DE10233955A1 - Preparation of quaterylene-bisimides, useful as fluorescent dyes, e.g. for natural or synthetic textiles or as markers for biomolecules, by base cyclization of a bis-perylene-dicarboxylic acid imide - Google Patents

Abstract

Preparing quaterylene-bisimides (I) comprising treating the corresponding 9,9'-bis(perylene-3,4-dicarboxylic acid-3,4-imide) (II) with a tertiary alkoxide (particularly potassium tert-amylate or, best tert-butylate) in presence of an auxiliary base, especially DBU (1,5-diazabicyclo(4,3,0)non-5-ene, is new. Preparing quaterylene-bisimides of formula (I) comprises treating the corresponding 9,9'-bis(perylene-3,4-dicarboxylic acid-3,4-imide) of formula (II) with a tertiary alkoxide (particularly potassium tert-amylate or, best tert-butylate) in presence of an auxiliary base, especially DBU (1,5-diazabicyclo(4,3,0)non-5-ene. R1, R2 = H or 1-4 (preferably 1-3) groups such as isocyclic aromatic groups (especially mono- to tetracyclic, particularly mono- or bicyclic groups such as phenyl, diphenyl, naphthyl or anthryl), heterocyclic aromatic groups (preferably mono- to tricyclic groups, which may be pure heterocyclic groups or a heterocyclic ring and one or more fused benzene rings) or Z. The isocyclic as well as the heterocyclic aromatic groups may be substituted by Z which do not impart water solubility Z = halo e.g. Cl, Br, I or F, alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C, the alkyl groups may be substituted by groups which do not impart water solubility, OR9, CN, N(R10)(R11), COR12 , N(R13)COR14, N(R15)COOR16, N(R17)CON(R18)(R19), NHSO2R20, SO2R21, SOR22, SO2OR23, CON(R24)(R25), SO2N(R26)(R27), N=N-R28, OCOR29, OCONHR30; R9 = H, alkyl, aryl, e.g. naphthyl or especially unsubstituted phenyl, 3-24C cycloalkyl; R10 , R11, R13, R20, R21, R22, R23, R24, R25, R26, R27, R29 = alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C. The alkyl groups may be substituted by groups which do not impart water solubility; R12, R30 = halo; R15-R19 = alkyl or cycloalkyl having 1-21 (especially 1-12, more especially 1- 8, particularly 1- 4) C, the alkyl groups may be substituted by groups which do not impart water solubility, or OR9; R28 = is the residue of coupling component or phenyl (optionally substituted by halo, alkyl or -O-alkyl). The full definitions are given in the DEFINITIONS (Full Definitions) Field. An Independent claim is also included for a method for preparing (II) by reacting the corresponding perylene-3,4,9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide (III) in presence of copper powder and an auxiliary base.

Description

Quaterrylenebisimides (1) are interesting Dyes due to their intense, long-wave, in the NIR range absorption and their fluorescence in the NIR range [1]; For for the calculation of the electron system see Ref. [2].

In contrast, the substances are extremely difficult to access, which has so far prevented further distribution. For one, they can Quaterrylenebisimide from the perylene-3,4-dicarboximides (2) by a cyclizing Coupling can be synthesized in a KOH melt [3].

So it was under these harsh reaction conditions synthesized the derivative 1a (R = H), which is extremely difficult to dissolve Pigment is. The derivative was also successful with this method 1b (R = 1-hexylheptyl), which is characterized by its long-chain sec-alkyl residue ("dovetail residue") in contrast to 1a easily soluble is. However, the yield was only 4% and required still a precise control of the reaction conditions. After all, it succeeded it, with the material so represented, the strong fluorescence of these compounds demonstrated.

On the other hand, as an alternative to the synthesis [4] of 1, 9-bromo-perylene-3,4-dicarboximide (3) was first synthesized, the synthesis of which has been worked out for the preparative scale [5], but a considerable amount of preparative work means. The key substances for its synthesis are the perylene-3,4-dicarboximides (2), for which there are various synthetic approaches, of which access according to Ref. [6] is the most efficient. The further synthesis of 4 starting from the bromo derivative 3 has been described in the literature as a particular challenge. The CC-linking bromine cleavage of 3 was achieved by the Yamamoto coupling using the highly toxic Ni (cod) ₂ . As an alternative, special palladium catalysts were used, of which only a few are obviously suitable, but with varying success. By using nickel chloride, triphenylphosphine, zinc and DMF [7] the handling of the dangerous Ni (cod) _{2 was} avoided and now more accessible and easier to use reagents were available. However, the synthesis was still sufficiently complicated.

The final cyclization of 4 to Quaterrylenebisimide (1) in melted KOH (initially without further information [4] using ethanol, then adding glucose as Oxidizing agent [8]) was difficult to control, and the Reaction products required a complicated one for the purest representation of 1 and complex chromatographic cleaning. This accumulation of experimental difficulties and the unusually large synthetic effort Presentation of the quaterrylene bisimide was not very motivating for its use and asked for their use as dyes in obstacles - so the Chem. Abstr. only 10 works on the substance class reports.

The C-C linkage products (4) of the perylene-3,4-dicarboximides (2) also arise in small quantities in the stepwise decarboxylation the perylene anhydride imide 5 using copper powder in boiling 3-picoline at 143 ° C is carried out [9]. Even under these already rough reaction conditions is decarboxylation not a particularly quick reaction, like has shown a kinetic analysis of the reaction.

It is all the more astonishing that a reaction even at significantly lower temperatures, at 120 ° C without protective gas, takes place and that also in this case the carboxylic acid functions of the anhydride be lost. Completely surprising is, however, that not the split off and then the second carboxyl function is in the foreground of the reaction, but the C-C link product 4 and that this is relatively simple can be isolated (for this can that in proportion responsible for the other products much higher molecular weight be made). There is therefore a new and harmless one synthetic access for the quaterrylene bisimide. As a KOH melt, 4 to 1 significant problems The mixture was prepared as a new reagent for the final cyclization from potassium tert-butoxide and DBU (1,5-diazabicyclo [4.3.0] non-5-ene) used [10], for that the authors used the expression "green mute ". This Reagent has been tested for the synthesis of perylene derivatives, so far but not for the presentation of quaterrylene derivatives used. It was also shown that the new reagent is not for presentation of quaterrylene from perylene-3,4-dicarboximides (2) is suitable; the formation of 1 could not even be traces in the implementation be detected. Leaves but the combination of potassium tert-butoxide and DBU on the C-C bond product 4 act, then it will be completely surprising the Quaterrylenbisimid (1) formed by a discoloration of the reaction solution from red to Dirty brown to recognize turquoise green gives. Even more surprising is the fact that there are few by-products in the reaction are formed, which are also easy to separate and that with appropriate reaction management practically no other colored substance is created. With these for both Steps surprising Results yourself a new and preparative develop little complex synthesis concept for 1, with which the Substances also in large Amounts accessible become; see scheme 1.

