DE102011018815A1 - New Substituted terrylene diimide compounds useful e.g. as energy donor groups in bi- and multichromophoric compounds for achieving broadband light absorption and as pigments and dyes for dyeing purposes and decorative and artistic purposes - Google Patents
New Substituted terrylene diimide compounds useful e.g. as energy donor groups in bi- and multichromophoric compounds for achieving broadband light absorption and as pigments and dyes for dyeing purposes and decorative and artistic purposes Download PDFInfo
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- DE102011018815A1 DE102011018815A1 DE102011018815A DE102011018815A DE102011018815A1 DE 102011018815 A1 DE102011018815 A1 DE 102011018815A1 DE 102011018815 A DE102011018815 A DE 102011018815A DE 102011018815 A DE102011018815 A DE 102011018815A DE 102011018815 A1 DE102011018815 A1 DE 102011018815A1
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- -1 terrylene diimide compounds Chemical class 0.000 title claims abstract description 26
- 239000000975 dye Substances 0.000 title claims description 35
- 239000000049 pigment Substances 0.000 title claims description 7
- 238000004043 dyeing Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 title claims description 3
- 230000031700 light absorption Effects 0.000 title claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
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- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
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Abstract
Substituted terrylene diimide compounds (I), preferably 7,22-bis(tridecan-7-yl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIa) (preferred) or 7,22-bis(4-amino-2,3,5,6-tetramethylphenyl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIb), are new. Substituted terrylene diimide compounds of formula (I), preferably 7,22-bis(tridecan-7-yl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIa) (preferred) or 7,22-bis(4-amino-2,3,5,6-tetramethylphenyl)-7,22-diazadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIb), are new. Either R1-R12 : at least 1-not > 37C linear alkyl (in which 1-10 CH 2groups may be replaced by T, and up to 12 individual H of CH 2groups at same C may be replaced by F, Cl, Br, I, CN or up to 18C linear alkyl (in which 1-6 CH 2groups may be replaced by T, and up to 12 H of CH 2groups of alkyl at same C may be replaced by F, Cl, Br, I, CN, or up to 18C linear alkyl (in which 1-6 CH 2groups may be replaced by T))) or H, where instead of carrying substituents the free valences of the methine groups or the quaternary carbon atoms are linked in pairs to form rings e.g. cyclohexane; or R1-R9 : F, Cl, Br or I; and T : C=O, O, S, Se, Te, cis- or trans-CH=CH- (in which 1 CH unit may be replaced by N), acetylenic CC, phenyl (1,2-, 1,3- or 1,4-disubstituted), pyridinyl (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted), thiophenyl (2,3-, 2,4-, 2,5- or 3,4-disubstituted), naphthalenyl (1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted and 1 or 2 CH groups may be replaced by N), anthracenyl (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 and 1 or 2 CH groups may be replaced by N). Independent claims are also included for: (1) terrylene tetracarboxylic acid bis-anhydride compounds of formula (II), preferably 7,22-dioxadecacyclo[14.14.2.2(2,5).2(17,20).0(3,12).0(4,9).0(13,31).0(18,27).0(19,24).0(28,32)]hexatriaconta-1(31),2,4,9,11,13,15,17,19,24,26,28(32),29,33,35-pentadecaene-6,8,21,23-tetrone (IIc); (2) preparing (I); (3) preparing (II), comprising reacting (I) with potassium hydroxide in tert-butyl alcohol under harsh reaction conditions, preferably at elevated temperature e.g. the boiling temperature of the reaction solution, preferably 80[deg] C, and for longer time, preferably 12 hours, or reacting (I) with acetic acid at elevated temperatures, preferably boiling temperature of the reaction solution, preferably 90[deg] C and for longer time, preferably 12 hours; and (4) preparing (IIa), comprises condensing (II), preferably (IIc) with primary amines in alkaline media, preferably imidazole (preferred) or quinoline, using condensation auxiliaries e.g. metal salts, preferably zinc acetate (preferred) or lead acetate. [Image] [Image].
Description
Stand der TechnikState of the art
Terrylentetracarbonsäurebisimide [1] erlangen ein zunehmendes Interesse in der Technik, da sie blaue Lösungen bilden, die im langwellig sichtbaren Bereich absorbieren und langwellig rot fluoreszieren. Die inherente Schwerlöslichkeit des chromophoren Systems stellt dabei ein erhebliches Probem dar, da sie die Verwendung des einfachen Tetracarbonsäurebisimids in homogener Lösung verhindert. Eine Lösung des Problems besteht in der Einfürung von löslichkeitssteigernden Gruppen in Substituenten an den Stickstoffatomen, die bisher jedoch nicht zu einem optimalen Ergebnis geführt haben. Zum einen sind hier 2,6-Di-iso-propylphenylreste eingeführt worden, die eine deutliche Löslichkeitssteigerung ergaben, aber tertiäre benzylische Wasserstoffatome tragen, die zu Radikalreaktionen neigen; vgl. den technischen Hock-Prozess zur Darstellung von Phenol und Aceton aus Isopropylbenzol (Cumol). Zum anderen ergaben einen erheblichen Löslichkeitssteigernden Effekt langkettig sec-Alkylreste (Schwalbenschwanzreste) [2], von denen das 1-Octylnonyl- und das 1-Heptyloctyl-System beschrieben worden sind [3]. Bei diesen Derivaten ist einen kräftige Löslichkeitssteigerung erzielt worden, so dass dieses Ziel zunächst erreicht worden ist. Von Standpunkt der Synthesechemie sind allerdings diese Derivate nicht optimal, denn die langen Alkylreste führen zu Substanzen mit mäßig ausgebildeten Kristallgittern und dadurch einer mehr wachsartigen Konsistenz, die die Reinigung und Handhabung erschwert. Außerdem nehmen die Alkyreste einen erhbliche Anteil am Gesamtmolekulargewicht der Substanzen ein, funktional ist aber nur der Chromophor-Anteil. Zudem sind die bisher als Ausgangsmaterial eingesetzten Amine mit den langkettig sec-Alkylresten nur unter erheblichem Syntheseaufwand mit hoher Reinheit darstellbar. Eine allgemeine Verbesserung der Situation würde hier einen erheblichen Fortschritt bringen.Terrylenetetracarboxylic bisimides [1] are gaining increasing interest in the art because they form blue solutions which absorb in the long wavelength visible region and fluoresce long-wavelength red. The inherent poor solubility of the chromophoric system is a considerable problem because it prevents the use of the simple Tetracarbonsäurebisimids in homogeneous solution. A solution to the problem is the introduction of solubility enhancing groups into substituents on the nitrogen atoms which have not yet yielded optimal results. On the one hand here 2,6-di-iso-propylphenyl residues have been introduced, which gave a significant increase in solubility, but carry tertiary benzylic hydrogen atoms, which tend to radical reactions; see. the technical Hock process for the preparation of phenol and acetone from isopropylbenzene (cumene). On the other hand, a considerable solubility-enhancing effect resulted in long-chain sec-alkyl residues (dovetail residues) [2], of which the 1-octylnonyl and 1-heptyloctyl systems have been described [3]. In these derivatives, a strong solubility increase has been achieved, so that this goal has been achieved first. From the point of view of synthetic chemistry, however, these derivatives are not optimal, because the long alkyl radicals lead to substances with moderately formed crystal lattices and thus a more waxy consistency, which makes cleaning and handling more difficult. In addition, the alkyl radicals occupy a significant proportion of the total molecular weight of the substances, but only the chromophore content is functional. In addition, the amines used hitherto as starting material with the long-chain sec-alkyl radicals can be prepared only with considerable expenditure of synthesis with high purity. A general improvement in the situation would bring significant progress here.
