DE102005045375A1 - New hydroxyperylene-bisimide-, aliphatic ether and aliphatic N-substituted perylene-lactamimide dyes, useful e.g. as intercalating or fluorescent dyes, pigments, tracers or starting materials for organic superconductor or in data storage - Google Patents

Abstract

New perylene dyes are hydroxy-perylene-3,4:9,10-tetracarbimides (I), in which the hydroxyl group and/or one or both nitrogen atoms may have a 1-37C alkyl substituent, where 1-10 methylene units may be replaced by carbonyl, oxygen, sulfur, selenium, tellurium, cis- or trans-dimethine, azadimethine, acetylene, divalent phenyl, pyridine or thiophene group or by a naphthylene or anthracene group, and where 1 or 2 methine groups may be replaced by nitrogen, and numerous other substituents. New perylene dyes are hydroxy-perylene-3,4:9,10-tetracarbimides (I) of formula (11): R1>-R3>H, 1-37C linear alkyl, in which 1-10 CH2 units may be replaced by X; X : carbonyl, O, S, Se, Te, or cis- or trans-CH=CH in which 1 CH unit may be replaced by N, Ctriple boundC, 1,2-, 1,3- or a 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-di-substituted pyridine, 2,3-, 2,4-, 2,5- or 3,4-di-substituted thiophene group or a 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-di-substituted naphthylene 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-di-substituted anthracene group in which 1 or 2 CH2 groups may be replaced by N, where 1-12 H atoms of the CH2 groups, including those on the same C atom, may be replaced by halogen, F, Cl, Br, I, CN, or 1-18 C linear alkyl in which 1-6 CH2 groups may be replaced by C and, in turn, 1-6 CH2 units of the alkyl groups may be replaced by C; or free valencies of the methine groups or quaternary C atoms may be linked in pairs to form rings, e.g. cyclohexane rings Independent claims are also included for the following (1) new N,N'-bis(2-alkyl-3-hydroxypropyl)-perylene-3,4:9,10-tetracarbimide dyes of formula (12); (2) new N,N'-bis(2-alkyl-3-hydroxypropyl)-1-hydroxy-perylene-3,4:9,10-tetracarbimide dyes of formula (13); (3) new N,N'-bis(2-alkyl-3-hydroxypropyl)-pyrrolo[3,4-bc]perylo[9,10-b'c']pyridine dyes of formula (14); (4) new N,N'-bis(2-alkyl-3-hydroxypropyl)-1-hydroxy-pyrrolo[3,4-bc]perylo[9,10-b'c']pyridine dyes of formula (15); (5) new N-2-alkyl-3-hydroxypropyl-pyrrolo[3,4-bc]perylo[9,10-b'c']pyridine dyes (16); (6) process using dipolar aprotic solvent with addition of alcohol as reaction medium. R4>as for R1>-R3>. [Image] [Image] [Image] [Image].

Description

Perylene dyes, perylene-3,4: 9,10-tetracarboxylic bisimides, 1 are characterized by their particular lightfastness [1,2]. By introducing solubility-enhancing groups, such as long-chain sec-alkyl radicals ("dovetail radicals") [3,4] or tert-butylphenyl radicals [5] at the nitrogen atoms of 1, readily soluble derivatives were obtained that fluoresce markedly [6] with fluorescence quantum yields The UV / Vis absorption and fluorescence spectra of 1 are very little dependent on the substituents R ¹ - orbital nodes [7] can be held responsible for the nitrogen atoms of 1 in the orbitals HOMO and LUMO electronic decoupling of the π color system from residues R ^1. As favorable as such invariance of the spectra is for analytical purposes, it does represent a limitation on the use of the dyes for fluorescence applications Substitution of the nucleus may lead to a change in the absorption, in particular a longer-wave fluorescence in Direction of red of interest, because red tones are particularly noticeable, so that many applications arise for this purpose.

In A previous work [8] has already shown that donor groups in items 1, 6, 7 and 12 generally to a long-wave Shift the absorption and fluorescence lead; see. also [2] - strong bathochromium shifted absorptions are in tetra-alkoxy or Acryloxy derivatives of perylenebisimides have been observed [9,10,11], they lead but by steric pressure to a strong deformation of the perylene core [12]. It is to ask if already a donor group for a strong long-wave displacement of the absorption is sufficient because of Chromophore is not disturbed as much. As donor groups come in principle Alkoxy, aryloxy and amino groups in question. Here are alkoxy groups prefers. Well could Remember to halogenate bisimides 1 and the halogen with on and for known methods, where appropriate under harsh conditions, to exchange with alkoxy groups [13]. This is contrary to that in the halogenation is easily a Mehrfachhalogenierung and the strongly halogenated bisimides extraordinarily difficult to separate [14]. This represents a special handicap for the preparative Pure representation the use of the crude product of a halogenation for the exchange of halogens for ether groups is also no preparative Alternative is because the separation of these reaction products is not less difficult. The targeted representation of a perylene bisimide with only one oxygen-donor group is an unsolved problem and would Significant progress, in particular perylenebisimides with an ether group, e.g. a methoxy group, in the relevant Positions and no further substituents on the nucleus completely unknown.

description

A bathochromic shift in absorption can be achieved from perylenebisimides (1) by a ring-narrowing reaction [15] to lactamimides (2). Here, predominantly representatives with aromatic radicals R ^{1 were} synthesized [16]; only Ref. [17] describes two derivatives of 2 with R ¹ = (C ₇ H ₁₅ ) ₂ CH and R ¹ = (C ₇ H ₁₅ ) (C ₂ H ₅ ) CH for electroluminescence applications.

We have carried out these ring constriction reactions - as before - with aromatic radicals having aliphatic radicals R ¹ , in particular first with sec-Alklylresten ("dovetail radicals"), such as the 1-hexylheptyl or 1-Heptyloctylrest. Methanol was added to the reaction medium DMSO. Dyes 2 were obtained which had a surprisingly strong fluorescence in solution. Surprisingly, as a by-product, the methoxy derivative (3) was also obtained, which showed a surprisingly intense red fluorescence in solution. The photostability of compounds 3 is so high that they are of interest for fluorescence applications. The absorption and fluorescence spectrum of 3c is in 1 shown. One sees the significant long-wave shift in comparison to 1a, which fluoresces yellow. The vibrational structures of 3c and 1a are similar, the fine structure of 3c is less pronounced than of 1.

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The Methoxy compounds are directly for applications in lipophilic Media and the vast majority Majority of polymer materials of interest. Even wider would be the application the new class of substance and also the perylene iminolactam, when Anchor groups would be present with which a shortcut possible to other structures is. This can be done by inserting done by hydroxy groups.

Around To synthesize hydroxyl-bearing dyes, e.g. in a simple way over linked an esterification can be will be first the cyanoacetic ester (4) with long-chain secondary radicals such as the 1-butylpentyl radical alkylated by reacting with 5-bromononane with potassium carbonate in DMF to give 5 is implemented. The reduction with lithium aluminum hydride provides the relevant aminoalcohol 6, which with the Perylentetracarbonsäurebisanhydrid is condensed. A ring constriction with KOH / potassium methoxide in tert-butyl alcohol leads to the imidolactam in question (2c). As a byproduct is the Obtain product 8, in which an unsubstituted imino group is present. This can act as a nucleophile after its deprotonation, so that here over more links possible are.

Becomes the reaction with KOH and methanol at higher temperatures in DMSO executed then a nuclear substitution takes place and the methoxybisimide (3c) is obtained, which then also carries free OH groups. When By-product is obtained In the reaction, a mixture of nucleus-substituted lactamimides which are assigned structures 9 and 10 based on their NMR spectra become. This product leaves Conclusions on the reaction course of the imide-lactam ring constriction too.

The UV / Vis spectroscopic properties of 3a to 3c are practical identical, so that the dyes are exchanged as required can be. The OH groups in 3c stand for more links to disposal.

The across from 1 long-wavelength shifted absorption of 3 is for many physicochemical applications of special interest. For example, the absorption of 3 im optimum working range of the frequently used Rhodamin 6G dye laser, which is very widespread and established - a use of high stable dyes 1 in combination with this laser is but because the hypsochromic absorption is not possible. The bathochrom moved Absorption of 3 opened for applications of perylene dyes completely New opportunities. The wide fluorescence spectrum of 3 also allows a wide frequency range for the Function as a dye laser. The broad, structured absorption spectrum of 3 possible In addition, a stimulation by flash lamps for laser applications.

