DE10132116A1

DE10132116A1 - New perylene-bis-imide dyes, useful e.g. for coloring polymers and textiles and as diagnostic reagents, have strong fluorescence in near infra-red

Info

Publication number: DE10132116A1
Application number: DE2001132116
Authority: DE
Inventors: Heinz Langhals; Patrick Blanke
Original assignee: Individual
Current assignee: Individual
Priority date: 2001-07-03
Filing date: 2001-07-03
Publication date: 2003-01-30

Abstract

Perylene-tetracarboxylic acid imide derivatives (I) are new. Perylene-tetracarboxylic acid imide derivatives of formula (I) are new. R<1>-R<4> = hydrogen or isocyclic or heterocyclic aromatic residues optionally substituted, or halo, linear or branched 1-21C alkyl, optionally substituted by non-water-solubilizing groups such as fluoro, hydroxy, cyano, OCOR<33>, OR<34>, OCOOR<35>, CONR<36>R<37>, OCONHR<38>, mono- or di-alkylamino, aryl, heterocyclic aromatic groups; OR<39>; cyano; NR<40>R<41>; COR<42>; NR<43>-COR<44>; NR<45>COOR<46>; NR<47>CONR<48>R<49>; NHSO2R<50>; SO2R<51> or SOR<52>; SO2OR<53>; CONR<54>R<55>; SO2NR<56>R<57>; -N=N-R<58>; COR<59>; or OCONHR<60>; R<33> = alkyl, aryl or heterocyclyl; R<34>-R<36> = hydrogen, alkyl (optionally substituted by cyano or hydroxy), 3-24C cycloalkyl, aryl or heteroaryl; or R<36> and R<37> together with any of R<33>-R<38> = a 5-6 membered (heterocyclic) ring; R<39> = hydrogen, alkyl, aryl, 3-24C cycloalkyl or (hetero)aryl; R<40>, R<41>, R<42>, R<43>, R<50>-R<57>, R<59> and R<60> = linear or branched 1-21C alkyl, optionally substituted by non-water-solubilizing groups such as fluoro, hydroxy, cyano, OCOR<33>, OR<34>, OCOOR<35>, CONR<36>R<37>, OCONHR<38>, mono- or di-alkylamino, aryl, heterocyclic aromatic groups; R<44> = hydrogen, alkyl, 3-20C cycloalkyl or (hetero)aryl, optionally substituted; R<45>-R<49> = linear or branched 1-21C alkyl, optionally substituted by non-water-solubilizing groups such as fluoro, hydroxy, cyano, OCOR<33>, OR<34>, OCOOR<35>, CONR<36>R<37>, OCONHR<38>, mono- or di-alkylamino, aryl, heterocyclic aromatic groups or OR<39>; and R<58> = residue of a coupler or phenyl, optionally substituted by halo, alkyl or alkoxy. Independent claims are also included for the following: (1) Benzoperyleneimide derivatives of formulae (II) and (III) and (2) Method for preparing (I)-(III).

Description

Farbstoffe für den nahen Infrarotbereich erhalten ein zunehmendes Interesse in der Technik und in der Medizin [1]. Für viele Anwendungen sind hier die verhältnismäßig kurzwellige Absorptionen von ubiquitär vorkommenden farbigen Substanzen von Bedeutung die dann im NIR-Bereich nur verhältnismäßig wenig stören, so dass z. B. eine große Eindringtiefe des Lichts in biologische Medien garantiert wird. Die langwellige Absorption ergibt zum anderen eine gute Anpassung an den Wellenlängenbereich von Halbleiterlasern, die besonders effizient im langwellig sichtbaren oder NIR-Bereich eingesetzt werden können. Derlei Anwendungen erfordern meist eine erhebliche Lichtechtheit der Farbstoffe, die im langwelligen Spektralbereich nur schwierig zu erzielen ist. Der Perylentetracarbonsäurebisimid-Chromophor 1 (R¹ bis R⁴ = H) zeichnet sich durch eine besondere Lichtechtheit aus, so dass er für solche Anwendungen grundsätzlich interessant wäre [2], seine Absorption liegt aber mit ca. 525 nm im mittleren Spektralbereich des sichtbaren Lichts. Eine Verschiebung seiner Absorption in den längerwelligen Spektralbereich brächte einen erheblichen Fortschritt. Es ist zu fragen, in wieweit man durch eine Erweiterung des aromatischen Kerns der Bisimide eine langwellige Verschiebung der Absorption erzielen kann. Dyes for the near infrared range are gaining increasing interest in technology and medicine [1]. For many applications, the relatively short-wave absorptions of ubiquitously occurring colored substances are of importance, which then interfere only relatively little in the NIR range. B. a great depth of penetration of light into biological media is guaranteed. On the other hand, the long-wave absorption results in a good adaptation to the wavelength range of semiconductor lasers, which can be used particularly efficiently in the long-wave visible or NIR range. Such applications usually require considerable lightfastness of the dyes, which is difficult to achieve in the long-wave spectral range. The perylene tetracarboxylic acid bisimide chromophore 1 (R ¹ to R ⁴ = H) is characterized by a special light fastness, so that it would be interesting for such applications in principle [2], but its absorption is at around 525 nm in the middle spectral range of visible light , Shifting its absorption into the longer-wave spectral range would bring considerable progress. To what extent can one achieve a long-wave shift in absorption by expanding the aromatic nucleus of the bisimide?

description

Da die Perylenbisimide verhältnismäßig elektronenarm sind, ist zu fragen, wie sich eine massive Substitution durch Donor- Gruppen am Perylen-Kern auswirkt. Hier soll die "Bay-Position" (S₃-Anordnung) das Ziel einer solchen Substitution sein (R¹ bis R⁴ von 1). Durch langkettige sec-Alkylreste (Schwalbenschwanz- Reste [3]) wird eine genügende Löslichkeit solcher Substanzen bewirkt, damit sie in homogener Lösung untersucht und eingesetzt werden können; dabei haben sich zwei gleichlange Ketten der sec-Alkylreste bewährt, wie z. B. in 2, da man sonst bei der Einführung zweier Reste mit unterschiedlichen Ketten mit der Bildung von Diastereomeren rechnen muss, die naturgemäß schwierig zu trennen sind. Since the perylene bisimides are relatively electron-poor, the question arises as to what effect massive substitution by donor groups on the perylene core has. Here the "bay position" (S ₃ arrangement) should be the target of such a substitution (R ¹ to R ⁴ of 1). Long-chain sec-alkyl residues (dovetail residues [3]) ensure that such substances are sufficiently soluble so that they can be examined and used in homogeneous solution; two chains of the same length of the sec-alkyl radicals have proven successful, such as, for. B. in 2, since otherwise one has to reckon with the introduction of two residues with different chains with the formation of diastereomers, which are naturally difficult to separate.

Ein einfaches Einführen von Gruppen in die Positionen R¹ bis R⁴ ist aber problematisch, da zum einen mit einer massiven Deformation des Perylen-Gerüsts durch sterische Wechselwirkungen gerechnet werden muss. Zum anderen ist es schwierig, vier Substituenten etwa über eine Halogenierung [4] und eine daran anschließende nucleophile Substitution einzuführen, da solche Rektionen kaum vollständig verlaufen und extreme Trenn-Probleme bei den erhaltenen Substanzgemischen bestehen. A simple introduction of groups into positions R ¹ to R ⁴ is problematic, however, because on the one hand massive deformation of the perylene skeleton due to steric interactions must be expected. On the other hand, it is difficult to introduce four substituents, for example via halogenation [4] and a subsequent nucleophilic substitution, since such rections hardly go completely and there are extreme separation problems in the substance mixtures obtained.

Die Diels-Alder-Reaktion bietet demgegenüber eine grundsätzliche Möglichkeit, den Kern der Perylenbisimide (1) abzuwandeln - die Perylen-Struktur enthält in der "Bay- Position" (S₃-Anordnung) die formale Struktur eines Diens, so dass Dienophile hier grundsätzlich angreifen sollten. The Diels-Alder reaction, on the other hand, offers a basic possibility of modifying the core of the perylene bisimide (1) - the perylene structure contains the formal structure of a diene in the "bay position" (S ₃ arrangement), so that dienophiles here in principle should attack.

Allerdings gelingt die Reaktion nur einmal, und hierfür sind bereits elektronenarme und damit reaktive Olefine erforderlich, wie z. B. Maleinsäureanhydrid - offensichtlich desaktivieren die zwei Carbonsäureimid-Gruppen das System durch ihren Elektronenzug bereits sehr stark. Verwendet man aber als hoch reaktives Olefin das Phenyltriazolindion und setzt dieses in hoher Konzentration und in großem Überschuss unter Zusatz eines Aromatisierungsreagenzes (Clar-Reaktion) ein, dann kann man zum Erstaunen einen doppelten Angriff an den Perylen-Kern beobachten. Man erhält dann nicht das primäre Diels-Alder-Produkt, sondern direkt den voll aromatisierten Heterocyclus 4 als blaues Pulver.

However, the reaction succeeds only once, and this already requires electron-deficient and thus reactive olefins, such as. B. Maleic anhydride - obviously the two carboximide groups deactivate the system very strongly due to their electron traction. However, if phenyltriazolinedione is used as a highly reactive olefin and this is used in high concentration and in large excess with the addition of a flavoring reagent (Clar reaction), then one can observe a double attack on the perylene core to the astonishment. The primary Diels-Alder product is then not obtained, but the fully flavored heterocycle 4 directly as a blue powder.

Die Diels-Alder Reaktion ist auch aus rein präparativen Gründen für das Einführen von Donor-Gruppen von besonderem Vorteil, da durch den Reaktionsweg sichergestellt ist, dass das Einführen von vier Donorgruppen auch tatsächlich vollständig ist. Versucht man demgegenüber als Alternative Donorgruppen in den betreffenden Positionen 1, 6, 7 und 12 über übliche Substitutionsreaktionen einzuführen, so lässt sich nicht vermeiden, dass solche Reaktionen unvollständig sind; die daraus resultierenden Substanzgemische an Perylen- Derivaten bereiten außerordentlich große Trennprobleme, die natürlich bei der Verwendung der Diels-Alder-Reaktion umgangen werden.

The Diels-Alder reaction is also of particular advantage for purely preparative reasons for the introduction of donor groups, since the reaction path ensures that the introduction of four donor groups is actually complete. On the other hand, if one tries to introduce alternative donor groups in the relevant positions 1, 6, 7 and 12 via conventional substitution reactions, it cannot be avoided that such reactions are incomplete; the resulting mixtures of perylene derivatives cause extraordinarily large separation problems, which of course are avoided when using the Diels-Alder reaction.

