DE102016014502A1 - Amination of aromatics under unusual mild conditions with negative activation energy and without the addition of other reagents - Google Patents

Abstract

Aromatic amines were synthesized by the simple treatment of carboxylic acid imides with concentrated azetidine. The reactions take place with strongly negative activation enthalpy and can be accelerated by cooling. Bathochromium-absorbing and partially strongly fluorescent dyes in the perylene series could be prepared in this way or via the reaction with pyrrolidine.

Description

introduction

The introduction of amino groups in aromatics is of fundamental interest to the chemist and concerns numerous fields of activity. However, this often requires harsh reaction conditions or multi-step syntheses, such as nitration ((a) Galabov, D. Nalbantova, P.v. R. Schleyer, HF Schaefer, Acc. Chem. Res. 2016, 49, 1191-1199. (B) MR Crampton, Organic Reaction Mechanisms 2011, 257-283 , (C) G. Yan, M. Yang, Organic Biomol. Chem. 2013, 11, 2554-2566. ) and reduction or halogenation and cross-coupling involving transition metals ((a) C. Kent, OM Ghoneim, SW Goldstein, Abstr., 39th Northeast Regional Meeting of the American Chemical Society, New Haven, CT, United States, October 23-26 (2013), NERM-384; Chem. Abstr. 2013, AN1648236. (B) Y. Li, X. Zhu, F. Meng, Y. Wan, Tetrahedron 2011, 67, 5450-5454 , (C) X. Deng, H. McAllister, NS Mani, J. Org. Chem. 2009, 74, 5742-5745. (C) BC Hamann, JF Hartwig, J. Am. Chem. Soc. 1998, 120, 7369-7370. ). There is increasing interest in transition metal-mediated C [BOND] H activation ((a) H. Kim, S. Chang, ACS Catalysis 2016 . 6 . 2341 - 2351 ; Chem. Abstr. 2016, 164, 383438. (b) S. Chiba, K. Narasaka, Simple molecules, highly efficient amination in A. Ricci (ed.), Amino Group Chemistry 2008, 1-54; Chem. Abstr. 2008, 150, 190748. ).

State of the art

We found in previous work ( H. Langhals, S. Christian, A. Hofer, J. Org. Chem. 2013, 78, 9883-9891 .) that the known as particularly chemically resistant aromatic carboxylic acid imides ( H. Langhals, Chromophores for picoscale optical computers in K. Sattler (ed.), Fundamentals of picoscience, p. 705-727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca / US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095. ) are nuclear-substituted by the action of concentrated pyrrolidine under surprisingly mild conditions. However, this unusual reaction is slow, and only small space-time yields are achieved, hindering large-scale industrial synthesis. The usual method in chemistry to increase reaction rates by increasing the temperature, brings here no success because negative activation enthalpies were found; an increase in temperature unusually leads to a slowing of the reaction. Cooling acceleration is also limited by the temperature dependence of the solubility of the carboxylic imides. An improvement of the synthesis, especially for the technical scale seems therefore hopeless.

task

The object of the invention was to improve a nuclear substitution of aromatic carboxylic acid imides by amine functions so that they can be carried out efficiently with high space-time yield.

description

We have found a new, unusually rapid response to the action of azetidine on aromatic carboxylic acid imides; becomes the perylene derivative 1 ( S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230 .) contacted with azetidine, spontaneous darkening occurs by the formation of the green mono-core substitution product 2 followed by a rapid second substitution to 3 under blue staining; please refer 1 , Perhaps the enormous and unexpected acceleration of the reaction is due to the weaker steric interactions of the four-membered ring compared to the earlier described five-membered reaction. Attractively, the reaction occurs quickly at room temperature without any additives. On the other hand, solvents such as chloroform do not interfere and may be added.

The UV / Vis absorption spectra of 1, 2 and 3 are in 2 specified. Starting from an absorption maximum at 525 nm for 1, a strong bathochromic shift to a less strongly structured absorption band at 618 nm for 2 and a further bathochromic shift up to 663 nm for 3. The well-spectrally separated spectra of 1 and 2 form the basis for a more extensive UV / Vis spectroscopic study of the reaction, whose progression UV / Vis spectroscopy in 3 and leads to an isosbestic point at 540.4 nm. We investigated the decrease in absorbance at 527 nm and found a precise first-order reaction kinetics; please refer 2 and 4 and Table 1.

Table 1. Reaction rate constants k in s ^-1 for the reaction of 1 with azetidine. Columns from left to right: reaction temperature in ° C, added volume of azetidine in chloroform at one Total volume of 300 μL, molar concentration c _a of azetidine, pseudo first order rate constant k of the decrease of 1 in s ^-1 , determined at 527 nm (12 measurements each with 5 min interval, standard deviation σ _k of k, correlation coefficient r at 12 readings): T ul c _a in mol·L ^-1 10 ⁴ · k 10 ⁴ · σ _k r ° C azetidin azetidin s ^-1 15 130 6:45 5.64 12:02 0.9999 20 130 6:45 6.29 12:04 0.9998 25 130 6:45 5.98 12:06 0.9995 30 130 6:45 5.71 12:13 0.9972 35 130 6:45 3.82 12:13 0.9941 40 130 6:45 3:04 12:11 0.9933 25 150 7:44 17.64 12:22 0.9992 25 140 6.95 3.11 12:05 0.9999 25 120 5.95 3:34 12:05 0.9988 25 110 5:46 2.15 12:01 0.9999

The pseudo-first-order rate constant k is extremely dependent on the concentration of azetidine c _a ; the application of ln k to ln c _a gives a formal reaction order of more than 7, which goes far beyond the otherwise familiar first or second order; see inset in 4 , This may also explain that the surprising substitution reaction of aromatics with amines has not been found so far, as it takes place only in very concentrated amine solutions with appreciable speed.

The temperature dependence of the rate constant k is also surprising, since the reaction slows down with increasing temperature, instead of being accelerated as usual in chemistry. This behavior was analyzed by Arrhenius (ln k vs. 1 / T applied) and Eyring's equation (ln k / T vs. 1 / T plotted). Because the Eyring equation results in a slightly better linear correlation, it is preferred in the further discussion and gives a strong negative activation enthalpy of -31.4 kJ · mol ^-1 and a strongly negative activation entropy; please refer 5 , Such a reaction is completely surprising and very unusual. We have searched for a further limitation of the facts for possible intermediates and quantum chemical (DFT, B3LYP) an energetic minimum for the structure of 6 found. This is energetically almost equivalent to the starting materials, but represents a structurally very strict energetic minimum, because minor geometric changes already lead to a significant increase in energy. This highly ordered potential intermediate can be seen as an indication of a cause for the unusual activation data and the unusual reaction order of the reaction with azetidine. Accordingly, one can post a reaction mechanism 7 accept.

Because of the rapid reaction of 1 with azetidine, we have explored the extent to which other carboxylic acid imides can also be substituted. First, we have the perylene bisimide N, N'-bis (2,5-di-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic bisimide ( 4 ) ( A. Rademacher, S. Märkle, H. Langhals, Chem. Ber. 1982, 115, 2927-2934. ), which, unlike 1, bears aromatic substituents on the nitrogen atoms; the tert-butyl groups in 4 serve to increase the solubility in lipophilic media.

