DE4338784A1 - Perylene-3,4-di:carboximide(s) and reaction prods. useful as fluorescent dye - Google Patents

Abstract

Prepn. of perylene-3,4-dicarboximides of formula (I) comprises reacting perylene-3,4-9,10-tetracarboxylic bis anhydride (II) with a prim. amine R<1>-NH2 (III) at 150-350 deg C and under pressure in the presence of water, a Zn, Pb, Ca or Mg salt (IV) and an N-heterocyclic (V) as base. In (I), R<1> = (cyclo)alkyl, aralkyl, aryl or hetaryl. Also claimed are new ((I: R<1> = alkyl with at least 9C, cycloalkyl, aralkyl, hetaryl or aryl with at least 8C); new perylene-3,4-dicarboxylic diesters (VI), ester-amides (VIII), diamides (VIII) and amidines (IX) and perylene-3,4-dicarbonyl derivs. (X); and a process for bulk colouration of high mol. organic material with (I), (VI), (VII), (VIII), (IX) or (X) and the coloured material per se.

Description

Subject of the invention

The present invention relates to a process for the preparation of perylene-3,4-dicarbon acid derivatives, the new derivatives thus produced, and their use as high lightfast fluorescent dyes.

The invention therefore relates to a process for the preparation of perylene-3,4-di carboximides of the formula I.

wherein R¹ is an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical means by reacting the perylene-3,4,9,10- tetracarboxylic acid bisanhydride with a primary amine R¹-NH₂ at a temperature of 150-350 ° C and under pressure, in the presence of water and in the presence of a zinc, Lead, calcium or magnesium salt and a nitrogen-containing heterocycle as base. The preferred temperature range is around 180-250 ° C. Has proven to be particularly suitable also proven a reaction temperature of 190 ° C or 210-220 ° C.

Salts which are particularly suitable for carrying out the process according to the invention are Lead acetate, zinc chloride and especially zinc acetate.

Particularly suitable nitrogen-containing heterocycles are quinoline, pyridine and in particular Imidazole. The reaction in the respective heterocyclic compound is preferred performed as a solvent.

The reaction goes particularly well with primary amines, which are steric derten, preferably solubilizing organic radical R¹. As particularly ge Suitable radicals R¹ have been found to be in particular the following radicals: 2,5-di-tert-butyl phenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 1-hexylheptyl, 1-octylnonyl, 1-nonyl decyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, Ada mantyl or 4-carbamoylphenyl.

Another object of the invention is thus a method for the production of Perylene-3,4-dicarboximides of the above formula I by reacting the Perylene-3,4-dicarboxylic acid anhydride with a primary amine R¹-NH₂ at a tempera ture of 150-350 ° C and under pressure in the presence of a zinc, lead, calcium or Manganese salt and a nitrogen-containing heterocycle as the base.  

With a few exceptions, the inventions defined according to the two above are perylene-3,4-dicarboximides (2) prepared according to the process according to new ones Links.

The invention therefore also relates to new perylene-3,4-dicarboximides of the formula II

wherein R² represents an alkyl group having at least 9 C atoms or cycloalkyl, Aralkyl, a heterocyclic aromatic radical or a carbocyclic aromatic Rest with a total of at least 8 carbon atoms.

From the above-described and now easily accessible perylene-3,4-dicarboximides (2) and perylene-3,4-dicarboxylic acid anhydride (4) can be easily applied using general my known reactions a variety of derivatives of perylene-3,4-dicarboxylic acid produce.

Another object of the invention are perylene-3,4-dicarboxylic acid diesters Formula III

wherein R³ and R⁴ independently of one another an alkyl, aralkyl or cycloalkyl group or represent a carbocyclic or heterocyclic aromatic radical. This connection gen can for example by hydrolysis of a monoimide or the monoanhydride and for example subsequent alkylation of the hydrolysis product. So can the anhydride 4 with sodium methylate and methyl iodide (or dimethyl sulfate) - (cf. also DE-OS 2,512,516) - who converted to dimethyl ester in N-methylpyrrolidone the. This forms yellow solutions that fluoresce intensely yellow-green.

The invention also relates to perylene-3,4-dicarboxylic acid ester amides Formula IV,

wherein R⁵ and R⁶ independently of one another H, an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical. This ver Bonds can, for example, by partial hydrolysis of a Pery by definition len-3,4-dicarboximide, optionally followed by alkylation or arylation of product obtained in this way.

The invention also relates to perylene-3,4-dicarboxylic acid diamides Formula V,

wherein the two R⁵ are the same or different and H, an alkyl, aralkyl or cycloal alkyl group or a carbocyclic or heterocyclic aromatic radical. These products can, for example, by partial hydrolysis of a by definition Perylene-3,4-dicarboximide and subsequent reaction of the product with a ge suitable amine can be produced.

Another object of the invention is processes for the preparation of perylene-3,4-dicar Bonyl derivatives of the formula VI

wherein R⁷ and R⁸ independently of one another H, an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical, by reak tion of perylene-3,4-dicarboxylic acid derivatives with C nucleopiles. So far only a few Tues Carbonyl derivatives of the formula VI have been described, the known derivatives (cf. Beilstein, E III 7, 4523 and 4526) by Friedel-Crafts acylation of perylene have been.

The invention therefore also relates to new perylene-3,4-dicarbonyl derivatives of the formula VI in which R⁷ and R⁸ have the meaning given above, with the proviso that that R⁷ and R⁸ are not simultaneously phenyl, p-tolyl or 4-chlorophenyl.

The implementation of the perylene-3,4-dicarboximides with primary dia mines leads to further new compounds, the perylene-3,4-dicarboxamides Formula VII

wherein A for C⁵-C⁷-cycloalkylene, phenylene, naphthylene, pyridylene, a higher based aromatic carbocyclic or heterocyclic radical or a divalent Radical of the formula VIII, IX or X

stands, where A can be substituted by halogen, alkyl, cyano or nitro, and R⁹ and R¹⁰ are independently C₁-C₄ alkyl, phenyl or 4-tolyl, which are also Ge are subject of the invention.

Preferred perylenamidines of the formula VII are compounds in which A is 1,2-cyclopentylene, 1,2-cyclohexylene, 1,2-phenylene, 2,3- or 1,8-naphthylene, 2,3- or 3,4-pyridylene, 9,10- Phenanthrylene or a divalent radical of the formula VIII, IX or X means, and ins especially those in which A is 1,2-phenylene, 1,8-naphthylene or a divalent radical of Formula VIII, XI or XII

The invention also relates to a process for the preparation of perylenamidines Formula VII by reacting the perylene-3,4-dicarboxylic anhydride with a primary Diamine of formula XIII

H₂N-A-NH₂ (XIII),

where A has the meaning given above, with the proviso that A is not a residue of Formula VIII is.

Another object of the invention is a process for the production of perylene amide NEN of formula VII, wherein A is a radical of formula VIII, by reacting one optionally substituted imidazole with perylene-3,4-dicarboxylic anhydride. This um Settlement is preferably in the presence of sterically hindered amines or in the presence of ter tertiary amines, such as. B. 3-amino-3-ethylpentane or 2,6-di-tert-butylpyridine.

The radicals R¹ to R⁸ alkyl defined above are preferably C₁-C₄₁ alkyl. The residues can be straight-chain or branched. Secondaries are preferred Alkyl residues, such as. B. 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl or 1-nonyldecyl.

R¹ to R⁸ aralkyl mean z. B. Benzyl.

Residues R¹ to R⁸ cycloalkyl can be mono- or polycyclic and have preference have 3-12 carbon atoms in the ring. Examples of suitable radicals are cyclopropyl, cyclo butyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl decalinyl or adamantyl.

Carbocyclic or heterocyclic aromatic radicals R¹ to R⁸ can also be one or have several, optionally condensed rings, which preferably five or are six members. The heterocyclic aromatic radicals preferably have one or two or three heteroatoms, in particular N, O or S atoms in the ring. The carbocyclic aromatic residues preferably have 6-12 carbon atoms. Examples of suitable residues are Phenyl, tolyl, naphthyl or biphenyl. Suitable heterocyclic aromatic radicals are e.g. B. furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazoly, isoxazoly, pyridyl, pyrazi nyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, quinolyl, isoquinolyl, quinazo linyl or carbazolyl.

The perylene-3,4-dicarboxylic acid derivatives of the formulas I to VII according to the invention are before preferably not substituted in the perylene ring system. But you can also use one or more rere, but usually have a maximum of six substituents in the ring system, the Substituents independently of one another alkyl, aralkyl, cycloalkyl, alkoxy, aryloxy, Al  kylaryl, alkylmercapto, arylmercapto, a carbocyclic or heterocyclic aromati rest or chloro, bromo, nitro, -SO₃H (and their metal salts) or -SO₃R (where R represents alkyl or aryl), amino, acylaminomethyl, such as. B. Acetylaminomethyl, Al kylamino, arylamino, phthalimidomethyl, aminomethyl, dimethylaminomethyl (made for example by cleavage of the corresponding phthalimido derivative), pyrazolomethyl, could be.

The latter sulfo or amino-substituted perylene-3,4-dicarboxylic acid derivatives proper are particularly useful as rheology improvers. Corresponding derivatives of other pigmentsy systems such as B. the phthalocyanine or quinacridone and their Her are for example from US 4,981,888, EP-A 356,390, EP-A 508,704, US 5,212,221 or EP-A 485,337. The present substituted perylene-3,4-dicarboxylic acid Derivatives can be prepared in an analogous manner.

The substituent or the substituents are preferably in 1-, 9- or 1.6-, 1.9-2.5-, 7.12, 8.11 or 9.10 position. The substituted perylene derivatives preferably have one or two substituents in the ring system, and in disubstituted compounds the substituents are preferably the same.

The substituted perylene derivatives can from the corresponding unsubstituted Ver bindings are produced by generally known methods or by Um conversion of an already substituted other derivative (e.g. substituted diesters from sub substituted imides) can be synthesized. The production of the Nitro, amino and bromo derivatives are described.

Another object of the invention is the use of the verb according to the invention security printing, as fluorescent dyes for machine-readable markings, as laser dyes and for the production of print toners ("non-impact printing to ners "), color filters, organic photoreceptors, electroluminescent and Photoluminescent elements or solar panels.

Compounds according to the invention which have one or more substituents selected from the group -SO₃H (and their metal salts) or -SO₃R (where R is alkyl or aryl stands), amino, acylaminomethyl, such as. B. acetylaminomethyl, alkylamino, arylamino, Phthalimidomethyl, aminomethyl, dimethylaminomethyl (made for example by May have cleavage of the corresponding phthalimido derivative) or pyrazolomethyl can also be used as a rheology improver.

introduction

While the perylene dyes, perylene-3,4: 9,10-tetracarboxylic bisimide (1), have long been Time as highly lightfast vat dyes and pigments, and more recently as a fluo Resence dyes are used in homogeneous solution (see e.g. Ref. 1)) are astonishing Licher of the perylene-3,4-dicarboximides (2) be only a few, special representatives knows.

While there is a general synthetic route available for 1 due to the condensation of the technically represented perylene-3,4: 9,10-tetracar bonic acid bisanhydride (3) with primary amines, there is no preparative access to the analogous perylene-3,4-dicarboxylic acid anhydride (4 ); 4 has only been obtained by gas phase decarboxylation ²⁾ of 3 in vanishing quantities.

In order to prepare the few known derivatives of 2, a detour had to be taken in literature ³⁾ , which, however, severely limits the selection of the R groups. For this purpose, the unsubstituted monoimide 2a (R = H) sulfo known since 1923 was first sulfonated and then saponified, the sulfonated anhydride 6 being formed. This can be condensed with short-chain (sufficiently hydrophilic), terminal aliphatic amines to give the sulfonated dicarboximides (6). The corresponding dyes (2) are prepared by desulfonation in semi-concentrated sulfuric acid. The rough reaction conditions required for this, which can lead to sulfonations and eliminations, and the problems in the preparative purification of sulfonated perylene derivatives severely restrict the process, so that so far only substances with the residues (hydrogen ⁴⁾ methyl, ethyl, 1 -Propyl, 1-butyl, isobutyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl, phenyl, p-tolyl and p-anisyl ( ^Ref . ^3,5) ).

An attempt to prepare 2c from the ⁶⁾ perylene-3,4-dicarboxylic acid anhydride-9,10-dicarboximides analogously to Ref. ³⁾ , which is now readily accessible by preparation, led to low yields (max. 4%), see above that this is also not a synthesis of 2 (see exp. part).

Synthesis of perylene-3,4-dicarboximides from 3

The condensation of bisanhydride 3 with primary amines is usually carried out in high Yields obtained the corresponding perylene tetracarboxylic bisimide 1. But if you do that Condensation in the presence of water at high temperatures, so you can find the In addition to the expected bisimides 1, the monoimides 2 are also astonishing. For 2b (R = 2,5-di-tert- butylphenyl) a yield of about 8% is achieved. Through implementation in an autoclave the isolated yield of 2b can be increased to 50%. The rest is essentially unreacted starting material, perylene and the corresponding bisimide 1b, which easily can be separated chromatographically.

The optimal amount of water added for the implementation of the invention, the primary amine R¹-NH₂, or the salt used may vary from case to case. At the preparation of the monoimide 2b (R¹ is 2,5-di-tert-butylphenyl) from the bisanhydride 3 can suitably about 0.7 ml of water / mmol 3, about 1.6 mol of 2,5-di-tert-butylani Use lin / mol 3 and about 135 mg zinc acetate / mmol 3.

The imide 2b fluoresces very strongly in solution - its absorption and fluorescence spectrum are shown in Fig. 1. In terms of lightfastness, it even surpasses the perylene dyes known as extraordinarily photo-stable. In dimethylformamide solution, it bleaches by a factor of 20 more slowly than 1b. Similar results are found for the other dyes 2.

The relatively narrow absorption and fluorescence band leads to brilliant color tones nen. The almost rectangular absorption band is favorable for a large color strength.

As a solid, 2b forms a bright red pigment that fluoresces intensely. The solid Fluorescence and excitation spectrum is given in Fig. 2. The intense, long-wave Fluorescence band is obtained from well-ordered crystallites. Conversely, the substance very finely pulverized or quickly precipitated from a solution, so the shorter-wave Fluo Rescence band to the highest intensity, and the solid spectrum then more closely resembles the Fluo Rescence spectrum of solutions, however, is slightly hypsochromically shifted. This is also typical for other perylene-3,4-dicarboximides.  

For the condensation, instead of aromatic amines, aliphatic amines with long-chain, secondary residues are used, the analog monoimides 2 are obtained, the yields but are significantly smaller - see Tab. 1.