Die zweifache Diels-Alder Reaktion an Perylentetracarbonsäurebisimide kann auch schrittweise erfolgen und führt dann zu weiteren, neuen, interessanten Farbstoffen, da nun zwei verschiedene Dienophile eingesetzt werden können. Als Beispiel wird hier die eine Reaktion von 2 mit Phenyltriazolin zum dunkelgrünen 3 und dann eine Weiterreaktion mit Maleinsäureanhydrid zu 5 aufgeführt. Man kann mit diesem neuen Typ an Substanzen verschiedene Spektralbereiche im langwellig Sichtbaren erreichen und insbesondere durch die breite Variationsmöglichkeit solcher Reaktionen die Absorption feinabstimmen. The double Diels-Alder reaction Perylene tetracarboxylic bisimides can also be gradual and then leads to further, new, interesting ones Dyes, since two different dienophiles are now used can be. As an example, here is a reaction from 2 with phenyltriazoline to the dark green 3 and then one Further reaction with maleic anhydride to 5 listed. you can be different with this new type of substance Reach spectral ranges in the long-wave visible and especially due to the wide range of options Reactions fine-tune absorption.

Die erstaunlichen bathochromen Verschiebungen der Diels-Alder- Addukte lassen sich bereits auf der Basis von HMO-Rechnungen verständlich machen:
Man kann mit diesen Rechnungen ausgeprägte bathochrome Farbverschiebungen bei 1 erklären, wenn die Positionen 1, 6, 7 und 12 Donor-Gruppen tragen; an den anderen Positionen wirken sich Donor- oder Acceptor-Gruppen erheblich schwächer aus. Man kann eine zunehmende bathochrome Farbverschiebung erwarten, wenn man diese Positionen mit einer steigenden Zahl von Aminogruppen versieht; siehe Abb. 1 und Tab. 1. The amazing bathochromic shifts of the Diels-Alder adducts can already be understood on the basis of HMO calculations:
These calculations can be used to explain pronounced bathochromic color shifts at 1 if the positions 1, 6, 7 and 12 have donor groups; at the other positions donor or acceptor groups have a considerably weaker effect. An increasing bathochromic color shift can be expected if these positions are provided with an increasing number of amino groups; see Fig. 1 and Tab. 1.

Fig. 1 Tab. 1

Experimentelle Ergebnisse, insbesondere mit Phenoxy- [5] und Amino-Derivaten [6, 7, 8], belegen diesen Substituenteneinfluss grundsätzlich. Zu einer weiteren Verstärkung des Effekts kann man daran denken, die Donor-Gruppen in Ringstrukturen einzuschließen. Werden die Positionen 1, 6, 7 und 12 mit Fünfring-Donor-Gruppen versehen, dann resultiert sogar erstaunlicherweise eine hypsochrome Farbverschiebung gegenüber 1a (1h, 1j): der Donor-Effekt schwächt sich durch die Substitution an zwei-Positionen des Perylen-Gerüst eher ab. Dies entspricht auch der experimentelle Erfahrung am Beispiel eines einfach ankondensierten Pyrrol-Rings [6]. Ausgeprägte bathochrome Verschiebungen sind dagegen durch die Verknüpfung von jeweils zwei Donorgruppen zu einem sechsgliedrigen Ring nach den Rechnungen zu erwarten (1i, 1l). Dies lässt sich dadurch erklären, dass sich die Donor-Funktionen der Donor- Gruppen gegenseitig durch den α-Effekt verstärken. Durch den Einbau der Donor-Funktionen in einen sechsgliedrigen Ring verhindert man darüber hinaus noch ein Verbiegen des Chromophors durch sterische Wechselwirkungen der Substituenten in den Bay-Positionen. Experimental results, especially with phenoxy- [5] and Amino derivatives [6, 7, 8] demonstrate this influence of substituents principle. Can further enhance the effect you remember the donor groups in ring structures include. Do positions 1, 6, 7 and 12 with Five-ring donor groups, then even results astonishingly compared to a hypsochromic color shift 1a (1h, 1j): the donor effect is weakened by the Substitution at two positions on the perylene scaffold tends to decrease. This also corresponds to the experimental experience using the example of a simply fused pyrrole ring [6]. pronounced By contrast, bathochromic shifts are due to the link of two donor groups to a six-membered ring to be expected according to the calculations (1i, 1l). This can be done by explaining that the donor functions of the donor Strengthen groups through the α effect. By the Installation of the donor functions in a six-membered ring you also prevent the Chromophore through steric interactions of the substituents in the bay positions.

Fig. 2

Die Strukturen der Verbindungen 3c und 4c sind mit der AM1- Methode berechnet worden [9, 10]; siehe Abb. 2. Man findet bei 3 und 4, wie erwartet, Planarität für die Perylen-Einheit inkl. des ankondensierten Dihydropyridazin-Rings. Der daran ankondensierte fünfgliedrig Ring knickt seinerseits allerdings um ca. 45° ab. Dies kann als Konsequenz des α-Effekts gesehen werden, denn eine Abweichung der Hybridisierung der Dihydropyridazin-Stickstoff-Atome von sp²in Richtung sp³ verringert die Abstoßung der N-Orbitale. Beim Farbstoff 4 beobachtet man dies für beide ankondensierte Dihydropyridazin- Ringe. Die Phenylreste an den fünfgliedrigen Ringen sind, wie erwartet um ca. 40° aus den Fünfring-Ebenen herausgedreht. The structures of compounds 3c and 4c have been calculated using the AM1 method [9, 10]; see Fig. 2. As expected, 3 and 4 find planarity for the perylene unit including the fused dihydropyridazine ring. The five-part ring that is condensed onto it, however, bends in turn by approx. 45 °. This can be seen as a consequence of the α effect, because a deviation of the hybridization of the dihydropyridazine nitrogen atoms from sp ² towards sp ³ reduces the rejection of the N orbitals. This is observed for dye 4 for both fused dihydropyridazine rings. The phenyl residues on the five-membered rings are, as expected, turned out of the five-membered ring by about 40 °.

Fig. 3

Das bekannte 3 absorbiert bereits verhältnismäßig langwellig [8], so dass grüne Lösungen erhalten werden (λ_max. = 650 nm in Chloroform). Die zwei weiteren verknüpften Donorgruppen in 4 ergeben noch einmal eine erstaunlich kräftige bathochrome Verschiebung der Absorption so dass mit λ_max. = 778 bereits der NIR-Bereich erreicht wird (blaugrüne, lichtechte Lösungen); siehe Abb. 3. Die langwellige Absorption von 4 ist bemerkenswert, da die Donor-Funktionen jeweils durch die beiden Carbonylgruppen erheblich abgeschwächt werden. Wenn diese Abschwächung wegfällt, sind noch stärker bathochrome Effekte zu erwarten. The known 3 already absorbs relatively long-wave [8], so that green solutions are obtained (λ _max. = 650 nm in chloroform). The two further linked donor groups in 4 again result in an astonishingly strong bathochromic shift in the absorption, so that with λ _max. = 778 the NIR range has already been reached (blue-green, lightfast solutions); see Fig. 3. The long-wave absorption of 4 is remarkable, since the donor functions are significantly weakened by the two carbonyl groups. If this weakening disappears, more bathochromic effects can be expected.

Fig. 4a and Fig. 4b; Legend: Fig. 4 Tab. 2

Die Verbindungen 3 und 4 fluoreszieren stark: die Emission von 3a liegt mit λ_max = 775 und 873 nm bereits deutlich im NIR- Bereich und ist bei 4b mit λ_max = 837 und 938 nm überraschend weit in den NIR-Bereich verschoben; Ausläufer der Fluoreszenz findet man bereits jenseits von 1100 nm. Für die UV/Vis- Absorptions- und Fluoreszenzspektren von 3a und 4b gelangen jeweils komplette Gaußanalysen [11]; R-Werte siehe Tab. 2. Das UV/Vis-Spektrum von 3a setzt sich aus zwei strukturierten Teilspektren im sichtbaren Spektralbereich zusammen, die den S_o-S₁- und den S_o-S₂-Übergängen zugeordnet werden. Das Spektrum des S_o-S₁-Übergangs weist verhältnismäßig breite Schwingungsteilbanden auf, und man findet nicht die für Perylenbisimide typische Strukturierung - diese tritt aber beim S_o-S₂-Übergang auf. Die Strukturierung des Fluoreszenzspektrums ist demgegenüber typisch für Perylenbisimide. Beim stärker symmetrischen, längerwellig absorbierenden Farbstoff 4b findet man im sichtbaren und NIR- Bereich dagegen nur eine Absorptionsbande mit einer für Perylenbisimide typischen Struktur. Die Fluoreszenzbande ist spiegelbildlich zur Absorptionsbande. Die langwellige Absorption bzw. Fluoreszenz ist für viele Bereiche von Interesse, insbesondere da Halbleiter-Laser bevorzugt im NIR- Bereich eingesetzt werden. Compounds 3 and 4 fluoresce strongly: the emission of 3a with λ _max = 775 and 873 nm is already clearly in the NIR range and for 4b with λ _max = 837 and 938 nm is surprisingly shifted far into the NIR range; Extensions of the fluorescence can already be found beyond 1100 nm. Complete Gauss analyzes are carried out for the UV / Vis absorption and fluorescence spectra of 3a and 4b [11]; R values see table 2. The UV / Vis spectrum of 3a is composed of two structured sub-spectra in the visible spectral range, which are assigned to the S _o -S ₁ and S _o -S ₂ transitions. The spectrum of the S _o -S ₁ transition shows relatively broad vibrational sub-bands, and the structuring typical of perylene bisimides is not found - but this occurs with the S _o -S ₂ transition. In contrast, the structuring of the fluorescence spectrum is typical of perylene bisimides. With the more symmetrical, longer-wave absorbing dye 4b, on the other hand, only one absorption band with a structure typical of perylene bisimides is found in the visible and NIR range. The fluorescence band is a mirror image of the absorption band. Long-wave absorption or fluorescence is of interest for many areas, in particular since semiconductor lasers are preferably used in the NIR area.

Experimental part

UV/VI/NIR-Absorptionsspektren: OMEGA 20 von Bruins Instruments, Fluoreszenzspektren: FluoroLog 2 mit Detektor R5108 von Jobin Yvon GmbH; das Spektrometer ist bis 1700 nm optimiert, die Fluoreszenzspektren sind unkorrigiert, so dass die Fluoreszenzintensitäten mit Unsicherheiten behaftet sind, die Bandenlagen konnten aber präzise bestimmt werden (vergleiche die Kettenregel der Differenzialrechnung). UV / VI / NIR absorption spectra: OMEGA 20 from Bruins Instruments, fluorescence spectra: FluoroLog 2 with detector R5108 from Jobin Yvon GmbH; the spectrometer is up to 1700 nm optimized, the fluorescence spectra are uncorrected so that the fluorescence intensities are subject to uncertainties, the band positions could be determined precisely (compare the chain rule of differential calculus).