Aufgabenstellungtask
Die Aufgabe der vorliegenden Erfindung war es, Terrylentetracarbonsärebisimide zu entwickeln, die zwar eine genügende Löslichkeit für Anwendungen in homogener Lösung aufweisen, deren Herstellung und Handhabung aber vereinfacht ist. Außerdem soll der Chromophoranteil der Substanzen möglichst hoch sein.The object of the present invention was to develop terrylenetetracarboxylic bisimides which, while having sufficient solubility for homogeneous solution applications, are simplified in their preparation and handling. In addition, the chromophore content of the substances should be as high as possible.
Beschreibungdescription
Wir haben uns als Ziel gesetzt, die Alkylketten an den Stickstoffatomen der Terrylentetracarbonsäurebisimide so weit zu verkürzen, dass die Löslichkeit der Substanzen noch genügend hoch ist, aber eine Handhabung der Substanzen und ihrer Vorstufen erleichtert wird. Als Ziel haben wir uns zunächst den 1-Hexylheptyl-Rest gesetzt (Verbindung 1) und hierfür das für die Reindarstellung gut geeignets 1-Hexylheptylamin mit dem Napthalin-1,8-dicarbonsäureanhydrid zu 3 kondensiert und dann mit dem N-1-Hexylheptyperylen-3,4-dicarbonsäureimid 2 [4] nach Sakamoto [5] mit Kalium-tert-butylat und DBN umgesetzt; siehe
Die gute präparative Zugänglichkeit von 1 macht dieses als Ausgangsmaterial für andere Terrylentetracarbonsäurebisimide interessant. Eine Schlüsselsubstanz ist hierfür das Terrylentetracarbonsäurebisanhydrid 4, dessen Darstellung aus 1 allerdings die Hydrolysestabilität des letzeren im Wege steht. Wird jedoch 1 unter rauen Reaktionsbedingungen mit KOH in tert-Butylakohol [6] umgesetzt und dann in Anlehnung an Ref. [4] mit Essigsäure aufgearbeitet, dann erhält man das Bisanhydrid 4 in erstaunlich glatter Reaktion in überraschend hoher chemischer Ausbeute von 98%. Der fördernde Zusatz von Essigsäure beruht möglicherweise auf einer Hydrolyse eines Intermediats.The good preparative accessibility of 1 makes it interesting as starting material for other terrylenetetracarboxylic bisimides. A key substance for this is the Terrylentetracarbonsäurebisanhydrid 4, the representation of 1, however, the hydrolytic stability of the latter is in the way. Will, however, 1 under reacted with KOH in tert-butyl alcohol [6] and then worked up in accordance with Ref. [4] with acetic acid, then the bisanhydride 4 is obtained in an astonishingly smooth reaction in a surprisingly high chemical yield of 98%. The promoting addition of acetic acid may be due to hydrolysis of an intermediate.
Das Bisanhydrid 4 ist zwar ausgesprochen schwerlöslich, es kann aber mit primären Aminen in an und für sich von anderen peri-Anhydriden her bekannter Weise [7] zu neuen Terrylenbisimiden kondensiert werden, wie z. B. mit 2,3,5,6-Tetramethylphenylen-1,4-diamin beispielsweise in Imidazol unter Verwendung von beispielsweise Zinkacetat zu 5, das wie 1 blau ist.Although the bisanhydride 4 is extremely poorly soluble, but it can be condensed with primary amines in per se known from other peri-anhydrides ago manner [7] to new Terrylenbisimiden, such. Example, with 2,3,5,6-tetramethylphenylene-1,4-diamine, for example in imidazole using, for example, zinc acetate to 5, which is blue as 1.