Table 1

Preparation of the perylene-3,4-dicarboximide (2) from 3 and primary amines in imidazole with the addition of water

The UV / Vis spectroscopic properties of the dyes 2 with alkyl substituents are very similar to those of the dyes with aromatic residues. These substances also fluoresce in solution with high fluorescence quantum yields and are strong fluorescent pigments as a solid. By combining the nitrogen atom with long-chain secondary aliphatic residues, dyes are obtained which are extremely easily soluble in organic solvents. A typical UV / Vis spectrum of such a substance (2d) is shown in Fig. 3.

Synthesis of Perylene-3,4-Dicarboxylic Acid Anhydride (4)
Scheme 1: Synthesis of 4.

With a yield of 50% in the reaction in an autoclave, 2b according to Scheme 1 is a useful starting material for the preparation of the anhydride 4. For this, 2b is reacted with KOH in tert-butyl alcohol and the saponification to give the monoamide of 3,4-perylene -dicarboxylic acid (8). The reaction proceeds according to pseudo 1st order with a half-life of 4.5 h at 70 ° C. The kinetics of the reaction followed by UV / Vis spectroscopy is shown in Fig. 4 for the saponification of the starting material (502 nm) and the formation of the reaction product (457 nm). An isosbestic point is found at 464 nm. The speed constants of the two measurements coincide within the measurement accuracy; however, the measurement at 457 nm is much more precise.

The structure of amide 8 is confirmed spectroscopically and by alkylation with methyl iodide in N-methylpyrrolidone, which takes place twice on the carboxyl group and on the amide nitrogen. The resulting ester amide 9 is highly fluorescent in solution and is a new type of fluorescent dye - see Fig. 5. If the alkaline solution of 8 is acidified with dil. HCl, it sometimes occurs. a further saponification, whereby the desired perylene-3,4-dicarboxylic anhydride (4) is formed in 23% yield, partly there is a back reaction to the starting material 2b. When using 50 percent. Acetic acid instead of hydrochloric acid, the proportion of the saponification reaction can be increased to 67%, and based on the conversion, the isolated yield is 4 91%. Under the reaction conditions, acetic acid obviously causes saponification to be considerably more efficient, and the remaining portion of cyclization product 2b can be removed without problems by dissolving with hot potassium carbonate solution, filtering and precipitating with acetic acid, so that the anhydride 4 is obtained in high purity.

The pure anhydride 4 is a red color pigment with red solid fluorescence. In contrast to 3, 4 is much more soluble in organic solvents. The UV / Vis spectra of 4 are given in Fig. 6.

Synthesis of perylene-3,4-dicarboximides (2) from 4

The anhydride 4 can now with any primary amines to the perylene-3,4-dicarboxylic acid rhyming (2) under usual reaction conditions, e.g. B. with zinc acetate in imidazole or Quinoline. Examples with yields and properties are shown in Tab. 2 given.

Table 2

Perylenedicarboximides 2 shown in FIG. 4

The imides 2 fluoresce in solution with high quantum yields. As fluorescent dyes are they surprisingly even perylene dyes in terms of their light fastness (1) think about who is currently most stable fluorescent dyes are. The solubility of the Dyes are generally higher than those of the corresponding perylene dyes 1.  

As a special feature, most of the imides 2 have a pronounced solid fluorescence, which makes them interesting as lightfast fluorescent pigments.

The crystal structures of the dyes 2b and 2g have been determined - see Fig. 8. The chromophores of 2b form layers of sheet structures with the side chains protruding alternately on both sides. The side chains of the next layering of folder structures then hit these side chains. The molecular structure is influenced by the resulting large crystal forces (cf. Ref. ⁷⁾ ). The m-tert-butyl group of the side chain is firmly fixed in the crystal structure, while the o-tert-butyl group is more freely movable. This manifests itself, inter alia, in the differently sized rotation ellipsoids of the methyl carbon atoms in these groups. The large crystal forces in this special structure also affect the chromophore itself, which is helically twisted as a result. Further information on the structure of 2b can be seen in Tables 3 and 4.

Table 3

Atomic coordinates (x 10⁴) and isotropic deflection parameters (pm² × 10 ^-1 ) of the dye 2b

Table 4

Anisotropic deflection parameters (pm² × 10 ^-1 ) of the dye 2b

The crystal lattice of the dye 2g is built according to a completely different principle. The Cy clooctylrest is bent as a side group, and there are alternating layers of Chromophore and side chain formed. The neighboring chromophore layer then stands perpendicular to the first etc. The chromophore is in this less strained structure also much less deformed than in 2b.

Table 5

Atomic coordinates (x 10⁴) and their calculated standard deviations of the dye 2g

Table 6

Anisotropic deflection parameters (pm² × 10 ^-1 ) of the dye 2g

Derivatives of perylene-3,4-dicarboximides (2)

The perylenedicarboximides (2) can be nitrided with various reagents. A reaction of 2b with nitric acid in glacial acetic acid leads to a large number of products of which the 1,6-dinitro derivative (15) chromatographically easily with a yield can be isolated by 13%. To avoid interference caused by nitration of the residue R in 2b close, the further reactions with dye 2c have taken place.

Scheme 2: Nitration of the perylene-3,4-dicarboximides (2)

A reaction of 2c with nitric acid in acetic anhydride can be carried out chromatographically 8% of the 1-nitro derivative (13), 35% of the 1,9-dinitro derivative (12) and 14% of the 9,10-dinitro- Isolate derivative (11).

A nitration of 2c with N₂O₄ in methylene chloride also produces a complex reaction mixture from which 7% of the 1-nitro compound (13) can be separated off by chromatography. Catalysis of the reaction by methanesulfonic acid promotes a second substitution. Then 12% 1,6-dinitro (14), 36% 9-nitro (10), 9% 2,5-dinitro (14) and 25% 9,10-dinitro substitution product (11) are found . The UV / Vis spectra of the latter are given in Fig. 9. Dye 11 has an increased Stokes shift compared to other perylene derivatives.

The nitration of 2c by N₂O₄ in methylene chloride is strongly influenced by light. Because of the broad light absorption of 2c in the visible range, nor is sufficient color daylight completely, and the photoreactions appear with high quantum yields to expire.

If the nitration of 2c with N₂O₄ in methylene chloride is carried out in complete darkness, 55% of the 9-nitro derivative (10) can be isolated as a pure substance as the reaction product. The rest is almost exclusively unreacted raw material that can be easily separated. This reaction is therefore the best way to prepare substance 10 on a preparative scale. The UV / Vis spectra are shown in Fig. 10.

The 9-nitro compound 10 can be reduced with iron in glacial acetic acid to the amine 17, from which get 30% directly. Through a chromatographic processing of the residues can be isolated another 20%. Better results are obtained when reducing with iron in Hydrochloric acid. This allows the amine to be isolated directly in 85% yield. At this About 10% of a by-product with a higher molecular weight is obtained in the reaction which is probably an azo compound.

In contrast to the perylene dyes 1, the amine 17 is remarkably positive sol vatochrome - the influence of solvents on its absorption spectrum can be seen in Fig. 11. Its absorption maximum is shifted from 554 nm in chloroform to 602 nm in methanol. The positive Sovatochromie indicates that the amino group in the most electronically excited state carries a larger positive partial charge, while the carbonyl groups are correspondingly more negatively charged, so that a larger Dipolmo element results. This corresponds to e.g. B. completely the charge distribution in 4-amino-N-me methylphthalimide. Since the dye 17 is relatively lightfast and also weakly fluorescent, it is of interest for the generation of the third harmonic wave in a nonlinear optic via a resonance effect.

A derivatization of 2c with bromine (see also ref. ²²⁾ in chlorobenzene yields the 9-bromo derivative 18 in addition to multiply brominated products in 63% yield. The reaction thus corresponds to nitriding with the exclusion of light. 2b can be brominated analogously. However, the reaction also produces polybrominated 2b, which could not be separated. On the other hand, if the bromination is carried out in chlorobenzene in the presence of potassium carbonate, 77% of 9-bromo-2b can be isolated.

Other derivatives of 4

The anhydride 4 can with sodium methylate and methyl iodide (or dimethyl sulfate) - cf. also ref. ⁸ ) - are converted into dimethyl ester (19) in N-methylpyrrolidone. This forms yellow solutions that fluoresce intensely yellow-green. The absorption and fluorescence spectrum of 19 is shown in Fig. 12

Condensation with neopentanediamine leads to the new type of dye (20), in which a carbonyl group is replaced by the imino group compared to 2. The inclusion of the imino function in a six-membered ring and its geminal methyl groups stabilize the substance against hydrolysis (see also ref. ⁹ ). The UV / Vis absorption and fluorescence spectra are given in Fig. 13. The dye 20 is distinguished by great fastness properties and can also be used as a fluorescent dye. It is interesting here that its fluorescence is long-wavelength shifted compared to the perylene dyes. As a solid, the substance forms a red color pigment.

A new basic chromophore (dye 21) can also be prepared by the condensation of 2 with o-phenylenediamine (cf. Ref. ⁹). Its UV / Vis spectra are given in Fig. 14. As a solid, the substance forms a stable, dark red-brown color pigment.

Experimental part 1-cyanohexane ¹⁰⁾

A mixture of 54.8 g (1.12 mol) sodium cyanide, 1 l DMSO and 165 g (1.00 mol) 1-bromohexane is heated under nitrogen and vigorous stirring, all of which is Na trium cyanide goes into solution and an oily phase forms. After cooling, 1 l Water added and then extracted three times with 300 ml of chloroform. The United Chloroform extracts are washed with 2N hydrochloric acid and with water and over magnesi dried sulfate. The mixture is concentrated on a rotary evaporator and the oily is distilled Residue in vacuo. Educ. 80.9 g (73%) - bp 55-60 ° C / 1 mbar.

7-tridecanone ^11.12)

Prepare from 17.75 g (0.73 mol) magnesium shavings, 170 ml absolute. Ether and 144.5 g (880 mmol) bromohexane a Grignard solution. As a starter you should do this Better to use 1,2-dibromoethane instead of iodine, since the former is used to a greater extent for bil formation of alkanes. 80.9 g (730 mmol) of 1-cyanohexane in 130 ml absolute Ether dropped. The processing takes place with sat. Ammonium chloride solution. The The reaction product is etherified, the ether is dried, evaporated and the residue was recrystallized from ethanol. Educ. 64. 16 g (45%).

7-tridecyl ketoxime ¹³⁾

64.2 g (320 mmol) of 7-tridecyl ketone are dissolved in a mixture of 325 ml of ethanol and 160 ml of water, and 33.8 g (480 mmol) of hydroxylammonium chloride and slowly 61.8 g (620 mmol) of calcium carbonate are added. The suspension is boiled under reflux for 6 h. Then it is stirred for 2 d at room temperature. It is etherified three times and the combined ether phases are dried with magnesium sulfate. The ether is distilled off and the oily residue is distilled in vacuo. Educ. 38.13 g (55.2%, Lit. ¹³⁾ 83%) - bp 96 ° C /0.6 mbar (Lit. ¹³⁾ 127-129 ° C /0.1 Torr). - n _D ²⁰: 1.4567. - IR (KBr): ν = 3236 cm ^-1 (broad, N-OH); 3108 (m); 2957 (s, CH₂); 2929 (s, CH₂); 2872 (s, CH₂); 2858 (s, CH₂); 1655 (w, C = N); 1467 (m); 1378 (w); 1119 (w); 1012 (w, broad); 952 (m, broad, NO); 889 (w); 725 (f). - 1 H-NMR (CCl₄): δ = 9.60 ppm (s, 1H, N-OH); 2.13 (m, 4H, CH₂ = N); 1.27 (m, 16H, CH₂); 0.87 (t, 6H, CH₃, J = 6Hz).

7-aminotridecane ¹⁴⁾

116 g (400 mol) of a 70 percent. Solution of sodium aluminum bis (2-methoxyethoxo) dihydride in absolute. Toluene is heated to 140 ° C. and then dropwise mixed with 21.3 g (100 mmol) of 7-tridecyl ketoxime in 50 ml of toluene, hydrogen being formed in a violent reaction. After the addition has ended, the mixture is kept at 140 ° C. for a further 4 h. After cooling, slowly add 200 ml of ice-cooled 20 percent with vigorous stirring and ice cooling. Sulfuric acid too. A colorless precipitate precipitates, which partially dissolves in excess acid. The acidic suspension is subjected to steam distillation in order to completely remove the toluene from the reaction mixture. The residue is then made strongly alkaline with ice cooling and vigorous stirring with sodium hydroxide solution and subjected to a further steam distillation, the 7-aminotridecane also being distilled over. The solution is acidified to drive off any dissolved carbon dioxide, made alkaline and then immediately shaken three times with tert-butyl methyl ether. The combined ether phases are dried over magnesium sulfate, concentrated on a rotary evaporator and the oily residue obtained is distilled in vacuo. Educ. 12.7 g (64%, ref. ¹⁴⁾ : 60%) colorless, fish-smelling liquid - bp. 128 ° C-130 ° C / 11 Torr (ref. ¹⁴⁾ 137 ° C / 10 Torr). - n _D ²⁰ = 1.4409. - IR (film): ν = 3372 cm ^-1 (w); 3300 (w); 2958 (m); 2925 (s); 2872 (m); 2855 (m); 1616 (w, broad); 1467 (m); 1457 (m); 1378 (w); 1149 (w); 812 (w); 782 (w); 724 (f). - 1 H-NMR (CCl₄): δ = 0.86 ppm (m, 6H); 1.06 (m, 2H); 1.26 (m, 20H); 2.54 (m, 1H).

9-heptadecylketoxime¹⁵)

30.0 g (118 mmol) of 9-heptadecyl ketone and 12.3 g (177 mmol) of hydroxylamine hydrochloride are dissolved in a mixture of 100 ml of ethanol and 50 ml of water and sodium carbonate is added in portions until the solution no longer foams. This mixture is boiled under reflux for 22 h, then poured onto 200 ml of water and extracted three times with tert-butyl methyl ether. The combined organic phases are dried over magnesium sulfate and concentrated on a rotary evaporator. The remaining yellow oil is distilled in vacuo. Educ. 18.5 g (59%, ref. ¹⁵⁾ 78%) slightly yellowish liquid - bp 140 ° C / 0.5 mbar (ref. ¹⁵⁾ 147-149 ° C / 0.005 Torr). - n _D ²⁰ = 1.4615. - IR (film): ν = 3245 cm ^-1 (m, broad, OH); 3110 (m, broad, OH); 2956 (s, CH₃); 2926 (s, CH₂); 2875 (m, CH₂); 2856 (s, CH₂); 1658 (m, broad, C = N); 1670 (m, CH₂); 1457 (m); 1378 (w); 1123 (w); 967 (m, broad, NO); 722 (f). - 1 H-NMR (CDCl₃) δ = 9.73 ppm (s, 1H, NOH); 2.23 (m, 4H, CH₂); 1.28 (m, 24H, CH₂); 0.87 (m, 6H, CH₃).

