DE4018830A1 - New perylene dyestuffs synthesised from perylene blue - used as biochemical tracers, dyestuffs and pigments, in optical light gathering systems, in polymerisation reactions, etc. - Google Patents

Abstract

Perylene dyes of formulae (I) are new. A=(II), (III) or (IV). R and R1 = H, isocyclic aromatic gps., heterocyclic aromatic gps. (opt. fused to benzo rings), halo, alkyl, OR6, CN, NR4R5, COR3, NR7COR3, NR6.COOR3, NR6.CONR4R5, NHSO2R3, SO2R3, SOR3, SO2OR3, CONR4R5, SO2NR4R5, -N=N-R8, OCOR3 or OCONHR3; R6 = H, alkyl, aryl or 3-24C cycloalkyl; R4 and R5 = H, alkyl, 3-24C cycloalkyl, aryl or heteroaryl, or together complete a ring. R3 = alkyl, aryl, benzyl or heterocyclyl; R7 = H, alkyl, benzyl, phenyl, cycloalkyl or heterocyclyl; R8 = residue of a coupling component, or phenyl; all gps. may carry a wide range of substituents; where the cpds. contain 2 R gps., these must be different. USE - The new cpds. are dyes/pigments with a very wide range of possible uses, e.g. in varnishes, paper colours and printing inks; as fluorescent dyes in scintillators or optical light collection systems; as cold light sources for light-induced polymerisation; in dry copying, laser printing, etc.; in chemiluminescent immunoassays; as security markers, for frequency conversion, etc. (16pp Dwg.No.0/7)

Description

Because of their amazingly good properties as fluorescent dyes it would be of interest to the perylene dyes in general as a tracer for biochemical, analytical and technical purposes (e.g. in polymer chemistry). For that they should have a reactive body that allows you to use it with any To link substrates, and they should also groups bear their solubility in organic solvents or increase in water. Key substances for this could be the Perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide (2) be, which then with any primary amines to perylene dyes (1) could be condensed, the two different ones Wear residues R.

The perylene dyes are usually represented by condensation of primary amines (R₁-NH₂ = R₂-NH₂) with the technically easily accessible perylene-3,4: 9,10-tetracarboxylic acid bisanhydride (3) ¹ ). Quinoline or molten imidazole is preferably used as the solvent for the synthesis with the addition of auxiliaries such as zinc acetate (see also ref. ^4-6 )). In this synthetic route, which provides very high yields of dyes, only symmetrically substituted perylene dyes (1, R₁ = R₂), but not the key substances 2, are accessible - a deficit of amines leads almost exclusively to a mixture of the corresponding bisimide (1, R₁ = R₂) and unreacted starting material, the bisanhydride (3). Using a mixture of two different amines generally results in. general only a difficult-to-separate mixture of perylene dyes, in which the asymmetrical dyes only make up the smaller portion (see also Ref. ^{15, 16} )).

By H. Tröster and co-workers. ^{17, 18} ) an elegant method for representing 2 has been developed. Here, the poor solubility of the monopotassium salt of perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride (4) is used, which can be prepared directly from 3 by an exact adjustment of the pH. This synthesis can be further improved and simplified by using acetic acid (see exp. Part). 4 is condensed to 2 with primary amines. This synthesis works very well with water-soluble aliphatic amines and can still be used with liquid, reactive and not too strongly hydrophobic aromatic amines. However, it fails with strongly hydrophobic or sterically hindered amines, which in turn are important for the preparation of easily soluble perylene dyes (e.g. 2, R = 2,5-di-tert-butylphenyl or 2, R = 1-hexylheptyl).

If alternative 4 is first reacted with ammonia to 5 and then with the amine in question to 1, R₁ = H, saponification of the group with R₁ = H succeeds neither under basic nor under strongly acidic reaction conditions, not even in conc. Sulfuric acid with the addition of sodium nitrite, so that 2 is not accessible in this way. With the dyes 1 with R₁ = H but under basic conditions S _N 2 reactions z. B. on aliphatic halides, so that fluorescent labels on sterically unhindered halides are possible in this way (see exp. Part).

Y. Nagao and T. Misono ^19-22 ) describe one-sided saponification of the symmetrical bisimides 1 to the monoimides 2 with concentrated sulfuric acid at elevated temperature. Under the reaction conditions, there is basically a risk of elimination reactions with aliphatic residues. If the R radicals are aromatic, the method fails completely, because the radicals are sulfonated rather than cleaving a carboximide (for example when R = 2,5-di-tert-butylphenyl in the p-position to the nitrogen).

A one-sided basic saponification of 1 is different Bases, e.g. B. aqueous KOH or NaOH using various solubilizers like 1,4-dioxane or THF, according to and for known saponification processes not possible. Saponification amazingly, however, succeeds smoothly with a high concentration on KOH in tert-butyl alcohol. The reaction is with a very high concentration of KOH (10 g KOH in 100 ml of tert-butyl alcohol), saponification takes place gradually  of bisimide to tetracarboxylate of bisanhydride 3 (see exp. Part of method I). It is only difficult to find the right one Time for partial saponification. This is e.g. B. by monitoring the reaction by thin layer chromatography possible. On the other hand, smaller concentrations of KOH are used (1 g KOH in 100 ml tert-butyl alcohol), it comes as a surprise a blue colored by-product just at the time if the concentration of mono-saponification product 2 is optimal (Method II). The reaction can thus be followed optically very easily and should be stopped when the Reaction solution discolored blue-black. The small amount of that then By-product can be created by removing it with glacial acetic acid can be easily removed. Another cleaning of 2 is done on the dipotassium salt obtained by saponification of the anhydride aqueous potassium carbonate solution is formed. In concentrated potassium carbonate solution is the dipotassium salt because of the concentrated ionic additive surprisingly hardly soluble. It will be with dil. hydrochloric acid converted back into the anhydride. In this can Traces of potassium salts finally amazed at the corresponding Triethylammonium salt are removed - other triethylammonium salts obviously sublimate at higher temperatures from the reaction product. For all cleaning operations the concentrations and temperatures need to be set so be that precipitates that can be filtered as well as possible are formed. However, favorable conditions can be found for this.

With the saponification method mentioned (preferably good soluble) bisimides 1 with both aliphatic and aromatic Saponify substituents. The question of which of these Both types of dyes are more easily saponified the reaction of dye 1 with R₁ = 2,5-di-tert-butylphenyl, R₂ = clarify ethyl. This substance is very preferably the aromatic residue split off from the aliphatic residue (Comparison with an authentic sample).

As already mentioned, the saponification reaction with low concentrations of KOH produces a very polar, blue by-product which can be separated off by means of chromatographic filtration (silica gel / ethyl acetate). The blue material can finally be eluted with acetone. This changes slowly, in the presence of acid, very quickly into a red-violet substance. The red-violet substance can be converted back into the blue in 10 min by the action of KOH in methanol / DMSO at 60 ° C. The extinction coefficient of the blue substance is relatively small [for the blue dye from 1, R₁ = R₂ = 2,5-di-tert-butylphenyl, λ _max (ε) is 520 nm sh, 604 (7460), 675 sh and out in acetone 1, R₁ = ethyl, R₂ = 2,5-di-tert-butylphenyl λ _max (ε) 628 nm (2570)] compared to the extinction coefficient of the perylene dyes (1, R₁ = R₂ = 2,5-di-tert-butylphenyl ; ε = 95 000 ⁵ )), and the absorption band is extremely wide. This suggests a charge transfer transition. The blue dye could then be a salt that was created by the attack of a nucleophile - the great polarity of the substance is also an indication of this.

The yield of the blue or red-violet substance can be Surprisingly, increase to 79% if as a medium instead KOH / tert-butyl alcohol used the mixture KOH / methanol / DMSO becomes. Due to their spectroscopic data, the red-violet Substance assigned the structure of lactam 6. Under these Reaction conditions become a carbon of the starting material Surprisingly released as CO₂, after acidifying the reaction solution can be determined quantitatively (87%, gravimetric). Is in the ring narrowing reaction 1 with R₁ = 2,5-di-tert-butylphenyl, R₂ = ethyl used, so the reaction occurs to lactam preferably on the side of the aromatic substituent a. This also corresponds to the preference for the aromatically substituted Imids during saponification (see above). A ring narrowing reaction this type is e.g. Currently only known from the perylene dyes. The structurally related naphthalene-1,8-dicarboximides result exclusively under the reaction conditions mentioned Saponification reactions. This again underlines the unusual and surprising reaction of the perylene dyes 1. It is  assume that the ring narrowing reaction is similar to the Lossen rearrangement has - about further mechanistic work will be reported elsewhere.

The imide anhydrides 2 can now due to the newly found reaction under the reaction conditions otherwise customary for the perylene dyes be converted into the dyes 1, the then wear two different residues R. For practical applications is z. B. the dye 1 with R₁ = 2,5-ditertbutylphenyl and R₂ = 2-aminoethyl of interest, the one with biochemically important Substrates can be linked. This way you can also bifluorophoric perylene dyes, such as. B. 7 represent. The new synthetic routes open up a multitude of for the dyes Applications, examples of which are given in key words should: lightfast tracer for biochemical, medical, scientific and technical applications, as colorants and Pigments, in highly sensitive analytical detection methods, in scintillators, in optical light collection systems such as fluorescent solar collectors, in cold light sources for light-induced Polymerization, as fluorescent dyes for various technical Purposes, as Lumiphore, and for the generation of laser beams.