Das nach dem verbesserten Verfahren gewonnene, reine N,N'-Bis-(1-hexylheptyl)terrylentetracarbonsäurebisanhydrid (1, „S-13-Terrylenbisimid”) ist in lipophilen Lösungsmitteln wie Chloroform erstaunlich gut löslich und weist eine verhältnismäßig kleine Aggregationstandenz auf. Es kann daher zur Überraschung bei der ganz überwiegenden Zahl von Anwendungen äquivalent zu den bisher bekannten höheren Homologen mit 1-Octylnonyl- und 1-Heptyloctylresten an den Stickstoffatomen eingesetzt werden und diese dadurch ersetzen. Die Kristallisiationstendenz von 1 ist allerdings wesentlich höher als bei den genannten Homologen, so dass die Reindarstellung der Substanz erheblich effizienter und mit kleinerem präparativem Aufwand erfolgen kann – es wurde ein hoher molarer Extinktionskoeffizient von 130300 erzielt –; vorteilhaft ist hier ebenfalls die effizientere Reinigungsmöglichkeit der Vorstufen mit 1-Hexylheptyl-Resten. Die verhältnismäßig hohe Fluoreszenzquantenausbeute von 1 – es wurden 94% im Vergleich zu dem als Fluoreszenzstandard angegebenen Derivat S-13 (siehe exp. Teil) gefunden – ist für Fluoreszenzanwendungen im langwellig sichtbaren und NIR-Bereich von Interesse. Die hohe Lichtechtheit der Substanz und starke Fluoreszenz ermöglicht nicht nur ihre Verwendung für vielerlei Fluoreszenzanwendungen, wie z. B. als Referenzmaterial [8] oder für Fluoreszenzmarkierungen, sondern darüber hinaus sogar für Anwendungen zur Gewinnung von Solarenergie, wie z. B. unter Verwendung des der Fluoreszenz-Solarkollektors [9] und auch für Laser-Anwendungen. Die Substanz ist ebenfalls als Sensibilisator für photovoltaische Zellen und in organischen Leuchtdioden (OLED) von Interesse. Sie kann sogar in organischen Photovoltaik-Zellen oder in Hybrid-Photovoltaik-Zellen, wie z. B. der Grätzel-Zelle verwendet werden.The pure N, N'-bis (1-hexylheptyl) terrylenetetracarboxylic bisanhydride (1, "S-13-terrylenebisimide", obtained according to the improved process, is surprisingly readily soluble in lipophilic solvents such as chloroform and has a relatively low aggregation stability. It can therefore be used to the surprise in the vast majority of applications equivalent to the previously known higher homologues with 1-octylnonyl and 1-Heptyloctylresten to the nitrogen atoms and replace them. The crystallization tendency of 1, however, is much higher than in the homologues mentioned, so that the purification of the substance can be done much more efficiently and with less preparative effort - it was achieved a high molar extinction coefficient of 130300 -; advantageous here is also the more efficient cleaning ability of the precursors with 1-hexylheptyl residues. The relatively high fluorescence quantum yield of 1 - 94% compared to the fluorescence standard derivative S-13 (see exp. Part) - is of interest for long wavelength visible and NIR fluorescence applications. The high light fastness of the substance and strong fluorescence not only allows its use for many fluorescence applications, such. As a reference material [8] or for fluorescent labels, but beyond even for solar energy applications such. Using the fluorescence solar collector [9] and also for laser applications. The substance is also of interest as a sensitizer for photovoltaic cells and in organic light emitting diodes (OLEDs). It can even be used in organic photovoltaic cells or in hybrid photovoltaic cells, such as. B. the Grätzel cell can be used.
Schlussfolgerungconclusion
Die einfache und effiziente Darstellung von reinem 1 nach der hier beschriebenen Methode macht die bisher als Reinsubstanzen nur kompliziert und schwierig zugänglichen Terrylentetracarbonsäurebisimide zu gut zugänglichen Fluoreszenzmaterialien für vielerlei Anwendungen im langwelligen Spektralbereich. Die weitere Umsetzung von 1 zum Terrylen-3,4:11,12-tetracarbonsäurebisanhydrid (4) stellt die Synthese eines Schlüsselbausteins für die Terrylenbisimide und allgemein für Terrylenderivate dar.The simple and efficient representation of pure 1 according to the method described here makes the Terrylene tetracarboxylic acid bisimides, which have hitherto been complicated only as pure substances and difficult to access, to readily available fluorescent materials for many applications in the long-wave spectral range. The further reaction of 1 to the terrylene-3,4: 11,12-tetracarboxylic bisanhydride (4) represents the synthesis of a key building block for the terrylene bisimides and in general for terrylene derivatives.
Experimenteller TeilExperimental part
Allgemeines. IR-Spektren: Perkin Elmer 1420 Ratio Recording Infrared Spektrometer, FT 1000; UV/Vis-Spektren: Varian Cary 5000 und Bruins Omega 20; Fluoreszenzspektren: Varian Eclispe; NMR-Spektroskopie: Varian Vnmrs 600 (600 MHz); Massenspektrometrie: Finnigan MAT 95. S-13 steht für N,N'-Bis(1-hexylheptyl)perylen-3,4:9,10-tetracarbonsäurebisimid.General. IR Spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000; UV / Vis spectra: Varian Cary 5000 and Bruins Omega 20; Fluorescence spectra: Varian Eclispe; NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95. S-13 is N, N'-bis (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide.
Fluoreszenzquantenausbeuten wurden analog zu Ref. [10] bestimmt.Fluorescence quantum yields were determined analogously to Ref. [10].