9-aminoheptadecane ¹⁶⁾

18.53 g (69.8 mmol) of 9-heptadecyl ketoxime are reacted and worked up analogously to the preparation of 7-aminotridecane. Educ. 11.34 g (64%) colorless, fish-smelling liquid - bp 90-95 ° C / 0.5 mbar (Lit. ¹⁶⁾ 128-130 ° C / 1 1 Torr). - n _D ²⁰ = 1.4487 (Ref. ¹⁶⁾ : n _D ²⁰ = 1.4509). - 1 H-NMR (CDCl₃) δ = 2.60 ppm (m, 1H, CH); 1.33-1.18 (m, 24H, CH₂); 1.15 (m, 2H, NH2); 0.82 (m, 6H, CH₃)

1-cyanodecane ¹⁶⁾

50 ml (260 mmol) of 1-bromononane are analogous to the representation of 1-Cyanohexane implemented and worked up. Educ. 34.7 g (86%) colorless liquid - bp. 67-70 ° C / 0.5 mbar. - 1 H-NMR (CDCl₃): δ = 2.28 ppm (m, 2H); 1.7-1.2 (m, 14H); 0.85 (t, 3H, CH₃).

10-nonadecyl ketone ¹⁶⁾

56.1 g (270 mmol) 1-bromononane and 34.7 g (230 mmol) 1-cyan odecan are implemented and processed analogously to the preparation of 7-tridecanone. Educ. 24.9 g (39%) pale yellow needles - mp 56-57 ° C. - 1 H-NMR (CDCl₃): δ = 2.35 ppm (m, 4H, CH₂C = O); 1.13-1.75 (m, 28H, CH₂); 0.85 (m, 6H, CH₃).

10-nonadecyl ketoxime ¹⁶⁾

24.9 g (88.3 mmol) of 10-nonadecyl ketone are reacted and worked up analogously to the representation of 9-heptadecyl ketoxime. 18.5 g (71%, ref. ¹⁶⁾ 94.5%) slightly yellowish solid - mp 22.5 ° C. - 1 H-NMR (CDCl₃): δ = 2.20 ppm (m, 4H, CH₂); 1.25 (m, 28H, CH₂); 0.85 (m, 6H, CH₃); IR (KBr): ν 3246 cm ^-1 (m, broad, OH); 3105 (m, broad, OH); 2956 (s, CH₃); 2926 (s, CH₂); 2870 (m, CH₂); 2854 (s, CH₂), 1658 (m, broad, C = N); 1467 (m); 1456 (m); 1378 (w); 1353 (w); 1341 (w); 1303 (w); 1164 (w); 1123 (w); 967 (m, broad, NO); 890 (w); 721 (m); 657 (f).

10-amino nonadecane ¹⁶⁾

18.5 g (63.2 mmol) of 10-nonadecyl ketoxime are reacted and worked up analogously to the preparation of 7-aminotridecane. Educ. 3.05 g (18%, ref. ¹⁶⁾ 57%) colorless oil (contains alkanes according to 1 H-NMR spectrum) - b.p. 132 ° C / 0.1 mbar (ref. ¹⁶⁾ 120-122 ° C / 0.1 Torr). - 1 H-NMR (CDCl₃): δ = 2.64 ppm (m, 1H, CH); 1.44 (m, 32H, CH₂); 1.21 (s, 2H, NH₂); 0.88 (m, 6H, CH₃).

1,4-di-tert-butylbenzene

294 ml (2.72 mol) of freshly distilled tert-butyl chloride (vigorous HCl evolution) are added dropwise to 151 ml (1.67 mol) of anhydrous benzene and 7.80 g of aluminum chloride at 5 ° C. with vigorous stirring and ice cooling. After the reaction has ended, the mixture is stirred at room temperature for a further 15 min. The dark red reaction product is poured into 1.5 l of ice water and stirred for 1 h. The aqueous phase is extracted five times with tert-butyl methyl ether, and the combined ether phases are dried over magnesium sulfate for 15 h. The solvent is evaporated off and the slightly yellowish residue is recrystallized from methanol. Educ. 192 g (75%) colorless crystals - mp 76-77 ° C. - IR (KBr): ν = 3470 cm ^-1 (s, NH); 3360 (s, NH); 2960 (s, CH); 2880 (s, CH); 1620 (m, NH); 1560 (m); 1510 (m); 1480 (m); 1410 (m); 1365 (m, CH); 1310 (m); 1260 (w); 1200 (w); 1140 (w); 1105 (w); 1020 (w); 940 (m); 875 (m); 815 (s). - 1 H-NMR (CCl₄): δ = 1.27 ppm (s, 18H); 7.12 (s, 4H).

2,5-di-t-butylnitrobenzene

8.4 g of fuming nitric acid are added dropwise to a suspension of 19.1 g (100 mmol) of 1,4-di-tert-butyl benzene in 21 ml of glacial acetic acid and 17 ml of acetic anhydride, the temperature should not exceed 40 ° C. After stirring for 24 h at room temperature, the mixture is poured onto ice, the precipitate is filtered off and crystallized from 50 ml of isopropyl alcohol. Educ. 7.57 g (60.3%) colorless crystals - mp 86 ° C. - IR (KBr): ν = 3010 cm ^-1 (w); 2966 (s); 2932 (m); 2910 (m); 2871 (m); 1528 (s); 1501 (m); 1476 (m); 1468 (m); 1373 (s); 1362 (m); 1266 (s); 1256 (m); 1061 (m); 883 (m); 832 (s); 770 (m); 753 (m). - 1 H-NMR (CCl₄): δ = 1.30 ppm (s, 9H); 7.08-7.28 (m, 3H).

2,5-di-t-butylaniline ¹⁷⁾

820 ml of glacial acetic acid and 120 ml of water are added to 110 g (470 mmol) of 2,5-di-tert-butylnitrobenzene in small portions at 90 ° C. with stirring (KPG stirrer!) Within 1.5 h. A change in color from red to black and then to gray is observed. 100 ml of water are then added and the mixture is stirred at 90 ° C. for a further 4 h. The cooled suspension is then concentrated. Sodium hydroxide solution made strongly alkaline. This mixture is subjected to steam distillation, where the product separates as a yellowish mass floating on the water. The product is filtered off with suction, recrystallized from methanol / water (3: 1) and 75.2 g (79%, ref. ¹⁷⁾ 83%) of colorless crystal needles - mp. 101 ° C. (ref. ¹⁷⁾ 100-101 ° C. ). - IR (KBr): ν = 3472 cm ^-1 (m); 3370 (s); 2964 (s); 2910 (m); 2870 (m); 1621 (s); 1561 (m); 1508 (m); 1482 (m); 1413 (m); 1392 (m); 1365 (m); 1312 (m); 874 (m); 813 (s). - 1 H-NMR (CCl₄): δ = 1.17 ppm (s, 9H); 1.28 (s, 9H); 3.37 (s, 2H); 6.27-6.87 (m, 3H).

2,5-di-tert-butyl-1,4-dinitrobenzene ^18.19)

While cooling with ice, 50 g (260 mmol) of 1,4-di-tert-butylbenzene are slowly added to 150 ml of red-smoking nitric acid (96%) at 0 ° C. After the addition has ended, the mixture is heated to 60 ° C. with stirring for 4 h and then poured onto 300 g of ice. The product is filtered off with suction and a yellow, waxy product is obtained, which is recrystallized from isopropyl alcohol. Educ. 27.4 g (37%, ref. ¹⁹⁾ 52%) colorless needles - mp. 191-192 ° C (ref. ¹⁸⁾ 192-193 ° C). - 1 H-NMR (CCl₄): δ = 1.42 ppm (s, 18H); 7.41 (m, 2H).

N- (2,5-di-t-butylphenyl) perylene-3,4-carhoximide (2b)

A mixture of 3.66 g (9.34 mmol) perylene-3,4: 9,10-tetracarboxylic acid bisanhide with 18.7 g imidazole, 1.32 g zinc acetate dihydrate, 8.0 ml (450 mmol) water and 1.05 g (5.12 mmol) of 2,5-di-tert-butylaniline heated to 210 ° C for 23 h. After the end of the reaction, the mixture is rinsed with ethanol from the autoclave, with water and conc. Hydrochloric acid added and cooked until all ethanol has evaporated. The brown-red residue is suctioned off and boiled at 10 percent. Potassium carbonate solution for 1 hour. The residue is suctioned off, dried in a drying cabinet at 120 ° C. and chromatographed over silica gel with chloroform. This gives perylene as a forerunner (yellow, fluorescent blue) followed by N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide (2b) and then N, N'-bis (2.5 -Di-tert-butylphenyl) perylene-3,4,9,10-dicarboximide (1b). Aub. 2.40 g (50.5%) - mp. <300 ° C. - R _f (CHCl₃ / silica gel) = 0.85. - UV (CHCl₃): λ _max (ε) = 489 nm (35300), 512 (33590). - Fluorescence (CHCl₃, Anr. 489 nm) λ _max (I _rel ) = 535 nm (1), 576 nm (0.36) - IR (KBr): ν = 2962 cm ^-1 (s, CH); 2906 (w, CH); 2867 (w, CH); 1701 (s, C = O); 1664 (s, C = O); 1653 (s); 1591 (m); 1577 (m); 1464 (w); 1398 (w); 1359 (s); 1293 (w); 1272 (w); 1247 (m); 831 (s, CH); 810 (m, CH); 759 (m, CH). - 1 H-NMR (CDCl₃): δ = 1.30 ppm (s, 9H, C (CH₃) ₃); 1.34 (s, 9H, C (CH₃) ₃); 7.04 (d, J₁ = 2.3 Hz, 28-H); 7.45 (dd, J₁ = 2.3Hz, J₂ = 8.5 Hz, 1H, 25-H); 7.59 (d, J₂ = 8.5 Hz, 1H, 26-H); 7.62 (t, J₃ = 7.7Hz, 2H, 11-H); 7.90 (d, J₃ = 7.7Hz, 2H, 10-H); 8.42 (d, J₄ = 8.2Hz, 2H, 1-H); 8.44 (d, J₃ = 7.7Hz, 2H, 12-H); 8.63 (d, J₄ = 8.2Hz, 2H, 2-H). - 13 C-NMR (CDCl₃): δ = 164.9 ppm (m, C = O); 150.0 (m; 143.8 (m); 137.4 (dd, ²J = 7.7Hz, ³J = 4.1Hz); 134.3 (t, ²J = 7.8Hz, C-18); 133.1 (d, ²J = 9.6Hz); 131.8 ( d, ¹J = 164.4Hz); 130.9 (dt, ¹J = 160.9Hz, ²J = 6.2Hz, C-11); 130.2 (t, ²J = 6.5Hz); 129.2 (m); 128.7 (d, ¹J = 157.1Hz ); 127.9; 127.8 (dd, ¹J = 156.2Hz, ²J = 7.1Hz); 127.0 (d, ¹J = 161.4Hz); 127.0 (d, ²J = 7.3Hz); 126.1 (dd, ¹J = 157.0Hz, ²J = 7.3Hz); 123.7 (dd, ¹J = 157.8Hz, ²J = 7.3Hz); 121.3 (d, ²J = 7.3Hz); 120.1 (dd, ¹J = 160.3Hz, ³J = 2.3Hz, C-28); 35.5 ( m, J = 3.8Hz); 34.3 (m, J = 3.4Hz); 31.7 (qm, ¹J = 126.1Hz, ³J = 4.6Hz); 31.3 (qm, ¹J = 126.0Hz, ³J = 4.6Hz). - MS (70eV): m / z (%) = 510 (5.76); 509 (M⁺, 14.8); 453 (30.21), 452 (M⁺-C (CH₃) ₃, 100), 437 (5.5), 436 ( 11.29).
C₃₆H₃₁NO₂ (509.7):

Calc .:
C 84.84, H 6.13, N 2.75
Found:
C 84.79, H 6.35, N 2.81

Crystal structure (diffractometer: ENRAF Nonius CAD4, radiation: MoKα, monochroma tor. Highly oriented graphite crystal). C₃₆H₃₁NO₂-M _r = 509.6, a = 6.217 (2), b = 9.798 (2), c = 43.767 (9), β = 93.53 (2) °, volume = 2.661 (1) nm³, Z = 4, density ( calc.) = 1,272 MG / M³, µ = 0.738, crystal system monoclinic, space group P2₁ / c (No. 14). - Data collection single crystal 0.27 × 0.13 × 0.6 mm³ (orange), ξ-scan, measured 2 R range: 4- 46 ° in ± hkl, scan width. 0.80 + 0.35 tan R, 3 standard reflections every 3600 s measuring time, index range: -6 h 6.0 k 10.0% 1 46, collected reflections: 3639, independent and observed: 2940, observe (I <2σ (I) ): 2355, no correction for absorption, calculation of the structure: direct method, anisotropic refinement of the non-hydrogen atoms, isotropic refinement of the H atoms, 352 parameters, R = 0.0643, R _w = 0.054, w ^-1 = σ² ( F _o ), mini male and maximum residual electron density 10⁶e / pm³) 0.28-0.38.

N-1-Hexylheptyl-perylene-3,4-dicarboximide (2c) from 3

1.2 g (3.1 mmol) perylene-3,4: 9,10- tetracarboxylic acid bisanhydride, 6.2 g imidazole, 470 mg (2.36 mmol) 7-aminotridecane 150 mg (0.68 mmol) zinc acetate dihydrate and 3.0 ml (170 mmol) water are combined in one Autoclave (100 ml) heated to 190 ° C for 24 h. The processing is carried out analogously to the representation from 2b. Educ. 1.25 g (27%) - spectroscopic data see u.