3a und 4a: Zu einer Lösung von 2a (3.00 mmol, 2.26 g) und p- Chloranil (3.00 mmol, 732 mg) in getrocknetem Toluol (100 ml, Molekularsieb 4 Å) wurde 4-Phenyl-1,2,4-triazolin-3,5-dion (30 mmol, 5.25 g) gegeben. Nach 10 h Sieden unter Rückfluss wurde auf Raumtemp. abgekühlt, abfiltriert (Glasfiltertiegel Por. 4), mit wenig Toluol gewaschen, das Filtrat eingedampft, getrocknet (90°C, 24 h, Trockenschrank, fast schwarzer Feststoff), mit wenig Chloroform aufgenommen und chromatographiert (Kieselgel, Chloroform). Das grüne 3a eluierte vor dem schwererlöslichen blaugrünen 4a, zu dessen Elution 10% Aceton zugesetzt wurde. Beide Farbstoffe wurden durch Einengen, Ausfällen mit Methanol als Feststoffe erhalten. 1. Fraktion 3a: Ausb. 1.36 g (48.9%) 3a als grünes Pulver, Schmp. > 300°C. - R_f (Kieselgel, Chloroform): 0.25. - Fluoreszenz (CHCl₃): λ_max = 775 nm, 873. - 2. Fraktion 4a: Ausb. 657 mg (19.9%) 4a als blaues Pulver, Schmp. > 300°C. - R_f (Kieselgel, Chloroform): 0.09. - IR (KBr): ≙ = 3150 cm^-1 (w), 2955 (m), 2926 (m), 2856 (m), 1775 (m), 1731 (s), 1705 (m), 1662 (s), 1604 (w), 1574 (w), 1500 (m), 1459 (w), 1432 (m), 1401 (m), 1368 (s), 1302 (s), 1233 (w), 1175 (w), 1075 (w), 984 (w), 925 (w), 808 (w), 754 (m), 730 (m), 688 (w), 643 (m) 546 (w), 505 (w). - ¹H NMR (C₂D₂Cl₄): δ = 0.83 (t, 12H, CH₃), 1.20-1.35 (m, 32H, CH₂), 1.80 (m, 4H, CH-CH₂), 2.12 (m, 4 H, CH-CH₂), 5.03 (tt, 2H, CH(CH₂)₂), 7.48 (t, 1H, ³J = 7.2 Hz, Phenyl), 7.55 (t, 2H, ³J = 7.2 Hz, Phenyl), 7.60 (d, 2H, ³J = 7.2 Hz, Phenyl), 9.06 (s, br, 4H, Perylen). - ¹³C NMR (C₂D₂Cl₄): δ = 14.1, 22.5, 26.7, 29.0, 29.6, 31.6, 32.0, 55.2, 69.0, 116.7, 118.2, 118.9, 123.4, 123.8, 125.1 125.4, 125.8, 127.1, 128.8, 129.2, 129.4, 129.5, 129.8, 130.8, 131.7, 133.1, 143.4, 149.4, 161.2. - UV/VIS (CHCl₃): λ_max (ε) = 310 nm (91740), 644 (6530), 705 (13240), 778 (15890). - MS (70 eV): m/z (%): 1100 (22) [M⁺], 918 (14) [M⁺ - C₁₃H₂₇], 736 (6) [M⁺ - 2.C₁₃H₂₇], 589 (4) [M+ - 2.C₁₃H₂₇-C₆H₅NCO-CO], 530 (9), 265 (8), 182 (27), 119 (21), 111 (12), 97 (36), 84 (27), 83 (56), 82 (10), 81 (7), 71 (17), 70 (61), 69 (100), 67 (18), 57 (40). - C₆₆H₆₈N₈O₈ (1101.3): ber. C 71.98, H 6.22, N 10.17; gef. C 71.79, H 6.34, N 10.09. 3a and 4a: 4-phenyl-1,2,4-triazoline became a solution of 2a (3.00 mmol, 2.26 g) and p-chloroanil (3.00 mmol, 732 mg) in dried toluene (100 ml, molecular sieve 4 Å) -3,5-dione (30 mmol, 5.25 g) was added. After boiling under reflux for 10 h, the temperature was raised to room temperature. cooled, filtered off (Por. 4 glass filter crucible), washed with a little toluene, the filtrate evaporated, dried (90 ° C., 24 h, drying cabinet, almost black solid), taken up with a little chloroform and chromatographed (silica gel, chloroform). The green 3a eluted before the sparingly soluble blue-green 4a, to whose elution 10% acetone was added. Both dyes were obtained by concentration, precipitation with methanol as solids. 1. Fraction 3a: educ. 1.36 g (48.9%) 3a as a green powder, mp> 300 ° C. - R _f (silica gel, chloroform): 0.25. - Fluorescence (CHCl ₃ ): λ _max = 775 nm, 873. - 2nd fraction 4a: yield. 657 mg (19.9%) 4a as a blue powder, mp> 300 ° C. - R _f (silica gel, chloroform): 0.09. - IR (KBr): ≙ = 3150 cm ^-1 (w), 2955 (m), 2926 (m), 2856 (m), 1775 (m), 1731 (s), 1705 (m), 1662 (s) , 1604 (w), 1574 (w), 1500 (m), 1459 (w), 1432 (m), 1401 (m), 1368 (s), 1302 (s), 1233 (w), 1175 (w) , 1075 (w), 984 (w), 925 (w), 808 (w), 754 (m), 730 (m), 688 (w), 643 (m) 546 (w), 505 (w). - ¹ H NMR (C ₂ D ₂ Cl ₄ ): δ = 0.83 (t, 12H, CH ₃ ), 1.20-1.35 (m, 32H, CH ₂ ), 1.80 (m, 4H, CH-CH ₂ ), 2.12 (m, 4 H, CH-CH ₂ ), 5.03 (tt, 2H, CH (CH ₂ ) ₂ ), 7.48 (t, 1H, ³ J = 7.2 Hz, phenyl), 7.55 (t, 2H, ³ J = 7.2 Hz, phenyl), 7.60 (d, 2H, ³ J = 7.2 Hz, phenyl), 9.06 (s, br, 4H, perylene). - ¹³ C NMR (C ₂ D ₂ Cl ₄ ): δ = 14.1, 22.5, 26.7, 29.0, 29.6, 31.6, 32.0, 55.2, 69.0, 116.7, 118.2, 118.9, 123.4, 123.8, 125.1 125.4, 125.8, 127.1, 128.8, 129.2, 129.4, 129.5, 129.8, 130.8, 131.7, 133.1, 143.4, 149.4, 161.2. UV / VIS (CHCl ₃ ): λ _max (ε) = 310 nm (91740), 644 (6530), 705 (13240), 778 (15890). - MS (70 eV): m / z (%): 1100 (22) [M ⁺ ], 918 (14) [M ⁺ - C ₁₃ H ₂₇ ], 736 (6) [M ⁺ - 2.C ₁₃ H ₂₇ ], 589 (4) [M + - 2.C ₁₃ H ₂₇ -C ₆ H ₅ NCO-CO], 530 (9), 265 (8), 182 (27), 119 (21), 111 (12) , 97 (36), 84 (27), 83 (56), 82 (10), 81 (7), 71 (17), 70 (61), 69 (100), 67 (18), 57 (40) , - C ₆₆ H ₆₈ N ₈ O ₈ (1101.3): calc. C 71.98, H 6.22, N 10.17; gef. C 71.79, H 6.34, N 10.09.