The starting material is the technical mass product perylene-3,4: 9,10-tetracarboxylic acid bisanhydride (6), which is condensed with primary amines to the bisimides 7. Long-chain sec-alkyl groups [11, 12] (“dovetail residues”) are particularly suitable here, ensuring good solubility of the compounds; the 1-hexylheptyl residue, 7b, is a good compromise between chain length and increase in solubility. The increase in solubility is not as great for shorter chains, while it is even stronger for longer chains. An alternative are aromatics substituted with tert-butyl groups [13,14], of which the 2,5-di-tert-butyl radical has proven particularly useful. Finally, there are isopropylphenyl radicals in the literature, in particular the 2,4-di-iso-propylphenyl radical. The presence of a tertiary H atom in the benzyl position creates the risk of radical reactions (cf. the Hock process for the industrial preparation of phenol and acetone from cumene). For example, the bisimide 7b is then converted into the monoimide monoanhydride "MIMA") 5b by the action of KOH in tert-butyl alcohol [15], which is then directly mixed with copper powder in Pi colin reacts to the bichromophore 4b. Its further reaction with potassium tert-butoxide and DBU leads to quaterrylene bisimide 1b as the end product.

The quaterrylene bisimide forms blue, stable, lightfast solutions with a slight green tinge. The concentrated solutions are black; the UV / Vis spectra are shown in Fig. 1. The high molar absorption coefficient of 1a, which is over 130,000, is remarkable. The fluorescence is in the NIR range. This is not the dye only for the usual colorations of interest but can also be used for special sun protection are used: the dye absorbs visible light, which it then emits again as NIR fluorescent light, thus becomes a Avoid heating the sample due to absorbed light.

experimental part

9,9'-bis- [perylene-3,4-dicarboxylic acid 3,4- (1-hexylheptylimide)] (4b): perylene-3,4,9,10-tetracarboxylic acid 3,4-anhydride-9, 10- (1-hexylheptylimide) (5b, 1.00 g, 1.75 mmol) are heated with copper (powder, 650 mg, 10.3 mmol) in 3-picoline (50 ml) to 120 ° C for 24 h without an inert gas atmosphere. After cooling to room temperature, it is poured onto hydrochloric acid (2 M, 250 ml) and stirred for 1 h. After filtration and drying in a drying cabinet at 90 ° C., it is chromatographed on silica gel using chloroform. In addition to perylene-3,4-dicarboxylic acid 3,4- (1-hexylheptylimide), 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4- (1-hexylheptylimide)] is obtained as a red solid. Y. 299 mg (34.1%). Mp> 250 ° C. - R _f (silica gel / CHCl ₃ ): 0.8. - IR (KBr): ṽ = 2953 cm ^-1 m, 2926 s, 2856 m, 1693 s, 1654 s, 1592 s, 1572 s, 1503 w, 1457 w, 1410 w, 1352 s, 1292 m, 1246 m, 1173 w, 1108 w, 1049 w, 844 w, 812 m, 755 m, 725 w, 670 w. - ¹ H NMR (CDCl ₃ , 300 MHz): δ = 0.82 [t, 12 H, CH ₃ ], 1.24-1.38 [m, 32 H, CH ₂ ] 1.85 - 1.91 [m, 4 H, CH-CH ₂ ], 2.25 - 2.31 [m, 4 H, CH-CH ₂ ], 5.21 [m, 2 H, N-CH- (CH ₂ ) ₂ ], 7.49 [t, 2 H, nucleus], 7.56 [d, 2H , Core], 7.74 [d, 2 H, core], 8.39 [d, 2 H, core] 8.42 [d, 2 H, core], 8.47 [d, 2 H, core], 8.57 [d, 2 H, Kern], 8.60 [m br., 2 H, Kern], 8.63 [m br., 2 H, Kern]. - UV / Vis (CHCl ₃ ): λ _max (I _rel. ) = 474 nm (0.70) sh, 500 (0.39) sh, 525 (1.0). - Fluorescence (CHCl ₃ ): λmax = 592 nm, 617 sh. - MS (70 eV): m / z (%): 1005 (6) [M ⁺ ], 1004 (10), 823 (4) [M ⁺ -C ₁₃ H ₂₆ ], 641 (10), 640 (14 ) [M ⁺ -2 · C ₁₃ H ₂₆ ], 321 (16) [M ⁺ -2 · C ₁₃ H ₂₆ -C ₂₂ H ₁₁ NO ₂ ], 97 (11), 83 (10), 71 (11) , 69 (13), 44 (100).

Quaterrylene-3,4,13,14-tetracarboxylic acid 3,4: 13,14-bis- (1-hexylheptylimide) (1b): To a solution of potassium tert-butanolate (0.042 g, heated to 120 ° C under nitrogen) , 0.372 mmol) and 1,5-diazabicyclo [4.3.0] non-5-ene (0.062 g, 0.496 mmol) in diglyme (3 ml) is 9,9'-bis- [perylene-3,4-dicarboxylic acid- 3,4- (1-hexylheptylimide)] (4b, 0.125 g, 0.124 mmol) was added and the mixture was stirred for 1.5 h. The color of the reaction mixture changes from red to dirty brown to turquoise green. After cooling to room temperature, methanol (25 ml) is added, whereby quaterrylene-3,4,13,14-tetracarboxylic acid 3,4: 13,14-bis- (1-hexylheptylimide) precipitates. Filtration and drying give a dark green solid, which is cleaned for high purification on the chromatotron (rotary chromatograph, silica gel / CH ₂ Cl ₂ ). Y. 112 mg (90.1%), mp> 250 ° C. - Rf (silica gel / CH ₂ Cl ₂ ): 0.45.- ¹ H-NMR (CDCl ₃ / 200MHz): 0.89 (t, 12H, CH ₃ ), 1.20-1.40 (m, 32 H, CH ₂ ), 1.99 (m, 4 H, CH-CH ₂ ), 2.31 (m, 4 H, CH-CH ₂ ), 5.18 (m, 2 H, N-CH), 7.59 (m, 4 H, aromatics-H), 7.95 (m, 8 H, aromatics-H), 8.27 (m, 4H, aromatics-H). - IR (KBr): ṽ = 2953 cm ^-1 m, 2926 s, 2856 m, 1692 s, 1652 s, 1596 m, 1576 s, 1503 w, 1459 w, 1406 m, 1350 s, 1287 m, 1250 w, 1220 w, 1158 w, 1136 w, 1107 w, 1050 w, 950 w, 840 w, 810 m, 788 w, 752 m, 726 w, 672 w, 612 w.