The reaction of 4 with azetidine to structurally to 2 and 3 completely analogous mono- and di-nuclear-substituted derivatives is much faster in chloroform solution than at 1. This can be attributed to the electron train of the phenyl radicals, which facilitate nucleophilic attack on the nucleus at 4 , However, the use of pure azetidine does not lead to the expected further acceleration, but surprisingly to a significant slowdown and therefore can not be recommended; this can be attributed to the low solubility of 4 there. For a preparative conversion of 4, therefore, solubilizers, such as chloroform, should be used. Because of the rapid and smooth reaction of azetidine with 1 and 4, we investigated whether the new reaction could be applied to other carboxylic acid imides and have the benzoperylene derivative 5 (H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380.), Which reacts smoothly and then doubly, but at a much slower rate than 1, and in the first reaction a nuclear substitution of 6, then but a ring opening of the five-membered ring to the two regioisomers 7a and 7b he follows; please refer 8th and 9 , Again, the reaction rate constant is highly dependent on the concentration of azetidine and is much faster in pure azetidine (k = 0.00164 ± 0.0000004 s ^-1 , r = 0.999999 for 5 measurements) than in dilute solution; Here, too, one finds a reaction order in azetidine of more than 7, which is also an indication of a complex reaction process. A completely analogous reaction is observed in the reaction of 5 with pyrrolidine instead of azetidine. In the imidazole derivative 8th ((A) H. Langhals, A. Hofer, J. Org. Chem. 2012, 77, 9585-9592 , (B) H. Langhals, A. Hofer, Ger. Open. (2013) . DE 102012005897 A1 20130919 ( 14.3 .2012); Chem. Abstr. 2013, 159, 502376 .), whose chemical structure relative to the imidazole unit on the in 10 X-ray crystal structure analysis of a degradation product ( 1 , KOH in tert-butyl alcohol, 2nd HCl / H ₂ O) could be clearly verified, no Kemsubstitution was observed, but 8 reacts directly under ring opening very uniformly with pyrrolidine to the regioisomeren reaction products 9a and 9b ; please refer 11 and the Isosbestic points shown there.

Furthermore, the synthesis method can also be extended to simple carboxylic acid imides, as exemplified by the perylenedicarboximide 10 (L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244.). However, this reacts very slowly in chloroform / azetidine mixtures. If, however, pure azetidine is used as the medium which has already led to considerable acceleration at 1 and 5, preparatively still acceptable reaction rates are achieved. Considering the reaction acceleration at 1 by increasing the concentration of azetidine and the measured rate constant of 10 in pure azetidine, one can estimate a factor of about 1300, with 10 reacts slower than 1.

The azetidine derivatives of perylene imides fluoresce significantly; fluorescence quantum yields of 20% are observed throughout. The azetidine derivatives are also clearly solvatochromic. at 2 a bathochromic shift of the absorption and likewise the fluorescence is observed during the transition from the less polar n-hexane to the more polar chlorine form; please refer 13 , The ring-opened products also fluoresce very strongly. Thus, a pronounced red fluorescence in the products 7a and 7b observed.

Azetidines can generally be ring-opened with nucleophiles, in particular using catalysts. This results in a reaction of the azetidine perylene imides that the amine nitrogen donor group remains at the perylene core and thereby unchanged causes a strong bathochromic shift in absorption and fluorescence, while the ring-opening nucleophile via an aliphatic C-3 spacer with the Amine function is connected. If the nucleophile is part of a more complex structure, it can be covalently linked to and labeled with the chromophore; this is of particular interest to C nucleophiles. Here, both the absorption and the fluorescence of the respective chromophore can be used for the purposes of labeling.

conclusion

Aromatic carboxylic acid imides are nucleus-substituted by the action of concentrated azetidine, unusually with negative activation enthalpy (the reaction is slower at higher temperature than at low temperature) and with very high azetidine reaction order. The reaction is compatible with heterocyclic structures such as imidazoles. Perylenimides consistently undergo a bathochromic shift in absorbance and fluorescence through substitution; a second substitution causes another smaller one. The compounds are clearly positive solvatochrom. Applications are diverse for the new dye class. Thus, the long-wavelength absorption is interesting for staining purposes, and the very long-wavelength, with relatively large Stokes shift fluorescence, for example, for marking purposes and optical energy converters.

Experimental part

4- (azetidin-1-yl) -2,9-di (1-hexylheptyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8 , 10 (2H, 9H) tetrazone ( 2 2,9-di (1-hexylheptyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 (2H, 9H) - tetrazone ( 1 (200mg, 0.265mmol) was stirred in azetidine (2.50g, 43.8mmol) at room temperature (TLC control of reaction progress, silica gel / chloroform), evaporated to dryness after 60min, taken up in chloroform to remove azetidine traces, and evaporated in vacuo, purified by column chromatography (silica gel, chloroform, first, intense green band) evaporated to dryness and dried at 110 ° C for 16 h. Y. 194 mg ( 0239 mmol, 90.4%) dark green solid, mp 90 ° C. R _f (silica gel, chloroform) = 0.62. IR (ATR): ṽ = 2954 (m), 2916 (vs), 2849 (s), 2361 (w), 1690 (s), 1650 (s), 1585 (s), 1569 (m), 1558 (m ), 1506 (w), 1462 (m), 1417 (s), 1365 (m), 1330 (s), 1272 (m), 1238 (s), 1176 (m), 1113 (m), 1037 (m ), 972 (w), 947 (m), 877 (m), 844 (m), 807 (s), 792 (m), 769 (w), 748 (m), 721 (m), 695 (m ), 659 (m) cm ^-1 . ¹ H-NMR (600 MHz, _CDCl3, 27 ° C, TMS): δ = 0.80 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 × CH _3), 0.81 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 x CH ₃ ), 1.15-1.38 (m, 32 H, 16 x CH ₂ ), 1.79-1.89 (m, 4 H, 2 x β-CH ₂ ), 2.19-2.31 (m, 4 H, 2 x β-CH ₂ ), 2.32-2.61 (m, 2 H, 2 x β-CH _azetidine ), 3.81-4.18 (m, 4 H, 4 x α-CH _azetidine ). , 5:12 to 5:26 (m, 2 H, 2 x NCH), 7.96 (d, ³ J (H, H) = 8.0 Hz, 1 H, CH _perylene), 8:13 to 8:22 (m, 1 H, CH _perylene), 8.41-8.56 (m, 3H, 3 x CH _perylene ), 8.57-8.73 (m, 2H, 2 x CH _perylene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 16.0, 22.6, 22.7, 26.9, 29.2, 29.2, 29.7, 31.8, 31.9, 32.4, 54.3, 54.5, 54.6, 54.7, 115.6, 120.8, 123.5, 123.7, 124.9, 127.3, 128.5, 129.2, 151.0 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 428.2 ( 15100 ), 619.0 nm ( 27700 L mol ^-1 cm ^-1 ). Fluorescence (CHCl ₃ , λ _exc = 619.0 nm): λ _max = 723.8 nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 619.0 nm, E _{619.0 nm / 1 cm} = 0.0522, reference: 1 where Φ = 1.00): 0.18. MS (FAB ⁺ ): m / z (%): 810.1 ( 100 ) [M] ⁺ , 628.8 ( 51 ), 446.0 ( 27 ), 418.5 ( 48 ), 416.5 ( 44 ), 373.0 ( 19 ), 346.4 ( 25 ), 154.3 ( 20 ), 55.1 ( 19 ). HRMS (C ₅₃ H ₆₇ N ₃ O _4): Calcd. m / z: 809.5132, Gef. m / z: 809.5126; Δ = 0.0006. C ₅₃ H ₆₇ N ₃ O ₄ ( 810.1 ): Ber. C 78.58, H 8.34, N 5.19; Gef. C 78.92, H 9.00, N 5.03.