2,11-Bis(1-hexylheptyl)benzo[13,14]pentapheno[3,4,5-def:10,9,8-d'e'f']diisochinolin-1,3,10,12(2H,11H)-tetraon (1, „S-13-Terrylenbisimid”):2,11-bis (1-hexylheptyl) -benzo [13,14] pentapheno [3,4,5-def: 10,9,8-d'e'f '] diisoquinoline-1,3,10,12 (2H , 11H) -tetraone (1, "S-13-Terrylenebisimide"):
Unter Luft- und Feuchtigkeitsausschluss (Ar-Schutzgas) wurden Kalium-tert-butylat (634 mg, 5.65 mmol), Diazabicyclo[4.3.0.]non-5-en (DBN. 946 mg, 7.62 mmol) in destilliertem Toluol (10 mL) vorgelegt, 15 min bei 120°C gerührt, unter Luft- und Feuchtigkeitsausschluss mit 2-(1-Hexylheptyl)benzo[de]isochinolin-1,3-dion (850 mg, 2.24 mmol) und 2-(1-Hexylheptyl)-1H-benzo[5,10]anthra[2,1,9-def]isochinolin-1,3(2H)-dion (640 mg, 1.27 mmol) in 8 mL wasser- und sauerstofffreiem, destilliertem Toluol gelöst innerhalb von 10 min versetzt (sofortige Dunkelblaufärbung), weitere 2 h bei 120°C gerührt, durch Zugabe von 2 M Salzsäure (50 mL) gefällt, über eine D4-Glasfritte abgesaugt, mit 2 M Salzsäure und destilliertem Wasser gewaschen, 16 h bei 110°C im Trockenschrank getrocknet und säulenchromatographisch gereinigt (Kieselgel, Chloroform). Ausb. 598 mg (54%) blauer Feststoff, Schmp. > 300°C. Rf (Kieselgel, Chloroform): 0.35. IR (ATR): v ~ = 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s), 1505 (w), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m), 1205 (m), 1172 (w), 1144 (w), 1104 (w), 1022 (w), 954 (w), 852 (w), 840 (w), 806 (s), 790 (m), 748 (m), 723 (w), 693 (w), 680 (m), 667 cm–1 (w). 1H-NMR (600 MHz, CDCl3, 25°C, TMS): δ = 0.84 (t, 3J(H,H) = 7.0 Hz, 12 H, 4 × CH3), 1.20-1.42 (m, 32H, 16 × CH2), 1.88-1.94 (m, 4H, β-CH2), 2.24-2.32 (m, 4 H, β-CH2), 5.18-5.25 (m, 2H, NCH), 8.38-8.46 (m, 8H, CHTerrylen), 8.54-8.63 (m, 4 H, CHTerrylen). 13C-NMR (150 MHz, CDCl3, 25°C, TMS): δ = 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.6, 121.3, 121.7, 122.5, 124.1, 125.9, 128.5, 129.7, 130.8, 131.0, 131.8, 135.3, 163.8, 164.8 ppm. UV/VIS (CHCl3): λmax(ε) = 555.2 (21800), 598.9 (66900), 651.8 (130300). Fluoreszenz (CHCl3): λmax (I) 666.2 (1.00), 731.7 (0.47). Fluoreszenzquantenausb. (CHCl3, λexc = 599 nm, E599 nm, 1 cm = 0.01360, Referenz: S-13 mit 0 = 1.00): 0.94. MS (DEP/EI) m/z (%): 880 (20) [M+ + 2H], 879 (35) [M+ + H], 878 (72) [M+], 701 (32), 698 (64), 696 (100), 85 (46), 83 (59), 67 (26), 57 (32), 55 (48), 44 (73), 43 (30), 41 (51). HRMS (C60H66N2O4): Ber. 878.5023; Gef. 878.5012, Δ = +0.0011. C60H66N2O4 (878.5) Ber. C 81.97, H 7.57, N 3.19; Gef. C 81.68, H 7.50, N 3.14.With exclusion of air and moisture (Ar protective gas), potassium tert-butoxide (634 mg, 5.65 mmol), diazabicyclo [4.3.0.] Non-5-ene (DBN: 946 mg, 7.62 mmol) in distilled toluene (10 mL), stirred for 15 min at 120 ° C, with exclusion of air and moisture with 2- (1-hexylheptyl) benzo [de] isoquinoline-1,3-dione (850 mg, 2.24 mmol) and 2- (1-hexylheptyl ) -1H-benzo [5,10] anthra [2,1,9-def] isoquinoline-1,3 (2H) -dione (640 mg, 1.27 mmol) dissolved in 8 mL of distilled toluene dissolved in water and oxygen over 10 min (immediate dark blue coloration), stirred for a further 2 h at 120 ° C., precipitated by addition of 2 M hydrochloric acid (50 mL), via a D4 Glass frit filtered off, washed with 2 M hydrochloric acid and distilled water, dried for 16 h at 110 ° C in a drying oven and purified by column chromatography (silica gel, chloroform). Y. 598 mg (54%) of blue solid, mp> 300 ° C. R f (silica gel, chloroform): 0.35. IR (ATR): v ~ = 2952 (m), 2919 (s), 2850 (m), 2361 (w), 1691 (s), 1649 (s), 1583 (s), 1572 (s), 1505 ( w), 1456 (m), 1418 (w), 1350 (s), 1323 (s), 1302 (m), 1248 (m), 1205 (m), 1172 (w), 1144 (w), 1104 ( w), 1022 (w), 954 (w), 852 (w), 840 (w), 806 (s), 790 (m), 748 (m), 723 (w), 693 (w), 680 ( m), 667 cm -1 (w). 1 H NMR (600 MHz, CDCl 3 , 25 ° C, TMS): δ = 0.84 (t, 3 J (H, H) = 7.0 Hz, 12 H, 4 x CH 3 ), 1.20-1.42 (m, 32H, 16 x CH2), 1.88-1.94 (m, 4H, β-CH 2), 2:24 to 2:32 (m, 4 H, β-CH 2), 5:18 to 5:25 (m, 2H, NCH), 8.38- 8.46 (m, 8H, CH terrylene ), 8.54-8.63 (m, 4H , CH terrylene ). 13 C-NMR (150 MHz, CDCl 3, 25 ° C, TMS): δ = 14.1, 22.6, 27.0, 29.3, 31.8, 32.4, 54.6, 121.3, 121.7, 122.5, 124.1, 125.9, 128.5, 129.7, 130.8, 131.0, 131.8, 135.3, 163.8, 164.8 ppm. UV / VIS (CHCl 3): λ max (ε) = 555.2 (21800), 598.9 (66900) 651.8 (130300). Fluorescence (CHCl 3 ): λ max (I) 666.2 (1.00), 731.7 (0.47). Fluoreszenzquantenausb. (CHCl 3 , λ exc = 599 nm, E 599 nm, 1 cm = 0.01360, reference: S-13 with 0 = 1.00): 0.94. MS (DEP / EI) m / z (%): 880 (20) [M + + 2H], 879 (35) [M + + H], 878 (72) [M + ], 701 (32), 698 (64), 696 (100), 85 (46), 83 (59), 67 (26), 57 (32), 55 (48), 44 (73), 43 (30), 41 (51). HRMS (C 60 H 66 N 2 O 4 ): Ber. 878.5023; Gef. 878.5012, Δ = +0.0011. C 60 H 66 N 2 O 4 (878.5) Ber. C 81.97, H 7.57, N 3.19; C 81.68, H 7.50, N 3.14.