Object of the invention

in der die Reste R¹ und R² gleich oder verschieden sein können. R¹ bis R² steht für Wasserstoff oder ein bis vier, vorzugsweise ein bis drei, Reste wie beispielsweise isocyclische aromatischen Reste. R¹ bis R⁴ bedeutet dann jeweils vorzugsweise einen mono- bis tetracyclischen, insbesondere mono- oder bicyclischen Rest, wie Phenyl, Diphenyl Naphthyl oder Anthryl. Bedeuten R¹ bis R² heterocyclischen aromatische Reste, dann vorzugsweise mono- bis tricyclische Reste. Diese Reste können rein heterocyclisch sein oder einen heterocyclischen Ring und einen oder mehrere ankondensierte Benzolringe enthalten. Beispiele von heterocyclischen aromatischen Resten sind Pyridyl, Pyrimidyl, Pyrazinyl, Triazinyl, Furanyl, Pyrrolyl, Thiophenyl, Chinolyl, Isochinolyl, Coumarinyl, Benzofuranyl, Benzimidazolyl, Benzoxazolyl, Dibenzfuranyl, Benzothiophenyl, Dibenzothiophenyl, Indolyl, Carbazolyl, Pyrazolyl, Imidazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Indazolyl, Benzthiazolyl, Pyridazinyl, Cinnolyl, Chinazolyl, Chinoxalyl, Phthalazinyl, Phthalazindionyl, Phthalimidyl, Chromonyl, Naphtholactamyl, Benzopyridonyl, ortho-Sulfobenimidyl, Maleinimidyl, Naphtharidinyl, Benzimidazolonyl, Benzoxazolonyl, Benzthiazolonyl, Benzthiazolinyl, Chinazolonyl, Pyrimidyl, Chinoxalonyl, Phthalazonyl, Dioxapyrinidinyl, Pyridonyl, Isochinolonyl, Isothiazolyl, Benzisoxazolyl, Benzisothiazolyl, Indazolonyl, Acridinyl, Acridonyl, Chinazolindionyl, Benzoxazindionyl, Benzoxazinonyl und Phthalimidyl. Sowohl die isocyclischen wie die heterocyclischen aromatischen Reste können die folgenden üblichen nicht wasserlöslich machenden Substituenten aufweisen, die auch R¹ bis R² bedeuten können, wie1. Process for the preparation of quaterrylenebisimides of the general formula I,

in which the radicals R ¹ and R ^{2 may be the} same or different. R ¹ to R ² represent hydrogen or one to four, preferably one to three, radicals such as, for example, isocyclic aromatic radicals. R ¹ to R ⁴ then preferably each denotes a mono- to tetracyclic, in particular mono- or bicyclic radical, such as phenyl, diphenyl naphthyl or anthryl. R ¹ to R ^{2 are} heterocyclic aromatic radicals, then preferably mono- to tricyclic radicals. These radicals can be purely heterocyclic or a heterocyclic ring and one or more fused benzene rings. Examples of heterocyclic aromatic radicals are pyridyl, pyrimidyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl, benzimidazolyl, benzoxazolyl, dibenzfuranyl, benzothiophenyl, dibenzothiophenyl, oxolylol Thiazolyl, indazolyl, benzthiazolyl, pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazinedionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho-sulfobenimidyl, benzimidazolonyl, benzimidazolonyl, benzimidazolonyl Dioxapyrinidinyl, pyridonyl, isoquinolonyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, benzoxazinedionyl, benzoxazinonyl and phthalimidyl. Both the isocyclic and the heterocyclic aromatic radicals can have the following customary water-insolubilizing substituents, which can also mean R ¹ to R ² , such as

