DE102007038422A1 - New anthracene dicarboxylic acid imide compounds useful e.g. as photodimerisation product for treating tumors, vat dye, dihydroanthercenebisimde compound and bisanthracene dicarboxylic acid imide compounds - Google Patents

Abstract

Anthracene dicarboxylic acid imide compounds (Xa), dihydroanthercenebisimde compound (VI), and bisanthracene dicarboxylic acid imide compounds (Xb), are new. Anthracene dicarboxylic acid imide compounds (Xa) of formulae (I)-(V), dihydroanthracene bisimide compound of formula (VI) and bisanthracene dicarboxylic acid imide compounds (Xb) of formulae (VII)-(XI), are new. X : C 2H 5, 1-butyl, 1-pentyl, 1-hexyl, 1-nonyl, 1-propylbutyl, 1-butlypentyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 2-ethylphenyl, 2,3-dimethylphenyl, 2,5-di-tert-butylphenyl or 2,6-di-isopropylphenyl; and R 1>-R 15>H, 37C-alkyl (in which 1-10 CH 2groups are substituted by carbonyl group, O, S, Se, Te, cis or trans -CH=CH- (in which one CH group is also substituted by N)), Ctriple boundC, 1,2-, 1,3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5 disubstituted pyridine, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene(in which one or two CH group or carbon is substituted by N), 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 (in which 1 or 2 CH group or carbon is substituted by N), halo, preferably F, Cl, Br or I, where up to 12 single H atoms of the CH 2groups are substituted by halo, preferably F, Cl, Br, I or CN, or a linear up to 18C-alkyl, in which 1-6 CH 2-groups are substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-group (in which one CH unit is also substituted by N), and the free valent of methine group and/or its quaternary carbon atoms are connected pair wise, such that the ring is a cyclohexane ring. Independent claims are included for: (1) the six preparations of (I); (2) preparation of aceanthrene quinone from anthracene and oxalylchloride under the addition of water-free aluminum chloride in sulfur carbon in a molar ratio of 1:5:1.5-1:6:2.5, preferably 1:5.2:2; and (3) preparation of a dye. [Image] [Image] [Image] [Image] [Image] [Image] ACTIVITY : Cytostatic. MECHANISM OF ACTION : None given.

Description

State of the art

Anthracene-1,9-dicarboximides 5 are of interest as cancerostatic [1,2,3,4,5,6,7,8,9] compounds. In addition, the substances received little attention [10]. So little is known about their chemical behavior, although this is of great importance for their application in medicine. In addition, the substances are suitable starting materials for the synthesis of Aceanthrengrün via an alkaline melt, which is known as lightfast textile dye. Aceanthrengrün was first synthesized by Kardos in 1913 [11, 12, 13, 14] and was used sporadically in the art as an emerald-green textile dye (CI 71125) and as a green pigment [15, 16]. The structure of the dye was initially unknown, could later be elucidated by Katzmeier [17] and co-workers, and represents a mixture of the two isomers 7a and 8a, with 7a as the main component; please refer 1 , When the nitrogen atoms of the starting materials are alkylated or arylated, one obtains almost exclusively the trans derivatives 7, which are more soluble than 7a.

task

The The task was to provide an efficient synthesis access to the anthracenedicarboximides 6 to find this special for optical effects and as Starting material for new carboxylic acid imide derivatives use. In particular, new Aceanthrengrün derivatives should getting produced.

description

For the synthesis of 7 we have corresponding 1 Anthracene (1) reacted with oxalyl chloride in CS ₂ to 2. The well-known synthesis instructions of Zfuffa and Liebermann [18] proved to be generally useful. Various attempts have been made in the literature [19, 20, 21, 22, 23, 24] to obtain increases in yield by changing the ratio of starting materials; this could be achieved here if 1, oxalyl chloride and AlCl ₃ in a molar ratio 1.0: 5.2: 2.0 was used. When the by-produced anthroic acid with bases is carefully removed, 2 remains as a pure, very sparingly soluble solid. The subsequent sublimation stated in the literature [18, 19] has a rather disadvantageous effect on the purity of the reaction product. 2 is obtained as a bright orange powder with a pronounced solid fluorescence; the spectra are in 4 shown. Because of its high lightfastness and low solubility, 2 can be used as a fluorescent pigment. 2 was reacted with hydroxylamine according to Ref. [18] to give the two regioisomeric oximes 4 and 5 in the ratio 55%: 45%. Since it can be assumed that the oximes can be converted into each other via the tautomeric nitroso compounds, cf. Ref. [25], they were used directly as a mixture for the subsequent reactions. The [12, 14] recrystallization of the mixture of glacial acetic acid, as reported in the literature, is rather detrimental to its purity. The isomer mixture 4 and 5 fluoresces in solution and also strongly as a solid, see the complicated fluorescence spectrum in 5 , and can be used as a fluorescent pigment because of its low solubility.

Alternatively, quinone 3 can be oxidized to anhydride 3 by Bergmann and Ikan [19]. When this is dissolved in base and precipitated with acid, it is in a pure form and can be used directly. A yield of 97% was achieved. The strong fluorescence and in particular the strong solid fluorescence of the extremely poorly soluble substance have hitherto been overlooked; please refer 6 , Because of the strong solid fluorescence and the lower solubility, the substance can therefore be used as a fluorescent pigment.

to Representation of Anthracenedicarbonsäureimids 6a is the Mixture of 4 and 5 after ref. [12, 13] a Beckmann rearrangement [26] with conc. Sulfuric acid and was subjected isolated in 73% yield as sparingly soluble pure substance. In the reaction product no portions of the starting material were more detectable. 6a was directly used for subsequent reactions used.

The Anhydride 3 was used for the general presentation of anthracenedicarboximides 6 condensed with primary amines. For the synthesis from 6a, the anhydride 3 was evaporated off after ref. [12, 13] with ammonia. In order to achieve a high conversion but only after repeated evaporation with ammonia. Since then from the sparingly soluble material 6a still residues of sparingly soluble starting material removed the synthesis of 6a from 3 and 4 is preferable.

The Ethyl derivative 6b is modified in a modification of a synthesis procedure in Ref. [14] from 3 and excess 70% aqueous Ethylamine solution shown. The 1-butyl, 1-pentyl and 1-hexyl derivatives 6c, 6d and 6e were prepared from the pure amines and 3 synthesized. The other derivatives of 6 were by condensation of 3 with the relevant amines analogous to Ref. [27] in imidazole receive. In the workup, the bisimides fall as compared to perylenetetracarboxylic acid significantly increase the lability of derivatives of 6 towards acids, so that the addition of the latter should be largely avoided in the workup

Carboxylic imides 6f, 6g and 6j are readily soluble in organic solvents, 6d and 6e are moderately good and 6c is moderately soluble. The other derivatives are sparingly soluble. By far the lowest solubility is found for 6a. An X-ray crystal structure analysis of the derivative 6d, which shows the best crystallization tendency, was achieved 7 , and formed from concentrated solution ordered crystals. The high crystallization tendency is important because of the photosensitivity of the substances (see below). According to the crystal structure, the anthracene moiety is essentially planar. The C and O atoms of the carboxylic acid imide unit form a new plane, which is twisted against you aromatic plane by about 5 °. The zigzag chain of the alkyl substituent is bent at C-1 and forms a new plane below the aromatic plane.

The carboxylic acid imides 6, such as. B. 6b, absorb in the short-wave visible range and fluoresce with quantum yields close to 100%. Many derivatives show a remarkably strong solid fluorescence, such as. The derivative 6b; please refer 8th ,

The Anthracencarbonsäureimide 6 are photosensitive and are a hitherto unknown and surprising dimerization to the isomeric compounds 10 and 11, see. but ref. [28, 29, 30, 31], which in the case of 6 is 55:45. The reaction leads almost exclusively to the head-tail dimers; the isomeric head-head dimers could not be detected. The photodimerization is already in daylight, so that the recording of absorption and fluorescence spectra should be done quickly and with appropriate care. A crystal growing, z. B. for the X-ray crystal structure analysis, should be done with complete exclusion of light. Irradiation with daylight leads to a photostationary equilibrium in which predominantly the dimerization products are present. For the quantitative photochemical conversion of 6 into the mixture of 10 and 11, light of a tungsten filament incandescent lamp was filtered with an aqueous solution of the dipotassium salt of naphthalene-1,8-dicarboxylic acid; UV / Vis spectrum see 9 , Irradiation has also been maintained throughout the crystallization of the products, yielding very pure products. The quantitative conversion can be recognized by the complete disappearance of the fluorescence.

The Reverse reaction of 10 and 11 to 6 is also purely thermal during the melting of the compounds. This gives the possibility generate latent fluorescent images that are thermally activated can. Because in daylight the conversion of the fluorescent 6 then returns to the dimers, the fluorescence images disappear again and can be thermally activated as latent images again become. In this way, z. B. a latent security mark be achieved. The substances 6 or 12 and 13 (see below) can be used. also use for fluorescent markers by exposure to light should disappear again, but if necessary, be re-activated can. So z. The fluorescent label of an article, z. B. by the application of a bar code or the like., For the respective production process. Becomes the object stored in darkness, the mark is stable, by light, it disappears slowly, so that about one End user not disturbed by the original mark becomes. However, the label can be reactivated by heating, so z. For identification during repairs or as identifier z. B. prove product piracy.

There Derivatives of 6 for the treatment of tumors use see - Introduction - is the photodimerization in daylight of marked importance. So one expects of the photoreaction products of Figure 6 have a different effect on tumors as of 6 itself. The reciprocal conversion from 6 to 10 and 11 by light of long wavelengths and back again with light of short wavelengths opens many new and unexpected possibilities in the treatment of tumors. Thus, locally by the application of light of long wavelengths the carboxylic acid imides 6 depleted or on demand be generated from the dimers, leaving a new tool for the local treatment of tumors is available. On the other hand, the photoreactivity of 6 requires special Attention to the now established treatment of tumors with derivatives of 6, because the synthesis of 6 is not absolute Exclusion of light - here already the workplace lighting - so the material contains more or less large proportions on dimerization products. Such Dimersisationsreaktionen can then also occur during treatment when the substances be exposed to the light.

To illustrate other derivatives, the anhydride 3 has been condensed with neopentanediamine to 12. 12 could be characterized by X-ray crystal structure analysis; See structure 10 , It is the first crystal structure for an aromatic carboxylic acid amidinimide. For the aromatic one finds the expected planar geometry, and for the alkyl moiety of the amidine imide unit a twist conformation. The bonds of this unit to the aromatic nucleus are significantly longer than the carboxylic acid imide 6d.

The UV / Vis absorption spectrum of 12 is markedly bathochromic at 497 nm compared to 6; please refer 11 , The substance fluoresces strongly in solution and also as a solid. In solution, a slow dimerization also occurs under the action of light.

The conjugated system of the anthracene carboxylic acid imide can be further extended by the condensation of 3 with o-phenylenediamine to form 13; see. Ref. [17]. By comparing the proton and ¹³ C nuclear resonances of 13 with 12 and 6, it can be concluded that 13 has a different regiochemistry than 12. 12 and 13 can be converted to analogues of 10 and 11 with light, so that the Carbonsäureamidinimid unit is not a fundamental obstacle to such a reaction. Since 12 and 13 can absorb longer wavelength than 6, one can adapt the wavelength range of the monomeric absorption to the respective requirements of dimerization.

The absorption of 13 in solution at 508 nm compared to 6 is even longer wavelength shifted than of 12, the absorption coefficient is increased to 12500 and the substance fluoresces with a quantum yield of 48%. 13 is described as a maroon powder with mp 234 ° C [17]. One finds for 13 two modifications, except the chestnut colored one also a light red with the masse. 228 ° C and a pronounced solid fluorescence. Both modifications can be converted into each other by crystallization. The maroon-colored modification fluoresces extremely long-wave; please refer 12 ,

The Anthracenedicarbonsäureimide 6 are starting materials for the Aceanthrengünderivate (7), the corresponding 1 be reacted with molten KOH. For 7a one can use 6a accordingly; see. Ref. [11, 12, 17]. Here you can use as an alternative, the Oximgemisch 4 and 5 in the alkali melt, which then reacts directly to 7 and leads to the saving of a synthesis step. The reaction is noteworthy because it is formally initiated by a Reckmann rearrangement [26] of the oxime to the carboxylic acid imide and the Reckmann reaction occurs rather under acid catalysis; However, it could be demonstrated that under the high reaction temperatures of 230 ° C, an isomerization of 4 and 5 to 6a takes place, cf. also Ref. [25]. The reaction of the oximes already described by Kardos could be improved, in particular with regard to the workup. Not only the emerald green trans dye 7a but also the green isomeric cis compound 8a in the ratio 5: 1 are obtained in the coupling and subsequent oxidation. Hereby it has been proven that during the alkaline melting of the oxime, the isomeric mixture is formed, which has been described by Kazmeier [17] for the alkaline fusion of 6a. However, a higher content of trans compound has been reported for the latter with an isomer ratio of 6.8: 1. The N-alkylated or N-arylated acetic acid green derivatives 7 have been synthesized from the N-alkylated anthraceneimides 6 by KOH melt. In this case, only the trans compounds 7 were obtained in accordance with Ref. [17] - cis compounds were undetectable (TLC and ¹ H NMR control).

In the synthesis of the anthracenedicarboxylic acid imides 7, in contrast to the preparation of the analogous perylenetetracarboxylic bisimides, a relatively stable, blood-red vat is first obtained, which must first be oxidized to 7; If the KOH melt from the synthesis of 7 is solidified, the red vat enclosed there is completely stable on storage. The UV / Vis spectrum of this vial is in 13 shown. By means of electrophoresis in methanol, it can be shown that the vat is a rapidly migrating anion. The electrically neutral structure proposed by Kazmeier [17] for the intermediate product is hardly compatible with its properties, since no migration tendency in electrophoresis would then be expected. In addition, this proposed structure corresponds to a doubly alkylated anthracenedicarboximide, since the two rings are isolated by sp ³ sites, so that their UV / Vis spectrum should be similar to those of compounds 6 and a maximum of one yellow color is expected. Finally, highly lipophilic properties are expected from the indicated structure, but the vat is very soluble in water. When the nitrogen atoms in 7 are linked to alkyl radicals, the vat becomes increasingly lipophilic, so that their solubility in water or methanol decreases, but it increases in ethanol. The determination of the structure of the red material is relatively difficult because it re-forms the starting material 6 when heated or acidified. In the cold slowly the sparingly soluble 7 slowly forms, so that the NMR spectroscopy is hindered. The red vat from 6g, which due to the dovetail substituent promises good solubility in lipophilic media, decomposes spontaneously to the starting material on contact with chloroform, even if the aqueous solution 10% hydrogen peroxide is added as an oxidizing agent.

There in the synthesis of 7 in contrast to the perylene dyes first there is no spontaneous reaction of the vat to the final products, a special oxidation step is needed. This reaction can according to Kardos [11, 12] by daily introduction of Air can be reached, which is not only tedious, but by the clumping of the lipophilic reaction product into inclusions of the starting material leads. A reaction in an ultrasonic bath already delivers significantly better results here. The oxidation can also be carried out with hydrogen peroxide. Whose Concentration should not exceed 10%, because at more concentrated solutions, such as 30%, with foaming destruction of the reaction product takes place. For N-substituted Derivatives of 7, in particular with alkyl radicals of medium length, Here, as a new process, a two-phase oxidation has been found Proved by the vial with 10% hydrogen peroxide added and simultaneously underlaid with chloroform. On In this way, the lipophilic 7 is removed equal to the oxidizing agent and it also prevents the clumping of the reaction solution. This method fails at 7g because of the spontaneous decomposition of the Add vat to the starting materials when using chloroform comes into contact, so here a single-phase oxidation is required becomes. The oxidation can be prevented by the addition of pyridine become. Add ascorbic acid to the vial, then if product formation is prevented, formic acid is without Influence on the reaction.

The Aceanthrengrün derivatives fluoresce at the border of visible and near infrared; please refer 14 , The substance also fluoresces strongly as a solid.

By the action of KOH in tert-butyl alcohol, six-membered carboxylic acid imides can be efficiently hydrolyzed, [32] as demonstrated by the example of perylene-3,4: 9,10-tetracarboxylic bisimides. However, this reagent leads to a violet coloration on exposure to 7, but surprisingly to no appreciable conversion; in aqueous workup, the starting material is completely recovered; In order to achieve a better solubility of 7, you can add the tert-butanol still DMSO. To trap the violet material, the electrophilic methyl iodide was added to the reaction solution and surprisingly gave the double methylated product 10, which is a new type of fluorescent dye. The unexpected core alkylation of the aromatic backbone is as unusual as it is surprising. The new substance class 10 is of interest for fluorescence applications. It forms a bright orange solid with intense solid fluorescence; please refer 15 , In solution, the substance fluoresces with 27% quantum yield.

Experimental part

Aceanthrenchinone (2) [18]: 10.00 g (56.11 mmol) of anthracene (1), 25 mL (37 g, 0.30 mol) of oxalyl chloride, 75 mL of carbon disulfide and 7.93 g (59.5 mmol) of sublimed aluminum chloride were stirred under argon atmosphere and ice cooling for 2 h , wherein a black, poorly stirrable mass formed. After addition of another 75 mL of CS ₂ and 7.32 g (54.9 mmol) of AlCl ₃ , the reaction mixture was stirred for 4 h at room temp. stirred and allowed to stand overnight. After hydrolysis by dropwise addition of 200 mL 2N HCl and distilling off the carbon disulfide (bp 42 ° C, oil bath temp 50-70 ° C, caution!) The orange, powdery crude product was filtered through a glass filter crucible of porosity G4. To remove the by-product anthroic acid, the crude product was washed twice with 100 mL 2.5 per cent. aqueous potassium carbonate solution for 20 min at 70 ° C and filtered off (G4 glass frit). This purification step was performed with 100 mL dist. Water repeated. Subsequently, the precipitate was washed once with a little methanol and dried at 115 ° C in a drying oven overnight. Y. 9.74 g (75%) (Lit. ^[18] 9.00 g 69%) orange, electrostatically charged powder with high solid-state fluorescence, mp 263-265 ° C (Ref. [18] 270 ° C), R _f (silica gel; CHCl ₃₎ = 0.58 IR (KBr) v = 3051 w, 1735 s (C = O), 1707 s (C = O), 1626 w (C = C), 1576 s (C = C), 1529 w ( C = C), 1454 w, 1436 w, 1339 w, 1282 w, 1226 w, 1152 w, 1086 m, 1016 w, 919 w, 883 w, 752 m, 741 m, 700 w, 483 w, 411 cm ^{- 1} w, ¹ H-NMR ([D ₆ ] DMSO / CDCl ₃ 10: 1): δ = 7.78 (m, 1H, aromatic-H), 7.90 (m, 2H, aromatic-H), 8.07 (d, J = 6.7 Hz, 1H, aromatic H), 8.38 (d, J = 8.5 Hz, 1H, aromatic H), 8.52 (d, J = 8.4 Hz, 1H, aromatic H), 9.01 (d, J = 8.5 Hz, 1H, aromatic H), 9.17 ppm (s, 1H, aromatic H), ¹³ C-NMR ([D ₆ ] DMSO / CDCl ₃ 10: 1): δ = 121.23, 122.87, 123.52, 126.54, 127.11 , 127.37, 127.90, 128.03, 129.84, 130.30, 132.18, 132.36, 134.02, 145.69, 187.38 (C = O), 188.29 ppm (C = O), UV (CHCl _3): λ _max (1 g ε) = 348 sh (3,558), 365 (3,804), 382 sh (3,678), 404 (3,695), 462 sh (3,122), 502 nm sh (2,648), Flu orescence (CHCl ₃ ): λ _max (I _rel ) = 481 (1), 512 (0.81), 557 nm sh (0.28), solid state fluorescence: λ _max = 485, 575 sh, 606 nm, MS (70 eV): m / z (%): 233 (9), 232 (55) [M ⁺ ], 205 (16), 204 (100) [M ⁺ - CO], 178 (3), 177 (11), 176 (73) [M ⁺ - 2 CO], 175 (12), 174 (10), 150 (11) [M ⁺ - 2 CO - C ₂ H ₂ ], 149 (3), 116 (4), 98 (2) 88 (24), 87 (6), 75 (8), C ₁₆ H ₈ O ₂ (232.2): Ber. C 82.75, H 3.47; Gef. C 80.60, H 3.50.

Aceanthrenchinone oxime isomer mixture (4, 5) [12]: 4.82 g (20.8 mmol) of acetic acid quenchinone (8) and 1.44 g (20.7 mmol) of hydroxylamine hydrochloride were dissolved in 50 ml of 96 percent strength by weight. Slurried ethanol and treated with 2.20 g (20.8 mmol) of anhydrous sodium carbonate. The mixture was refluxed on the water bath for 30 minutes and stirred. The color of the solid changed from orange to ocher yellow. Subsequently, the ocher yellow product was filtered through a glass filter crucible G4, with little dist. Washed water and dried in a desiccator over calcium chloride. Y. 4.66 g (91%, Ref. ^[12] 100%) ocher-colored, electrostatically charged powder, mp 251 ° C dec. (Ref. ^[12] 251 ° C), R _f (silica gel, CHCl ₃ ): = 0.03, IR (KBr): ṽ = 3248 m (OH), 3050 W, 2850 W, 1705 s (C = O), 1635 m (C = N), 1619 m (C = C), 1576 m (C = C), 1530 W (C = C), 1456 s (OH), 1394 W, 1225 W, 1178 W, 1158 W, 1079 w, 1021 m, 999 m, 877 s, 793 m, 738 m, 630 w, 561 w, 491 w cm ^{-1, 1} H-NMR (CDCl _3, 600 MHz): ¹ H-NMR spectroscopy are two isomers found: isomer (10) (C = O in para position to proton H-10): δ = 7.68 (m, 2H, aromatic-H), 7.84 (m, 1H, aromatic-H), 7.93 (d, J = 6.6 Hz, 1H, aromatic H), 8.10 (d, J = 8.7 Hz, 1H, aromatic H), 8.20 (d, J = 8.5 Hz, 1H, aromatic H), 8.83 ppm (s, 1H, Aromatic-H), 9.06 (d, J = 8.5 Hz, 1H, aromatic-H). Isomer (11) (C = NOH in the para position to the proton H-10): ¹ H NMR (CDCl _3): δ = 7.68 (m, 2H, aromatic-H), 7.78 (m, aromatic-H 1H,) , 8.10 (d, J = 8.7 Hz, 1H, aromatic H), 8.16 (d, J = 8.5 Hz, 1H, aromatic H), 8.35 (d, J = 6.6 Hz, 1H, aromatic H), 8.73 (s, 1H, aromatic H), 9.19 ppm (d, J = 8.7 Hz, 1H, aromatic H), UV (CHCl ₃ ): λ _max (1 g ε) = 342 sh (3,457), 361 (3,548 ), 393 (3,461), 407 sh (3,429), 432 (3,428), 463 nm sh (2,979), fluorescence (CHCl ₃ ): λ _max = 481 nm, solid state fluorescence: λ _max = 485, 524, 543, 614 nm , MS (70 eV): m / z (%): 248 (12), 247 (63) [M ⁺ ], 233 (2), 232 (16), 231 (69), 230 (99) [M ⁺ - OH], 205 (3), 204 (26), 203 (100) [M ⁺ - OH - HCN], 202 (59) [M ⁺ - OH - CO], 201 (30), 200 (2), 190 (3), 187 (4), 178 (3), 177 (8), 176 (27), 175 (22) [203 - CO], 174 (12), 151 (4), 150 (7), 149 (5), 115 (7), 101 (16), 88 (21), 87 (15), 75 (7), 74 (4).