Experimental part N- (2,5-di-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

Method I: 7.7 g (10 mmol) of N, N'-di (2,5-di-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ⁵ ) are suspended in 100 ml of tert-butyl alcohol and then with stirring with 10 g (150 mmol) of 85 porz. solid KOH added. The reaction mixture is refluxed for 30 min and, after cooling, is poured into 100 ml of glacial acetic acid with vigorous stirring. It is heated briefly and then mixed with 50 ml of 2N HCl. The precipitated product is filtered off, three times with 100 ml of dist. Washed water and dried at 130 ° C in a drying cabinet. For cleaning over the dipotassium salt, the product with 200 ml 10 percent. Potassium carbonate solution boiled under reflux for 20 min (low solubility of the substance through concentrated addition of the same ion). After cooling to room temp. the product is sucked off via a G-4 glass filter and with 10 percent. Potassium carbonate solution washed. The filter cake is then washed with hot dist. Treated water, whereby the dipotassium salt goes into solution. Traces of the insoluble diimide are separated by filtration and the solution is acidified with 2N hydrochloric acid. The dark red reaction product is suctioned off, several times with dist. Washed water, dried in a drying cabinet at 130 ° C. and recrystallized from toluene ⁵ ). - Education 600 mg (10%).

Method II: 4.0 g (5.2 mmol) N, N'-di (2,5-di-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10 -biscarboximid ⁵ ) are suspended in 100 ml of tert-butyl alcohol and then with stirring with 1.0 g (15 mmol) 85 percent. solid KOH added. The reaction mixture is refluxed until a deep blue to black discoloration sets in and, after cooling, is poured into a mixture consisting of 100 ml of glacial acetic acid and 50 ml of 2N hydrochloric acid with vigorous stirring. It is heated briefly and, after cooling, suction filtered, washed twice with 100 ml of methanol each time and dried at 130 ° C. in a drying cabinet. For further purification, the substance is boiled under reflux with 200 ml of potassium carbonate solution for 20 minutes (low solubility of the substance through concentrated addition of the same ion). After cooling to room temp. the product is sucked off via a G-4 glass filter and with 10 percent. Potassium carbonate solution washed. Then it is washed twice with 2 N HCl and three times with dist. Washed water. The product is dried at 130 ° C, again in 100 ml dist. Bring water to boiling temperature with triethylamine (30 min) and then filter. The clear filtrate is acidified with 2N HCl and the precipitate is filtered off with dist. Washed water several times, dried in a drying cabinet at 130 ° C and recrystallized from toluene ⁵ ). - Education 1.0 g (18%). - R _F (CHCl₃) = 0.23. - IR (Kbr): = 2964 cm ^-1 (m), 1775 (s), 1733 (s), 1711 (s), 1668 (s), 1596 (s), 1580 (m), 1507 (w), 1406 (m), 1362 (s), 1324 (s), 1269 (w), 1249 (s), 1201 (w), 1180 (w), 1168 (w), 1153 (w), 1122 (w), 1023 (s), 810 (s), 650 (w), 500 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.4241), 455 (4.1900), 485 (4.6671), 522 (4.8889). - Fluorescence (CHCl₃): λ _max = 528 nm, 570. - 1 N-NMR (CDCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.32 [s, 9 H, C (CH₃) ₃], 7.00 [d, J _{4 ′, 6 ′} = 2 Hz, 1 aromatic H], 7.48 [dd, J _{4 ′, 6 ′} = 2 Hz, J _{3 ′, 4 ′} = 8 Hz, 1 aromatic H], 7.60 [d, J _{3 ′, 4 ′} = 8 Hz, 1 aromatic H], 8.70 [m, 8 H]. - MS (70 eV): m / z (%) = 579 (7.6%) [M⁺], 564 (19) [M⁺ - CH₃], 522 (100%) [M⁺ - C (CH₃) ₃], 507 (11.4).

C₃₈H₂₉NO₅ (579.7)
Calc .:
C 78.74; H 5.04; N 2.42
Found:
C 78.71; H 5.01; N 2.42

N- (2-methyl-5-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

7.0 g (10 mmol) of N, N'-di (2-methyl-5-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ⁴ ) in 100 ml of tert-butyl alcohol with 10 g (150 mmol) of 85 percent. solid KOH implemented according to Method I (30 min reaction time). - Education 2.3 g (42%) dark red powder. - R _F (CHCl₃) = 0.14. - IR (Kbr): = 3055 cm ^-1 (w), 2960 (m), 1772 (s), 1733 (s), 1711 (s), 1668 (s), 1619 (w), 1596 (s), 1579 (m), 1507 (m), 1405 (s), 1363 (s), 1325 (s), 1298 (w), 1278 (w), 1250 (w), 1202 (w), 1170 (w), 1154 (w), 1123 (m), 1024 (s), 855 (w), 810 (s), 739 (s), 652 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.7935), 455 (4.2802), 485 (4.7109), 522 (4.9185). - Fluorescence (CHCl₃): λ _max = 528, 570 nm. - 1 H-NMR (CDCl₃): δ = 1.35 [s, 9 H, C (CH₃) ₃], 2.2 [s, 3 H, CH₃ ], 7.15 [s, 1 aromatic H], 7.35 [d, J _{3 ′, 4 ′} = 9 Hz, 1 aromatic H], 7.45 (d, J _{3 ′, 4 ′} = 9 Hz, 1 aromatic-H], 8.71 [m, 8 H). - MS (70 eV): m / z (%) = 579 (7.6) [M⁺], 564 (19) [M⁺ - CH₃], 522 (100) [M⁺ - C₄H₉], 507 (11 , 4).

C₃₅H₂₃NO₅ (537.6)
Calc .:
C 78.20; H 4.31; N 2.61
Found:
C 78.22; H 4.28; N 2.84

N- (1-Hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

4.0 g (5.3 mmol) of N, N'-di (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ⁶ ) are analogous to Method II dissolved in 100 ml of tert-butyl alcohol and then with stirring with 1.00 mg (1.5 mmol) 85 percent. KOH added. The solution is heated to boiling for 20 min and then, after cooling with ice, made acidic with 50 ml of glacial acetic acid followed by 200 ml of 2N HCl. After leaving to stand overnight, aspirate with a D-4 glass frit and repeatedly with dist. Washed water. Twice the product with 10 percent. Potassium carbonate solution and then treated with 2N HCl. It is dissolved in aqueous trethylamine solution and precipitated with 2N HCl. After the reprecipitation, the mixture is recrystallized from ethanol ⁵ ). - Education 1.8 g (59%). - R _F (CHCl₃) = 0.52. - IR (KBr): = 2955 cm ^-1 (m), 2927 (s), 2856 (m), 1771 (s), 1734 (s), 1700 (s), 1660 (s), 1620 (w), 1595 (s), 1510 (w), 1460 (w), 1406 (s), 1357 (m), 1320 (s), 1268 (w), 1249 (m), 1200 (w), 1175 (w), 1153 (w), 1142 (w), 1024 (m), 850 (w), 810 (s), 739 (s). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.7466), 456 (4.2551), 485 (4.6811), 522 (4.8958). - Fluorescence (CHCl₃): λ _max = 528 nm, 570. - 1 H-NMR (CHCl₃): δ = 0.80 (t, 6 H, 2 CH₃), 1.25 (m, 16 H, 8 CH₂), 1.88 (m, 2 H, CH₂), 2.22 (m, 2 H, CH₂), 5.18 (m, 1 H, CH), 8.62 (m, 8 H). - 13 C-NMR (CDCl₃): δ = 163.7 (s, C = O), 159.7 (s, C = O), 136.2 (s, C-3), 133.4 (d, C -2), 133.4 (s, C-9), 131.7 (s, C-3a), 131.5 (d, C-8), 129.4 (s, C-1a), 126, 6 (s, C-9a), 126.4 (s, C-1b), 124.4 (s, C-6b), 123.8 (d, C-1), 123.0 (d, C- 7), 118.9 (s, 12b), 55.0 (d, C-1 ′), 32.4 (t, C-2 ′), 31.8 (t, C-3 ′), 29, 2 (t, C-4 ′), 27.0 (t, C-5 ′), 22.6 (t, C-6 ′), 14.0 (q, C-7 ′) (cf. ²³ )). - MS (70 eV): m / z (%) = 573 (40.3) [M⁺], 404 (4.3), 391 (100), 347 (8.8), 319 (7.7) .

C₃₇H₃₅NO₅ (755.1)
Calc .:
C 77.46; H 6.15; N 2.44
Found:
C 77.25; H 6.23; N 2.51

N- (1-heptyloctyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

4.05 g (5.0 mmol) of N, N′-di (1-heptyloctyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ²⁴ ) are analogous to Method II dissolved in 100 ml of tert-butyl alcohol and then with stirring with 1.68 g (25 mmol) 85 percent. powdered KOH added. The reaction mixture is heated to boiling and the progress of the saponification is monitored by thin layer chromatography (silica gel / CHCl₃). The reaction is terminated after 12 min by adding 120 ml of glacial acetic acid while cooling with ice (the starting material is no longer detectable by thin layer chromatography - R _F = 0.82 with CHCl₃ on silica gel). After adding 50 ml of 2N HCl, the mixture is filtered off with a D-4 glass suction filter and the red-brown solid is distilled with dist. Washed water neutral. To separate any perylene tetracarboxylic bisanhydride formed, the crude product is twice with 200 ml of 10 percent. Potassium carbonate solution boiled up and then suctioned off with a D-4 glass filter funnel. The crude product thus obtained is dried at 100 ° C. for 8 hours. Educ. 1.68 g (52%). The crude product is further purified by column chromatography (80 × 4 cm) on silica gel with chloroform / glacial acetic acid 10: 1 as the eluent. Traces of impurities can be removed by re-chromatography using 10: 1 chloroform / triethanolamine as the eluent. The isolated dye is spun in with glacial acetic acid and washed with water. - Education 1.44 g (48%) - mp. 316 ° C - R _F (silica gel / CHCl₃) = 0.44 - R _F [silica gel; CHCl₃ / glacial acetic acid (10: 1)] = 0.85. - IR (KBr): = 2972 cm ^-1 (s), 2855 (m), 1771 (s), 1733 (m), 1701 (s), 1660 (s), 1618 (w), 1595 (s), 1579 (m), 1406 (m), 1357 (m), 1321 (s), 1247 (m), 1154 (w), 1142 (w), 1024, 810 (s), 739 (s). - UV (CHCl₃) λ _max (ε) = 455 nm (17 350), 485 (46 255), 522 (70 380). - Fluorescence (CHCl₃): λ _max = 528 nm, 570. - MS (70 eV): m / z (%) = 602 (14, M⁺), 601 (34), 404 (4), 391 (100) , 347 (16), 319 (13). - 1 H-NMR (CDCl₃) δ = 0.8 (t, 6 H), 1.25 (m, 20 H), 1.85 (m, 2 H), 2.22 (m, 2 H), 5 , 15 (m, 1H), 8.60 (m, 8H). - 13 C-NMR (CDCl₃): 159.85, 136.33, 133.54, 133.46, 131.79, 131.24, 129.47, 126.74, 126.49, 123.87, 123, 07, 118.99, 54.94, 32.35, 31.77, 29.47, 29.19, 26.96, 22.58, 14.02.