4,7-di (azetidin-1-yl) -2,9- (1-hexylheptyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3 , 8,10 (2H, 9H) tetrazone (3): 2,9-di (1-hexylheptyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline 1, 3,8,10 (2H, 9H) tetrazone ( 1 , 200 mg, 0.265 mmol) was stirred in azetidine (2.50 g, 43.8 mmol) at room temperature (TLC monitoring of the progress of the reaction, silica gel / chloroform), evaporated to dryness after 16 h, taken up in chloroform to remove traces of azetidine in Vacuum evaporated, purified by column chromatography (silica gel, chloroform, second, intense blue band) evaporated to dryness, dissolved in a little chloroform, precipitated with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C for 16 h. Y. 77 mg ( 0089 mmol, 33.6%) dark blue Solid, mp 185 ° C. R _f (silica gel, chloroform) = 0.64. IR (ATR): ṽ = 2953 (m), 2922 (m), 2855 (m), 2361 (w), 2338 (w), 1687 (s), 1650 (s), 1601 (m), 1580 (s ), 1561 (m), 1537 (m), 1524 (m), 1510 (m), 1455 (m), 1429 (m), 1382 (m), 1344 (s), 1324 (vs), 1261 (s ), 1251 (m), 1240 (m), 1211 (m), 1184 (m), 1146 (m), 1118 (m), 1105 (m), 1080 (m), 1034 (m), 1002 (m ), 975 (w), 940 (m), 876 (m), 832 (vw), 812 (w), 801 (s), 774 (m), 752 (s), 721 (m), 667 (w ), 657 (m) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.82 (t, ³ J (H, H) = 7.1 Hz, 6 H, 2 x CH ₃ ), 0.83 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 x CH ₃ ), 1.18-1.40 (m, 32 H, 16 x CH ₂ ), 1.80-1.91 (m, 4 H, 2 x β-CH ₂ ), 2.22-2.33 (m, 4 H, 2 x β-CH ₂ ), 2.33-2.43 (m, 4 H, 4 x β-CH _azetidine ), 3.94 (s br., 4 H, 4 x α-CH _azetidine ). , 5.18 (tt, ³ J (H, H) = 9.5 Hz, ³ J (H, H) = 5.6 Hz, 1 H, NCH), 5.25 (tt, ³ J (H, H) = 9.4 Hz, ³ J (H, H) = 5.7 Hz, 1 H, NCH), 7.98 (d, ³ J (H, H) = 8.2 Hz, 2 H, 2 x CH _{1 aryl} ), 7.96 (s br., 1 H, CH _perylene ), 8.00 (s br., 1 H, CH _perylene ), 8.02 (d, ³ J (H, H) = 8.0 Hz, 2 H, 2 x CH _perylene ), 8.67 (d, ³ J (H, H) = 7.9 Hz, 1 H, CH _perylene ), 8.71 (d, ³ J (H, H) = 7.8 Hz, 1 H, CH _perylene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 16.0, 22.6, 26.9, 27.0, 29.2, 29.3, 29.7, 31.8, 32.5, 54.2, 54.3, 54.7, 115.5, 116.4, 117.1, 117.1, 118.1, 118.9, 123.8, 128.2, 128.7, 129.9, 130.6, 130.7, 134.4, 134.5, 152.3, 164.3, 165.3 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 327.4 ( 17400 ), 452.4 ( 6500 ), 543.4 ( 18400 ), 629.6 ( 25800 ), 664.0 nm ( 26100 L mol ^-1 cm ^-1 ). Fluorescence (CHCl3, λ _exc = 543.0 nm): λ _max (I _rel ) = 732.0 ( 1:00 ) nm. fluorescence (CHCl ₃ , λ _exc = 630.0 nm): λ _max (I _rel ) = 733.8 ( 1:00 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 543.0 nm, E _{543.0nm / 1 cm} = 0.2278, reference: 1 where Φ = 1.00): 0.08. Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 630.0 nm, E _{630.0 nm / 1 cm} = 0.3194, reference: 1 with Φ = 1.00): 0.12. MS (FAB ⁺ ): m / z (%): 864.8 ( 88 ) [M] ⁺ , 683.6 ( 60 ), 443.3 ( 100 ), 400.3 ( 52 ), 360.3 ( 19 ), 55.1 ( 41 ). HRMS (C ₅₆ H ₇₂ N ₄ O ₄ ): Ber. m / z: 864.5554, Gef. m / z: 864.5571; Δ = -0.0017. C ₅₆ H ₇₂ N ₄ O ₄ ( 810.1 ): Ber. C 77.74 H 8.39 N 6.48; Gef. C 77.63, H 8.59, N 6.35.

N, N ', N "-tris (1-hexylheptyl) benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid 1,2: 4,5: 10,11-tris (dicarboximide) ( 5 ): N, N'-bis (1-hexylheptyl) benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid 1,2-anhydride-4,5: 10,11-bis (dicarboximide (400 mg, 0.471 mmol) (H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365-380.), 1-Hexylheptylamine (141 mg, 0.707 mmol), imidazole (3.00 g), and Toluene ( 1.0 ml) were stirred at 140 ° C for 5 h, after cooling with 2 _M aqueous HCl ( 20 mL), stirred for 16 h at room temperature and extracted several times with CHCl ₃ . The combined organic phases were washed with 2 _M aqueous HCl, dried over MgSO ₄ , evaporated to dryness, purified by chromatography (silica gel, toluene, first yellow band), evaporated and precipitated from a little CHCl ₃ with methanol. Y. 286 mg ( 58.9 %) orange solid, mp 280-283 ° C. R _f (silica gel, chloroform) = 0.89. ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.79-0.84 (m, 18 H, 6 x CH ₃ ), 1.18-1.44 (m, 48 H, 24 x CH ₂ ), 1.83-1.89 (m, 2H, β-CH _2), 1.89-1.98 (m, 4 H, 3 x β-CH _2), 2:24 to 2:30 (m, 2H, β-CH _2), 2:30 to 2:40 (m, 4 H, 2 x β-CH ₂ ), 4.42-4.49 (m, 1 H, 1 x α-CH ₂ ), 5.25-5.36 (m, 2 H, 2 x α-CH ₂ ), 9.11- 9.21 (m, 2 H, 2 x CH _{benzoperylene} ), 9.39 (d, ³ J (H, H) = 8.3 Hz, 2 H, 2 x CH _{benzoperylene} ), 10.45-10.55 (m, 2 H, 2 x CH _{benzoperylene} ) ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 372.8 ( 0.60 ), 410.2 ( 12:24 ), 436.0 ( 0.63 ), 465.8 ( 1:00 ) nm. fluorescence (CHCl ₃ , λ _exc = 436.0 nm): λ _max (I _rel ) = 476.1 ( 1:00 ), 509.5 ( 0.66 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 436.0 nm, E _{436.0 nm / 1 cm} = 0.0146, reference: 1 with Φ = 1.00): 0.24. MS (DEP / EI): m / z (%): 1031.65 ( 19.6 ) [M ⁺ + 2 H], 1030.66 ( 50.5 ) [M ⁺ + H], 1029.66 ( 68.4 ) [M ⁺ ], 850.46 ( 17.4 ), 849.47 ( 53.3 ), 848.48 ( 100.0 ), 847.48 ( 51.8 ), 678.28 ( 12.0 ), 668.28 ( 17.0 ), 667.28 ( 48.2 666.27 ( 76.9 ), 665.25 ( 41.8 ), 580.17 ( 16.9 ), 497.08 ( 23.2 ), 496.07 ( 50.7 ), 485.06 ( 27.7 ), 484.07 ( 70.9 ), 466.05 ( 25.0 ), 83.09 ( 18.2 ), 69.07 ( 29.5 ), 57.07 ( 14.0 ), 56.06 ( 14.6 ), 55.06 ( 45.6 ), 43.07 ( 21.3 ), 41.06 ( 17.6 ). HRMS (C ₆₇ H ₈₇ N ₃ O ₆ ): Ber. 1029.6595 m / z, Gef. 1029.6567 m / z; Δ = 0.0028.