N-1-octylnonyl-perylene-3,4-dicarboximide (2d) from 3

1.4 g (3.1 mmol) perylene-3,4: 9,10-tetracarboxylic acid bisanhydride, 6.1 g imidazole, 960 mg (3.7 mmol) 9-aminoheptadecane 150 mg (0.68 mmol) zinc acetate dihydrate and 3.0 ml (170 mmol) water are placed in an autoclave (100 ml) heated to 190 ° C for 24 h. The processing is carried out analogously to the representation of 2b. Educ. 130 mg (7% extractive ²⁰⁾ recrystallized from methanol) orange-red crystals with strong solid fluorescence - mp. 143-143.6 ° C. - R _f (CHCl₃ / silica gel) = 0.94. - UV (CHCl₃): λ _max (ε) = 454 nm (sh, 17620), 485 (32530), 508 (29480). - Fluorescence (CHCl₃, Anr. 485 nm): λ _max (I _rel ) = 572 (sh, 0.49), 536 (1). - IR (KBr): ν = 2959 cm ^-1 (m, CH₂), 2926 (s, CH₂), 2855 (m, CH₂), 1694 (s, C = O), 1650 (s), 1594 (m) , 1578 (w), 1501 (w), 1497 (w, wide), 1409 (w), 1375 (w), 1356 (s), 1293 (w), 1245 (m), 1172 (w), 838 ( w), 809 (s), 754 (s). - 1 H-NMR (CDCl₃): δ = 8.47 ppm (m, 2H), 8.27 (d, 2H, J = 7.1Hz), 8.24 (d, 2H, J = 8.1Hz), 7.8 (d, 2H, J = 7.9Hz), 7.53 (t, 2H, J = 7.8Hz), 5.22-5.17 (m, 1H, CH-N), 2.30-2.24 (m, 2H, CH₂), 1.90-1.85 (m, 2H, CH₂) , 1.38-1.22 (m, 24H, CH₂), 0.88 (t, 6H, J = 6.8Hz, CH₃). - 13 C-NMR (CDCl₃): δ = 165.1 ppm (C = O), 164.1 (C = O), 136.7, 134.2, 131.8, 131.0, 130.6, 129.8, 129.1, 127.8, 126.9, 126.5, 123.4, 120.0, 54.4 (CH-N), 32.4 (CH₂), 31.8 (CH₂), 29.6 (CH₂), 29.5 (CH₂), 29.3 (CH₂), 27.0 (CH₂), 22.6 (CH₂), 14.7 (CH₃). - MS (70eV): m / z (%): 561.5 (2.8), 560.5 (13.3), 559 (M⁺, 32.3), 543 (3.0), 542 (M⁺-OH, 7.4), 323 (8.1) , 322 (42.9), 321 (M⁺-C₁₇H₃₄, 100), 304 (5.1), 277 (5.9), 276 (5.6), 275 (2.3).
C₃₉H₄₅NO₂ (559.8):

Calc .:
C 83.68, H 8.10, N 2.50
Found:
C 83.62, H 8.02, N 2.73

Perylene-3,4-dicarboxylic anhydride (4)

510 mg (1.0 mmol) of N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide (2b) and 1.4 g (18 mmol) of KOH (85 percent) are dissolved in 47 ml of tert-butyl alcohol suspended and boiled with stirring for 2 h. The result is a light orange colored solution, the color of which slowly changes to yellow. A pure yellow precipitate of perylene-3-carboxylic acid-4-N- (2,5-di-tert-butylphenyl) carboxamide potassium salt (8) precipitates, which is very readily soluble in water and fluoresces intensely yellow-green in solution. The suspension of the crude reaction solution is added dropwise with 100 ml of 50 percent in the heat. It added acetic acid. This creates a red-orange suspension, which is stirred for 2 h at room temperature and then suctioned off. The red-brown solid thus obtained is dried in a drying cabinet at 120 ° C. and then with 200 ml of 10 percent. Potassium carbonate solution boiled and washed several times with warm water until the wash water runs colorless. The filtration residue consists essentially of N- (2,5-di-tert-butylphenyl) perylene 3,4-carboximide (2a) (yield 27%). When cooling, perylene-3,4-dicarboxylic acid potassium salt crystallizes out of the aqueous phases (mp. <250 ° C. - UV (H₂O): λ _max (ε): 450 (28110), 424 (23490), 402 (sh, 11870) - Fluorescence (H₂O, very strong) λ _max (I _rel ): 465 (1), 491 (0.98). - IR (KBr): ν = 3649 cm ^-1 (w, OH), 3405 (m, wide, OH bridge), 1592 (s, COO⁻), 1549 (s), 1503 (w), 1447 (w), 1415 (s), 1370 (s), 1343 (m), 842 (w), 812 (s), 776 (m), 768 (m). 1 H-NMR (D₂O / DSS): δ = 8.16 ppm (m, very broad, 4H), 7.66 (d, 2H, J = 7.9Hz), 7.61 (m, broad, 2H), 7.38 (m, broad, 2H). - MS (70 eV): m / z (%) = 322 (M⁺-H₂O), 297 (1.13), 296 (5.08, M⁺ -CO₂), 294 (2.76), 253 (20.29), 252 (M⁺-CO₂-CO₂, 100), 251 (9.21), 250 (M⁺- H₂O-CO-CO₂), 249 (4.90), 248 ( 6.38), 224 (2.16), 126 (15.00), 125.5 (4.31), 125 (15.66), 124.5 (3.95), 124 (6.59), 113 (4.44), 112 (3.97), 44 (25.4). - C₂₂H₁₁O₄K 0.3K₂CO₃H₂O (437.9) calc. C 61.16 H 2.99 found C 60.87 H 2.97). The combined, hot, aqueous phases are acidified with glacial acetic acid. To agglomerate the precipitate, boil up briefly and then suction. Educ. 220 mg (67%) - mp. <260 ° C. - R _f (CHC₃ / silica gel) = 0.16. - UV (CHCl₃): λ _max (ε): 472 (sh); 487 (32900); 508 (29910). - Fluorescence (CHCl₃): λ _max (I _rel ) = 544 (1), 578 (0.46). - IR (KBr): ν = 1753 cm ^-1 (m, C = O), 1718 (m, C = O), 1592 (s), 1570 (s), 1501 (w), 1372 (w), 1342 (m), 1285 (m), 1231 (w), 1152 (w), 1132 (m), 1021 (m), 1000 (w), 860 (w), 840 (m), 815 (s), 770 (w), 740 (s). - 1 H-NMR (D₆-DMSO): δ = 8.73 ppm (d, 4H, J = 8.1Hz), 8.51 (d, 2H, J = 8.2Hz), 8.12 (d, 2H, J = 8.2Hz), 7.76 (t, 2H, J = 8Hz). - MS (70eV): m / z (%) = 324 (3.0), 323 (22.6), 322 (M⁺, 100), 279 (5.4), 278 (M⁺- CO₂, 24.2), 251 (10.1) , 250 (M⁺-CO₂-CO, 46.3), 249 (10.6), 248 (14.3), 125.6 (2.2), 125.1 (13.4), 124.6 (4.1), 124.1 (7.8).
C₂₂H₁₀O₃ (322.3):

Calc .:
C 81.98, H 3.12
Found:
C 81.69, H 3.24

Perylene-3-carboxylic acid methyl ester-4-N- (2,5-di-tert-butylphenyl) -N-met-hylcarboxamide (9)

530 mg (1.04 mmol) of N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide (2b) become perylene-3-carboxylic acid-4-N- (2,5-di-tert -butylphenyl) carboxamide potassium salt (8) is converted, which is then dissolved in 10 ml of N-methylpyrrolidone. A mixture of 1.00 ml (3.20 mmol) of methyl iodide in 5 ml of N-methylpyrrolidone is slowly added dropwise to the warm solution at 30 ° C. After 48 hours, the solvent is distilled off in vacuo, the residue is taken up in chloroform, filtered and chromatographed on silica gel using chloroform. The first fraction obtained is N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide (2a) (30 mg, 6%). The ester is obtained as the second fraction. Educ. 260 mg (45%) mp. 297-298 ° C. - R _f (CHCl₃ / silica gel) = 0.36. - UV (CHCl₃). λ _max (ε). 459 (27940), 430 (23980), 409 (sh, 10500), 259 (30240). - Fluorescence (CHCl₃) λ _max. 482.501 (sh). - IR (KBr): ν = 2955 cm ^-1 (s, CH₃), 2928 (m, CH₃), 2869 (w), 1716 (s, COOCH₃), 1648 (s, C = ON), 1591 (w) , 1504 (f), 1436 (m), 1399 (f), 1359 (m), 1346 (m), 1270 (s), 1204 (s),
1141 (s), 1133 (s), 1082 (w), 1032 (w), 829 (s), 810 (s), 762 (m). 1 H-NMR (CDCl₃): δ = 8.27 ppm (d, 1H, J = 8.1Hz), 8.23 (d, 1H), 8.22 (d, 1H), 8.17 (d, 1H, J = 7.9Hz), 7.87 ( d, 1H, J = 7.9Hz), 7.84 (d, 1H, J = 7.9Hz), 7.82 (d, 1H, J = 2.3Hz), 7.76 (d, 1H, J = 8.1Hz), 7.75 (d, 1H, J = 8.1Hz), 7.51 (d, 1H, J = 7.8Hz), 7.50 (d, 1H, J = 7.8Hz), 7.45 (d, 1H, J = 8.5Hz), 7.34 (dd, 1H, J = 8.3Hz, J = 2.3Hz), 3.96 (s, 3H, COOCH₃), 3.60s, 3H, NCH₃), 1.51 (s, 9H, C (CH₃) ₃), 1.41 (s, 9H, C (CH₃ ) ₃). - 13 C-NMR (CDCl₃): δ = 173.4 ppm (C = O), 170.0 (C = O), 150.3, 143.6, 143.1, 134.5, 134.2, 133.2, 133.0, 130.3, 130.2, 130.1, 129.7, 129.3, 129.0 , 128.8, 127.9, 127.6, 127.5, 127.3, 126.8, 126.7, 124.8, 121.9, 121.6, 119.6, 119.5, 53.1 (COOCH₃), 35.1 (CH₃), 34.4 (CH₃), 31.41 (t-Bu), 31.38 (t -Bu), 29.7 (N-CH₃). - MS (70 eV): m / z (%) = 556 (5.5), 555 (M⁺, 13.6), 500 (5.4), 499 (29.5), 498 (M⁺-C₄H₈, 91.8), 338 (20.6 ), 337 (M⁺-CH₃N-C₁₄H₂₁, 100), 323 (6.4), 322 (28.1), 278 (8.9), 250 (13.5), 249 (11.2).
C₃₈H₃₇NO₃ (555.718):

Calc .:
C 82.13, H 6.71, N 2.52
Found:
C 81.85, H 6.90, N 2.59

N-1-Hexylheptyl-perylene-3,4-dicarboximide (2c) from 4

200 mg (620 mmol) of perylene-3,4-dicarboxylic acid anhydride are heated to 135-140 ° C. for 1 h with 250 mg (0.12 mmol) of 7-aminotridecane, 110 mg of zinc acetylene dihydrate and 1.2 g of imidazole under an Ar protective atmosphere. After cooling, the dark red melt cake is digested with 100 ml of ethanol and the resulting suspension with 100 ml of 15 percent. Hydrochloric acid are added and the mixture is boiled until all of the ethanol has evaporated (the reaction product is readily soluble in ethanol). The solid is suctioned off and washed with warm water until the filtrate running off no longer fluoresces yellow. The crude product is then dried in a drying cabinet at 120 ° C. for 2 hours and then chromatographed on silica gel using chloroform. The first colored fraction is recrystallized from methanol ²⁰⁾ . Educ. 200 mg (63%) - orange-red crystals with strong solid fluorescence - mp. 166-168 ° C. - R _f (chloroform / silica gel) = 0.87. - UV (CHCl₃): λ _max (ε) = 506 (30250), 484 (31580). - Fluorescence (CHCl₃, Anr. 506 nm) λ _max (I _rel ): 540 (1), 568 (0.52). - IR (KBr): ν = 2960 cm ^-1 (m, CH₂), 2930 (s, CH₂), 2860 (m, CH₂), 1690 (s, C = O), 1650 (s), 1595 (m) , 1578 (w), 1460 (w), 1360 (s), 1250 (m), 1175 (w), 815 (s), 760 (s). - 1 H-NMR (CDCl₃): δ = 8.50 ppm (m, 2H, broad), 8.32 (d, 2H, J = 7.4Hz), 8.29 (d, 2H, J = 8.1Hz), 7.82 (d, 2H J = 8Hz), 7.56 (t, 2H, J = 7.9Hz), 5.15-5.22 (m, 1H, CH-N), 2.20-2.30 (m, 2H, N-CH-CH₂), 1.82-1.90 (m, 2H, N-CH-CH₂), 1.17-1.38 (m, 16H, CH₂), 0.82 (t, 6H, CH₃, J = 7Hz). - 13 C-NMR (CDCl₃): δ = 165.1 ppm (C = O), 164.2 (C = O), 136.8, 134.3, 131.8, 131.1, 130.7, 129.9, 129.2, 127.9, 126.9, 123.5, 120.1, 54.4 (N -CH), 32.5 (CH₂), 31.8 (CH₂), 29.3 (CH₂), 27.0 (CH₂), 22.6 (CH₂), 14.0 (CH₃). - MS (70eV): m / z (%) = 505 (2.1), 504 (11.3), 503 (29.6, M⁺), 487 (2.8), 486 (7.0, M⁺-OH) 323 (7.1), 322 (39.1), 321 (100, M⁺-C₁₃H₂₆), 304 (4.8), 277 (6.6), 276 (5.9), 250 (3.7).
C₃₅H₂₇NO₂ (503.7):

Calc .:
C 83.50, H 7.36, N 2.78
Gef.
C 83.58, H 7.28, N 2.92

N-1-nonyldecyperylene-3,4-dicarboxide (2e) from 4

230 mg (0.70 mmol) of perylene-3,4-dicarboxylic acid anhydride are reacted with 400 mg (1.40 mmol) of 10-aminononadecane and 1.0 g of imidazole under an Ar protective atmosphere as in 2c and worked up. After chromatography with chloroform on silica gel, the reaction product is applied to petroleum ether on silica gel, and the purely aliphatic by-products are washed out with about 1 liter of petroleum ether. The reaction product is then eluted with toluene and then recrystallized from pentane ex traktiv²⁰). Educ. 400 mg (85%) - mp 143-143.5 ° C. - R _f (silica gel / CHCl₃) = 0.94. - UV (CHCl₃): λ _max (ε) = 507 nm (31319), 482 (32213), 453 (sh, 17450). - Fluorescence (CHCl₃, Anr. 507 nm) λ _max (I _rel ) = 539 (1), 557 (0.47). - IR (KBr): ν = 2956 cm ^-1 (m, CH₂), 2924 (s, CH₂), 2853 (m, CH₂), 1995 (m, C = O), 1653 (s), 1594 (m) , 1576 (w), 1465 (w), 1457 (w), 1375 (w), 1356 (s), 1293 (w), 1246 (m), 840 (m), 811 (s), 754 (s) . - 1 H-NMR (CDCl₃): δ = 8.54 ppm (m, 2H), 8.38 (d, 2H, J = 7.2Hz), 8.35 (d, 2H, J = 8.1Hz), 7.86 (d, 2H J = 7.9 Hz), 7.59 (t, 2H, J = 7.8Hz), 5.19 (m, 1H, N-CH), 2.2-2.3 (m, 2H, N-CH-CH₂), 1.82-1.90 (m, 2H, N -CH-CH₂), 1.19-1.39 (m, 28H, CH₂), 0.83 (t, 6H, CH₃, J = 6.9Hz). - 13 C-NMR (CDCl₃): δ = 165.2 ppm (C = O), 164.2 (C = O), 136.9, 134.3, 131.9 (broad), 131.1 (broad), 130.7, 129.94, 129.3, 128.0, 127.0, 126.7 , 123.5, 120.1, 54.4 (N-CH), 32.4 (CH₂), 31.9 (CH₂), 29.59 (CH₂), 29.56 (CH₂), 29.54 (CH₂), 29.3 (CH₂), 27.0 (CH₂), 22.6 (CH₂ ), 14.1 (CH₃). - MS (70eV): m / z (%) = 589 (2.7), 588 (11.8), 587 (M⁺, 27.0), 570 (M⁺-OH, 7.2), 323 (8.2), 322 (43.2) , 321 (M⁺-C₁₉H₃₈, 100), 277 (6.0), 276 (5.5).
C₄₁H₄₉NO₂ (587.8):

Calc .:
C 83.77, H 8.40, N 2.38
Found:
C 84.03, H 8.47, N 2.52

When heating N- (1-nonyldecyl) perylene-3,4-carboximide with polyethylene to 60 ° C the dye diffuses into the plastic and results in uniform, orange colors, that fluoresce strongly. This ability is also possessed by solutions of N- (10-nonadecyl) perylene-3,4-carboximide or the solid at room temperature. Here the coloring takes place however, take place slowly.