The impressive, red emission of 3 is also for any decorative applications Purposes of interest. These range from simple light-harvesting systems up to chemiluminescence applications.

Experimental part

1,8-bis (1-hexylheptyl) -1H-indolo [5 ', 4', 3 ': 10,5,6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (2a) and 2,9-bis (1-hexylheptyl) -5-methoxyanthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8 , 10-tetrazone (3a): 2,9-bis (1-hexylheptyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8, 10-tetrazone (1a, 380 mg, 0.500 mmol) is treated with 85 per cent. Potassium hydroxide (700 mg, 12.5 mmol) in a mixture of 4 ml of DMSO and 6 ml of methanol for 5 h at 100 ° C heated. The deep green reaction solution is distilled with 100 ml. Water is added, this precipitate already precipitates (partly red, partly blue-black). With 2 N hydrochloric acid is neutralized to pH 7. The precipitate is drawn off sharply; In this case, the blue-black compound decomposes into a purple one. The crude product is washed twice with 200 ml 10 percent. K ₂ CO ₃ solution boiled to remove saponification products (monoimide-mnonoanhydrid, bisanhydride). The insoluble residue is chromatographed on silica gel with chloroform. In addition to mainly rückisoliertem reactant and the violet methoxy derivative with slightly greater R _f value than the bisimide 1a, the desired second lactofluoride 2a is obtained as a second fraction in admixture with the blue-violet methoxy derivative 3a. For high purification is chromatographed again on silica gel with chloroform and then on silica gel with chloroform / acetone (5: 1). Again, due to the very similar R _f values, no complete separation of the bands is obtained. The last part of the double band consists of pure lactamimide 2a. 1. Product Group: Ausb. 30 mg (8%) of fine, purple powder 3a. - R _f (CHCl ₃ ) = 0.64. - IR (KBr): ṽ = 3443 cm ^-1 m, 2980 m, 2925 s, 2859 m, 1695 s, 1680 s, 1670 s, 1660 s, 1615 m, 1590 s, 1575 m, 1556 m, 1520 s, 1498w, 1489w, 1469m, 1450s, 1428m, 1405s, 1490s, 1485s, 1349s, 1330s, 1266m, 1250m, 1240m, 1145m, 1110w, 930w, 902m , 865 m, 850 m, 811 m, 795 W, 751 m, 712 W, 695 W, 640 m. ¹ H-NMR (400 MHz / CDCl ₃ ): δ = 0.83 ppm (t, 12 H, 2 CH ₃ ), 1.24-1.39 (m, 32 H, 16 CH ₂ ), 1.83-1.92 (m, 4 H , 2 CH ₂ ), 2.17-2.31 (m, 4 H, 2 CH ₂ ), 4.34 (s, 3 H, O-CH ₃ ), 5.19 (m, 2 H, 2 CH), 8.47 (s, broad, 1H, perylene), 8.55 (d, 2H, perylene), 8.58 (d, 1H, perylene), ca. 8.56 (s, broad, 1H, perylene), 8.64 (s, broad, 2H, perylene ), 9.48 (d, 1H, perylene). ¹³ C-NMR (CDCl ₃ ): δ = 164.1 ppm, 165.2, 158.3, 134.5, 134.3, 134.0, 5 signals between 133 and 130 ppm, 129.2, 128.6, 128.4, 127.0, 124.5, 123.4, 122.8, 122.4, 121.9 , 120.8, 118.0, 117.4, 56.9, 54.6, 32.4, 31.8, 29.2, 27.0, 22.6, 14.1. - UV (CHCl ₃ ): λ _max = 372 nm, 387, 408, 485, 515, 552. - Fluorescence (CHCl ₃ ): λ _max = 575 nm, 604. - MS (70 eV): m / z (% ) = 784 (100) [M ⁺ ], 767 (14) [M ⁺ -OH], 713 (1), 699 (4) [M ⁺ -C ₆ H ₁₃ ], 615 (2) [699 - C ₆ H ₁₃ ], 602 (45) [M ⁺ - C ₁₃ H ₂₆ ], 585 (9) [602 - OH], 517 (1) [602 - C ₆ H ₁₃ ], 420 (78) [M ⁺ -2 × C ₁₃ H ₂₆ ], 406 (20), 405 (16) [420-CH ₃ ], 403 (5), 378 (2), 362 (9), 360 (5), 334 (5). HRMS (70 eV) C ₅₁ H ₆₄ N ₂ O ₅ : Ber., Gef. 784.4765. - 2. Product Group: Ausb. 25 mg (6%) violet powder 2a. - R _f (CHCl ₃ ) = 0.43 - R _f (CHCl ₃ / acetone 10: 3) = 0.96. - IR (KBr): ṽ = 3440 cm ^-1 m, 2960 s, 2934 s, 2862 s, 1719 s, 1700 s, 1665 s, 1605 s, 1626 m, 1590 s, 1560 W, 1542 W, 1521 W, 1511w, 1497m, 1470m, 1460m, 1405m, 1358s, 1342m, 1290w, 1270w, 1252w, 1225w, 1070w, 826w, 815w, 749w. ¹ H-NMR (400 MHz / CDCl ₃ ): δ = 0.82 ppm (t, 12 H, 4 CH ₃ ), 1.19-1.29 (m, 32 H, 16 CH ₂ ), 1.78-1.86 (m, 4 H , 2 CH ₂ ), 2.10-2.15 (m, 2 H, CH ₂ ), 2.20-2.25 (m, 2 H, CH ₂ ), 4.51 (m, broad, 1 H, CH), 5.17 (m, 1 H , CH), 7.14 (d, J = 7.8 Hz, 1H, perylene), 8.14 (d, J = 7.6 Hz, 1H, perylene), 8.23 (d, J = 7.9 Hz, 1H, perylene), 8.33 (d, J = 8.1, 1H, perylene), 8.47 (d, J = 8.1, 1H, perylene), 8.48 (d, J = 7.8Hz, 1H, perylene), 8.57 (dd, broad, 2H , Perylene). ¹³ C-NMR (CDCl ₃ ): δ = 168.3 ppm, 135.8, 134.8, 133.8, 130.2, 126.4, 126.3, 126.0, 125.6, 124.8, 124.5, 123.8, 123.7, 122.0, 120.1, 108.2, 55.2 (CH), 55.15 (CH), 33.4 (2 CH ₂ ), 32.4 (2 CH ₂ ), 31.8 (2 CH ₂ ), 31.6 (2 CH ₂ ), 29.2 (2 CH ₂ ), 29.0 (2 CH ₂ ), 27.0 (2 CH ₂ ), 26.6 (2 CH ₂ ), 22.6 (2 CH ₂ ), 22.5 (2 CH ₂ ), 14.0 (2 CH ₃ ), 13.99 (2 CH ₃ ). - UV (CHCl ₃ ): λ _max = 578 nm sh, 543 sh, 482, 444, 411, 396, 362. - Fluorescence (CHCl ₃ ): λ _max = 621 nm. - MS (70 eV): m / z (%) = 726 (100) [M ⁺ ], 709 (8) [M ⁺ -OH], 641 (9) [M ⁺ - C ₆ H ₁₃ ], 544 (23) [M ⁺ - C ₁₃ H ₂₆ ], 527 (3) [544 - OH], 459 (15) [544 - C ₆ H ₁₃ ], 389 (3), 375 (14), 362 (21) [544 - C ₁₃ H ₂₆ ], 345 ( 3) [362 - OH], 317 (3) [345 - CO].