• a) A halogen atom, for example chlorine, bromine, iodine or Fluorine.
• b) branched or unbranched alkyl groups or cycloalky groups having preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. These alkyl groups can have non-water-solubilizing substituents, such as fluorine, hydroxy, cyano, -OCOR ³ , -OR ⁴ , -OCOOR ⁵ , -CON (R ⁶ ) (R ⁷ ) or -OCONHR ⁸ , wherein R ³ to R ⁸ alkyl, aryl such as naphthyl, or unsubstituted or by halogen, alkyl or -O-alkyl substituted benzyl, or a heterocyclic radical, is hydrogen, unsubstituted or substituted by cyano or hydroxy alkyl, C 3 to C ₂₄ - cycloalkyl, preferably C ₅ - C ₆ -, C ₁₂ -, C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or in which R ³ to R ⁸ together with one of the other radicals R ⁴ to R ¹ ° form a 5-6 membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for example, the 2-thienyl, 2-benzoxazolyl , 2-benzothiazolyl-, 2-benzimidazolyl-, 6-benzimidazolonyl-, 2-, 3- or 4-pyridinyl-, 2-, 4- or 6-quinoly- or 1-, 3-, 4-, 6- , or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched, unbranched or cyclic and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpeptyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ .
• c) The group -OR ⁹ , in which R ^{9 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C3 to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ - , C ₂₀ -, and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R ⁹ can have, for example, one of the number of C atoms indicated as preferred under b). Examples of R ⁹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benz -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl.
• e) The cyano group.
• f) The group of the formula -N (R ¹⁰ ) (R ^{1 1} ), in which R ¹⁰ and R ^{11 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, disec-butylamino, tert-butylamino, tert -Amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3, -Tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-outylamino, di-n-octylamino, n-nonyl, di- n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylam 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylhydroxymethylamino, 1-ethylhydroxymethylamino N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, phenylamino , Diphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanylamino, cy clotetracosanylamino, thienylamino or pyranylmethylamino, piperidyl or morpholyl.
• g) The group of the formula -COR ¹² , wherein R ^{12 has} the meaning given under a). Examples of R ¹² are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benz -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl, benzyl or furfuryl.
• h) The group of the formula-N (R ¹³ ) COR ¹⁴ , in which R ^{13 has} the meaning given under b), R ^{16 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-ohtylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheyl 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, Cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl or furfuryl. Alkyl occurring in the definitions of R ¹⁴ can have, for example, one of the number of C atoms preferably given under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.
• i) The group of the formula -N (R ¹⁵ ) COOR ¹⁶ , in which R ¹⁵ and R ^{16 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ .
• j) The group of the formula -N (R ¹⁷ ) CON (R ¹⁸ ) (R ¹⁹ ), in which R ¹⁷ , R ¹⁸ and R ^{19 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N-2 ', 4'-dimethylphenylureido.
• k) The group of the formula -NHSO ₂ R ²⁰ , wherein R ^{20 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.
• l) The groups of the formula -SO ₂ R ²¹ or -SOR ²² , wherein R ²¹ or R ^{22 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.
• m) The group of the formula -SO ₂ OR ²³ , wherein R ^{23 has} the meaning given under b). Examples of R ²⁵ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.
• n) The group of the formula -CON (R ²⁴ ) (R ²⁵ ), in which R ²⁴ and R ^{25 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.
• o) The group of the formula -SO ₂ N (R ^Z8 ) (R ²⁷ ), in which R ²⁶ and R ^{27 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.
• p) The group of the formula -N = NR ²⁸ , in which R ^{28 is} the residue of a coupling component or a phenyl radical which is optionally substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ²⁸ can have, for example, one of the number of C atoms given as preferred under b). The following may be mentioned as examples of R ³⁰ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.
• q) The group of the formula -OCOR ²⁹ in which R ^{29 has} the meaning given under b). Examples of R ²⁹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• r) The group of the formula -OCONHR ³⁰ , wherein R ^{30 has} the meaning given under a). Examples of R ³⁰ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

R ¹ to R ² can be hydrogen and one to four of the following radicals

• a) Halogen atoms, for example chlorine, bromine, iodine or fluorine.
• b) Branched or unbranched alkyl groups with preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4 carbon atoms. These alkyl groups may have non-water solubilizing substituents such as fluorine, hydroxy, cyano, -OCOR ³³ , -OR ³² , -OCOOR ³³ , -CON (R ³⁴ ) (R ³⁵ ) or -OCONHR ³⁶ , wherein R ^{31 is} alkyl, aryl such as Naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O-alkyl or a heterocyclic radical, R ³² , R ³³ and R ^{35 are} hydrogen, unsubstituted or substituted by cyano or hydroxy, C ₃ - to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ -, C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or wherein R ³⁴ and R ³⁵ together with one each the other radicals R ³¹ to R ^{36 form} a 5-6 membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for example, the 2-thienyl, 2-benzoxazolyl , 2-benzothiazolyl-, 2-benzimidazolyl-, 6-benzimidazolonyl-, 2-, 3- or 4-pyridinyl-, 2-, 4- or 6-quinoly- or 1-, 3-, 4-, 6- , or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched or unbranched and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ .
• c) The group -OR ³⁷ , in which R ^{37 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C ₃ to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ -, and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R ³⁷ can have, for example, one of the number of C atoms indicated as preferred under b). Examples of R ³⁹ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl Benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, moder p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, Cyclotetracosanyl, thienyl or pyranylmethyl.
• e) The cyano group.
• f) The group of the formula -N (R ³⁸ ) (R ³⁹ ), in which R ³⁸ and R ^{3 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, disec-butylamino, tert-butylamino, tert -Amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3, -Tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di- n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-ndodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylamino Pentylhexylamino, 1-Hexylheptylamino, 1-Heptyloctylamino, 1-Octylnonylamino, 1-Nonyldecylamino, 1-Decylundecylamino, 1-Ethylbutylamino, 1-Ethylpentylamino, 1-Ethylheptylamino, 1-Ethylnymethylamino, 2-Hydroxymononethylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, Bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, phenylamino, Diphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanylaminoamino or cyclo tetraamylamino or cyclotetraamino pino morpholyl
• g) The group of the formula -COR ⁴⁰ , in which R ^{40 has} the meaning given under a). Examples of R ⁴⁰ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl Benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, Cycloeicosanyl, Cyclotetracosanyl, Thienyl, Pyranylmethyl, Benzyl or Furfuryl.
• h) The group of the formula-N (R ⁴¹ ) COR ⁴² , in which R ^{41 has} the meaning given under b), R ^{42 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl -Ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, especially unsubstituted or substituted by halogen, alkyl or -O-alkyl Phenyl, for example o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, Pyranylmethyl, benzyl or furfuryl. Alkyl occurring in the definitions of R ⁴⁵ can have, for example, one of the number of C atoms preferably given under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.
• i) The group of the formula -N (R ⁴³ ) COOR ⁴⁴ , in which R ⁴³ and R ^{44 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ .
• j) The group of the formula -N (R ⁴⁵ ) CON (R ⁴⁶ ) (R ⁴⁷ ), in which R ⁴⁵ , R ⁴⁶ and R ^{47 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.
• k) The group of the formula -NHSO ₂ R ⁴⁸ , wherein R ^{48 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino
• l) The groups of the formula -SO ₂ R ⁴⁹ or -SOR ⁵⁰ , wherein R ⁴⁹ or R ^{50 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.
• m) The group of the formula -SO ₂ OR ⁵¹ , wherein R ^{51 has} the meaning given under b). Examples of R ⁵³ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.
• n) The group of the formula -CON (R ⁵² ) (R ⁵³ ), in which R ⁵² and R ^{53 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, NN-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.
• o) The group of the formula -SO ₂ N (R ⁵⁴ ) (R ⁵⁵ ), in which R ⁵⁴ and R ^{55 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.
• p) The group of the formula -N = NR ⁵⁶ , in which R ^{56 is} the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -0-alkyl. Alkyl occurring in the definitions of R ⁵⁶ can have, for example, one of the number of C atoms given as preferred under b). The following may be mentioned as examples of R ⁵⁶ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.
• q) The group of the formula -OCOR ⁵⁷ , in which R ^{57 has} the meaning given under b). Examples of R ⁵⁹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• r) The group of the formula -OCONHR ⁵⁸ , wherein R ^{58 has} the meaning given under a). Examples of R ⁶⁰ include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

