Perylene-3,4-dicarboxylic imides are prepared by a new decarboxylizing condensation with moderately sterically hindered primary amines. Perylene-3,4-dicarboxylic anhydride is prepared via a saponification reaction of the dicarboximide and is a starting material for a number of
 new types of chromophores. A second route to novel perylene derivatives is a partial hydrolysis of perylene dyes and a condensation with diamines. The dyes thus obtained are orange to red fluorescing in solution

Langhals, Heinz

German

CHIMIA

12. INTERNATIONALES FARBENSYMPOSIUM 503CHI MIA 48( 1994) Nr. 1I (November)G = various methoxy substitution patterns(Eq.1)R NH R(Eq.2)Me Ar Me13. R - Me14. R-OMe[6] G.W. Morrow, lS. Swenton, lA. Filppi,R.L. Wolgemuth, I. Org. Chem. 1987,52,713.[7] S.P. Khanapure, E.R. Biehl, J. Org. Chem.1987,52,5685; ibid. 1990,54, 1471.[8] S.P. Khanapure, E.R. Biehl, 1. Nat. Prod.1989,52, 1357.[9] S.P. Khanapure, E.R. Biehl, Heterocycles1988, 27, 2643.[10] W. Han, E.R. Biehl, unpublished results.[II] M. Dutt, B. Fravel, G.P. Ford, E.R. Biehl,l.Org. Chern. 1994,59,497.[12] E.R. Biehl, unpublished results.[13] B.M. Bhawal, S.P. Khanapure, E.R. Biehl,J. Org. Chern. 1991. 56, 2846.[14] A.R. Deshmukh, L. Tran, M. Morgan, E.R.Biehl, Synthesis 1992, 765.[I5] E.R. Biehl, A.R. Deshmukh, M. Dutt, Syn-thesis 1993, 885.[16] E.R. Biehl, S.P. Khanapure, M. Hansen, D.Swartling, Synthesis 1994, in press.eNBr~+I~ 01.THF!# 2.Wo12, R = Me7. R = MeO[I] E.R. Biehl, S.P. Khanapure, Ace. Chern.Res. 1989,22,275.[2] S.P. Khanapure, L. Crenshaw, R.T. Reddy,E. R. Biehl, Heterocycles 1988, 27, 4915.[3] P.O. Pansegrau, W.F. Rieker, A.I. Meyers,I. Arn. Chern. Soc. 1988, I/O, 7] 78.[4] L. Crenshaw, S.P. Khanapure, E.R. Biehl,Tetrahedron Lett. 1988,29,3777.[5] D.J. Dodson, M. Calcagno, E. Ehrmann, B.Devades, P.G. Sammes, I. Chern. Soc.,Perkins Trans. 1981, 2120.cent materials, whose excitation wave-lengths occur from 320 to 360 nm andemission wavelengths range from 520 to560 nm [12].Financial support for this work was providedby grants from the Welch Foundation, Houston,TX and the Petroleurn Research Foundation, asadministered by the American Chemical Society.methodology by using 3-lithiated 3-cyan-ophthalides which not only greatly in-creased the reaction workup time « ] hcompared to overnight in the case ofSammes lithiumphthlalide-mediate reac-tion), but also because of readily availabil-ity using Swenton's elegant methodology[6], enables one to prepare a wide varietyof anthraquinones, such as methyl ethersof the natural products chrysophanol [7],helmintho-sporin [7], morindpaparvin [8],and biologically acti ve azaanthraquinones[9]. Recently, we have prepared hexacenequi nones 11 by the reaction of 4-bromopyrene and cyanophthalides [10](Scheme 3).Other dipolar nucleophiles have beendiscovered that react with arynes to givepolycyclics. E.g., as shown in Scheme 4,the generation of another equiv. of arynein the presence of a-lithiated rearrangednitriles 12 and 7 from the reaction of 2-bromo-] ,4-dimethy lbenzene and 2-bromo-4-methylanisole yields the respective 9-imino derivatives of lO-arylanthrones 13[IIJ and 14 [12]. 1O-Hydroxy-9-anthra-cenecarboni tri Ies [13] can be prepared sim-ilarly by generating arynes in the presenceof a-lithiated o-(methoxycarbonyl)aryl-acetonitriles, with no apparent restrictionon the nature of the aryne. 