Other imides with strongly solubility-increasing residues, such as. B. the 1-hexylheptyl or the 1-octylnonyl residue have similar diffusion properties.

N-cyclooctyl-perylene-3,4-dicarhoximide (2f) from 4

300 mg (0.93 mmol) of perylene-3,4-dicarboxylic anhydride are reacted with 1.5 g (2.15 mmol) of cyclooctylamine and 3 g of imidazole under an Ar protective atmosphere as in 2c for 12 h at 140 ° C. and worked up. After drying in a drying cabinet, 10 percent is used to remove unreacted starting material. Boil the potassium carbonate solution and wash with hot water until the filtrate runs colorless. The brown-red product is dried in a drying cabinet at 120 ° C. and then recrystallized ²⁰⁾ from ethanol. Educ. 290 mg (72%) dark red crystal powder without solid fluorescence - mp. 342-343 ° C. - R _f (CHCl₃ / silica gel) 0.78. - UV (CHCl₃): λ _max (ε) = 506 nm (32,000), 484 (32,100), 264 (35,200). - Fluorescence (CHC₃) λ _max (I _rel ) = 511 nm, 542 (1), 573 (sh, 0.51). - IR (KBr): ν = 2923 cm ^-1 (m, CH₂), 2854 (w, CH₂), 1690 (s, C = O), 1648 (s, C = O), 1593 (s), 1577 ( m), 1501 (f), 1413 (f), 1373 (m), 1354 (s), 1293 (m), 1247 (m), 1175 (m), 838 (f), 810 (s), 754 ( m). - 1 H-NMR (CDCl₃): δ = 8.49 ppm (d, 2H, J = 7.9Hz), 8.34 (d, 2H, broad), 8.30 (d, 2H, J = 8.1Hz), 7.85 (d, 2H, J = 7.8Hz), 7.58 (t, 2H, J = 7.8Hz), 5.36 (m, 1H, CH-N), 2.58- 2.48 (m, 2H, CH₂), 1.85-1.55 (m, 12H, CH₂) . - 13 C-NMR (CDCl₃): δ = 163.9 ppm (C = O), 136.7, 134.3, 130.7, 129.7, 129.2, 127.9, 126.9, 126.6, 123.5, 120.1, 53.8 (CH-N), 32.1 (CH₂), 26.5 (CH₂), 26.2 (CH₂), 23.8 (CH₂). - MS (70eV): m / z (%) = 431 (7.6), 431 (M⁺, 23.6), 414 (M⁺-OH, 1.4), 323 (4.7), 322 (30.1), 321 (M⁺ -C₈H₁₄, 100), 277 (9.5).
C₃₀H₂₅NO₂ (431.5):

Calc .:
C 83.50, H 5.84, N 3.25
Found:
C 83.22, H 5.83, N 3.53

N-Cyclododecyl-perylene-3,4-dicarboximide (2g) from 4

190 mg (0.56 mmol) of perylene-3,4-dicarboxylic anhydride are reacted with 140 mg (1.28 mmol) of cyclododecylamine and 2.0 g of imidazole under an Ar protective atmosphere as in 2c and worked up. After chromatography with Chloroforman silica gel, the reaction product with toluene is extractively crystallized ²⁰⁾ . Educ. 190 mg (66%) - mp 285 ° C. - R _f (CHCl₃ / silica gel) = 0.58. - UV (CHCl₃): λ _max (ε): 454 (shoulder, 19085), 484 (32630), 507 (32015). - Fluorescence (CHCl₃, Anr. 584 nm) λ _max (I _rel ) = 538 (1), 572 (sh, 0.44). - IR (KBr): ν = 2925 cm ^-1 (s, CH₂), 2850 (m, CH₂)), 1685 (s, C = O), 1645 (s), 1592 (s), 1570 (s), 1440 (w), 1410 (w), 1373 (w), 1355 (s), 1290 (m), 1245 (m), 1170 (w), 1120 (w), 1043 (w), 840 (w), 810 (s), 754 (s). - 1 H-NMR (CDCl₃): δ = 8.51 ppm (d, broad, 2H, J = 7.9Hz), 8.37 (d, 2H, J = 7.7Hz), 8.34 (d, 2H, J = 8.2Hz), 7.86 (d, 2H, J = 8.1Hz), 7.59 (t, 2H, J = 7.9Hz), 5.43 (m, R₂CH-N, 1H), 2.26-2.36 (m, 2H, CH₂), 1.9-2.0 (m , 2H, CH₂), 1.32-1.50 (m, 14H, CH₂). - 13 C-NMR (CDCl₃): δ = 164.7 ppm (C = O), 136.8, 134.3, 131.4 (broad), 130.7, 129.9, 129.3, 128.0, 127.0, 126.7, 123.5, 120.1, 49.0 (CH-N), 28.3 (CH₂), 24.6 (CH₂), 24.3 (CH₂), 23.2 (CH₂), 22.9 (CH₂), 22.3 (CH₃). - MS (70 eV): m / z (%) = 488 (5.9), 487 (M⁺, 15.0), 323 (5.7), 322 (33.7), 321 (M⁺-C₁₂H₂₂, 100), 304 (M⁺ -C₁₂H₂₂-OH, 4.1), 277 (7.4), 276 (5.3), 250 (4.1), 146.5 (4.1), 125 (5.7), 124 (4.1).
C₃₄H₃₃NO₂ (487.6):

Calc .:
C 83.75, H 6.82, N 2.87
Found:
C 83.75, H 6.81, N 2.91

Crystal structure (diffractometer: ENRAF-Nonius CAD4, radiation: MoKα, monochromator: highly oriented graphite crystal): C₃₄H₃₃NO₂ - M _r = 487.65, a = 1632.2 (5), b = 780.3 (2), c = 1998.5 (6), β = 99.64 (2) °, volume = 2.5092 nm³, Z = 4, density (calc.) = 1.291 MG / M³, µ = 0.738, crystal system monoclinic, space group P21 / n (No. 14). - Data collection single crystal 0.33 × 0.53 × 0.53 mm³ (orange), ξ - scan, measured 2 R range. 4- 46 °, in ± hkl, scan width. 0.80 + 0.35 tan R, 3 standard reflections every 3600 s measuring time, index range. 0 h 8, 0 k 6, 0 l 12, reflections collected: 3907, independent and observed. 3784, observe (I <2σ (I)): 2521, no correction for absorption, calculation of the structure: direct method, anisotropic refinement of the non-hydrogen atoms, isotropic refinement of the H atoms, 334 parameters, R _w = 0.0568, R _w = 0.0674, w ^-1 = σ² (F _o ), maximum and minimum residual electron density 10⁶ e / pm³) 0.238-0.351.

N-2-hydroxyethyl-perylene-3,4-dicarboximide (2h) from 4

190 mg (0.56 mmol) of perylene-3,4-dicarboxylic anhydride are reacted with 0.85 ml (1.40 mmol) of 2-aminoethanol and 1.18 g of imidazole under an Ar protective atmosphere as in 2c for 96 h and worked up. After drying in a drying cabinet, 10 percent is used to remove unreacted starting material. Boil the potassium carbonate solution and wash with hot water until the filtrate runs colorless. The brown-red product is dried at 120 ° C. in a drying cabinet and then recrystallized ²⁰⁾ from toluene. Educ. 50 mg (23%) - mp. <260 ° C. - UV (CHCl₃): λ _max = 489 nm, 509. - Fluorescence (CHCl₃, Anr. 489 nm) λ _max (I _rel ) = 546 nm (1), 579 (sh, 0.46). - IR (KBr): ν = 3483 cm ^-1 (s, OH), 3060 (w), 2960 (w, CH₂), 2880 (w, CH₂), 1689 (s, C = O), 1646 (s, C = O), 1592 (s), 1570 (s), 1501 (w), 1420 (w), 1373 (s), 1354 (s), 1292 (m), 1243 (m), 1169 (w), 1062 (m), 1044 (m), 836 (m), 810 (s), 764 (m), 752 (s). - MS (70eV): m / z (%) = 366 (18.49), 365 (M⁺, 70.65), 347 (M⁺-H₂O, 3.35), 346 (4.07), 335 (M⁺-CH₂OH, 16.34) , 334 (19.93), 322 (23.9), 321 (M⁺-C₂H₄OH), 307 (5.17), 304 (12.28), 277 (18.55), 276 (18.94), 275 (9.71), 251 (13.03), 250 (28.14), 125 (19.20), 124 (6.94)
C₂₄H₁₅NO₃ (365.4):

Calc .:
C 78.89, H 4.14, N 3.83
Gef.
C 78.26, H 4.27, N 3.84

N-1-Hexylheptyl-perylene-3,4-dicarboximide (2c) from N-1-Hexylheptyl-perylene-3,4-dicar bonic anhydride-9,10-dicarboximide

300 mg (0.6 mmol) of N- (1-hexylheptyl) perylene-3,4-dicarboxylic acid anhydride-9,10-dicarboximide and 6 ml of 12 percent. KOH are heated in an autoclave at 205 ° C for 22 h based on Ref. ³⁾ . After cooling, it is suctioned off and washed twice with water. From the remaining residue (20 mg) can be obtained by chromatography with chloroform on silica gel in addition to a little perylene 10 mg (4%) Dicarbonsäu reimid 2c. See above for mp and spectroscopic data.

Nitration of N-1-hexylheptyl-perylene-3,4-dicarboximide with acetane drid / nitric acid

Based on Ref. ^21), 120 mg (240 mmol) of N-1-hexylheptyl-perylene-3,4-carboximide is suspended in 1 ml of acetic anhydride and a mixture of 0.057 ml of conc. Nitric acid in 0.15 ml acetic anhydride. After 2 h, the mixture is allowed to warm slowly to room temperature and stirred for a further 72 h. The dark red product is evaporated in vacuo and the residue is chromatographed with chloroform on silica gel. The first fraction obtained is a mixture of 60% N- (1-hexylheptyl) perylene-3,4-carboximide and 40% N- (1-hexylheptyl) -2-nitro-perylene-3,4-carboximide, each but could not be separated by chromatography (R _f value 0.85; chloroform / Kiesekgel). 1 H-NMR (CDCl₃): δ = 8.54 ppm (s, broad, 2H), 8.33 (d, 1H, J = 7.9Hz), 8.31 (d, 1H, J = 7.8Hz), 7.94 (d, 1H, J = 7.7Hz), 7.90 (d, 1H, J = 7.9Hz), 7.87 (d, 1H, J = 8.1Hz), 7.57 (t, 1H, J = 7.9Hz), 7.50 (t, 1H, J = 7.9 Hz), 5.19 (m, 1H, N-CH), 2.26 (m, 2H, CH₂), 1.88 (m, 2H, CH₂), 1.37-1.22 (m, 16H, CH₂), 0.83 (t, 6H, CH₃ , J = 6.9Hz). The second fraction is eluted with N- (1-hexylheptyl) -9-nitro-perylene-3,4-carboximide. 1 H-NMR (CDCl₃): δ = 8.58 ppm (s, broad, 2H), 8.53 (d, 1H, J = 8.3Hz), 8.43 (d, 1H, J = 7Hz), 8.40 (d, 1H, J = 8.3Hz), 8.39 (d, 1H, J = 8.1Hz), 8.33 (d, 1H, J = 8.5Hz), 8.22 (d, 1H, J = 8.4Hz), 7.76 (dd, 1H, J₁ = 7.6Hz , J₂ = 8.7Hz), 5.19 (m, 1H, N-CH), 2.26 (m, 2H, CH₂), 188 (m, 2H, CH₂), 1.37-1.22 (m, 16H, CH₂), 0.83 (t , 6H, CH₃ J = 6.9Hz).