N, N ', N "-Tris (1-hexylheptyl) -6-azetidin-1-yl-benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid-1,2: 4,5 : 10,11-tris (dicarboximide) ( 6 ): N, N ', N "-Tris (1-hexylheptyl) benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid-1,2: 4,5: 10,11-tris ( dicarboximide) ( 5 , 101 mg, 0.098 mmol) was stirred in azetidine (2.50 g, 43.8 mmol) at room temperature for 16 h, the azetidine was removed under reduced pressure to remove azetidine residues in CHCl ₃ ( 40 mL) and evaporated to dryness in vacuo and purified by column chromatography with exclusion of light (silica gel, CHCl ₃ / isohexane 3: 1, second, intensely red fluorescent band). Y. 10 mg ( 9.4 %, 0.009 mmol) red solid, mp. 94-98 ° C. R _f (silica gel, CHCl ₃ / isohexane 3: 1) = 0.55. IR (ATR): ṽ = 3082 (w), 2953 (m), 2919 (s), 2850 (m), 1864 (vw), 1763 (w), 1698 (s), 1656 (vs), 1618 (m ), 1588 (m), 1562 (w), 1523 (w), 1457 (m), 1417 (m), 1407 (m), 1392 (m), 1362 (s), 1331 (s), 1309 (s ), 1252 m, 1240 m, 1224 m, 1185 m, 1158 m, 1110 m, 1093 m, 1049 w, 1021 w, 971 m ), 944 (m), 934 (m), 897 (w), 877 (m), 846 (w), 808 (m), 790 (m), 781 (m), 766 (s), 71 (m ), 721 (m), 678 (w), 657 (m) cm ^-1 . ¹ H-NMR (600 MHz, _CDCl3, 27 ° C, TMS): δ = 0.81 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 × CH _3), 0.81 (t, ³ J (H, H) = 7.1 Hz, 6 H, 2 × CH _3), 0.87 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 × CH _3), 1:16 to 1:44 (m, 48 H , 24 × CH ₂ ), 1.79-1.86 (m, 2 H, β-CH ₂ ), 1.86-1.95 (m, 4 H, 2 × β-CH ₂ ), 2.21-2.30 (m, 2 H, β- CH ₂ ), 2.30-2.41 (m, 4 H, 2 x β-CH ₂ ), 2.44-2.62 (m, 2 H, 2 x β-CH _azetidine ), 3.93-4.31 (m, 4 H, 4 x α -CH _azetidine ), 4.43 (tt, ³ J (H, H) = 10.2 Hz, ³ J (H, H) = 5.1 Hz, 1 H, NCH), 5.22-5.38 (m, 2 H, 2 x NCH) , 8.56 (s br., 1 H, CH _{benzoperylene} ), 9.05-9.17 (m, 2 H, 2 x CH _{benzoperylene} ), 10.30 (d, J = 17.7 Hz, 1 H, CH _{benzoperylene} ), 10.50 (d, J = 17.8 Hz, 1 H, CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 16.3, 22.6, 22.7, 26.7, 26.8, 26.9, 29.0, 29.2, 29.3, 29.7, 30.0, 30.1, 31.7, 31.8, 31.9, 32.5, 32.7, 33.2, 52.9, 54.7, 54.9, 117.3, 119.862, 123.2, 124.1, 125.8.7, 125.8, 126.1, 126.5, 127.3, 128.3, 128.7, 133.0, 152.0, 169.0, 169.1 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 363.4 ( 12:45 ), 414.6 ( 1:00 ), 575.0 ( 12:51 ) nm. fluorescence (CHCl ₃ , λ _exc = 575.0 nm): λ _max (I _rel ) = 644.6 ( 1:00 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 575.0 nm, E _{575.0 nm /} 1cm = 0.0151, CHCl ₃ , reference 1 with Φ = 1.00): 0.94. MS (FAB ⁺ ): 1084.7 ( 48 ) [M] ⁺ , 903.5 ( 29 ), 721.4 ( 15 ), 663.5 ( 27 ), 647.0 ( 20 ), 551.0 ( 9 ), 537.0 ( 13 ), 513.0 ( 16 ), 511.2 ( 27 ), 509.2 ( 21 ), 464.0 ( 14 ), 489.0 ( 16 ), 55.0 ( 56 ). HRMS (C ₇₀ H ₉₂ N ₄ O ₆ ): Ber. m / z: 10847017, Gef. m / z: 1084.7021; Δ = 0.0004. C ₇₀ H ₉₂ N ₄ O ₆ ( 1085.5 ): Ber. C 77.45, H 8.54, N 5.16; Gef. C 77.52, H 9.45 N 4.10.

7a and 7b: The third, intensely red fluorescent band: mixture of N, N'-bis (1-hexylheptyl) -6-azetidin-1-yl-benzo [ghi] perylene-1,2,4,5,10, 11-hexacarboxylic acid 4,5: 10,11-tris (dicarboximide) -2- (N-1-azetidinylamide) -1- (N-1-hexylheptylamide) ( 7a ) and N, N'-bis (1-hexylheptyl) -6-azetidin-1-yl-benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid 4,5: 10,11- tris (dicarboximide) -1- (N-1-azetidinylamide) -2- (N-1-hexylheptylamide) ( 7b ). Y. 36 mg ( 32.2 %, 0.032 mmol) dark red solid, mp 107 ° C. R _f ( Silica gel, CHCl ₃ ) = 0.29. IR (ATR): ṽ 3319 (w), 2953 (m), 2921 (s), 2853 (m), 1759 (w), 1697 (s), 1657 (vs), 1590 (s), 1520 (m) , 1454 (s), 1430 (m), 1414 (s), 1393 (s), 1326 (s), 1311 (vs), 1238 (s), 1185 (s), 1143 (m), 1051 (m) , 1022 (m), 945 (m), 921 (m), 875 (m), 852 (m), 809 (s), 759 (m), 722 (m) cm ^-1 . ¹ H NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.73-0.96 (m, 18 H, 6 x CH ₃ ), 1.13-1.49 (m, 48 H, 24 x CH ₂ ), 1.49-1.63 (m, 2 H, β-CH ₂ ), 1.64-1.80 (m, 2 H, β-CH ₂ ), 1.81-1.98 (m, 4 H, 2 x β-CH ₂ ), 2.23-2.35 (m, 4 H, 2 x β-CH ₂ ), 2.35-2.43 (m, 2 H, 2 x β-CH _azetidine ), 2.44-2.59 (m, 2 H, 2 x β-CH _azetidine ), 3.63-3.72 (m, 1H , α-CH _azetidine ), 3.90-4.26 (m, 3 H, 3 x α-CH _azetidine ), 4.27-4.31 (m, 1 H, α-CH _azetidine ), 4.31-4.38 (m, 1 H, α- CH _azetidin), 4:38 to 4:45 (m, 1 H, NCH), 4:46 to 4:50 (m, 1H, α-CH _azetidin), 4:51 to 4:59 (m, 1H, α-CH _azetidin), 5:19 to 5:36 ( m, 2H, 2 x NCH), 6.26-6.41 (mbr., 1H, NH), 8.45-8.57 (m, _1H , CH _{benzoperylene} ), 8.97-9.12 (m, _1H , CH _{benzoperylene} ), 9.12-9.21 (m, _1H , CH _{benzoperylene} ), 9.32-9.44 (m, _1H , CH _{benzoperylene} ), 9.55-9.65 (m, _1H , CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 15.6, 16.3, 22.6, 22.7, 25.9, 26.0, 26.9, 29.2, 29.4, 29.6, 29.7, 31.7, 31.8, 31.9, 32.2, 32.5, 32.8, 34.6, 35.2, 48.9, 51.0, 51.2, 54.5, 54.5, 54.8, 54.9, 55.0, 117.3, 117.4, 118.7, 119.8, 122.5, 123.0, 123.7, 124.1, 124.1, 124.5, 125.5, 125.9, 126.0, 126.1, 126.2, 126.9, 127.9, 130.0, 130.6, 130.7, 131.1, 132.8, 132.9, 133.1, 133.7, 134.0, 151.8, 164.0, 164.2, 165.2, 165.3, 166.3, 166.4, 167.7, 167.8 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 300.0 ( 1:00 ), 365.4 ( 0.89 ), 379.4 ( 0.90 ), 431.4 ( 12:35 ), 458.0 ( 0.60 ), 565.4 ( 0.74 ) nm. fluorescence (CHCl ₃ , λ _exc = 565.0 nm): λ _max (I _rel ) = 639.0 ( 1:00 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 565.0nm, E _{565.0nm / 1cm} = 0.0484; CHCl ₃ , reference 1 with Φ = 1.00): 1.00. MS (FAB ⁺ ): 1141.8 ( 100 ) [M] ⁺ , 1085.8 ( 55 ) [M-C ₃ H ₆ N] ⁺ , 960.0 ( 13 ), 943.5 ( 35 ), 915.0 ( 18 ), 903.0 ( 27 ), 733.0 ( 17 ), 721.4 ( 94 ), 683.0 ( 20 ), 551.0 ( 26 ), 539.0 ( 55 ), 523.0 ( 48 ), 511.3 ( 93 ), 440.2 ( 51 ), 396.2 ( 22 ), 198.0 ( 18 ), 69.0 ( 45 ), 55.1 ( 79 ), 43.0 ( 68 ). HRMS (C ₇₃ H ₉₉ N ₅ O ₆ ): Ber. m / z: 1141.7595, Gef. m / z: 1141.7531; Δ = 0.0064.