C₃₉H₃₉NO₅ (601.7)
Calc .:
C 77.84; H 6.53; N 2.33
Found:
C 78.04; H 6.64; N 2.54

N- (1-Nonyldecyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

923 mg (1.00 mmol) N, N'-di (1-nonyldecyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ²⁴ ) are analogous to Method II in 50 ml of tert-butyl alcohol dissolved with heating and then with stirring with 225 mg (3.41 mmol) 85 percent. KOH added. The solution is heated to boiling and the course of saponification is followed by thin layer chromatography. After 13 minutes, no more educt can be detected in the reaction mixture, and the reaction is stopped by ice cooling and the addition of 50 ml of glacial acetic acid. 25 ml of 2N HCl are added, and the red-brown precipitate is filtered off with suction over a D-4 glass frit, with dist. Washed water and dried at 100 ° C for 8 h. - Education 0.62 g (crude product). Further purification is carried out analogously to N- (1-heptyloctyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide. - Education 330 mg (50.1%). - mp 308 ° C. - R _F (silica gel / CHCl₃) = 0.77. - R _F [silica gel; CHCl₃ / glacial acetic acid (10: 1)] = 0.85. - IR (KBr): = 2925 cm ^-1 (s), 2854 (m), 1771 (s), 1733 (s), 1701 (s), 1660 (s), 1617 (w), 1595 (s), 1578 (m), 1406 (s), 1356 (m), 1321 (s), 1267 (w), 1250 (m), 1141 (w), 1124 (m), 1015 (m), 809 (s), 737 (s). - UV (CHCl₃): λ _max (ε) = 455 nm (20 690), 486 (48 920), 522 (77 990). - 1 H-NMR (CDCl₃): δ = 0.8 (t, 6 H, 2 CH₃), 1.25 (m, 28 H, 14 CH₂), 1.85 (m, 2 H, CH₂), 2, 22 (m, 2 H, CH₂), 5.15 (m, 1 H, CH), 8.62 (m, 8 H, H-aromatic). - 13 C-NMR (CDCl₃): δ = 159.87, 154.91, 136.35, 133.57, 133.49, 131.82, 129.48, 126.76, 126.51, 123.87, 123.08, 119.0, 54.93, 32.33, 31.83, 29.50, 29.23, 26.94, 22.61, 14.04. - MS (70 eV): m / z (%) = 657 (19) [M⁺], 404 (2), 391 (66), 347 (12), 319 (9).

C₄₃H₄₇NO₅ (657.9)
Calc .:
C 78.50; H 7.20; N 2.13
Found:
C 78.53; H 7.14; N 2.24

N- (1-decylundecyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

4.98 g (5.00 mmol) of N, N'-di (1-decylundecyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-biscarboximide ²⁴ ) are tert in 100 ml -Butyl alcohol dissolved and then stirring with 1.12 g (17 mmol) 85 percent. KOH added. The solution is heated to boiling and the course of saponification is followed by thin layer chromatography. After 12 min, the reaction is stopped by ice cooling and the addition of 150 ml of glacial acetic acid. Further purification is carried out analogously to N- (1-heptyloctyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide. - Education 1.95 g (57%). - mp 302 ° C. - R _F (silica gel / CHCl₃) = 0.80. - R _F [silica gel; CHCl₃ / glacial acetic acid (10: 1)] = 0.85. - IR (KBr): = 2924 cm ^-1 (s), 2853 (m), 1772 (s), 1734 (m), 1701 (s), 1660 (s), 1616 (w), 1594 (s), 1577 (m), 1406 (s), 1356 (m), 1319 (s), 1265 (m), 1248 (m), 1140 (w), 1124 (m), 1015 (m), 809 (s), 736 (s). - UV (CHCl₃): λ (ε) = 455 nm (18 470), 486 (47 840), 522 (77 690). - 1 H-NMR (CDCl₃): δ = 0.8 (t, 6 H, 2 CH₃), 1.25 (m, 32 H, 16 CH₂, 1.85 (m, 2 H, CH₂), 2.22 (m, 2 H, CH₂), 5.15 (m, 1 H, CH), 8.60 (m, 8 H, H-aromatics). ¹³C-NMR (CDCl₃): δ = 159.82, 136 , 30, 133.50, 133.44, 131.77, 129.46, 123.05, 118.97, 54.94, 32.34, 31.85, 29.55, 29.54, 29.51 , 29.27, 26.95, 22.63, 14.04 - MS (70 eV): m / z (%) = 686 (13) [M⁺], 685 (48), 404 (4), 391 (100), 347 (10), 319 (6).

C₄₅H₅₁NO₅ (685.9)
Calc .:
C 78.80; H 7.49; N 2.04
Found:
C 78.76; H 7.46; N 2.18

N, N'-Di (2,5-di-tert-butylphenyl-3-aminoperylene-4: 9,10-tricarboxylic acid-3,4-lactam-9,10-carboximide

3.0 g (3.9 mmol) of N, N '- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) with 7 g (106 mmol) 85 percent. KOH in a mixture of 60 ml of methanol and 40 ml of DMSO heated to 80 ° C. for 3 hours with stirring. The mixture is then poured into 300 ml of water and concentrated. Acidified hydrochloric acid to pH 3. After cooling to room temperature, the reaction product is suctioned off with a G-4 glass suction filter and repeatedly with dist. Washed water until the wash water is neutral. Finally it is dried in a drying cabinet at 120 ° C. - Education 2.3 g (79%) deep purple dye. - R _F (CHCl₃) = 0.89. - IR (KBr): = 3065 cm ^-1 (w), 2962 (m), 2869 (w), 1721 (s), 1705 (s), 1668 (s), 1627 (w), 1584 (s), 1492 (s), 1461 (m), 1402 (m), 1357 (s), 1321 (w), 1286 (w), 1247 (m), 1201 (w), 1169 (w), 1148 (w), 1070 (w), 965 (w), 820 (m), 807 (w), 748 (w), 647 (w). - UV (CHCl₃): λ _max (lg ε) = 328 nm (3.8999), 362 (3.8999), 389 (4.0019), 403 (4.0405), 540 (4.5207). - Fluorescence (CHCl₃): λ _max = 640 nm. ¹H-NMR (CDCl₃): δ = 1.32 [m, 36 H, 4 C (CH₃) ₃], 6.73 (d, 1 H), 7 , 05 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.15 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.50 (2dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 2 H), 7.61 (2dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 2 H), 8 , 30 (m, 2H), 8.40 (d, 1H), 8.65 (m, 4H). - 13 C-NMR (CDCl₃): δ = 168.3 (s, C = O), 164.7 (s, C = O), 150.8 (s, C-5 ′), 150.0 (s, C-5 ′ ′), 146.5 (s, C-1 ′ ′), 143.8 (s, C-2 ′ ′), 143.6 (s, C-2 ′ ′), 136.5 (s ), 135.2 (s), 134.2 (s), 132.9 (s), 132.3 (s), 132.0 (d), 131.6 (d), 130.6 (s) , 128.7 (d), 128.2 (d), 127.8 (s), 126.9 (s), 126.8 (d), 126.5 (s), 126, (d), 125 , 2 (s), 124.6 (s), 124.2 (d), 124.1 (s), 123.6 (s), 122.2 (d), 121.6 (s), 120, 3 (d), 35.6 (s, C (CH₃) ₃), 35.4 (s, C (CH₃) ₃), 34.3 (s, C (CH₃) ₃), 34.3 (s, C (CH₃) ₃), 31.8 (q, C (CH₃) ₃), 31.8 (q, C (CH₃) ₃), 31.2 (q, 2 C (CH₃) ₃). - MS (70 eV): m / z (%) = 738 (59.8 [M⁺], 681 (100) [M⁺ - C (CH₃) ₃].