1,8-bis (1-heptyloctyl) -1H-indolo [5 ', 4', 3 ': 10,5,6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (2b) and 2,9-bis- (1-heptyloctyl) -5-methoxyanthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8 , 10-tetraone (3b): 2,9-bis (1-heptyloctyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8, 10-tetrazone (1b, 390 mg, 0.500 mmol) is treated with 85 per cent. Potassium hydroxide (700 mg, 12.5 mmol) in a mixture of 4 ml of DMSO and 6 ml of methanol for 5 h at 100 ° C heated. The deep green reaction solution is distilled with 100 ml. Water is added, this precipitate already precipitates (partly red, partly blue-black). With 2 N hydrochloric acid is neutralized to pH 7. The precipitate is drawn off sharply. The crude product is boiled in 50 ml of glacial acetic acid for 15 minutes, with dist. Water is precipitated and sucked off. Subsequently, twice with 200 ml of 10 per cent. K ₂ CO ₃ solution boiled to remove saponification products (monoimide-monoanhydride, bisanhydride). The insoluble residue is chromatographed over silica gel with chloroform. In addition to mainly back-isolated starting material 1b and the violet, strongly fluorescent methoxy derivative 3b with slightly greater R _f value than the bisimide 1b, the desired lactamimide 2b is obtained in admixture with a second, non-fluorescent, blue-violet by-product as the third fraction. For high purification is chromatographed again with a mixture of toluene and acetone in the ratio 10: 1 and then on fine silica gel with chloroform. The blue-violet by-product is difficult to separate from the lactamimide. Y. 5 mg (1%) violet powder 3c. - R _f (CHCl ₃ ) = 0.92. ¹ H-NMR (400 MHz / CDCl ₃ ): δ = 0.81 ppm (t, 12 H, 4 CH ₃ ), 1.19-1.52 (m, 20 H, 10 CH ₂ ), 1.85 (m, 4 H, 2 CH ₂ ), 2.23 (m, 4 H, 2 CH ₂ ), 4.34 (s, 3 H, O-CH ₃ ), 5.17 (m, 2 H, 2 CH), 8.50 (m, 2 H, perylene), 8.64 (d, J = 7.6Hz, 2H, perylene), 8.68 (d, J = 8.0Hz, 2H, perylene), 9.56 (d, J = 8.4Hz, 1H, perylene). MS (70 eV): m / z (%) = 840 (71) [M ⁺ ], 823 (12) [M ⁺ - OH], 755 (1), 741 (3) [M ⁺ - C ₇ H ₁₅ ], 644 (6) [M ⁺ -2 × C ₇ H ₁₄ ], 630 (45) [M ⁺ - C ₁₅ H ₃₀ ], 613 (9) [630 - OH], 450 (3), 434 ( 11), 420 (100) [M ⁺ - 2 × C ₁₅ H ₃₀ ] '407 (11), 406 (30), 405 (20), 403 (6), 362 (10), 360 (6). - UV (CHCl ₃ ): λ _max = 371 nm, 388, 408, 485, 516, 553. - Fluorescence (CHCl ₃ ): λ _max = 574 nm, 606.

2-cyano-3-butyl-1-methylheptanoate (5): To a mixture of methyl cyanoacetate (4, 3.96 g, 39.6 mmol), 5-bromononane (10.5 g, 50.6 mmol) in dry DMF (20 mL) was anhydrous K Added ₂ CO ₃ (6.9 g, 50 mmol). The mixture was stirred vigorously under argon at room temperature for 12 h, then diluted with water and extracted with ether (3 x 50 mL). The combined ether extracts were washed with water (3 × 30 ml), dried (MgSO ₄ ), filtered and evaporated (10.25 g of a viscous oil). The crude product was chromatographed by flash chromatography (silica gel, isohexane) to remove the unreacted 5-bromononane. After addition of 10% ethyl acetate, the reaction product was eluted. Y. 3.19 g (86% based on reacted material) of colorless oil. IR (KBr): ṽ = 2933 s cm ^-1 , 2958 s, 2862 s, 2249 w, 1749 s, 1467 m, 1459 m, 1437 m, 1380 w, 1256 s, 1209 s, 1018 m, 732 w. ¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.91 (m, 6 H, 2 CH ₃ ), 1.4 (m, 12 H, 6 CH ₂ ), 2.1 (m, 1 H, CH), 3.62 (m. d, J = 4.15Hz, 1H, CH) 3.82 (s, 3H, CO ₂ CH ₃ ). ¹³ C NMR (100 MHz), CDCl ₃ ): δ = 13.89, 13.93, 22.58, 22.67, 28.86, 29.03, 31.36, 31.52, 39.41, 41.87, 53.27, 115.53, 166.98. MS (70 eV, EI): m / z (%) = 226 (68) [M + H] ⁺ , 227 (8) [M + H + 1] ⁺ , 196 (2) [M + H - C ₂ H ₆ ] ⁺ , 168 (12), 143 (4), 140 (22), 136 (12), 108 (4), 100 (100) [M + H - C ₉ H ₁₈ ] ⁺ , 85 (8) , 71 (10), 41 (13). C ₁₃ H ₂₃ NO ₂ (225.3): calc. C 69.29, H 10.29, N 6.22; gef. C 69.37, H 10.38, N 6.37%.

2-Aminomethyl-3-butyl-1-heptanol (6): To a stirred suspension of LiAlH ₄ (3.56 g, 93.6 mmol) in tert-butyl methyl ether (50 ml) under argon was added a solution of 2-cyano-3-butyl 1-methylheptanoate (5.6 g, 16 mmol) in tert-butyl methyl ether (50 ml) over 1 h at 5 ° C (ice bath). The ice bath was removed and the mixture allowed to react at room temperature for 1 h. Thereafter, it was refluxed for 5 hours and allowed to stand overnight. The reaction was quenched by addition of 10% NaOH and then partitioned between tert-butyl methyl ether (4 x 50 mL). The combined extracts were washed with water (3 × 50 ml), dried (MgSO ₄ ) and filtered. The solvent was distilled off and the residue (3.31 g of viscous oil) was distilled in vacuo. Y. 2.35 g (73%) of colorless oil. - IR (KBr): ṽ = 3293 br cm ^-1 , 2956 s, 2928 s, 2860 s, 1574 m, 1467 s, 1378 m, 1327 w, 1152 m, 1035 s, 828 w, 729 w. - ¹ H NMR (300 MHz, CDCl _3): δ = 0.89 (t, J = 6.6 Hz, 6 H, 2 CH _3), 1.26 (m, 12 H, 6 CH _2), 1.70 (m, 1 H , CH), 2.70 (2 H, CH ₂₎ 3.75 (2 H, CH _2). ¹³ C NMR (75 MHz), CDCl ₃ ): δ = 14.11 (6 C, 2 CH ₃ ), 38.62 (1 C, CH), 43.65 (1 C, CH), 23.05 (2 C, 2 CH ₂ ) , 30.04 (2 C, 2 CH ₂ ), 30.73 (1 C, CH ₂ ), 30.91 (1 C, CH ₂ ), 45.37 (1 C, CH ₂ -NH ₂ ), 67.06 (1 C, CH ₂ -OH ). MS (70 eV, EI): m / z (%) 202 (13) [M + H] ⁺ , 172 (11), 168 (10), 144 (12), 126 (32), 112 (30) , 98 (35), 84 (28), 75 (70), 70 (73), 69 (48), 58 (16), 57 (50), 56 (52), 55 (100), 46 (19) , C ₁₂ H ₂₇ NO (201.4): calc. C 71.58, H 13.52, N 6.96; gef. C 72.16, H 13.60, N 6.57%.