10-Amino-9-anthracenecarbonitriles can also be pre-pared by the reaction of a-lithiated a-cyano-o-tolunitrile with methoxy substi-tutedarynes [14], 1-naphthalynes [15] and1-pyrynes [12]. However, it yields rear-ranged dinitriles when treated with 3,6-dimethoxybenzyne, 9-phenanthryne [16]and 4-pyryne [12]. The lO-amino- and 10-aminoanthracenes are powerful fluores-Chimia 48 (1994) 503-505© Neue Schweizerische Chemische Gesellschaft1SSN 0009-4293Novel Perylene Derivatives asHighly Photostable FluorescentDyesHeinz Langhals*1. IntroductionPerylene-3,4:9, lO-tetracarboxylic bis-anhydride (1, C.1. No. 71127) is preparedin an analytically pure state on technicalscale and it is the starting material for thepreparation of perylene dyes (perylene-3,4:9, lO-tetracarboxylic bisimides, 2) [IJ.The perylenes 2 are well-known as highlyphotostable pigments and fluorescent dyes;for a review see [2]. An essential point forthe lightfastness and inertness of 2 is theAbstract. Perylene-3,4-dicarboxylic imides are prepared by a new decarboxylizingcondensation with moderately sterically hindered primary amines. Perylene-3,4-dicarboxylic anhydride is prepared via a saponification reaction of the dicarboximideand is a starting material for a number of new types of chromophores. A second routeto novel perylene derivatives is a partial hydrolysis ofperylenedyes and a condensationwith diamines. The dyes thus obtained are orange to red fluorescing in solution.*Correspondence: Prof. Dr. H. LanghalsInstitut fUr Organische Chemie derUniversitat MUnchenKarlstrasse 230-80333 MUnchen12. INTERNATIONALES FARBENSYMPOSIUM 503CHI MIA 48( 1994) Nr. 1I (November)G = various methoxy substitution patterns(Eq.1)R NH R(Eq.2)Me Ar Me13. R - Me14. R-OMe[6] G.W. Morrow, lS. Swenton, lA. Filppi,R.L. Wolgemuth, I. Org. Chem. 1987,52,713.[7] S.P. Khanapure, E.R. Biehl, J. Org. Chem.1987,52,5685; ibid. 1990,54, 1471.[8] S.P. Khanapure, E.R. Biehl, 1. Nat. Prod.1989,52, 1357.[9] S.P. Khanapure, E.R. Biehl, Heterocycles1988, 27, 2643.[10] W. Han, E.R. Biehl, unpublished results.[II] M. Dutt, B. Fravel, G.P. Ford, E.R. Biehl,l.Org. Chern. 1994,59,497.[12] E.R. Biehl, unpublished results.[13] B.M. Bhawal, S.P. Khanapure, E.R. Biehl,J. Org. Chern. 1991. 56, 2846.[14] A.R. Deshmukh, L. Tran, M. Morgan, E.R.Biehl, Synthesis 1992, 765.[I5] E.R. Biehl, A.R. Deshmukh, M. Dutt, Syn-thesis 1993, 885.[16] E.R. Biehl, S.P. Khanapure, M. Hansen, D.Swartling, Synthesis 1994, in press.eNBr~+I~ 01.THF!# 2.Wo12, R = Me7. R = MeO[I] E.R. Biehl, S.P. Khanapure, Ace. Chern.Res. 1989,22,275.[2] S.P. Khanapure, L. Crenshaw, R.T. Reddy,E. R. Biehl, Heterocycles 1988, 27, 4915.[3] P.O. Pansegrau, W.F. Rieker, A.I. Meyers,I. Arn. Chern. Soc. 1988, I/O, 7] 78.[4] L. Crenshaw, S.P. Khanapure, E.R. Biehl,Tetrahedron Lett. 1988,29,3777.[5] D.J. Dodson, M. Calcagno, E. Ehrmann, B.Devades, P.G. Sammes, I. Chern. Soc.,Perkins Trans. 1981, 2120.cent materials, whose excitation wave-lengths occur from 320 to 360 nm andemission wavelengths range from 520 to560 nm [12].Financial support for this work was providedby grants from the Welch Foundation, Houston,TX and the Petroleurn Research Foundation, asadministered by the American Chemical Society.methodology by using 3-lithiated 3-cyan-ophthalides which not only greatly in-creased the reaction workup time « ] hcompared to overnight in the case ofSammes lithiumphthlalide-mediate reac-tion), but also because of readily availabil-ity using Swenton's elegant methodology[6], enables one to prepare a