N, N ', N "-tris (1-hexylheptyl) -6-pyrrolidin-1-yl-benzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3,8,9 , 11,12-tris (dicarboximide) ( 11 ): N, N ', N "-tris (1-hexylheptyl) benzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid 2,3,8,9,11,12-tris ( dicarboximide) ( 5 , 200 mg, 0.194 mmol) was stirred in pyrrolidine (2.50 g, 43.8 mmol) at room temperature (TLC control of the reaction progress, silica gel / chloroform), after 60 min evaporated to dryness, taken to remove traces of pyrrolidine in chloroform and in Vacuum evaporated, purified by column chromatography under exclusion of light (silica gel, chloroform / isohexane 3 :1; second, intensely red fluorescent band). Y. 38 mg ( 0035 mmol, 17.8%) dark green solid; Mp 118-120 ° C. R _f (silica gel, CHCl ₃ / isohexane 3: 1) = 0.58. IR (ATR): ṽ = 2955 (m), 2916 (vs), 2848 (s), 2358 (vw), 1761 (w), 1700 (s), 1657 (s), 1618 (m), 1586 (m ), 1560 (w), 1525 (w), 1506 (w), 1462 (m), 1422 (m), 1407 (m), 1396 (m), 1358 (m), 1336 (s), 1310 (s ), 1264 m, 1243 m, 1176 m, 1156 m, 1127 w, 1108 w, 1080 w, 990 w, 937 w, 926 w ), 872 (w), 844 (vw), 807 (m), 793 (m), 767 (m), 758 (m), 739 (m), 720 (m), 673 (vw), 663 (m ) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.81 (t, ³ J (H, H) = 6.7 Hz, 6 H, 2 x CH ₃ ), 0.81 (t, ³ J (H, H) = 7.1 Hz, 6 H, 2 × CH _3), 0.87 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 × CH _3), 1:16 to 1:43 (m, 48 H , 24 × CH ₂ ), 1.79-1.86 (m, 2 H, β-CH ₂ ), 1.86-1.95 (m, 4 H, 2 × β-CH ₂ ), 2.05 (mbr., 2 H, 2 × β-CH _pyrollidine ), 2.20-2.29 (m, 4 H, β-CH ₂ , 2 x β-CH _pyrollidine ), 2.29-2.40 (m, 4 H, 2 x β-CH ₂ ), 2.85 (mbr. , 2 H, α-CH _pyrollidine ), 4.01 ( _mbr ., 2 H, α-CH _pyrollidine ), 4.43 (tt, ³ J (H, H) = 10.2 Hz, ³ J (H, H) = 5.1 Hz , 1H, NCH), 5.22-5.37 (m, 2H, 2 x NCH), 8.84-8.93 (m, 2H, 2 x CH _{benzoperylene} ), 9.00-9.11 (m, _1H , CH _{benzoperylene} ), 10.28 (d, J = 18.4 Hz, _1H , CH _{benzoperylene} ), 10.50 (d, J = 18.7 Hz, _1H , CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 22.6, 22.7, 25.7, 26.8, 27.0, 29.0, 29.2, 29.3, 29.7, 31.7, 31.8, 31.9, 32.5, 32.7, 52.6, 52.9, 54.9, 119.9, 124.0, 125.3, 126.5, 127.3, 128.8, 149.6, 169.2 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 365.4 ( 12:52 ), 401.0 ( 0.67 ), 420.8 ( 1:00 ), 599.0 ( 12:53 ) nm. fluorescence (CHCl ₃ , λ _exc = 599.0 nm): λ _max (I _rel ) = 647.4 ( 1:00 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 599.0 nm, E _{599.0 nm / 1 cm} = 0.0245, CHCl ₃ , reference 1 with Φ = 1.00): 1.00. MS (FAB ⁺ ): m / z (%): 1100.4 ( 11 ) [M + 2H] ⁺ , 1099.4 ( 10 ) [M + H] ⁺ , 918.1 ( 4 ), 735.9 ( 2 ), 553.6 ( 3 ). HRMS (C ₇ H ₉₄ N ₄ O ₆ ): Ber. m / z: 1098.7173, Gef. m / z: 1098.7156; Δ = 0.0017.

12a and 12b: The third, intensely red fluorescent band, eluted with chloroform: mixture of N, N'-bis (1-hexylheptyl) -6-pyrrolidin-1-yl-benzo [ghi] perylene-1,2,4, 5,10,11-hexacarboxylic acid 4,5: 10,11-tris (dicarboximide) -2- (N1-azetidinylamide) -1- (N-1-hexylheptylamide) ( 12a ) and N, N'-bis (1-hexylheptyl) -6-pyrrolidin-1-yl-benzo [ghi] perylene-1,2,4,5,10,11-hexacarboxylic acid 4,5: 10,11- tris (dicarboximide) -1- (N-1-pyrrolidinylamide) -2- (N-1-hexylheptylamide) ( 12b ). Y. 126 mg ( 0108 mmol, 55.5%) dark green solid, mp 113-114 ° C. R _f (silica gel, CHCl ₃ ) = 0.19. IR (ATR): ṽ = 2922 (m), 2854 (m), 2360 (vs), 2336 (s), 1983 (vw), 1698 (s), 1658 (s), 1589 (m), 1521 (m ), 1456 (m), 1414 (m), 1312 (m), 1242 (m), 809 (m), 759 (w), 668 (s) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.80 (td, ³ J (H, H) = 7.0 Hz, J = 2.3 Hz, 6 H, 2 x CH ₃ ), 0.85 (td, ³ J (H, H) = 7.0 Hz, J = 3.5 Hz, 6 H, 2 x CH ₃ ), 0.91-0.94 (m, 6 H, 2 x CH ₃ ), 1.14-1.47 (m, 48 H, 24 x CH ₂ ), 1.47-1.59 (m, 2 H, β-CH ₂ ), 1.58-1.70 (m, 2 H, β-CH ₂ ), 1.70-1.79 (m, 2 H, β-CH ₂ ), 1.80-1.98 (m, 4 H, β-CH ₂ , 2 x β-CH _pyrollidine ), 1.99-2.17 (m, 4 H, 4 x β-CH _pyrollidine ), 2.18-2.25 (m, 2H , 2 × β-CH _pyrollidine ), 2.25-2.38 (m, 4H, 2 × β-CH ₂ ), 2.71-2.85 (m, 1H, α-CH _pyrollidine ), 2.85-2.91 (m, 1H, α -CH _pyrollidine ), 2.91-3.03 (m, 1H, α-CH _pyrollidine ), 3.42-3.52 (m, 1H, α-CH _pyrollidine ), 3.82-3.91 (m, 1H, α-CH _pyrollidine ), 3.93-4.04 (m, 2H, 2 x α-CH _pyrollidine ), 4.31-4.41 (m, 1H, NCH), 5.02-5.10 (m, 1H, α-CH _pyrollidine ), 5.19-5.34 (m, 2 H, 2 x NCH), 6.43-6.54 (mbr., 1H, NH), 8.79-8.89 (m, _1H , CH _{benzoperylene} ), 8.89-8.95 (m, _1H , CH _{benzoperylene} ), 8.95- 9.15 (m, _1H , CH _{benzoperylene} ), 9.21-9.41 (m, _1H , CH _{benzoper ylen} ), 9.56-9.64 (m, _1H , CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 22.6, 22.7, 24.6, 25.6, 25.8, 25.9, 26.0, 27.0, 29.2, 29.4, 29.5, 29.7, 31.7, 31.8, 31.9, 32.2, 32.5, 32.6, 34.5, 35.3, 46.0, 48.5, 48.6, 50.9, 51.0, 52.2, 52.3, 54.7, 55.0, 118.6, 118.7, 119.3, 119.9, 120.0, 120.1, 122.5, 122.9, 123.2, 123.3, 123.6, 123.7, 124.0, 124.1, 125.1, 125.4, 125.8, 126.1, 126.2, 126.4, 126.6, 126.8, 126.9, 128.2, 128.4, 128.9, 129.1, 129.7, 130.5, 131.4, 132.6, 132.9, 133.4, 133.7, 133.8, 133.9, 134.2, 149.4, 163.6, 164.0, 164.2, 164.4, 164.8, 165.1, 165.2, 165.6, 166.0, 166.3, 166.4, 166.7, 166.8 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 372.0 ( 23200 ), 385.4 ( 24000 ), 435.0 ( 12500 ), 462.4 ( 19400 ), 591.4 ( 19100 ) nm. fluorescence (CHCl ₃ , λ _exc = 591.0 nm): λ _max (I _rel ) = 641.3 ( 1:00 ) nm. Fluorescence quantum eff. (CHCl ₃ , λ _cxc = 591.0 nm, E _{591.0 nm / 1cm} = 0.0298, CHCl ₃ , reference 1 with Φ = 1.00): 1.00. MS (FAB ^-): m / z (%): (1169.3 100 ) [M] ^- , 1168.3 ( 32 ) [MH] ^- , 1100.0 ( 22 ), 986.1 ( 13 ), 985.1 ( 5 ), 917.1 ( 4 ), 438.5 ( 2 ). HRMS (C ₇₅ H ₁₀₃ N ₅ O ₆ ): Ber. m / z: 1169.7908, Gef. m / z: 1169.7875; Δ = 0.0033. C ₇₅ H ₁₀₃ N ₅ O ₆ ( 1170.7 ): Ber. C 76.95, H 8.87, N 5.98; Gen. C 76.93, H 8.89, N 5.83.