2,9-bis (3-butyl-2-hydroxymethylheptyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 1c): A mixture of perylene-3,4: 9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (2.10 g, 5.36 mmol), 2-aminomethyl-3-butyl-1-heptanol (6, 2.42 g, 12.1 mmol) and imidazole (20 g) was heated to 140 ° C with stirring and argon for 5 h. The mixture was allowed to cool, while warm (about 90 ° C) with 100 ml of 2 N HCl, stirred for 1 h at room temperature and filtered with suction. The solid was washed with distilled water, dried at 80 ° C for 16 h and chromatographed (silica gel, chloroform / 5% methanol). Y. 3.50 g (86%) of red powder 1c, mp 266-268 ° C. - IR (KBr): ṽ = 3447 br cm ^-1 , 2956 s, 2928 s, 2860 m, 1695 s, 1652 s, 1595 s, 1579 m, 1508 W, 1443 m, 1404 m, 1342 s, 1153 m, 1170w, 1017w, 975w, 854w, 811s, 747m. ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.94 (t, J = 6.8 Hz, 12 H, 4 CH ₃ ), 1.38-1.58 (m, 24 H, 12 CH ₂ ), 1.68 (m, 2 H, 2 CH), 2.01 (m, 2 H, 2 CH), 3.54 (AB q, J = 3.6 Hz, 2 H, CH ₂ ), 3.71 (AB q, J = 4.4 Hz, 2 H, CH ₂ ), 4.24 (AB q, J = 4Hz, 2H, CH ₂ ), 4.36 (m, 2H, CH ₂ ), 8.58 (d, J = 8Hz, 4H, perylene), 8.67 (d, J = 8 Hz, 4H, perylene). ¹³ C NMR (100 MHz), CDCl ₃ ): δ = 14.18 (4 C, 4 CH ₃ ), 23.15 (4 C, 4 CH ₂ ), 29.57 (2 C, CH ₂ ), 29.67 (2 C, 2 CH ₂ ), 30.54 (2C, 2CH ₂ ), 30.63 (2C, CH ₂ ), 38.71 (1C, CH), 40.75 (1C, CH ₂ ), 42.04 (1C, CH), 61.39 (1 C, CH ₂ ), 123.15 (4 C, 4 CH perylene), 131.72 (4 C, 4 CH perylene), 126.35 (2 C, 2 C perylene), 129.34 (2 C, 2 C perylene), 134.71 (4C , 4 C perylene), 164.15 (4 C, 4 CO perylene). UV / Vis (CHCl ₃ ): λ _max (ε) = 529 nm (86320), 492 (51880), 461 (18860). - Fluorescence quantum yield (CHCl ₃ , reference: N, N'-bis (1-hexylheptyl) perylene-3,4: 9,10-bis (dicarboximd) (1a) with Φ = 100%) = 100%. MS (70 eV, EI): m / z (%) = 760 (21), 759 (15), 758 (13) [M] ⁺ , 587 (22), 576 (27), 575 (62), 557 (13), 431 (19), 417 (19), 416 (19), 405 (43), 404 (65), 403 (39), 393 (23), 392 (72), 391 (100), 390 (27), 376 (21), 375 (19), 373 (21), 347 (13), 346 (18), 345 (13), 321 (17). C ₄₈ H ₅₈ N ₂ O ₆ (759.0): calc. C 75.96, H 7.70, N 3.69; gef. C 75.99, H 8.00, N 3.63%.

1,8-bis (3-butyl-2-hydroxymethyl-heptyl) -1 H-indolo [5 ', 4', 3 ': 10,5,6] anthra [2,1,9-def] isoquinolin-2 , 7,9 (8H) -trione (2c) and 1- (3-butyl-2-hydroxymethyl-heptyl) -4,11-dimethoxy-1H-indolo [5 ', 4', 3 ': 10.5, 6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (8): a mixture of 2,9-bis- (3-butyl-2-hydroxymethylheptyl) anthra [2, 1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone (1c, 100 mg, 0.130 mmol) and 85% KOH powder (400 mg, 6.07 mmol ) in methanol (30 ml) was refluxed for 1.5 h and then evaporated to dryness (50 ° C). The residue was added with tert-butanol (50 ml), refluxed (100 ° C) with vigorous stirring for 5 hours and then poured into distilled water (300 ml), added with 2N HCl (20 ml) and then redistilled Water (200 ml). The mixture was then heated at 100 ° C for 10 minutes and allowed to cool to room temperature. The precipitate was filtered off with suction, dried at 120 ° C. for 2 h (88 mg) and chromatographed (silica gel, 2% MeOH / CHCl ₃ ). 1st Fraction: Ausb. 14 mg (15%) 2c, red violet powder. - MS (70 eV, EI): m / z (%) = 730. (100) [M] ⁺ . 2nd fraction: 8, Ausb. 15 mg 8 (21%) dark purple powder. - IR (KBr): ṽ = 3442 br cm ^-1 , 2954 w, 2925 m, 2856 w, 1692 s, 1644 s, 1583 s, 1492 s, 1462 w, 1441 w, 1390 s, 1352 w, 1319 w, 1243m, 1164w, 843w, 806m, 740m. - MS (70 eV): m / z (%) = 546 (30) [M] ⁺ . C ₃₅ H ₃₄ N ₂ O ₄ (546.7): calc. C 76.90, H 6.27, N 5.12; gef. C 75.33, H 6.77, N 4.74%.

• [1] Review: H. Langhals, Heterocycles 1995, 40, 477-500.
• [2] Review: H. Langhals, Helv. Chim. Acta 2005, 88, 1309-1343.
• [3] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748.
• [4] S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230.
• [5] H. Langhals, Ger. Offen. DE 3016764 (April 30, 1980); Chem. Abstr. 1982, 96, P70417x.
• [6] H. Langhals, J. Karolin, L. B.-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.
• [7] H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta 1988, 44A, 1189-1193.
• [8] H. Langhals, P. Blanke, Ger. Offen. DE 10132116.3 (3. Juli 2001).
• [9] P. P. Karpukhin, T. A. Korotenko, M. I. Rudkevich, U.S.S.R. Patent SU 206782 (20.5.1966), Chem. Abstr. 1968, 69, 20409.
• [10] M. I. Rudkevich, T. A. Korotenko, Ref. Zh., Khim. 1970, 11B288; Chem. Abstr. 1971, 75, 7375.
• [11] BASF AG (Erf. G. Seybold, A. Stange) Ger. Patent DE 3545004 (19.12.1985); Chem. Abstr. 1988, 108, 77134.
• [12] M. O. Vysotsky, V. Boehmer, F. Wuerthner, Frank, Chang-Cheng You, K. Rissanen, Org. Lett. 2002, 4, 2901-2904.
• [13] R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Bundesminist. Forsch. Technol., Technol. Forsch. Entwickl. 1984, BMFT-FB-T 84-164; Chem. Abstr. 1985, 102, 150903.
• [14] BASF AG (Erf. G. Seybold, A. Stange, Ger. Patent DE 85-3545004; Chem. Abstr. 1988, 108, 77134.
• [15] H. Langhals, P. v. Unold, Angew. Chem. 1995, 107, 2436-2439; Angew. Chem., Int. Ed. Engl. 1995, 34, 2234-2236.
• [16] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535.
• [17] M. Nakatsuka, N. Kitamoto, (Mitsui Toatsu Chemicals, Inc., Japan), Jpn. Kokai Tokkyo Koho 1998, JP 10060426 (August 21, 1996); Chem. Abstr. 1998, 128, 250505.

• 1. Perylenfarbstoffe der allgemeinen Formel 11,
  
  in denen die Reste R¹ bis R³ gleich oder verschieden voneinander sein können und unabhängig voneinander Wasserstoff oder lineare Alkylreste mit mindestens einem und höchstens 37 C-Atome bedeuten, bei denen eine bis 10 CH₂-Enheiten unabhängig voneinander ersetzt sein können durch jeweils Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen, 1,2-, 1,3- oder 1,4-substituierten Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂-Gruppen können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder die Cyanogruppe oder eine lineare Alkylkette mit bis zu 18 C-Atomen, bei der eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei denen eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen, 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierter Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei dem ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂-Gruppen der Alkylreste können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder oder Cyanogruppen oder lineare Alkylketten mit bis zu 18 C-Atomen, bei denen eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Statt Substituenten zu tragen können die freien Valenzen der Methingruppen bzw. der quartären C-Atome paarweise verknüpft werden, so dass Ringe entstehen, wie z.B. Cyclohexanringe. Die Gruppe A in 6 ein in den Positionen 1 und 2 substituierter Cycloalkylrest mit mindestens drei und höchstens 20 C-Atome bedeuten, bei denen eine bis 6 CH₂-Enheiten unabhängig voneinander ersetzt sein können durch jeweils Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen 1,2-, 1,3- oder 1,4-substituierten Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂-Gruppen können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder die Cyanogruppe oder eine lineare Alkylkette mit bis zu 18 C-Atomen, bei der eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei denen eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen, 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierter Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei dem ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH₂-Gruppen der Alkylreste können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder oder Cyanogruppen oder lineare Alkylketten mit bis zu 18 C-Atomen, bei denen eine bis 6 CH₂-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Statt Substituenten zu tragen können die freien Valenzen der Methingruppen bzw. der quartären C-Atome paarweise verknüpft werden, so dass Ringe entstehen, wie z.B. Cyclohexanringe.
• 2. Perylenfarbstoffe mit der allgemeinen Formel 12,
  