wide varietyof anthraquinones, such as methyl ethersof the natural products chrysophanol [7],helmintho-sporin [7], morindpaparvin [8],and biologically acti ve azaanthraquinones[9]. Recently, we have prepared hexacenequi nones 11 by the reaction of 4-bromopyrene and cyanophthalides [10](Scheme 3).Other dipolar nucleophiles have beendiscovered that react with arynes to givepolycyclics. E.g., as shown in Scheme 4,the generation of another equiv. of arynein the presence of a-lithiated rearrangednitriles 12 and 7 from the reaction of 2-bromo-] ,4-dimethy lbenzene and 2-bromo-4-methylanisole yields the respective 9-imino derivatives of lO-arylanthrones 13[IIJ and 14 [12]. 1O-Hydroxy-9-anthra-cenecarboni tri Ies [13] can be prepared sim-ilarly by generating arynes in the presenceof a-lithiated o-(methoxycarbonyl)aryl-acetonitriles, with no apparent restrictionon the nature of the aryne. 10-Amino-9-anthracenecarbonitriles can also be pre-pared by the reaction of a-lithiated a-cyano-o-tolunitrile with methoxy substi-tutedarynes [14], 1-naphthalynes [15] and1-pyrynes [12]. However, it yields rear-ranged dinitriles when treated with 3,6-dimethoxybenzyne, 9-phenanthryne [16]and 4-pyryne [12]. The lO-amino- and 10-aminoanthracenes are powerful fluores-Chimia 48 (1994) 503-505© Neue Schweizerische Chemische Gesellschaft1SSN 0009-4293Novel Perylene Derivatives asHighly Photostable FluorescentDyesHeinz Langhals*1. IntroductionPerylene-3,4:9, lO-tetracarboxylic bis-anhydride (1, C.1. No. 71127) is preparedin an analytically pure state on technicalscale and it is the starting material for thepreparation of perylene dyes (perylene-3,4:9, lO-tetracarboxylic bisimides, 2) [IJ.The perylenes 2 are well-known as highlyphotostable pigments and fluorescent dyes;for a review see [2]. An essential point forthe lightfastness and inertness of 2 is theAbstract. Perylene-3,4-dicarboxylic imides are prepared by a new decarboxylizingcondensation with moderately sterically hindered primary amines. Perylene-3,4-dicarboxylic anhydride is prepared via a saponification reaction of the dicarboximideand is a starting material for a number of new types of chromophores. A second routeto novel perylene derivatives is a partial hydrolysis ofperylenedyes and a condensationwith diamines. The dyes thus obtained are orange to red fluorescing in solution.*Correspondence: Prof. Dr. H. LanghalsInstitut fUr Organische Chemie derUniversitat MUnchenKarlstrasse 230-80333 MUnchen12. INTERNA TIONALES FARBENSYMPOSIUM 504CHIMIA 48(1994) Nr, II (November)linkage of two units of the strongly reso-nance stabilized cyclic carboxylic bisimidestructure element (3) to the perylene skel-eton in peri-position.The anhydride 1 is predominantly usedfor the preparation of 2, but it is also a-1 2valuable starting material for other deriv-atives with a perylene structure element.This has been reported for the preparationof carboximides with five-membered rings[3], and will be demonstrated for a numbernovel fluorescent dyes.RI0yNyO~"-y----I32. Results2.1. Perylene-3,4-dicarboxylicImides 4Whereas 1 is a well established class ofdyes there are only a few derivatives of therelated 4, because there is no preparationprocedure for 5. However, if moderatelysterically hindered primary amines like2,5-di(tert-butyl)aniline are condensedwith 1 in presence of H20 a decarboxyla-tion proceeds with the condensation to theimide 4a in 50% yield.The imides 4 are hydrolysed