Imidazoloperylen 8th : The corresponding five-membered anhydride of 8 (180 mg, 0.186 mmol) (H. Langhals, M. Eberspächer, Ger. Offen. DE 102016010081.8 ( 12.8 .2016).), 1-hexylheptylamine (74 mg, 0.373 mmol), Imidazole (3.00 g) and toluene ( 1.0 ml) were stirred for 4 h at 145 ° C, after cooling with 2 м aqueous HCl ( 20 mL) and stirred for 16 h at room temperature. The organic phase was separated and the aqueous phase extracted several times with chloroform. The combined organic phases were washed with distilled water, dried over Na ₂ SO ₄ , evaporated in a rough vacuum, purified by chromatography (silica gel, toluene, first orange fluorescent strip), taken up in a little CHCl ₃ , precipitated with methanol, a D4 glass frit filtered off and dried for 16 h at 110 ° C in a drying oven. Y. 148 mg ( 69.2 %, 0.129 mmol) bright orange solid, mp> 300 ° C. R _f (silica gel, toluene) = 0.96. ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.73-0.92 (m, 18 H, 6 x CH ₃ ), 1.12-1.55 (m, 48 H, 24 x CH ₂ ), 1.85-1.98 (m, 2 H, β-CH ₂ ), 1.98-2.13 (m, 4 H, 2 x β-CH ₂ ), 2.30-2.41 (m, 2 H, β-CH ₂ ), 2.41-2.59 (m, 4 H, 2 x β-CH ₂ ), 4.50 (t, ³ J (H, H) = 10.1 Hz, ³ J (H, H) = 5.3 Hz, 1H, NCH), 5.31-5.50 (m , 2H, 2 x NCH), 7.73-7.80 (m, 3H, 3 x CH _aryl ), 8.32-8.60 (m, 2H, 2 x CH _aryl ), 9.29 (s, _1H , CH _{benzoperylene} ), 10.35-10.71 (m, 2H, 2 x CH _{benzoperylene} ), 11.57 (s, _1H , CH _{benzoperylene} ), 11.88 (s, _1H , NH) ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 394.8 ( 0.67 414.2 ( 0.91 ), 488.6 ( 0.76 ), 524.8 ( 1:00 ) nm. fluorescence (CHCl ₃ , λ _exc = 489.0 nm): λ _max (I _rel ) = 540.4 ( 1:00 ), 582.8 ( 12:58 ) nm. fluorescence quantum. (CHCl ₃ , λ _exc = 489.0 nm, E _{489.0 nm / 1 cm} = 0.0190, reference: 1 with Φ = 1.00): 0.61. MS (FAB ⁺ ): m / z (%): 1146.0 ( 1 ) [M + H] ⁺ , 964.0 ( 1 ), 641.0 ( 2 ). HRMS (C ₇₄ H ₉₁ N ₅ O ₆ ): Ber. m / z: 1145.6969, Gef. m / z: 1145.6987; Δ = -0.0018.

Imidazolopyrrolo-Bisimides 9a and 9b : The imidazolobenzoperylene trisimide 8th (140 mg, 0.122 mmol) was dissolved in pyrrolidine ( 250 mL) at room temperature 8th d stirred, evaporated in a rough vacuum, purified by chromatography several times (silica gel, chloroform, second orange fluorescent band), precipitated from a little chloroform with methanol, suction filtered in vacuo (D4 glass frit) and 16 h at 110 ° C in air. Y. 101 mg ( 68.0 %, 0.083 mmol) orange solid, mp 218-219 ° C. R _f (silica gel, chloroform) = 0.32. IR (ATR): ṽ = 3418 (w), 3245 (w), 3072 (vw), 2953 (m), 2923 (s), 2854 (m), 1965 (vw), 1697 (s), 1661 (m ), 1645 (s), 1621 (vs), 1594 (m), 1572 (w), 1532 (m), 1453 (s), 1440 (s), 1424 (m), 1401 (m), 1376 (m ), 1332 (s), 1314 (s), 1277 (m), 1243 (m), 1212 (m), 1161 (m), 1143 (m), 1125 (m), 1057 (w), 1026 (w ), 1001 (w), 938 (w), 914 (w), 867 (m), 813 (m), 772 (m), 757 (m), 724 (m), 706 (m), 683 (s ), 658 (m) cm ^-1 . ¹ H NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.79-0.85 (m, 6H, 2 x CH ₃ ), 0.88 (t, ³ J (H, H) = 7.0 Hz, 6 H, 2 x CH ₃ ), 0.95 (t, ³ J (H, H) = 6.5 Hz, 6 H, 2 x CH ₃ ), 1.63-1.84 (m, 4 H, 2 x β-CH ₂ ), 1.85-2.04 (m, 6H, 2 x β-CH ₂ , 2 x β-CH _pyrrolidine ), 2.04-2.18 (m, 2H, 2 x β-CH _pyrrolidine ), 2.27-2.46 (m, 4H, 2 × β-CH ₂ ), 2.98-3.08 (m, 1H, α-CH- _pyrrolidine ), 3.45-3.56 (m, 1H, α-CH- _pyrrolidine ), 3.88-3.95 (m, 1H, 1H, α-CH _pyrrolidine ), 4.00-4.08 (m, 1H, α-CH _pyrrolidine ), 4.37-4.45 (m, 1H, NCH), 5.27-5.40 (m, 2H, 2 x NCH), 6.52 (m br., 1H, NH), 7.67-7.76 (m, 3H, 3 x CH _aryl ), 8.50-8.56 (m, 2H, 2 x CH _aryl ), 9.21-9.41 (m, 2H, 2 x CH _{benzoperylene} ), 9.60-9.75 (s, _1H , CH _{benzoperylene} ), 11.55-11.68 (m, _1H , CH _{benzoperylene} ), 11.92 (s, 1H, NH) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 14.2, 22.6, 22.7, 22.8, 24.6, 25.8, 25.9, 26.1, 27.1, 29.3, 29.4, 29.6, 31.8, 31.9, 32.2, 32.6, 34.5, 35.3, 46.1, 48.7, 51.1, 54.9, 55.1, 123.9, 124.8, 127.7, 128.7, 129.5, 130.8, 131.9, 132.5, 133.3, 143.3, 155.9, 166.3 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 346.4 ( 20200 ), 392.0 ( 8400 ), 457.8 ( 25500 ), 487.2 ( 56800 ), 523.6 nm ( 61000 L mol ^-1 cm ^-1 ). Fluorescence (CHCl ₃ , λ _exc = 487.0 nm): λ _max (I _rel ) = 538.0 ( 1:00 ), 579.1 ( 12:56 ) nm.

Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 487.0 nm, E _{487.0 nm / 1 cm} = 0.0281, CHCl ₃ , reference 1 with Φ = 1.00): 0.48. MS (FAB ^-): m / z (%): (1216.5 100 ) [M] ^- , 1215.5 ( 50 ) [MH] ^- , 1034.4 ( 14 ), 1033.4 ( 14 ), 624.2 ( 2 528.2 ( 3 ), 500.2 ( 2 ), 153.1 ( 5 ), 152.1 ( 5 ), 46.0 ( 1 ). HRMS (C ₇₈ H ₁₀₁ N ₆ O ₆ ): Ber. m / z: 1217.7783, Gef. m / z: 1217.7759; Δ = 0.0024. C ₇₈ H ₁₀₀ N ₆ O ₆ ( 1217.7 ): Ber. C 76.94, H 8.28, N 6.90; Gen. C 76.78, H 8.44, N 6.84.