Nitration of N- (2,5-di-tert-butyl-phenyl) perylene-3,4-carboximide with N₂0₄ under Exposure to light

Following a procedure according to Ref. ²¹⁾ , 250 mg (0.49 mmol) of N- (2,5-di-tert-butyl-phenyl) -perylene-3,4-carboximide is dissolved in 17 ml of dichloromethane under the influence of daylight and then adds 1.5 ml of a solution of NO₂ in di chloromethane containing 15.7 g / l (0.5 mmol). After a reaction time of 17 h at room temperature, the solvent is evaporated off on a rotary evaporator. A thin layer chromatogram (chloroform / silica gel) shows that the residue obtained consists mainly of 3 dyes with the R _f values of 0.27, 0.38 and 0.49, the compound with the R _f value of 0.38 being the starting material, such as a comparison with an authentic sample shows. The crude product is chromatographed on silica gel using chloroform, 80 mg (32%) of N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide being able to be recovered. By multiple chromatography with chloroform over silica gel and subsequent extractive ²⁰⁾ recrystallization with methanol, the compound with an R _f value of 0.49 could be obtained in pure form and by 1 H, COZY and NOESY NMR spectra as 1 -nitro-N- ( 2,5-di-t-butylphenyl) perylene-3,4-carboximide can be identified. Educ. 20 mg (7%) - mp 331-335 ° C (dec.). - R _f (chloroform / silica gel) = 0.49. - UV (CHCl₃): λ _max (ε): 514 (25290), 409 (wide, 4350), 356 (wide, 6250). - IR (KBr): ν = 2964 cm ^-1 (CH₃, w), 1711 (C = O, s), 1668 (C = O, s), 1594 (m), 1576 (w), 1567 (w) , 1533 (m), 1406 (w), 1353 (ss), 1316 (w), 1247 (w), 813 (m), 757 (w). - 1 H-NMR (CDCl₃): δ = 8.76 ppm (d, 1H, J = 8.IHz, H-5), 8.71 (s, 1H, H-2), 8.57 (d, 1H, J = 8th IHz , H-7), 8.55 (dd, 1H, J₁ = not resolved due to overlap, J₂ = 0.8Hz, H-6), 8.15 (dd, 1H, J₂ = 0.8Hz, J₃ = 7.7Hz, H-12), 8.03 (d, 1H, J = 8.1Hz, H-10), 8.02 (d, 1H, J = 8.1Hz, H-9), 7.73 (d, 1H, J = 7.8Hz, H-8), 7.61 ( d, 1H, J = 7.8Hz, H-11), 7.60 (d, 1H, J₅ = 8.7Hz), 7.46 (dd, 1H, J₄ = 2.1Hz, J₅ = 8.6Hz), 7.00 (d, 1H, J₄ = 2.1Hz), 1.34 (s, 9H, CH₃), 1.31 (s, 9H, CH₃). - 13 C-NMR (CDCl₃): δ = 164.2 ppm (C = O), 163.4 (C = O), 150.3, 138.3, 134.1, 133.2, 133.0, 132.0, 130.2, 129.2, 128.9, 128.3, 127.8, 127.4, 127.3 , 126.9, 126.4, 124.9, 124.6, 122.0, 121.9, 121.4, 35.6, 34.3, 31.8 (CH₃), 31.3 (CH₃). - MS (70eV): m / z (%) = 555 (3.2), 554 (M⁺, 8.9), 499 (6.6), 498 (34.1), 497 (M⁺-C₄H₉, 100), 467 (M⁺ -C₄H₉- NO, 452 (13.1), 451 (M⁺-C₄H₉-NO₂, 37.8), 437 (6.9), 436 (8.6), 435 (17.6), 275 (5.1), 149 (16.1).
C₃₆H₃₀N₂O₄ (554.6):

Ber.
C 77.96, H 5.45, N 5.05
Found:
C 77.17, H 5.64, N 4.84

Nitration of N- (2,5-di-tert-butyl-phenyl) perylene-3,4-carboximide with N₂0₄ under Exposure to light catalyzed by methanesulfonic acid

430 mg (0.85 mmol) of N- (1-hexylheptyl) perylene-3,4-carboximide is dissolved in 25 ml of dichloromethane based on Ref. ²¹⁾ and 10 μl of methanesulfonic acid are added to the red solution. 5 ml of a solution of 15.7 g of nitrous oxide in liters of dichloromethane (0.85 mmol) are then added dropwise, after which it changes color to wine red. The solution is left to stand overnight and the dichloromethane is then evaporated off on a rotary evaporator. The formation of 4 main products and a few by-products can be seen from a thin layer chromatogram (chloroform / silica gel) of the wine-red residue. The residue is chromatographed on silica gel using chloroform, all 4 main products being able to be obtained in pure form. The following fractions are obtained in succession: 1st fraction: 60 mg of a wine-red powder which is further purified by extraction with ethyl acetate, multiple chromatography with chloroform over silica gel. Educ. 30 mg (5%) 1,6-dinitro-N- (1-hexyl heptyl) perylene-3,4-carboximide. Mp 142-144 ° C - R _f (chloroform / silica gel) = 0.81. - UV (CHCl₃): λ _max = 508, 482. - Fluorescence (CHCl₃): λ _max (I _rel ) = 541 (1), 573 (sh, 0.72). - IR (KBr): ν = 2956 cm ^-1 (m), 2927 (m), 2856 (m), 1706 (C = O, m), 1662 (C = O, s), 1594 (m), 1576 (w), 1538 (s), 1517 (w), 1464 (w), 1457 (w), 1411 (w), 1344 (s), 1310 (m), 1248 (m), 842 (w), 813 (m), 765 (w), 748 (w), 689 (w) - 1 H-NMR (CDCl₃): δ = 8.77 ppm (2H, broad, H-2.5), 8.17 (2H, dJ = 7.6Hz), 8.13 (2H, d, J = 7.8Hz), 7.68 (2H, t, J = 7.9Hz. H-8.11), 5.15 (1H, m, CH-N), 2.23-2.20 (2H, m, CH₂ ), 1.86-1.81 (2H, m, CH₂), 1.36-1.23 (16H, m, CH₂), 0.84 (6H, t, J = 6.9Hz). - 13 C-NMR (CDCl₃): δ = 147.4 ppm, 133.7, 133.5, 129.9, 129.7, 129.5, 129.3, 128.2, 127.7, 127.5, 123.2, 120.8, 55.5 (CH-N), 32.2 (CH₂), 31.9 (CH₂ ), 31.7 (CH₂), 29.7 (CH₂), 29.1 (CH₂), 26.8 (CH₂), 22.6 (CH₂), 14.0 (CH₃). - MS (70eV): m / z (%) = 595 (3.1), 594 (16.4), 593 (M⁺, 41.9), 576 (M⁺-OH, 6.5), 413 (20.5), 412 (71.0) , 411 (M⁺-C₁₃H₂₆, 100), 394 (M⁺-C₁₃H₂₆-OH, 13.9), 381 (M⁺-C₁₃H₂₆-NO, 6.1), 367 (8.7), 366 (M⁺-C₁₃H₂₆-NO₂, 33.6 ), 353 (6.5), 351 (M⁺-C₁₃H₂₆-NO-NO, 11.8), 348 (11.0), 338 (6.3), 337 (9.4), 336 (9.2), 335 (15.5), 321 (9.8) , 320 (M⁺-C₁₃H₂₆-NO₂-NO₂, 35.4), 319 (9.4), 292 (8.0), 291 (8.1), 275 (9.9), 274 (17.4), 273 (6.5), 264 (11.6), 263 (9.8), 262 (12.6), 249 (9.6), 28 (10.3), 92 (13.3), 91 (27.6), 69 (18.0), 55 (29.6), 32 (51.1).
C₃₅H₃₅N₃O₆ (593.7):

Calc .:
C 70.81, H 5.94, N 7.08
Found:
C 70.88, H 5.94, N 6.61.

2nd fraction: contaminated 9-nitro-N- (1-hexylheptyl) perylene-2,4-carboximide.

3rd fraction: 0.22 g of a wine-red substance, which according to the 1 H-NMR spectrum 81% 9-nitro-N- (1-hexylheptyl) perylene-3,4-carboximide and 19% 2,5-dinitro-N- (1-hexyl heptyl) perylene-3,4-carboximide. However, these could not be caused by columnar chroma topography with chloroform or toluene on silica gel or by fractional crystallization Acetonitrile or other solvents can be obtained in pure form.

4. Fraction: 130 mg of a dark red substance which is recrystallized with methanol ²⁰⁾ . 90 mg (25%) of dark red crystals are obtained, which could be identified by a 1 H and a NOESY NMR spectrum as 9,10-dinitro-N- (1-hexylheptyl) perylene-3,4-carboximide. Mp 245-246 ° C. - R _f (chloroform / silica gel) = 0.54. - UV (CHCl₃). λ _max (ε) = 506 nm (58 015), 474 (40 792), 446 (16 730). - IR (KBr): ν 2958 cm ^-1 (CH₃, w), 2927 (CH₂, m), 2856 (CH₂, w), 1700 (C = O, s), 1662 (C = O, s), 1594 (m), 1534 (m), 1518 (w), 1409 (w), 1349 (ss), 1328 (s), 1247 (w), 852 (w), 825 (w), 805 (w), 800 (w), 751 (w), 734 (w). - 1 H-NMR (CDCl₃): δ = 8.67 ppm (2H, m), 8.58 (2H, d, J-8.1Hz, H-1.6), 8.55 (2H, d, J = 8.5Hz, H-7 , 12), 8.37 (2H, d, J = 8.5Hz, H-8.11), 5.17 (1H, m, CH-N), 2.27-2.21 (2H, m, CH₂), 1.89-1.83 (2H , m, CH₂), 1.36-120 (16H, m, CH₂), 0.82 (6H, t, CH₃). - 13 C-NMR (CDCl₃): δ = 163.2 ppm (C = O), 145.9, 134.6, 133.1, 131.8 (broad), 131.2 (broad), 130.0, 129.2, 126.9, 125.6, 123.9, 122.7, 118.8, 54.9 ( CH-N), 32.3 (CH₂), 31.7 (CH₂), 29.2 (CH₂), 16.9 (CH₂), 22.6 (CH₂), 14.0 (CH₂). - MS (70eV): m / z (%) = 595 (5.1), 594 (27.4), 593 (M⁺. 72.6), 576 (M⁺-OH, 7.0), 548 (5.1), 547 (M⁺ -NO₂, 13.9), 518 (11.1), 517 (M⁺- NO₂-NO, 19.4), 508 (3.7), 413 (24.9), 412 (65.1), 411 (M⁺-C₁₃H₂₆, 77.0), 367 ( 13.1), 366 (39.4), 365 (M⁺-C₁₃H₂₆-NO₂, 91.3), 349 (7.7), 348 (9.0), 338 (6.6), 337 (36.6), 336 (84.2), 335 (M⁺- C₁₃H₂₆-NO₂-NO, 100), 320 (7.7), 319 (3.1), 309 (14.0), 308 (70.2), 307 (64.2), 263 (14.3), 262 (45.8), 251 (31.9), 237 (15.8), 117.6 (26.7), 92 (60.2), 91 (13.6), 44 (42.9), 30 (NO, 85.1).
C₃₅H₃₅N₃O₆ (593.7):

Calc .:
C 70.81, H 5.94, N 7.08
Found:
C 70.65, H 5.78, N 7.38

9-nitro-N- (1-hexylheptyl) perylene-3,4-carboximide (10)

500 mg (1.00 mmol) of N- (1-hexylheptyl) perylene-3,4-carboximide is dissolved in 100 ml of dichloromethane, and 2.9 ml of a solution of nitrogen dioxide in dichloromethane (15.7 g NO₂ per liter, 1.00 mmol). The mixture is then left to stand at room temperature for 17 hours with the exclusion of light, and the dichloromethane is then evaporated using the rotary evaporator. A thin layer chromatogram (chloroform / silica gel) shows that the residue obtained consists mainly of 2 compounds with the R _f values 0.89 and 0.73. The substance with the larger R _f value is unreacted starting material, from which 210 mg (42%) can be recovered by column chromatography (chloroform / silica gel). The 2nd chromatography fraction is purified by extractive ²⁰⁾ order crystallization from methanol. Educ. 300 mg (55%) wine-red needles (structural evidence by 1 H-NMR, COZY, and NOESY spectra) - mp. 184-185 ° C. - R _f (chloroform / silica gel) = 0.73. - UV (CHCl₃): λ _max (ε) = 510 nm (34 344), 483 nm (30 844), 357 nm (broad, 4470). - Fluorescence (CHCl₃): λ _max = 549 nm. - IR (KBr): v = 2962 cm ^-1 (CH₃, m), 2928 (CH₂, w), 2870 (CH₂), 1708 (C = O, s) , 1666 (C = O, s), 1591 (s), 1565 (w), 1399 (m), 1350 (s), 1242 (w), 1204 (w), 1168 (w), 829 (w), 806 (w), 756 (w). - 1 H-NMR (CDCl₃): δ = 8.58 ppm (broad, 2H, H-2.5), 8.53 (d, 1H, J = 7.6Hz, H-10), 8.44 (d, 1H, J = 7.2Hz, H -12), 8.41 (d, 1H, J = 8.2Hz, H-1), 8.40 (d, 1H, J = 8.1Hz, H-6), 8.33 (d, 1H, J = 8.4Hz, H-7 ), 8.22 (d, 1H, J = 8.4Hz, H-8), 7.77 (dd, 1H, J₁ = 7.7Hz, J₂ = 8.5Hz, H-II), 5.19 (m, CH-N, 1H), 2.26-2.23 (m, 2H, CH₂), 1.89-1.86 (m, 2H, CH₂), 1.36 1.22 (m, 16H, CH₂), 0.83 (t, 6H, CH₃). - 13 C-NMR (CDCl₃). δ = 164.7 ppm (C = O), 163.9 (C = O), 147.2, 137.5, 135.5, 134.7, 134.3, 131.6 (broad), 129.7, 129.5, 128.9, 126.5, 126.1, 125.3, 124.5, 124.2, 122.4, 121.6, 121.4, 54.7 (CH-N), 32.4 (CH₂), 31.8 (CH₂), 29.2 (CH₂), 27.0 (CH₂), 22.6 (CH₂), 14.0 (CH₃). - MS (70eV): m / z (%) = 549 (10.0), 548 (M⁺, 26.3), 513 (M⁺ OH), 368 (11.5), 367 (53.8), 366 (M⁺-C₁₃H₂₆, 100), 337 (8.7), 336 (M⁺ C₁₃H₂₆ NO, 16.1), 322 (5.8), 321 (20.4), 320 (13.8), 308 (7.9), 303 (7.1), 275 (M⁺-C ₁₃H₂₆ -NO₂-CO₂H, 16.2), 264 (9.2), 85 (27.6), 83 (45.4), 44 (44.8), 32 (50.2).
C₃₅H₃₆N₂O₄ (548.7):

Calc .:
C 76.62, H 6.61, N 5.11
Found:
C 76.60, H 6.58, N 5.41

9-acetamido-N- (1-hexylheptyl) perylene-3,4-carboximide

100 mg (0.18 mmol) of 9-nitro-N- (1-hexylheptyl) perylene-3,4-carboximide (10) are suspended in 15 ml of glacial acetic acid, then 80 mg (0.72 mmol) of iron dust are added and the red suspension is boiled 4½ hours under reflux, whereby a slow change in color from red to reddish brown and purple to dark purple can be observed. Water is first added to the cooled, violet solution and then neutralized with 10 percent. KOH. The now reddish-purple colored suspension is shaken out three times with chloroform, the combined organic phases are dried with anhydrous sodium sulfate and then evaporated. According to the thin layer chromatogram (chloroform / silica gel), the purple product obtained consists of 2 main products with the R _f values of 0.02 and 0.43. This is filtered chromatographically with chloroform over silica gel until no more violet solution emerges. The red colored silica gel is extracted with chloroform, 50 mg of red powder being obtained after spinning in, which is then recrystallized with methanol ²⁰⁾ . Educ. 30 mg (30%) - mp. <230 ° C; from 172-175 ° C brown color. - R _f (CHCl₃ / glacial acetic acid 20: 1; silica gel) = 0.90. - UV (CHCl₃): λ _max (ε) = 506 nm (31589, broad), 356 (2995). - Fluorescence (CHCl₃): λ _max = 574 nm (broad). - IR (KBr): ν = 3294 cm ^-1 (w, C = ONH), 2954 (m, CH₂), 2927 (m, CH₂), 2857 (w, CH₃), 1695 (s, C = O), 1648 (s, C = O), 1593 (m), 1576 (m), 1539 (w), 1516 (w), 1394 (w), 1356 (s), 1293 (w), 1261 (w), 1247 (w), 808 (m), 752 (w). - 1 H-NMR (CDCl₃, 90 ° C): δ = 9.89 ppm (s, 1H, NH-CO), 8.67 (d, 1H, J = 7.4Hz), 8.64 (d, 1H, J = 8.2Hz) , 8.61 (d, 1H, J = 8.6Hz), 8.57 (d, 1H, J = 8.1Hz), 8.47 (d, 1H, J = 8.0Hz), 8.46 (d, 1H, J = 7.8Hz), 8.25 (d, 1H, J = 8.6Hz), 8.00 (d, 1H, J = 8.5Hz), 7.73 (t, 1H, J = 8.2Hz), 5.08 (m, 1H, CH-N), 2.23 (s, 3H, COCH₃), 2.18-2.15 (m, 2H, CH₂), 1.80 (m, 2H, CH₂), 1.27-1.18 (m, 16H, CH₂), 0.78 (t, 6H, CH₃, J = 6.9Hz). - MS (70eV): m / z (%) = 561 (13.0), 560 (M⁺. 31.6), 544 (3.8), 543 (M⁺-OH, 9.1), 517 (M⁺-CH₃CO, 1.3) , 380 (6.1), 379 (30.6), 378 (M⁺-C₁₃H₂₆, 66.4), 361 (M⁺-C₁₃H₂₆-OH, 4.4), 338 (11.4), 337 (45.9), 336 (M⁺-C₁₃H₂₆- CH₂CO, 100), 335 (9.0), 308 (9.4), 292 (8.1), 291 (12.8), 290 (9.6), 265 (7.7), 264 (11.4), 57 (37.1), 43 (CH₃CO +, 27.2 ).
C₃₇H₄₀N₂O₃ (560.7):

Calc .:
C 79.25, H 7.19
Found:
C 77.66, H 7.27.