Terrylen-3,4:11,12-tetracarbonsäurebisanhydrid:Terylene-3,4: 11,12-tetracarboxylic:
2,11-Bis(1-hexylheptyl)-benzo[13,14]pentapheno[3,4,5-def:10,9,8-d'e'f']diisochinolin-1,3,10,12(2H,11H)-tetraon (460 mg, 0.523 mmol), Kaliumhydroxid (85%, 1.17 g, 17.7 mmol) wurden in tert-Butanol (50 mL) 12 h bei 80°C gerührt, mit Essigsäure (50 gew.-%, 30 mL) versetzt, weitere 4 h bei 90°C gerührt, durch die Zugabe von destilliertem Wasser (100 mL) gefällt, noch heiß über eine D4-Glasfritte abgesaugt, mehrmals sorgfältig mit destilliertem Wasser und im Anschluss mit Methanol gewaschen und getrocknet. Ausb. 265 mg (98%) bronzefarbener Feststoff, Schmp. > 300°C. Rf (Kieselgel, Chloroform): 0.00. IR (ATR): v ~ = 1753.1 (s), 1719.1 (s), 1571.8 (s), 1504.5 (m) 1396.2 (w), 1373.6 (s), 1348.2 (s), 1288.7 (vs), 1210.7 (s), 1128.7 (vs), 1012.9 (s), 935.7 (m), 888.8 (w), 844.6 (m), 807.5 (vs), 789.7 (s), 687.9 (s), 665.7 (w) cm–1. MS (DEP/EI) m/z (%): 516 (34) [M+], 372 (18), 111 (18), 105 (26), 97 (39), 91 (43), 83 (53), 70 (41), 67 (44), 57 (51), 55 (100), 41 (97). HRMS (C34H12O6): Ber. 516.0634; Gef. 516.0619, Δ = +0.0015.
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[1] (a) D. Desilets, P. M. Kazmaier and R. A. Burt, Can. J. Chem., 1995, 73, 319–324. (b) M. Wehmeier, M. Wagner and K. Mullen, Chem. Eur. J., 2001, 7, 2197–2205. (c) M. Adachi and Y. Nagao, Chem. Mater., 2001, 13, 662–669. (d) F. O. Holtrup, R. R. J. Mueller, H. Quante, S. De Feyter, F. C. De Schryver and K. Muellen, Chem. Eur., J. 1997, 3, 219–225. (e) F. Nolde, J. Qu, C. Kohl, N. G. Pschirer, E. Reuter and K. Müllen, Chem. Eur. J., 2005, 11, 3959–3967. -
[2] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733–748. -
[3] H. Langhals, S. Poxleitner, Eur. J. Org. Chem. 2008, 797–800. -
[4] L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229–1244. -
[5] (a) T. Sakamoto, C. Pac, J. Org. Chem., 2001, 66, 94–98. (b) H. Langhals, J. Buttner and P. Blanke, Synthesis, 2005, 364–366. -
[6] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529–535. -
[7] (a) H. Langhals, Heterocycles 1995, 40, 477–500. (b) H. Langhals, Helv. Chim. Acta. 2005, 88, 1309–1343. (c) H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51–63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4. -
[8] H. Langhals, A. Walter, E. Rosenbaum, L. B.-Å. Johansson, Phys. Chem. Chem. Phys. 2011, DOI: 10.1039/c1cp20467j -
[9] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716–718, Chem. Abstr. 1981, 95, R9816q. -
[10] H. Langhals, J. Karolin, L. B.-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919–2922.
-
[1] (a) D. Desilets, PM Kazmaier and RA Burt, Can. J. Chem., 1995, 73, 319-324. (b) M. Wehmeier, M. Wagner and K. Mullen, Chem. Eur. J., 2001, 7, 2197-2205. (c) M. Adachi and Y. Nagao, Chem. Mater., 2001, 13, 662-669. (d) FO Holtrup, RRJ Mueller, H. Quante, S. De Feyter, DeSchryver FC and K. Muellen, Chem. Eur., J. 1997, 3, 219-225. (e) F. Nolde, J. Qu, C. Kohl, NG Pschirer, E. Reuter and K. Müllen, Chem. Eur. J., 2005, 11, 3959-3967. -
[2] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748. -
[3] H. Langhals, S. Poxleitner, Eur. J. Org. Chem. 2008, 797-800. -
[4] L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244. -
[5] (a) T. Sakamoto, C. Pac, J. Org. Chem., 2001, 66, 94-98. (b) H. Langhals, J. Buttner and P. Blanke, Synthesis, 2005, 364-366. -
[6] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535. -
[7] (a) H. Langhals, Heterocycles 1995, 40, 477-500. (b) H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343. (c) H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4. -
[8] H. Langhals, A. Walter, E. Rosenbaum, LB-Å. Johansson, Phys. Chem. Chem. Phys. 2011, DOI: 10.1039 / c1cp20467j -
[9] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q. -
[10] H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.
Gegenstand der ErfindungSubject of the invention
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a. Terrylenbisimide der allgemeinen Formel 6, in denen die Reste R1 bis R12 gleich oder verschieden voneinander sein können und unabhängig voneinander Wasserstoff oder lineare Alkylreste mit mindestens einem und höchstens 37 C-Atome bedeuten, bei denen eine bis 10 CH2-Enheiten unabhängig voneinander ersetzt sein können durch jeweils Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen 1,2-, 1,3- oder 1,4-substituierten Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei CH-Gruppen durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH2-Gruppen können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder die Cyanogruppe oder eine lineare Alkylkette mit bis zu 18 C-Atomen, bei der eine bis 6 CH2-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei denen eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen, 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierter Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Bis zu 12 einzelne Wasserstoffatome der CH2-Gruppen der Alkylreste können jeweils unabhängig voneinander auch an gleichen C-Atomen ersetzt sein durch die Halogene Fluor, Chlor, Brom oder Iod oder Cyanogruppen oder lineare Alkylketten mit bis zu 18 C-Atomen, bei denen eine bis 6 CH2-Einheiten unabhängig voneinander ersetzt sein können durch Carbonylgruppen, Sauerstoffatome, Schwefelatome, Selenatome, Telluratome, cis- oder trans-CH=CH-Gruppen, bei der eine CH-Einheit auch durch ein Stickstoffatom ersetzt sein kann, acetylenische C≡C-Gruppen 1,2-, 1,3- oder 1,4-substituierte Phenylreste, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-disubstituierte Pyridinreste, 2,3-, 2,4-, 2,5- oder 3,4-disubstituierte Thiophenreste, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- oder 2,7-disubstituierte Naphthalinreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können, 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- oder 9,10-disubstituierte Anthracenreste, bei denen ein oder zwei Kohlenstoffatome durch Stickstoffatome ersetzt sein können. Statt Substituenten zu tragen können die freien Valenzen der Methingruppen bzw. der quartären C-Atome paarweise verknüpft werden, so dass Ringe entstehen, wie z. B. Cyclohexanringe. Die Reste R1 bis R9 können außerdem unabhängig voneinander die Halogenatome F, Cl, Br oder I bedeuten.Insbesondere die Terrylenbisimide 1 und 5 und von diesen bevorzugt das Terrylenbisimid 1.a. Terrylenbisimide of the general formula 6,in which the radicals R 1 to R 12 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-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-dis substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH 2 groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH 2 units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups are 1,2-, 1,3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted Pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1 , 7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2, 9, 2, 10 or 9, 10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R 1 to R 9 may also independently of one another denote the halogen atoms F, Cl, Br or I.In particular, the terrylenbisimides 1 and 5 and of these preferred the Terrylenbisimid 1.