C₅₁H₅₀N₂O₃ (739.0)
Calc .:
C 82.89; H 6.84; N 3.79
Found:
C 82.82; H 6.84; N 3.86

N- (2,5-di-tert-butylphenyl) -N'-ethyl-2-aminoperylene-4: 9,10-tricarboxylic acid-3,4-lactam-9,10-carboximide

3.0 g (4.9 mmol) of N- (2,5-di-tert-butylphenyl) -N'-ethyl-3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide ) are completely analogous to N, N'-di (2,5-di-tert-butylphenyl) -3-aminoperylene-4: 9,10-tricarboxylic acid-3,4-lactam-9,10-carboximide and worked up. - Education 2.0 g (68%) deep purple dye. - R _F (CHCl₃) = 0.78. - IR (KBr): = 3070 cm ^-1 (w), 2965 (m), 1721 (s), 1694 (s), 1656 (s), 1626 (m), 1585 (s), 1492 (s), 1460 (m), 1403 (m), 1385 (m), 1371 (m), 1251 (m), 1160 (w), 1120 (w), 1072 (m), 950 (w), 848 (w), 820 (w), 806 (m), 752 (w), 741 (m), 650 (w), 583 (w), 522 (w). - UV (CHCl₃): λ _max (lg ε) = 238 nm (3.7764), 362 (3.8022), 389 (3.9123), 403 (3.9554), 540 (4.4432). - Fluorescence (CHCl₃): λ _max = 630 nm. ¹H-NMR (CDCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.33 (t, 3 H, CH₃), 1.35 [s, 9 H, C (CH₃) ₃], 4.15 (q, 2 H, CH₂), 6.65 (d, 1 H), 7.30 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.51 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.62 (d, J _{3 ′, 4 ′} = 8 Hz, 1 H), 8.07 (m, 2 H), 8.15 (t, 2 H), 8.30 (m, 3 H). - 13 C-NMR (CDCl₃): δ = 168.2 (s, C = O), 163.2 (s, C = O), 150.9 (s, C-5 ′), 146.4 (s, C-2 ′), 143.5 (d, C-3 ′), 135.8 (s), 134.5 (s), 133.9 (s), 132.2 (s), 132.2 ( d), 130.8 (d), 129.7 (s), 128.6 (d), 128.4 (d), 126.8 (d), 126.4 (s), 126.1 (s ), 126.0 (d), 124.9 (d), 124.2 (s), 123.9 (d), 123.8 (s), 123.0 (s), 121.9 (d) , 121.0 (s), 120.0 (d), 108.3 (d, C-11), 35.6 (t, CH₂) 35.4 [s, C (CH₃) ₃], 34.4 [s, C (CH₃) ₃], 31.8 [q, C (CH₃) ₃], 31.3 [q, C (CH₃) ₃], 13.4 (q, CH₃). - MS (70 eV): m / z (%) = 578 (100) [M⁺], 549 (21) [M⁺ - C₂H₅], 521 (22) [M⁺ - C (CH₃) ₃], 281 , 5 (28).

C₃₉H₃₄N₂O₃ (578.7)
Calc .:
C 80.94; H 5.92; N 4.84
Found:
C 80.67; H 6.02; N 4.66

Perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9-carboxylic acid-10-carboxylic acid potassium salt (4)

10.0 g (25.5 mmol) perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-bisanhydride (3) and 40 g (0.61 mol) 85 percent. Potassium hydroxide are distilled in 1 l. Water dissolved with gentle warming and swirling (1-2 h). The dark red, fir green fluorescent solution is filtered through a glass filter with porosity 4, then boiled under reflux and treated with glacial acetic acid through the reflux condenser so that it is diluted by the reflux. The dropping begins at about 1 drop per second and, after the mixture has turned brown-black, is reduced to 1 drop in 3 to 5 seconds and continued until the solution reaches a pH of 5. The progress and completion of the reaction is checked by a spot test on filter paper. The brown-black precipitate remains at the spot and the spreading aqueous phase must fluoresce only weakly. After the addition has ended, the mixture is boiled under reflux for a further 15 min. The precipitate is then filtered off, and three times with dist. Washed water. The precipitate is then twice with 1 l dist. Water boiled for 15 min and suction filtered. It is finally washed twice with methanol and dried in a drying cabinet at 120 ° C. for 8 hours. - Education 10.9 g (95%) (ref. ¹⁷ ) 98%).

C₂₄H₂₉KO₇ (448.4)
Calc .:
C 64.28; H 2.02
Found:
C 64.35; H 2.15

N- (2,5-dimethylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide ²⁵ )

3.9 g (10.0 mmol) of perylene-3,4: 9,10-tetracarboxylic acid bisanhydride are dissolved in a mixture of 5 ml of triethylamine and 100 ml of water at 90 ° C. After adding 1.2 g (9.9 mmol) of 2,5-dimethylaniline, a pH value between 6.3 and 6.6 is set with glacial acetic acid. The mixture is stirred at room temperature for 6 h and the pH range specified is maintained by dropping further glacial acetic acid. A total of 30 ml of glacial acetic acid are consumed. After the reaction has ended, another 20 ml of glacial acetic acid are added. The reaction product is suctioned off with 2 percent. Hydrochloric acid and then washed acid-free with water. To separate unreacted perylenetetracarboxylic acid bisanhydride and the resulting diimide, proceed as follows: the moist filter cake is dissolved in 150 ml of 5 percent. aqueous potassium hydroxide solution stirred at 90 to 95 ° C for 2 h, filtered off after cooling to 20 to 25 ° C and with 5 percent. aqueous potassium hydroxide solution until the colorless filtrate drain. The filter cake is then treated with hot water, the dipotassium salt of N- (2,5-dimethylphenyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide having a deep red-violet color goes into solution. The insoluble diimide is separated off by filtration and the anhydride imide is precipitated by acidification, suction filtered and dried. - Education 1.7 g (33%). - R _F (silica gel / CHCl₃) = 0.30. - IR (KBr): = 3048 cm ^-1 (w), 2925 (w), 1773 (s), 1735 (s), 1706 (s), 1664 (s), 1620 (w), 1594 (s), 1579 (m), 1507 (m), 1405 (s), 1366 (s), 1324 (s), 1296 (w), 1276 (w), 1247 (s), 1185 (w), 1154 (w), 1125 (w), 1026 (s), 860 (w), 809 (s), 798 (w), 770 (w), 736 (w), 650 (w). - UV (CHCl₃): λ _max = 428 nm, 455, 485, 520. - Fluorescence (CHCl₃): λ _max = 542 nm, 570. - MS (70 eV): m / z (%) = 495 (32) [M⁺], 480 (19) [M⁺ - CH₃], 479 (48), 478 (100) [M⁺ - OH], 463 (2), 450 (1).

C₃₂H₁₇NO₅ (495.5)
Calc .:
C 77.56; H 3.45; N 2.82
Found:
C 77.27; H 3.41; N 2.56

Perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide

5.61 g (12.5 mmol) of perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9-carboxylic acid-10-carboxylic acid potassium salt (4) are stirred up in 70 ml of one 0-5 ° C chilled 3 percent. Ammonia solution entered (see Ref. ¹⁷ )) and then post-treated at 90 ° C for 2 h. Then 16 g 25 percent. Potassium carbonate solution. It is stirred for a further 1 h at 90 ° C. and after cooling to room temperature. aspirated and with 2 percent. Potassium carbonate solution washed until the filtrate runs colorless. The residue is 10 percent in 325 g. KOH dissolved at 95 ° C and freed of residues of bisimide by filtration through a glass filter with porosity 4. Acidification with 2 N HCl and filtering off gives the anhydride imide as a brown-red powder. For further purification, it is distilled in a mixture of 100 ml. Water and 10 ml of triethylamine dissolved (20 min reflux), filtered and precipitated by acidification with 2 N HCl. It is suctioned off with a D-4 glass filter funnel, several times with dist. Washed water and dried in a drying cabinet at 130 ° C for 24 hours (for high cleaning, sublimation can still be carried out in a vacuum at 0.001 Torr and 360 ° C). - Education 3.8 g (78%). - R _F (DMF) = 0.21. - IR (KBr): = 3061 cm ^-1 (m), 1779 (s), 1758 (s), 1731 (s), 1696 (s), 1618 (w), 1594 (s), 1507 (w), 1427 (w), 1403 (m), 1371 (m), 1319 (s), 1271 (s), 1230 (w), 1180 (w), 1153 (w), 1143 (w), 1035 (w), 1023 (m), 860 (w), 810 (m), 736 (m), 655 (m), 454 (m). - UV (CHCl₃): λ _max = 455 nm, 483, 517. - Fluorescence (DMF): λ _max = 535 nm, 578. - MS (70 eV): m / z (%) = 391 (100) [M ⁺], 363 (13) [M⁺ - CO], 347 (11) [M⁺ - CO₂], 319 (15), 275 (5), 248 (9).

C₂₄H₉NO₅ (391.3)
Calc .:
C 73.66; H 2.32; N 3.58
Found:
C 73.58; H 2.61; N 3.61

N, N ′ - (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide)

The display and cleaning is completely analogous to Ref. ⁵ ). - 13 C-NMR (CDCl₃): δ = 164.4 (s, C = O), 150.2 (s, C-5 '), 143.8 (s, C-3'), 135.0 (s , C-3), 132.6 (s, C-1 ′), 131.8 (d, C-2), 129.9 (s, C-3a), 128.8 (d, C-3 ′ ), 127.7 (d, C-4 ′), 126.8 (s, C-1a ′), 126.3 (d, C-6 ′), 123.8 (s, C-1b), 123, 3 (d, C-1).