Anthracene-1,9-dicarboxylic anhydride (3) [19]: 9.25 g (39.8 mmol) of acetic acid quenchinone (8), 200 ml of dioxane and 55.5 ml of 2N sodium hydroxide solution were initially charged. With stirring and reflux cooling 46.3 mL 30 percent. Hydrogen peroxide solution added. The exothermic reaction brought the mixture to a boil. There was a yellow solution. After 45 minutes, 200 mL of dist. Water was added and the free anthracene-1,9-dicarboxylic acid precipitated by the addition of about 400 mL of 2 N sulfuric acid as a pale yellow precipitate. It was allowed to stand overnight, with the pale yellow acid in the acidic solution is converted into the orange-colored anhydride 3, and the crude product is filtered through a glass filter crucible G4. For purification, the crude product was dissolved in 2N potassium hydroxide solution, filtered from the insoluble (G4 frit) and the anhydride 3 again by dropwise addition of conc. Hydrochloric acid precipitated. The purified product was filtered off (G4 frit), with dist. Washed water several times and dried at 115 ° C. Y. 10.15 g (97%) of an orange, electrostatically charged powder (ref. ^{[ 19]} 100% crude product), mp 285-290 ° C. (lit. ^{[ 19]} 290 ° C.), R _f (silica gel, CHCl ₃ ) = 0.40, IR (KBr): ṽ = 3050w, 1760s (C = O), 1720s (C = O), 1622w (C = C), 1561s (C = C), 1535m (C = C), 1432w, 1365w, 1285w, 1268w, 1249w, 1160w, 1139m (CO), 1086m (CO), 1054w, 1010m, 940w, 863w, 794m, 745m , 733 m, 511 w cm ^{-1, 1} H NMR (CDCl _3): δ = 7.72 (m, 1H aromatic H), 7.80 (m, aromatic-H 1H,), 7.92 (m, 1H, aromatic H), 8.19 (d, J = 8.4 Hz, 1H, aromatic H), 8.48 (d, J = 8.4 Hz, 1H, aromatic H), 8.78 (d, J = 7.0 Hz, 1H, aromatic-H) , 8.97 (s, aromatic-H 1H,), 9.75 ppm (d, J = 9.1 Hz, aromatic-H 1H,), ¹³ C NMR (CDCl _3): δ = 125.80, 126.31, 127.23, 129.94, 132.32, 135.70 , 136.43, 137.87 ppm, UV (CHCl _3): λ _max (1 g ε) = 269 (4,704), 358 (3,657), 376 (4,037), 414 (3,848), 435 (3,913), 459 nm (3,784) , fluorescence (CHCl _3): λ _max (I _rel) = 481 (1), 513 (0.80) 553 nm sh (12:28). Fluorescence quantum yield: 81% based on tetramethylperylene-3,4: 9,10-tetracarboxylic acid ester [33] with a fluorescence quantum yield of 100%. Solid state fluorescence: λ _max = 485, 525, 605 nm, MS (70 eV): m / z (%): 249 (17), 248 (100) [M ⁺ ], 205 (8), 204 (52) [M ⁺ - CO ₂ ], 177 (7), 176 (50) [M ⁺ - CO ₂ - CO], 175 (8), 174 (7), 150 (8), 124 (3), 88 (18), 87 (5), 75 (7).

Anthracene-1,9-dicarboximide (6a) [12,13] from anthracene-1,9-dicarboxylic anhydride (3) [12]: 520 mg (2.09 mmol) of anthracene-1,9-dicarboxylic anhydride (3) were stirred for 1 h 50 mL conc. Heated ammonia and to complete the reaction several times with conc. Ammonia evaporated. The solid reaction residue was taken up in water, filtered through a glass frit G4, with dist. Washed water and dried at 130 ° C. Y. 440 mg (85%) ocher-colored, electrostatically charged powder, mp 288-294 ° C (ref. ^{[ 12]} 293-294 ° C), R _f (silica gel, CHCl ₃ ) = 0.16., IR (KBr): ṽ = 3185m, 3067m, 2922w, 2850w, 1687s (C = O), 1678s (C = O), 1653w, 1622w (C = C), 1563s (C = C), 1532 m (C = C), 1435m, 1397m, 1368m, 1313m, 1281m, 1251w, 1235m, 1153w, 909w, 858w, 799w, 746w, 733m, 677w, 625 w, 505 w, 416 cm ^-1 w, ¹ H NMR ([D ₆ ] DMSO / CDCl ₃ 10: 1): δ = 7.71 (m, 1H, aromatic H), 7.86 (m, 2H, aromatics H ), 8.30 (d, J = 9.0 Hz, 1H, aromatic H), 8.62 (2 d, J = 7.0 Hz, 2H, aromatic H), 9.21 (s, 1H, aromatic H), 9.94 (d, J = 9.3 Hz, 1H, aromatic H), 11.70 ppm (s, 1H, NH), ¹³ C NMR ([D ₆ ] DMSO / CDCl ₃ 10: 1): δ = 114.86, 122.58, 125.45, 125.93, 126.27 , 129.02, 129.25, 129.86, 131.05, 131.91, 132.35, 132.60, 135.59, 136.89, 163.42 (C = O), 165.60 ppm (C = O). UV (CHCl ₃ ): λ _max (1 g ε) = 360 (3570), 379 (3,928), 416 (3,785), 437 (3,900), 462 nm (3,752), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 494 (1), 518 nm (0.91), Solid state fluorescence: λ _max = 485 sh, 524, 597, 633 nm sh, MS (70 eV): m / z (%): 248 (17), 247 ( 100) [M ⁺ ], 246 (6), 219 (10) [M ⁺ - CO], 204 (4), 203 (13), 202 (3), 191 (3), 190 (8), 177 (3), 176 (10), 175 (3), 163 (3), 150 (3), 124 (3), 110 (4), 88 (7), 87 (3), 75 (3).

Anthracene-1,9-dicarboxylic acid imide (6a) from aceanthrenequinone oxime (4,5) [14]: 450 mg (1.82 mmol) of triturated aceanthrenequinone oxime (4,5) were mixed with 3 ml conc. Sulfuric acid heated for 30 min on a water bath, the original brown color of the solution went over in a short time in cherry red. The cooled solution was distilled with 50 mL. Water is added. The ocher-colored product was filtered off (glass frit G4), with dist. Wash water and dry at 130 ° C in a drying oven. Y. 330 mg (73%) (ref. ^{[ 14]} "almost quant. Yield") ocher-colored, electrostatically charged powder, mp 285-292 ° C (ref. ^[14] 293-294 ° C), R _f (silica gel ; CHCl ₃ ) = 0.16, for further spectroscopic data see the synthesis of anthracene-1,9-dicarboximide (6a) from anthracene-1,9-dicarboxylic anhydride (3) with ammonia.

N-ethylanthracene-1,9-dicarboxylic acid imide (6b): 1.94 g (7.82 mmol) of anthracene-1,9-dicarboxylic anhydride (3) were dissolved in 75 mL of 70 percent strength by weight. aqueous ethylamine solution boiled under reflux at 150 ° C oil bath temperature for 1.5 h. Then another 25 mL of 70 percent was added. Ethylamine solution and kept the reaction mixture for a further 3.5 h boiling. To remove excess ethylamine, the reaction mixture was carefully acidified with conc. HCl, the precipitated carboxylic acid imide filtered through a glass filter crucible (G4), washed several times with a little distilled. Water and dried at 115 ° C in a drying oven. For high purification, the light brown, powdery crude product was rapidly chromatographed on silica gel under pressure with chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10b and 11b are formed in part, which can not be thermally completely converted back into the carboxylic acid imide 6b.) Yield 1.63 g (76%) of bright golden yellow powder with lemon-yellow solid-state fluorescence, mp. 186 ° C, R _f (silica gel, CHCl ₃ ) = 0.30, IR (KBr): ṽ = 3050w, 2980w, 2935w, 1685s (C = O), 1653s (C = O), 1640s ( C = O), 1621w (C = C), 1560s (C = C), 1533m (C = C), 1456m, 1437m, 1400m, 1368m, 1351m, 1312s, 1247m, 1231 m, 1146 W, 1103 m, 900 W, 875 W, 855 W, 795 m, 747 m, 732 S, 539 cm ^-1 m, ¹ H-NMR ([D ₆ ] DMSO / CDCl ₃ 10: 1) : δ = 1.31 (t, J = 7.0 Hz, 3H, CH ₃ ), 4.23 (q, J = 6.9 Hz, 2H, NCH ₂ CH ₃ ), 7.72 (t, J = 7.1 Hz, 1H, aromatic-H) , 7.88 (m, 2H, aromatic H), 8.31 (d, J = 8.0 Hz, 1H, aromatic H), 8.61 (d, J = 8.5 Hz, 1H, aromatic H), 8.69 (d, J = 7.0 Hz, 1H aromatic H), 9.22 (s, 1H, aromatic H), 9.95 ppm (d, J = 9.1 Hz, 1H, aromatic H), ¹³ C NMR ([D ₆ ] DMSO / CDCl ₃ 10 : 1): δ = 1 3.13 (CH ₃ ), 34.92 (CH ₂ ), 118.52, 121.92, 125.55, 125.95, 126.23, 127.83, 128.63, 130.00, 131.20, 132.03, 132.72, 133.22, 135.53, 136.92, 162.74 (C = O), 164.33 ppm ( C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 361 (3,514), 380 (3,914), 416 (3,790), 437 (3,913), 460 nm (3,771), fluorescence (CHCl ₃ ) λ _max (I _rel ) = 486 (1), 516 (0.81), 556 nm sh (0.29), fluorescence quantum yield: 44% based on tetramethylperylene-3,4: 9,10-tetracarboxylic acid ester ^[33] with a fluorescence quantum yield of 100% , Solid state fluorescence: λ _max = 537, 606 nm sh, MS (70 eV): m / z (%): 276 (20), 275 (94) [M ⁺ ], 274 (9), 260 (17) [M ⁺ - CH ₃ ], 259 (5), 248 (19), 247 (100) [M ⁺ - C ₂ H ₄ ], 246 (7), 233 (8), 231 (9), 230 (4) [247 - OH], 219 (7), 205 (11), 204 (9) [M ⁺ - C ₂ H ₅ NCO], 203 (22) [204 - H], 202 (9), 190 (9), 177 (19), 176 (27) [204 - CO], 175 (9), 174 (6), 150 (7), 116 (7), 88 (29) [176 - C ₇ H ₄ ], 75 (6 ), C ₁₈ H ₁₃ NO ₂ (275.3) Ber. C 78.53, H 4.76, N 5.09; Gef. C 78.62, H 4.86, N 4.83.

N-Butylanthracene-1,9-dicarboximide (6c): 3.96 g (16.0 mmol) of anthracene-1,9-dicarboxylic anhydride (3) were refluxed in 100 mL (1.01 mol) of n-butylamine and 10 mL of toluene under argon atmosphere for 2.5 h cooked. Excess n-butylamine was then distilled off under atmospheric pressure. The dark red distillation residue was taken up in 250 ml of chloroform, successively with 2N HCl and dist. Shaken out water and concentrated. For high purification, the crude product was rapidly chromatographed on silica gel with pressure and chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in an oil pump vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10c and 11c, which can not be thermally completely converted back into the imide 6c, are formed in part). Y. 3.53 g (73%) of bright golden powder with high solid-state fluorescence, mp 140-142 ° C, R _f (silica gel, CHCl ₃ ) = 0.39, IR (KBr) ṽ = 3067 w, 3040 w, 2951 m, 2935 m, 2872 m, 1689 s (C = O), 1642 s (C = O), 1621 m (C = C), 1563 s (C = C), 1533 m (C = C), 1433 m, 1401 m, 1370 m, 1354 m, 1313 m, 1279 m, 1220 m, 1204 m, 1150 m, 1111 s, 903 m, 861 m, 828 m, 797 m, 750 s, 741 s, 662 W, 625 W, 544 W, 516 cm ^-1 w, ¹ H-NMR (CDCl _3): δ = 1:01 (m, 3H, CH _3), 1:49 (m, 2H, CH ₂ CH _3), 1.76 (m, 2H, NCH ₂ CH ₂₎ , 4.24 (m, 2H, NCH ₂ ), 7.58 (m, 1H, aromatic H), 7.67 (m, 1H, aromatic H), 7.78 (m, 1H, aromatic H), 8.05 (d, J = 8.5 Hz, 1H, aromatic H), 8.27 (d, J = 8.4 Hz, 1H, aromatic H), 8.69 (d, J = 7.1 Hz, 1H, aromatic H), 8.73 (s, 1H, aromatic) H), 9.95 ppm (d, J = 9.2 Hz, 1H, aromatic H), ¹³ C-NMR (CDCl _3): δ = 14:30 (CH _3), 20.94 _(CH2), 30.69 _(CH2), 40.88 (NCH ₂ ), 115.80, 123.03, 125.81, 126.82, 127.23, 128.50, 129.20, 130.07, 131.61, 132.84, 133.79, 133.95, 135.35, 136.56, 164.10 ( C = O), 165.58 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 361 (3,196), 380 (3,616), 416 (3,505), 436 (3,631), 459 nm ( 3.486), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 484 (1), 514 (0.79), 556 nm sh (0.23), fluorescence quantum yield: 100% based on tetramethylperylene-3,4: 9,10-tetracarboxylic acid ester ^[33] with a fluorescence quantum yield of 100%, solid-state fluorescence: λ _max = 535 nm, MS (70 eV): m / z (%): 304 (19), 303 (87) [M ⁺ ], 286 (16) [M ⁺ - OH], 274 (6), 262 (6) 261 (36), 260 (16) [M ⁺ - C ₃ H ₇ ], 259 (8), 248 (22), 247 (100) [M ⁺ - C ₄ H ₈ ], 231 (6), 230 ( 7) [247 - OH], 219 (5), 204 (5) [M ⁺ - C ₄ H ₉ NCO], 203 (11) [204 - H], 202 (8), 190 (5), 177 ( 9), 176 (14) [204 - CO], 150 (2), 88 (4) [176 - C ₇ H ₄ ], C ₂₀ H ₁₇ NO ₂ (303.4) Ber. C 79.19, H 5.65, N 4.62; Gef. C 79.45, H 5.67, N 4.53.

N-Pentylanthracene-1,9-dicarboximide (6d): 4.00 g (16.1 mmol) of anthracene-1,9-dicarboxylic anhydride (3) were boiled in 65 ml (0.56 mol) of n-pentylamine under argon atmosphere and under reflux for 3 h. Excess n-pentylamine was then removed by distillation. The red distillation residue was taken up in chloroform, successively with 2 N HCl and dist. Shaken out water and concentrated. The crude product thus obtained was chromatographed over silica gel for high purification with pressure and chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, some of the corresponding dimers 10d and 11d are formed, which can not be thermally completely converted back into the carboxylic acid imide 6d). Y. 2.60 g (51%) bright orange, analytically pure crystals with high solid-state fluorescence, mp 133-135 ° C, R _f (silica gel, CHCl ₃ ) = 0.57, IR (KBr): ṽ = 3063 W, 2950 s, 2936 m, 2872 m, 2849 m, 1685 s (C = O), 1644 s (C = O), 1619 s (C = C), 1561 s (C = C), 1533 s (C = C), 1431 s, 1400 s, 1371 s, 1348 s, 1310 s, 1279 m, 1268 m, 1221 m, 1193 m, 1150 s, 1109 s, 964 w, 915 m, 883 m, 864 m, 797 s, 750 s, 737 s, 664 m, 626 m, 528 m, 435 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.93 (m, 3H, CH _3), 1:45 [m, 4H, (CH _{2) 2} CH _3] , 1.76 (m, 2H, CH ₂ CH ₂ N), 4.22 (m, 2H, CH ₂ N), 7.62 (m, 1H aromatic H), 7.71 (m, aromatic-H 1H,), 7.80 (m , 1H, aromatic H), 8.08 (d, J = 6.3 Hz, 1H, aromatic H), 8.33 (d, J = 7.6 Hz, 1H, aromatic H), 8.74 (d, J = 5.8 Hz, 1H , Aromatic H), 8.80 (s, 1H, aromatic H), 10.01 ppm (d, J = 8.0 Hz, 1H, aromatic H), ¹³ C-NMR (CDCl ₃ ): δ = 14.05 (CH ₃ ) , 22.44, 27.94, 29.26, 40.49 (CH ₂ N), 115.96, 123.31, 125.86, 126.85, 127.30, 128.71, 129.29, 130.12, 131.65, 132.53, 132.92 , 133.84, 135.40, 136.62, 164.15 (C = O), 165.65 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 361 (3,433), 380 (3,889), 416 (3,778) , 436 (3,910), 460 nm (3,760), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 484 (1), 513 (0.77), 559 nm sh (0.21), solid state fluorescence: λ _max = 474, 505 , 523, 610 nm, MS (70 eV): m / z (%): 318 (23), 317 (100) [M ⁺ ], 300 (11) [M ⁺ - OH], 274 (5), 261 (33), 260 (15) [M ⁺ - C ₄ H ₉ ], 248 (24), 247 (90) [M ⁺ - C ₅ H ₁₀ ], 230 (6) [247 - OH], 219 (4 ), 204 (4) [M ⁺ - C ₅ H ₉ NCO], 203 (9), 202 (7), 190 (4), 177 (8), 176 (11) [204 - CO], 88 (3 ) [176 - C ₇ H ₄ ], C ₂₁ H ₁₉ NO ₂ (317.4) Ber. C 79.47, H 6.03, N 4.41; Gef. C 79.43, H 5.93, N 4.32.

Crystal structure: (Diffractometer: ENRAF-Nonius CAD4, radiation: MoK _α , monochromator: highly oriented graphite crystal): C ₂₁ H ₁₉ NO ₂ , M _r = 317.37, a = 11.525 (5) Å, b = 15.794 (6) Å, c = 9.563 (4) Å, β = 113.16 (2) °, volume = 1600.4 (11) Å ³ , Z = 4, density (calculated) = 1.317 g · cm ^-3 , μ = 0.084 mm ^-1 , crystal system monoclinic, room group P2 ₁ / c (no. 14). - Data collection single crystal 0.40 × 0.47 × 0.53 mm ³ (orange block); ω data collection, scan width: 0.80 + 0.35 tan θ; maximum measurement time 90 s per reflex, number of reflections: 2344 (total), 2223 (independent), 1739 (observed) [I> 2σ (I)], no correction for absorption, structure solution with SHELXS86, refinement with SHELXL93, 218 parameters, R1 = 0.0499 (2σ (I)), wR2 = 0.1386 (2σ (I)), weighting w = 1 / [σ ₂ F _o ² + 0.0693, GOF = 1080, max. and min. Residual electron density (e / Å ³ ) 0.310 / -0.182. Table 1: Atomic coordinates [× 10 ⁴ ] and equivalent isotropic displacement parameters in [Å ² × 10 ³ ] of 6d. U (eq) is defined as one third of the trace of the orthogonalized Uij tensor. atom x y z U (eq) O (1) 5611 (2) 2446 (1) 1465 (2) 65 (1) O (2) 8375 (2) 983 (1) 146 (3) 79 (1) N (1) 6974 (2) 1693 (1) 784 (2) 47 (1) C (1) 5709 (2) 970 (1) 1911 (3) 44 (1) C (2) 4835 (2) 1001 (2) 2549 (3) 55 (1) C (3) 4437 (3) 264 (2) 3047 (3) 60 (1) C (4) 4902 (2) -494 (2) 2891 (3) 57 (1) C (5) 5810 (2) -565 (2) 2228 (3) 47 (1) C (6) 6282 (2) -1336 (2) 2015 (3) 52 (1) C (7) 7131 (2) -1405 (2) 1318 (3) 49 (1) C (8) 7539 (3) -2215 (2) 1048 (3) 62 (1) C (9) 8335 (3) -2296 (2) 339 (4) 69 (1) C (10) 8791 (3) -1571 (2) -121 (3) 66 (1) C (11) 8443 (2) -784 (2) 121 (3) 58 (1) C (12) 7580 (2) -658 (1) 844 (3) 46 (1) C (13) 7128 (2) 138 (1) 1077 (3) 44 (1) C (14) 6232 (2) 187 (1) 1737 (3) 42 (1) C (15) 6065 (2) 1761 (2) 1385 (3) 48 (1) C (16) 7551 (2) 940 (2) 636 (3) 50 (1) C (17) 7395 (3) 2477 (2) 279 (3) 55 (1) C (18) 8598 (3) 2829 (2) 1480 (3) 60 (1) C (19) 9005 (3) 3656 (2) 1010 (4) 67 (1) C (20) 8263 (3) 4396 (2) 1150 (4) 77 (1) C (21) 8741 (3) 5255 (2) 896 (5) 90 (1) Table 2: Anisotropic displacement parameters in [Å ² × 10 ³ ] of 6d. The exponent of the anisotropic excursion factor has the form: - 2π ² [h ² 2 a * ² U11 + ... + 2 hka * b * U12]. atom U11 U22 U33 U23 U13 U12 O (1) 70 (1) 45 (1) 90 (1) -1 (1) 42 (1) 4 (1) O (2) 93 (2) 53 (1) 127 (2) -4 (1) 83 (2) -12 (1) N (1) 50 (1) 39 (1) 57 (1) 2 (1) 26 (1) -4 (1) C (1) 40 (1) 48 (1) 46 (1) -2 (1) 17 (1) -4 (1) C (2) 51 (2) 56 (2) 63 (2) -5 (1) 28 (1) 0 (1) C (3) 56 (2) 70 (2) 64 (2) 2 (1) 35 (1) -4 (1) C (4) 56 (2) 62 (2) 58 (2) 7 (1) 30 (1) -10 (1) C (5) 46 (1) 49 (1) 45 (1) 5 (1) 18 (1) -9 (1) C (6) 57 (2) 43 (1) 57 (2) 5 (1) 23 (1) -9 (1) C (7) 50 (1) 41 (1) 53 (2) 1 (1) 17 (1) -2 (1) C (8) 64 (2) 46 (2) 77 (2) 2 (1) 27 (2) -2 (1) C (9) 70 (2) 49 (2) 87 (2) -8 (1) 30 (2) 7 (1) C (10) 60 (2) 64 (2) 82 (2) -9 (2) 37 (2) 5 (1) C (11) 56 (2) 53 (2) 71. (2) -3 (1) 32 (1) 0 (1) C (12) 44 (1) 45 (1) 50 (1) -1 (1) 17 (1) -3 (1) C (13) 42 (1) 44 (1) 46 (1) -1 (1) 18 (1) -6 (1) C (14) 39 (1) 44 (1) 42 (1) -1 (1) 15 (1) -6 (1) C (15) 45 (1) 46 (2) 51 (2) -2 (1) 17 (1) -3 (1) C (16) 52 (2) 48 (2) 58 (2) -3 (1) 29 (1) -9 (1) C (17) 65 (2) 44 (1) 60 (2) 7 (1) 29 (1) -7 (1) C (18) 65 (2) 50 (2) 70 (2) -2 (1) 32 (1) -12 (1) C (19) 71 (2) 58 (2) 83 (2) -5 (2) 42 (2) -13 (1) C (20) 90 (2) 58 (2) 100 (2) 7 (2) 54 (2) 4 (2) C (21) 97 (3) 55 (2) 126 (3) 3 (2) 53 (2) -3 (2) Table 3: Hydrogen Coordinates [× 104] and Isotropic Displacement Parameters in [Å2 × 103] of 6d. atom x y z U (eq) H (2) 4499 (2) 1521 (2) 2655 (3) 66 H (3) 3848 (3) 299 (2) 3487 (3) 72 H (4) 4627 (2) -979 (2) 3220 (3) 68 H (6) 6021 (2) -1825 (2) 2349 (3) 63 H (8) 7250 (3) -2697 (2) 1366 (3) 75 H (9) 8582 (3) -2830 (2) 155 (4) 83 H (10) 9347 (3) -1632 (2) -604 (3) 79 H (11) 8771 (2) -317 (2) -189 (3) 69 H (17A) 6734 (3) 2900 (2) 35 (3) 66 H (17B) 7534 (3) 2360 (2) -638 (3) 66 H (18A) 8470 (3) 2917 (2) 2414 (3) 72 H (18B) 9268 (3) 2416 (2) 1687 (3) 72 H (19A) 9889 (3) 3751 (2) 1637 (4) 80 H (19B) 8919 (3) 3609 (2) -37 (4) 80 H (20A) 8251 (3) 4390 (2) 2158 (4) 93 H (20B) 7399 (3) 4330 (2) 422 (4) 93 H (21A) 8174 (11) 5689 (2) 943 (24) 108 H (21B) 8786 (19) 5265 (5) -86 (10) 108 H (21C) 9565 (9) 5354 (6) 1670 (14) 108