The process is characterized by that the corresponding 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4imide] with the same residues as I using tertiary alcoholates, such as potassium tert-butoxide) or potassium tert-amylate, preferably potassium tert-butoxide, and a second auxiliary base such as DBU or DBN, preferably DBU (1,5-diazabicyclo [4.3.0] non-5-ene) is implemented. Preferred solvents are ethers, especially oligomeric ethers, diglyme is preferred. The reaction is preferably carried out at elevated temperature, so e.g. at temperatures from 50 to 120 ° C, most preferably at 120 ° C.

in der die Reste R¹ und R² gleich oder verschieden sein können und R¹ und R² die unter 1 genannte Bedeutung haben.2. Process for the preparation of the 9,9'-bis- [perylene-3,4-dicarboxylic acid 3,4-imides] of the general formula II,

in which the radicals R ¹ and R ^{2 may be the} same or different and R ¹ and R ^{2 have} the meaning given under 1.

The process is characterized by that the corresponding perylene-3,4,9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide with the same residues as II using copper powder, and an auxiliary base such as picoline, quinoline or isoquinoline, preferably 3-picoline, is implemented. The reaction is preferred under increased Temperature carried out so e.g. at temperatures from 50 to 120 ° C, most preferably at 120 ° C.

3. Use of the substances after 1 to 2 as dyes.

4. Use of the substances after 1 to 2 as fluorescent dyes.

5. Application of the dyes from 1 up to 2 for mass coloring of polymers. Examples are materials made of polyvinyl chloride, Cellulose acetate, polycarbonates, polyamides, polyurethanes, polyimides, Polybenzimidazoles, melamine resins, silicones, polyesters, polyethers, Polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, Polyacrylonitrile, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of the monomers mentioned.

6. Application of the dyes of 1 up to 2 as vat dyes, e.g. for coloring of natural products. Examples are paper, wood, straw, leather, skins or natural Fiber materials such as cotton, wool, silk, jute, sisal, hemp, Flax or animal hair (e.g. horsehair) and their conversion products such as the viscose fiber, nitrate silk or copper rayon (rayon).

7. Application of the dyes of 1 to 2 as mordant dyes, e.g. for coloring natural products. Examples are paper, wood, straw, leather, skins or natural fiber materials such as Cotton, wool, silk, jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products such as the viscose fiber, nitrate silk or copper rayon (rayon). Preferred salts for pickling are aluminum, Chromium and iron salts.

8. Application of the dyes of 1 to 2 as colorants, e.g. for coloring of paints, varnishes and other paints, paper paints, printing inks, Inks and other colors for Painting and writing purposes.

9. Application of the dyes of 1 to 2 as pigment dyes, e.g. for coloring paints, varnishes and other paints, paper colors, printing inks, inks and other colors for Painting and writing purposes.

10. Application of the dyes from 1 to 2 as pigments in electrophotography: e.g. for dry copy systems (Xerox process) and laser printer ("non-impact printing").

11. Application of the dyes by 1 to 2 for Security marking purposes, the major chemical and photochemical resistance and possibly also the fluorescence of the substances is important. Prefers is this for Checks, credit cards, banknotes, coupons, documents, identity papers and the like, in which a special, unmistakable color impression should be achieved.

12. Application of the dyes by 1 to 2 as an addition to other colors in which a certain color shade should be achieved, particularly bright colors are preferred.

13. Application of the dyes from 1 to 2 for marking objects for machine recognition of these items over the Fluorescence, preferably the automatic detection of objects for Sorting, e.g. also for the recycling of plastics.

14. Application of the dyes from 1 to 2 as fluorescent dyes for machine-readable markings, alphanumeric imprints or barcodes are preferred.

15. Application of the dyes from 1 to 2 for frequency conversion of light, e.g. order from shortwave Light longer-wave, to make visible light.

16. Application of the dyes by 1 to 2 in display elements for various display, information and marking purposes, e.g. passive Display elements, information and traffic signs, such as traffic lights.

17. Application of the dyes by 1 to 2 in inkjet printers, preferably in a homogeneous solution fluorescent ink.

18. Application of the dyes by 1 to 2 as starting material for superconducting organic materials.

19. Application of the dyes from 1 to 2 for Solid fluorescent labels.

20. Application of the dyes by 1 to 2 for decorative purposes.

21. Application of the dyes by 1 to 2 for artistic Purposes.

22. Application of the dyes by 1 to 2 for tracer purposes, e.g. in biochemistry, medicine, technology and Natural Science. Here you can the dyes are covalently linked to substrates or via secondary valences like hydrogen bonds or hydrophobic interactions (adsorption).

23. Application of the dyes by 1 to 2 as fluorescent dyes in highly sensitive detection methods (see C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z.Analyt.Chem. 1985, 320, 361).

24. Application of the dyes by 1 to 2 as fluorescent dyes in scintillators.

25. Application of the dyes from 1 to 2 as dyes or fluorescent dyes in optical light collection systems.

26. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in fluorescent solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716).

27. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in fluorescence-activated Displays (see W. Greubel and G. Baur, Elektronik 1977, 26, 6).

28. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in cold light sources light-induced polymerization for the production of plastics.

29. Application of the dyes from 1 to 2 as dyes or fluorescent dyes for material testing, e.g. in the manufacture of semiconductor circuits.

30. Application of the dyes by 1 to 2 as dyes or fluorescent dyes for the investigation of Microstructures of integrated semiconductor components.

31. Application of the dyes from 1 to 2 as dyes or fluorescent dyes in photoconductors.

32. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in photographic processes.

33. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in display, lighting or image converter systems in which the excitation by electrons, Ion or UV radiation takes place, e.g. in fluorescent displays, Braunschen roar or in fluorescent tubes.

34. Application of the dyes by 1 to 2 as dyes or fluorescent dyes as part of one integrated semiconductor circuit, the dyes as such or in connection with other semiconductors e.g. in the form of an epitaxy.

35. Application of the dyes from 1 to 2 as dyes or fluorescent dyes in chemiluminescent systems, e.g. in chemiluminescent light sticks, in luminescent immunoassays or other luminescence detection methods.