  in denen die Reste R¹ bis R⁴ gleich oder verschieden voneinander sein können und die als R¹ unter 1 genannte Bedeutung haben.
• 3. Perylenfarbstoffe mit der allgemeinen Formel 13,
  
  in denen die Reste R¹ bis R⁵ gleich oder verschieden voneinander sein können und die als R¹ unter 1 genannte Bedeutung haben.
• 4. Perylenfarbstoffe mit der allgemeinen Formel 14,
  
  in denen die Reste R¹ bis R⁴ gleich oder verschieden voneinander sein können und die als R¹ unter 1 genannte Bedeutung haben.
• 5. Perylenfarbstoffe mit der allgemeinen Formel 15,
  
  in denen die Reste R¹ bis R⁵ gleich oder verschieden voneinander sein können und die als R¹ unter 1 genannte Bedeutung haben.
• 6. Perylenfarbstoffe mit der allgemeinen Formel 16,
  
  in denen die Reste R¹ bis R² gleich oder verschieden voneinander sein können und die als R¹ unter 1 genannte Bedeutung haben.
• 7. Verfahren dadurch gekennzeichnet, dass als Reaktionsmedium dipolar aprotische Lösungsmittel wie DMSO (Dimethylsulfoxid) verwendet werden, bevorzugt DMSO, unter Zusatz von Alkoholen, bevorzugt aliphatische Alkohole, am meisten bevorzugt Methanol.
• 8. Verwendung der Substanzen nach 1 bis 6, als intercalierende Substanzen, insbesondere als intercalierende Fasrbstoffe für DNA und dort insbesondere für analytische Zwecke, so z.B. zur Fluoreszenzdetektion.
• 9. Verwendung der Substanzen nach 1 bis 6 als Pigmente.
• 10. Verwendung der Substanzen nach 1 bis 6 als Pigmente für Leimfarben und verwandten Farben wie Aquarell-Farben und Wasserfarben und Farben für Tintenstrahldrucker Papierfarben, Druckfarben, Tinten und Tuschen und andere Farben für Mal- und Schreib-Zwecke und in Anstrichstoffen.
• 11. Verwendung der Substanzen nach 1 bis 6 als Pigmente in Lacken. Bevorzugte Lacke sind Kunstharz Lacke wie Acryl- oder Vinyl-Harze, Polyesterlacke, Novolacke, Nitrocellulose-Lacke (Nitrolacke) oder auch Naturstoffe wie Zaponlack, Schellack oder Qi-Lack (Japanlack bzw. Chinalack oder ostasiatischer Lack).
• 12. Verwendung der Farbstoffe nach 1 bis 6 in Datenspeichern, bevorzugt in optischen Speichern. Beispiele sind Systeme wie die CD- oder DVD-Disk.
• 13. Verwendung der Substanzen nach 1 bis 6 als Fluoreszenzfarbstoffe.
• 14. Verwendung der Substanzen nach 1 bis 6 in OLEDS (organischen Leuchtdioden).
• 15. Verwendung der Substanzen nach 1 bis 6 in photovoltaischen Anlagen.
• 16. Anwendung der Farbstoffe von 1 bis 6 zur Masse-Färbung von Polymeren. Beispiele sind Materialien aus Polyvinylchlorid, Celluloseacetat, Polycarbonaten, Polyamiden, Polyurethanen, Polyimiden, Polybenzimidazolen, Melaminharzen, Silikonen, Polyestern, Polyethern, Polystyrol Polymethylmethacrylat, Polyethylen, Polypropylen, Polyvinylacetat, Polyacrylnitril, Polybutadien, Polychlorbutadien oder Polyisopren bzw. die Copolymeren der genannten Monomeren.
• 17. Anwendung der Farbstoffe von 1 bis 6 als Küpenfarbstoffe, z.B. zur Färbung von Naturstoffen. Beispiele sind Papier, Holz, Stroh, Leder, Felle oder natürliche Fasermaterialien wie Baumwolle, Wolle, Seide, Jute, Sisal, Hanf, Flachs oder Tierhaare (z.B. Rosshaar) oder menschlichen Haaren und deren Umwandlungsprodukte wie z.B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon).
• 18. Anwendung der Farbstoffe von 1 bis 6 als Beizenfarbstoffe, z.B. zur Färbung von Naturstoffen. Beispiele sind Papier, Holz, Stroh, Leder, Felle oder natürliche Fasermaterialien wie Baumwolle, Wolle, Seide, Jute, Sisal, Hanf, Flachs oder Tierhaare (z.B. Roßhaar) und deren Umwandlungsprodukte wie z.B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon). Bevorzugte Salze zum beizen sind Aluminium-, Chrom- und Eisensalze.
• 19. Anwendung der Farbstoffe von 1 bis 6 als Farbmittel, z.B. zur Färbung von Farben, Lacken und anderen Anstrichsstoffen, Papierfarben, Druckfarben, Tinten und andere Farben für Mal- und Schreib-Zwecke.
• 20. Anwendung der Farbstoffe von 1 bis 6 als Pigmente in der Elektrophotographie: z.B. für Trockenkopiersysteme (Xerox-Verfahren) und Laserdrucker ("Non-Impact-Printing").
• 21. Anwendung der Farbstoffe von 1 bis 6 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.
• 22. Anwendung der Farbstoffe von 1 bis 6 als Zusatz zu anderen Farben, bei denen eine bestimmte Farbnuance erzielt werden soll, bevorzugt sind besonders leuchtende Farbtöne.
• 23. Anwendung der Farbstoffe von 1 bis 6 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.
• 24. Anwendung der Farbstoffe von 1 bis 6 als Fluoreszenzfarbstoffe für maschinenlesbare Markierungen, bevorzugt sind alphanumerische Aufdrucke oder Barcodes.
• 25. Anwendung der Farbstoffe von 1 bis 6 zur Frequenzumsetzung von Licht, z.B. um aus kurzwelligem Licht längerwelliges, sichtbares Licht zu machen.
• 26. Anwendung der Farbstoffe von 1 bis 6 in Anzeigeelementen für vielerlei Anzeige-, Hinweis- und Markierungszwecke, z.B. passive Anzeigeelemente, Hinweis- und Verkehrszeichen, wie Ampeln.
• 27. Anwendung der Farbstoffe von 1 bis 6 in Tintenstrahldruckern in homogener Lösung als fluoreszierende Tinte.
• 28. Anwendung der Farbstoffe von 1 bis 6 als Ausgangsmaterial für supraleitende organische Materialien.
• 29. Anwendung der Farbstoffe von 1 bis 6 für Feststoff-Fluoreszenz-Markierungen.
• 30. Anwendung der Farbstoffe von 1 bis 6 für dekorative Zwecke.
• 31. Anwendung der Farbstoffe von 1 bis 6 für künstlerische Zwecke.
• 32. Anwendung der Farbstoffe von 1 bis 6 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).
• 33. Anwendung der Farbstoffe von 1 bis 6 als Fluoreszenzfarbstoffe in hochempfindlichen Nachweisverfahren (siehe C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher und H. Langhals, Z.Analyt.Chem. 1985, 320, 361).
• 34. Anwendung der Farbstoffe von 1 bis 6 als Fluoreszenzfarbstoffe in Szintillatoren.
• 35. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in optischen Lichtsammelsystemen.
• 36. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Fluoreszenz-Solarkollektoren (siehe H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716).
• 37. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Fluoreszenz-aktivierten Displays (siehe W. Greubel und G. Baur, Elektronik 1977, 26, 6).
• 38. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Kaltlichtquellen zur lichtinduzierten Polymerisation zur Darstellung von Kunststoffen.
• 39. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe zur Materialprüfung, z.B. bei der Herstellung von Halbleiterschaltungen.
• 40. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe zur Untersuchung von Mikrostrukturen von integrierten Halbleiterbauteilen.
• 41. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Photoleitern.
• 42. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in fotografischen Verfahren.
• 43. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Anzeige-, Beleuchtungs- oder Bildwandlersystemen, bei denen die Anregung durch Elektronen, Ionen oder UV-Strahlung erfolgt, z.B. in Fluoreszenzanzeigen, Braunschen Röhren oder in Leuchtstoffröhren.
• 44. Anwendung der Farbstoffe von 1 bis 6 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.
• 45. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Chemilumineszenzsystemen, z.B. in Chemilumineszenz-Leuchtstäben, in Lumineszenzimmunoassays oder anderen Lumineszenznachweisverfahren.
• 46. Anwendung der Farbstoffe von 1 bis 6 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.
• 47. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe oder Fluoreszenzfarbstoffe in Farbstoff-Lasern, bevorzugt als Fluoreszenzfarbstoffe zur Erzeugung von Laserstrahlen.
• 48. Anwendung der Farbstoffe von 1 bis 6 als Farbstoffe in Farbstoff-Lasern als Q-Switch Schalter.
• 49. Anwendung der Farbstoffe von 1 bis 6 als aktive Substanzen für eine nichtlineare Optik, z.B. für die Frequenzverdopplung und die Frequenzverdreifachung von Laserlicht.
• 50. Anwendung der Farbstoffe von 1 bis 6 als Rheologieverbesserer.
• 51. Anwendung der Farbstoffe von 1 bis 6 zur Dichtigkeitsprüfung geschlossener Systeme.