N-Hexylanthracene-1,9-dicarboximide (6e): 4.10 g (16.5 mmol) of anthracene-1,9-dicarboxylic anhydride (3) were boiled in 120 ml (0.908 mol) of n-hexylamine for 1 h 45 min under an argon atmosphere and under reflux , Excess n-hexylamine was then distilled off under atmospheric pressure. The red-brown residue was taken up in 100 ml of chloroform, successively with 2N HCl and dist. Shaken out water and concentrated. For high purification, the crude product thus obtained was rapidly chromatographed over silica gel with pressure and chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, some of the corresponding dimers 10e and 11e form, which can not be thermally completely converted back into the imide 6e). Y. 4.42 g (81%) bright yellow crystals with strong solid fluorescence, mp 109-110 ° C, R _f (silica gel, CHCl ₃ ): = 0.56, IR (KBr): ṽ = 3120 W, 3060 W, 2957 s, 2925 s, 2853 s, 1685 s (C = O), 1644 s (C = O), 1620 m (C = C), 1561 s (C = C), 1532 s (C = C), 1452 m, 1431 s , 1402 m, 1370 m, 1353 s, 1312 s, 1279 m, 1253 m, 1219 m, 1190 m, 1149 m, 1111 s, 914 m, 862 m, 798 s, 752 s, 737 s, 660 W, 621 w, w 559, w 528 cm ^{-1 1} H-NMR (CDCl _3): δ = 0.89 (m, 3H, CH _3), 1:40 [m, 6H, (CH _{2) 3} CH _3], 1.78 [m , 2H, CH ₂ CH ₂ N], 4.25 (m, 2H, CH ₂ N), 7.61 (m, 1H, aromatic H), 7.71 (m, 1H, aromatic H), 7.81 (m, 1H, aromatics -H), 8.10 (d, J = 7.8Hz, 1H, aromatic-H), 8.33 (d, J = 8.4Hz, 1H, aromatic-H), 8.74 (d, J = 7.1Hz, 1H, aromatic-H ), 8.81 (s aromatics-H, 1H,), 1.10 ppm (d, J = 9.2 Hz, 1H, aromatic H), ¹³ C NMR (CDCl _3): δ = 14.6 _(CH3), 22.61, 26.81, 28.14, 31.58, 40.72 (CH ₂ N), 115.55, 122.71, 125.45, 126.44, 126.88, 128.40, 128.88, 129.70, 131.23, 132.51, 133.42, 133.62, 134.98, 136.2 1, 163.73 (C = O), 165.23 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 361 (3.269), 380 (3.591), 416 (3.484), 436 (3.596) , 460 nm (3.464), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 481 (1), 512 nm (0.77), solid-state fluorescence: λ _max = 560 nm, MS (70 eV): m / z (% ): 332 (23), 331 (100) [M ⁺ ], 314 (9) [M ⁺ - OH], 274 (4), 262 (6), 261 (31), 260 (15), 259 (6 ), 248 (24), 247 (81) [M ⁺ - C ₆ H ₁₂ ], 230 (6) [247 - OH], 219 (4), 204 (4) [M ⁺ - C ₆ H ₁₃ NCO] , 203 (8), 202 (6), 190 (4), 177 (6), 176 (9) [204 - CO], C ₂₂ H ₂₁ NO ₂ (331.4) Calcd. C 79.73, H 6.39, N 4.23; Gen. C 79.30, H 6.28, N 4.33.

N-Nonylanthracene-1,9-dicarboxylic acid imide (61): 2.03 g (8.18 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 2.07 g (14.4 mmol) of n-nonylamine and 350 mg of zinc acetate dihydrate were dissolved in 9 g imidazole for 4 h heated to 150 ° C under an argon atmosphere. Into the hot melt was added 10 mL conc. HCl dropped. The reaction Mi was taken up in chloroform and the red hydrochloric acid phase separated. The organic phase was extracted again with a little 2N HCl and concentrated. For high purification, the crude product was rapidly chromatographed on silica gel with pressure and chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10f and 11f are partially formed, which can not be thermally completely converted back into the imide 6f thermally.). Y. 2.00 g (65%) of bright yellow powder with high solid-state fluorescence, mp 141-143 ° C, R _f (silica gel, CHCl ₃ ) = 0.67, IR (KBr): ṽ = 3068 W, 2957 m, 2926 s, 2854 m , 1685s (C = O), 1660s (C = O), 1601w (C = C), 1560m (C = C), 1534w (C = C), 1462w, 1452w, 1394w, 1355 s, 1311 w, 1280 w, 1243 w, 1170 w, 1109 w, 902 w, 820 w, 778 w, 750 m, 712 w, 605 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.85 (m, 3H, CH ₃ ), 1.38 [m, 12H, (CH ₂ ) ₆ CH ₃ ], 1.77 (m, 2H, NCH ₂ CH ₂ ), 4.26 (m, 2H, NCH ₂ ), 7.63 (m , 1H, aromatic H), 7.72 (m, 1H, aromatic H), 7.81 (m, 1H aromatic H), 8.11 (d, J = 8.4 Hz, 1H, aromatic H), 8.35 (d, J = 8.4 Hz, 1H, aromatic H), 8.75 (d, J = 7.1 Hz, 1H, aromatic H), 8.82 (s, 1H, aromatic H), 10.02 ppm (d, J = 9.2 Hz, 1H, aromatics-H), ¹³ C-NMR (CDCl _3): δ = 13.99 (CH _3), 22:56, 27.20, 28.11, 29.18, 29.35, 29.46, 31.76, 40.64 (CH ₂ N), 122.64, 125.37, 126.35, 126.80 , 128.32, 128.63, 129.62, 131.15, 132.21, 132.76, 133.36, 134.90, 136.14, 162.27 (C = O), 165.05 ppm (C = O), UV (CH Cl ₃ ): λ _max (1 g ε) = 361 (3,457), 380 (3,722), 416 (3,590), 437 (3,696), 461 nm (3,555), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 485 (1), 513 nm (0.77), solid state fluorescence: λ _max = 536, 635 nm sh, MS (70 eV): m / z (%): 374 (26), 373 (100) [M ⁺ ], 356 (7) [M ⁺ - OH], 261 (29), 260 (17) [M ⁺ - C ₈ H ₁₇ ], 248 (29), 247 (72) [M ⁺ - C ₉ H ₁₈ ], 230 (7) [247 - OH], 205 (5), 204 (5) [M ⁺ - C ₉ H ₁₉ NCO], 203 (10), 202 (7), 177 (9), 176 (10) [204 - CO], C ₂₅ H ₂₇ NO ₂ (373.5) Ber. C 80.40, H 7.29, N 3.75; Gef. C 80.41, H 7.30, N 3.79.

N- (1-Hexylheptyl) anthracene-1,9-dicarboximide (6g): 1.94 g (7.82 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 2.22 g (11.1 mmol) of 1-hexylheptylamine and 350 mg of zinc acetate dihydrate were added 10 g of imidazole 4 h under argon atmosphere at 140 ° C stirred. Into the hot melt was added 10 mL conc. HCl dropped. The reaction mixture was taken up in chloroform, the hydrochloric acid phase separated and the organic phase extracted again with 2 N HCl. The organic phase was washed with a little dist. Shaken out water and concentrated. For high purification was rapidly chromatographed on silica gel with toluene under pressure. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10g and 11g are partially formed, which can not be thermally completely converted back into the imide 6g.). Y. 2.15 g (64%) yellow crystals with pale yellow solid-state fluorescence, mp 245 ° C., R _f (silica gel, toluene) = 0.80, IR (KBr): ṽ = 3050 W, 2955 m, 2925 s, 2855 m, 1689 s ( C = O), 1653s (C = O), 1617w (C = C), 1563m (C = C), 1533m (C = C), 1457m, 1430m, 1399m, 1369m, 1309 m, 1280 m, 1243 m, 1212 m, 1191 m, 1150 w, 1114 m, 895 w, 793 w, 750 w, 730 m, 624 w, 610 w cm ^{-1, 1} H-NMR _(CDCl3): δ = 0.79 (t, J = 6.8 Hz, 6H, CH ₃ ), 1.26 [m, 16H, (CH ₂ ) ₄ ], 1.88 [m, 2H, (CH ₂ ) CHN], 2.28 [m, 2H, ( CH ₂ ) CHN], 5.27 [m, 1H, (CH ₂ ) ₂ CHN], 7.61 (m, 1H, aromatic H), 7.72 (m, 1H, aromatic H), 7.81 (m, 1H, aromatic) H), 8.10 (d, J = 8.4 Hz, 1H, aromatic H), 8.33 (d, J = 8.4 Hz, 1H, aromatic H), 8.72 (d, J = 6.9 Hz, 1H, aromatic-H) , 8.81 (s, 1H, aromatic H), 9.96 ppm (d, J = 9.1 Hz, 1H, aromatic H), ¹³ C NMR (CDCl ₃ ) δ = 14.02 (CH ₃ ), 22.57, 27.01, 29.27, 31.76, 32.57, 54.57 (NCHR ₂ ), 125.52, 126.37, 127.02, 128.54, 128.82, 129.72, 131.03, 132.62, 134.61, 135.82 ppm, UV (CHCl ₃ ): λ _max (1 g ε) = 361 (2,628), 380 (3,016), 415 (2,929), 435 (3,051), 459 nm (2,898), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 481 (1), 512 nm (0.78) , Solid state fluorescence: λ _max = 485, 524, 632 nm, MS (70 eV): m / z (%): 430 (10), 429 (33) [M ⁺ ], 344 (3) [M ⁺ - C ₆ H ₁₃ ], 260 (6), 248 (45), 247 (100) [M ⁺ - C ₁₃ H ₂₆ ], 230 (7) [247 - OH], 205 (4), 204 (2) [M ⁺ - C ₁₃ H ₂₇ NCO], 203 (4), 202 (5), 177 (3), 176 (3) [204 - CO], C ₂₉ H ₃₅ NO ₂ (429.6) Ber. C 81.08, H 8.21, N 3.29; Gef. C 80.90, H 8.29, N 3.14.

N- (2-ethylphenyl) anthracene-1,9-dicarboxylic acid imide (6h): 2.06 g (8.30 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 2.01 g (16.6 mmol) of 2-ethylaniline and 330 mg of zinc acetate dihydrate were added 10 g of imidazole under argon atmosphere for 4 h at 150 ° C stirred. Into the hot melt was carefully added 10 mL conc. HCl dropped. The reaction mixture was taken up in chloroform, the hydrochloric acid phase separated and the organic phase extracted again with 2 N HCl. Subsequently, the organic phase was washed with dist. Shaken out water, concentrated and chromatographed rapidly on silica gel with chloroform under pressure for further purification. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10h and 11h are partially formed, which can not be thermally completely converted back to the imide 6h). Y. 1.31 g (45%) bright yellow-orange powder with strong solid-state fluorescence, mp 175-176 ° C, R _f (silica gel, CHCl ₃ ) = 0.21, IR (KBr): ṽ = 3060 W, 2970 W, 2935 W, 2875 W , 1695 s (C = O), 1658 s (C = O), 1623 m (C = C), 1563 s (C = C), 1532 m (C = C), 1493 m, 1454 m, 1430 m, 1392 m, 1370 m, 1320 m, 1254 m, 1214 s, 1197 m, 1148 m, 1054 w, 888 m, 860 w, 795 m, 751 s, 735 s, 659 m, 493 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 1.18 (t, J = 7.7 Hz, 3H, CH _3), 2:57 (q, J = 7.5 Hz, 2H, CH ₂ CH _3), 7.27 (d, J = 7.4 Hz, aromatic-H 1H,), 7:41 ( m, 1H, aromatic H), 7.49 (m, 2H, aromatic H), 7.65 (m, 1H, aromatic H), 7.81 (m, 2H, aromatic H), 8.17 (d, J = 8.4 Hz , 1H, aromatic H), 8.45 (d, J = 7.6 Hz, 1H, aromatic H), 8.83 (d, J = 7.0 Hz, 1H, aromatic H), 8.93 (s, 1H, aromatic-H) , 9.98 ppm (d, J = 9.1 Hz, aromatic-H 1H,), ¹³ C NMR (CDCl _3): δ = 13.87 _(CH3), 24.08 _(CH2), 115.53, 122.82, 125.56 (CH), 126.66 (CH), 126.95 (CH), 127.05 (CH), 127.17, 128.81 (CH), 129.08 (CH), 129.11, 129.15 (CH), 129.74 (CH), 131.57 (CH), 132.60, 133.94, 133.99 (CH ), 134.76, 135.50 (CH), 136.81 (CH), 141.39, 163.79 (C = O), 165.42 ppm (C = O), UV (CHCl _3): λ _max (1 g δ) = 361 (3,294) 380 (3,623), 418 (3,538), 438 (3,651), 462 nm (3,521), fluorescence (CHCl _3): λ _max (I _rel) = 481 (1), 512 nm (0.77), Festkörperf luminescence: λ _max = 486, 524, 544 sh, 600, 630 nm sh, MS (70 eV): m / z (%): 352 (16), 351 (66) [M ⁺ ], 335 (24), 334 (91) [M ⁺ - OH], 323 (17), 322 (71) [M - C ₂ H ₅ ], 319 (24), 306 (12), 291 (16), 247 (11), 204 (5) [M ⁺ - C ₂ H ₅ -C ₆ H ₄ -NCO], 203 (9), 202 (12), 177 (11), 176 (24) [204 - CO], 175 (11) 150 (10) [176 - C ₂ H ₂ ], 121 (43), 106 (100), 101 (13), C ₂₄ H ₁₇ NO ₂ (351.4) Ber. C 82.03, H 4.88, N 3.99; Gef. C 82.47, H 5.17, N 4.15.

N- (2,3-dimethylphenyl) anthracene-1,9-dicarboxylic acid imide (6i): 1.99 g (8.02 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 1.98 g (16.3 mmol) of 2,3-dimethylaniline and 370 mg of zinc acetate dihydrate were stirred in 10 g of imidazole under an argon atmosphere for 4 h at 150 ° C. Into the hot melt was added 10 mL conc. HCl dropped. Subsequently, the reaction mixture was taken up in chloroform, the hydrochloric acid phase separated and the organic phase extracted with 2 N HCl. The organic phase was then washed with dist. Shaken out water, concentrated and chromatographed under rapid pressure on silica gel with chloroform. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10i and 11i form partially, which can not be thermally completely converted back into the imide 6i.). Y. 1.57 g (56%) orange crystals with yellow solid-state fluorescence, mp 290-291 ° C, R _f (silica gel, CHCl ₃ ) = 0.24, IR (KBr): ṽ = 3070 W, 2920 W, 1718 m, 1695 W, 1680s (C = O), 1660s (C = O), 1602w (C = C), 1565m (C = C), 1535w (C = C), 1472m, 1452w, 1392w, 1366 s, 1321 m, 1267 m, 1239 m, 1215 m, 1200 W, 1152 W, 884 W, 777 m, 753 m, 738 m, 710 m, 610 W, 557 cm ^-1 W, ¹ H-NMR (CDCl3) _3): δ = 2.11 (s, 3H, CH ₃₎ 2.48 (s, 3H, CH _3), 7:36 (m, 2H, aromatic-H), 7.65 (m, aromatic-H 1H,), 7.80 (m , 2H, aromatic-H), 7.89 (m, 1H, aromatic-H), 8.16 (d, J = 7.7 Hz, 1H, aromatic-H), 8.44 (d, J = 8.3 Hz, 1H, aromatic-H) , 8.82 (d, J = 7.1 Hz, 1H, aromatic-H), 8.93 (s, 1H, aromatic-H), 9.98 ppm (d, J = 9.1 Hz, 1H, aromatic-H), ¹³ C NMR (CDCl ₃ ): δ = 14.59 (CH ₃ ), 20.92 (CH ₃ ), 113.64, 123.23, 125.97, 126.31, 126.53, 126.89, 127.05, 127.37, 127.54, 127.82, 129.51, 130.15, 130.93, 131.33, 131.97, 133.01, 134.41 , 135.90, 137.22, 138.60, 163.00 (C = O), 163.50 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 361 (3,539), 380 (3,946), 418 (3,857), 438 (3,986), 463 nm (3,839), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 483 (1), 513 nm (0.76), solid state fluorescence: λ _max = 484, 523, 540 sh, 631 nm, MS (70 eV): m / z (%): 352 (11), 351 (46) [M ⁺ ], 337 ( 8), 336 (36), 335 (25), 334 (100) [M ⁺ - OH], 319 (11), 306 (6) [334 - CO], 291 (8), 230 (3), 202 (4), 176 (14), 175 (3), 168 (3), C ₂₄ H ₁₇ NO ₂ (351.4) Calcd. C 82.03, H 4.88, N 3.99; Gef. C 82.23, H 5.07, N 3.99.

N- (2,5-di-tert-butylphenyl) anthracene-1,9-dicarboxylic acid imide (6j): 1.98 g (7.98 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 2.37 g (11.5 mmol) of 2,5 -Di-tert-butylaniline and 350 mg of zinc acetate dihydrate were stirred in 10 g of imidazole under argon atmosphere at 140 ° C for 5 h. Into the hot melt was carefully added 10 mL conc. HCl dropped. The reaction mixture was taken up in chloroform, the hydrochloric acid phase separated and the organic phase with 2N HCl and then with dist. Extracted water. The organic phase was then concentrated and chromatographed on silica gel under pressure with chloroform under pressure. From the bright yellow product fraction, the solvent was removed immediately and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the corresponding dimers 10j and 11j, which can not be thermally completely converted back into the imide 6j, form in part.). 2.22 g (64%) of bright golden yellow crystals with high solid state fluorescence, mp 335-337 ° C, R _f (silica gel, CHCl ₃ ) = 0.73, IR (KBr): ṽ = 3050 W, 2963 m, 2910 W, 2875 W , 1700 s (C = O), 1662 s (C = O), 1621 W (C = C), 1563 s (C = C), 1532 m (C = C), 1430 m, 1398 m, 1372 m, 1318m, 1279w, 1251w, 1213m, 1185w, 1176w, 1145w, 1055w, 895w, 840w, 796w, 752w, 736m, 722w, 667w, 625cm ^-1 w , ¹ H-NMR (CDCl _3): δ = 1.31 [s, 9H, C (CH _{3) 3],} 1:34 [s, 9H, C (CH _{3) 3],} 7:07 (d, J = 2.2 Hz, 1H , Aromatic H), 7.47 (dd, J ₁ = 8.4 Hz, J ₂ = 2.2 Hz, 1H, aromatic H), 7.61 (d, J = 8.5 Hz, 1H, aromatic H), 7.66 (m, 1H , Aromatic H), 7.83 (m, 2H, aromatic H), 8.17 (d, J = 8.6 Hz, 1H, aromatic H), 8.45 (d, J = 8.4 Hz, 1H, aromatic H), 8.84 (d, J = 7.2 Hz, 1H, aromatic H), 8.93 (s, 1H, aromatic H), 9.97 (d, J = 9.3 Hz, 1H, aromatic H), ¹³ C NMR (CDCl ₃ ): δ = 31.26 (CH ₃ ), 31.72 (CH ₃ ), 34.25 [C (CH ₃ ) ₃ ], 35.49 [C (CH ₃ ) ₃ ], 113.41, 123.10, 125.57, 126.08, 126.61, 126.95, 128.08, 128.6 5, 128.98, 129.15, 129.69, 131.45, 132.63, 133.49, 133.85, 133.92, 135.34, 136.55, 143.70, 150.01, 164.68 (C = O), 166.47 ppm (C = O), UV (CHCl _3): λ _max ( 1 g ε) = 361 (3,583), 379 (3,868), 416 (3,753), 436 (3,873), 462 nm (3,731), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 481 (1), 512 nm (0.77), fluorescence quantum yield: 92% based on tetramethylperylene-3,4 : 9,10-tetracarboxylic acid ester ^[33] with a fluorescence quantum yield of 100%, solid state fluorescence: λ _max = 529, 559 nm sh, MS (70 eV): m / z (%): 435 (2) [M ⁺ ], 380 (5), 379 (28), 378 (100) [M ⁺ - C ₄ H ₉ ], 363 (5), 362 (12), 346 (3), 279 (5), 167 (10), 149 ( 33), 112 (4), 111 (5), 109 (3), 105 (3), 97 (7), 95 (5), 91 (4), 85 (10), 83 (17), 81 ( 6), 71 (11), 69 (11), 57 (18), 55 (12), C ₃₀ H ₂₉ NO ₂ (435.6) Ber. C 82.73, H 6.71, N 3.22; Gef. C 82.77, H 6.66, N 3.22.