with KOHin tert-butyl alcohol to 5. The anhydride 5is a general starting material for 4 andotherperylene derivatives. The pure anhy-dride 5 is a red pigment with an intensesolid-state fluorescence; the UV NIS spec-tra are shown in the Figure.The dyes 4 are extraordinarily photo-stable: in solution more even than afactor of 20 (!) compared to 2. Thismay be a consequence of the stabi-lizing structure element 3, The dyesare highly fluorescent. Some derivatives- - '-12-47-586912. INTERNATIONALES FARBENSYMPOSIUM 505CHIMIA 48 (1994) Nr. II (Novemher)E. I O. 80.60.40.2o300 500 700nmE. Io300 500 700nmFigure. UVNIS Spectra in CHCf]" Left: 5 (absorption, fluorescence and solid-state fluorescence); right 4b (absorption and fluorescence).of 4 exhibit an intense solid-state fluores-cence.2.2. Peryleneamidineimides 8 or 9Many properties of 2 can be controlledby the substituents R, but not the UVNISspectra in solution [4] because of nodes inthe orbitals HOMO and LUMO at the N-atoms [5]. On the other hand, little isachieved by altering the basic chromophoreof 2. A possibility of shifting the UVNISspectra is an exchange of carbonyl groupsof the imide structure 3 by the related iminogroup. This has been done in a precedingwork [6] for one carbonyl group of eachimino ring. A bathochromic shift was ob-tained, but the fluorescence quantum yieldswent down to 60% or even lower.A more moderate altering of thechromophore of 2 is the exchange of onesingle carbonyl group to an imino group[7]. This can be attained by a partial alka-line saponification of 2 to 7 and a conden-sation of 7 with diamines to amidineim-ides like 8 or 9. These are intensely orangeto red fluorescing photostabe dyes.[I] See e.g. H. Zollinger, 'Color Chemistry', 1stedn., VCH Verlagsgemeinschaft, Weinheim,1987.[2] H. Langhals, Heterocycles, in press.[3] H. Langhals, S. Grundner, Chern. Ber. 1986,] ]9,2373.[4] A. Rademacher, S. Markle, H. Langhals,Chern. Ber. 1982, /15,2927.[5] H. Langhals, S. Demmig, H. Huber, Spectro-chirn. Acta, Part A 1988, 44, I 189.[6] 1. Lukae, H. Langhals, Chern.Ber. 1983,//6,3524.[7] H. Langhals, S. Sprenger, M.-T. Brandherm,Chern. Ber., in press.Chimia 48 (/994) 505-507© Neue Schweizerische Chemische Gesellschaft/SSN 0009-4293Malononitrile, a Synthetic Toolfor New Chromophoric SystemsJean-Marie Adam*, Peter Sutter, and Tammo WinklerAbstract. New near-IR-absorbing dyes were synthesized by condensation of thedicyanovinyl derivative of l-acetyl-3-oxo-2,3-dihydroindole with nitroso compounds.The resulting products were found to be mixtures (ca. 9: 1) of the (E)- and (Z)-isomers.The more bathochromic (E)-form could be converted into the (Z)-form by heating inmethanol. At higher temperature new cyclization products were obtained. A mecha-nism of the isomerisation and cyclization is proposed.1. IntroductionAt the present time, there is currentinterest in the development of near-IRabsorbing dyes for use e.g. in diode-laseroptical storage systems. Several investi-gations have been reported on the synthe-sis and properties of IR dyes suitable forelectro-optical applications [1]. Methinedyes are widely applied in this area be-cause their absorption bands can be easilyshifted into the longwave region by thesuitable choice of dye end-groups or byextending the methine chain. In this re-*Correspondence: Dr. J.M. AdamTextile Dyes DivisionCiba-Geigy Ltd.CH-4002 Basel

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