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Some New Nitrogen Bridgehead Heterocyclic Cyanine Dyes

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Some New Nitrogen Bridgehead Heterocyclic Cyanine Dyes Some New Nitrogen Bridgehead Heterocyclic Cyanine Dyes A. I. M. KORAIEM, H. A. SHINDY, and R. M. ABU EL-HAMD Department of Chemistry, Aswan Faculty of Science, Aswan, Egypt Received 21 July 1998 Accepted for publication 30 December 1999 New monomethine, trimethine, and azomethine cyanine dyes of pyrazolo^o'iSjôJÍpyrazinio/l^- oxa£Ínio)[2,3,4-ij']quinolin-ll-ium bromides were prepared. These cyanines were identified by ele­ mental and spectral analyses. The visible absorption spectra of some selected dyes were investigated in single and mixed solvents, and also in aqueous buffer solutions. The spectral shifts are discussed in relation to molecular structure and in terms of medium effects. Molecular complex formation with DMF was verified through mixed-solvent studies. As an extension to our earlier work on the syn­ Extra quaternization of the former intermediates thesis and studies of cyanine dyes [1—3], some new using an excess amount of ethyl iodide under con­ nitrogen bridgehead heterocyclic cyanine dye moi­ trolled conditions gave 9-ethyl-8-R-10-methylpyrazo- eties have been synthesized in view of the applica­ lo[4^5^5,6](pyrazinio/l,4-oxazinio) [2,3,4- zj']quinolin- bility of such compounds in production of photother- ll(9)-ium bromides iodides (IVa—IVe). Further re­ mographic imaging materials [4], electrophotographic action of the latter compounds with iV-methylpyridi- lithographic printing material for semiconductor laser nium, -quinolinium, resp. -isoquinolinium iodide in­ exposure [5], and as indicator and pH sensors [6], or volving active hydrogen atom in the position 11 or as antitumour agents [7]. 8 under piperidine catalysis gave the correspond­ Within these respects, pyrazolo[4',5':5,6](pyrazi- ing unsymmetrical bromides iodides of 9-ethyl-8-R- nio/1,4-oxazinio) [2,3,4- i,j\ quinolin-11-ium bromides pyrazolo[4^5^5,6](pyrazinio/l,4-oxazinio) [2,3,4- i,j]- Ilia—IIIc were used as key intermediates for the dye quinolin-ll-ium-10[4(l)]-monomethine cyanine dyes synthesis. Va, Vb, Via, VIb, Vila, Vllb (Scheme 2, Table 2). Interaction of 4-bromo-3-methyl-l-R-pyrazol-5-one Meanwhile the condensation reaction of IVc with (la/lb) [8] and 8-amino/hydroxyquinoline (IIa/IIb) in triethyl orthoformate under piperidine catalysis gave the presence of butan-l-ol as solvent afforded under the intermediate compound VIII. Further reaction of dehydration and selective quaternization processes the compound VIII with 7V-ethyl-a-picolinium, -quinal- new nitrogen bridgehead heterocycles (key intermedi­ dinium, and -7-picolinium iodide in the presence of ate compounds), namely S-R-lO-methylpyrazolo^ö': piperidine afforded the corresponding unsymmetrical 5,6](pyrazinio/l,4-oxazinio)[2,3,4-zj]quinolin-ll-ium trimethine cyanine dyes IX, X, XI. bromides Ilia—IIIc (Scheme 1, Table 1). The polar- Interaction