2,9-bis (3-butyl-2-hydroxymethyl-heptyl) -5-methoxy-anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3 , 8,10-tetrazone (3c), 1,8-bis (3-butyl-2-hydroxymethylheptyl) -4,11-dimethoxy-1H-indolo [5 ', 4', 3 ': 10.5 , 6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (9) and 1,8-bis- (3-butyl-2-hydroxymethyl-heptyl) -5,11 -dimethoxy-1H-indolo [5 ', 4', 3 ': 10.5,6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (10): A mixture from N, N'-bis (2-hydroxymethyl-3-butylheptyl) perylene-3,4: 9,10-bis (dicarboximide) (1c, 400 mg, 0.520 mmol) and 85% KOH powder (1.72 g, 26 mmol) in DMSO / MeOH (80/40, 120 ml) was refluxed at 110 ° C for 3 hours. After cooling to room temperature, the mixture was added to 2N HCl (100 ml) and stirred for 2 h. The precipitate was filtered off, dried at 120 ° C for 2 h (265 mg of a dark purple powder) and chromatographed (silica gel, 2% MeOH / CHCl ₃ ). 1st fraction: about 100 mg (24%) of 2,9-bis- (3-butyl-2-hydroxymethyl-heptyl) -5-methoxy-anthra [2,1,9-def; 6,5,10- d'e'f '] diisoquinoline-1,3,8,10-tetrazone (3c) red violet powder, mp> 250 ° C. R _f (silica gel, CHCl ₃ / ethanol 20: 1) = 0.31. - IR (KBr): ṽ = 3468.0 cm ^-1 w br, 2956.5 s, 2924.6 vs, 2854.6 s, 1737.8 m, 1693.1 m, 1649.9 m, 1593.6 m, 1462.8 m, 1404.2 w, 1378.0 w, 1335.0 w, 1268.1 w, 1120.0 w, 1072.0 w, 808.0 w, 746.0 w. ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.84-0.88 (m, 12 H, 4 CH ₃ ), 1.25-1.69 (m, 28 H, 12 CH ₂ + 4 CH), 2.04 (s, 2H, CH ₂ ), 2.95 (s br., 2H, 2OH), 3.57 (m, 2H, N-CH ₂ ), 3.73 (m, 2H, N-CH ₂ ), 4.13-4.40 (m, 7H, 2OCH ₂ R + ROCH ₃ ), 8.13-8.48 (m, 6H, aromat. CH), 9.17-9.28 (m, 1H, aromat. CH). - ¹³ C NMR (151 MHz, CDCl _3, 25 ° C): δ = 14.2, 23.0, 23.2, 29.7, 30.5, 30.7, 38.7, 40.7, 40.9, 42.0, 56.8 (ROCH _3), 61.8, 117.3, 121.2 , 121.6, 122.2, 122.3, 123.2, 123.4, 123.7, 126.2, 128.5, 128.7, 130.3, 131.8, 134.0, 158.0, 163.6, 164.0, 164.1. UV / VIS (CHCl ₃ ): λ _max (E _rel ) = 391 nm (0.10), 411 (0.09), 489 sh. (0.27), 520 (0.66), 558 (1.00). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 575 nm (1.00), 620 (0.61). - Fluorescence quantum eff. (CHCl ₃ , λ _exc = 483 nm, E ₄₈₃ nm = 0.0138 cm ^-1 , reference: 1a with Φ = 1.00) = 0.86. MS (DEI ⁺ / 70 eV): m / z (%): 788 (100) [M ⁺ ], 770 (17) [M ⁺ - OH], 760 (14) [M ⁺ - CO], 758 ( 13) [M ⁺ - OCH ₃ ], 727 (10) [M ⁺ - 2 × CH ₂ -OH], 605 (79) [M ⁺ - C ₁₂ H ₂₅ O], 587 (16) [M ⁺ - C ₁₂ H ₂₅ O - OH], 575 (8) [M ⁺ - C ₁₂ H ₂₅ O - OCH ₃ ], 420 (56) [M ⁺ - 2 x C ₁₂ H ₂₅ O], 390 (9) [M ⁺ - 2 × C ₁₂ H ₂₅ O - OCH ₃ ]. HMRS (C ₄₉ H ₆₀ N ₂ O ₇ ): m / z: calc. 788.4401, m.p. 788.4452. - 2nd fraction: about 30 mg (7%) mixture of 1,8-bis (3-butyl-2-hydroxymethyl-heptyl) -4,11-dimethoxy-1H-indolo [5 ', 4', 3 ': 10.5.6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione (9) and 1,8-bis (3-butyl-2-hydroxymethyl-heptyl ) -5,11-dimethoxy-1H-indolo [5 ', 4', 3 ': 10.5,6] anthra [2,1,9-def] isoquinoline-2,7,9 (8H) -trione ( 10) blue-violet powder, mp> 250 ° C. R _f (silica gel, CHCl ₃ / ethanol 20: 1) = 0.21. - IR (KBr): ṽ = 3435.9 cm ^-1 vs br., 2955.6 s, 2924.8 vs, 2855.1 m, 1685.7 m, 1637.1 m, 1583.7 m, 1501.3 w, 1463.5 m, 1390.5 m, 1344.1 w, 1240.0 w, 1166.5 w, 1068.0 w, 802.5 w, 740.6 w. ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.80-0.90 (m, 12H, 4 × CH ₃ ), 1.19-1.64 (m, 28H, 4 × CH + 12 × CH ₂ ), 1.88 - 2.02 (m, 2H, CH ₂ ), 3.42 - 3.68 (m, 4H, 2 x CH ₂ ), 3.83 - 4.39 (m, 7H, 2 x CH ₂ + OCH ₃ ), 6.87 - 6.92 (m, 1H, aromat. CH), 8.26 - 8.63 (m, 5H, aromat. CH), 8.96 - 9.06 (m, 1H, aromat. CH). - 2D-NMR (dQCOSY, 400 MHz, CDCl ₃ , 24 ° C): two sets of signals in the aromatic region, several sets of signals in the aliphatic region by stereoisimers. - ¹³ C NMR (151 MHz, CDCl _3, 25 ° C): δ = 14.1, 23.1, 29.5, 29.6, 29.7, 29.8, 30.0, 30.1, 30.2, 30.6, 30.7, 38.3, 38.7, 40.0, 42.1, 42.5 , 56.0 (OCH ₃ ), 56.8 (OCH ₃ ), 61.2. UV / VIS (CHCl ₃ ): λ _max (E _rel ) = 373 nm (0.28), 389 (0.40), 408 (0.52), 574 (1.00). - Fluorescence (CHCl ₃ ): not detectable. MS (DEI ⁺ / 70 eV): m / z (%): 760 (100) [M ⁺ ], 730 (7) [M ⁺ - OCH ₃ ], 577 (48) [M ⁺ - C ₁₂ H ₂₅ O], 435 (3) [M ⁺ - OCH ₃ - C ₉ H ₁₉ - C ₁₂ H ₂₅ NO], 419 (9) [M ⁺ - C ₁₂ H ₂₅ O - OCH ₃ - C ₉ H ₁₉ ], 391 (15) [M ⁺ - C ₁₂ H ₂₅ O - OCH ₃ - C ₉ H ₁₉ - CO], 346 (3) [M ⁺ - C ₁₂ H ₂₅ O - OCH ₃ - C ₉ H ₁₉ - C ₃ H ₇ NO]. HMRS (C ₄₉ H ₆₀ N ₂ O ₇ ): m / z: calc. 790.4557, m.p. 790.4650.