36. Application of the dyes by 1 to 2 as dyes or fluorescent dyes as signal colors, preferably for the optical highlighting of lettering and drawings or others graphic products, for labeling signs and others objects where a special optical color impression can be achieved should.

37. Application of the dyes by 1 to 2 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams.

38. Application of the dyes from 1 to 2 as dyes in dye lasers as Q-switch.

39. Application of the dyes of 1 to 2 as active substances for non-linear optics, e.g. for the Frequency doubling and the frequency tripling of laser light.

40. Application of the dyes from 1 to 2 as a rheology improver.

• [1] K. S. Lee, Y. Zu, A. Herrmann, Y. Geerts, K. Müllen, A. J. Bard, J. Am. Chem. Soc. 1999, 121, 3513-3520.
• [2] M. Adachi, Y. Nagao, Chem. Mater. 2001, 13, 662-669.
• [3] H. Langhals, G. Schönmann, L. Feiler, Tetrahedron Lett. 1995, 36, 6423-6424.
• [4] H. Quante, K, Müllen, Angew. Chem. 1995, 107, 1487-1489; Angew. Chem. Int. Ed. Engl. 1995, 43, 1323-1325.
• [5] L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, From 1229 to 1244.
• [6] H. Langhals, P. von Unold, M. Speckbacher, Liebigs Ann./Recueil 1997, 467-468.
• [7] H. Langhals, F. Süßmeier, J. Prakt. Chem. 1999, 341, 309-311.
• [8] Y. Geerts, H. Quante, H. Platz, R. Mahrt, M. Hopmeier, A. Bohm, K. Müllen, J. Mater. Chem. 1998, 8, 2357-2369.
• [9] F. Süßmeier, H. Langhals, Eur. J. Org. Chem. 2001, 607-610.
• [10] T. Sakamoto, C. Pac, J. Org. Chem. 2001, 66, 94-98.
• [11] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748.
• [12] H. Langhals, Ger. Offen. DE 3703495 (February 5, 1987); Chem. Abstr. 1989, 110, P59524s.
• [13] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q.
• [14] H. Langhals, Ger. Patent 3016764 (April 30, 1980); Chem. Abstr. 1982, 96, P70417x.
• [15] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535.

Illustration 1.

synthesis from 1b.

Illustration Second

UV / Vis absorption and fluorescence spectrum of 1b.

Claims (40)