The violet filtrate running off in the chromatographic filtration is evaporated with the rotary evaporator and flash chromatographed with chloroform over silica gel. By renewed flash chromatography with toluene over silica gel, 40 mg (39%) of powdery blue 9-amino-N- (1-hexylheptyl) -perylene-3,4-carboximide (17) is obtained, which is recrystallized from methanol extractive ²⁰⁾ . Educ. 20 mg (20%) - mp 127-129 ° C. - R _f (CHCl₃ / silica gel) 0.43. - UV (CHCl₃): λ _max (ε) 554 nm (26260), 374 (4260), 357 (4780.- UV (CH₃OH): λ _max = 602 nm, 382.- Fluorescence (CHCl₃) λ _max = 645 nm (weak) .IR (KBr): ν 3364 cm ^-1 (m, NH₂), 3247 (w, NH₂), 2954 (m, CH₃), 2926 (m, CH₃), 2855 (w, CH₃), 1685 ( s, CO), 1635 (s, C = O), 1595 (m), 1563 (s), 1505 (m), 1458 (w), 1414 (w), 1396 (w), 1352 (s), 1279 (s), 1249 (w), 804 (m), 754 (m). ¹H-NMR (CDCl₃): δ = 8.35 ppm (2H, broad), 8.16 (d, 1H, J = 7.6Hz) , 8.05 (d, 1H, J = 8.1Hz), 7.98 (d, 1H, J = 8.3Hz), 7.87 (d, 1H, J = 8.3Hz), 7.66 (d, 1H, J = 8.2Hz), 7.39 (t, 1H, J = 7.9Hz), 6.70 (d, 1H, J = 8.2Hz), 5.21 (m, 1H, CH-N), 4.56 (s, 2H, NH₂), 2.28-2.24 (m, 2H , CH₂), 1.91-1.88 (m, 2H, CH₂), 1.38-1.23 (m, 16H, CH₂), 0.83 (t, 6H, CH₃, J = 7.0Hz). - 13 C-NMR (CDCl₃): δ = 165.3 ppm (C = O), 164.5 (C = O), 145.6, 137.9, 137.0, 131.9, 131.4, 130.6, 130.0, 129.4, 128.5, 125.8, 125.7, 125.3, 124.0, 123.2, 122.8, 119.6, 119.1, 117.5 , 110.8, 54.2 (CH-N), 32.5 (CH₂), 31.8 (CH₂), 29.3 (CH₂) , 27.1 (CH₂), 22.6 (CH₂), 14.0 (CH₃).

9-amino-N- (1-hexylheptyl) perylene-3,4-carboximide (17)

100 mg (0.18 mmol) of 9-nitro-N- (1-hexylheptyl) perylene-3,4-carboximide and 70 mg of iron powder are suspended in 30 ml of ethanol, and then 2 ml of conc. Hydrochloric acid too. The mixture is heated under reflux for 1 hour, a color change to yellow-brown being observed. The mixture is neutralized with KOH, the dark precipitate is filtered off and dried at 120 ° C. in a drying cabinet. A thin layer chromatogram (chloroform / silica gel) shows that 2 substances with the R _f values of 0.21 and 0.32 were formed. It is chromatographed with chloroform over silica gel, the first fraction being 10 mg of a blue-colored powder. According to the NMR and mass spectra, this probably consists of two azo compounds with very high mass numbers. The second fraction is 9-amino-N- (1-hexylheptyl) perylene-3,4-carboximide. Educ. 80 mg (85%) blue powder - mp. 211 ° C. - R _f (chloroform / silica gel) = 0.20. - UV (CHCl₃): λ _max (ε) = 554 nm (27 940), 375 (4903), 356 (5412), 277 (29 123), 262 (23 798). - Fluorescence (CHCl₃): λ _max = 642 nm (weak). - IR (KBr): ν = 3246 cm ^-1 (m, NH₂), 2953 (m, CH₃), 2926 (m, CH₂), 2856 (w, CH₂), 1658 (m, C = O), 1635 ( s), 1595 (m), 1565 (s), 1506 (m), 1457 (w), 1414 (w), 1396 (w), 1353 (s), 1279 (s), 1249 (w), 804 ( m), 754 (m). - 1 H-NMR (CDCl₃): δ = 8.33 ppm (broad, 2H), 8.11 (d, 1H, J = 7.3Hz), 8.00 (d, 1H, J = 8.2Hz), 7.93 (d, 1H, J = 8.4Hz), 7.82 (d, 1H, J = 8.2Hz), 7.63 (d, 1H, J = 8.2Hz), 7.36 (t, 1H, J = 7.9Hz), 6.67 (d, 1H, J = 8.2Hz ), 5.21 (m, 1H, CH-N), 2.25-2.28 (m, 2H, CH₂), 1.92-1.90 (m, 2H, CH₂), 1.38-1.24 (m, 16H, CH₂), 0.83 (t, 6H, CH₃, J = 7Hz). - 13 C-NMR (CDCl₃): δ = 165.4 ppm (C = O), 164.4 (C = O), 145.6, 137.8, 136.9, 131.9, 131.3, 131.1, 130.5, 129.9, 129.3, 129.0, 128.4, 128.2, 125.8 , 125.6, 125.3, 123.9, 123.1, 122.8, 119.6, 119.0, 117.4, 110.7, 54.2 (CH-N), 32.5 (CH₂), 31.8 (CH₂), 29.3 (CH₂), 27.1 (CH₂), 22.6 (CH₂) , 14.0 (CH₃). MS (70eV): m / z (%) - 519 (11.5), 518 (M⁺, 30.7), 501 (M⁺-OH, 6.7), 338 (7.0), 337 (37.9), 336 (M⁺- C₁₃H₂₆, 100), 292 (6.7), 291 (10.8), 264 (7.8).
C₃₅H₃₈N₂O₂ (518.7):

Calc .:
C 81.05, H 7.35, N 5.40
Found:
C 80.08, H 7.35, N 5.48

9-N, N-Dimetylamino-N ′ - (1-hexylheptyl) perylene-3,4-carhoximide.

Mix 190 mg (0.37 mmol) of 9-amino-N '- (7-tridecyl) perylene-3,4-carboximide with 2 g of formic acid and then add 40 mg 37 percent. wss. Formaldehyde solution too. This suspension is heated to 75-80 ° C for 18 h, during which a change in color from red to blue can be observed. By adding 20 ml 50 percent. KOH solution, the purple product is precipitated. The mixture is stirred for a further 1 h, then the product is filtered off with suction, washed with water and dried in a drying cabinet. Repeated chromatography of the product with chlorine form over silica gel allows two substances with the R _f values 0.92 and 0.51 to be isolated. The substance with the larger R _f value can be obtained by 1 H-NMR spectroscopy as 9-N, N-dimetylamino-N '- (1-hexylheptyl) -perylene-3,4-carboximide (70 mg = 39%), which Substance with the smaller R _f value can be identified as a starting product (40 mg = 48%) by comparing the thin-layer chromatograms and 1 H-NMR spectra. Educ. 70 mg (39%) - mp 168-169 ° C. - UV (CHCl₃): λ _max (ε) = 542 (26400), 506 sh (21,000), 382 (3000), 357 (3200), 269 (25,800), 262 (25,700). - Fluorescence (CHCl₃): λ _max (I _rel ) = 662. - IR (KBr): ∼ = 2955 cm ^-1 (m), 2927 (m), 2856 (m), 1691 (m, C = O), 1649 (s, C = O), 1594 (w), 1570 (s), 1503 (w), 1457 (w), 1409 (w), 1394 (w), 1354 (s), 1290 (m), 1246 (w), 1209 (w), 1173 (w), 807 (m), 766 (w), 754 (w). - 1 H-NMR (CDCl₃): δ = 8.54 ppm (m, 2H), 8.44 (d, 1H, J = 7Hz, broad), 8.36 (d, 1H, J = 8.2Hz), 8.35 (d, 1H, J = 8.4Hz), 8.27 (d, 1H, J = 8.3Hz), 8.26 (d, 1H, J = 8.4Hz), 7.26 (t, 1H, J = 8.0Hz), 7.16 (d, 1H, J = 8.3 Hz). - 13 C-NMR (CDCl₃): δ = 167.19 ppm (C = O), 153.95, 148.18, 133.54, 131.91, 130.20, 129.65, 129.40, 128.67, 127.46, 126.32, 125.82, 124.71, 123.89, 123.15, 119.64, 118.71, 114.83, 54.30 (N-CH), 44.99 (NCH₃), 32.48 (CH₂), 31.80 (CH₂), 29.29 (CH₂), 26.99 (CH₂), 22.61 (CH₂), 14.05 (CH₃).
C₃₇H₄₂N₂O₂ (546.8):

Calc .:
C 81.28, H 7.74, N 5.12
Found:
C 80.96, H 7.67, N 5.04

9-bromo-N- (1-hexylheptyl) perylene-3,4-carboximide (18c)

Based on Ref. ^22), 410 mg (1.0 mmol) of N- (1-hexylheptyl) perylene-3,4-carboximide (2c) is dissolved in 70 ml of chlorobenzene, heated to 40 ° C. and then a solution is quickly added from 100 µl (4 mmol) bromine in 10 ml chlorobenzene to the orange solution, which changes color immediately to wine red. The solution is stirred for 2½ hours at 40-50 ° C and then the chlorobenzene is evaporated using the rotary evaporator. A thin layer chromatogram (toluene / silica gel) shows the presence of 4 products, one with the R _f value of 0.77 being the main product. The residue is chromatographed 8 times with toluene on silica gel, whereby 30 mg (7%) of N- (1-hexylheptyl) perylene-3,4-carboximide could be obtained. As a forerunner, a purely yellow product is isolated which, according to the mass spectrum, is (2-5) brominated N- (1-hexyl heptyl) perylene-3,4-carboximide. The compounds cannot be separated chromatographically. The main fraction is recrystallized with pentane ²⁰⁾ . Educ. 310 mg (65%) orange powder, which has a strong solid-state fluorescence - mp. 186-187 ° C. - R _f (chloroform / silica gel) = 0.77. - UV (CHCl₃): λ _max (ε) = 508 (35 675), 484 (33 985). - Fluorescence (CHCl₃) λ _max (I _rel ) = 540 (1), 568 (Sh, 0.49). - IR (KBr): ν = 2955 cm ^-1 (CH₃, m), 2927 (CH₂, s), 2856 (CH₂, m), 1695 (C = O, s), 1653 (C = O, s), 1591 (s), 1567 (m), 1497 (w), 1457 (w), 1410 (w), 1352 (s), 1247 (m), 1175 (w), 863 (w), 812 (w), 803 (m), 750 (m). - 1 H-NMR (CDCl₃): δ = 8.45 ppm (m, 2H, H-2.5), 8.18 (d, 1H, J = 8.3Hz, H-12), 8.17 (d, 1H, J = 7.0Hz, H -1), 8.09 (d, 1H, J = 8.2Hz, H-10), 7.91 (d, 1H, J = 7.7Hz, H-7), 7.68 (d, 1H, J = 8.1Hz, H-8 ), 7.52 (dd, 1H, J₁ = 7.6Hz, J₂ = 8.4Hz, H-11), 5.20 (m, 1H, CH-N), 2.28-2.24 (m, 2H, CH₂), 1.89 (m, 2H , CH₂), 1.37-1.22 (m, 16H, CH₂), 0.84 (t, 6H, CH₃) (The position of the bromine atom could be elucidated by a combination of 1 H, NOESY and COZY NMR spectra). - 13 C-NMR (CDCl₃): δ = 165.0 ppm (C = O), 163.9 (C = O), 135.9, 135.7, 132.6, 131.7, 130.9, 129.6, 129.6, 129.3, 128.8, 128.8, 127.8, 125.9, 125.8, 123.9, 123.2, 121.9, 120.4, 120.1, 54.5 (CH-N), 32.4 (CH₂), 31.8 (CH₂), 29.3 (CH₂), 27.0 (CH₂), 22.6 (CH₂), 14.0 (CH₃). - MS (70 eV): m / z (%) = 584 (7.8), 583 (M⁺, 21.4), 582 (8.1), 581 (M⁺, 20.1), 566 (M⁺-OH, 5.5), 564 (M⁺-OH, 5.1), 403 (7.2), 402 (39.4), 401 (M⁺-C₁₃H₂₆, 100), 400 (40.4), 399 (M⁺-C₁₃H₂₆, 93.4), 384 (M⁺-C₁₃H₂₆ -OH, 7.0), 382 (M⁺-C₁₃H₂₆-OH, 6.7), 275 (20.1), 124 (13.4).
C₃₅H₃₆NO₂Br (582.6):

Calc .:
C 72.16, H 6.23, N 2.4.0 Br 13.72
Found:
C 72.13, H 6.31, N 2.63, Br 12.88

9-bromo-N- (2,5-di-tert-butylphenyl) perylene-3,4-carboximide (18b)