• [1] Review: H. Langhals, Heterocycles 1995, 40, 477-500.
• [2] Review: H. Langhals, Helv. Chim. Acta 2005, 88, 1309-1343.
• [3] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748.
• [4] S.Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230.
• [5] H. Langhals, Ger. Open. DE 3016764 (April 30, 1980); Chem. Abstr. 1982, 96, P70417x.
• [6] H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.
• [7] H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta 1988, 44A, 1189-1193.
• [8] H. Langhals, P. Blanke, Ger. Offen. DE 10132116.3 (3 July 2001).
• [9] PP Karpukhin, TA Korotenko, MI Rudkevich, USSR Patent SU 206782 (20.5.1966), Chem. Abstr. 1968, 69, 20409.
• [10] MI Rudkevich, TA Korotenko, ref. Zh., Khim. 1970, 11B288; Chem. Abstr. 1971, 75, 7375.
• [11] BASF AG (inventor G. Seybold, A. Stange) Ger DE 3545004 (12.19.1985); Chem. Abstr. 1988, 108, 77134.
• [12] MO Vysotsky, V. Boehmer, F. Wuerthner, Frank, Chang-Cheng You, K. Rissanen, Org. Lett. 2002, 4, 2901-2904.
• [13] 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.
• [14] BASF AG (inventor G. Seybold, A. Stange, Ger. Patent DE 85-3545004; Chem. Abstr. 1988, 108, 77134.
• [15] H. Langhals, P. v. Unold, Angew. Chem. 1995, 107, 2436-2439; Angew. Chem., Int. Ed. Engl. 1995, 34, 2234-2236.
• [16] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535.
• [17] M. Nakatsuka, N. Kitamoto, (Mitsui Toatsu Chemicals, Inc., Japan), Jpn. Kokai Tokkyo Koho 1998, JP 10060426 (August 21, 1996); Chem. Abstr. 1998, 128, 250505.

• 1. perylene dyes of general formula 11,
  
  in which the radicals R ¹ to R ^{3 may be} identical or different and independently of one another denote hydrogen 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-substituted 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 can be replaced by nitrogen atoms, 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 i 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-substituted 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, 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-disub substituted 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 or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to six CH ₂ units can be replaced independently by carbonyl groups, oxygenato me, 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-substituted 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, 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. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The group A in FIG. 6 represents a cycloalkyl radical substituted in positions 1 and 2 and having at least 3 and at most 20 C atoms, in which one to 6 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 of 1,2-, 1,3- or 1,4-substituted 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 can be replaced by nitrogen atoms, 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-substituted 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, 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-disub substituted 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 or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one 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 can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted 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, 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-od he 9,10-disubstituted 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 of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings.
• 2. perylene dyes having the general formula 12,
  
  in which the radicals R ¹ to R ^{4 may be the} same or different and have the meaning given as R ¹ under 1 meaning.
• 3. perylene dyes having the general formula 13,
  
  in which the radicals R ¹ to R ^{5 may be the} same or different from each other and have the meaning mentioned under R ¹ as 1.
• 4. perylene dyes having the general formula 14,
  
  in which the radicals R ¹ to R ^{4 may be the} same or different and have the meaning given as R ¹ under 1 meaning.
• 5. perylene dyes having the general formula 15,
  
  in which the radicals R ¹ to R ^{5 may be the} same or different from each other and have the meaning mentioned under R ¹ as 1.
• 6. perylene dyes having the general formula 16,
  
  in which the radicals R ¹ to R ^{2 may be the} same or different and have the meaning given as R ¹ under 1 meaning.
• 7. Process characterized in that dipolar aprotic solvents such as DMSO (dimethylsulfoxide) are used as the reaction medium, preferably DMSO, with the addition of alcohols, preferably aliphatic alcohols, most preferably methanol.
• 8. Use of the substances according to 1 to 6, as intercalating substances, in particular as intercalating Fasrbstoffe for DNA and there in particular for analytical purposes, such as for fluorescence detection.
• 9. Use of the substances according to 1 to 6 as pigments.
• 10. Use of the substances according to 1 to 6 as pigments for glues and related colors such as watercolors and watercolors and inks for inkjet printers, paper inks, printing inks, inks and inks and other colors for painting and writing purposes and in paints.
• 11. Use of the substances according to 1 to 6 as pigments in paints. Preferred lacquers are synthetic resin lacquers 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).
• 12. Use of the dyes according to 1 to 6 in data storage, preferably in optical storage. Examples are systems such as the CD or DVD disc.
• 13. Use of the substances according to 1 to 6 as fluorescent dyes.
• 14. Use of the substances according to 1 to 6 in OLEDS (organic light-emitting diodes).
• 15. Use of the substances according to 1 to 6 in photovoltaic systems.
• 16. Application of dyes from 1 to 6 for mass-dyeing of polymers. Examples are materials 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 said monomers.
• 17. Application of dyes from 1 to 6 as vat dyes, eg for coloring natural products. Examples are paper, wood, straw, leather, hides or natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax or animal hair (eg horsehair) or human hair and their conversion products such as viscose, nitrate silk or copper rayon (Reyon ).
• 18. Application of the dyes from 1 to 6 as mordant dyes, eg for coloring natural products. Examples are paper, wood, straw, leather, fur or natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax or animal hair (eg horsehair) and their conversion products such as viscose, nitrate silk or copper rayon (rayon). Preferred salts for pickling are aluminum, chromium and iron salts.
• 19. Use of the dyes from 1 to 6 as colorants, eg for coloring paints, varnishes and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes.
• 20. Application of dyes from 1 to 6 as pigments in electrophotography: eg for dry copying systems (Xerox process) and laser printers ("non-impact printing").
• 21. Use of the dyes from 1 to 6 for security marking purposes, whereby the great 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, identity documents and the like, in which a special, unmistakable color impression is to be achieved.
• 22. Application of the dyes from 1 to 6 as an additive to other colors in which a certain shade of shade is to be achieved, preferred are particularly bright shades.
• 23. Application of the dyes of 1 to 6 for marking objects for machine recognition of these objects on the fluorescence, preferably the machine detection of objects for sorting, for example, also for the recycling of plastics.
• 24. Application of the dyes from 1 to 6 as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes.
• 25. Application of the dyes from 1 to 6 for frequency conversion of light, for example, to make shortwave light longer-wavelength, visible light.
• 26. Application of the dyes 1 to 6 in display elements for a variety of display, hint and marking purposes, such as passive display elements, traffic signs and traffic signs, such as traffic lights.
• 27. Application of dyes from 1 to 6 in inkjet printers in homogeneous solution as a fluorescent ink.
• 28. Application of the dyes from 1 to 6 as starting material for superconducting organic materials.
• 29. Application of dyes from 1 to 6 for solid fluorescence labels.
• 30. Application of dyes from 1 to 6 for decorative purposes.
• 31. Application of dyes 1 to 6 for artistic purposes.
• 32. Application of the dyes 1 to 6 for tracer purposes, eg in biochemistry, medicine, technology and natural sciences. In this case, the dyes may be covalently linked to substrates or via secondary valences such as hydrogen bonds or hydrophobic interactions (adsorption).
• 33. Application of dyes from 1 to 6 as fluorescent dyes in highly sensitive detection Verfah (See C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z. Analyt. Chem., 1985, 320, 361).
• 34. Application of dyes from 1 to 6 as fluorescent dyes in scintillators.
• 35. Application of Dyes 1 to 6 as Dyes or Fluorescent Dyes in Optical Light Collector Systems.
• 36. Application of the Dyes 1 to 6 as Dyes or Fluorescent Dyes in Fluorescence Solar Collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716).
• 37. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in fluorescence-activated displays (see W. Greubel and G. Baur, Electronics 1977, 26, 6).
• 38. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics.
• 39. Application of the dyes from 1 to 6 as dyes or fluorescent dyes for material testing, eg in the manufacture of semiconductor circuits.
• 40. Application of Dyes 1 to 6 as Dyes or Fluorescent Dyes for Investigating Microstructures of Integrated Semiconductor Devices.
• 41. Application of Dyes 1 to 6 as Dyes or Fluorescent Dyes in Photoconductors.
• 42. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in photographic processes.
• 43. Application of the dyes from 1 to 6 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 example in fluorescent displays, Braun tubes or in fluorescent tubes.
• 44. Application of the dyes from 1 to 6 as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in combination with other semiconductors, for example in the form of an epitaxy.
• 45. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in chemiluminescence systems, for example in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods.
• 46. Application of the dyes from 1 to 6 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.
• 47. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams.
• 48. Use of dyes from 1 to 6 as dyes in dye lasers as Q-switch switches.
• 49. Application of the dyes from 1 to 6 as active substances for nonlinear optics, eg for frequency doubling and frequency tripling of laser light.
• 50. Application of Dyes 1 to 6 as rheology improver.
• 51. Application of dyes from 1 to 6 for leak testing of closed systems.