Process for the preparation of quaterrylene bisimides of the general formula I,

in which the radicals R ¹ and R ^{2 may be the} same or different. R ¹ to R ² represent hydrogen or one to four, preferably one to three, radicals such as, for example, isocyclic aromatic radicals. R ¹ to R ⁴ then preferably each denotes a mono- to tetracyclic, in particular mono- or bicyclic radical, such as phenyl, diphenyl naphthyl or anthryl. R ¹ to R ^{2 are} heterocyclic aromatic radicals, then preferably mono- to tricyclic radicals. These radicals can be purely heterocyclic or contain a heterocyclic ring and one or more fused-on benzene rings. Examples of heterocyclic aromatic radicals are pyridyl, pyrimidyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl, benzimidazolyl, benzoxazolyl, dibenzfuranyl, benzothiophenyl, dibenzothiophenyl, oxolylol Thiazolyl, indazolyl, benzthiazolyl, pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazinedionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho-sulfobenimidyl, benzimidazolonyl, benzimidazolonyl, benzimidazolonyl Dioxapyrinidinyl, pyridonyl, isoquinolonyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, benzoxazinedionyl, benzoxazinonyl and phthalimidyl. Both the isocyclic and the heterocyclic aromatic radicals can have the following customary water-insolubilizing substituents, which can also mean R ¹ to R ² , such as a) a halogen atom, for example chlorine, bromine, iodine or fluorine. b) branched or unbranched alkyl groups or cycloalky groups having preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. These alkyl groups can have non-water-solubilizing substituents, such as fluorine, hydroxy, cyano, -OCOR ³ , -OR ⁴ , -OCOOR ⁵ , -CON (R ⁶ ) (R ⁷ ) or -OCONHR ⁸ , wherein R ³ to R ⁸ alkyl, aryl such as naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O-alkyl, benzyl or a heterocyclic radical, hydrogen, unsubstituted or substituted by cyano or hydroxyalkyl, C ₃ - to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ -, C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ - cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl, or wherein R ³ to R ⁸ together with one of the other radicals R ⁴ to R ¹⁰ each form a 5-6-membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for example, the 2-thienyl, 2-benzoxazolyl , 2-benzothiazolyl-, 2-benzimidazolyl-, 6-benzimidazolonyl-, 2-, 3- or 4-pyridinyl-, 2-, 4- or 6-quinoly- or 1-, 3-, 4-, 6- , or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched, unbranched or cyclic and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ . c) The group -OR ⁹ , in which R ^{9 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C ₃ to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ -, and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R ⁹ can have, for example, one of the number of C atoms indicated as preferred under b). Examples of R ⁹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benz -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl. e) The cyano group. f) The group of the formula -N (R ¹⁰ ) (R ¹¹ ), in which R ¹⁰ and R ^{1 1 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, di sec-butylamino, tert-butylamino, tert-Amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3, -tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di -n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentyl , 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylnonylamino, hydroxymethylamino, dihydroxymethylamino, 2-hydroxyethyl, N, N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, phenylamino, phenylamino, benzylamino, benzylamino, benzylamino, benzylamino, benzylamino, benzylamino, benzylamino, benzylamino, phenylamino, benzylamino, benzylamino, benzylamino, phenylamino, benzylamino, phenylamino, benzylamino, phenylamino, benzylamino, phenylamino, benzylamino, phenylamino, benzylamino, phenylamino, benzylamino, phenylamino, phenylamino, phenylamino, benzylamino, phenylamino, phenylamino, phenylamino, phenylamino, benzylamino, phenylamino, phenylamino, phenylamino, benzylamino, phenylamino, phenylamino - or p-chlorophenylamino, o-, m-, or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanylamino, cyclotetracosanylamino or pyranylaminoamino or thienylidylamino or thienylamylamino or thienylamylamino or thienylamylamino or thienylamylamino or thienylamylamino or thienylamylamino or thienylaminoamino. g) The group of the formula -COR ¹² , wherein R ^{12 has} the meaning given under a). Examples of R ¹² are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benz -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl, benzyl or furfuryl. h) The group of the formula-N (R ¹³ ) COR ¹⁴ , in which R ^{13 has} the meaning given under b), R ^{16 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tent-butyl, tent-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2- Naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl or furfuryl. Alkyl occurring in the definitions of R ¹⁴ can have, for example, one of the number of C atoms preferably given under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido. i) The group of the formula -N (R ¹⁵ ) COOR ¹⁶ , in which R ¹⁵ and R ^{16 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ . j) The group of the formula -N (R ¹⁷ ) CON (R ¹⁸ ) (R ¹⁹ ), in which R ¹⁷ , R ¹⁸ and R ^{19 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N-2 ', 4'-dimethylphenylureido. k) The group of the formula -NHSO ₂ R ²⁰ , wherein R ^{20 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino. l) The groups of the formula -SO2R ²¹ or -SOR ²² , wherein R ²¹ or R ^{22 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl. m) The group of the formula -SO ₂ OR ²³ , wherein R ^{23 has} the meaning given under b). Examples of R ²⁵ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl. n) The group of the formula -CON (R ²⁴ ) (R ²⁵ ), in which R ²⁴ and R ^{25 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, NN-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl. o) The group of the formula -SO ₂ N (R ^{2 &} ) (R ²⁷ ), in which R ²⁶ and R ^{27 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl. p) The group of the formula -N = NR ²⁸ , in which R ^{28 is} the residue of a coupling component or a phenyl radical which is optionally substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ²⁸ can have, for example, one of the number of C atoms given as preferred under b). The following may be mentioned as examples of R ³⁰ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals. q) The group of the formula -OCOR ²⁹ in which R ^{29 has} the meaning given under b). Examples of R ²⁹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. r) The group of the formula -OCONHR ³⁰ , wherein R ^{30 has} the meaning given under a). Examples of R ³⁰ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. R ¹ to R ² can be hydrogen and one to four of the following radicals a) halogen atoms, for example chlorine, bromine, iodine or fluorine. b) Branched or unbranched alkyl groups with preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4 carbon atoms. These alkyl groups may have non-water solubilizing substituents such as fluorine, hydroxy, cyano, -OCOR ³³ , -OR ³² , -OCOOR ³³ , -CON (R ³⁴ ) (R ³⁵ ) or -OCONHR ³⁶ , wherein R ^{31 is} alkyl, aryl such as Naphthyl, or unsubstituted or by halo gene, alkyl, or -O-alkyl-substituted benzyl or a heterocyclic radical, R ³² , R ³³ and R ^{35 are} hydrogen, unsubstituted or cyano or hydroxy-substituted alkyl, C ₃ - to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or in which R ³⁴ and R ³⁵ together with one of the other radicals R ³¹ to R ^{36 form} a 5-6-membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for example, the 2-thienyl, 2-benzoxazolyl , 2-benzothiazolyl-, 2-benzimidazolyl-, 6-benzimidazolonyl-, 2-, 3- or 4-pyridinyl-, 2-, 4- or 6-quinoly- or 1-, 3-, 4-, 6- , or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched or unbranched and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ . c) The group -OR ³⁷ , in which R ^{37 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C3 to C24-cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ³⁷ can have, for example, one of the number of C atoms indicated as preferred under b). Examples of R ³⁹ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl or acetoxymethyl Benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, moder p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, Cyclotetracosanyl, thienyl or pyranylmethyl. e) The cyano group. f) The group of the formula -N (R ³⁸ ) (R ³⁹ ), in which R ³⁸ and R ^{3 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, disec-butylamino, tent-butylamino, tent -Amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3, -Tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di- n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-ndodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylamino Pentylhexylamino, 1-Hexylheptylamino, 1-Heptyloctylamino, 1-Octylnonylamino, 1-Nonyldecylamino, 1-Decylundecylamino, 1-Ethylbutylamino, 1-Ethylpentylamino, 1-Ethylheptylamino, 1-Ethylnymethylamino, 2-Hydroxymononethylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, 2-Hydroxymononylamino, Bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, phenylamino, D iphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanylaminoamino or cyclotetraamylamino or cyclotetraamino pino Morpholyl g) The group of the formula -COR ⁴⁰ , in which R ^{40 has} the meaning given under a). Examples of R ⁴⁰ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl or acetoxymethyl Benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, moderp-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl , Thienyl, pyranylmethyl, benzyl or furfuryl. h) The group of the formula-N (R ⁴¹ ) COR ⁴² , in which R ^{41 has} the meaning given under b), R ^{42 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl -Ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, especially unsubstituted or substituted by halogen, alkyl or -O-alkyl Phenyl, for example o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, pyranylmethyl, benzyl or furfuryl. Alkyl occurring in the definitions of R ⁴⁵ can have, for example, one of the number of C atoms preferably given under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido. i) The group of the formula -N (R ⁴³ ) COOR ⁴⁴ , in which R ⁴³ and R ^{44 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ . j) The group of the formula -N (R ⁴⁵ ) CON (R ⁴⁶ ) (R ⁴⁷ ), in which R ⁴⁵ , R ⁴⁶ and R ^{47 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido. k) The group of the formula -NHSO ₂ R ⁴⁸ , wherein R ^{48 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino l) The groups of the formula -SO ₂ R ⁴⁹ or -SOR ⁵⁰ , in which R ⁴⁹ or R ^{50 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl. m) The group of the formula -SO ₂ OR ⁵¹ , wherein R ^{51 has} the meaning given under b). Examples of R ⁵³ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl. n) The group of the formula -CON (R ⁵² ) (R ⁵³ ), in which R ⁵² and R ^{53 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl. o) The group of the formula -SO ₂ N (R ⁵⁴ ) (R ⁵⁵ ), in which R ⁵⁴ and R ^{55 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl. p) The group of the formula -N = NR ⁵⁶ , in which R ^{56 is} the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ⁵⁶ can have, for example, one of the number of C atoms given as preferred under b). The following may be mentioned as examples of R ⁵⁶ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals. q) The group of the formula -OCOR ⁵⁷ , in which R ^{57 has} the meaning given under b). Examples of R ⁵⁹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. r) The group of the formula -OCONHR ⁵⁸ , wherein R ^{58 has} the meaning given under a). Examples of R ⁶⁰ include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl. The process is characterized in that the corresponding 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4imides] with the same radicals as I using tertiary alcoholates, such as potassium tert-butoxide) or potassium tert-amylate, preferably potassium tert-butoxide, and a second auxiliary base such as DBU or DBN, preferably DBU (1,5-diazabicyclo [4.3.0] non-5-ene) is reacted. Preferred solvents are ethers, especially oligomeric ethers, diglyme is preferred. The reaction is preferably carried out at elevated temperature, for example at temperatures from 50 to 120 ° C., most preferably at 120 ° C. Process for the preparation of the 9,9'-bis [perylene-3,4-dicarboxylic acid 3,4imide] of the general formula II,