Dimerization of anthracene-1,9-dicarboxylic acid imides

manufacturing the filter solution irradiation apparatus: a beaker (1 liter volume) was treated with KOH and naphthalene-1,8-dicarboxylic anhydride prepared a solution of the naphthalene-1,8-dicarboxylate (KOH-Pläzchen, distilled water), and an absorbance at 250 to 320 nm between 4 to 5 / cm set. For wavelengths bigger as 360 nm, the extinction must go to zero. The to be implemented Naphthalenedicarboximides were dissolved in chloroform filled in 5 mm NMR tubes, in the vicinity the center of the beaker housed. Irradiation took place laterally with a 150 W tungsten filament light bulb.

photoreaction of anthracene-1,9-dicarboximides - general Working instructions: 200 mg (about 0.7 mmol to 0.50 mmol depending on the substituent R) N-substituted anthracene-1,9-dicarboxylic acid imide (6) was in an NMR tube (internal diameter 4 mm) in Chloroform dissolved and through the filter solution Naphthalene-1,8-dicarboxylic acid di-potassium salt a few days irradiated with a 150 watt incandescent bulb until the fluorescence is complete had disappeared. The NMR tube was opened and the solvent evaporate under irradiation conditions.

N-Ethylanthracene-1,9-dicarboximide dimers (10b) and (11b): Approach 200 mg (7.3 mmol) of N-ethylanthracene-1,9-dicarboximide (6b). Y. 200 mg (≈ 100%) pale yellow powder, mp 173-175 ° C, R _f (silica gel, CHCl ₃ ) = 0.34, IR (KBr): ṽ = 3079 W, 2980 W, 2936 W, 1707 m (C = O), 1666s (C = O), 1603w (C = C), 1560w, 1482w (C = C), 1452w, 1437w, 1388w, 1371w, 1356m, 1312w, 1250m , 1231 w, 1138 w, 1096 m, 824 w, 796 w, 780 w, 751 w, 732 w, 708 w, 670 w, 609 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.90 ( m, 6H, CH ₃ ), 4.23 (m, 2H, NCH ₂ CH ₃ ), 4.33 (m, 2H, NCH ₂ CH ₃ ), 4.81 (s, 1H), 4.83 (s, 1H), 6.78 (m, 1H, aromatic-H), 6.86 (m, 1H, aromatic-H), 7.00 (m, 5H, aromatic-H), 7.12 (m, 1H, aromatic-H), 7.51 (m, 3H, aromatic-H) , 7.72 (m, 1H, aromatic-H), 7.81 (m, 1H, aromatic-H), 7.83 ppm (m, 1H, aromatic H), ¹³ C-NMR (CDCl _3): δ = 13.94 (CH ₃ ), 36.09 (CH ₂ ), 58.21, 62.39 (CH), 123.55, 125.96, 126.04, 127.35, 127.60, 128.00, 129.21, 130.01, 131.27, 132.52, 132.80, 135.52, 140.15, 140.68, 141.15, 143.16, 143.97, 165.29 (C = O), 173.73 ppm (C = O), UV (CHCl _3): λ _max (1 g ε) = 264 (4026) sh, 300 (3,366), 313 nm (3,280), Fl fluorescence (CHCl ₃ ): λ _max (I _rel ) = 484 (1), 513 (0.85), 557 nm sh (0.29), MS (70 eV): m / z (%): 276 (20), 275 ( 94) [M ⁺ ], 274 (9), 260 (17) [M ⁺ - CH ₃ ], 259 (5), 248 (19), 247 (100) [M ⁺ - C ₂ H ₄ ], 246 ( 7), 233 (8), 231 (9), 230 (4) [247 - OH], 219 (7), 205 (11), 204 (9) [M ⁺ - C ₂ H ₅ NCO], 203 ( 22) [204-H], 202 (9), 190 (9), 177 (19), 176 (27) [204-CO], 175 (9), 174 (6), 150 (7), 116 ( 7), 88 (29) [176 - C ₇ H ₄ ], 75 (6).

N-Butylanthracene-1,9-dicarboximide dimers (10c) and (11c): Approach: 200 mg (6.6 mmol). 6c. Y. 200 mg (100%) pale yellow powder, mp 170-172 ° C, R _f (silica gel, CHCl ₃ ) = 0.50, IR (KBr): ṽ = 3068 W, 2960 m, 2932 m, 2872 W, 1709 s ( C = O), 1667s (C = O), 1602w (C = C), 1481w (C = C), 1462m, 1452m, 1433w, 1390m, 1355s, 1322w, 1275w, 1239 m, 1190 W, 1139 W, 1099 m, 939 W, 819 W, 779 W, 755 m, 708 m, 671 W, 610 cm ^-1 m, ¹ H-NMR (CDCl ₃ ): δ = 1.03 ( t, J = 7.3 Hz, 6H, CH _3), 1:49 (m, 4H, CH ₂ CH _3), 1.76 (q, J = 7.1 Hz, 4H, NCH ₂ CH _2), 4.24 (m, 4H, NCH ₂ ), 4.79 (s, 1H), 4.80 (s, 1H), 6.77 (m, 1H, aromatic-H), 6.84 (m, 1H, aromatic-H), 6.98 (m, 5H, aromatic-H), 7.10 (m, 1H, aromatic H), 7.25 (m, 1H, aromatic H), 7.48 (m, 3H, aromatic H), 7.78 (m, 1H, aromatic H), 7.81 ppm (m, 1H, aromatics-H), ¹³ C-NMR (CDCl _3): δ = 14:27 (CH _3), 20.78 _(CH2), 30.76 _(CH2), 40.70 (NCH _2), 58.25, 62.41 (CH), 62.54 (CH ), 123.31, 123.49, 125.95, 126.19, 127.14, 127.32, 127.39, 127.57, 127.63, 127.76, 127.98, 128.70, 130.01, 132.52, 133.92, 140.19, 140.50, 140.65, 141.14, 141.38, 1 42.20, 142.66, 163.65 (C = O), 163.76 (C = O), 173.91 (C = O), 174.07 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 264 (4,123 ) sh, 302 (3.512), 313 nm (3.466), fluorescence (CHCl ₃ ); λ _max (I _rel ) = 484 (1), 514 (0.83), 558 nm sh (0.32), MS (70 eV): m / z (%): 304 (19), 303 (87) [M ⁺ ] , 286 (16) [M ⁺ - OH], 274 (6), 262 (6), 261 (36), 260 (16) [M ⁺ - C ₃ H ₇ ], 259 (8), 248 (22) , 247 (100) [M ⁺ - C ₄ H ₈ ], 231 (6), 230 (7) [247 - OH], 219 (5), 204 (5) [M ⁺ - C ₄ H ₉ NCO], 203 (11) [204-H], 202 (8), 190 (5), 177 (9), 176 (14) [204-CO], 150 (2), 88 (4) [176-C ₇ H ₄ ].

N-Pentylanthracene-1,9-dicarboximide dimers (10d) and (11d): Approach 200 mg (6.3 mmol) of N-pentylanthracene-1,9-dicarboximide (6d). Y. 200 mg (≈ 100%) pale yellow powder, mp 159-162 ° C, R _f (silica gel, CHCl ₃ ) = 0.62, IR (KBr): ṽ = 3069 W, 2957 m, 2930 m, 2860 W, 1709 s (C = O), 1668s (C = O), 1602w (C = C), 1481w (C = C), 1462w, 1452w, 1434w, 1390w, 1355m, 1309w, 1262w , 1241 w, 1187 w, 1141 w, 1102 m, 1073 w, 819 w, 779 w, 756 w, 709 w, 670 w, 610 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.96 ( m, 6H, CH ₃ ), 1.45 [m, 8H, (CH ₂ ) ₂ CH ₃ ], 1.79 (m, 4H, CH ₂ CH ₂ N), 4.25 (m, 4H, CH ₂ N), 4.81 (s, 1H), 4.82 (s, 1H ), 6.79 (m, 1H, aromatic-H), 6.86 (m, 1H, aromatic-H), 7.01 (m, 5H, aromatic-H), 7.11 (m, 1H, aromatic-H), 7.27 (m, 1H, aromatic H), 7.45 (m, 3H, aromatic H), 7.80 (m, 1H, aromatic H), 7.83 ppm (m, 1H, aromatic H), ¹³ C NMR (CDCl ₃ ): δ = 12.15 (CH ₃ ), 20.53, 26.03, 27.35, 38.60 (CH ₂ N), 55.94, 60.09 (CH), 60.22 (CH), 120.98, 121.17, 123.63, 123.88, 124.83, 125.01, 125.07, 125.25, 125.31 , 125.44, 125.65, 126.39, 127.69, 130.21, 131.60, 137.88, 138.18, 138.37, 138.83, 139.07, 139.88, 140.35, 161.33 (C = O), 161.43 (C = O), 171.61 (C = O), 171.76 ppm (C = O), UV (CHCl _3): λ _max (1 g ε) = 266 (4,733), 300 (3,619), 313 (3,591), 360 (3,233), 380 (3,584), 415 (3,466) 437 (3,595), 461 nm (3,446), fluorescence (CHCl _3): λ _max (I _rel) = 485 (1), 515 (0.78) 557 nm sh (12:27), MS (70 eV): m / z (%): 318 (23), 317 (100) [M ⁺ ], 300 (11) [M ⁺ - OH], 274 (5), 261 (33), 260 (15) [M ⁺ - C ₄ H ₉ ], 24 8 (24), 247 (90) [M ⁺ - C ₅ H ₁₀ ], 230 (6) [247 - OH], 219 (4), 204 (4) [M ⁺ - C ₅ H ₉ NCO], 203 (9), 202 (7), 190 (4), 177 (8), 176 (11) [204 - CO], 88 (3) [176 - C ₇ H ₄ ].

N-Hexylanthracene-1,9-dicarboximide dimers (10e) and (11e): Approach 200 mg (6.0 mmol) of N-hexylanthracene-1,9-dicarboximide (6c). Y. 200 mg (≈ 100%) pale yellow powder, mp 165-166 ° C, R _f (silica gel, CHCl ₃ ): = 0.89, IR (KBr) ṽ = 2957 m, 2930 s, 2858 m, 1708 s (C = O), 1667s (C = O), 1602w (C = C), 1462w (C = C), 1434w, 1390w, 1355s, 1250w, 1182w, 1140w, 1101w, 1073w , 820 w, 779 w, 757 w, 709 w, 671 w, 610 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.91 (m, 6H, CH _3), 1:40 [m, 12H, ( CH ₂ ) ₃ CH ₃ ], 1.78 [m, 4H, CH ₂ CH ₂ N], 4.25 (m, 4H, CH ₂ N), 4.80 (s, 1H), 4.82 (s, 1H), 6.77 (m, 1H, aromatic H), 6.85 (t, J = 7.1 Hz, 1H, aromatic H), 6.98 (m, 5H, aromatic H), 7.10 (t, J = 7.7 Hz, 1H, aromatic H), 7.27 (m, 1H, aromatic-H), 7.48 (m, 3H, aromatic-H), 7.79 (m, 1H, aromatic-H), 7.81 ppm (m, 1H, aromatic-H), ¹³ C-NMR ( CDCl ₃ ): δ = 14.46 (CH ₃ ), 23.05, 27.23, 28.66, 31.96, 40.94 (CH ₂ N), 58.26, 62.41 (CH), 62.55 (CH), 123.31, 123.50, 125.96, 126.21, 127.15, 127.33 , 127.39, 127.57, 127.63, 127.76, 127.97, 128.71, 130.02, 132.53, 133.92, 140.20, 140.51, 140.67, 140.70, 141.15, 141.39, 142.21, 142.67, 163.64 (C. = O), 163.75 (C = O), 173.93 (C = O), 174.08 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 265 (4.418), 301 (3.302), 313 nm (3,154), fluorescence (CHCl _3): λ _max (I _rel) = 482 (1), 512 nm (0.78), MS (FAB, 3-nitrobenzyl alcohol) m / z = 685 [m ⁺ + Na], 663 [M ⁺ ], MS (70 eV): m / z (%): 332 (23), 331 (100) [M ⁺ ], 314 (9) [M ⁺ - OH], 274 (4), 262 (6), 261 (31), 260 (15), 259 (6), 248 (24), 247 (81) [M ⁺ - C ₆ H ₁₂ ], 230 (6) [247 - OH], 219 ( 4), 204 (4) [IV - C ₆ H ₁₃ NCO], 203 (8), 202 (6), 190 (4), 177 (6), 176 (9) [204 - CO].

N-Nonylanthracene-1,9-dicarboximide dimers (101) and (III): Approach 200 mg (5.4 mmol) of N-nonylanthracene-1,9-dicarboximide (6f). Y. 200 mg (≈ 100%) pale yellow powder, mp 151-153 ° C, R _f (silica gel, CHCl ₃ ) = 0.76, IR (KBr): ṽ = 2927 m, 2856 m, 1707 s (C = O), 1663 s (C = O), 1462 w w (C = C), 1391, 1356 m, 1242 w, 1170 w, 1102 w, 820 w, 778 w, 752 w, 710 w, 606 m cm ^{-1, 1} H-NMR (CDCl ₃ ): δ = 0.86 (m, 6H, CH ₃ ), 1.26-1.42 [m, 24H, (CH ₂ ) ₆ CH ₃ ], 1.76 (m, 4H, NCH ₂ CH ₂ ), 4.23 (m, 4H, NCH ₂ ), 4.79 (s, 1H), 4.80 (s, 1H), 6.75 (m, 1H, aromatic-H), 6.84 (m, 1H, aromatic-H), 6.92-7.01 (m , 5H, aromatic-H), 7.09 (m, 1H, aromatic-H), 7.26 (m, 1H, aromatic-H), 7.45 (m, 3H, aromatic-H), 7.79 (m, 1H, aromatic-H ), 7.81 ppm (m, 1H, aromatic H), ¹³ C-NMR (CDCl ₃ ): δ = 13.52 (CH ₃ ), 22.09, 26.59, 27.72, 28.68, 28.80, 29.01, 31.29, 39.95 (CH ₂ N ), 57.27, 61.42 (CH), 61.56 (CH), 122.32, 124.97, 125.22, 126.16, 126.33, 126.63, 126.76, 126.98, 127.72, 129.03, 131.54, 132.93, 139.52, 139.68, 140.16, 140.40, 162.76 (C = O), 172.93 (C = O), 173.09 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 266 (4,214) sh, 303 (3,059), 313 nm (3.068), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 483 (1), 513 (0.78), 557 nm sh (0.25), MS (70 eV): m / z (%): 374 ( 26), 373 (100) [M ⁺ ], 356 (7) [M ⁺ - OH], 261 (29), 260 (17) [M ⁺ - C ₈ H ₁₇ ], 248 (29), 247 (72 ) [M ⁺ - C ₉ H ₁₈ ], 230 (7) [247 - OH], 205 (5), 204 (5) [M ⁺ - C ₉ H ₁₉ NCO], 203 (10), 202 (7) , 177 (9), 176 (10) [204-CO].

N- (1-Aexylheptyl) anthracene-1,9-dicarboximide dimer (10 g) and (11 g): Approach 200 mg (4.7 mmol) of N- (1-hexylheptyl) anthracene-1,9-dicarboximide (6 g). Y. 200 mg (≈ 100%) pale yellow powder, mp 142-144 ° C, R _f (silica gel, toluene) = 0.90, IR (KBr): ṽ = 2955 m, 2926 s, 2856 m, 1708 s (C = O ), 1666 s (C = O), 1462 s (C = C), 1402 W, 1353 m, 1320 W, 1245 m, 1180 W, 1105 W, 1072 W, 881 W, 819 W, 778 W, 752 W , 710 w, 670 w, 612 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.84 (m, 12H, CH _3), 1:20 to 1:45 [m, 32 H, (CH _{2) 4],} 1.88 [m, 8 H, (CH ₂ ) CHN], 2.34 [m, 8H, (CH ₂ ) CHN], 4.82 (s, 2H), 5.18-5.32 [m, 2H, (CH ₂ ) ₂ CHN], 6.77 (m, 1H, aromatic-H), 6.84 (m, 1H, aromatic-H), 6.90-7.04 (m, 5H, aromatic-H), 7.08 (m, 1H, aromatic-H), 7.27 (m, 1H, aromatic-H), 7.38 (m, 2H, aromatic-H), 7.47 (m, 1H, aromatic-H), 7.77 (s, 1H, aromatic-H), 7.79 ppm (s, 1H, aromatic-H ), ¹³ C-NMR (CDCl _3): δ = 14:48 (CH _3), 22.99, 27.36, 29.60, 32.25, 42.51, 54.67 (NCHR _2), 58.53, 62.65 (CH), 123.82, 124.05, 125.09, 125.67, 125.99, 127.23, 127.35, 127.43, 127.64, 127.84, 128.76, 130.05, 132.29, 133.74, 140.71, 140.90, 141.12, 141.38, 143.40, 143.63 ppm, UV (CHCl _3): λ _max (1 g ε) = 266 (4,647), 301 (3,622), 314 (3,585), 380 (3,518), 410 (3,395), 434 (3,556), 458 (3,492), 489 (3,262), 526 nm ( 3.474), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 482 (1), 512 nm (0.78). MS (70 eV): m / z (%): 430 (10), 429 (33) [M ⁺ ], 344 (3) [M ⁺ - C ₆ H ₁₃ ], 260 (6), 248 (45) , 247 (100) [M ⁺ -C ₁₃ H ₂₆ ], 230 (7) [247 - OH], 205 (4), 204 (2) [M ⁺ - C ₁₃ H ₂₇ NCO], 203 (4), 202 (5), 177 (3), 176 (3) [204-CO].

N- (2-ethylphenyl) anthracene-1,9-dicarboximide dimer (10h) and (11h): Mixture 200 mg (5.7 mmol) of N- (2-ethylphenyl) anthracene-1,9-dicarboximide (6h). Y. 200 mg (≈ 100%) of pale yellow powder, mp 148-150 ° C, R _f (silica gel, CHCl ₃ ) = 0.30, IR (KBr): ṽ = 3066w, 3034w, 2968w, 2932w, 2875w , 1718 s (C = O), 1679 s (C = O), 1600 W (C = C), 1491 W (C = C), 1452 m, 1363 s, 1321 W, 1264 m, 1234 W, 1208 W , 1145 w, 1055 w, 910 w, 852 w, 779 w, 757 m, 735 m, 707 w, 615 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 1.13 (m, 3H, CH ₃ , 1.47 (m, 3H, CH ₃ ), 2.41 (m, 2H, CH ₂ CH ₃ ), 2.81 (m, 2H, CH ₂ CH ₃ ), 5.01 (m, 1H), 5.03 (m, 1H), 6.95-7.02 (m, 7H, aromatic-H), 7.10-7.18 (m, 3H, aromatic-H), 7.41 (m, 3H, aromatic-H), 7.50-7.56 (m, 7H, aromatic-H), 7.84-7.86 ppm (m, 2H, aromatic-H), ¹³ C-NMR (CDCl _3): δ = 14:37 (CH _3), 14:54 (CH _3), 24.26 _(CH2), 24.71 _(CH2), 59.65 , 60.00, 63.13 (CH), 63.59 (CH), 124.17, 124.86, 127.29, 127.41, 127.58, 127.86, 128.00, 128.31, 128.98, 129.55, 130.03, 134.25, 134.47, 141.31, 141.89, 142.70, 143.39 ppm, UV CHCl _3): λ _max (1 g ε) = 262 (4,294), 301 (3,610), 316 (3,594), 380 (2,913), 412 (2,726), 437 (2,898), 46 3 nm (2,700), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 485 (1), 515 (0.77), 559 nm sh (0.27), MS (70 eV): m / z (%): 352 (16), 351 (66) [M ⁺ ], 335 (24), 334 (91) [M ⁺ - OH], 323 (17), 322 (71) [M ⁺ - C ₂ H ₅ ], 319 ( 24), 306 (12), 291 (16), 247 (11), 204 (5) [M-C ₂ H ₅ -C ₆ H ₄ -NCO], 203 (9), 202 (12), 177 ( 11), 176 (24) [204-CO], 175 (11), 150 (10) [176-C ₂ H ₂ ], 121 (43), 106 (100), 101 (13).