LIST OF REFERENCE NUMBERS

• 1 , Absorption and fluorescence spectrum of 3c in chloroform (thick line) compared to 1a (R ¹ = 1-hexylheptyl) (thin line).

It follows a sequence listing according to WIPO St. 25. This can from the official publication platform downloaded from the DPMA.

Claims (51)

Perylene dyes of general formula 11,

in which the radicals R ¹ to R ^{3 may be} identical or different and independently of one another denote hydrogen 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-substituted 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 can be replaced by nitrogen atoms, 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 i 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-substituted 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, 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-disub substituted 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 or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one 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 can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted 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, 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-od he 9,10-disubstituted 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 of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The group A in FIG. 6 represents a cycloalkyl radical substituted in positions 1 and 2 and having at least 3 and at most 20 C atoms, in which one to 6 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 of 1,2-, 1,3- or 1,4-substituted 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 can be replaced by nitrogen atoms, 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-substituted 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, 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 or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one 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 can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted 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, 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-od he 9,10-disubstituted 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 of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. Perylene dyes having the general formula 12,

in which the radicals R ¹ to R ^{4 may be the} same or different and have the meaning given as R ¹ under 1 meaning. Perylene dyes having the general formula 13,

in which the radicals R ¹ to R ^{5 may be the} same or different from each other and have the meaning mentioned under R ¹ as 1. Perylene dyes of the general formula 14,

in which the radicals R ¹ to R ^{4 may be the} same or different and have the meaning given as R ¹ under 1 meaning. Perylene dyes having the general formula 15,

in which the radicals R ¹ to R ^{5 may be the} same or different from each other and have the meaning mentioned under R ¹ as 1. Perylene dyes having the general formula 16,

in which the radicals R ¹ to R ^{2 may be the} same or different and have the meaning given as R ¹ under 1 meaning. Process characterized in that as the reaction medium dipolar aprotic solvents such as DMSO (dimethylsulfoxide), preferably DMSO, below Addition of alcohols, preferably aliphatic alcohols, most preferably methanol. Use of the substances according to 1 to 6, as intercalating Substances, in particular as intercalating fibrous substances for DNA and there in particular for analytical purposes, e.g. for fluorescence detection. Use of the substances according to 1 to 6 as pigments. Use of the substances according to 1 to 6 as pigments for glue colors and related colors such as watercolor paints and watercolors and colors for inkjet printers Paper colors, printing inks, inks and inks and other colors for painting and writing purposes and in paints. Use of the substances according to 1 to 6 as pigments in paints. Preferred paints are synthetic resin Lacquers such as acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer). Use of Dyes 1 to 6 in Data Memories, preferably in optical memories. Examples are systems like the CD or DVD disc. Use of the substances according to 1 to 6 as fluorescent dyes. Use of the substances according to 1 to 6 in OLEDS (organic light-emitting diodes). Use of the substances according to 1 to 6 in photovoltaic Attachments. Application of dyes from 1 to 6 for mass staining of Polymers. Examples are materials of polyvinyl chloride, cellulose acetate, Polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, Melamine resins, silicones, polyesters, polyethers, polystyrene polymethylmethacrylate, Polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, Polychlorobutadiene or polyisoprene or the copolymers of the mentioned Monomers. Application of the dyes from 1 to 6 as vat dyes, e.g. for coloring of natural substances. 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) or human hair and hair their conversion products such as e.g. the viscose fiber, nitrate silk or copper rayon (Reyon). Application of the dyes from 1 to 6 as mordant dyes, e.g. for coloring of natural substances. Examples are paper, wood, straw, leather, skins or natural Fiber materials such as cotton, wool, silk, jute, sisal, hemp, Flax or animal hair (for example horsehair) and their conversion products such as e.g. the viscose fiber, nitrate silk or copper rayon (Reyon). Preferred salts for pickling are aluminum, Chromium and iron salts. Application of the dyes from 1 to 6 as colorants, e.g. for coloring paints, varnishes and other paints, paper inks, printing inks, Inks and other colors for Maland writing purposes. Application of the dyes from 1 to 6 as pigments in electrophotography: e.g. for dry copying systems (Xerox process) and laser printers (non-impact printing). Application of dyes 1 to 6 for security marking purposes, being the big one chemical and photochemical resistance and possibly also the Fluorescence of the substances is important. This is preferred for checks, Check cards, banknotes coupons, documents, identity documents and the like, in which a special, unmistakable color impression should be achieved. Application of the dyes from 1 to 6 as an additive to other colors where a certain shade of color is achieved should, are particularly bright shades. Application of dyes from 1 to 6 for marking of objects for machine recognition of these objects via fluorescence is the machine detection of articles for sorting, e.g. also for the Recycling of plastics. Application of dyes from 1 to 6 as fluorescent dyes for machine readable Markings, preferred are alphanumeric imprints or barcodes. Application of dyes from 1 to 6 for frequency conversion of light, e.g. from short-wave light, longer-wave, visible light close. Application of dyes from 1 to 6 in display elements for many things Display, hint and marking purposes, e.g. passive display elements, Signs and traffic signs, such as traffic lights. Application of dyes from 1 to 6 in inkjet printers in homogeneous solution as a fluorescent ink. Application of the dyes from 1 to 6 as starting material for superconducting organic materials. Application of dyes from 1 to 6 for solid fluorescence labels. Application of dyes from 1 to 6 for decorative Purposes. Application of dyes from 1 to 6 for artistic Purposes. Application of the dyes from 1 to 6 for tracer purposes, e.g. in biochemistry, medicine, engineering and science. in this connection can the dyes are covalently linked to substrates or via minor valences like hydrogen bonds or hydrophobic interactions (adsorption). Application of dyes from 1 to 6 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 6 as fluorescent dyes in scintillators. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in optical light harvesting systems. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in fluorescence solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716). Application of the dyes from 1 to 6 as dyes or fluorescent dyes in fluorescence-activated displays (see W. Greubel and G. Baur, Electronics 1977, 26, 6). Application of the dyes from 1 to 6 as dyes or fluorescent dyes in cold light sources for light-induced Polymerization for the preparation of plastics. Application of the dyes from 1 to 6 as dyes or fluorescent dyes for material testing, e.g. in the preparation of of semiconductor circuits. Application of the dyes from 1 to 6 as dyes or fluorescent dyes for the study of microstructures of integrated semiconductor devices. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in photoconductors. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in photographic processes. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in display, illumination or image converter systems, where the excitation by electrons, ions or UV radiation takes place, e.g. in fluorescent displays, Braun tubes or in fluorescent tubes. Application of the dyes from 1 to 6 as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors e.g. in the form of an epitaxy. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in chemiluminescent systems, e.g. in Chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods. Application of the dyes from 1 to 6 as dyes or fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or other graphic products, for marking of signs and other objects, where a special one optical color impression is to be achieved. Application of the dyes from 1 to 6 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams. Application of the dyes from 1 to 6 as dyes in dye lasers as a Q-switch switch. Application of dyes from 1 to 6 as active Substances for a non-linear optics, e.g. For the frequency doubling and frequency tripling of laser light. Application of the dyes from 1 to 6 as Rheologieverbesserer. Application of dyes from 1 to 6 for leak testing closed Systems.