of equimolar ratios of IVa or IVc and izability of N—H/O—H bonds of 8-amino/hydroxy­ nitrosophenols (4-nitrosophenol, l(2)-nitroso-2(l)-na- quinoline expressed a higher nucleophilic character of phthol) under basic catalysis afforded the correspond­ nitrogen/oxygen atoms and the nucleophilic attack ing unsymmetrical bromides iodides of 9-ethyl-8-R- proceeded stronger and faster on the electron-deficient pyrazolo[4',5':5,6](l,4-pyrazinio)[2,3,4-2,t;]quinolin-ll- C-5 atom (in case of iV-phenyl-substituted pyrazolone (9)-ium-10-azomethine cyanine dyes Xlla, Xllb, XIII, it was easier than in case of unsubstituted derivatives). XIV The resulted OH group abstracts a proton from proto- The structure of the newly synthesized compounds nated secondary amine or oxygenated ethereal groups Ilia—IIIc, IVa—IVc, Va, Vb, Via, VIb, Vila, Vllb, leading to the loss of water molecule followed by trans­ VIII, IX, X, XI, Xlla, Xllb, XIII, and XIV was estab­ fer of negative charge forming the double bond. The lished by elemental analysis and IR [9] and 1H NMR electron deficiency of the С—Br bond was increased [10] spectral data (Table 3). and attacked by the lone pair of the quinoline-nitrogen atom leading to the formation of bridgehead hetero­ Relation between Molecular Structure and cyclic quaternary salts. Thus, pyrazinium bromide is Spectral Behaviour of the Synthesized Cyanine separated practically after a relatively short-time re­ Dyes flux when compared with that for oxazinium bromide formation. The electronic absorption spectra of unsymmetri- 78 Chem. Papers 54 (2) 78—86 (2000) NITROGEN BRIDGEHEAD HETEROCYCLIC CYANINE DYES НзСч .Br НзСч /Br %^0 <лО Н I R НзС НзС Н3С IafIb tfa, IIb R X ŕ/ H я NH Л C6H5 6 О - Н20 a H NH /> C6H5 О с СбН5 NH Scheme 1 Table 1. Characterization Data for New Starting and Intermediate Compounds w,(caic.)/% Compound Formula u/i(found)/% Yield M.p. Colour Mr С H N % °c Ilia Ci3HnBrN4 51.51 3.66 18.48 63 182—185 Yellow red 303.16 51.63 3.60 18.25 im Ci9Hi4BrN30 60.02 3.71 11.05 67 142—145 Red 380.24 59.85 3.78 10.95 IIIc Ci9Hi5BrN4 60.17 3.99 14.78 72 164—167 Brownish red 379.26 59.90 4.13 14.53 IVa Ci5Hi6BrIN4 39.24 3.51 12.20 64 207—210 Brown 459.13 39.01 3.33 11.99 IVb C2iHi9BrIN30 47.04 3.57 7.84 73 190—193 Brownish red 536.21 46.77 3.31 7.70 IVc C2iH20BrIN4 47.13 3.77 10.47 76 182—185 Red 535.22 46.86 3.83 10.75 VIII C26H3oBrIN402 49.00 4.74 8.79 92 164—167 Reddish violet 637.36 49.15 4.65 8.51 Compounds Ilia—IIIc treated in saturated KI gave iodine vapour in concentrated H2S04. Compounds IVa—IVc and VIII were soluble in concentrated H2S04 liberating iodine vapour on heating. Chem. Papers 54 (2) 78—86 (2000) 79 A. I. M. KORAIEM, H. A. SHINDY, R. M. ABU EL-HAMD 0 © I Ur Э © N® Г I Br ix Illa—IIIc H3C СНз Water bath Piperidine/EtOH /N© CH3 Et N X ;ЯЬ Et N R IVa—IVe Va, Vb, Via, VIb, Vila, Vllb R X R X A a H NH Va H NH l-methyl-pyridinium-4-yl NH l-methyl-pyridinium-4-yl 6 C6H5 О Vb СбНб Via NH l-methyl-quinolinium-4-yl с С6Н5 NH СбНб VIb СбНб О l-methyl-quinolinium-4-yl Vila 