3b und 4b: Eine Lösung von 2b (1.117 mmol, 1.030 g) und p- Chloranil (1.117 mmol, 273 mg) in getrocknetem Toluol (30 ml) wurde analog zu 3a und 4a mit 4-Phenyl-1,2,4-triazolin-3,5- dion (11.17 mmol, 1.955 g) umgesetzt und aufgearbeitet. Ausb. 477 mg (38.1%) 11,12-Diaza-11,12-dihydrobenzo[ghi]perylen- 2,3,8,9,11,12-hexacarbonsäure-2,3:8,9-bis-(1-nonyldecylimid)- 11,12-phenylimid (3b) als grünes Harz, Schmp. > 300°C. - R_f (Kieselgel, Chloroform): 0.56. - IR (KBr): ≙ = 3108 cm^-1 (w), 2955 (m), 2925 (s), 2853 (m), 1774 (m), 1727 (s), 1703 (s) 1663 (s), 1600 (m), 1577 (m), 1502 (m), 1458 (w), 1422 (m), 1393 (s), 1378 (m), 1338 (m), 1299 (m), 1243 (w), 1179 (w), 1169 (w), 928 (w), 851 (w), 809 (m), 750 (m), 742 (m), 729 (w), 687 (w), 645 (w), 538 (w), 504 (w). - ¹H NMR (CDCl₃): δ = 0.84 (t, 12H, CH₃), 1.20-1.35 (m, 56H, CH₂), 1.85 (m, 4H, CH- CH₂), 2.18 (m, 4H, CH-CH₂), 5.10 (tt, 2H, CH(CH₂)₂), 7.51 (t, 1H, ³J = 7.2 Hz, Phenyl), 7.59 (t, 2H, ³J = 7.2 Hz, Phenyl), 7.67 (d, 2H, ³J = 7.2 Hz, Phenyl), 8.22 (d, 2H, ³J = 7.5 Hz, Perylen), 8.39 (d, 2H, ³J = 7.5 Hz, Perylen), 9.30 (s, 2H, Perylen). - ¹³C NMR (CDCl₃): δ = 14.1, 22.7, 27.0, 29.3, 29.6, 31.9, 32.3, 55.1, 117.3, 123.7, 125.2, 126.6, 129.2, 129.5, 130.1, 132.7, 133.7, 143.5. - UV/VIS (CHCl₃): λ_max (ε) = 291 nm (54060), 348 (11590), 358 (11060), 396 (7700), 418 (12750) 443 (23580), 648 (15120), 692 (12690) sh. - MS (70 eV): m/z (%): 1097 (32), 1069 (80) [M⁺], 1095 (100), 831 (11), 830 (20) [M⁺ - C₁₉H₃₉], 829 (12), 564 (12), 563 (24) [M⁺ - 2.C₁₉H₃₉], 562 (17), 418 (6), 417 (21) [M+ - 2.C₁₉H₃₉-C₆H₅NCO-CO], 416 (24). - C₇₀H₈₉N₅O₆ (1096.5): ber. C 76.68, H 8.18, N 6.39; gef. C 76.66, H 8.07, N 6.39. - Ausb. 317 mg (21.9%) 5,6,11,12- Tetraaza-5,6,11,12-tetrahydrocoronen-2,3,5,6,8,9,11,12- octacarbonsäure-2,3:8,9-bis(1-nonyldecylimid)-5,6:11,12- bisphenylimid (4b) als blaues Pulver, Schmp. > 300°C. - R_f (Kieselgel, Chloroform): 0.19. - IR (KBr): ≙ = 3110 cm^-1 (w), 2955 (m), 2925 (m), 2854 (m), 1776 (m), 1731 (s), 1704 (m), 1662 (s), 1605 (w), 1574 (w), 1500 (m), 1459 (w), 1432 (m), 1401 (m), 1368 (s), 1302 (s), 1228 (w), 1173 (w), 1075 (w) 1030 (w), 989 (w), 925 (w), 808 (w), 751 (m), 730 (m), 687 (w), 644 (m), 546 (w), 504 (w). - ¹H NMR (CD₂Cl₂): δ = 0.85 (t, 12H, CH₃), 1.23-1.30 (m, 56H, CH₂), 1.84 (m, 4H, CH-CH₂), 2.12 (m, 4H, CH-CH₂), 5.01 (tt, 2H, CH(CH₂)₂), 7.55 (t, 1H, ³J = 7.2 Hz, Phenyl), 7.62 (t, 2H, ³J = 7.2 Hz, Phenyl), 7.66 (d, 2H, ³J = 7.2 Hz, Phenyl), 8.92 (d, br, 4H, Perylen). - ¹³C NMR (CDCl₃): δ = 14.3, 23.1, 27.4, 29.8, 30.0, 30.5, 32.3, 32.5, 55.8, 117.0, 123.8, 124.4, 126.4 126.8, 129.8, 129.9, 130.4, 133.7, 143.8. - UV/VIS (CHCl₃): λ_max (ε) = 310 nm (91980), 645 (6430), 705 (13210), 778 (16180). - Fluoreszenz (CHCl₃): λ_max = 837 nm, 938. - MS (70 eV): m/z (%): 1271 (12), 1270 (39) [M⁺], 1269 (77), 1268 (100), 1005 (11), 1004 (26), 1003 (78), 1002 (92) [M⁺ - C₁₉H₃₉], 738 (27), 737 (51) [M⁺ - 2.C₁₉H₃₉], 736 (49), 590 (28), 589 (31) [M⁺ - 2.C₁₉H₃₉-C₆H₅NCO-CO], 443 (19), 442 (38), 268 (37). - C₇₈H₉₂N₈O₈ (1269.7): ber. C 73.79, H 7.30, N 80837; gef. C 73.63, H 7.08, N 8.83. 3b and 4b: A solution of 2b (1,117 mmol, 1,030 g) and p-chloroanil (1,117 mmol, 273 mg) in dried toluene (30 ml) was treated analogously to 3a and 4a with 4-phenyl-1,2,4- triazolin-3,5-dione (11.17 mmol, 1,955 g) reacted and worked up. Y. 477 mg (38.1%) 11,12-diaza-11,12-dihydrobenzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3: 8,9-bis- (1-nonyldecylimide ) - 11,12-phenylimide (3b) as a green resin, mp> 300 ° C. - R _f (silica gel, chloroform): 0.56. - IR (KBr): ≙ = 3108 cm ^-1 (w), 2955 (m), 2925 (s), 2853 (m), 1774 (m), 1727 (s), 1703 (s) 1663 (s), 1600 (m), 1577 (m), 1502 (m), 1458 (w), 1422 (m), 1393 (s), 1378 (m), 1338 (m), 1299 (m), 1243 (w), 1179 (w), 1169 (w), 928 (w), 851 (w), 809 (m), 750 (m), 742 (m), 729 (w), 687 (w), 645 (w), 538 (w), 504 (w). - ¹ H NMR (CDCl ₃ ): δ = 0.84 (t, 12H, CH ₃ ), 1.20-1.35 (m, 56H, CH ₂ ), 1.85 (m, 4H, CH-CH ₂ ), 2.18 (m, 4H , CH-CH ₂ ), 5.10 (tt, 2H, CH (CH ₂ ) ₂ ), 7.51 (t, 1H, ³ J = 7.2 Hz, phenyl), 7.59 (t, 2H, ³ J = 7.2 Hz, phenyl) , 7.67 (d, 2H, ³ J = 7.2 Hz, phenyl), 8.22 (d, 2H, ³ J = 7.5 Hz, perylene), 8.39 (d, 2H, ³ J = 7.5 Hz, perylene), 9.30 (s, 2H, perylene). - ¹³ C NMR (CDCl ₃ ): δ = 14.1, 22.7, 27.0, 29.3, 29.6, 31.9, 32.3, 55.1, 117.3, 123.7, 125.2, 126.6, 129.2, 129.5, 130.1, 132.7, 133.7, 143.5. UV / VIS (CHCl ₃ ): λ _max (ε) = 291 nm (54060), 348 (11590), 358 (11060), 396 (7700), 418 (12750) 443 (23580), 648 (15120), 692 (12690) sh. - MS (70 eV): m / z (%): 1097 (32), 1069 (80) [M ⁺ ], 1095 (100), 831 (11), 830 (20) [M ⁺ - C ₁₉ H ₃₉ ], 829 (12), 564 (12), 563 (24) [M ⁺ - 2.C ₁₉ H ₃₉ ], 562 (17), 418 (6), 417 (21) [M + - 2.C ₁₉ H ₃₉ -C ₆ H ₅ NCO-CO], 416 (24). - C ₇₀ H ₈₉ N ₅ O ₆ (1096.5): calc. C 76.68, H 8.18, N 6.39; gef. C 76.66, H 8.07, N 6.39. - Education 317 mg (21.9%) 5,6,11,12-tetraaza-5,6,11,12-tetrahydrocoronen-2,3,5,6,8,9,11,12-octacarboxylic acid-2,3: 8, 9-bis (1-nonyldecylimide) -5,6: 11,12-bisphenylimide (4b) as a blue powder, mp> 300 ° C. - R _f (silica gel, chloroform): 0.19. - IR (KBr): ≙ = 3110 cm ^-1 (w), 2955 (m), 2925 (m), 2854 (m), 1776 (m), 1731 (s), 1704 (m), 1662 (s) , 1605 (w), 1574 (w), 1500 (m), 1459 (w), 1432 (m), 1401 (m), 1368 (s), 1302 (s), 1228 (w), 1173 (w) , 1075 (w) 1030 (w), 989 (w), 925 (w), 808 (w), 751 (m), 730 (m), 687 (w), 644 (m), 546 (w), 504 (f). - ¹ H NMR (CD ₂ Cl ₂ ): δ = 0.85 (t, 12H, CH ₃ ), 1.23-1.30 (m, 56H, CH ₂ ), 1.84 (m, 4H, CH-CH ₂ ), 2.12 (m , 4H, CH-CH ₂ ), 5.01 (tt, 2H, CH (CH ₂ ) ₂ ), 7.55 (t, 1H, ³ J = 7.2 Hz, phenyl), 7.62 (t, 2H, ³ J = 7.2 Hz, Phenyl), 7.66 (d, 2H, ³ J = 7.2 Hz, phenyl), 8.92 (d, br, 4H, perylene). - ¹³ C NMR (CDCl ₃ ): δ = 14.3, 23.1, 27.4, 29.8, 30.0, 30.5, 32.3, 32.5, 55.8, 117.0, 123.8, 124.4, 126.4 126.8, 129.8, 129.9, 130.4, 133.7, 143.8. UV / VIS (CHCl ₃ ): λ _max (ε) = 310 nm (91980), 645 (6430), 705 (13210), 778 (16180). - Fluorescence (CHCl ₃ ): λ _max = 837 nm, 938. - MS (70 eV): m / z (%): 1271 (12), 1270 (39) [M ⁺ ], 1269 (77), 1268 ( 100), 1005 (11), 1004 (26), 1003 (78), 1002 (92) [M ⁺ - C ₁₉ H ₃₉ ], 738 (27), 737 (51) [M ⁺ - 2.C ₁₉ H ₃₉ ], 736 (49), 590 (28), 589 (31) [M ⁺ - 2.C ₁₉ H ₃₉ -C ₆ H ₅ NCO-CO], 443 (19), 442 (38), 268 (37 ). - C ₇₈ H ₉₂ N ₈ O ₈ (1269.7): calc. C 73.79, H 7.30, N 80837; gef. C 73.63, H 7.08, N 8.83.

11,12-Diaza-11,12-dihydrocoronen-2,3,5,6,8,9,11,12- octacarbonsäure-5,6-anhydrid-2,3:8,9-bis-(1-hexylheptylimid)- 11,12-phenylimid (5a): 11,12-Diaza-11,12- dihydrobenzo[ghi]perylen-2,3,8,9,11,12-hexacarbonsäure- 2,3:8,9-bis-(1-hexylheptylimid)-11,12-phenylimid (3a) (250 mg, 0.270 mmol) und p-Chloranil (132 mg, 0.541 mmol) werden in etwa 10 g bei 95°C geschmolzenem Maleinsäureanhydrid unter Zugabe von wenigen Millilitern Chloroform gelöst. Der Ansatz wird offen erhitzt, bis die Temperatur im Kolben etwa 125°C beträgt. Unter Rückflußkühlung wird über 4 Wochen erhitzt. Noch im Kolben verbliebenes Chloroform löst verdampfendes Maleinsäureanhydrid aus dem Kühler und spült es in den Kolben zurück. Während dieser Zeitspanne geht trotz Kühler eine gewisse Menge Chloroform verloren, wodurch die Temperatur im Kolben ansteigt. Durch Zugabe von wenig Chloroform wird die Temperatur auf 125°C gehalten. Der noch warme Ansatz wird in Salzsäure (2 M, 100 ml) gegossen und 24 h bei Raumtemperatur gerührt. Der entstandene Niederschlag wird abfiltriert, mit wenig Dichlormethan aufgenommen und auf eine Kieselgelsäule (250 mm × 20 mm) aufgetragen. Zunächst wird nicht umgesetztes 11,12-Diaza-11,12-dihydrobenzo[ghi]perylen-2,3,8,9,11,12- hexacarbonsäure-2,3:8,9-bis-(1-hexylheptylimid)-11,12- phenylimid mit Dichlormethan eluiert, dann wird die Chromatographie mit einer Mischung aus Dichlormethan mit 5% Eisessig fortgesetzt um das Produkt 11,12-Diaza-11,12- dihydrocoronen-2,3,5,6,8,9,11,12-octacarbonsäure-5,6-anhydrid- 2,3:8,9-bis-(1-hexylheptylimid)-11,12-phenylimid zu eluieren. Ausb. 156 mg (57%) 11,12-Diaza-11,12-dihydrocoronen- 2,3,5,6,8,9,11,12-octacarbonsäure-5,6-anhydrid-2,3:8,9-bis-(1- hexylheptylimid)-11,12-phenylimid (5a) als dunkelblauviolettes Pulver, Schmp. > 300°C. - IR (KBr): ≙ - 3103 cm^-1 w, 2955 s, 2928 s, 2857 m, 1849 m, 1778 s, 1730 s, 1710 s, 1666 s, 1624 m, 1600 m, 1575 w, 1523 w, 1490 m, 1460 m, 1417 m, 1392 s, 1351 s, 1307 s, 1268 w, 1239 m, 1196 m, 1166 m, 1127 m, 974 w, 915 m, 812 m, 755 m, 731 w, 702 w, 688 w, 668 w, 643 w, 607 w, 543 w, 503 m. - ¹H NMR (300 MHz, CDCl₃) δ = 0.83 (t, 12H, CH₃), 1.20-1.35 (m, 32H, CH₂), 1.85 (m, 4H, CH-CH₂), 2.25 (m, 4H, CH-CH₂), 5.15, tt, 2H, CH(CH₂)₂), 7.55 (t, 1H, ³J = 7.2 Hz, Phenyl), 7.63 (t, 2H, ³J = 7.2 Hz, Phenyl), 7.70 (d, 2H, ³J = 7.2 Hz, Phenyl), 9.78 (s, 2H, Perylen), 9.99 (s, 2H, Perylen). - ¹³C NMR (75 MHz, CDCl₃): δ = 14.4, 23.0, 27.4, 29.6, 32.2, 32.1, 32.7, 56.1, 117.9, 123.0, 125.0, 126.3, 126.4, 128.2, 129.7, 130.0, 130.3, 134.4, 144.2, 162.2. - UV/Vis (CHCl₃): λ_max (ε) = 272 nm sh (26900), 297 (49800), 324 (41700), 368 sh (17600), 387 (26400), 409 (36200), 536 sh (6800), 605 (9100), 655 sh (6600). - Fluoreszenz (CHCl₃): λ_max = 740 nm, 820 sh. MS (70 eV): m/z (%): 929 (23), 928 (68), 927 (100) [M⁺], 910 (6) [M⁺ - OH], 747 (11), 746 (21), 745 (23) [M⁺ - OH-C₁₃H₂₇], 565 (17), 564 (38), 563 (42) [M⁺ - 2.C₁₃H₂₇], 418 (12), 417 (44), 416 (53) [M⁺ - 2.C₁₃H₂₇-C₆H₅NCO-CO], 399 (14). C₆₂H₆₃N₅O₉ (1022.2): ber. C 72.85, H 6.21, N 6.85; gef. C 72.49, H 6.21, N 6.71.