Subject of the invention

• a. 2-Azetidinoperylenbisimide of general formula I,
  
  in which the radicals R ¹ to R ^{9 may be} identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units may be replaced independently by carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3- , 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6 -, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10 disubstituted anthracene residues in which one or two i CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10-d isubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9 , 10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The radicals R ¹ to R ¹³ may also independently of one another denote the halogen atoms F, Cl, Br or I.
• b. 2,11-diazetidinoperylenebisimides of general formula II,
  
  in which the radicals R ¹ to R ^{8 have} the meaning given under a.
• c. Benzoperylene derivatives of the general formulas III and IV, and imidazoloperylenebisimides of the general formula V,
  
  
  in which the radicals R ¹ to R ^7, the meaning indicated under a and the radicals R ⁸ to R ^12, the meaning of R ¹ to R ^{5 have} the meaning given under a and aryl is an aryl radical or heteroaryl radical, such as. Pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl, coumarinyl, benzofuranyl, benzimidazolyl, benzoxazolyl, dibenzfuranyl, benzothiophenyl, dibenzothiophenyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, indazolyl, Benzothiazolyl, pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazinedionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho -sulfobenimidyl, maleimidyl, naphtharidinyl, benzimidazolonyl, benzoxazolonyl, benzthiazolonyl, benzthiazolinyl, quinazolonyl, pyrimidyl, quinoxalonyl, phthalazonyl, dioxapyrinidinyl, pyridonyl, Isoquinolonyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, benzoxazinedioyl, benzoxazinonyl and phthalimidyl. These radicals may be substituted with donor groups, preferably with one to five donor groups, of which alkoxy, in particular methoxy, ethoxy, isopropoxy and tert-butyloxy, and amino groups and disubstituted amino groups, in particular dimethylamino groups, are preferred. R ⁹ and R ¹⁰ in III and R ¹² and R ¹³ in IV preferably form carbon rings, preferably the ring size 3 to 6 , which may be saturated or unsaturated and may also contain heteroatoms such as oxygen, sulfur and nitrogen, and may be preferably aziridine, azetidine, pyrolidine, piperidine, morpholine, but also pyrrole or indole.
• d. 2-Azetidinoperylenimides of general formula VI,
  
  in which the radicals R ¹ to R ^{9 have} the meaning given under a and R ^{10 has} the meaning given by R ¹ under a.
• e. A process characterized in that Azetidinoarylcarbonsäureimide, in particular the substances are synthesized according to a to d using azetidine, by the action of azetidine as a pure substance on Carbonsäureimide or in solution in inert solvents such as chloroform or dichloromethane, preferably in concentrations of 1 molar to pure Azetidine, about 15 molar.
• f. Method characterized in that using the substances according to a to d nucleophilic substrates are labeled optically, using the light absorption or fluorescence, whereby typical nucleophilic substrates may be alcohols, alcoholates, phenols, phenolates, thiols, thiolates, thiophenols, thiophenolates, in particular under the action of catalysts, or else C-nucleophiles such as organometallic reagents, such as, for example, zinc organyls, or else the anions CH-acid compounds, for example acetoacetic esters, malonic esters, acetylacetone, benzyl cyanides, cyclopentadiene or else 2- or 4-picoline.
• G. Use of the substances according to a to d as a frequency converter in optical information collecting, information processing and forwarding systems, in particular in optical light guides, preferably in fast optical systems
• H. Use of the substances according to a to d as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as e.g. for glues and related colors such as watercolors and watercolors and inks for inkjet printers, paper inks, printing inks, inks and inks and other inks for painting and writing and in paints, as pigments in paints, the preferred paints are synthetic resin paints such as acrylic paints. or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or also natural substances such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples being materials of polyvinyl chloride, polyvinylidene chloride , Polyacrylic acid, polyacrylamide, polyvinyl butyral, polyvinyl pyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, polyacrylnit ril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such as the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, e.g. for coloring natural products, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as colorants, e.g. for coloring paints, lacquers and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, particularly luminous shades are preferred.
• i. Use of the substances according to a to d for marking, security and display purposes, in particular taking into account their fluorescence, such as dyes or fluorescent dyes for signal colors, preferably for visual highlighting lettering and drawings or other graphic products, for marking signs and others Articles and in display elements for a variety of display, reference and marking purposes, where a special optical Color impression is to be achieved for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, where necessary, the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents, identity documents and the like in which a particular, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via fluorescence, machine recognition of objects for sorting, eg also for the recycling of plastics, as fluorescent dyes for machine-readable markings is preferred are alphanumeric imprints or barcodes, as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, illumination or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for B in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, for example in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or Fluorescent dyes in chemiluminescence systems, for example in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods and as a material for leak testing of closed systems.
• j. Use of the dyes of a to d as functional materials, e.g. in data memories, preferably in optical memories, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: e.g. for dry copying systems (Xerox process) and laser printers ("non-impact printing"), for the frequency conversion of light, e.g. to make shortwave light of longer wavelength visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collecting systems, e.g. the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, e.g. in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit containing dyes as such or in combination with other semiconductors e.g. in the form of epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as Q-switch switches and as active substances for non-linear optics, e.g. for frequency doubling and frequency tripling of laser light.

LIST OF REFERENCE NUMBERS

• 1 , Reaction of 1 with azetidine to 2 and further to 3.
• 2 , UV / Vis absorption spectra of 1 (dotted curve left), 2 (solid curve center and 3 (dashed curve right).
• 3 , UV / Vis spectra of the progressive reaction of 1 with azetidine ( 130 μL) at 25 ° C in chloroform ( 170 μL) and 1 mm layer thickness and an interval time of 5 min; Isosbestic point at 540.4 nm. Inset right: Detail view of the isosbestic point. Inset left: pseudo-first order kinetics of 1 with azetidine; see also Tab. 1.
• 4 , Reaction of 1 with azetidine ( 130 μL) at 25 ° C in chloroform ( 170 μL) and 1 mm layer thickness. Circles and solid curve: decrease in absorbance of 1 at 527 nm. Diamonds and dashed curve: increase of 2 at 622 nm. Inset: Determination of the reaction order in azetidine (molar concentration c _a ) with respect to the pseudo first-order rate constant k of 1; Slope: 7.54 ± 0.18; correlation coefficient 0.9994 for 4 readings.
• 5 , Plot of ln k / T against 1 / T according to Eyring's theory. pitch 3771 ± 786, ordinate section -25.8, correlation coefficient 0.94 at 5 readings.
• 6 , Calculated structure (DFT, B3LYP) of an adduct of azetidine to the N, N'-dimethyl derivative of 1.
• 7 , Possible reaction mechanism for the substitution of 1 with azetidine.
• 8th , Reaction of azetidine with benzoperylene trisimides and pyrrolidine with imidazolobenzoperylene trisimides. R = 1-hexylheptyl, i) azetidine, ii) pyrrolidine.
• 9 , Substitution of various carboxylic acid imides with azides ( 130 μL) in chloroform ( 170 μL) and 1 mm layer thickness and measurement of extinction E. Triangles and dotted line: 4 (N, N'-bis (2,5-di-tert-butylphenyl) perylene-3,4: 9,10-tetracarboxylic bisimide) k = 0.0035 ± 0.0003 s ^-1 , r = 0.994 for 4 measurements at 527 nm; only the first three measurements are shown); Squares and dashed line: 8 (k = 0.00180 ± 0.000005 s ^-1 , r = 0.99997 for 7 measurements at 430 nm); Diamond and dot-dash line: 5 (k = 0.000 0047 ± 0.000 0001 s ^-1 , r = 0.997 for 19 measurements at 468 nm). Circles and solid line: 1 for comparison (k = 0.000 598 ± 0.000 006 s ^-1 , r = 0.9995 for 12 measurements at 527 nm).
• 10 , X-ray crystal structure for the verification of 8.
• 11 , UV / Vis spectra of the progressive reaction of 8 with azetidine ( 130 μL) at 25 ° C in chloroform ( 170 μL) and 1 mm layer thickness and an interval time of 5 min; isosbestic points at 387.4, 483.0 and 587.4. Insets: Detailed views of the isosbestic points.
• 12 , UV / Vis spectra of the progressive reaction of 10 in azetidine at 25 ° C and 1 mm layer thickness. Isosbestic point at 524.5 nm. Right insertion: Detailed view of the isosbestic point. Left slot: first-order evaluation in 10 at 483 nm: k = 4.7 · 10 ^-7 ± 2 · 10 ^-8 s-1, r = 0.988 for 19 measured values.
• 13 , Solvatochromism of 2. Left: Absorption, right fluorescence. Solid thick curves: spectra in chloroform, thin, dotted curves: spectra in n-hexane.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102012005897 A1 [0010]
• DE 102016010081 [0022]