N- (2,3-dimethylphenyl) anthracene-1,9-dicarboximide dimers (10i) and (11i): Preparation 200 mg (5.7 mmol) of N- (2,3-dimethylphenyl) anthracene-1,9-dicarboximide ( 6i). Y. 200 mg (≈ 100%) pale yellow powder, mp 290-292 ° C, R _f (silica gel, CHCl ₃ ) = 0.29, IR (KBr): ṽ = 3071 W, 2924 W, 1718 s (C = O), 1681s (C = O), 1602w (C = C), 1472m (C = C), 1453w, 1365s, 1322w, 1267m, 1239m, 1153w, 1048w, 912w, 884w , 835 w, 818 w, 777 m, 756 m, 738 w, 708 w, 610 w, 558 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 2:00 (s, 3H, CH _3), 2:40 (s, 6H, _CH3), 2:49 (s, 3H, CH _3), 5:03 (m, 2H), 6.95-7.52 (m, 18H aromatics-H), 7.87 ppm (m, 2H, aromatic-H) , ¹³ C-NMR (CDCl ₃ ): δ = 14.52 (CH ₃ ), 14.94 (CH ₃ ), 20.89 (CH ₃ ), 58.94, 62.54 (CH), 62.87 (CH), 123.23, 126.32, 127.05, 127.22, 127.55, 128.02, 128.28, 128.92, 131.32, 133.02, 134.45, 134.67, 138.72, 139.01, 140.54, 141.46, 142.50, 164.48 (C = O), 165.06 (C = O), 174.55 (C = O), 175.25 ppm ( C = O), UV (CHCl _3): λ _max (1 g ε) = 264 (4,525), 301 (3,639), 312 (3,628), 379 (3,415), 414 (3,314), 437 (3,446), 462 nm (3,296), fluorescence (CHCl _3): λ _max (I _rel) = 485 (1), 516 (0.77) 558 nm sh (12:28), MS (70 eV): m / z (%): 352 (11), 351 (46) [M ⁺ ], 337 (8), 336 (36), 335 (25), 334 (100) [M ⁺ - OH], 319 (11), 306 (6) [ 334 - CO], 291 (8), 230 (3), 202 (4), 176 (14), 175 (3), 168 (3).

N- (2,5-di-tert-butylphenyl) anthracene-1,9-dicarboximide dimers (10j) and (11j): 200 mg (4.6 mmol). N- (2,5-di-tert-butylphenyl) anthracene-1,9-dicarboxylic acid imide (6j). Y. 200 mg (≈ 100%) of pale yellow powder, mp> 300 ° C., R _f (silica gel, CHCl ₃ ) = 0.83, IR (KBr): ṽ = 3069 W, 2963 m, 2869 W, 1719 s (C = O ) 1679s (C = O), 1601w (C = C), 1481w (C = C), 1462w, 1394w, 1360s, 1321w, 1251m, 1204w, 1158w, 1054w, 910 w, 836 m, 778 w, 755 w, 735 w, 709 w, 674 w, 616 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 1.24 (m, 20H) 1.44 (s, 6H ), 1.61 (m, 10H), 4.94 (m, 1H), 5.11 (m, 1H), 6.75 ppm (m, 1H, aromatic H), ¹³ C-NMR (CDCl ₃ ): δ = 31.55 (CH ₃ ), 31.70 (CH ₃ ), 32.29 (CH ₃ ), 32.63 (CH ₃ ), 36.46 [C (CH ₃ ) ₃ ], 58.44, 63.83 (CH), 64.16 (CH), 125.06, 125.11, 125.97, 126.01, 127.24, 127.63, 127.79, 128.73, 129.14, 129.63, 130.05, 134.97 ppm, UV (CHCl _3): λ _max (1 g ε) = 265 (4,460), 303 (3,701) 315 (3,664), 379 (3,370) , 416 (3,283), 436 (3,386), 460 nm (3,253), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 482 (1), 513 (0.78), 555 nm sh (0.27), MS (70 eV): m / z (%): 435 (2) [M ⁺ ], 380 (5), 379 (28), 378 (100) [M ⁺ - C ₄ H ₉ ], 363 (5), 362 ( 12), 346 (3), 279 ( 5), 167 (10), 149 (33), 112 (4), 111 (5), 109 (3), 105 (3), 97 (7), 95 (5), 91 (4), 85 ( 10), 83 (17), 81 (6), 71 (11), 69 (11), 57 (18), 55 (12).

Amidine from anthracene-1,9-dicarboxylic anhydride and neopentanediamine (12): 1.27 g (5.12 mmol) of anthracene-1,9-dicarboxylic anhydride (3), 5 mL (48.9 mmol) of neopentanediamine and 30 mL of dist. Water was stirred under argon atmosphere and reflux for 1 h at room temperature and then at 170 ° C for 3 h. After cooling the reaction mixture to room temperature, the orange crude product was filtered off (glass filter crucible G4) and with a little distilled. Washed water. For further purification, the crude product was chromatographed over silica gel as quickly as possible with pressure and chloroform. The yellow fluorescent product fraction, the solvent was removed under argon atmosphere immediately in vacuo and the product pre-dried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. (If the product is exposed in solution, the dimers 14 and 15 corresponding to 10 and 11, which can not be thermally completely converted back into the amidine 12, are formed in part). Y. 1.77 g (79% crude product) bright yellow powder with high solid-state fluorescence, mp 175-177 ° C, R _f (silica gel, CHCl ₃ ) = 0.10, IR (KBr): ṽ = 3125 W, 3060 W, 2960 W, 2950 w, 2847w, 1661s (C = O), 1631s (C = N), 1603s (C = C), 1562m (C = C), 1533w (C = C), 1428m, 1369m , 1355w, 1330w, 1298m, 1261s, 1196m, 1169m, 1144m, 1091w, 1023w, 895m, 790m, 731m, 668m, 532cm ^-1 w, ¹ H NMR. CDCl ₃ ): δ = 1.10 (s, 6H, CH ₃ ), 3.49 (s, 2H, CH ₂ N), 3.82 (s, 2H, CH ₂ N), 7.59 (m, 2H, aromatic H), 7.72 (m, 1H, aromatic H), 8.04 (d, J = 7.9 Hz, 1H, aromatic H), 8.16 (d, J = 8.2 Hz, 1H, aromatic H), 8.69 (d, J = 7.4 Hz , 1H, aromatic H), 8.72 (s, 1H, aromatic H), 10.00 ppm (d, J = 9.2 Hz, 1H, aromatic H), ¹³ C NMR (CDCl ₃ ): δ = 24.82 (CH ₃ ), 27.74 (CH ₂ N), 50.94 (CH ₂ N =), 57.77 [C (CH ₃ ) ₂ ], 113.31, 116.08, 125.10, 125.53, 126.00, 127.09, 127.47, 128.87, 129.34, 129.93, 131.50, 132.29, 132.65, 134.87, 146.42 (C = N), 163.88 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 253 (4,476), 271 (4,795), 368 (3.408), 381 (3.643), 387 (3.773), 419 sh (3.666), 445 (3.870), 466 (3.895), 497 nm sh (3.633), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 518 (1), 558 (0.59), 601 nm sh (0.32), solid state fluorescence: λ _max = 555 nm, MS (70 eV): m / z (%): 316 (3), 315 (23), 314 ( 100) [M ⁺ ], 313 (12), 300 (7), 299 (33) M ⁺ - CH ₃ ], 284 (9), 271 (10) [299 - CO], 259 (10), 258 ( 27) [M - C ₄ H ₈ ], 246 (9), 231 (19), 230 (59) [258 - CO], 203 (15), 202 (32) [M ⁺ - C ₅ H ₁₀ NCO] , 201 (13), 176 (6) [202 - CN], 175 (7), C ₂₁ H ₁₈ N ₂ O (314.4) Calcd. C 80.23, H 5.77, N 8.91; Gef. C 79.96, H 5.80, N 8.95. Crystal structure: (diffractometer: ENRAF-Nonius CAD4, radiation: MoK _α , monochromator: highly oriented graphite crystal): C ₂₁ H ₁₈ N ₂ O, M = 314.37, a = 9.134 (3) 1, b = 10.189 (2) Å, c = 16,816 (4) Å, β = 101.22 (3) °, volume = 1535.1 (7) Å ³ , Z = 4, density (calculated) = 1,360 g / cm ³ , μ = 0.085 mm ^-1 , monoclinic crystal system , Room group P2 ₁ / c (no. 14). - Data collection single crystal 0.10 × 0.40 × 0.47 mm ³ (yellow plate); ω data collection, scan width [°]: 0.50 + 0.35 tan θ; maximum measurement time 90 s per reflex, number of reflexes: 2275 (total), 2120 (independent), 1641 (observed) [I> 2σ (I)], minimum correction for absorption, structure solution with SHELXS86, refinement with SHELXL93, 219 parameters, R1 = 0.0462 (2σ (I)), wR2 = 0.1293 (2σ (I)), weighting w = 1 / [σ ₂ F _o ² + 0.0621], GOF = 1.108, max. and min. Residual electron density (e / Å ³ ) 0.170 / -0.168. Table 4: Atomic coordinates [× 10 ⁴ ] and equivalent isotropic displacement parameters in [Å ² × 10 ³ ] of 12. U (eq) is defined as one third of the trace of the orthogonalized Uij tensor. atom x y z U (eq) O (1) 6363 (3) -1388 (2) 9218 (1) 81 (1) N (1) 5444 (2) 610 (2) 8893 (1) 40 (1) N (2) 4423 (2) 2729 (2) 8562 (1) 47 (1) C (1) 7537 (2) 345 (2) 10049 (1) 38 (1) C (2) 8624 (3) -448 (2) 10546 (1) 42 (1) C (3) 8818 (3) -1822 (2) 10441 (2) 50 (1) C (4) 9881 (3) -2512 (3) 10950 (2) 56 (1) C (5) 10839 (3) -1897 (3) 11598 (2) 57 (1) C (6) 10714 (3) -600 (3) 11717 (2) 54 (1) C (7) 9620 (3) 166 (3) 11203 (1) 44 (1) C (8) 9514 (3) 1499 (3) 11334 (1) 49 (1) C (9) 8471 (3) 2298 (2) 10853 (1) 43 (1) C (10) 8390 (3) 3660 (3) 10985 (2) 52 (1) C (11) 7367 (3) 4412 (3) 10500 (2) 53 (1) C (12) 6373 (3) 3831 (2) 9854 (1) 47 (1) C (13) 6400 (3) 2520 (2) 9700 (1) 40 (1) C (14) 7461 (2) 1698 (2) 10195 (1) 38 (1) C (15) 6441 (3) -225 (2) 9372 (1) 45 (1) C (16) 5342 (3) , 1964 (2) 9008 (1) 40 (1) C (17) 3393 (3) 2194 (2) 7871 (1) 47 (1) C (18) 3907 (2) 937 (2) 7527 (1) 39 (1) C (19) 4361 (3) 1 (2) 8231 (1) 43 (1) C (20) 5209 (3) 1188 (2) 7110 (1) 48 (1) C (21) 2624 (3) 325 (3) 6925 (2) 53 (1) Table 5: Anisotropic excursion parameters in [Å ² × 10 ³ ] of 12. The exponent of the anisotropic excursion factor has the form: - 2π ² [h ² 2 a * ² U11 + ... + 2 hka * b * U12]. atom U11 U22 U33 U23 U13 U12 O (1) 105 (2) 36 (1) 79 (1) -5 (1) -39 (1) 3 (1) N (1) 48 (1) 36 (1) 34 (1) -1 (1) -2 (1) -1 (1) N (2) 49 (1) 45 (1) 41 (1) -3 (1) 0 (1) 7 (1) C (1) 40 (1) 43 (2) 31 (1) 1 (1) 4 (1) -4 (1) C (2) 43 (1) 48 (2) 35 (1) 3 (1) 11 (1) -2 (1) C (3) 52 (2) 49 (2) 46 (2) 3 (1) 5 (1) 6 (1) C (4) 52 (2) 52 (2) 61 (2) 6 (1) 7 (1) 6 (1) C (5) 45 (2) 69 (2) 56 (2) 14 (2) 5 (1) 7 (1) C (6) 46 (2) 72 (2) 41 (1) 4 (1) 1 (1) -1 (1) C (7) 44 (1) 54 (2) 35 (1) 3 (1) 6 (1) -1 (1) C (8) 48 (2) 63 (2) 35 (1) -4 (1) 0 (1) -9 (1) C (9) 45 (1) 51 (2) 34 (1) -4 (1) 6 (1) -6 (1) C (10) 59 (2) 54 (2) 42 (1) -13 (1) 5 (1) -9 (1) C (11) 62 (2) 43 (2) 52 (2) -11 (1) 7 (1) -2 (1) C (12) 53 (2) 44 (2) 44 (1) -5 (1) 7 (1) 1 (1) C (13) 46 (1) 39 (1) 34 (1) -2 (1) 9 (1) -1 (1) C (14) 45 (1) 43 (1) 28 (1) -1 (1) 9 (1) -6 (1) C (15) 54 (2) 38 (2) 39 (1) 3 (1) 1 (1) 0 (1) C (16) 45 (1) 39 (1) 35 (1) -2 (1) 9 (1) 1 (1) C (17) 44 (1) 51 (2) 42 (1) -2 (1) -1 (1) 3 (1) C (18) 40 (1) 40 (1) 35 (1) -1 (1) 2 (1) 0 (1) C (19) 44 (1) 43 (1) 38 (1) -3 (1) 0 (1) -5 (1) C (20) 49 (2) 52 (2) 42 (1) 1 (1) 4 (1) 0 (1) C (21) 50 (2) 61 (2) 44 (1) -4 (1) -4 (1) -3 (1) Table 6: Hydrogen Coordinates [× 10 ⁴ ] and Isotropic Displacement Parameters in [Å ² × 10 ³ ] of 19. atom x y z U (eq) H (3) 8204 (3) -2256 (2) 10016 (2) 59 H (4) 9977 (3) -3408 (3) 10868 (2) 67 H (5) 11557 (3) -2385 (3) 11942 (2) 69 H (6) 11355 (3) -197 (3) 12145 (2) 65 H (8) 10171 (3) 1877 (3) 11765 (1) 59 H (10) 9049 (3) 4047 (3) 11412 (2) 63 H (11) 7322 (3) 5309 (3) 10594 (2) 63 H (12) 5676 (3) 4356 (2) 9521 (1) 57 H (17A) 3224 (3) 2851 (2) 7445 (1) 56 H (17B) 2445 (3) 2029 (2) 8030 (1) 56 H (19A) 3482 (3) -263 (2) 8435 (1) 52 H (19B) 4799 (3) -780 (2) 8045 (1) 52 H (20A) 4894 (5) 1753 (11) 6651 (5) 58 H (20B) 5554 (10) 370 (3) 6931 (7) 58 H (20C) 6004 (7) 1601 (13) 7483 (3) 58 H (21A) 2307 (11) 921 (7) 6483 (5) 64 H (21B) 1806 (7) 152 (14) 7192 (3) 64 H (21C) 2952 (6) -481 (8) 6722 (7) 64

Amidine from anthracene-1,9-dicarboxylic anhydride and o-phenylenediamine (13): 560 mg (2.26 mmol) of anthracene-1,9-dicarboxylic anhydride (3) and 1.56 g (14.4 mmol) of o-phenylenediamine were dissolved in 100 ml of glacial acetic acid under an argon atmosphere Boiled under reflux for 3 h, giving a dark red solution. Subsequently, the solvent was distilled off in a water-jet vacuum and the crude product was chromatographed on silica gel over a 40 cm long column while applying pressure with chloroform. The pure product was obtained as the first fraction. The orange-red fluorescent product fraction was immediately removed from the solvent under an argon atmosphere and the product was predried in an argon stream. Last solvent residues were removed in a fine vacuum. The product was stored under argon in the dark. Recrystallization in chloroform resulted in reddish brown acicular crystals. (If the product is exposed in solution, the dimers 10 and 11, analogous to dimers 16 and 17, which can not be thermally completely converted back into the amidine 13, are formed in part). 260 mg (36%) of bright red, analytically pure powder with orange-red solid-state fluorescence, mp 228 ° C., R _f (silica gel, CHCl ₃ ) = 0.75, IR (KBr): ṽ = 3050 W, 2930 W, 1690 s (C = O ), 1622 m (C = N), 1559 m (C = C), 1532 m (C = C), 1522 m (C = C), 1450 m, 1403 s, 1371 W, 1362 m, 1331 m, 1299 w, 1272 m, 1214 m, 1157 w, 1058 w, 878 w, 748 s, 714 m, 442 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 7.51 (m, 2H, aromatic-H) , 7.64 (m, 1H, aromatic-H), 7.76 (m, 1H, aromatic-H), 7.89 (m, 1H, aromatic-H), 7.97 (m, 1H, aromatic-H), 8.09 (d, J = 8.4 Hz, 1H, aromatic H), 8.40 (d, J = 8.4 Hz, 1H, aromatic H), 8.63 (m, 1H, aromatic H), 8.69 (s, 1H, aromatic H), 8.91 (d, J = 7.1 Hz, 1H, aromatic H), 10.64 ppm (d, J = 9.1 Hz, 1H, aromatic H), ¹³ C-NMR (CDCl _3): δ = 114.87, 116.04 (CH), 120.23 (CH), 123.14, 125.32 (CH), 125.48 (CH), 125.71 (CH), 126.35, 126.74 (CH), 127.97 (CH), 129.46 (CH), 129.58, 130.47 (CH), 131.04, 131.48, 132.52, 133.39 (CH), 133.65 (CH), 136.53 (CH), 144.11, 150.10 (C = N), 160.78 ppm (C = O), UV (CH 2 Cl 2 ₃ ): λ _max (1 g ε) = 366 (3,469), 385 (3,535), 461 (3,998), 482 (4,098), 508 nm (3,927), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 554 (0.79), 589 nm (1), fluorescence quantum yield: 48% based on N, N'-di (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide ^[33] with a fluorescence quantum yield of 100%, Solid state fluorescence (bright red powder): λ _max = 607, 680 nm sh, solid state fluorescence (brown-red needles): λ _max = 578, 670 nm, MS (70 eV): m / z (%): 322 (2), 321 (20 ), 320 (100) [M ⁺ ], 319 (12), 292 (3) [M ⁺ - CO], 291 (8), 290 (3), 289 (1), 265 (1), 264 (1 ), 160 (6) [M ^{2 +} ], 146 (10) [M ²⁺ - CO], 145 (10), 133 (1), 132 (2), 131 (2), 118 (2), C ₂₂ H ₁₂ N ₂ O (320.4) Ber. C 82.49, H 3.78, N 8.75; Gef. C 82.52, H 4.08, N 8.66.

Preparation of Aceanthrenis Bisimides (7, 8th)

Aceanthrengrün (7a, 8a): In a pre-heated to 150-155 ° C nickel crucible were successively 30.01 g (454.7 mmol) 85 percent. KOH and at this temperature 6.01 g (24.3 mmol) Aceanthrenchinonoxim (10, 11). During the reaction time of 10-15 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was precisely controlled with an iron / constantan armored thermocouple (if the temperature in the nickel crucible can not be precisely controlled, the reaction is carried out in a tempered at 200-230 ° C oil bath.). The cooled melt was carefully poured into 150 mL dist. Water taken up, with 62.5 mL 30 percent. Acetic acid and 200 mL 30 percent. Hydrogen peroxide solution added, because of the strong foaming immediately distributed on several crystallizing dishes and allowed to stand in the air. After 6 d, the green precipitate was filtered off (G4 frit), with little dist. Washed water and dried at 115 ° C. The dry, finely pulverized crude product was extracted with ethanol for a few days for purification until no red coloration of the effluent alcohol was discernible and then dried at 115.degree. Y. 5.89 g (99% crude product) (Ref. ^[11] 90% crude product). Mp> 300 ° C, R _f (silica gel, CHCl ₃ ) = 0.00 for the main product trans-Aceanthrengrün (7a). R _f (silica gel, CHCl ₃ ) = 0.03 for by-product cis-Aceanthrengrün (8a), IR (KBr): ṽ = 3067 w, 2850 w, 1674 s (C = O), 1655 m (C = O), 1583 w, 1565m, 1534m, 1426m, 1394w, 1371w, 1331w, 1282w, 1259w, 1236w, 1164w, 813w, 775w, 745w, 651w, 591w, 574w, 518 w, 420 w cm ^{-1, 1} H-NMR (CDCl ₃ / F ₃ COOD): δ = 7:49 (t, 2H, J = 6:06 Hz, 6-H, 6'-H cis isomer), 7.63 ( d, 2H, J = 6.74 Hz, 5-H, 5'-H cis isomer), 7.86 (t, 2H, J = 8.08 Hz, 6-H, 6'-H trans isomer), 7.94 (t, 2H, J = 6.74 Hz, 7-H, 7'-H cis isomer), 8.05 (t, 2H, J = 6.74 Hz, 7-H, 7'-H trans isomer), 8.63 (m, 4H, 3-H, 3'-H, 5-H, 5'-H trans isomer), 8.90 (m, 4H, 2-H, 2'-H trans isomer, 3-H, 3'-H cis- Isomer), 9.03 (d, 2H, J = 8.76 Hz, 2-H, 2'-H cis isomer), 9.87 (d, 2H, J = 8.08 Hz, 8-H, 8'-H cis isomer) , 9.99 ppm (d, 2H, J = 9.43 Hz, 8-H, 8'-H trans isomer), UV (DMSO): λ _max (1 g ε) = 285 (4,556), 300 sh (4,497), 419 (3,940), 442 sh (3,901), 578 sh (3,807), 635 (4,100), 691 nm (4,269), fluorescence (DMSO): λ _max = 750 nm., Solid state fluorescence: λ _max = 796 nm, MS (70 eV): m / z (%): 491 (22), 490 (61) [M ⁺ ], 422 (18), 421 (56), 420 ( 12), 419 (13), 373 (10), 352 (11), 350 (13), 349 (10), 348 (11), 247 (22), 222 (12), 217 (11), 194 (19). 24), 178 (13), 176 (18), 175 (15), 174 (22), 173 (20), 172 (10), 168 (10), 167 (10), 165 (19), 161 ( 12), 63 (11), 44 (100), 32 (17), 28 (88), C ₃₂ H ₁₄ N ₂ O _4: calcd 490.0953, Found 490.0967 (MS)...

