth. Catal. 2002, 344, 1142-1145 ,
• [5] N. Roussel, TNH Nguyen, P Coussot, Phys. Rev. Lett. 2007, 98, 114502-1-114502-4 ,

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 2307085 [0074]
• - DE 2381973 [0074]
• - DE 1941411 [0074]
• - DE 23121970 [0074]

Cited non-patent literature

• - Review: H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343 [0074]
• Review: H. Langhals, Heterocycles 1995, 40, 477-500 [0074]
• H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 [0074]
• - R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Federal Minister. Research. Technol., Technol. Research. Develop. 1984, BMFT-FB-T 84-164; Chem. Abstr. 1985, 102, 150903 [0074]
• - H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380 [0074]
• - MI Rudkevich, TA Korotenko, Vestn. Khar'kov. Politekh. Inst. 1969, 41, 21-26; Chem. Abstr. 1971, 75, 7375 [0074]
• - Y. Zhao, WMR Wasielewski, Tetrahedron Lett. 1999, 40, 7047-7050 [0074]
• - S.Demmig, H.Langhals, Chem. Ber. 1988, 121, 225-230 [0074]
• H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748 [0074]
• M. Lautens (ed.), M. Science of Synthesis, Houben-Weyl Methods of Molecular Transformations; Organometallics: Compounds with Transition Metal-Carbon π-Bonds and Compounds of Groups 10-8 (Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) 2002, vol. 1, 1112 pp., Georg Thieme Verlag, Stuttgart (Germany); Chem. Abstr. 2002, 139, 22333 [0074]
• A. Behr, F. Naendrup, D. Obst, Adv. Synth. Catal. 2002, 344, 1142-1145 [0074]
• N. Roussel, TNH Nguyen, P. Coussot, Phys. Rev. Lett. 2007, 98, 114502-1-114502-4 [0074]

Claims (10)

Perylene dye of the general formula 6,

wherein: R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halo, optionally with one or more CH ₂ units within the aforementioned optionally substituted alkyl, the above-mentioned optionally substituted alkenyl or the above-mentioned optionally substituted alkynyl independently by a respective replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or Heterocycloalkylene, and further wherein the aforementioned optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforesaid optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ^{3 is} hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen optionally having one or more CH ₂ units within the aforementioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the above-mentioned optionally substituted alkynyl are independently replaced by a respective substituting radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforesaid optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen optionally with one or more CH ₂ units within the aforementioned optionally substituted alkyl, the abovementioned optionally substituted alkenyl or the abovementioned optionally substituted alkynyl independently of one another by a respective replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkyl, the aforesaid optionally substituted alkenyl or the aforementioned optionally substituted alkynyl may be substituted with one or more substituents independently selected from halogen, cyano or oxo; R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl or halogen, optionally with one or more CH ₂ units within the aforementioned optionally substituted alkyl, the abovementioned optionally substituted alkenyl or the abovementioned optionally substituted alkynyl independently of one another by a respective replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the above-mentioned optionally substituted alkyl, the aforementioned optionally substituted alkenyl or the aforementioned optionally substituted alkynyl having one or more substituents independently selected from halogen, cyano or oxo, may be substituted; X is optionally substituted alkylene, optionally substituted alkenylene or optionally substituted alkynylene, optionally wherein one or more CH ₂ units within the aforesaid optionally substituted alkylene, the aforementioned optionally substituted alkenylene or the aforementioned optionally substituted alkynylene are each independently replaced by one replacing radical selected from oxygen, sulfur, selenium, tellurium, -CH = N-, -N = CH-, arylene, heteroarylene, cycloalkylene or heterocycloalkylene, and further wherein the aforementioned optionally substituted alkylene, the aforementioned optionally substituted alkenylene or the The above-mentioned optionally substituted alkynyls having one or more substituents independently selected from halogen, cyano or oxo may be substituted. A perylene dye according to claim 1, wherein R ¹ and R ² each independently have the meaning unsubstituted C _6-20 alkyl. A perylene dye according to claim 1 or 2 wherein R ^{3 is} phenyl, naphthyl, anthracenyl or heteroaryl having 5 or 6 ring atoms wherein one, two or three of the ring atoms are independently selected from nitrogen, oxygen or sulfur and the remaining ring atoms are carbon atoms. A perylene dye according to any one of claims 1 to 3, wherein R ⁴ , R ⁵ and R ⁶ each independently have the meaning of hydrogen or C _1-20 alkyl. A perylene dye according to any one of claims 1 to 4, wherein R ⁷ , R ⁸ and R ⁹ each independently have the meaning C _1-4 alkyl. Perylene dye according to one of Claims 1 to 5, wherein X is methylene, ethylene, Propylene or butylene has. A perylene dye according to claim 1, wherein the perylene dye is a perylenetetracarboxylic bisimide of formula 4:

Use of the substances according to 1 to 4 as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, as pigments in paints, preferred paints are synthetic resin paints such as acrylic or vinyl resins, polyester lacquers, novolaks, nitrocellulose lacquers (nitro lacquers) or even natural substances such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples are materials of polyvinyl chloride, Polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, Polyacrylni tril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for the dyeing of Na Examples of materials are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As for coloring paints, varnishes and other paints, paper inks, inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades. Use of the substances according to 1 to 4 for Marking, security and display purposes, in particular under Considering their fluorescence, such as. B. as dyes or fluorescent dyes for signal colors, preferred for the visual highlighting of lettering and drawings or other graphic products, for signage and other objects and in display elements for various display, reference and marking purposes in which a special optical color impression is to be achieved for Passive display elements, information and traffic signs, such as traffic lights for security marking purposes, being the big one chemical and photochemical resistance and possibly also the fluorescence of the substances is of importance, is preferred this for checks, check cards, banknotes, coupons, documents, Identification papers and the like, in which a special, unmistakable Color impression is to be achieved, for marking objects for machine recognition of these objects the fluorescence, preferred is the machine detection of objects to sort, z. B. also for the recycling of plastics, as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes, as dyes in ink-jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems in which the Excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, e.g. B. in biochemistry, medicine, technology and Science, here, the dyes can be covalent be associated with substrates or on minor valences such as hydrogen bonds or hydrophobic interactions (Adsorption), as dyes or fluorescent dyes in Chemi lumineszenzsystemen, z. As in chemiluminescent light rods, in Lumineszenzimmunoassays or other luminescence detection method and as a material for leak testing closed systems. Use of the dyes according to 1 to 4 as functional Materials, such. B. in data storage, preferably in optical Save as the CD or DVD disks, in OLEDS (Organic Light Emitting Diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers (Non-Impact Printing), for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light-harvesting systems, such as B. the fluorescence solar collector or fluorescence activated Displays, in liquid crystals for redirecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, z. B. in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic Process, as dyes or fluorescent dyes as part of a Semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. In the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferred as fluorescent dyes for generating laser beams, but also as Q switch switch and as active substances for a non-linear optics, z. B. for frequency doubling and the frequency tripling of laser light.