650 mg (1.28 mmol) of N- (2,5-di-tert-butyl-phenyl) -perylene-3,4-carboximide (2b) are dissolved in 100 ml of chlorobenzene, the red solution is mixed with 650 mg of anhydrous potassium carbonate and Then add 0.30 ml of bromine in 10 ml of chlorobenzene to the mixture. The mixture is stirred at 40-50 ° C. for 2 hours, then the temperature is raised to 50-60 ° C. for a further 5 hours and the chlorobenzene is then evaporated off using a rotary evaporator, substantial amounts of bromine also being removed. A thin layer chromatogram (toluene / silica gel) no longer shows any starting product in the residue obtained, which would be very difficult to remove. Repeated column chromatographic separations with chloroform over silica gel can give 610 mg of orange powder, which is recrystallized with ethyl acetate ²⁰⁾ . Educ. 570 mg (77%) orange needles, which have a slight solid-state fluorescence - mp. <320 ° C. - R _f (CHCl₃ / silica gel) = 0.43. - UV (CHCl₃): λ _max (ε) = 511 nm (36 058), 486 (35 564), 357 (3430). - Fluorescence (CHCl₃): λ _max (I _rel ) = 542 nm (I), 572 (0.47). - IR (KBr): ν = 2963 cm ^-1 (m, CH₂), 2905 (w), 2870 (w), 1705 (s, C = O), 1666 (s, C = O), 1592 (s) , 1563 (m), 1497 (w), 1408 (w), 1394 (w), 1357 (s), 1248 (m), 1202 (w), 1178 (w), 1040 (w), 822 (w) , 805 (m), 755 (m). - 1 H-NMR (CDCl₃): δ = 8.61 ppm (d, 1H, J = 8Hz), 8.59 (d, 1H, J = 7.9Hz), 8.37 (d, 1H, J = 7.1Hz), 8.35 (d, 1H, J = 7.1Hz), 8.30 (d, 1H, J = 8.2Hz), 8.23 (d, 1H, J = 8.4Hz), 8.11 (d, 1H, J = 8.2Hz), 7.82 (d, IH, J = 8.3Hz), 7.64 (dd, 1H, J₁ = 7.6Hz, J₂ = 8.4Hz), 7.59 (d, 1H, J₃ = 8.5Hz), 7.46 (dd, 1H, J₃ = 8.7Hz, J₄ = 2.1Hz ), 7.05 (d, 1H, J₄ = 2.1Hz), 1.34 (9H, CH₃), 1.31 (9H, CH₃) (The position of the bromine substituent could be compared with the spectrum of 9-bromo-N- (1-hexylheptyl ) -perylene-3,4-carboximide and 1 H spectra were determined. The substitution pattern of the reference substance was determined by a combination of COZY and NOESY spectra). - 13 C-NMR (CDCl₃). δ 164.8 ppm (C = O), 150.0, 143.8, 136.6, 136.5, 132.9, 132.8, 131.9, 131.8, 131.1, 130.0, 129.9, 129.5, 129.0, 128.9, 128.7, 128.0, 127.8, 126.5, 126.2, 126.1, 124.3 , 123.6, 121.7, 120.6, 120.4, 35.5 (C (CH₃) ₃), 34.2 (C (CH₃) ₃), 31.7 (CH₃), 31.2 (CH₃). - MS (70eV): m / z (%) = 589 (M⁺, 6.9), 06104 00070 552 001000280000000200012000285910599300040 0002004338784 00004 05985587 (M⁺), 534 (5.3, 533 (32.6), 532 (M⁺-C₄H₉, 100 ), 531 (33.9), 530 (M⁺-C₄H₉, 93.2), 518 (4.2), 517 (11.8), 516 (26.1), 515 (11.5), 514 (23.1), 502 (4.1), 500 (7.3 ), 451 (M⁺ Br, 4.8), 435 (6.0), 356 (4.2), 275 (10.8), 250 (9.8), 249 (7.2), 248 (8.5), 244 (15.0), 243 (14.5) , 91 (21.2), 57 (C₄H₉⁺, 18.3).
C₃₆H₃₀NO₂Br (588.6):

Calc .:
C 73.47, H 5.14, N 2.38, Br 13.58
Found:
C 73.54, H 5.32, N 2.40, Br 13.19

(From the pre-fraction, after repeated column chromatography with chloroform Little silica by thin-layer chromatography over silica gel (Chloroform / silica gel) pure. The mass spectrum gives a molecular mass of 667 with the typical isotope pattern of 3 bromine atoms. However, the substance shows one UV / Vis absorption and fluorescence spectrum very similar to 9-bromo-N- (2,5-di-tert- butyl-phenyl) -perylene-3,4-carboximide so that the chromophore is definitely preserved must be.)

Benz [6,10] anthra [2,1,9-def] benz [3,4] imidazolo [2,1-a] isoquinolin-7-one- (21)

400 mg (1.24 mmol) of perylene-3,4-dicarboxylic anhydride, 0.17 g of zinc acetate dihydrate, 590 mg (5.46 mmol) of o-phenylenediamine are suspended in 10 ml of quinoline and everything is heated to 210 ° C. under argon for 5½ hours. At the end of the reaction, 30 ml of ethanol are added, the mixture is boiled and then filtered. The dark red colored product is acidified with hydrochloric acid, suction filtered, washed with water and then dried in a drying cabinet at 120 ° C. Then crystallize three times with toluene extractively ²⁰⁾ . Educ. 480 mg brown violet powder - mp. <370 ° C. - UV (CHCl₃): λ _max (ε _rel ) = 549 nm (0.55), 522 (0.71), 492 (Sh, 0.49), 354 (0.17), 342 (0.16), 286 (0.75), 270 (1) , 262 (0.96), 255 (0.95). - Fluorescence (CHCl₃): λ _max (I _rel ) = 588 nm. - IR (KBr): ν = 3055 cm ^-1 (w), 1687 (s), 1611 (w), 1593 (m), 1567 (s ), 1547 (w), 1501 (w), 1446 (m), 1366 (s), 1356 (s), 1295 (m), 1283 (w), 1293 (m), 1158 (m), 1142 (m ), 1016 (w), 939 (w), 900 (m), 833 (m), 808 (s), 751 (s). - MS (70eV): m / z (%) = 396 (4.6), 395 (29.2), 394 (M⁺, 100), 366 (4.6), 365 (M⁺-HCO, 10.4), 340 (5.2) , 338 (4.1), 197 (14.0).
C₂₈H₁₄N₂O (394.4):

Calc .:
C 85.26, H 3.58, N 7.10
Found:
C 85.43, H 3.61, N 7.12

3,3-dimethylpyrimido [2,1-a] hen [6,10] anthra [2,1,9-def] isoquinolin-6 (2H, 3H, 4H) -one (20)

According to Ref. ^9), 380 mg (1.20 mmol) of perylene-3,4-dicarboxylic acid anhydride are mixed with 600 mg (5.88 mmol) of neopentanediamine, 15 ml of dist. Add water and stir for 1 h at room temperature. The mixture is then boiled under reflux for 3 hours, a red suspension slowly forming. This is mixed with 50 ml of a 5 percent. KOH solution, boil once, suction and wash twice with water and then with ethanol. The orange residue is dried at 120 ° C. in a drying cabinet and recrystallized from methanol ²⁰⁾ . Yield: 320 mg (70%) orange powder with red solid fluorescence - mp. 273-274 ° C. - IR (KBr): ν = 3050 cm ^-1 (w), 2958 (w), 2900 (w), 2885 (w), 2845 (w), 1664 (s, C = O), 1626 (s, C = O), 1612 (s), 1591 (s), 1571 (m), 1502 (w), 1473 (w), 1373 (s), 1292 (w), 1264 (m), 1172 (m), 1029 (m), 834 (m), 809 (s), 760 (m), 747 (m). - UV (CHCl₃) λ _max (ε _rel ) 259 nm (22 400), 266 (30 900), 339 (3160), 353 (2770), 484 (28 100), 506 (30 000). - Fluorescence (CHCl₃). λ _max (I _rel ) - 541 nm (1), 573 (0.80). - 1 H-NMR (CDCl₃): δ = 8.45 ppm (d, J = 8.1 Hz, 1 H), 8.34 (d, J = 7.9 Hz, 1 H), 8.23 (d, J = 7.3 Hz, 1 H), 8.22 (d, 7.2 Hz, 1 H), 8.19 (d, J = 8.3 Hz, 1 H), 8.18 (d, 8.1 Hz, 1 H), 7.76 (d, 1H), 7.74 (d, 1 H), 7.51 (t, J 7.8, 1 H), 7.50 (t, J = 7.8, 1 H), 3.75 (s, 2 H), 3.50 (s, 2 H), 1.10 (s, 6H. - 13 C-NMR ( CDCl₃): δ = 162.2 ppm (C = O), 146.1, 136.2, 134.4, 133.8, 129.93, 129.89, 129.8, 129.44, 129.36, 128.2, 127.0, 126.8, 126.74, 126.71, 123.7, 122.6, 122.2, 121.6, 120.3 , 119.9, 57.9, 50.7, 27.4, 24.7.
C₂₇H₂₀N₂O (388.5):

Calc .:
C 83.48, H 5.19, N 7.21
Found:
C 82.39, H 5.21, N 7.39.

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Claims (21)

1. Process for the preparation of perylene-3,4-dicarboximides of the formula I, wherein R¹ is an alkyl, aralkyl or cycloalkyl group or is a carbocyclic or heterocyclic aromatic radical, by reacting the perylene-3,4: 9,10-th tracarboxylic acid bisanhydride with a primary amine R¹-NH₂ at a temperature of 150-350 ° C and under pressure, in the presence of water and in the presence of a zinc, lead, calcium or magnesium salt and a nitrogen-containing heterocycle as the base. 2. The method of claim 1, wherein the salt is lead acetate, zinc chloride or in particular Is zinc acetate. 3. The method of claim 1 or 2, wherein the nitrogen-containing heterocycle quinoline, Py ridin or especially imidazole. 4. The method according to any one of claims 1 to 3, wherein R¹ is a solubilizing organic Is the rest, and especially for 2,5-di-tert-butylphenyl, 4-tert-butylphenyl, 2,3-dimethylphe  nyl, 1-hexylheptyl, 1-octylnonyl, 1-nonyldecyl, cyclopropyl, cyclopentyl, cyclohexyl, Cycloheptyl, cyclooctyl, cyclododecyl, adamantyl, or 4-carmoylphenyl. 5. Process for the preparation of perylene-3,4-dicarboximides of the formula I according to An claim 1 by reacting the perylene-3,4-dicarboxylic anhydride with a primary Amine R¹-NH₂ at a temperature of 150-350 ° C and under pressure in the presence of egg nes zinc, lead, calcium or manganese salt and a nitrogen-containing heterocycle as Base. 6. perylene-3,4-dicarboximides of the formula II, wherein R² is an alkyl group containing at least 9 carbon atoms or is cycloalkyl, aralkyl, a heterocyclic aromatic radical or a carbocyclic aromatic radical with a total of at least 8 carbon atoms. 7. perylene-3,4-dicarboxylic acid diester of the formula III, wherein R³ and R⁴ independently of one another represent an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical. 8. perylene-3,4-dicarboxylic acid ester amides of the formula IV, wherein R⁵ and R⁶ independently of one another denote H, an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical. 9. perylene-3,4-dicarboxylic acid diamides of the formula V, wherein the two R⁵ are the same or different and are H, an alkyl, aralkyl or cycloal kylgruppe or a carbocyclic or heterocyclic aromatic radical. 10. A process for the preparation of perylene-3,4-dicarboxylic acid ester amides according to claim 9, given by partial hydrolysis of a perylene-3,4-dicarboximide according to claim 1 if followed by alkylation or arylation of the product thus obtained. 11. Process for the preparation of perylene-3,4-dicarbonyl derivatives of the formula VI, in which R⁷ and R⁸ independently of one another denote H, an alkyl, aralkyl or cycloalkyl group or a carbocyclic or heterocyclic aromatic radical, by reduction of the perylene-3,4-dicarboxylic acid or by reaction of perylene-3,4-dicarboxylic acid with C -Nucleophiles. 12. Perylene-3,4-dicarbonyl derivatives of the formula VI according to claim 11, with the proviso that R⁷ and R⁸ are not simultaneously phenyl, p-tolyl or 4-chlorophenyl. 13. perylene-3,4-dicarboxamides of the formula VII, wherein A is C₅-C₇-cycloalkylene, phenylene, naphthylene, pyridylene, a more condensed aromatic carbocyclic or heterocyclic radical or a divalent radical of the formula VIII, IX or X stands, where A can be substituted by halogen, alkyl, cyano or nitro, and R⁹ and R¹⁰ are independently C₁-C₄ alkyl, phenyl or 4-tolyl. 14. Perylenamidines according to claim 13, wherein A is 1,2-cyclopentylene, 1,2-cyclohexylene, 1,2- Phenylene, 2,3- or 1,8-naphthylene, 2,3- or 3,4-pyridylene, 9,10-phenanthrylene or one means divalent radical of the formula VIII, IX or X. 15. Perylenamidines according to claim 13 or 14, wherein A is 1,2-phenylene, 1,8-naphthylene or a divalent radical of the formula VIII, XI or XII. 16. A process for the preparation of perylenamidines according to claim 13 by reacting the Perylene-3,4-dicarboxylic anhydride with a primary diamine of formula XIII H₂N-A-NH₂ (XIII), wherein A has the meaning given in claim 13, with the proviso that A is not a Radical of formula VIII is. 17. A process for the preparation of perylenamidines according to claim 13, wherein A is for a The rest of the formula VIII is obtained by reacting an optionally substituted imidazole with perylene-3,4-dicarboxylic acid anhydride. 18. Bulk colored high molecular organic material containing a verb manure according to one of claims 6 to 9 or 12 to 15, or a connection according to one of claims 1-5, 10, 11, 16 or 17. 19. A method of coloring high molecular weight organic material in bulk characterized by using a connection according to one of claims 6 to 9 or 12 to 15, or a compound prepared according to any one of claims 1-5, 10, 11, 16 or 17th 20. Use of compounds according to one of claims 6 to 9 or 12 to 15, or of connections made according to any one of claims 1-5, 10, 11, 16 or 17 in the safe printing, as fluorescent dyes for machine-readable markings, as laser dyes fabrics, as well as for the production of printing toners ("non-impact printing toners"), color fil tern, organic photoreceptors, electroluminescent and photoluminescent elements or solar panels. 21. Use of compounds according to one of claims 6 to 9 or 12 to 15, or of compounds made according to any of claims 1-5, 10, 11, 16 or 17, one or several substituents selected from the group -SO₃H (and their metal salts) or - SO₃R, where R is alkyl or aryl, amino, acylaminomethyl, alkylamino, Arylamino, phthalimidomethyl, aminomethyl, dimethylaminomethyl or pyrazolomethyl exhibit as a rheology improver.