in which the radicals R ¹ and R ^{2 may be the} same or different and R ¹ and R ^{2 have} the meaning given under 1. The process is characterized in that the corresponding perylene-3,4,9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide with the same radicals as II using copper powder, and an auxiliary base as the Picoline, Quinoline or isoquinoline, preferably 3-picoline, is reacted. The reaction is preferably carried out at elevated temperature, for example at temperatures from 50 to 120 ° C., most preferably at 120 ° C. Use of the substances according to 1 to 2 as dyes. Use of the substances according to 1 to 2 as fluorescent dyes. Application of dyes from 1 to 2 for mass coloring Polymers. Examples are materials made from polyvinyl chloride, cellulose acetate, Polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, Melamine resins, silicones, polyesters, polyethers, polystyrene, polymethyl methacrylate, Polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, Polychlorobutadiene or polyisoprene or the copolymers of the above Monomers. Application of dyes from 1 to 2 as vat dyes, e.g. for coloring of natural products. Examples are paper, wood, straw, leather, skins or natural Fiber materials such as cotton, wool, silk, jute, sisal, hemp, Flax or animal hair (e.g. horsehair) and their conversion products such as the viscose fiber, nitrate silk or copper rayon (rayon). Application of dyes from 1 to 2 as stain dyes, e.g. for coloring of natural products. Examples are paper, wood, straw, leather, skins or natural Fiber materials such as cotton, wool, silk, jute, sisal, hemp, Flax or animal hair (e.g. horsehair) and their conversion products such as the viscose fiber, nitrate silk or copper rayon (rayon). Preferred salts for pickling are aluminum, Chromium and iron salts. Application of dyes from 1 to 2 as colorants, e.g. for coloring of paints, varnishes and other paints, paper paints, printing inks, Inks and other colors for Painting and writing purposes. Application of dyes from 1 to 2 as pigment dyes, e.g. for coloring of paints, varnishes and other paints, paper paints, printing inks, Inks and other colors for Painting and writing purposes. Application of dyes from 1 to 2 as pigments in electrophotography: e.g. for dry copy systems (Xerox process) and laser printers ("non-impact printing"). Application of dyes from 1 to 2 for security marking purposes, being the big one chemical and photochemical resistance and possibly also Fluorescence of the substances is important. This is preferred for checks, Credit cards, bank notes, coupons, documents, identification papers and the like, in which a special, unmistakable color impression should be achieved. Application of dyes from 1 to 2 as an additive to other colors in which a certain shade is achieved should, particularly bright colors are preferred. Application of dyes from 1 to 2 for marking of objects for machine detection of these objects via fluorescence, preferred is the automatic detection of objects for sorting, e.g. also for the Recycling of plastics. Application of dyes from 1 to 2 as fluorescent dyes for machine readable Markings, preferably alphanumeric imprints or barcodes. Application of dyes from 1 to 2 for frequency conversion of light, e.g. around longer-wave, visible light from short-wave light close. Application of dyes from 1 to 2 in display elements for many things Display, information and marking purposes, e.g. passive display elements, Information and traffic signs, such as traffic lights. Application of dyes from 1 to 2 in inkjet printers, preferably in homogeneous solution as fluorescent ink. Application of dyes from 1 to 2 as the starting material for superconducting organic materials. Application of dyes from 1 to 2 for solid fluorescent labels. Application of dyes from 1 to 2 for decorative Purposes. Application of dyes from 1 to 2 for artistic Purposes. Application of dyes from 1 to 2 for tracer purposes, e.g. in biochemistry, medicine, technology and science. in this connection can the dyes are covalently linked to substrates or via secondary valences like hydrogen bonds or hydrophobic interactions (adsorption). Application of dyes from 1 to 2 as fluorescent dyes in highly sensitive detection methods (see C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z.Analyt.Chem. 1985, 320, 361). Application of dyes from 1 to 2 as fluorescent dyes in scintillators. Application of dyes from 1 to 2 as dyes or fluorescent dyes in optical light collection systems. Application of dyes from 1 to 2 as dyes or fluorescent dyes in fluorescent solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716). Application of dyes from 1 to 2 as dyes or fluorescent dyes in fluorescence-activated displays (see W. Greubel and G. Baur, Elektronik 1977, 26, 6). Application of dyes from 1 to 2 as dyes or fluorescent dyes in cold light sources for light-induced Polymerization to represent plastics. Application of dyes from 1 to 2 as dyes or fluorescent dyes for material testing, e.g. in the preparation of of semiconductor circuits. Application of dyes from 1 to 2 as dyes or fluorescent dyes for examining microstructures of integrated semiconductor components. Application of dyes from 1 to 2 as dyes or fluorescent dyes in photoconductors. Application of dyes from 1 to 2 as dyes or fluorescent dyes in photographic processes. Application of dyes from 1 to 2 as dyes or fluorescent dyes in display, lighting or image converter systems, where excitation by electrons, ions or UV radiation takes place, e.g. in fluorescent displays, Braun tubes or in fluorescent tubes. Application of dyes from 1 to 2 as dyes or fluorescent dyes as part of an integrated semiconductor circuit, the dyes as such or in combination with other semiconductors e.g. in the form of an epitaxy. Application of dyes from 1 to 2 as dyes or fluorescent dyes in chemiluminescent systems, e.g. in Chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods. Application of dyes from 1 to 2 as dyes or fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or other graphic products for identification of signs and other objects where a special optical color impression should be achieved. Application of dyes from 1 to 2 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams. Application of dyes from 1 to 2 as dyes in dye lasers as Q-switch. Application of dyes from 1 to 2 as active Substances for non-linear optics, e.g. For frequency doubling and frequency tripling of laser light. Application of dyes from 1 to 2 as a rheology improver.