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b. Terrylentetracarbonsäurebisanhydride der allgemeinen Formel 7, in denen die Reste R1 bis R12 die unter a angegebene Bedeutung haben.Insbesondere das Terrylen-3,4:11,12-tereacarbonsäurebisanhydrid (4).b. Terrylentetracarbonsäurebisanhydride of the general formula 7,in which the radicals R 1 to R 12 have the meaning given under a.Specifically, the terrylene 3,4: 11,12-tereacarboxylic bisanhydride (4).
- c. Verfahren dadurch gekennzeichnet, dass die Perylenderivate nach a aus Perylendicarbonsäureimiden und Naphthalindicarbonsäureimiden in einer Kreuzkupplung in stark basischem Medium synthetisiert werden, insbesondere nach der Sakamoto-Methode unter Verwendung von Kalium-tert-butylat und DBN, insbesondere unter Ausschluß von Sauerstoff und Feuchtigkeit, und hier bevorzugt unter Verwendung des Lösungsmittels Toluol.c. A process characterized in that the perylene derivatives are synthesized according to a from Perylendicarbonsäureimiden and Naphthalindicarbonsäureimiden in a cross-coupling in strongly basic medium, in particular according to the Sakamoto method using potassium tert-butoxide and DBN, in particular with the exclusion of oxygen and moisture, and here preferably using the solvent toluene.
- d. Verfahren dadurch gekennzeichnet, dass die Farbstoffe nach b aus den Substanzen nach a durch die Umsetzung mit Kaliumhydroxid in tert-Butylalkohol unter rauen Reaktionsbedingungen dargestellt werden, insbesondere bei erhöhter Temperatur wie der Siedetemperatur der Reaktionslösung, und bei einer längeren Reaktionszeit, wie z. B. 12 h und 80°C.d. A process characterized in that the dyes are represented by b from the substances according to a by reaction with potassium hydroxide in tert-butyl alcohol under harsh reaction conditions, especially at elevated temperature such as the boiling temperature of the reaction solution, and at a longer reaction time, such. For example 12 h and 80 ° C.
- e. Verfahren dadurch gekennzeichnet, dass die Farbstoffe nach b unter Verwendung von Essigsäure hergestellt werden, insbesondere bei erhöhter Temperatur, wie der Siedetemperatur der Reaktionslösung, und bei einer längeren Reaktionszeit, wie z. B. 12 h und 90°C.e. A process characterized in that the dyes are prepared according to b using acetic acid, in particular at elevated temperature, such as the boiling temperature of the reaction solution, and at a longer reaction time, such as. B. 12 h and 90 ° C.
- f. Verfahren dadurch gekennzeichnet, dass Terrylentetracarbonsäurebisimide aus den Anhydriden 7, insbesondere aus dem Anhydrid 4 durch Kondensation mit primären Aminen dargestellt werden, insbesondere in basischen Medien, und hier bevorzugt Imidazol oder Chinolin, von denen besonders Imidazol bevorzugt wird, und auch unter Verwendung von Kondensationshilfsmitteln, wie Schwermetallsalze, wie z. B. Zinkacetat oder Bleiacetat, von denen Zinkacetat bevorzugt wird.f. Process characterized in that terrylenetetracarboxylic acid bisimides are prepared from the anhydrides 7, in particular from the anhydride 4 by condensation with primary amines, especially in basic media, and here preferably imidazole or quinoline, of which imidazole is particularly preferred, and also with the use of condensation auxiliaries, such as heavy metal salts, such as. As zinc acetate or lead acetate, of which zinc acetate is preferred.
- g. Verwendung der Substanzen nach a bis b als Energiedonorgruppen in bi- und multichromophoren Verbindungen, so z. B. zum Erzielen einer breitbandigen Lichtabsorption beispielsweise in Fluoreszenzfarbstoffen oder in Systemen zur lichtbetriebenen Ladungstrennung, so z. B. in Bichromophoren mit Perylen-3,4:9,10-tetracarbonsäurebisimid-Derivaten oder Corrol-Derivaten.G. Use of the substances according to a to b as energy donor groups in bi- and multichromophoric compounds, such. B. for achieving a broadband light absorption, for example, in fluorescent dyes or in systems for light-driven charge separation, such. B. in Bichromophoren with perylene-3,4: 9,10-tetracarbonsäurebisimid derivatives or corrole derivatives.