N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide)

1.0 g (1.7 mmol) of perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-carboximide are mixed with 2.05 g (10.0 mmol) of 2,5-di -tert-butylaniline, 330 mg Zn (OAc) ₂ and 5 ml quinoline heated to 220 ° C for 2 h. After cooling, the mixture in 60 percent. Ethanol suspended and left at room temperature for 2 h. The solid is suctioned off through a D-4 glass filter crucible, with 96 percent. Washed ethanol and dried at 120 ° C in a drying cabinet. For further purification, the product is boiled with water / triethylamine (10: 1) under reflux, traces of the starting material dissolving. The product is filtered off with suction, dried in a drying cabinet at 120 ° C. and recrystallized from toluene ⁵ ). Educ. 1.3 g (88%). - R _F (DMF) = 0.22. - IR (KBr): = 3067 cm-1 (w), 2964 (m), 1706 (s), 1668 (s), 1594 (s), 1588 (m), 1507 (w), 1437 (w), 1407 (m), 1357 (s), 1347 (s), 1269 (m), 1248 (w), 811 (m), 656 (w), 501 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.7571), 457 (4.2886), 488 (4.7209), 525 (4.9446). - Fluorescence (CHCl₃): λ _max = 535 nm, 574. - 1 H-NMR (CHCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.35 [s, 9 H, C (CH₃) ₃], 7.05 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.42 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.55 (d, J _{3 ′, 4 ′} = 8 Hz, 1 H), 8.76 (m, 8 H). - MS (70 eV): m / z (%) = 578 (2) [M⁺], 563 (4) [M⁺ - CH₃], 521 (100) [M⁺ - C₄H₉], 507 (4).

C₃₈H₃₀N₂O₄ (578.7)
Calc .:
C 78.87; H 5.23; N 4.84
Found:
C 78.64; H 5.30; N 4.88

N- (2,5-di-tert-butylphenyl) -N'-ethyl-3,4: 9,10-perylenetetracar bonic acid-3,4: 9,10-bis (dicarboximide)

2.9 g (4.8 mmol) of N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) are mixed with 11 , 0 (101 mmol) of ethyl bromide and 9.0 g (65.1 mmol) of anhydrous potassium carbonate in 100 ml of anhydrous DMF were stirred for 16 h and then heated to 80 ° C. for 2 h. The mixture is distilled in 400 ml. Poured water, acidified with 2N HCl and stirred for 30 min. The reaction product is suctioned off, three times with dist. Washed water, dried in a drying cabinet at 120 ° C., extractively ⁵ ) recrystallized from toluene and dried in vacuo at 80 ° C. and 0.001 Torr for 4 h. - Education 1.2 g (40%). - R _F (silica gel / CHCl₃) = 0.10. - IR (KBr): = 3065 cm ^-1 (w), 2964 (m), 1700 (s), 1664 (s), 1616 (w), 1502 (w), 1458 (w), 1439 (w), 1404 (m), 1361 (s), 1342 (s), 1255 (m), 1202 (w), 1179 (w), 1152 (w), 1124 (w), 1050 (w), 962 (w), 911 (m), 748 (w), 650 (w), 498 (w), 431 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.8765), 458 (4.3351), 488 (4.7605), 524 (4.9841). - Fluorescence (CHCl₃): λ _max = 537 nm, 577. - 1 H-NMR (CDCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.35 [t, J = 8 Hz , 3 H, CH₃], 1.38 [s, 9 H, C (CH₃) ₃], 4.24 (q, J = 8 Hz, 2 H, CH₂), 7.05 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.43 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 8 Hz, 1 H), 7.54 (d, J _{3 ′, 4 ′} = 8 Hz, 1 H), 8.76 (m, 8 H). - MS (70 eV): m / z (%) = 606 (0.3) [M⁺], 591 (1.4) [M⁺ - CH₃], 577 (0.3) [M⁺ - C₂H₅] , 562 (0.8) [M⁺ - CO₂], 549 (100) [M⁺ - C₄H₈], 535 (8.8).

C₄₀H₃₄N₂O₄ (606.7)
Calc .:
C 79.19; 5.65; N 4.62
Found:
C 79.08; H 5.64; N 4.45

N- (2,5-di-tert-butylphenyl) -N '- (2-hydroxyethyl) -3,4: 9,10-pery lentetracarboxylic acid 3,4: 9,10-bis (dicarboximide)

2.0 g (3.4 mmol) of N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) are mixed with 14, 0 g (112 mmol) of ethylene bromohydrin and 13 g (94 mmol) of anhydrous potassium carbonate in 100 ml of anhydrous DMF were stirred at 100 ° C. for 24 h (reflux condenser). After cooling, the mixture is distilled in 50 ml. Poured water, acidified with 2N HCl while stirring and continued stirring for 30 min. The reaction product is suctioned off, three times with dist. Washed water, dried at 120 ° C drying cabinet. - Education 0.5 g (24%). - R _F (silica gel / dioxane) = 0.87. - IR (KBr): = 3150 cm ^-1 (m), 2964 (m), 1699 (s), 1664 (s), 1616 (w), 1595 (s), 1579 (m), 1507 (w), 1437 (f), 1404 (m), 1358 (s), 1345 (s), 1252 (m), 1172 (w), 825 (w), 811 (m), 748 (w), 651 (w), 501 (w), 431 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.5867), 457 (4.2399), 488 (4.6944), 525 (4.9267). - Fluorescence (CHCl₃): λ _max = 538 nm, 578. - 1 H-NMR (CDCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.35 [s, 9 H, C (CH₃) ₃], 4.05 (t, J = 6 Hz, 2 H), 4.52 (t, J = 6 Hz, 2 H), 7.07 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.48 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.58 (d, J _{3 ′, 4 ′} = 8 Hz, 1H), 8.67 (m, 8H). - MS (70 eV): m / z (%) = 578 (1.8) [M⁺], 563 (4.2) [M⁺ - CH₃], 521 (100) [M⁺ - C (CH₃) ₃], 507 (3.6).

C₄₀H₃₄N₂O₅ (622.7)
Calc .:
C 77.15; H 5.50; N 4.50
Found:
C 77.05; H 5.48; N 4.21

N- (2,5-di-tert-butylphenyl) -N ′ - (3-cyanophenyl) -3.4: 9.10-perylene tetracarboxylic acid 3,4: 9,10-bis (dicarboximide)

3.5 g (6.0 mmol) of N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) are 4 g (12 mmol) of 3-aminobenzonitrile, 330 mg of zinc acetate and 5 ml of quinoline were heated to 200 ° C. under nitrogen for 3 h. After cooling, the mixture is 60 percent. Suspended ethanol and 16 h at room temp. ditched. The precipitated solid is suctioned off with a D-4 glass suction filter, with 96 percent. Washed ethanol, twice with 10 percent. Boiled potassium carbonate solution and then with dist. Washed water. After drying at 130 ° C. in a drying cabinet, the mixture is recrystallized from ethanol ⁵ ). - Education 2.6 g (63%). - R _F (silica gel / CHCl₃) = 0.46. - IR (KBr): = 3070 cm ^-1 (w), 2965 (w), 2195 (w), 1707 (s), 1669 (s), 1653 (w), 1636 (w), 1594 (s), 1579 (m), 1520 (w), 1480 (w), 1432 (w), 1404 (m), 1356 (s), 1347 (s), 1255 (m), 1200 (w), 1175 (w), 1148 (w), 1125 (w), 975 (w), 811 (m), 800 (w), 750 (w), 650 (w), 501 (w). - UV (CHCl₃): λ _max (lg ε) = 430 nm (3.8812), 458 (4.3583), 490 (4.7562), 525 (4.9746). - Fluorescence (CHCl₃): λ _max = 542 nm, 577. - 1 H-NMR (CDCl₃): δ = 1.29 [s, 9 H, C (CH₃) ₃], 1.35 [s, 9 H, C (CH₃) ₃], 7.06 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.48 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.61 (d, J _{3 ′, 4 ′} = 8 Hz, 1 H), 7.66 (d, 1 H), 7.71 (s, 1 H), 7.71 ( t, J = 7 Hz, 1H), 7.81 (s, 1H), 8.75 (m, 8H). - 13 C-NMR (CDCl₃): δ = 164.2 (s, C = O), 163.2 (s, C = O), 155.8, 151.2, 150.2, 143.7, 135, 9, 135.5, 134.6, 133.6, 132.7, 132.5, 132.1, 131.8, 130.2, 129.8 128.8, 127.8 126.8, 126, 4, 124.1, 123.6, 123.2, 122.9, 117.8, 113.8, 112.3, 111.8, 111.3, 35.6 (s, C (CH₃) ₃) , 34.3 (s, C (CH₃) ₃), 31.8 (q, C (CH₃) ₃), 31.2 (q, C (CH₃) ₃). - MS (70 eV): m / z (%) = 679 (2.4) [M⁺], 622 (100) [M⁺ - C (CH₃) ₃], 592 (3.65).

C₄₅H₃₃N₃O₄ (679.8
Calc .:
C 79.51; H 5.92; N 6.18
Found:
C 79.40; H 4.80; N 6.10

N- (2,5-di-tert-butylphenyl) -N '- (4-aminobutyl) -3.4: 9.10-perylene tetracarboxylic acid 3,4: 9,10-bis (dicarboximide)

1.0 g (1.7 mmol) of N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) are mixed with 30 ml (300 mmol) 1,4-diaminobutane and 60 ml of benzene boiled under reflux for 2 h. Then 90 ml of chloroform are added, and it is repeatedly washed with dist. Water shaken out. The organic phase is dried with magnesium sulfate, the solvent mixture is distilled off and the residue is dried over phosphorus pentoxide. - Education 1.0 g (89%). - R _F [silica gel; HCO₂H / acetone / CHCl₃ (1: 1: 4)] = 0.78. - IR (KBr): = 3048 cm ^-1 (w), 2960 (m), 2868 (w), 1696 (s), 1653 (s), 1594 (s), 1577 (m), 1559 (w), 1506 (w), 1482 (w), 1457 (w), 1437 (w), 1403 (m), 1356 (s), 1345 (s), 1254 (m), 1203 (w), 1177 (w), 1165 (w), 815 (w), 811 (s), 795 (w), 749 (m), 735 (w), 651 (w). - UV (CHCl₃): λ _max (lg ε) = 435 nm (3.8024), 458 (4.2106), 490 (4.6017), 528 (4.8067). - Fluorescence (CHCl₃): λ _max = 530 nm, 573. - 1 H-NMR (CDCl₃): δ = 1.25 (s, 2 H, NH₂), 1.29 [s, 9 H, C (CH₃) ₃ ], 1.35 [s, 9 H, C (CH₃) ₃], 1.63 [quint, 4 H, C (CH₂) ₂], 2.82 (t, 2 H, CH₂), 4.23 ( t, 2 H, CH₂), 7.12 (d, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.52 (dd, J _{3 ′, 4 ′} = 8 Hz, J _{4 ′, 6 ′} = 2 Hz, 1 H), 7.61 (d, J _{3 ′, 4 ′} = 8 Hz, 1 H), 8.66 (m, 8 H). - MS (70 eV): m / z (%) = 649 (9.6) [M⁺], 631 (17.4) [M⁺ - H₂O], 592 (51) [M⁺ - C (CH₃) ₃], 574 (100), 521 (29.7).