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[9] Rechencode von MNDO: M. J. S. Dewar, W. Thiel, J. Am. Chem. Soc. 1977, 99, 4899.
[10] Parametrisierung von MNDO (AM1): J. J. P. Stewart, Programm MOPAC, Version 6.0; Programm-Parameter: PRECISE.
[11] H. Langhals, Spectrochim. Acta Part A 2000, 56, 2207-2210. 11,12-diaza-11,12-dihydrocorones-2,3,5,6,8,9,11,12-octacarboxylic acid-5,6-anhydride-2,3: 8,9-bis- (1-hexylheptylimide ) - 11,12-phenylimide (5a): 11,12-diaza-11,12-dihydrobenzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3: 8,9-bis - (1-Hexylheptylimide) -11,12-phenylimide (3a) (250 mg, 0.270 mmol) and p-chloroanil (132 mg, 0.541 mmol) are mixed in about 10 g at 95 ° C maleic anhydride with the addition of a few milliliters of chloroform solved. The mixture is heated open until the temperature in the flask is approximately 125 ° C. The mixture is heated under reflux for 4 weeks. Chloroform still remaining in the flask releases evaporating maleic anhydride from the cooler and rinses it back into the flask. During this period, despite the cooler, a certain amount of chloroform is lost, causing the temperature in the flask to rise. The temperature is kept at 125 ° C. by adding a little chloroform. The still warm batch is poured into hydrochloric acid (2 M, 100 ml) and stirred for 24 h at room temperature. The resulting precipitate is filtered off, taken up with a little dichloromethane and applied to a silica gel column (250 mm × 20 mm). First, unreacted 11,12-diaza-11,12-dihydrobenzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid 2,3: 8,9-bis- (1-hexylheptylimide) - 11,12-phenylimide eluted with dichloromethane, then the chromatography is continued with a mixture of dichloromethane with 5% glacial acetic acid to give the product 11.12-diaza-11.12-dihydrocoronen-2,3,5,6,8,9, Elute 11,12-octacarboxylic acid-5,6-anhydride-2,3: 8,9-bis- (1-hexylheptylimide) -11,12-phenylimide. Y. 156 mg (57%) 11,12-diaza-11,12-dihydrocorones-2,3,5,6,8,9,11,12-octacarboxylic acid-5,6-anhydride-2,3: 8,9- bis- (1-hexylheptylimide) -11,12-phenylimide (5a) as a dark blue violet powder, mp> 300 ° C. - IR (KBr): ≙ - 3103 cm ^-1 w, 2955 s, 2928 s, 2857 m, 1849 m, 1778 s, 1730 s, 1710 s, 1666 s, 1624 m, 1600 m, 1575 w, 1523 w, 1490 m, 1460 m, 1417 m, 1392 s, 1351 s, 1307 s, 1268 w, 1239 m, 1196 m, 1166 m, 1127 m, 974 w, 915 m, 812 m, 755 m, 731 w, 702 w , 688 w, 668 w, 643 w, 607 w, 543 w, 503 m. - ¹ H NMR (300 MHz, CDCl ₃ ) δ = 0.83 (t, 12H, CH ₃ ), 1.20-1.35 (m, 32H, CH ₂ ), 1.85 (m, 4H, CH-CH ₂ ), 2.25 (m , 4H, CH-CH ₂ ), 5.15, tt, 2H, CH (CH ₂ ) ₂ ), 7.55 (t, 1H, ³ J = 7.2 Hz, phenyl), 7.63 (t, 2H, ³ J = 7.2 Hz, Phenyl), 7.70 (d, 2H, ³ J = 7.2 Hz, phenyl), 9.78 (s, 2H, perylene), 9.99 (s, 2H, perylene). - ¹³ C NMR (75 MHz, CDCl ₃ ): δ = 14.4, 23.0, 27.4, 29.6, 32.2, 32.1, 32.7, 56.1, 117.9, 123.0, 125.0, 126.3, 126.4, 128.2, 129.7, 130.0, 130.3, 134.4, 144.2, 162.2. - UV / Vis (CHCl ₃ ): λ _max (ε) = 272 nm sh (26900), 297 (49800), 324 (41700), 368 sh (17600), 387 (26400), 409 (36200), 536 sh (6800), 605 (9100), 655 sh (6600). - Fluorescence (CHCl ₃ ): λ _max = 740 nm, 820 sh. MS (70 eV): m / z (%): 929 (23), 928 (68), 927 (100) [M ⁺ ], 910 (6) [M ⁺ - OH], 747 (11), 746 ( 21), 745 (23) [M ⁺ - OH-C ₁₃ H ₂₇ ], 565 (17), 564 (38), 563 (42) [M ⁺ - 2.C ₁₃ H ₂₇ ], 418 (12), 417 (44), 416 (53) [M ⁺ - 2.C ₁₃ H ₂₇ -C ₆ H ₅ NCO-CO], 399 (14). C ₆₂ H ₆₃ N ₅ O ₉ (1022.2): calcd. C 72.85, H 6.21, N 6.85; gef. C 72.49, H 6.21, N 6.71.

[1] S. Daehne, U. Resch-Genger, O. Wolfbeis, Near-Infrared Dyes for High Technology Applications, 1st edition, Kluwer Academic Publishers, Dordrecht, 1998, ISBN 0-7923-5101-0.
[2] Review: H. Langhals, Heterocycles 1995, 40, 477-500.
[3] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748.
[4] BASF AG (Erf. G. Seybold, A. Stange, Ger. Patent DE 85-3545004 (); Chem. Abstr. 1988, 108, 77134.
[5] R. Iden, G. Seybold, A. Stange, H. Eilingsfeld, Forschungsber. - Federal Minister. Research Technol., Technol. Research Development 1984, BMFT-FB-T 84-164; Chem. Abstr. 1985, 102, 150903.
[6] MI Rudkevich, TA Korotenko, Vestn. Khar'kov. Politekh. Inst. 1969, 41, 21-26; Chem. Abstr. 1971, 75, 7375.
[7] Y. Zhao, WMR Wasielewski, Tetrahedron Lett. 1999, 40, 7047-7050.
[8] H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380.
[9] MNDO calculation code: MJS Dewar, W. Thiel, J. Am. Chem. Soc. 1977, 99, 4899.
[10] Parameterization of MNDO (AM1): JJP Stewart, program MOPAC, version 6.0; Program parameters: PRECISE.
[11] H. Langhals, Spectrochim. Acta Part A 2000, 56, 2207-2210.

Subject of the invention

1. perylenetetracarboximide derivatives of the general formula I,

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

a) a halogen atom, for example chlorine, bromine, iodine or fluorine,

b) branched or unbranched alkyl groups or cycloalky groups having preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. These alkyl groups can have non-water-solubilizing substituents, such as fluorine, hydroxy, cyano, -OCOR 5 , -OR 6 , -OCOOR 7 , -CON (R 8 ) (R 9 ) or -OCONHR 10 , wherein R 5 to R 10 Alkyl, aryl such as naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O- alkyl or a heterocyclic radical, hydrogen, unsubstituted or substituted by cyano or hydroxyalkyl, C 3 - to C 24 -cycloalkyl, preferably C 5 - , C 6 -, C 12 -, C 15 -, C 16 -, C 20 - and C 24 - cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or in which R 5 to R 10 together with one of the other radicals R 6 to R 11 form a 5-6 membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for. B. the 2-thienyl, 2-benzoxazolyl, 2-benzthiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinoly- or 1-, 3-, 4-, 6-, or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched, unbranched or cyclic and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms.
Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C 3 to C 20 .

c) The group -OR 11 , in which R 11 is hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C 3 to C 24 -cycloalkyl, preferably C 5 -, C 6 -, C 12 , C 15 -, C 16 -, C 20 -, and C 24 -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R 11 can e.g. B. have one of the number b) given as preferred number of carbon atoms. Examples of R 11 are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl.

d) The cyano group.

e) The group of the formula -N (R 12 ) (R 13 ), in which R 12 and R 13 have the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, di-sec-butylamino, tert-butylamino , tert-amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3-tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di -n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylam , 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylhydroxymethylamino, 2-ethylhydroxymethylamino , N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, pheny lamino, diphenylamino, o-, m- or p-chlorophenylamino, o-, m-, or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicosanyylamino, cycloeicosanyylamino, cycloeicosanyaminoamino, cycloeicosanyaminoamino Piperidyl or morpholyl.

f) The group of the formula -COR 14 , wherein R 14 has the meaning given under a). Examples of R 14 are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl -, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl, benzyl or furfuryl.

g) The group of the formula -N (R 15 ) COR 16 , wherein R 15 has the meaning given under b), R 16 is hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2- Naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl or furfuryl. Alkyl occurring in the definitions of R 16 can e.g. B. have one of the preferred number of b atoms specified under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.