Cited non-patent literature

• Galabov, D. Nalbantova, P.v. R. Schleyer, H.F. Schaefer, Acc. Chem. Res. 2016, 49, 1191-1199. [0001]
• M.R. Crampton, Organic Reaction Mechanisms 2011, 257-283 [0001]
• G. Yan, M. Yang, Organic Biomol. Chem. 2013, 11, 2554-2566. [0001]
• C. Kent, O.M. Ghoneim, S.W. Goldstein, Abstr., 39th Northeast Regional Meeting of the American Chemical Society, New Haven, CT, United States, October 23-26 (2013), NERM-384; Chem. Abstr. 2013, AN1648236. [0001]
• Y. Li, X. Zhu, F. Meng, Y. Wan, Tetrahedron 2011, 67, 5450-5454 [0001]
• X. Deng, H. McAllister, N.S. Mani, J. Org. Chem. 2009, 74, 5742-5745. [0001]
• C. Hamann, J.F. Hartwig, J. Am. Chem. Soc. 1998, 120, 7369-7370. [0001]
• A. Ricci (ed.), Amino Group Chemistry 2008, 1-54; Chem. Abstr. 2008, 150, 190748. [0001]
• H. Langhals, S. Christian, A. Hofer, J. Org. Chem. 2013, 78, 9883-9891 [0002]
• H. Langhals, Chromophores for picoscale optical computers in K. Sattler (ed.), Fundamentals of picoscience, p. 705-727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca / US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095. [0002]
• S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230 [0004]
• A. Rademacher, S. Märkle, H. Langhals, Chem. Ber. 1982, 115, 2927-2934. [0009]
• H. Langhals, A. Hofer, J. Org. Chem. 2012, 77, 9585-9592 [0010]
• H. Langhals, A. Hofer, Ger. Open. (2013) [0010]
• Chem. Abstr. 2013, 159, 502376 [0010]

Claims (10)

2-Azetidinoperylenbisimide of general formula I,

in which the radicals R ¹ to R ^{9 may be} identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units may be replaced independently by carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3- , 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6 -, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10 disubstituted anthracene residues in which one or two i CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-disubstituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10-d isubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9 , 10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The radicals R ¹ to R ¹³ may also independently of one another denote the halogen atoms F, Cl, Br or I. 2,11-Diazetidinoperylenebisimides of general formula II,

in which the radicals R ¹ to R ^{8 have} the meaning given under 1. Benzoperylene derivatives of the general formulas III and IV, and imidazoloperylenebisimides of the general formula V,

in which the radicals R ¹ to R ^7, the meaning given under 1 and the radicals R ⁸ to R ^12, the meaning of R ¹ to R ^{5 have} the meaning given under 1 and aryl is an aryl radical or heteroaryl radical, such as. Pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thiophenyl, quinolyl, isoquinolyl, coumarinyl, benzofuranyl, benzimidazolyl, benzoxazolyl, dibenzfuranyl, benzothiophenyl, dibenzothiophenyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, indazolyl, Benzothiazolyl, pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl, phthalazinedionyl, phthalimidyl, chromonyl, naphtholactamyl, benzopyridonyl, ortho -sulfobenimidyl, maleimidyl, naphtharidinyl, benzimidazolonyl, benzoxazolonyl, benzthiazolonyl, benzthiazolinyl, quinazolonyl, pyrimidyl, quinoxalonyl, phthalazonyl, dioxapyrinidinyl, pyridonyl, Isoquinolonyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, benzoxazinedioyl, benzoxazinonyl and phthalimidyl. These radicals may be substituted with donor groups, preferably with one to five donor groups, of which alkoxy, in particular methoxy, ethoxy, isopropoxy and tert-butyloxy, and amino groups and disubstituted amino groups, in particular dimethylamino groups, are preferred. R ⁹ and R ¹⁰ in III and R ¹² and R ¹³ in IV preferably form carbon rings, preferably ring size 3 to 6, which may be saturated or unsaturated and may also contain heteroatoms such as oxygen, sulfur and nitrogen, and preferably aziridine, azetidine, pyrolidine , Piperidine, morpholine, but also pyrrole or indole. 2-Azetidinoperylenimides of general formula VI,

in which the radicals R ¹ to R ^{9 have} the meaning given under 1 and R ^{10 has} the meaning given by R ¹ under 1. A process characterized in that Azetidinoarylcarbonsäureimide, in particular the substances are synthesized according to 1 to 4 using azetidine, by the action of azetidine as a pure substance on Carbonsäureimide or in solution in inert solvents such as chloroform or dichloromethane, preferably in concentrations of 1 molar to pure Azetidine, about 15 molar. A method characterized in that using the substances according to 1 to 4 nucleophilic substrates are labeled optically, using the light absorption or fluorescence, whereby typical nucleophilic substrates may be alcohols, alcoholates, phenols, phenolates, thiols, thiolates, thiophenols, thiophenolates, in particular under the action of catalysts, or else C-nucleophiles such as organometallic reagents, such as, for example, zinc organyls, or else the anions CH-acid compounds, for example acetoacetic esters, malonic esters, acetylacetone, benzyl cyanides, cyclopentadiene or else 2- or 4-picoline. Use of the substances according to 1 to 4 as a frequency converter in optical information collecting, information processing and forwarding systems, in particular in optical light guides, preferably in fast optical systems Use of the substances according to 1 to 4 as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as e.g. for glues and related colors such as watercolors and watercolors and inks for inkjet printers, paper inks, printing inks, inks and inks and other inks for painting and writing and in paints, as pigments in paints, the preferred paints are synthetic resin paints such as acrylic paints. or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or also natural substances such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples being materials of polyvinyl chloride, polyvinylidene chloride , Polyacrylic acid, polyacrylamide, polyvinyl butyral, polyvinyl pyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate, polyacrylnit ril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such as the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, e.g. for coloring natural products, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as colorants, e.g. for coloring paints, lacquers and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, particularly luminous shades are preferred. Use of the substances according to 1 to 4 for marking, security and display purposes, in particular taking into account their fluorescence, such as dyes or fluorescent dyes for signal colors, preferably for visual highlighting lettering and drawings or other graphic products, for marking signs and others Objects and in display elements for many display, hint and marking purposes, in which a particular optical color impression is to be achieved, for passive display elements, traffic signs, such as traffic lights for security marking purposes, where appropriate, the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents, identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via fluorescence, machine recognition of objects for sorting, eg also for the recycling of plastics, as fluorescent dyes for machine-readable markings, preferred are alphanumeric imprints or barcodes, as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or Bildwandl ersystemen, in which the excitation by electrons, ions or UV radiation takes place, for example in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, for example in biochemistry, medicine, technology and science, here, the dyes can be covalently linked to substrates or via secondary valences such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, for example in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection methods and as a material for leak testing of closed systems. Use of the dyes of 1 to 4 as functional materials, e.g. in data memories, preferably in optical memories, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: e.g. for dry copying systems (Xerox process) and laser printers ("non-impact printing"), for the frequency conversion of light, e.g. to make shortwave light of longer wavelength visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collecting systems, e.g. the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, e.g. in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit containing dyes as such or in combination with other semiconductors e.g. in the form of epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as Q-switch switches and as active substances for non-linear optics, e.g. for frequency doubling and frequency tripling of laser light.

Images