1,4-bis [N- (2,5-di-tert-butylphenyl) -N'-yl-3,4: 9,10-perylene tetracarboxylic acid 3,4: 9,10-bis (dicarboximide) butane

To a solution of 1.0 g (1.7 mmol) of N- (2,5-di-tert-butylphenyl) -3,4: 9,10-perylenetetracarboxylic acid-3,4: 9,10-bis (dicarboximide) 3 ml (30 mmol) of 1,4-diaminobutane are added to 60 ml of benzene. The mixture is boiled under reflux for 2 h, the reaction product is filtered off with suction, washed with benzene and dried. - Education 1.0 g (98%). - R _F [silica gel; HCOOH / acetone / CHCl₃ (1: 1: 4)] = 0.81. - IR (KBr): = 3065 cm ^-1 (w), 2994 (m), 2875 (w), 1698 (s), 1662 (s), 1594 (s), 1579 (m), 1506 (w), 1457 (w), 1437 (m), 1404 (s), 1385 (s), 1356 (s), 1348 (s), 1252 (m), 1203 (w), 1179 (w), 1166 (w), 1125 (w), 970 (w), 811 (s), 749 (m), 734 (w), 650 (w). - UV (CHCl₃): λ _max (lg ε) = 435 nm (3.9989), 460 (4.5248), 490 (4.9531), 528 (5.1315). - Fluorescence (CHCl₃): λ _max = 535 nm, 575. - 1 H-NMR (CDCl₃): δ = 1.30 [C (CH₃) ₃], 1.63, 4.23, 7.12, 752, 7 , 61, 8.66. - MS (70 eV): m / z (%) = 1211 (0.3) [M⁺ + 1], 1210 (0.1) [M⁺], 1153, 34 (100) [M⁺ - C ( CH₃) ₃], 578.24 (13.8), 577.28 (34.2), 521.17 (7.3).

C₈₀H₆₆N₄O₈ (1211.4)
Calc .:
C 79.32; H 5.49; N 4.62
Found:
C 78.93; H 5.63; N 4.71

N- (2,5-di-tert-butylphenylnaphthalene-1,8-dicarboximide

2.0 g (6.2 mmol) are boiled with 4.0 g (19.5 mmol) of 2,5-di-tert-butylaniline in 300 ml of glacial acetic acid for 6 hours under reflux naphthalene-1,8-dicarboxylic anhydride ^26). After the solution has cooled, the precipitated naphthalimide is filtered off with suction and the filtrate is distilled. Given water. The product which crystallizes out is sucked off through a porosity 4 of a glass filter. The substance is dried, then chromatographed on a silica gel column (100 × 4 cm) with chloroform, recrystallized from n-heptane and dried at 0.001 Torr and 80 ° C. for 4 h. - Education 0.5 g (13%). - mp 255 ° C. - R _F (silica gel / CHCl₃) = 0.88. - IR (KBr): = 3065 cm ^-1 (w), 2963 (s), 2869 (w), 1709 (s), 1670 (s), 1627 (w), 1587 (s), 1510 (w), 1434 (w), 1398 (m), 1393 (m), 1356 (s), 1237 (s), 1202 (w), 1192 (m), 1152 (w), 1130 (w), 1075 (w), 1072 (w), 1027 (w), 970 (w), 904 (m), 873 (w), 850 (w), 835 (w), 820 (w), 780 (s), 728 (w), 670 (w), 630 (w), 528 (w), 510 (w). - UV (CHCl₃): λ _max (lg ε) = 323 nm (4.0483), 334 (4.1585), 350 (4.0941). - 1 H-NMR (CDCl₃): δ = 1.28 [s, 9 H, C (CH₃) ₃], 1.30 [s, 9 H, C (CH₃) ₃], 6.93 (d, 1 H ), 7.35 (q, 1H), 7.53 (d, 1H), 7.65 (t, 2H), 8.23 (d, 2H), 8.60 (d, 2H) ). - 13 C-NMR (CDCl₃): δ = 165.1 (s, C = O), 150.0 (s, C-5 '), 143.8 (s, C-2'), 134.0 (i.e. , C-2), 132.9 (s, C-1 ′), 131.9 (s, C-1), 131.6 (d, C-4), 128.7 (d, C-3 ′ ), 127.8 (d, C-4 ′), 127.0 (d, C-3 ′), 126.1 (d, C-6 ′), 123.2 (s, C-4a), 35, 5 (s, C (CH₃) ₃], 34.2 [s, C (CH₃) ₃], 31.7 [q, C (CH₃) ₃], 31.2 [q, C (CH₃) ₃]. - MS (70 eV): m / z (%) = 385 (2) [M⁺], 370 (8) [M⁺ - CH₃], 328 (100) [M⁺ - C (CH₃) ₃], 313 (7).

C₂₆H₂₇NO₂ (385.5)
Calc .:
C 81.01; H 7.06; N 3.63
Found:
C 81.22; H 7.33; N 3.54

¹) W. Herbst, K. Hunger, Industrial Organic Pigments, 1st edition, Verlag Chemie, Weinheim 1987.
²) Hoechst AG (Erf. G. Geissler and H. Remy) DOS 11 130 099 (October 24, 1959), [Chem. Abstr. 57 (1962) P11 346 f].
3) H. Langhals, DOS 30 16 764 (April 30, 1980) [Chem. Abstr. 96 (1982) 70 417x].
Rad) A. Rademacher, S. Märkle, H. Langhals, Chem. Ber. 115 (1982) 2927.
Lang) H. Langhals, Chem. Ber. 118 (1985) 4641.
Dem) S. Demmig, H. Langhals, Chem. Ber. 121 (1988) 225.
Lang) H. Langhals, DOS 37 03 495 (February 5, 1987) [Chem. Abstr. 110 (1989) 59 524 s].
⁸) H.-G. Löhmannsröben, H. Langhals, Appl. Phys. B48 (1989) 449.
⁹) EM Ebeid, SA El-Daly, H. Langhals, J. Phys. Chem. 92 (1988) 4565.
¹⁰) M. Sadrai, GR Bird, Opt. Commun. 51 (1984) 62.
¹¹) H. Langhals, Nachr. Chem. Tech. Lab. 28 (1980) 716.
¹²) H. Langhals, Z. Analyt. Chem. 320 (1985) 361.
13) H. Langhals, Chem. Ind. (Düsseldorf) 37 (1985) 470.
¹⁴) H. Langhals, H. Schott, RA Schwendener, DOS 39 35 257.9 (October 23, 1989).
¹⁵) Hoechst AG (Erf. E. Spitschka, H. Tröster) DOS 34 36 206 (10. 10. 1984) [Chem. Abstr. 105 (1986) P192 870q].
¹⁶) Hoechst AG (Erf. E. Spitschka, H. Tröster) DOS 34 36 209 (October 3, 1984) [Chem. Abstr. 106 (1986) P6430u].
¹⁷) H. Tröster, Dyes and Pigm. 4 (1983) 171.
¹⁸) Hoechst AG (Erf. E. Spitschka, H. Tröster) DOS 30 08 420 (5. 3. 1980) [Chem. Abstr. 96 (1982) P8149h].
¹⁹) Y. Nagao, T. Misono, Dyes and Pigm. 5 (1984) 171.
²⁰) Y. Nagao, T. Misono, Bull. Chem. Soc. Jpn. 54 (1984) 1191.
²¹) Y. Nagao, T. Misono, Bull. Chem. Soc. Jpn. 52 (1979) 1191.
²²) Y. Nagao, T. Misono, Bull. Chem. Soc. Jpn. 54 (1984) 1269.
23) H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta, 44A (1988) 1189.
²⁴) Heinz Langhals, Stefan Demmig, DOS 40 07 618.0 (March 10, 1990).
²⁵) Hoechst AG (Erf. E. Spietschka, H. Tröster) DOS 33 09 060 (March 14, 1983) [Chem. Abstr. 102 (1984) 63 604v].
²⁶) RW Middleton, JR Parrick, J. Heterocyclic. Chem. 23 (1986) 849.

The perylene dyes, perylene-3,4: 9,10-tetracarboxylic acid bisimide, (1) are characterized by their unusually high light fastness and chemical resistance and are used industrially as pigment dyes¹). However, the poor solubility of the dyes desired for pigments stands in the way of their use in homogeneous solution, so that their strong fluorescence in solution was also recognized only late. The disturbing poor solubility in organic solvents can be introduced by introducing aryl radicals substituted with tert-butyl groups ³) (e.g. 1, R₁ = R₂ = 2,5-di-tert-butylphenyl) ^{4, 5} ) or long-chain secondary radicals ^{6 , 7} ) are eliminated. The dyes then have a surprisingly high light fastness and can be used as highly lightfast laser dyes ^{8, 9, 10} ), in fluorescent solar collectors¹¹), as tracers in highly sensitive analytical detection methods ^{12, 13} ) or fluorescence immunoassays¹⁴).