N, N'-Diethylaceanthrenbisimid (7b): In a preheated to 225-235 ° C nickel crucible were successively 3.90 g (59.1 mmol) 85 percent. KOH and at this temperature 750 mg (2.72 mmol) of N-ethylanthracene-1,9-dicarboximide (6b). During the reaction time of 10 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into 400 mL dist. Dissolved water and for oxidation 1 d air is introduced. The resulting precipitate was filtered through a G4 glass filter crucible, with dist. Washed water and dried at 115 ° C. The crude product was dissolved in chloroform and chromatographed on silica gel with toluene under pressure. By adding tert-butyl methyl ether and chloroform, the product is eluted from the column and extracted with ethanol for 1 week for high purification. Y. 210 mg (28%) of dark green powder and violet crystals, mp> 350 ° C., R _f (silica gel, CHCl ₃ ) = 0.01, R _f (silica gel, CHCl ₃ / n-butanol 40: 1) = 0.32, IR ( KBr): ṽ = 3125 w, 2978 w, 2934 w, 2875 w, 2854 w, 1685 s (C = O), 1648 s (C = O), 1583 w (C = C), 1565 m (C = C ), 1539w (C = C), 1436m, 1432w, 1399w, 1387w, 1375w, 1355w, 1323m, 1279w, 1254w, 1238w, 1106m, 962w, 813m, 774 m, 630 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 1:46 (t, J = 6.8 Hz, 6H, CH _3), 4:37 (q, J = 6.9 Hz, 4H, CH ₂ N), 7.58 (m, 2H, aromatic H), 7.80 (m, 2H, aromatic H), 8.18 (d, J = 7.2 Hz, 2H, aromatic H), 8.32 (d, J = 8.2 Hz, 2H, aromatics -H), 8.56 (d, J = 7.3 Hz, 2H, aromatic H), 9.95 ppm (d, J = 8.8 Hz, 2H, aromatic H), ¹³ C-NMR (CDCl ₃ ): δ = 13.86 ( CH ₃ ), 36.48 (CH ₂ ), 116.27, 124.40, 126.25, 127.36, 127.65, 127.86, 129.23, 130.32, 130.90, 131.57, 133.57, 134.53, 162.98 (C = O), 164.45 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 257 (4,750), 285 (4,562), 299 (4,608), 376 (3,718), 424 (3,847), 543 sh (3,409), 586 sh (3,904), 639 (4,349), 696 nm (4,601), fluorescence (CHCl ₃ ) λ _max = 730 nm, MS (70 eV): m / z (%): 548 (7); 547 (37), 546 (100) [M ⁺ ], 531 (6), 519. (8), 518 (22) [M ⁺ - C ₂ H ₄ ], 504 (5), 503 (6), 491 (6), 490 (19) [M ⁺ - 2 C ₂ H ₄ ], 476 (10), 475 (8), 474 (4), 448 (8), 447 (11), 446 (8), 433 (5), 420 (11), 419 (5), 377 (5), 376 (5), 375 (7), 374 (4), 373 (4), 364 (5), 362 (7), 349 (6), 348 (6), 188 (4), 187 (8), 174 (9), 85 (25), 83 (40), 47 (7), C ₃₆ H ₂₂ N ₂ O ₄ Ber. 546.1580, Gef. 546.1580 (MS), C ₃₆ H ₂₂ N ₂ O ₄ (546.6) Ber. C 79.11, H 4.06, N 5.13; Gef. C 78.00, H 4.61, N 5.05.

N, N'-Dibutylaceanthrenbisimid (7c): In a pre-heated to 225-235 ° C nickel crucible successively 4.05 g (61.4 mmol) 85 percent. KOH and at this temperature 1.00 g (3.30 mmol) of N-butylanthracene-1,9-dicarboximide (6c). During the reaction time of 14 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into 120 mL 10 percent. Hydrogen peroxide solution was added, underlaid with 200 ml of chloroform and stirred gently for 20 min, so that the phase boundary between the cherry red, aqueous phase and the deep green chloroform phase remains visible. Subsequently, the organ. Phase separated and the aqueous two more times with chloroform - as described - treated. The united organ. Phases are treated with dist. Shaken out water and freed from the solvent. Methanol is added to the distillation residue, filtered through an extraction sleeve and extracted with methanol until the extract is colorless. It was then extracted rapidly with chloroform, the chloroform extract was concentrated and chromatographed on silica gel under pressure with chloroform. By addition of ethyl acetate, the product was eluted from the column and extracted for high purification again 1-3 d with methanol. Y. 110 mg (11%) analytically pure dark green powder, mp> 350 ° C., R _f (silica gel, CHCl ₃ ) = 0.16, IR (KBr): ṽ = 2962 m, 2932 W, 2871 W, 1683 s (C = O ), 1644s (C = O), 1583m (C = C), 1567s (C = C), 1538m (C = C), 1438w, 1435m, 1401w, 1389m, 1344w, 1326 m, w 1198, 1112 m, 812 m, 773 m, 730 w, 574 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 1:06 (t, J = 7.3 Hz, 6H, CH _3), 1:53 (m, 4H, CH ₂ CH ₃ ), 1.83 (m, 4H, CH ₂ CH ₂ N), 4.28 (m, 4H, CH ₂ N), 7.56 (m, 2H, aromatic-H), 7.77 (m, 2H, aromatic H), 8.14 (d, J = 7.8 Hz, 2H, aromatic H), 8.28 (d, J = 8.6 Hz, 2H, aromatic H), 8.54 (d, J = 7.8 Hz, 2H, aromatics-H), 9.92 ppm (d, J = 8.8 Hz, 2H, aromatic-H), ¹³ C-NMR (CDCl _3): δ = 14:34 (CH _3), 21:00 _(CH2), 30.68 (CH ₂₎ , 41.22 (CH ₂ N), 116.17, 122.41, 124.33, 127.14, 127.52, 127.86, 129.19, 130.04, 130.84, 130.91, 131.46, 133.36, 133.47, 134.24, 163.11 (C = O), 164.53 ppm (C = O) , UV (CHCl ₃ ): λ _max (1 g ε) = 258 (4,807), 287 (4,610), 300 (4,666), 372 sh (3,719), 423 (3,875), 583 sh (3,928), 640 (4,426), 696 nm (4,678), fluorescence (CHCl ₃₎ λ _max = 740 nm, MS (70 eV): m / z (%): 604 (10), 603 (44), 602 (100) [M ⁺ ] 586 (9), 585 (20) [M ⁺ - OH], 547 (9), 546 (10) [M ⁺ - C ₄ H ₈ ], 529 (8) [546 - OH], 505 (5 ), 504 (12), 503 (3) [M ⁺ - C ₄ H ₉ NCO], 491 (12), 490 (20) [M ⁺ - 2 C ₄ H ₈ ], 420 (7), 419 (7 ), 374 (5), 373 (5), 348 (5), C ₄₀ H ₃₀ N ₂ O ₄ (602.7) Ber. C 79.72, H 5.02, N 4.65; Gef. C 79.86, H 5.08, N 4.79.

N, N'-dipentylaceticthrene-bisimide (7d): Into a nickel crucible preheated to 225-235 ° C were successively added 21.12 g (340 mmol) of 85 percent by weight. KOH and at this temperature 4.92 g (15.5 mmol) of N-pentylanthracene-1,9-dicarboximide (6d). During the reaction time of 10-15 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into 200 mL 10 percent strength. Hydrogen peroxide solution was added, underlaid with 300 ml of chloroform and stirred gently for 20 min, so that the phase boundary between the cherry red, aqueous phase and the deep green chloroform phase remains visible. The organic phase was then separated and the aqueous was treated twice more with chloroform as described. The combined organic phases were washed with dist. Shaken out water and freed from the solvent. Methanol was added to the distillation residue, filtered through an extraction sleeve and extracted with methanol until the extract was colorless. It was then extracted rapidly with chloroform, the chloroform extract was concentrated and chromatographed on silica gel under pressure with chloroform. By addition of ethyl acetate, the product was eluted from the column and extracted for high purification again 1-3 d with methanol. Y. 1.09 g (22%) analytically pure turquoise-green powder, mp 345-348 ° C, R _f (silica gel, CHCl ₃ ) = 0.18, IR (KBr): ṽ = 3070 W, 2957 m, 2931 W, 2870 W, 1685 s (C = O), 1647s (C = O), 1583w (C = C), 1568m (C = C), 1539m (C = C), 1434m, 1421w, 1388m, 1343w, 1326 m, 1256 w, 1238 w, 1192 w, 1111 m, 812 m, 773 m, 730 w, 575 w, 430 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.97 (t, J = 7.0 Hz, 6H, CH ₃ ), 1.47 [m, 8H, (CH ₂ ) ₂ CH ₃ ], 1.84 (quint, J = 7.3 Hz, 4H, CH ₂ CH ₂ N), 4.29 (m, 4H, CH ₂ N), 7.59 (m, 2H, aromatic H), 7.79 (m, 2H, aromatic H), 8.19 (d, J = 7.8 Hz, 2H, aromatic H), 8.34 (d, J = 8.6 Hz, aromatic H 2H,), 8:58 (d, J = 7.8 Hz, 2H, aromatic-H), 9.94 ppm (d, J = 8.7 Hz, 2H, aromatic-H), ¹³ C-NMR _(CDCl3): δ = 14.10 (CH ₃ ), 22.54 (CH ₂ ), 27.90 (CH ₂ ), 29.46 (CH ₂ ), 41.02 (CH ₂ N), 115.89, 122.09, 124.06, 126.87, 127.26, 127.51, 128.82, 129.81, 130.47, 130.62, 131.15, 133.12, 133.25, 133.96, 162.78 (C = O), 164.21 ppm (C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 256 (4,805), 286 (4,624 ), 300 (4,662), 361 sh (3,791), 376 (3,851), 422 (3,937), 495 (3,323), 532 (3,541), 585 sh (3,995), 639 (4,423), 696 nm (4,672), Fluorescence (CHCl ₃ ) λ _max = 738 nm, solid state fluorescence λ _max = 791 nm, MS (70 eV): m / z (%): 632 (11), 631 (45), 630 (100) [M ⁺ ], 614 (5), 613 (11) [M - OH], 562 (5), 561 (13), 560 (8) [M ⁺ - C ₅ H ₁₀ ], 543 (3) [560 - OH], 505 (5), 504 (10), 492 (6), 491 (13), 490 (17) [M ⁺ -2 C ₅ H ₁₀ ], 445 (3) [490 - CO - OH], 420 (6) , 419 (5) [560 - C ₅ H ₁₁ NCO - CO], 376 (2) [M ⁺ - 2 C ₅ H ₁₁ NCO - CO], 375 (4), 374 (4), 373 (4), 362 (3), 349 (4), 348 (3), C ₄₂ H ₃₄ N ₂ O ₄ (630.7) Ber. C 79.98, H 5.43, N 4.44; Gef. C 80.07, H 5.52, N 4.28.

N, N'-Dihexylaceanthrenbisimid (7e): In a pre-heated to 225-235 ° C nickel crucible were successively 5.00 g (75.7 mmol) 85 percent. KOH and at this temperature 1.26 g (3.80 mmol) of N-hexylanthracene-1,9-dicarboximide (6e). During the reaction time of 10-15 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into 90 mL 10 percent strength. Hydrogen peroxide solution was added, underlaid with 200 ml of chloroform and stirred gently for 20 min, so that the phase boundary between the cherry red, aqueous phase and the deep green chloroform phase remained visible. The organic phase was then separated and the aqueous was treated twice more with chloroform as described. The combined organic phases were washed with dist. Shaken out water and freed from the solvent. Methanol is added to the distillation residue, filtered through an extraction sleeve and extracted with methanol until the extract is colorless. It was then extracted rapidly with chloroform, the chloroform extract was concentrated and chloroform on silica gel under pressure chro matographiert. By addition of ethyl acetate, the product was eluted from the column and extracted for high purification again 1-3 d with methanol. Y. 200 mg (16%) of analytically pure green powder, mp 325-327 ° C, R _f (silica gel, CHCl ₃ ) = 0.19, R _f (silica gel, CHCl ₃ / n-butanol 40: 1) = 0.66, IR (KBr ): ṽ = 3122w, 3045w, 2955m, 2929m, 2857m, 1685s (C = O), 1647s (C = O), 1583m (C = C), 1565s (C = C) , 1539 m (C = C), 1433 m, 1420 m, 1400 W, 1386 m, 1343 m, 1325 m, 1255 W, 1236 W, 1187 W, 1112 m, 883 W, 812 m, 773 m, 728 m , 574 cm ^-1 m, ¹ H-NMR (CDCl _3): δ = 0.94 (t, J = 6.9 Hz, 6H, CH _3), 1:46 [m, 12H, (CH _{2) 3} CH _3], 1.82 ( m, 4H, CH ₂ CH ₂ N), 4.22 (t, J = 7.6Hz, 4H, CH ₂ N), 7.42 (m, 2H, aromatic-H), 7.69 (m, 2H, aromatic-H), 7.90 (d, J = 7.8Hz, 2H, aromatic H), 8.03 (d, J = 8.6Hz, 2H, aromatic H), 8.34 (d, J = 7.8Hz, 2H, aromatic-H), 9.81ppm (d, J = 8.8 Hz, 2H, aromatic H), ¹³ C-NMR (CDCl ₃ ): δ = 14.54 (CH ₃ ), 23.10 (CH ₂ ), 27.44 (CH ₂ ), 28.52 (CH ₂ ), 32.05 (CH ₂ ), 41.46 (CH ₂ N), 115.91, 122.22, 123.99, 126.82, 127.16, 127.77, 129.09, 129.63, 130.63, 130.70, 131.21, 132.97, 133.97, 162.88 (C = O), 164.30 ppm ( C = O), UV (CHCl ₃ ): λ _max (1 g ε) = 257 (4,790), 286 (4,593), 300 (4,651), 360 sh (3,649), 376 (3,652), 422 (3,836), 585 sh (3,933), 639 (4,421), 696 nm (4,676), fluorescence (CHCl ₃ ): λ _max = 736 nm, MS (70 eV): m / z (%): 660 (13), 659 (48 ), 658 (100) [M ⁺ ], 642 (9), 641 (10) [M - OH], 588 (4), 576 (8), 575 (19), 574 (8) [M ⁺ - C ₆ H ₁₂ ], 505 (7), 504 (11), 492 (8), 491 (16), 490 (17) [M ⁺ - 2 C ₆ H ₁₂ ], 446 (3), 445 (4), 432 (4), 421 (4), 420 (7), 419 (6), 375 (4), 374 (5), 373 (4), 349 (4), 348 (4), 174 (3), C ₄₄ H ₃₈ N ₂ O ₄ (658.8) Ber. C 80.22, H 5.81, N 4.25; Gef. C 80.41, H 6.03, N 4.31.

N, N'-Dinonylaceanthrenbisimid (71): In a preheated to 225-235 ° C nickel crucible were successively 6.00 g (90.0 mmol) 85 percent. KOH and at this temperature 250 mg (0.67 mmol) of N-nonylanthracene-1,9-dicarboximide (6f). During the reaction time of 10 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into 60 mL 10 percent strength. Hydrogen peroxide solution was added, underlaid with 200 ml of chloroform and stirred gently for 20 min, so that the phase boundary between the cherry red, aqueous phase and the deep green chloroform phase remains visible. The organic phase was then separated and the aqueous was treated twice more with chloroform as described. The combined organic phases were washed with dist. Shaken out water and freed from the solvent. Methanol was added to the distillation residue, filtered through an extraction sleeve and extracted with methanol until the extract was colorless. It was then extracted rapidly with chloroform, the chloroform extract was concentrated and chromatographed on silica gel under pressure with chloroform. For high purification, the product was extracted again with methanol for 2 d. Y. 17.8 mg (7%) analytically pure dark green powder, mp 293-295 ° C, R _f (silica gel, CHCl ₃ ) = 0.32, R _f (silica gel, CHCl ₃ / n-butanol 40: 1) = 0.75, IR (KBr ): ṽ = 3122w, 3084w, 3040w, 2955m, 2923s, 2854s, 1687s (C = O), 1644s (C = O), 1583m (C = C), 1567s (C = C), 1538 m (C = C), 1467 m, 1433 s, 1400 m, 1388 m, 1356 m, 1341 m, 1326 m, 1278 m, 1252 m, 1234 m, 1183 W, 1154 W, 1114 s , 1077 w, 880 w, 812 s, 772 s, 725 m, 655 w, 637 w, 573 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.88 (t, J = 6.4 Hz, 6H, CH ₃ ), 1.36 [m, 24H, (CH ₂ ) ₆ CH ₃ ], 1.83 (quint, J = 7.0 Hz, 4H, CH ₂ CH ₂ N), 4.24 (t, J = 7.4 Hz, 4H, CH ₂ N), 7.47 (m, 2H, aromatic H), 7.72 (m, 2H, aromatic H), 7.98 (d, J = 7.8 Hz, 2H, aromatic H), 8.11 (d, J = 8.6 Hz, aromatic H 2H,), 8.40 (d, J = 7.8 Hz, 2H, aromatic-H), 9.84 ppm (d, J = 8.9 Hz, 2H, aromatic-H), ¹³ C-NMR _(CDCl3): δ = 14.54 (CH ₃ ), 23.11 (CH ₂ ), 27.81 (CH ₂ ), 28.62 (CH ₂ ), 29.74 (CH ₂ ), 29.89 (CH ₂ ), 30.06 (CH ₂ ), 32.32 (CH ₂ ), 41.48 (CH ₂ N), 116.01, 12 2.30 124.12, 126.94, 127.29, 127.81, 129.12, 129.77, 130.74, 131.29, 133.12, 133.17, 134.06, 162.95 (C = O), 164.38 ppm (C = O), UV (CHCl _3): λ _max (1 g ε) = 258 (4,783), 287 (4,582), 301 (4,633), 371 sh (3,660), 425 (3,834), 584 sh (3,905), 640 (4,404), 696 nm (4,660), fluorescence (CHCl ₃ λ _max = 736 nm, MS (70 eV): m / z (%): 745 (3), 744 (15), 743 (58), 742 (100) [M ⁺ ], 726 (5), 725 (10) [M ⁺ - OH], 630 (4), 629 (4), 618 (11), 617 (22), 616 (6) [M ⁺ - C ₉ H ₁₈ ], 599 (2) 505 (6), 504 (9), 503 (4), 493 (3), 492 (9), 491 (18), 490 (13) [M ⁺ - 2 C ₉ H ₁₈ ], 446 (3) 445 (3), 432 (4), 421 (4), 420 (7), 419 (5), 375 (3), 374 (4), 349 (3), 174 (4), 173 (5), 83 (3), 57 (3), 55 (6), C ₅₀ H ₅₀ N ₂ O ₄ (743.0) Ber. C, 80.83, H, 6.78, N, 3.77; Gef. C 81.07, H 7.03, N 3.75.

N, N'-di- (1-hexylheptyl) acetic acid bisimide (7g): In a pre-heated to 238-240 ° C nickel crucible were successively 10.25 g (155.3 mmol) 85 percent. KOH and at this temperature 70 mg (0.16 mmol) of N- (1-hexylheptyl) anthracene-1,9-dicarboximide (6 g). During the reaction time of 1 h 50 minutes, the mixture was stirred efficiently with a stainless steel paddle stirrer for 20 minutes and the reaction temperature in the crucible was accurately controlled with an iron / constantan armored thermocouple. The cooled melt was carefully poured into a mixture of dist. Dissolved water, methanol and ethanol and for the oxidation 1 d air was introduced. The resulting precipitate was filtered off (G4 glass filter crucible) and taken up in a mixture of methanol and petroleum ether. The green petroleum ether phase was separated off, extracted with methanol, freed from the solvent and chromatographed on silica gel with n-hexane / toluene 1: 1. Y. 3.2 mg (5%) bright green, translucent highly viscous oil, R _f (silica gel, toluene / n-hexane 1: 1) = 0.42, IR (film): ṽ = 2955 m, 2925 s, 2856 m, 1691 s (C = O), 1652s (C = O), 1567m (C = C), 1539m (C = C), 1456w, 1421m, 1388w, 1377w, 1344w, 1323m, 1279w , 1227 w, 1162 w, 1117 w, 884 w, 813 m, 774 m, 730 m, 668 w cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.81 (t, J = 7.0 Hz, 12H, CH ₃ ), 1.30 [m, 32H, (CH ₂ ) ₄ CH ₃ ], 1.94 [m, 4H, (CH ₂ ) CHN], 2.35 [m, 4H, (CH ₂ ) CHN], 5.33 [m, 2H, (CH ₂ ) ₂ CHN], 7.79 (m, 2H, aromatic H), 7.90 (m, 2H, aromatic H), 8.55 (d, J = 7.8 Hz, 2H, aromatic H), 8.77 (d, J = 8.9 Hz, 2H, aromatic H), 8.86 (d, J = 7.8 Hz, 2H, aromatic H), 10.00 ppm (d, J = 9.1 Hz aromatic H, 2H,), ¹³ C-NMR (CDCl _3): δ = 14.3 (CH _3), 22:59 _(CH2), 27.02 _(CH2), 29.27 _(CH2), 31.78 _(CH2), 32.61 (CH ₂ ), 45.78 (NCHR ₂ ), 113.37, 124.70, 127.60, 127.77, 127.98, 128.84, 130.46, 130.79, 130.96, 132.75, 133.64, 134.51 ppm, UV (CHCl ₃ ): λ _max = 257, 286, 301 , 364 sh, 385 sh, 423, 580 sh, 638, 694 nm, fluorescence (CHCl ₃ ): λ _max = 729 nm, MS (70 eV): m / z (%): 857 (5), 856 (21 ), 855 (64), 854 (100) [M ⁺ ], 838 (3), 837 (4) [M ⁺ - OH], 769 (2), 675 (4), 674 (13), 673 (22 ), 672 (17) [M ⁺ - C ₁₃ H ₂₆ ], 656 (3), 655 (4), 588 (3), 504 (4), 503 (6), 494 (3), 493 (11) , 492 (33), 491 (55), 490 (57) [M ⁺ - 2 C ₁₃ H ₂₆ ], 489 (3), 475 (4), 474 (6), 473 (5), 446 (6) , 445 (10), 444 (3), 421 (7), 420 (14), 419 (7), 375 (4), 374 (6), 37 3 (5), 349 (3), 173 (3), 167 (3), 149 (8), 125 (3), 111 (6), 97 (11), 83 (13), 71 (12), 69 (19), 57 (20), 56 (11), 55 (27), C ₅₈ H ₆₆ N ₂ O ₄ : Ber. 854.5023, Gef. 854.5046 (MS).

Attempts to Hydrolysis of Aceanthrenbisimide (7, 8):

attempt for the acidic hydrolysis of acetic acid green (7a, 8a): 160 mg (0.33 mmol) Aceanthrengrün (7a, 8a) were mixed with 30 mL conc. Sulfuric acid added. The dark brown solution was stirred for 3 h at 120 ° C, after cooling with 200 mL dist. Water diluted and the brown, microcrystalline Solid filtered through a glass frit G5. The rainfall was with little dist. Washed water and dried at 115 ° C. UV / Vis and MS spectroscopic examination of the reaction product resulted in complete degradation of the aceanthren scaffold. A TLC study (silica gel / chloroform) indicated complete Decomposition.

tries for alkaline hydrolysis of Aceanthrengrüns (7a, 8a): 170 mg (0.35 mmol) Aceanthrengrün (7a, 8a) were in 50 mL tert-butanol slurried and heated. One gave 1.06 g (16.0 mmol) 85 percent. KOH, allowed to reflux for 2 h boiled and hydrolyzed with the addition of glacial acetic acid and conc. HCl. The mixture was washed with dist. Water to 100 mL, the solid filtered off (G4), with dist. Water washed and at Dried 115 ° C. An IR, MS, UV / Vis spectroscopic Examination of the isolated material and a thin-layer chromatographic Comparison revealed that the starting material recovered had been.