h) The group of the formula -N (R 17 ) COOR 18 , in which R 17 and R 18 have the meaning given under b) and c). Examples include the groups -NHCOOCH 3 , -NHCOOC 2 H 5 , or - NHCOOC 6 H 5 .

i) The group of the formula -N (R 19 ) CON (R 20 ) (R 21 ), in which R 19 , R 20 and R 21 have the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.

j) The group of the formula -NHSO 2 R 22 , wherein R 22 has the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.

k) The groups of the formula -SO 2 R 23 or -SOR 24 , wherein R 23 or R 24 have the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.

l) The group of the formula -SO 2 OR 25 , wherein R 25 has the meaning given under b). Examples of R 25 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.

m) The group of the formula -CON (R 26 ) (R 27 ), in which R 26 and R 27 have the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.

n) The group of the formula -SO 2 N (R 28 ) (R 29 ), in which R 28 and R 29 have the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.

o) The group of the formula -N = NR 30 , in which R 30 is the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R 30 can e.g. B. have one of the number b) given as preferred number of carbon atoms. The following may be mentioned as examples of R 30 : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.

p) The group of the formula -OCOR 31 wherein R 31 has the meaning given under b). Examples of R 31 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

q) The group of the formula -OCONHR 32 , in which R 32 has the meaning given under a). Examples of R 32 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

R 1 to R 4 can be hydrogen and one to four of the following radicals

a) Halogen atoms, for example chlorine, bromine, iodine or fluorine.

b) Branched or unbranched alkyl groups with preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4 carbon atoms. These alkyl groups can have non-water-solubilizing substituents such as fluorine, hydroxy, cyano, -OCOR 33 , -OR 34 , -OCOOR 35 , -CON (R 36 ) (R 37 ) or -OCONHR 38 , wherein R 33 is alkyl, aryl such as naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O-alkyl, benzyl or a heterocyclic radical, R 34 , R 35 and R 37 are hydrogen, unsubstituted or substituted by cyano or hydroxy, C 3 - to C 24 -cycloalkyl , preferably C 5 -, C 6 -, C 12 -, C 15 -, C 16 -, C 20 - and C 24 -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl , or wherein R 36 and R 37 together with one of the other radicals R 33 to R 38 form a 5-6-membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for. B. the 2-thienyl, 2-benzoxazolyl, 2-benzthiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinoly- or 1-, 3-, 4-, 6-, or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched or unbranched and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms.
Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C 3 to C 20 .

c) The group -OR 39 , in which R 39 is hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C 3 to C 24 -cycloalkyl, preferably C 5 -, C 6 -, C 12 , C 15 -, C 16 -, C 20 -, and C 24 -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R 39 can e.g. B. have one of the number b) given as preferred number of carbon atoms. Examples of R 39 are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl or acetoxymethyl Benzyl or cycloalkyl with C 3 to C 20 , phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, Cycloeicosanyl, Cyclotetracosanyl, Thienyl or Pyranylmethyl.

d) The cyano group.

e) The group of the formula -N (R 40 ) (R 41 ), in which R 40 and R 41 have the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, di-sec-butylamino, tert-butylamino , tert-amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3-tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di -n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylam , 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylhydroxymethylamino, 2-ethylhydroxymethylamino , N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, pheny lamino, diphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicetraanyaminoamino, cycloicotanyaminoamino, or or morpholyl.

f) The group of the formula -COR 42 , wherein R 42 has the meaning given under a). Examples of R 42 are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl or acetoxymethyl Benzyl or cycloalkyl with C 3 to C 20 , phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, Cycloeicosanyl, Cyclotetracosanyl, Thienyl, Pyranylmethyl, Benzyl or Furfuryl.

g) The group of the formula -N (R 43 ) COR 44 , wherein R 43 has the meaning given under b), R 44 is hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl , 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1- Ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl or cycloalkyl with C 3 to C 20 , phenyl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl , for example o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, pyranylmethyl , Benzyl or furfuryl. Alkyl occurring in the definitions of R 45 can e.g. B. have one of the preferred number of b atoms specified under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.

h) The group of the formula -N (R 45 ) COOR 46 , wherein R 45 and R 46 have the meaning given under b) and c). Examples include the groups -NHCOOCH 3 , -NHCOOC 2 H 5 , or - NHCOOC 6 H 5 .

i) The group of the formula -N (R 47 ) CON (R 48 ) (R 49 ), in which R 47 , R 48 and R 49 have the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.

j) The group of the formula -NHSO 2 R 50 , in which R 50 has the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.

k) The groups of the formula -SO 2 R 51 or -SOR 52 , wherein R 51 or R 52 have the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.

l) The group of the formula -SO 2 OR 53 , wherein R 53 has the meaning given under b). Examples of R 53 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.

m) The group of the formula -CON (R 54 ) (R 55 ), in which R 54 and R 55 have the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.

n) The group of the formula -SO 2 N (R 56 ) (R 57 ), in which R 56 and R 57 have the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.

o) The group of the formula -N = NR 58 , in which R 58 is the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R 58 can e.g. B. have one of the number b) given as preferred number of carbon atoms. The following may be mentioned as examples of R 58 : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.

p) The group of the formula -OCOR 59 , wherein R 59 has the meaning given under b). Examples of R 59 are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

q) The group of the formula -OCONHR 60 , wherein R 60 has the meaning given under a). Examples of R 60 include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
2. benzoperylenimide derivatives of the general formula II,

in which the radicals R 1 to R 3 have the meaning given under 1.
3. benzoperylenimide derivatives of the general formula III,

in which the radicals R 1 to R 3 have the meaning given under 1.
4. Process characterized in that the Compounds after 1 to 3 via Diels-Alder reactions being represented. Preferred dienophiles are Maleic anhydride and N-phenyltriazolinedione. Prefers becomes a large excess of these dienophiles, like z. B. three to fifty times; this in turn becomes a tenfold surplus more preferred. If the Dienophiles are liquid under the reaction conditions, then these are preferably used as solvents.
5. The method characterized in that the Diels-Alder reactions after 4 at elevated temperature is carried out. A temperature range is preferred from 70 to 250 ° C, most preferred are 100 to 200 ° C.
6. The method characterized in that for the synthesis of the dyes according to 4 Flavoring reagent is added. examples for Flavoring reagents are p-chloranil, platinum dioxide, p-benzoquinone, tetracyano-p-benzoquinone, Dicyanodichloro-p-benzoquinone and tetrachloro-p-benzoquinone.
7. The method characterized in that at the Diels-Alder reaction after 4 when using Maleimide or other solid at room temperature Solvents a small amount of a liquid solvent is added so that reflux is achieved. An example of such an auxiliary solvent is Chloroform.
8. Use of the substances according to 1 to 3 as Dyes.
9. Use of the substances according to 1 to 3 as Fluorescent dyes.
10. Application of the dyes from 1 to 3 Bulk staining of polymers. Examples are materials made of polyvinyl chloride, cellulose acetate, polycarbonates, Polyamides, polyurethanes, polyimides, Polybenzimidazoles, melamine resins, silicones, polyesters, Polyethers, polystyrene, polymethyl methacrylate, Polyethylene, polypropylene, polyvinyl acetate, Polyacrylonitrile, polybutadiene, polychlorobutadiene or Polyisoprene or the copolymers of the monomers mentioned.
11. Application of the dyes from 1 to 3 as Vat dyes, e.g. B. for coloring natural products. Examples are paper, wood, straw, leather, or skins natural fiber materials such as cotton, wool, silk, Jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products such. B. the viscose fiber, Nitrate silk or copper rayon (rayon).
12. Application of the dyes from 1 to 3 as Pickling dyes, e.g. B. for coloring natural products. Examples are paper, wood, straw, leather, or skins natural fiber materials such as cotton, wool, silk, Jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products such. B. the viscose fiber, Nitrate silk or copper rayon (rayon). Preferred salts aluminum, chrome and iron salts are available for pickling.
13. Application of the dyes from 1 to 3 as Colorants, e.g. B. for coloring paints, varnishes and other paints, paper colors, printing inks, Inks and other colors for painting and writing purposes.
14. Application of the dyes from 1 to 3 as Pigment dyes, e.g. B. for coloring paints, varnishes and other paints, paper colors, printing inks, Inks and other colors for painting and writing purposes.
15. Application of the dyes from 1 to 3 as Pigments in electrophotography: e.g. B. for Dry copy systems (Xerox process) and laser printers ( "Non-Impact Printing").
16. Application of dyes from 1 to 3 for Security marking purposes, the big chemical and photochemical resistance and possibly also the Fluorescence of the substances is important. Prefers is this for checks, check cards, bank notes, coupons, Documents, identity documents and the like, in which a special, unmistakable color impression can be achieved should.
17. Application of the dyes from 1 to 3 as Addition to other colors where a certain Color shade should be achieved, are preferred bright colors.
18. Application of the dyes from 1 to 3 to Marking objects for machine recognition of these items over fluorescence is preferred the mechanical detection of objects for sorting, z. B. also for the recycling of plastics.
19. Application of the dyes from 1 to 3 as Fluorescent dyes for machine-readable markings, alphanumeric imprints or barcodes are preferred.
20. Application of the dyes from 1 to 3 Frequency conversion of light, e.g. B. order from short-wave To make light longer-wave, visible light.
21. Application of dyes from 1 to 3 in Display elements for various display, information and Marking purposes, e.g. B. passive display elements, information and traffic signs, such as traffic lights.
22. Application of dyes from 1 to 3 in Inkjet printers, preferably in a homogeneous solution fluorescent ink.
23. Application of the dyes from 1 to 3 as Starting material for superconducting organic Materials.
24. Application of dyes from 1 to 3 for Solid fluorescent labels.
25. Application of dyes from 1 to 3 for decorative purposes.
26. Application of dyes from 1 to 3 for artistic purposes.
27. Application of dyes from 1 to 3 too Tracer purposes e.g. B. in biochemistry, medicine, technology and science. Here the dyes be covalently linked to substrates or via Secondary valences such as hydrogen bonds or hydrophobic interactions (adsorption).
28. Application of the dyes from 1 to 3 as Fluorescent dyes in highly sensitive Detection method (see C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z. Analyt. Chem. 1985, 320, 361).
29. Application of dyes from 1 to 3 as Fluorescent dyes in scintillators.
30. Application of the dyes from 1 to 3 as Dyes or fluorescent dyes in optical Light-harvesting systems.
31. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in fluorescent Solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716).
32. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in Fluorescence activated displays (see W. Greubel and G. Baur, Electronics 1977, 26, 6).
33. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in cold light sources for light-induced polymerization to display Plastics.
34. Application of dyes from 1 to 3 as Dyes or fluorescent dyes for Material testing, e.g. B. in the manufacture of Semiconductor circuits.
35. Application of dyes from 1 to 3 as Dyes or fluorescent dyes for examination of microstructures of integrated semiconductor components.
36. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in photoconductors.
37. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in photographic Method.
38. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in display, Lighting or imaging systems where the Excitation by electrons, ions or UV radiation takes place, e.g. B. in fluorescent displays, Braun tubes or in fluorescent tubes.
39. Application of dyes from 1 to 3 as Dyes or fluorescent dyes as part of one integrated semiconductor circuit, the dyes as such or in connection with other semiconductors z. B. in Form of an epitaxy.
40. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in Chemiluminescent systems, e.g. B. in chemiluminescent Glow sticks, in luminescent immunoassays or others Luminescence detection.
41. Application of dyes from 1 to 3 as Dyes or fluorescent dyes as signal colors preferred for visual highlighting of lettering and Drawings or other graphic products to Marking signs and other objects, at which achieve a special visual color impression shall be.
42. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in dye Lasers, preferably as fluorescent dyes for production of laser beams.
43. Application of dyes from 1 to 3 as Dyes in dye lasers as Q-switches.
44. Application of dyes from 1 to 3 as active substances for nonlinear optics, e.g. B. for frequency doubling and frequency tripling of laser light.
45. Application of dyes from 1 to 3 as Rheology.