Claims (67)

. Perylene dyes of the general formula 1, each with two different radical residues R₁ and R₂, where R₁ and R₂ are hydrogen or hydrogen and one or two isocyclic aromatic radicals, then preferably mono- to tetracyclic, in particular mono- or bicyclic radicals, such as phenyl, Diphenyl or naphthyl are available. R₁ or R₂ mean a heterocyclic aromatic radical, then preferably a mono- to tricyclic radical. These radicals can be purely heterocyclic or contain a heterocyclic ring and one or more fused benzene rings. Examples of heterocyclic aromatic residues 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 usual non-water-soluble substituents, such as

• a) Halogen atoms, for example chlorine, bromine, iodine or fluorine.
• b) Branched or unbranched alkyl groups with preferably 1 to 18, 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, -OCOR₃, -OR₄, -OCOOR₃, -CON (R₄) (R₅) or -OCONHR₃, wherein R₃ is alkyl, aryl such as naphthyl, or unsubstituted or benzyl or a heterocyclic radical substituted by halogen, alkyl, or -O-alkyl, R₄ and R₅ hydrogen, unsubstituted or cyano or hydroxy-substituted alkyl, C₃- to C₂₄-cycloalkyl, preferably C₅-, C₆-, C₁₂-, C₁₅- , C₁₆-, C₂₀- and C₂₄-cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl, or wherein R₄ and R₅ together with one of the other radicals R₂ to R₄ a 5-6-membered Form 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 further heterocyclic aromatic radicals, such as, for B. the 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinolyl 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 18, 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9-heptadecyl , 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl, 3 -Nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl.

• c) the group -OR₆, where R₆ is hydrogen, alkyl, aryl, for example naphthyl or especially unsubstituted phenyl, C₃ to C₂₄-cycloalkyl, preferably C₅-, C₆-, C₁₂-, C₁₅-, C₁₆-, C₂ C-, and C₂₄- Cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. In the definitions of R₆ occurring alkyl z. B. have one of the preferred number of carbon atoms given under b). Examples of R₆ 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9 -Heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl , 3-nonyl, 3-undecyl, 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.
• e) The cyano group.
• f) The group of the formula -N (R₄) (R₅), wherein R₄ and R₅ have the meaning given under b). Examples are: amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N, N-bis (2-hydroxyethyl) amino, cyclopentylamino, cyclohexylamino, Cyclododecylamino, Cyclopentadecylamino, Cyclohecadecylamino, Cycloeicosanylamino, Cyclotetracosanylamino , Phenylamino, N-methylphenylamino, benzylamino, dibenzylamino, piperidyl or morpholyl.
• g) The group of the formula -COR₃, wherein R₃ has the meaning given under a). Examples of R₃ 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9 -Heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl , 3-nonyl, 3-undecyl, 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, pyranylmethyl, benzyl or furfuryl.
• h) The group of the formula -N (R₇) COR₃, wherein R₃ has the meaning given under b), R₇ is hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl , n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8 -Pentadecal, 9-heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl , 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, 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. In the definitions of R₇ occurring alkyl z. 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.
• i) The group of the formula -N (R₆) COOR₃, wherein R₃ and R₆ have the meaning given under b) or c). Examples include the groups -NHCOOCH₃, -NHCOOC₂H₅, or -NHCOOC₆H₅.
• j) The group of the formula -N (R₆) CON (R₄) (R₅), wherein R₄, R₅ and R₆ have the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.
• k) The group of the formula NHSO₂R₃, wherein R₃ has the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.
• l) The groups of the formula -SO₂R₃ or -SOR₃, wherein R₃ has the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.
• m) The group of the formula -SO₂OR₃, wherein R₃ has the meaning given under b). Examples of R₃ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.
• n) The group of the formula -CON (R₄) (R₅), wherein R₄ and R₅ 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-piperidylcarbamoyl.
• o) The group of the formula -SO₂N (R₄) (R₅), wherein R₄ and R₅ have the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.
• p) The group of the formula -N = N-R₈, where R₈ is the residue of a coupling component or a phenyl radical which is optionally substituted by halogen, alkyl or O-alkyl. In the definitions of R₈ occurring alkyl z. B. have one of the number b) given as preferred number of carbon atoms. Examples of R₈ are: the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.
• q) The group of the formula -OCOR₃, wherein R₃ has the meaning given under b). Examples of R₃ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• r) The group of the formula -OCONHR₃, wherein R₃ has the meaning given under a). Examples of R₃ are: methyl, ethyl, phenyl, o-, m-, or p-chlorophenyl.

R₁ and R₂ can be hydrogen and one or two of the following radicals:

• a) Halogen atoms, for example chlorine, bromine, iodine or fluorine.
• b) Branched or unbranched alkyl groups with preferably 1 to 18, 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, -OCOR₃, -OR₄, -OCOOR₃, -CON (R₄) (R₅) or -OCONHR₃, wherein R₃ is alkyl, aryl such as naphthyl, or unsubstituted or benzyl or a heterocyclic radical substituted by halogen, alkyl, or -O-alkyl, R₄ and R₅ hydrogen, unsubstituted or cyano or hydroxy-substituted alkyl, C₃- to C₂₄-cycloalkyl, preferably C₅-, C₆-, C₁₂-, C₁₅- , C₁₆-, C₂₀- and C₂₄-cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl, or wherein R₄ and R₅ together with one of the other radicals R₂ to R₄ a 5-6-membered Form 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 further heterocyclic aromatic radicals, such as, for B. the 2-thienyl, 2-benzoxazolyl, 2-benzothiazolyl, 2-benzimidazolyl, 6-benzimidazolonyl, 2-, 3- or 4-pyridinyl, 2-, 4-, or 6-quinolyl or 1-, 3-, 4-, 6-, or 8-isoquinolyl residues.

In turn contain the substituents mentioned under b) Alkyl, this alkyl can be branched or unbranched and preferably 1 to 18, in particular 1 to 12, especially 1 to 8 and particularly preferably contain 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9-heptadecyl , 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl, 3 -Nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl or benzyl.

• c) The group -OR₆, where R₆ is hydrogen, alkyl, aryl, for example naphthyl or in particular unsubstituted phenyl, C₃ to C₂₄-cycloalkyl, preferably C₅-, C₆-, C₁₂-, C₁₅-, C₁₆-, C₂₀-, and C₂₄- Cycloalkyl, aryl or heteroaryl, in particular unsubstituted or substituted by halogen, alkyl or -O-alkyl phenyl. In the definitions of R₆ occurring alkyl z. B. have one of the number b) given as preferred number of carbon atoms. Examples of R₆ 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9 -Heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl , 3-nonyl, 3-undecyl, 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.
• e) The cyano group.
• f) The group of the formula -N (R₄) (R₅), wherein R₄ and R₅ have the meaning given under b). Examples are: amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, 2-hydroxyethylamino, 2-hydroxypropylamino, N, N-bis (2-hydroxyethyl) amino, cyclopentylamino, cyclohexylamino, Cyclododecylamino, Cyclopentadecylamino, Cyclohecadecylamino, Cycloeicosanylamino, Cyclotetracosanylamino , Phenylamino, N-methylphenylamino, benzylamino, dibenzylamino, piperidyl or morpholyl.
• g) The group of the formula -COR₃, wherein R₃ has the meaning given under a). Examples of R₃ 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, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8-pentadecal, 9 -Heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl, 3-heptyl , 3-nonyl, 3-undecyl, 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, pyranylmethyl, benzyl or furfuryl.
• h) The group of the formula -N (R₇) COR₃, wherein R₃ has the meaning given under b), R₇ is hydrogen, alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl , n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, 3-pentyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 8 -Pentadecal, 9-heptadecyl, 10-nonadecyl, 11-heneicosyl, 12-tricosyl, 13-pentacosyl, 14-heptacosyl, 15-nonacosyl, 16-hentriacontyl, 17-tritriacontyl, 18-pentatriacontyl, 19-heptatriacontyl, 3-hexyl , 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, 2-hydroxyethyl, cyanomethyl, methoxycarbonylmethyl, acetoxymethyl, benzyl, 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. In the definitions of R₇ occurring alkyl z. 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.
• i) The group of the formula -N (R₆) COOR₃, wherein R₃ and R₆ have the meaning given under b) or c). Examples include the groups -NHCOOCH₃, -NHCOOC₂H₅, or -NHCOOC₆H₅.
• j) The group of the formula -N (R₆) CON (R₄) (R₅), wherein R₄, R₅ and R₆ have the meaning given under b) or c). Examples include: ureido, N-methylureido, N-phenylureido, or N, N'-2 ', 4'-dimethylphenylureido.
• k) The group of the formula -NHSO₂R₃, wherein R₃ has the meaning given under b). Examples include: methylsulfonylamino, phenylsulfonylamino, p-tolylsulfonylamino or 2-naphthylsulfonylamino.
• l) The groups of the formula -SO₂R₃ or -SOR₃, wherein R₃ has the meaning given under b). Examples include: methylsulfonyl, ethylsulfonyl, phenylsulfonyl, 2-naphthylsulfonyl, phenylsulfoxidyl.
• m) The group of the formula -SO₂OR₃, wherein R₃ has the meaning given under b). Examples of R₃ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, 1- or 2-naphthyl.
• n) The group of the formula -CON (R₄) (R₅), wherein R₄ and R₅ have the meaning given under b). Examples include: carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-phenylcarbamoyl, N-1-naphthylcarbamoyl or N-piperdylcarbamoyl.
• o) The group of the formula -SO₂N (R₄) (R₅), wherein R₄ and R₅ have the meaning given under b). Examples include: sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl, N-methyl-N-phenylsulfamoyl or N-morpholylsulfamoyl.
• p) The group of the formula -N = N-R₈, where R₈ is the residue of a coupling component or a phenyl radical which is optionally substituted by halogen, alkyl or -O-alkyl. In the definitions of R₈ occurring alkyl z. B. have one of the number b) given as preferred number of carbon atoms. The following may be mentioned as examples of R₈: the acetoacetarylide, pyrazolyl, pyridonyl, o-, p-hydroxyphenyl, o-hydroxynaphthyl, p-aminophenyl or pN, N-dimethylaminophenyl radicals.
• q) The group of the formula -OCOR₃, wherein R₃ has the meaning given under b). Examples of R₃ are: methyl, ethyl, phenyl, o-, m- or p-chlorophenyl.
• r) The group of the formula -OCONHR₃, wherein R₃ has the meaning given under a). Examples of R₃ are: methyl, ethyl, phenyl, o-, m-, or p-chlorophenyl.