Attempts to N-alkylate the acetic acid green (7a, 8a): 110 mg (0.22 mmol) Aceanthrengrün (3a, 4a), 1.00 g (5.64 mmol) potassium carbonate and 1.06 mL (6.72 mmol) 1-bromoheptane were dissolved in 10 mL DMF ( dried over molecular sieve 4 Å) under reflux for 24 h. Subsequently, the solution appearing green-violet in 10 mL dest. Water, acidified with 2 N HCl and stirred for 45 min at room temperature. The dark brown organic phase was separated from the aqueous with 100 ml of chloroform, washed with dist. Washed water and concentrated. By thin layer chromatography only traces of emerald green product (R _f (silica gel; CHCl ₃ ) = 0.47) could be detected. Since the by-products were very numerous (at least 14), this synthetic route is less promising.

Reactions of the N, N'-dialkylacetonated bisimides (7) with alkali

tries for the reaction of 7 with KOH in tert-butanol: 3 mg (about 0.05 mmol) N, N'-dialkylacetonated bisimide (7b, c, d, e) was dissolved in 60 mL tert-butanol boiled under argon atmosphere under reflux for 2 h. After addition of 1.00 g (15.2 mmol) 85 percent. potassium hydroxide The green solution immediately turned violet. The reaction mixture was refluxed for an additional 10 minutes to 50 minutes. By addition of glacial acetic acid / 2N HCl 2: 1, glacial acetic acid, 50 percent. acetic acid or acetic anhydride, the reaction mixture was acidified and thus the saponification reaction stopped. The obtained dark green Precipitate was filtered through a glass frit G4, with dist. Washed water and dried at 115 ° C. To IR, DC and MS studies returned only the starting material Service.

tries for the reaction of 7 with KOH in tert-butanol / DMSO: per 100 mg (ca. 0.16 mmol) of N, N'-dialkylacetonated bisimide (7b, c, d, e) were prepared in Individual batches in each case in 15 mL DMSO and 15 mL tert-butanol under Argonatmospäre boiled under reflux for 2 h. After addition of 120 mg (1.82 mmol) 85 percent. potassium hydroxide the deep dark green solution stained each immediately violet. The reaction mixture was stirred for a further 10 min boiled under reflux for 50 min. By addition of glacial acetic acid / 2 N HCl 2: 1, glacial acetic acid, 50 percent. Acetic acid or acetic anhydride The reaction mixture was acidified and thus the saponification reaction canceled. The resulting dark green precipitate was over a glass frit G4 filtered off, with dist. Water washed and at Dried 115 ° C. In all cases, IR, DC and MS assays recover the starting materials Service.

Methylation of the Violet Intermediate from 7d and KOH in tert-Butanol / DMSO: 160 mg (0.25 mmol) of N, N'-dipentylaceticthrene-bisimide (7d) were dissolved in 25 mL DMSO and 25 mL tert-butanol at 130 ° C oil bath temperature. After addition of 170 mg (2.57 mmol) of potassium hydroxide powder (85 percent), the color of the solution immediately changed from green to violet. The violet-colored solution was boiled under reflux for 1 h and then the solvent was removed on a rotary evaporator in a water-jet vacuum. The distillation residue was admixed with 13 mL (208 mmol) of methyl iodide and stirred overnight. After stripping off the excess methyl iodide, the red-brown residue was chromatographed on silica gel under pressure with chloroform. Y. 14 mg (9%) bright orange crystals with high solid-state fluorescence, mp 132-135 ° C, R _f (silica gel; CHCl ₃ ) 0.65, IR (KBr): ṽ = 2958 m, 2929 m, 2859 w, 1723 s ( C = O), 1678 s (C = O), 1626 m (C = C), 1449 m, 1432 m, 1386 m, 1360 s, 1334 m, 1291 W, 1258 W, 1229 W, 1207 W, 1178 W , 1107 m, 1079 w, 851 w, 766 m, 745 m cm ^{-1, 1} H-NMR (CDCl _3): δ = 0.90 (t, J = 6.9 Hz, 6H, CH _3), 1:37 [m, 8H , (CH ₂ ) ₂ ], 1.66 (m, 4H, CH ₂ CH ₂ N), 1.72 (s, 6H, CH ₃ ), 4.03 (m, 4H, CH ₂ N), 7.19 (d, J = 7.9 Hz , 2H, aromatic H), 7.59 (d of t, J _t = 7.4 Hz, J _d = 1.3 Hz, 2H, aromatic H), 7.71 (m, 2H, aromatic H), 7.79 (dd, J ₁ = 7.7 Hz, J ₂ = 1.5 Hz, 2H, aromatic H), 8.14 (d, J = 7.7 Hz, 2H, aromatic H), 8.75 ppm (dd, J ₁ = 8.2 Hz, J ₂ = 1.0 Hz, aromatic H 2H,), ¹³ C-NMR (CDCl _3): δ = 13.98 (CH _3), 22:38 _(CH2), 27.77 _(CH2), 29.18 _(CH2), 40.65 _(CH3), 41.69 ( CH ₂ N), 45.33 C _quaternary , 122.56 (CH), 124.32, 124.96, 128.01 (CH), 129.31 (CH), 130.40 (CH), 130.58 (CH), 130.68 (CH), 13 3.84, 134.78, 137.64, 144.38, 163.50 (C = O), 173.95 ppm (C = O), UV (CHCl _3): λ _max (1 g ε) = 256 (4,504), 267 sh (4,495), 351 ( 3,802), 378 sh (3,436), 447 (2,433), 474 nm (2,509), fluorescence (CHCl ₃ ): λ _max (I _rel ) = 511 sh (0.80), 543 nm (1), fluorescence quantum yield: 27% on tetramethylperylene-3,4: 9,10-tetracarboxylic acid ester ^[33] with a fluorescence quantum yield of 100%, solid-state fluorescence: λ _max (I _rel ) = 555 (1), 584 nm sh (0.83), MS (70 eV): m / z (%): 662 (13), 661 (46), 660 (92) [M ⁺ ], 647 (11), 646 (46), 645 (100) [M ⁺ - CH ₃ ], 631 (6 ), 630 (13), 548 (6), 547 (14) [M ⁺ - C ₅ H ₁₁ NCO], 534 (6), 533 (26), 532 (65) [M ⁺ - C ₅ H ₁₁ NCO -CH ₃ ], 505 (8), 504 (19) [532-CO], 435 (13), 434 (14) [M ⁺ - 2 C ₅ H ₁₁ NCO], 363 (6), 217 (49) [434-217], 189 (27), 182 (20), 181 (16), C ₄₄ H ₄₀ N ₂ O ₄ : Ber. 660,298, Gef. 660,291 (MS), C ₄₄ H ₄₀ N ₂ O ₄ (660.8) Ber. C 79.98, H 6.10, Gef. C 76.84, H 6.17.

• [1] D. S. Alberts, R. T. Dorr, W. A. Remers, S. M. Sami (Research Corp. Technologies, Inc., USA) PCT Int. Appl. WO 9200281 (1.1.1992); Chem. Abstr. 1992, 116, 214369.
• [2] S. M. Sami, R. T. Dorr, D. S. Alberts, W. A. Remers, J. Med. Chem. 1993, 36, 765–770.
• [3] S. M. Sami, R. T. Dorr, A. M. Solyom, D. S. Alberts, W. A. Remers, J. Med. Chem. 1995, 38, 983–993.
• [4] S. M. Sami, R. T. Dorr, A. M. Solyom, D. S. Alberts, B. S. Iyengar, W. A. Remers, J. Med. Chem. 1996, 39, 1609–1618.
• [5] W. A. Remers, R. T. Dorr, S. M. Sami, D. S. Alberts, S. Bear, C. -A. Mayr, A. M. Solyom, Current Topics in Med. Chem. 1997, 2 45–61; Chem. Abstr. 1998, 130, 104534.
• [6] R. T. Dorr, J. D. Liddil, S. M. Sami, W. Remers, E. M. Hersh, D. S. Alberts, Anti-Cancer Drugs 2001, 12, 213–220; Chem. Abstr. 2001, 135, 70842.
• [7] R. P. Verma, C. Hansch, Mol. Pharm. 2006), 3, 441–450; Chem. Abstr. 2006, 145, 957948.
• [8] N. Habib, (Nabil Habib Lab, Lebanon; Vianova Labs, Inc.), PCT Int. Appl. WO 2007064691 (7.6.2007); Chem. Abstr. 2007, 147, 46112.
• [9] E. Van Quaquebeke, J. Tuti, L. Van Den Hove, R. Kiss, F. Darro (Unibioscreen S. A., Belg.), PCT Int. Appl. WO 2007054292 (18.5.2007); Chem. Abstr. 2007, 146, 521689.
• [10] R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. – Bundesminist. Forsch. Technol., Technol. Forsch. Entwickl. 1984, BMFT-FB-T 84-164, ISSN: 0340–7608; Chem. Abstr. 1985, 102, 150903.
• [11] M. Kardos, Dissertation, Universität Berlin 1913, 26.
• [12] M. Kardos, Ber. Dtsch. Chem. Ges. 1913, 46, 2086–2091; Chem. Abstr. 1913, 7, 23197.
• [13] C. Liebermann, M. Kardos, Ber. dtsch. chem. Ges. 1914, 47, 1203–1210.
• [14] M. Kardos, Friedländers Fortschritte der Teerfarbenfabrikation 1914–1916, 12, 485–492.
• [15] A. M. Richter, R. Ackermann, IS&T's International Congress on Advances in Non-Impact Printing Technologies, 10th, New Orleans, Oct. 30-Nov. 4, 1994 1994, 246–248; Chem. Abstr. 1995, 124, 131261.
• [16] T. Sakamoto, Y. Yonehara, S. Boku, Jpn. Kokai Tokkyo Koho JP 11029499 (2.2.1999); Chem. Abstr. 1999, 130, 53479.
• [17] D. Désilets, P. M. Kazmaier, R. A. Burt, G. K. Hamer, Can. J. Chem. 1995, 73, 325–335.
• [18] C. Liebermann, M. Zsuffa, Ber. dtsch. chem. Ges. 1911, 44, 202–209.
• [19] E. D. Bergmann, R. Ikan, J. Org. Chem. 1958, 23, 907–908.
• [20] M. M. Sidky, F. H. Osman, J. Prakt. Chem. 1973, 315, 881–886.
• [21] E. Klingsberg, C. E. Lewis, J. Org. Chem. 1975, 40, 366–368.
• [22] T. K. Bandyopadhyay, A. J. Bhattacharya, Indian J. Chem. 1982 Sect. B, 21B, 91–94.
• [23] S. Mondal, T. K. Bandyopadhyay, A. J. Bhattacharya, Curr. Sci. 1985, 54, 455–458.
• [24] S. J. Chang, B. K. Ravi Shankar, H. Shechter, J. Org. Chem. 1982, 47, 4226–4234.
• [25] V. Enchev, G. Ivanova, A. Ugrinov, G. D. Neykov, Journ. Mol. Struc. 1999, 508, 149–161; Chem. Abstr. 1999, 131, 350907.
• [26] L. G. Donaruma, W. Z. Held, Org. Reactions 1960, 11, 1.
• [27] H. Langhals, Chem. Ber. 1985, 118, 4641-4645.
• [28] K. Gollnick, G. O. Schenck in Organic Chemistry Vol. 8, 1,4-Cycloaddition Reaktions (Ed.: J. Hamer), Academic Press, New York, London, 1967, 255–337.
• [29] R. Calas, R. Lalande, Bull. Soc. Chim. France 1959, 763–770.
• [30] R. M. Hochstrasser, G. B. Porter, Quart. Rev. (London) 1960, 14, 146–173.
• [31] R. Hoffmann, R. B. Woodward, J. Am. Chem. Soc. 1965, 87, 2046–2048.
• [32] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529–535.
• [33] H. Langhals, J. Karolin, L. B. -Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919–2922.

Methylation of the Violet Intermediate from 7d and KOH in: DMSO: 160 mg (0.25 mmol) of N, N'-dipentylaceticthrene-bisimide (7d) were boiled under reflux for 1 h in 25 mL DMSO under an argon atmosphere and thus completely dissolved. After addition of 170 mg (2.57 mmol) of potassium hydroxide powder (85 percent), the color of the solution changed from green to violet. The violet-colored solution was stirred for 10 min at 150 ° C oil bath temperature, the solvent removed on a rotary evaporator under water pump vacuum and the distillation residue with 13 mL (208 mmol) of methyl iodide. After removal of the excess methyl iodide 24 h later, the red-brown residue was chromatographed under pressure with chloroform on silica gel. DC and MS spectra of the methylated orange-red compound were identical to those of the previously described experiment in tert-butanol / DMSO; Characterization of the reaction product see there.

• [1] DS Alberts, RT Dorr, WA Remers, SM Sami (Research Corp. Technologies, Inc., USA) PCT Int. Appl. WO 9200281 (1.1.1992); Chem. Abstr. 1992, 116, 214369.
• [2] SM Sami, RT Dorr, DS Alberts, WA Remers, J. Med. Chem. 1993, 36, 765-770.
• [3] SM Sami, RT Dorr, AM Solyom, DS Alberts, WA Remers, J. Med. Chem. 1995, 38, 983-993.
• [4] SM Sami, RT Dorr, AM Solyom, DS Alberts, BS Iyengar, WA Remers, J. Med. Chem. 1996, 39, 1609-1618.
• [5] WA Remers, RT Dorr, SM Sami, DS Alberts, S. Bear, C. -A. Mayr, AM Solyom, Current Topics in Med. Chem. 1997, 2 45-61; Chem. Abstr. 1998, 130, 104534.
• [6] RT Dorr, JD Liddil, SM Sami, W. Remers, EM Hersh, DS Alberts, Anti-Cancer Drugs 2001, 12, 213-220; Chem. Abstr. 2001, 135, 70842.
• [7] RP Verma, C. Hansch, Mol. Pharm. 2006), 3, 441-450; Chem. Abstr. 2006, 145, 957948.
• [8] N. Habib, (Nabil Habib Lab, Lebanon, Vianova Labs, Inc.), PCT Int. Appl. WO 2007064691 (7.6.2007); Chem. Abstr. 2007, 147, 46112.
• [9] E. Van Quaquebeke, J. Tuti, L. Van Den Hove, R. Kiss, F. Darro (Unibioscreen SA, Belg.), PCT Int. Appl. WO 2007054292 (18.5.2007); Chem. Abstr. 2007, 146, 521689.
• [10] R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Federal Minister. Research. Technol., Technol. Research. Develop. 1984, BMFT-FB-T 84-164, ISSN: 0340-7608; Chem. Abstr. 1985, 102, 150903.
• [11] M. Kardos, Dissertation, University of Berlin 1913, 26.
• [12] M. Kardos, Ber. Dtsch. Chem. Ges. 1913, 46, 2086-2091; Chem. Abstr. 1913, 7, 23197.
• [13] C. Liebermann, M. Kardos, Ber. chem. Ges. 1914, 47, 1203-1210.
• [14] M. Kardos, Friedländer's Progress in Tarpainting 1914-1916, 12, 485-492.
• [15] AM Richter, R. Ackermann, IS &T's International Congress on Advances in Non-Impact Printing Technologies, 10th, New Orleans, Oct. 30 November 4, 1994, 1994, 246-248; Chem. Abstr. 1995, 124, 131261.
• [16] T. Sakamoto, Y. Yonehara, S. Boku, Jpn. Kokai Tokkyo Koho JP 11029499 (2.2.1999); Chem. Abstr. 1999, 130, 53479.
• [17] D. Désilets, PM Kazmaier, RA Burt, GK Hamer, Can. J. Chem. 1995, 73, 325-335.
• [18] C. Liebermann, M. Zsuffa, Ber. chem. Ges. 1911, 44, 202-209.
• [19] ED Bergmann, R. Ikan, J. Org. Chem. 1958, 23, 907-908.
• [20] MM Sidky, FH Osman, J. Prakt. Chem. 1973, 315, 881-886.
• [21] E. Klingsberg, CE Lewis, J. Org. Chem. 1975, 40, 366-368.
• [22] TK Bandyopadhyay, AJ Bhattacharya, Indian J. Chem. 1982 Sect. B, 21B, 91-94.
• [23] S. Mondal, TK Bandyopadhyay, AJ Bhattacharya, Curr. Sci. 1985, 54, 455-458.
• [24] SJ Chang, BK Ravi Shankar, H. Shechter, J. Org. Chem. 1982, 47, 4226-4234.
• [25] V. Enchev, G. Ivanova, A. Ugrinov, GD Neykov, Journ. Mol. Struc. 1999, 508, 149-161; Chem. Abstr. 1999, 131, 350907.
• [26] LG Donaruma, WZ Hero, Org. Reactions 1960, 11, 1.
• [27] H. Langhals, Chem. Ber. 1985, 118, 4641-4645.
• [28] K. Gollnick, GO Schenck in Organic Chemistry Vol. 8, 1,4-Cycloaddition Reaction (Ed .: J. Hamer), Academic Press, New York, London, 1967, 255-337.
• [29] R. Calas, R. Lalande, Bull Soc. Chim. France 1959, 763-770.
• [30] RM Hochstrasser, GB Porter, Quart. Rev. (London) 1960, 14, 146-173.
• [31] R. Hoffmann, RB Woodward, J. Am. Chem. Soc. 1965, 87, 2046-2048.
• [32] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535.
• [33] H. Langhals, J. Karolin, LB-A. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.

Subject of the invention

• 1. anthracenedicarboximides of general formula 18,
  
  in which X represents the radicals ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-nonyl, 1-propylbutyl, 1-butylpentyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 2-ethylphenyl, 2,3-dimethylphenyl, 2,5-di-tert-butylphenyl or 2,6-diisopropylphenyl and in which the radicals R1 to R8 may be the same or different and are each independently hydrogen or linear alkyl radicals having at least one and at most 37 carbon atoms, in which one to 10 CH ₂ units can be replaced independently of one another 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, 2,3-, 2,4-, 2,5-, 2,6 , 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4- , 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2 , 7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 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 a 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 disubs 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 a 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 are 1,2-, 1,3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted Pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1 , 7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 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 the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I.
• 2. anthracenedicarboximides of general formula 19,
  
  in which the radicals R1 to R14 can be identical or independent of one another and the meaning of the radicals R1 to R8 of 1 and the radicals R9 to R14 have the meaning of the test R1 to R6 of FIG.
• 3. anthracenamidinimides of general formula 20,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1.
• 4. Anthracenamidinimides of general formula 21,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1.
• 5. Aceanthrenbisimide the general formula 22,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 14 have the meaning of the radicals R 1 to R 6 of 1.
• 6. dihydroacethrene bisimides of general formula 23,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 16 have the meaning of the radicals R 1 to R 8 of 1.
• 7. bisanthracenedicarboximides of the general formula 24,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radical R 9 has the meaning of the radicals R 1 of 1.
• 8. bisanthracenedicarboximides of the general formula 25,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radical R 9 has the meaning of the radicals R 1 of 1.
• 9. Bisanthracene dicarboxylic acid amidinimides of general formula 26,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1.
• 10. bisanthracene dicarboxylic acid amidinimides of general formula 27,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1.
• 11. bisanthracene dicarboxylic acid amidinimides of general formula 28,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1.
• 12. bisanthracene dicarboxylic acid amidinimides of general formula 29,
  