LIST OF REFERENCE NUMBERS

Abb. 1. Berechnete HOMO-LUMO-Energiedifferenzen (ΔE, HMO- Modell) von Perylenbisimiden 1 mit n Aminogruppen in den Positionen 1, 6, 7 und 12 (•) und Ausgleichsgerade; für n = 3: von oben nach unten: 1,6- (1c), 1,12- (1e), 1,7- Diaminoverbindung (1d). Vergleich mit den Energien des Bis- Hydrazino-Derivats 1l (▪), des Bis-Pyrrolo-Derivats 1j (▴) und dem gemischten Hydrazino-Pyrrolo-Derivat 1k (♦). Fig. 1. Calculated HOMO-LUMO energy differences (ΔE, HMO model) of perylene bisimides 1 with n amino groups in positions 1, 6, 7 and 12 (•) and a straight line; for n = 3: from top to bottom: 1,6- (1c), 1,12- (1e), 1,7-diamino compound (1d). Comparison with the energies of the bis-hydrazino derivative 1l (▪), the bis-pyrrolo derivative 1j (▴) and the mixed hydrazino-pyrrolo derivative 1k (♦).

Abb. 2. Berechnete Strukturen von 3c und 4c. Fig. 2. Calculated structures of 3c and 4c.

Abb. 3. Normierte UV/Vis-Absorptionsspektren in Chloroform- Lösung; von links nach rechts: 2a, 3a und 4b. Fig. 3. Normalized UV / Vis absorption spectra in chloroform solution; from left to right: 2a, 3a and 4b.

Abb. 4. UV/Vis-Absorptionsspektrum (dicke Linie links) und Fluoreszenzspektrum (dicke Linie rechts) von 3a und 4b in Chloroform. Dünne Linien: simulierte Spektren auf der Basis von Gaußanalysen. Striche: berechnete Bandenlagen und Intensitäten der Schwingungsteilbanden. Tab. 1 Berechnete Energien (HMO) von substituierten Perylenbisimiden (1)

Tabelle 2 Gaußanalyse der UV/Vis Spektren in Chloroform (330-757 nm)

Fig. 4. UV / Vis absorption spectrum (thick line on the left) and fluorescence spectrum (thick line on the right) of 3a and 4b in chloroform. Thin lines: simulated spectra based on Gaussian analyzes. Lines: calculated band positions and intensities of the vibrating sub-bands. Tab. 1 Calculated energies (HMO) of substituted perylene bisimides (1)

Table 2 Gaussian analysis of the UV / Vis spectra in chloroform (330-757 nm)

Claims

1. perylenetetracarboximide derivatives of the general formula I,

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

a) a halogen atom, for example chlorine, bromine, iodine or fluorine,

b) branched or unbranched alkyl groups or cycloalky groups having preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms. These alkyl groups can have non-water-solubilizing substituents, such as fluorine, hydroxy, cyano, -OCOR ⁵ , -OR ⁶ , -OCOOR ⁷ , -CON (R ⁸ ) (R ⁹ ) or -OCONHR ¹⁰ , wherein R ⁶ to R ¹⁰ Alkyl, aryl such as naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O- alkyl or a heterocyclic radical, hydrogen, unsubstituted or substituted by cyano or hydroxyalkyl, C ₃ - to C ₂₄ -cycloalkyl, preferably C ₅ - , C ₆ -, C ₁₂ -, C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ - cycloalkyl, aryl or heteroaryl, in particular phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or in which R ⁵ to R ¹⁰ together with one of the other radicals R ⁶ to R ^{11 form} a 5-6 membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for. B. the 2-thienyl, 2-benzoxazolyl, 2-benzthiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinoly- or 1-, 3-, 4-, 6-, or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched, unbranched or cyclic and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms.
Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ .

c) The group -OR ¹¹ , in which R ^{11 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C ₃ to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ -, and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R ¹¹ can e.g. B. have one of the number b) given as preferred number of carbon atoms. Examples of R ¹¹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl -, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl.

d) The cyano group.

e) The group of the formula -N (R ¹² ) (R ¹³ ), in which R ¹² and R ^{13 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, di-sec-butylamino, tert-butylamino , tert-amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3-tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di -n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylam , 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylhydroxymethylamino, 2-ethylhydroxymethylamino , N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, pheny lamino, diphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicetraanyaminoamino, cycloicotanyaminoamino, or or morpholyl.

f) The group of the formula -COR ¹⁴ , wherein R ^{14 has} the meaning given under a). Examples of R ¹⁴ are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, - tetramethylbutyl, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl , 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluorethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl -, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl, benzyl or furfuryl.

g) The group of the formula -N (R ¹⁵ ) COR ¹⁶ , wherein R ^{15 has} the meaning given under b), R ^{16 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, phenyl, o-, m- or p-chlorophenyl, o-, m-, or p-methylphenyl, 1- or 2- Naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl or pyranylmethyl or furfuryl. Alkyl occurring in the definitions of R ¹⁶ can e.g. B. have one of the preferred number of b atoms specified under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.

h) The group of the formula -N (R ¹⁷ ) COOR ¹⁸ , in which R ¹⁷ and R ^{18 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ .

i) The group of the formula -N (R ¹⁹ ) CON (R ²⁰ ) (R ²¹ ), in which R ¹⁹ , R ²⁰ and R ^{21 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.

j) The group of the formula -NHSO ₂ R ²² , wherein R ^{22 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.

k) The groups of the formula -SO ₂ R ²³ or -SOR ²⁴ , wherein R ²³ or R ^{24 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.

l) The group of the formula -SO ₂ OR ²⁵ , wherein R ^{25 has} the meaning given under b). Examples of R ²⁵ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.

m) The group of the formula -CON (R ²⁶ ) (R ²⁷ ), in which R ²⁶ and R ^{27 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.

n) The group of the formula -SO ₂ N (R ²⁸ ) (R ²⁹ ), in which R ²⁸ and R ^{29 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.

o) The group of the formula -N = NR ³⁰ , in which R ^{30 is} the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ³⁰ can e.g. B. have one of the number b) given as preferred number of carbon atoms. The following may be mentioned as examples of R ³⁰ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.

p) The group of the formula -OCOR ³¹ , in which R ^{31 has} the meaning given under b). Examples of R ³¹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

q) The group of the formula -OCONHR ³² , in which R ^{32 has} the meaning given under a). Examples of R ³² are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

R ¹ to R ⁴ can be hydrogen and one to four of the following radicals

a) Halogen atoms, for example chlorine, bromine, iodine or fluorine.

b) Branched or unbranched alkyl groups with preferably 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4 carbon atoms. These alkyl groups can have non-water-solubilizing substituents such as fluorine, hydroxy, cyano, -OCOR ³³ , -OR ³⁴ , -OCOOR ³⁵ , -CON (R ³⁶ ) (R ³⁷ ) or -OCONHR ³⁸ , wherein R ^{33 is} alkyl, aryl such as naphthyl, or unsubstituted or substituted by halogen, alkyl, or -O-alkyl, benzyl or a heterocyclic radical, R ³⁴ , R ³⁵ and R ^{37 are} hydrogen, unsubstituted or substituted by cyano or hydroxy, C ₃ - to C ₂₄ -cycloalkyl , preferably C ₅ -, C ₆ -, C ₁₂ -, C ₁₅ -, C ₁₆ -, C ₂₀ - and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl , or wherein R ³⁶ and R ³⁷ together with one of the other radicals R ³³ to R ^{38 form} a 5-6-membered ring or hetero ring, such as a pyridine, pyrrole, furan or pyran ring. Further possible substituents on the alkyl groups are mono- or dialkylated amino groups, aryl radicals, such as naphthyl or, in particular, phenyl which is unsubstituted or substituted by halogen, alkyl or -O-alkyl, or furthermore heterocyclic aromatic radicals, such as, for. B. the 2-thienyl, 2-benzoxazolyl, 2-benzthiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinoly- or 1-, 3-, 4-, 6-, or 8-isoquinolyl residues. If the substituents mentioned under b) in turn contain alkyl, this alkyl can be branched or unbranched and preferably contain 1 to 21, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 4, carbon atoms.
Examples of unsubstituted alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1- Octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl with C ₃ to C ₂₀ .

c) The group -OR ³⁹ , in which R ^{39 is} hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C ₃ to C ₂₄ -cycloalkyl, preferably C ₅ -, C ₆ -, C ₁₂ , C ₁₅ -, C ₁₆ -, C ₂₀ -, and C ₂₄ -cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. Alkyl occurring in the definitions of R ³⁹ can e.g. B. have one of the number b) given as preferred number of carbon atoms. Examples of R ³⁹ are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, Cyclotetracosanyl, thienyl or pyranylmethyl.

d) The cyano group.

e) The group of the formula -N (R ⁴⁰ ) (R ⁴¹ ), in which R ⁴⁰ and R ^{41 have} the meaning given under b). Examples include: amino, methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, sec-butylamino, di-sec-butylamino, tert-butylamino , tert-amylamino, n-hexylamino, di-n-hexylamino, 1,1,3,3-tetramethylbutylamino, n-heptylamino, di-n-heptylamino, n-octylamino, di-n-octylamino, n-nonyl, di -n-nonylamino, n-decylamino, di-n-decylamino, n-undecylamino, di-n-undecylamino, n-dodecylamino, di-n-dodecylamino, n-octadecylamino, 1-ethylpropylamino, 1-propylbutylamino, 1-butylpentylam , 1-pentylhexylamino, 1-hexylheptylamino, 1-heptyloctylamino, 1-octylnonylamino, 1-nonyldecylamino, 1-decylundecylamino, 1-ethylbutylamino, 1-ethylpentylamino, 1-ethylheptylamino, 1-ethylhydroxymethylamino, 2-ethylhydroxymethylamino , N-bis (2-hydroxyethyl) amino, trifluoromethylamino, trifluoroethylamino, cyanomethylamino, methoxycarbonylmethylamino, acetoxymethylamino, benzylamino, dibenzylamino, pheny lamino, diphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, 1- or 2-naphthylamino, cyclopentylamino, cyclohexylamino, cyclododecylamino, cyclopentadecylamino, cyclohexadecylamino, cycloeicetraanyaminoamino, cycloicotanyaminoamino, or or morpholyl.