- h. Verwendung der Substanzen nach a bis b als Pigmente und Farbmittel für Färbezwecke, auch für dekorative und künstlerische Zwecke, so wie z. B. für Leimfarben und verwandten Farben wie Aquarell-Farben und Wasserfarben und Farben für Tintenstrahldrucker Papierfarben, Druckfarben, Tinten und Tuschen und andere Farben für Mal- und Schreib-Zwecke und in Anstrichstoffen, als Pigmente in Lacken, bevorzugte Lacke sind Kunstharz Lacke wie Acryl- oder Vinyl-Harze, Polyesterlacke, Novolacke, Nitrocellulose-Lacke (Nitrolacke) oder auch Naturstoffe wie Zapolack, Schellack oder Qi-Lack (Japanlack bzw. Chinalack oderostasiatischer Lack), zur Masse-Färbung von Polymeren, Beispiele sind Materialien aus Polyvinylchlorid, Polyvinylidenchlorid, Polyacrylsäure, Polyacrylamid, Polyvinylbutyral, Polyvinylpyridin, Celluloseacetat, Nitrocellulose, Polycarbonaten, Polyamiden, Polyurethanen, Polyimiden, Polybenzimidazolen, Melaminharzen, Silikonen wie Polydimethylsiloxan, Polyester, Polyethern, Polystyrol, Polydivinylbenzol, Polyvinyltoluol, Polyvinylbenzylchlorid, Polymethylmethacrylat, Polyethylen, Polypropylen, Polyvinylacetat, Polyacrylnitril, Polyacrolein, Polybutadien, Polychlorbutadien oder Polyisopren bzw. die Copolymeren der genannten Monomeren, zur Färbung von Naturstoffen, beispiele sind Papier, Holz, Stroh, oder natürliche Fasermaterialien wie Wolle, Haare, Tierhaare, Borsten, Baumwolle, Jute, Sisal, Hanf, Flachs oder deren Umwandlungsprodukte wie z. B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon), als Beizenfarbstoffe, z. B. zur Färbung von Naturstoffen, Beispiele sind Papier, Holz, Stroh, oder natürliche Fasermaterialien wie Wolle, Haare, Tierhaare, Borsten, Baumwolle, Jute, Sisal, Hanf, Flachs oder deren Umwandlungsprodukte wie z. B. die Viskosefaser, Nitratseide oder Kupferrayon (Reyon), bevorzugte Salze zum Beizen sind Aluminium-, Chrom- und Eisensalze, als Farbmittel, z. B. zur Färbung von Farben, Lacken und anderen Anstrichsstoffen, Papierfarben, Druckfarben, Tinten und andere Farben für Mal- und Schreib-Zwecke, als Zusatz zu anderen Farben, bei denen eine bestimmte Farbnuance erzielt werden soll, bevorzugt sind besonders leuchtende Farbtöne.H. Use of the substances according to a to b as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, as pigments in paints, preferred paints are synthetic resin paints such as acrylic - or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapol lacquer, shellac or Qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for bulk dyeing of polymers, examples are materials of polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers , Polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzyl chloride, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples being paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As for coloring paints, varnishes and other paints, paper inks, 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, preferred are particularly bright shades.
- i. Verwendung der Substanzen nach a bis b für Markierungs-, Sicherheits- und Anzeigezwecke, insbesondere unter Berücksichtigung ihrer Fluoreszenz, wie z. B. als Farbstoffe oder Fluoreszenzfarbstoffe für Signalfarben, bevorzugt zum optischen Hervorheben von Schriftzügen und Zeichnungen oder anderen graphischen Produkten, zum Kennzeichnen von Schildern und anderen Gegenständen und in Anzeigeelementen für vielerlei Anzeige-, Hinweis- und Markierungszwecke, bei denen ein besonderer optischer Farbeindruck erreicht werden soll, für passive Anzeigeelemente, Hinweis- und Verkehrszeichen, wie Ampeln für Sicherheitsmarkierungs-Zwecke, wobei die große chemische und photochemische Beständigkeit und ggf. auch die Fluoreszenz der Substanzen von Bedeutung ist, bevorzugt ist dies für Schecks, Scheckkarten, Geldscheine, Coupons, Dokumente, Ausweispapiere und dergleichen, bei denen ein besonderer, unverkennbarer Farbeindruck erzielt werden soll, zum Markieren von Gegenständen zum maschinellen Erkennen dieser Gegenstände über die Fluoreszenz, bevorzugt ist die maschinelle Erkennung von Gegenständen zum Sortieren, z. B. auch für das Recycling von Kunststoffen, als Fluoreszenzfarbstoffe für maschinenlesbare Markierungen, bevorzugt sind alphanumerische Aufdrucke oder Barcodes, als Farbstoffe in Tintenstrahldruckern in homogener Lösung, bevorzugt als fluoreszierende Tinte, als Farbstoffe oder Fluoreszenzfarbstoffe in Anzeige-, Beleuchtungs- oder Bildwandlersystemen, bei denen die Anregung durch Elektronen, Ionen oder UV-Strahlung erfolgt, z. B. in Fluoreszenzanzeigen, Brauschen Röhren oder in Leuchtstoffröhren, zu Tracer-Zwecken, z. B. in der Biochemie, Medizin, Technik und Naturwissenschaft, hierbei können die Farbstoffe kovalent mit Substraten verknüpft sein oder über Nebenvalenzen wie Wasserstoffbrückenbindungen oder hydrophobe Wechselwirkungen (Adsorption), als Farbstoffe oder Fluoreszenzfarbstoffe in Chemilumineszenzsystemen, z. B. in Chemilumineszenz-Leuchtstäben, in Lumineszenzimmunoassays oder anderen Lumineszenznachweisverfahren und als Material zur Dichtigkeitsprüfung geschlossener Systeme.i. Use of the substances according to a to b for marking, security and display purposes, in particular taking into account their fluorescence, such. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also 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 the fluorescence, preferably the machine detection of objects for sorting, z. As well as for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for. As in fluorescent displays, shower tubes or in fluorescent tubes, for tracer purposes, eg. As 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 chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems.