2. Perylene tetracarboxylic acid monoimide monoanhydrides of the general Formula 2, wherein the radical R has the meaning of R₁ of claim 1 has. 3. Perylene lactam dyes, 3-aminoperylene-4: 9,10-perylene-3,4-lactam-8,10-imide of the general formula 6, wherein the two radicals R₁ and R₂ may be the same or different and R₁ and R₂ have the meaning given in claim 1. 4. Perylene blue dyes of unknown structure, which carry two radicals R₁ and R₂, which mentioned in claim 1 Have meaning - R₁ and R₂ may be the same or different. Perylene blue are polar, deep blue colored substances that the action of the mixture KOH / dimethyl sulfoxide with the addition of Alcohols, preferably methanol, are formed, taking care must be made sure that no acidification occurs during processing - the Otherwise the reaction conditions are the same as in the illustration the perylene lactam dyes (see claim 3). 5. The method characterized in that perylene blue is produced from the perylene lactam dyes according to 3. Preferred reagents are KOH / DMSO with the addition of an alcohol, preferably methanol. 6. The method characterized in that the under 1 specified dyes from 2 by condensation with primary Amines are shown. 7. The method characterized in that the Condensation according to claim 6 water-releasing agents in certain Media are used. Preferred dehydrating Agents are zinc acetate, lead acetate or dicyclohexylcarbodiimide.  Preferred media are quinoline, molten imidazole, benzene, Toluene, pyridine, 2-picoline, 3-picoline or 4-picoline. 8. The method characterized in that the dyes according to claim 2 by alkaline saponification of the symmetrical Perylenetetracarboxylic acid bisimides (1, R₁ = R₂) are produced will. 9. The method characterized in that as the base is used in the saponification reaction after 8 KOH or NaOH, with KOH being preferred. 10. The method characterized in that the saponification reaction after 8 in tert-butyl alcohol or tert-amyl alcohol is carried out. Tert-butyl alcohol is preferred. 11. The method characterized in that the saponification reaction after 8 in the alcohol / dimethyl sulfoxide mixture is carried out. Preferred alcohols are methanol or ethanol, most preferred is methanol. 12. The method characterized in that the saponification reaction after 8 with a certain concentration NaOH or KOH is carried out. 13. The method characterized in that the saponification reaction after 9 with KOH in a concentration of 10 g / 100 ml carried out. A thin layer chromatography is then preferred Control the response. 14. The method characterized in that the saponification reaction after 9 with KOH in a concentration of 1 g / 100 ml is carried out. Preferred indicator for the endpoint the reaction is discolored after the reaction mixture Blue-black. 15. The method characterized in that the Saponification reaction after 8 by-products by dissolving in acetic acid be removed. 16. The method characterized in that the saponification product after 8 with concentrated potassium carbonate solution  is treated to remove by-products. Preferred concentrations of potassium carbonate, 0.5 to 15% is most preferred becomes 10%. 17. The method characterized in that the saponification reaction after 8 performed at a certain temperature becomes. Preferred are 20 to 150 ° C, more preferred 30 to 100 ° C, most preferred is refluxing the mixture. 18. The method characterized in that the Purification of the dyes after 2 so that the raw products into the triethylammonium salts under the action of aqueous triethylamine solution transferred, filtered and with acid, preferred dil. hydrochloric acid, into which anhydrides are converted back. 19. The method characterized in that the Perylene lactam dyes according to claim 3 made from perylene-3,4: 9,10-tetracarboxylic acid-3,4: 9,10-bisimides be synthesized. 20. The method characterized in that the Perylene lactam dyes according to 3 from perylene tetracarboxylic acid bisimides using the mixture KOH / methanol / dimethyl sulfoxide synthesized. 21. The method characterized in that the Representation of the perylene lactam dyes according to 3 according to claim 5 Perylene blue compound reacted with acids, preferred Mineral acids, most preferred is hydrochloric acid. 22. The method characterized in that the Representation of perylene lactam dyes after 3 perylene dyes 1 treated with alkalis and then directly without further cleaning converted into lactam dyes by acidification. 23. The method characterized in that the asymmetrical perylene dyes according to 1 generally as a tracer, e.g. B. in biochemistry, medicine, technology and science used.   24. The method characterized in that the asymmetrical or symmetrical (R₁ and R₂ the same or different) Perylene lactam dyes according to 3 generally as tracers, e.g. B. in biochemistry, medicine, technology and science used. 25. The method characterized in that the asymmetrical perylene blue dyes according to 5 generally as tracers, e.g. B. in biochemistry, medicine, technology and science used. 26. The method characterized in that one for Tracer applications after 23, 24 or 25 the dyes covalently attaches to a substrate. 27. The method characterized in that one for Tracer applications after 23, 24 or 25 the dyes 2 for linking with substrates with primary amino groups of the substrates connected. 28. The method characterized in that one for Tracer applications after 23, 24 or 25 the dyes via secondary valences such as hydrogen bonds or hydrophobic Interacts with a substrate. 29. The method characterized in that for tracer applications after 23, 24 or 25 the dyes from one Substrate included - examples are cyclodextrins. 30. The method characterized in that for tracer applications after 23, 24 or 25 the dyes are absorbed recognized or proven quantitatively. 31. The method characterized in that for tracer applications after 23, 24 or 25 the dyes over their Fluorescence recognized or detected quantitatively. 32. Method characterized in that for tracer applications after 23, 24 or 25 the dyes for the detection their fluorescence are excited with laser beams.   33. The method characterized in that for tracer applications after 23, 24 or 25 the dyes in synthetic Polymers are stored. 34. The method characterized in that for tracer applications after 23, 24 or 25 the dyes on biopolymers ties. Examples of biopolymers are enzymes or antibodies, here especially preferred monoclonal antibodies. 35. The method characterized in that for tracer applications after 23, 24 or 25 the dyes on liposomes to be knotted. 36. Use of the perylene dyes according to 1 as a colorant and Pigments. Examples are uses in paints, paper colors, Printing inks. 37. Use of the perylene dyes according to 2 as colorants and Pigments. Examples are uses in paints, paper colors, Printing inks. 38. Use of the perylene dyes according to 3 as colorants and Pigments. Examples are uses in paints, paper colors, Printing inks. 39. Use of the perylene dyes according to 5 as colorants and Pigments. Examples are uses in paints, paper colors, Printing inks. 40. Use of the perylene dyes according to 1, 3, 2 or 5 as Fluorescent dyes in highly sensitive detection methods (see C. Aubert, J. Fünfschilling, I. Zschokke-Gränacher and H. Langhals, Z. Analyt. Chem. 320 (1985) 361). 41. Use of the perylene dyes according to 1, 3, 2 or 5 as Fluorescent dyes in scintillators. 42. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in optical light collection systems.   43. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in fluorescent solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 28 (1980) 716). 44. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in fluorescence activated Displays (see W. Greubel and G. Baur, Elektronik 26 (1977) 6). 45. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in cold light sources light-induced polymerization for the production of plastics. 46. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes for material testing, e.g. B. in the manufacture of semiconductor circuits. 47. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes for examining microstructures of integrated semiconductor components. 48. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in photoconductors. 49. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in dry copy systems, Laser printers and other recording systems (Xerox process). 50. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in photographic processes. 51. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in display, lighting or image converter systems in which the excitation by electrons, Ion or UV radiation takes place, e.g. B. in fluorescent displays, Braun tubes or in fluorescent tubes. 52. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes as part of an integrated  Semiconductor circuit, the dyes as such or in combination with other semiconductors z. B. in the form of an epitaxy. 53. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in chemiluminescent systems, e.g. B. in chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods. 54. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes as signal colors, preferred for the visual highlighting of lettering and drawings or other graphic products for marking signs and other objects with a special optical Color impression should be achieved. 55. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes for security markings, preferably checks, check cards, banknotes, coupons, identity papers and the like, in which a special, unmistakable Color impression should be achieved. 56. Use of the perylene dyes according to 1, 3, 2 or 5 as an additive to other colors where a certain color shade is achieved especially bright colors are preferred. 57. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes for marking objects for machine recognition of these objects via the Fluorescence, preferably the automatic detection of objects for sorting, e.g. B. for recycling plastics. 58. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes used for machine readable markings are preferred, alphanumeric imprints or barcodes. 59. Use of the perylene dyes according to 1, 3, 2 or 5 as Fluorescent dyes for frequency conversion of light, e.g. B. um to make longer-wave, visible light from short-wave light.   60. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in passive display elements for various display, information and marking purposes, e.g. B. passive display elements, signs and traffic signs, such as traffic lights. 61. Use of the perylene dyes according to 1, 3, 2 or 5 as Starting material for superconducting organic materials. 62. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes for solid fluorescent labels. 63. Use of the perylene dyes according to 1, 3, 2 or 5 as Dyes or fluorescent dyes in dye lasers, preferred as fluorescent dyes for generating laser beams.