f) The group of the formula -COR ⁴² , wherein R ^{42 has} the meaning given under a). Examples of R ⁴² are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-hexyl, 1,1,3,3-tetramethylbutyl, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1-ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, Cyclotetracosanyl, thienyl, pyranylmethyl, benzyl or furfuryl.

g) The group of the formula -N (R ⁴³ ) COR ⁴⁴ , wherein R ^{43 has} the meaning given under b), R ^{44 is} hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , tert-butyl, tert-amyl, n-hexyl, 1,1,3,3, -tetramethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Octadecyl, 1-ethylpropyl, 1-propylbutyl, 1-butylpentyl, 1-pentylhexyl, 1-hexylheptyl, 1-heptyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl 1-ethylbutyl, 1-ethylpentyl, 1-ethylheptyl, 1 -Ethylnonyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl or cycloalkyl with C ₃ to C ₂₀ , phenyl, especially unsubstituted or substituted by halogen, alkyl or -O-alkyl Phenyl, for example o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl, cyclohexadecyl, cycloeicosanyl, cyclotetracosanyl, thienyl, pyranylmethy l, benzyl or furfuryl. Alkyl occurring in the definitions of R ⁴⁵ can e.g. B. have one of the preferred number of b atoms specified under b). Examples include: acetylamino, propionylamino, butyrylamino, benzoylamino, p-chlorobenzoylamino, p-methylbenzoylamino, N-methylacetamino, N-methylbenzoylamino, N-succinimido, N-phthalimido or N- (4-amino) phthalimido.

h) The group of the formula -N (R ⁴⁵ ) COOR ⁴⁶ , wherein R ⁴⁵ and R ^{46 have} the meaning given under b) and c). Examples include the groups -NHCOOCH ₃ , -NHCOOC ₂ H ₅ , or - NHCOOC ₆ H ₅ .

i) The group of the formula -N (R ⁴⁷ ) CON (R ⁴⁸ ) (R ⁴⁹ ), in which R ⁴⁷ , R ⁴⁸ and R ^{49 have} the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.

j) The group of the formula -NHSO ₂ R ⁵⁰ , in which R ^{50 has} the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino

k) The groups of the formula -SO ₂ R ⁵¹ or -SOR ⁵² , wherein R ⁵¹ or R ^{52 have} the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.

l) The group of the formula -SO ₂ OR ⁵³ , wherein R ^{53 has} the meaning given under b). Examples of R ⁵³ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.

m) The group of the formula -CON (R ⁵⁴ ) (R ⁵⁵ ), in which R ⁵⁴ and R ^{55 have} the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.

n) The group of the formula -SO ₂ N (R ⁵⁶ ) (R ⁵⁷ ), in which R ⁵⁶ and R ^{57 have} the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.

o) The group of the formula -N = NR ⁵⁸ , in which R ^{58 is} the residue of a coupling component or a phenyl radical which may be substituted by halogen, alkyl or -O-alkyl. Alkyl occurring in the definitions of R ⁵⁸ can e.g. B. have one of the number b) given as preferred number of carbon atoms. The following may be mentioned as examples of R ⁵⁸ : the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.

p) The group of the formula -OCOR ⁵⁹ , wherein R ^{59 has} the meaning given under b). Examples of R ⁵⁹ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

q) The group of the formula -OCONHR ⁶⁰ , wherein R ^{60 has} the meaning given under a). Examples of R ⁶⁰ include: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.

2. benzoperylenimide derivatives of the general formula II,

in which the radicals R ¹ to R ^{3 have} the meaning given under 1.

3. benzoperylenimide derivatives of the general formula III,

in which the radicals R ¹ to R ^{3 have} the meaning given under 1.

4. Process characterized in that the Compounds after 1 to 3 via Diels-Alder reactions being represented. Preferred dienophiles are Maleic anhydride and N-phenyltriazolinedione. Prefers becomes a large excess of these dienophiles, like z. B. three to fifty times; this in turn becomes a tenfold surplus more preferred. If the Dienophiles are liquid under the reaction conditions, then these are preferably used as solvents.

5. The method characterized in that the Diels-Alder reactions after 4 at elevated temperature is carried out. A temperature range is preferred from 70 to 250 ° C, most preferred are 100 to 200 ° C.

6. The method characterized in that for the synthesis of the dyes according to 4 Flavoring reagent is added. examples for Flavoring reagents are p-chloranil, platinum dioxide, p-benzoquinone, tetracyano-p-benzoquinone, Dicyanodichloro-p-benzoquinone and tetrachloro-p-benzoquinone.

7. The method characterized in that at the Diels-Alder reaction after 4 when using Maleimide or other solid at room temperature Solvents a small amount of a liquid solvent is added so that reflux is achieved. An example of such an auxiliary solvent is Chloroform.

8. Use of the substances according to 1 to 3 as Dyes.

9. Use of the substances according to 1 to 3 as Fluorescent dyes.

10. Application of the dyes from 1 to 3 Bulk staining of polymers. Examples are materials made of polyvinyl chloride, cellulose acetate, polycarbonates, Polyamides, polyurethanes, polyimides, Polybenzimidazoles, melamine resins, silicones, polyesters, Polyethers, polystyrene, polymethyl methacrylate, Polyethylene, polypropylene, polyvinyl acetate, Polyacrylonitrile, polybutadiene, polychlorobutadiene or Polyisoprene or the copolymers of the monomers mentioned.

11. Application of the dyes from 1 to 3 as Vat dyes, e.g. B. for coloring natural products. Examples are paper, wood, straw, leather, or skins natural fiber materials such as cotton, wool, silk, Jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products such. B. the viscose fiber, Nitrate silk or copper rayon (rayon).

12. Application of the dyes from 1 to 3 as Pickling dyes, e.g. B. for coloring natural products. Examples are paper, wood, straw, leather, or skins natural fiber materials such as cotton, wool, silk, Jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products such. B. the viscose fiber, Nitrate silk or copper rayon (rayon). Preferred salts aluminum, chrome and iron salts are available for pickling.

13. Application of the dyes from 1 to 3 as Colorants, e.g. B. for coloring paints, varnishes and other paints, paper colors, printing inks, Inks and other colors for painting and writing purposes.

14. Application of the dyes from 1 to 3 as Pigment dyes, e.g. B. for coloring paints, varnishes and other paints, paper colors, printing inks, Inks and other colors for painting and writing purposes.

15. Application of the dyes from 1 to 3 as Pigments in electrophotography: e.g. B. for Dry copy systems (Xerox process) and laser printers ( "Non-Impact Printing").

16. Application of dyes from 1 to 3 for Security marking purposes, the big chemical and photochemical resistance and possibly also the Fluorescence of the substances is important. Prefers is this for checks, check cards, bank notes, coupons, Documents, identity documents and the like, in which a special, unmistakable color impression can be achieved should.

17. Application of the dyes from 1 to 3 as Addition to other colors where a certain Color shade should be achieved, are preferred bright colors.

18. Application of the dyes from 1 to 3 to Marking objects for machine recognition of these items over fluorescence is preferred the mechanical detection of objects for sorting, z. B. also for the recycling of plastics.

19. Application of the dyes from 1 to 3 as Fluorescent dyes for machine-readable markings, alphanumeric imprints or barcodes are preferred.

20. Application of the dyes from 1 to 3 Frequency conversion of light, e.g. B. order from short-wave To make light longer-wave, visible light.

21. Application of dyes from 1 to 3 in Display elements for various display, information and Marking purposes, e.g. B. passive display elements, information and traffic signs, such as traffic lights.

22. Application of dyes from 1 to 3 in Inkjet printers, preferably in a homogeneous solution fluorescent ink.

23. Application of the dyes from 1 to 3 as Starting material for superconducting organic Materials.

24. Application of dyes from 1 to 3 for Solid fluorescent labels.

25. Application of dyes from 1 to 3 for decorative purposes.

26. Application of dyes from 1 to 3 for artistic purposes.

27. Application of dyes from 1 to 3 too Tracer purposes e.g. B. in biochemistry, medicine, technology and science. Here the dyes be covalently linked to substrates or via Secondary valences such as hydrogen bonds or hydrophobic interactions (adsorption).

28. Application of the dyes from 1 to 3 as Fluorescent dyes in highly sensitive Detection method (see C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z. Analyt. Chem. 1985, 320, 361).

29. Application of dyes from 1 to 3 as Fluorescent dyes in scintillators.

30. Application of the dyes from 1 to 3 as Dyes or fluorescent dyes in optical Light-harvesting systems.

31. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in fluorescent Solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716).

32. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in Fluorescence activated displays (see W. Greubel and G. Baur, Electronics 1977, 26, 6).

33. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in cold light sources for light-induced polymerization to display Plastics.

34. Application of dyes from 1 to 3 as Dyes or fluorescent dyes for Material testing, e.g. B. in the manufacture of Semiconductor circuits.

35. Application of dyes from 1 to 3 as Dyes or fluorescent dyes for examination of microstructures of integrated semiconductor components.

36. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in photoconductors.

37. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in photographic Method.

38. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in display, Lighting or imaging systems where the Excitation by electrons, ions or UV radiation takes place, e.g. B. in fluorescent displays, Braun tubes or in fluorescent tubes.

39. Application of dyes from 1 to 3 as Dyes or fluorescent dyes as part of one integrated semiconductor circuit, the dyes as such or in connection with other semiconductors z. B. in Form of an epitaxy.

40. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in Chemiluminescent systems, e.g. B. in chemiluminescent Glow sticks, in luminescent immunoassays or others Luminescence detection.

41. Application of dyes from 1 to 3 as Dyes or fluorescent dyes as signal colors, preferred for visual highlighting of lettering and Drawings or other graphic products to Marking signs and other objects, at which achieve a special visual color impression shall be.

42. Application of dyes from 1 to 3 as Dyes or fluorescent dyes in dye Lasers, preferably as fluorescent dyes for production of laser beams.

43. Application of dyes from 1 to 3 as Dyes in dye lasers as Q-switches.

44. Application of dyes from 1 to 3 as active substances for nonlinear optics, e.g. B. for frequency doubling and frequency tripling of laser light.

45. Application of dyes from 1 to 3 as Rheology.