- j. Verwendung der Farbstoffe nach a bis b als funktionale Materialien, wie z. B. in Datenspeichern, bevorzugt in optischen Speichern, wie die CD- oder DVD-Platten, in OLEDS (organischen Leuchtdioden), in photovoltaischen Anlagen, als Pigmente in der Elektrophotographie: z. B. für Trockenkopiersysteme (Xerox-Verfahren) und Laserdrucker (”Non-Impact-Printing”), zur Frequenzumsetzung von Licht, z. B. um aus kurzwelligem Licht längerwelliges, sichtbares Licht zu machen, als Ausgangsmaterial für supraleitende organische Materialien, als Fluoreszenzfarbstoffe in Szintillatoren, als Farbstoffe oder Fluoreszenzfarbstoffe in optischen Lichtsammelsystemen, wie z. B. dem Fluoreszenz-Solarkollektor oder fluoreszenzaktivierten Displays, in Flüssigkristallen zum Umlenken von Licht, als Farbstoffe oder Fluoreszenzfarbstoffe in Kaltlichtquellen zur lichtinduzierten Polymerisation zur Darstellung von Kunststoffen, als Farbstoffe oder Fluoreszenzfarbstoffe zur Materialprüfung, z. B. bei der Herstellung und Prüfung von Halbleiterschaltungen und Halbleiterbauteilen, als Farbstoffe oder Fluoreszenzfarbstoffe in Photoleitern, als Farbstoffe oder Fluoreszenzfarbstoffe in fotografischen Verfahren, als Farbstoffe oder Fluoreszenzfarbstoffe als Teil einer integrierten Halbleiterschaltung, die Farbstoffe als solche oder in Verbindung mit anderen Halbleitern z. B. in Form einer Epitaxie, als Farbstoffe oder Fluoreszenzfarbstoffe in Farbstoff-Lasern, bevorzugt als Fluoreszenzfarbstoffe zur Erzeugung von Laserstrahlen, aber auch als Q-Switch-Schalter und als aktive Substanzen für eine nichtlineare Optik, z. B. für die Frequenzverdopplung und die Frequenzverdreifachung von Laserlicht.j. Use of the dyes according to a to b as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave 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 collection systems, such as. As 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, eg. As 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, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.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.
Zitierte Nicht-PatentliteraturCited non-patent literature
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011100745A1 (en) | 2011-05-06 | 2012-11-08 | Heinz Langhals | Fluorescent solar collector comprises a plate stack made from two plates having different fluorescent dyes, where the collector is partially or completely transparent |
| DE102012008287A1 (en) | 2012-04-16 | 2013-10-17 | Heinz Langhals | New imidazoloterrylene bisimide compounds, useful as e.g. pigments and colorants for dyeing purposes, and in lacquers, preferably synthetic resin lacquers such as acrylic or vinyl resins, polyester lacquers and novolak resins |
| DE102012019495A1 (en) | 2012-10-02 | 2014-04-17 | Heinz Langhals | New substituted imidazolo-perylene bisanhydride compounds useful e.g. as reference materials for fluorescence measurements, as pigments and dyes for dyeing purposes, and as pigments in lacquers, preferably synthetic resin lacquers |
| DE102012023247A1 (en) | 2012-11-27 | 2014-06-26 | Ludwig-Maximilians-Universität München | Terrylene and Quaterrylenfarbstoffe with adjacent to the carbonyl groups amino groups and their use in Grätzel solar cells |
| WO2020193309A1 (en) | 2019-03-22 | 2020-10-01 | Basf Se | Plant cultivation method |
| CN118359635A (en) * | 2024-04-17 | 2024-07-19 | 天津大学 | A type of small molecule compound based on triphenylene diimide structure, polymer, preparation method and application |
-
2011
- 2011-04-27 DE DE102011018815A patent/DE102011018815A1/en not_active Withdrawn
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| Title |
|---|
| [1] (a) D. Desilets, P. M. Kazmaier and R. A. Burt, Can. J. Chem., 1995, 73, 319-324. (b) M. Wehmeier, M. Wagner and K. Mullen, Chem. Eur. J., 2001, 7, 2197-2205. (c) M. Adachi and Y. Nagao, Chem. Mater., 2001, 13, 662-669. (d) F. O. Holtrup, R. R. J. Mueller, H. Quante, S. De Feyter, F. C. De Schryver and K. Muellen, Chem. Eur., J. 1997, 3, 219-225. (e) F. Nolde, J. Qu, C. Kohl, N. G. Pschirer, E. Reuter and K. Müllen, Chem. Eur. J., 2005, 11, 3959-3967. |
| [10] H. Langhals, J. Karolin, L. B.-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922. |
| [2] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748. |
| [3] H. Langhals, S. Poxleitner, Eur. J. Org. Chem. 2008, 797-800. |
| [4] L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. Chem. 1995, 1229-1244. |
| [5] (a) T. Sakamoto, C. Pac, J. Org. Chem., 2001, 66, 94-98. (b) H. Langhals, J. Buttner and P. Blanke, Synthesis, 2005, 364-366. |
| [6] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529-535. |
| [7] (a) H. Langhals, Heterocycles 1995, 40, 477-500. (b) H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343. (c) H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4. |
| [8] H. Langhals, A. Walter, E. Rosenbaum, L. B.-Å. Johansson, Phys. Chem. Chem. Phys. 2011, DOI: 10.1039/c1cp20467j |
| [9] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q. |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011100745A1 (en) | 2011-05-06 | 2012-11-08 | Heinz Langhals | Fluorescent solar collector comprises a plate stack made from two plates having different fluorescent dyes, where the collector is partially or completely transparent |
| DE102012008287A1 (en) | 2012-04-16 | 2013-10-17 | Heinz Langhals | New imidazoloterrylene bisimide compounds, useful as e.g. pigments and colorants for dyeing purposes, and in lacquers, preferably synthetic resin lacquers such as acrylic or vinyl resins, polyester lacquers and novolak resins |
| DE102012019495A1 (en) | 2012-10-02 | 2014-04-17 | Heinz Langhals | New substituted imidazolo-perylene bisanhydride compounds useful e.g. as reference materials for fluorescence measurements, as pigments and dyes for dyeing purposes, and as pigments in lacquers, preferably synthetic resin lacquers |
| DE102012023247A1 (en) | 2012-11-27 | 2014-06-26 | Ludwig-Maximilians-Universität München | Terrylene and Quaterrylenfarbstoffe with adjacent to the carbonyl groups amino groups and their use in Grätzel solar cells |
| EP2925817A2 (en) * | 2012-11-27 | 2015-10-07 | Ludwig-Maximilians-Universität München | Amino substituted peri-arylene dye |
| WO2020193309A1 (en) | 2019-03-22 | 2020-10-01 | Basf Se | Plant cultivation method |
| CN118359635A (en) * | 2024-04-17 | 2024-07-19 | 天津大学 | A type of small molecule compound based on triphenylene diimide structure, polymer, preparation method and application |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R119 | Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal fee |
Effective date: 20131101 |