  in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1.
• 13. A method characterized in that aceanthrenchinone from anthracene and oxalyl chloride with the addition of anhydrous aluminum chloride in carbon disulfide in the molar ratios of 1: 5: 1.5 to 1: 6: 2.5, preferably 1: 5.2: 2.0 is synthesized.
• 14. Method characterized in that for the Synthesis of anthracene-1,9-dicarboxylic acid imide the anthracene-1,9-dicarboxylic anhydride with conc. Ammonia solution is repeatedly evaporated to dryness, two to nine times, preferably three times.
• 15. Process characterized in that anthracene-1,9-dicarboximides from the corresponding primary amines as pure substance and the anthracene-1,9-dicarboxylic anhydride become.
• 16. Process characterized in that anthracene-1,9-dicarboximides from concentrated aqueous solutions of the corresponding primary amines and the anthracene-1,9-dicarboxylic anhydride be synthesized.
• 17. A process characterized in that anthracene-1,9-dicarbonsäureimide from the corresponding primary amines and the anthracene-1,9-dicarboxylic anhydride Use of imidazole can be synthesized. Other additives may be zinc salts such as zinc acetate or zinc chloride.
• 18. Process characterized in that anthracene-1,9-dicarbonsäureimide be synthesized in the absence of light.
• 19. A method characterized in that anthracene-1,9-dicarbonsäureamidinimide from anthracene-1,9-dicarboxylic anhydride and primary Diamines are synthesized, in particular to the exclusion of Light.
• 20. Method characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt as a color generator for Aceanthrengrün dyes is used by the vat on the to be colored Applied object and slowly oxidized to Aceanthrengrün is, preferably by Luftoxidation for
• 21. Method characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt by ascorbic acid or pyridine or by alkylated Pyridines, such as. As 1-, 2-, or 3-methylpyridine or lutidine stabilized becomes.
• 22. Method characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt is hydrogenated using hydrogen peroxide is preferred Hydrogen peroxide in concentrations of 5 to 25% in water, on most preferably 10% hydrogen peroxide.
• 23. Method characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt is oxidized in two-phase systems. Preference is given to systems 10% aqueous hydrogen peroxide and chloroform, preferred with medium stirring.
• 24. Process characterized in that Aceanthrengrün is substituted by the action of alkali, preferably under the action of KOH in tert-butyl alcohol, even with the addition of dipolar aprotic Solvents such as DMSO. Preferred substitution agent is methyl iodide.
• 25. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using Light can be dimerized, preferably light with wavelengths larger as 350 nm, most preferably light larger 360 nm.
• 26. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using Light the line 365 nm of a mercury vapor lamp can be dimerized.
• 27. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using filtered light of a tungsten filament light bulb. Filter solutions of naphthalene-1,8-dicarboxylic acid are preferred or their anhydride, alkali such as KOH or NaOH, and water distilled or deionized water.
• 28. Use of aceanthrenchinone as a fluorescent pigment.
• 29. Use of anthracene-1,9-dicarboxylic anhydride as a fluorescent pigment.
• 30. Use of Aceanthrenchononmonoxim isomer mixture as Fluorescent pigment.
• 31. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides according to 1 to 4 for the generation of fluorescence images, which fade in daylight but can be thermally re-activated; Applications are z. Eg in process control.
• 32. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides of 1 to 4 for producing latent ones Fluorescence images that can be thermally activated; Applications are z. B. at security markings, such. B. against Piracy.
• 33. Use of Aceanthrengrün derivatives, see 5, as fluorescent dyes for the NIR range.
• 34. Use of aceantreen green derivatives, see 5, as solid fluorescent dyes for the NIR range.
• 35. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides according to 1 to 4 for the treatment of tumors, prefers compounds that have been synthesized under exclusion of light are.
• 36. Use of the photodimerization products of anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4, such as. B. 24 to 29 after 7 to 12, for the treatment of tumors.
• 37. Use of the dyes according to 1 to 4 as vat dyes, z. As for the dyeing of textiles, preferably textiles herbal Origin like cotton or else preferably synthetic fibers like polyester or nylon.
• 38. Use of allotropic anthracene-1,9-dicarboxylic acid amidinimides for data storage in the form that the metastable modification is thermally converted into the thermally stable modification.
• 39. Use of the substances according to 1 to 12 as pigments.
• 40. Use of the substances according to 1 to 12 as pigments for Paints and related colors such as watercolor paints and watercolors and colors for inkjet printers paper inks, printing inks, Inks and inks and other colors for painting and writing purposes and in paints.
• 41. Use of the substances according to 1 to 12 as pigments in Paints. Preferred paints are synthetic resin paints such as acrylic or vinyl resins, Polyester lacquers, novolaks, nitrocellulose lacquers (nitro lacquers) or also natural substances such as Zaponlack, shellac or Qi-Lack (Japanlack or Chinese lacquer or East Asian lacquer).
• 42. Use of Dyes 1 to 12 in Data Memories, preferably in optical memories. Examples are systems like the CD or DVD disc.
• 43. Use of the substances according to 1 to 12 as fluorescent dyes.
• 44. Application of the dyes from 1 to 12 for mass staining of polymers. Examples are polyvinyl chloride materials, 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, as well as alkyd resin and Acrylics.
• 45. Application of the dyes according to 1 to 12 as mordant dyes, z. B. for coloring natural products. Examples are paper, Wood, straw, leather, skins or natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax and their Transformation products such. As the viscose, nitrate or Copper rayon (Reyon). Preferred salts for pickling are aluminum, Chromium and iron salts.
• 46. Application of the dyes according to 1 to 12 as a colorant, z. B. for coloring paints, varnishes and other paints, Paper colors, printing inks, inks and other colors for Painting, writing and coloring purposes of all kinds.
• 47. Application of the dyes according to 1 to 12 as nano-pigments in electrophotography: z. B. for Trockenkopiersysteme (Xerox process) and laser printers (non-impact printing).
• 48. Use of the dyes according to 1 to 12 for security marking purposes, being the great chemical and photochemical resistance and possibly also the fluorescence of the substances is of importance. Prefers is this for checks, check cards, banknotes coupons, Documents, identity documents and the like which require a special unmistakable color impression to be achieved.
• 49. Application of the dyes of 1 to 12 as an additive to other colors that achieve a certain shade of color should, are particularly bright shades.
• 50. Application of the dyes of 1 to 12 for marking of objects for machine recognition of these objects the fluorescence, preferred is the machine detection of objects to sort, z. B. also for the recycling of plastics.
• 51. Application of the dyes of 1 to 12 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes.
• 52. Application of the dyes according to 1 to 12 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light.
• 53. Application of the dyes of 1 to 12 in display elements for many display, reference and marking purposes, z. B. passive display elements, information and traffic signs, such as Lights.
• 54. Application of Dyes 1 to 12 in Inkjet Printers as an ink or as a fluorescent ink, in particular as non-water washable ink.
• 55. Application of the dyes according to 1 to 12 as starting material for superconducting organic materials.
• 56. Application of Dyes 1 to 12 for Solid Fluorescent Marking.
• 57. Application of the dyes of 1 to 12 for decorative purposes.
• 58. Application of dyes from 1 to 12 for artistic Purposes.
• 59. Use of the dyes according to 1 to 12 for tracer purposes, z. B. in biochemistry, medicine, technology and science. Here, the dyes can be covalently linked to substrates or via minor valences such as hydrogen bonds or hydrophobic interactions (adsorption).
• 60. Application of the dyes according to 1 to 12 as fluorescent dyes in highly sensitive detection methods.
• 61. Application of the dyes according to 1 to 12 as fluorescent dyes in scintillators.
• 62. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in optical light harvesting systems.
• 63. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in fluorescence solar collectors.
• 64. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in fluorescence-activated displays.
• 65. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in cold light sources for light-induced polymerization for the representation of plastics.
• 66. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes for material testing, eg. B. in the Production of semiconductor circuits.
• 67. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes for the study of integrated microstructures Semiconductor devices.
• 68. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in photoconductors.
• 69. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in photographic processes.
• 70. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in display, illumination or image converter systems, where the excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braun tubes or in fluorescent tubes.
• 71. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. In the form of an epitaxy.
• 72. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in chemiluminescence systems, eg. In chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods.
• 73. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or others graphical products, signage and others Items where a special optical color impression should be achieved.
• 74. Application of the dyes according to 1 to 12 as dyes or Fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams.
• 75. Application of the dyes according to 1 to 12 as dyes in Dye lasers as a Q-switch switch.
• 76. Application of the dyes according to 1 to 12 as active substances for a nonlinear optics, e.g. B. for frequency doubling and the frequency tripling of laser light.
• 77. Application of the dyes according to 1 to 12 for leak testing closed systems.
• 78. Application of the dyes according to 1 to 12 as Rheologieverbesserer.

LIST OF REFERENCE NUMBERS

1 , Synthesis pathway to Aceanthrengün derivatives.

2 , Dimerization of anthracenedicarboximides.

3 , Anthracenamidinimide.

4 , UV / Vis absorption (left) and fluorescence (right) of Chnone 2 in chloroform. Dashed line: fluorescence spectrum of the solid.

5 , UV / Vis absorption (left) and fluorescence spectrum (right) of the oxime isomer mixture 4 and 5 in chloroform. Dashed line: fluorescence spectrum of the solid.

6 , UV / Vis absorption (left) and fluorescence spectrum (right) of the anhydride 3 in chloroform. Dashed line: fluorescence spectrum of the solid.

7 , X-ray crystal structure of anthracenedicarboximide 6d.

8th , UV / Vis absorption (left) and fluorescence spectrum (right) of the anthracenedicarboximide 6b in chloroform. Dashed line: fluorescence spectrum of the solid.

9 , UV / Vis absorption spectrum of the filter solution for irradiation of 6 (1 cm layer thickness).

10 , X-ray crystal structure of amidine imide 12.

11 , UV / Vis absorption and fluorescence spectra of 12 in chloroform (solid line) and solid fluorescence (dashed line compared to 6b (dotted line).

12 , UV / Vis absorption and fluorescence spectra of 13 in chloroform (solid line) and solid fluorescence of the two modifications (dashed lines) compared to 6b (dotted line).

13 , UV / Vis absorption spectra. Left. Anthracene carboxylic acid imide 6g. Middle, dashed: vat from the alkaline melt of 6g. Right: 7g in chloroform.

14 , UV / Vis absorption (left) and fluorescence spectrum (right) of Aceanthrentetracarbonsäurebisimids 7d in chloroform. Dashed line: fluorescence spectrum of the solid.

15 , UV / Vis absorption (left) and fluorescence spectrum (right) of 9d in chloroform. Dashed line: fluorescence spectrum of the solid. 6-11 R a H b C ₂ H ₅ c C ₄ H ₉ d C ₅ H ₁₁ e C ₆ H ₁₃ f C ₉ H ₁₉ G CH (C ₆ H ₁₃ ) ₂ H 2- (C ₂ H ₅ ) C ₆ H ₄ i 2,3- (CH ₃ ) ₂ C ₆ H ₃ j 2.5- (tC ₄ H ₉ ) ₂ C ₆ H ₃

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• WO 9200281 [0063]
• - WO 2007064691 [0063]
• - WO 2007054292 [0063]
• - JP 11029499 [0063]

Cited non-patent literature

• SM Sami, RT Dorr, DS Alberts, WA Remers, J. Med. Chem. 1993, 36, 765-770. [0063]
• SM Sami, RT Dorr, AM Solyom, DS Alberts, WA Remers, J. Med. Chem. 1995, 38, 983-993. [0063]
• SM Sami, RT Dorr, AM Solyom, DS Alberts, BS Iyengar, WA Remers, J. Med. Chem. 1996, 39, 1609-1618. [0063]
• WA Remers, RT Dorr, SM Sami, DS Alberts, S. Bear, C. -A. Mayr, AM Solyom, Current Topics in Med. Chem. 1997, 2 45-61; Chem. Abstr. 1998, 130, 104534. [0063]
• RT Dorr, JD Liddil, SM Sami, W. Remers, EM Hersh, DS Alberts, Anti-Cancer Drugs 2001, 12, 213-220; Chem. Abstr. 2001, 135, 70842. [0063]
• RP Verma, C. Hansch, Mol. Pharm. 2006), 3, 441-450; Chem. Abstr. 2006, 145, 957948. [0063]
• - R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Federal Minister. Research. Technol., Technol. Research. Develop. 1984, BMFT-FB-T 84-164, ISSN: 0340-7608; Chem. Abstr. 1985, 102, 150903. [0063]
• - M. Kardos, Dissertation, University of Berlin 1913, 26. [0063]
• - M. Kardos, Ber. Dtsch. Chem. Ges. 1913, 46, 2086-2091; Chem. Abstr. 1913, 7, 23197. [0063]
• C. Liebermann, M. Kardos, Ber. chem. Ges. 1914, 47, 1203-1210. [0063]
• - M. Kardos, Friedländer's Advances in Tarpainting 1914-1916, 12, 485-492. [0063]
• - AM Richter, R. Ackermann, IS &T's International Congress on Advances in Non-Impact Printing Technologies, 10th, New Orleans, Oct. 30 November 4, 1994, 1994, 246-248; Chem. Abstr. 1995, 124, 131261. [0063]
• D. Désilets, PM Kazmaier, RA Burt, GK Hamer, Can. J. Chem. 1995, 73, 325-335. [0063]
• C. Liebermann, M. Zsuffa, Ber. chem. Ges. 1911, 44, 202-209. [0063]
• ED Bergmann, R. Ikan, J. Org. Chem. 1958, 23, 907-908. [0063]
• - MM Sidky, FH Osman, J. Prakt. Chem. 1973, 315, 881-886. [0063]
• E. Klingsberg, CE Lewis, J. Org. Chem. 1975, 40, 366-368. [0063]
• TK Bandyopadhyay, AJ Bhattacharya, Indian J. Chem. 1982 Sect. B, 21B, 91-94. [0063]
• - S. Mondal, TK Bandyopadhyay, AJ Bhattacharya, Curr. Sci. 1985, 54, 455-458. [0063]
• - SJ Chang, BK Ravi Shankar, H. Shechter, J. Org. Chem. 1982, 47, 4226-4234. [0063]
• - V. Enchev, G. Ivanova, A. Ugrinov, GD Neykov, Journ. Mol. Struc. 1999, 508, 149-161; Chem. Abstr. 1999, 131, 350907. [0063]
• - LG Donaruma, WZ Held, Org. Reactions 1960, 11, 1. [0063]
• H. Langhals, Chem. Ber. 1985, 118, 4641-4645. [0063]
• - K. Gollnick, GO Schenck in Organic Chemistry Vol. 8, 1,4-Cycloaddition Reaction (Ed .: J. Hamer), Academic Press, New York, London, 1967, 255-337. [0063]
• R. Calas, R. Lalande, Bull Soc. Chim. France 1959, 763-770. [0063]
• - RM Hochstrasser, GB Porter, Quart. Rev. (London) 1960, 14, 146-173. [0063]
• R. Hoffmann, RB Woodward, J. Am. Chem. Soc. 1965, 87, 2046-2048. [0063]
• H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535. [0063]
• H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922. [0063]

Claims (78)

Anthracenedicarboximides of general formula 18,

in which X represents the radicals ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-nonyl, 1-propylbutyl, 1-butylpentyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 2-ethylphenyl, 2,3-dimethylphenyl, 2,5-di-tert-butylphenyl or 2,6-di-isopropylphenyl and in which the radicals R 1 to R 8 may be identical or different and independently of one another hydrogen or linear alkyl radicals mean at least one and at most 37 C-atoms, in which one to 10 CH ₂ units can be replaced independently by each carbonyl, oxygen, sulfur, selenium, tellurium, cis- or trans-CH = CH groups, in which one CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-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 disubs 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- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I. Anthracenedicarbonsäureimide the general formula 19,

in which the radicals R1 to R14 can be identical or independent of one another and the meaning of the radicals R1 to R8 of 1 and the radicals R9 to R14 have the meaning of the test R1 to R6 of FIG. Anthracenamidinimide of general formula 20,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1. Anthracenamidinimide of general formula 21,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1. Aceanthrenbisimide the general formula 22,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 14 have the meaning of the radicals R 1 to R 6 of 1. Dihydrocethrenone bisimides of general formula 23,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 16 have the meaning of the radicals R 1 to R 8 of 1. Bisanthracenedicarboximides of general formula 24,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radical R 9 has the meaning of the radicals R 1 of 1. Bisanthracenedicarboximides of general formula 25,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radical R 9 has the meaning of the radicals R 1 of 1. Bisanthracenedicarboxylic acid amidinimides of general formula 26,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1. Bisanthracene dicarboxylic acid amidinimides of general formula 27,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 and R 10 have the meaning of the radicals R 1 and R 2 of 1. Bisanthracene dicarboxylic acid amidinimides of general formula 28,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1. Bisanthracene dicarboxylic acid amidinimides of general formula 29,

in which the radicals R 1 to R 8 have the meaning mentioned under 1 and the radicals R 9 to R 12 have the meaning of the radicals R 1 to R 4 of 1. A process characterized in that aceanthrenchinone from anthracene and oxalyl chloride with the addition of anhydrous aluminum chloride in carbon disulfide in the molar ratios of 1: 5: 1.5 to 1: 6: 2.5, preferably 1: 5.2: 2.0 is synthesized. Method characterized in that for the synthesis of anthracene-1,9-dicarboximide the anthracene-1,9-dicarboxylic anhydride with conc. Ammonia solution is repeatedly evaporated to dryness, two to nine times, preferably three times. Process characterized in that anthracene-1,9-dicarboximides from the corresponding primary amines as pure substance and the anthracene-1,9-dicarboxylic anhydride become. Process characterized in that anthracene-1,9-dicarboximides from concentrated aqueous solutions of the corresponding primary amines and the anthracene-1,9-dicarboxylic anhydride be synthesized. Process characterized in that anthracene-1,9-dicarboximides from the corresponding primary amines and the anthracene-1,9-dicarboxylic anhydride be synthesized using imidazole. Other additives may be zinc salts such as zinc acetate or zinc chloride. Process characterized in that anthracene-1,9-dicarboximides be synthesized in the absence of light. A method characterized in that anthracene-1,9-dicarbonsäureamidinimide from anthracene-1,9-dicarboxylic anhydride and primary Diamines are synthesized, in particular to the exclusion of Light. Process characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt as a color generator for Aceanthrengrün dyes is used by the vat on the to be colored Applied object and slowly oxidized to Aceanthrengrün is, preferably by Luftoxidation for Process characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt by ascorbic acid or pyridine or by alkylated Pyridines, such as. As 1-, 2-, or 3-methylpyridine or lutidine stabilized becomes. Process characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt is hydrogenated using hydrogen peroxide is preferred Hydrogen peroxide in concentrations of 5 to 25% in water, on most preferably 10% hydrogen peroxide. Process characterized in that the vat from anthracene-1,9-dicarboximides via alkaline melt is oxidized in two-phase systems. Preference is given to systems 10% aqueous hydrogen peroxide and chloroform, preferred with medium stirring. Process characterized in that Aceanthrengrün is substituted by the action of alkali, preferably under the action of KOH in tert-butyl alcohol, even with the addition of dipolar aprotic Solvents such as DMSO. Preferred substitution agent is methyl iodide. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using Light can be dimerized, preferably light with wavelengths greater than 350 nm, most preferably light greater than 360 nm. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using Light the line 365 nm of a mercury vapor lamp can be dimerized. Process characterized in that anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4 using filtered light of a tungsten filament light bulb dimerizes become. Filter solutions of naphthalene-1,8-dicarboxylic acid are preferred or their anhydride, alkali such as KOH or NaOH, and water distilled or deionized water. Use of aceanthrenchinone as fluorescent pigment. Use of anthracene-1,9-dicarboxylic anhydride as a fluorescent pigment. Use of Aceanthrenchononmonoxim isomer mixture as a fluorescent pigment. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides according to 1 to 4 for the generation of fluorescence images, which fade in daylight but can be thermally re-activated; Applications are z. Eg in process control. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides of 1 to 4 for producing latent ones Fluorescence images that can be thermally activated; Applications are z. B. at security markings, such. B. against Piracy. Use of Aceanthrengrün derivatives, 5, as fluorescent dyes for the NIR region. Use of aceantreengreen derivatives, 5, as solid fluorescent dyes for the NIR region. Use of anthracene-1,9-dicarboxylic acid imides and anthracene-1,9-amidinimides according to 1 to 4 for the treatment of tumors, prefers compounds synthesized under exclusion of light have been. Use of the photodimerization products of anthracene-1,9-dicarboximides and anthracene-1,9-amidinimides of 1 to 4, such as. B. 24 to 29 after 7 to 12, for the treatment of tumors. Use of the dyes according to 1 to 4 as vat dyes, z. As for the dyeing of textiles, preferably textiles herbal Origin like cotton or else preferably synthetic fibers like polyester or nylon. Use of allotropic anthracene-1,9-dicarboxylic acid amidinimides for data storage in the form that the metastable modification is thermally converted into the thermally stable modification. Use of the substances according to 1 to 12 as pigments. Use of the substances according to 1 to 12 as pigments for glue colors and related colors such as Watercolor paints and watercolors and inks for inkjet printers Paper inks, inks, inks and inks and other inks for painting and writing purposes and in paints. Use of the substances according to 1 to 12 as pigments in paints. Preferred paints are synthetic resin paints such as acrylic or Vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro paints) or natural substances such as zapon varnish, shellac or Qi varnish (Japanese varnish or Chinese lacquer or East Asian lacquer). Use of dyes from 1 to 12 in data stores, preferably in optical memories. Examples are systems like the CD or DVD disc. Use of the substances according to 1 to 12 as fluorescent dyes. Application of dyes from 1 to 12 for mass staining of polymers. Examples are polyvinyl chloride materials, 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, as well as alkyd resin and Acrylics. Application of the dyes according to 1 to 12 as mordant dyes, z. B. for coloring natural products. Examples are paper, Wood, straw, leather, skins or natural fiber materials such as cotton, wool, silk, jute, sisal, hemp, flax and their Transformation products such. As the viscose, nitrate or Copper rayon (Reyon). Preferred salts for pickling are aluminum, Chromium and iron salts. Use of the dyes according to 1 to 12 as colorants, z. B. for coloring paints, varnishes and other paints, Paper colors, printing inks, inks and other colors for Painting, writing and coloring purposes of all kinds. Application of the dyes according to 1 to 12 as nano-pigments in electrophotography: z. B. for Trockenkopiersysteme (Xerox process) and laser printers (non-impact printing). Application of the dyes according to 1 to 12 for Security marking purposes, the big chemical and photochemical stability and possibly also the fluorescence the substances of importance. This is preferred for Checks, check cards, banknotes coupons, documents, identification documents and the like, in which a special, unmistakable color impression should be achieved. Application of the dyes of 1 to 12 as an additive to other colors where a certain shade of color is achieved should, are particularly bright shades. Application of the dyes of 1 to 12 for marking of objects for machine recognition of these objects the fluorescence, preferred is the machine detection of objects to sort, z. B. also for the recycling of plastics. Application of the dyes from 1 to 12 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes. Application of the dyes according to 1 to 12 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light. Application of the dyes from 1 to 12 in display elements for many display, reference and marking purposes, z. B. passive display elements, information and traffic signs, such as Lights. Application of Dyes 1 to 12 in Inkjet Printers as an ink or as a fluorescent ink, in particular as non-water washable ink. Application of the dyes according to 1 to 12 as starting material for superconducting organic materials. Application of the dyes according to 1 to 12 for Solid fluorescent labels. Application of dyes from 1 to 12 for decorative purposes. Application of the dyes according to 1 to 12 for artistic purposes. Application of the dyes according to 1 to 12 for tracer purposes, z. B. in biochemistry, medicine, technology and science. Here, the dyes can be covalently linked to substrates or via minor valences such as hydrogen bonds or hydrophobic interactions (adsorption). Application of the dyes according to 1 to 12 as fluorescent dyes in highly sensitive detection methods. Application of the dyes according to 1 to 12 as fluorescent dyes in scintillators. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in optical light harvesting systems. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in fluorescence solar collectors. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in fluorescence-activated displays. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in cold light sources for light-induced Polymerization for the preparation of plastics. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes for material testing, eg. B. at the production of semiconductor circuits. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes for the study of microstructures of integrated semiconductor devices. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in photoconductors. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in photographic processes. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in display, illumination or image converter systems, where the excitation is by electrons, ions or UV radiation, z. B. in fluorescent displays, Braun tubes or in Fluorescent tubes. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. In the form of an epitaxy. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in chemiluminescence systems, z. As in chemiluminescent light rods, in Lumineszenzimmunoassays or other luminescence detection method. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or others graphical products, signage and others Items where a special optical color impression should be achieved. Application of the dyes according to 1 to 12 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams. Application of the dyes according to 1 to 12 as dyes in dye lasers as a Q-switch switch. Application of the dyes according to 1 to 12 as active Substances for nonlinear optics, e.g. For example the frequency doubling and frequency tripling of laser light. Application of the dyes according to 1 to 12 for leak testing closed systems. Application of the dyes according to 1 to 12 as Rheologieverbesserer.