1-methyl-isoquinolinium- 1-yl с6н5 NH Vllb 1-methyl-isoquinolinium- 1-yl с6н5 О © © 0© 1M CH (OEt)3 I Br N ,,cВг ô Piperidine / EtOH Piperidine / EtOH (ЕЮ)2НСН2С^ / <e>- - w R=C6Hs,H; X=NH R=C6Hs, H; X=NH f Ph R Xlla, Xllb, XIII, XIV VIII R Y © © H3O l Br -нс=нс-нс^ / Xlla H 4-OH J? Piperidine / EtOH Xllb C6H5 4-OH Et IS I XIII C6H5 2-OH, 5,6-benzo Ph H XIV C6H5 2-OH, 3,4-benzo IX, X, XI А IX l-ethyl-pyridinium-2-yl X l-ethyl-quinolinium-2-yl XI l-ethyl-pyridinium-4-yl Scheme 2 cal mono/trimethine cyanine dyes Va, Vb, Via, VIb, e Vila, Vllb, IX, X, XI in 95 % ethanol showed ab­ Br sorption bands with a strong bathochromic shift on increasing the conjugation of the quaternary hetero­ cyclic residue. Thus, the absorption spectra of dyes Vb, IX, and XI incorporating pyridinium salt moiety Et N H showed an absorption band hypsochromically shifted i R if compared with dyes Via and X containing the quino- linium moiety. This can be attributed to a more exten­ Va, Vb sive 7T-delocalization within the respective quaternary e e heterocyclic system. I Br Changing the linkage position of heterocyclic qua­ ternary residue from 4 to 2 in monomethine (com­ Me— pounds Via (VIb) and Vila (Vllb)) and/or from 4 Qs- to 2 in trimethine cyanines (compounds IX and XI) x showed that the linkage in the position 2 results in о ^i a hypsochromic shift in the absorption bands. This Ph is due to lower extended conjugation in the linkage in the position 2 resulting in a decrease of the 7r- Via, VIb delocalization of electron through cyanine molecule pathway. Monomethine dyes incorporating either pyrazolo chromically shifted in comparison with those incor­ (Va) or pyrazine moieties (Via and Vila) are batho- porating 8-phenylpyrazole (Vb) or oxazine derivatives 80 Chem. Papers 54 (2)78—86 (2000) NITROGEN BRIDGEHEAD HETEROCYCLIC CYANINE DYES Table 2. Characterization Data for Unsymmetrical Mono-, Tri-, and Azomethine Cyanine Dyes Wi(calc.)/% Absorption spectra in 95% ethanol Compound Formula Wi(found)/% Yield M.p. Colour Amax £max Mr H % cm2 mol * Va C2iH2iBrIN5 45.86 3.85 12.73 64 217—220 Reddish violet 450 1218 550.24 46.01 3.77 12.88 Vb С27Н25ВГШ5 51.78 4.02 11.18 65 172—175 Reddish violet 400 3200 626.34 51.61 4.05 11.35 Via С31Н27ВГШ5 55.05 4.02 10.35 75 180—183 Violet 520 1600 676.40 54.82 4.24 10.30 VIb C3iH26BrIN50 54.97 3.87 8.27 71 154—157 Violet 415, 515 2106, 1173 677.38 55.21 3.39 8.41 Vila С31Н27ВГШ5 55.05 4.02 10.35 67 190—193 Brownish violet 500 2584 676.40 54.91 4.10 10.50 Vllb C3iH26BrIN40 54.97 3.87 8.27 67 165—168 Brownish violet 460 1800 677.38 54.81 3.70 8.39 IX С30Н29ВГШ5 54.07 4.38 10.51 59 174—177 Brownish violet 500 4600 666.40 53.81 4.62 10.46 X С34Н31ВГШ5 56.99 4.36 9.77 73 202—205 Deep violet 465, 510, 555 2520, 2532, 2200 716.46 57.13 4.25 9.91 XI С30Н29ВГШ5 54.07 4.38 10.51 62 188—191 Reddish violet 510 1360 666.40 53.89 4.22 10.77 Xlla С21Н19ВГШ5О 44.70 3.39 12.41 55 140—142 Brown 470 1800 564.22 44.71 3.52 12.46 Xllb С27Н23ВГШ5О 50.65 3.62 10.94 58 135—138 Brown 522 2120 640.32 50.73 3.65 11.27 XIII С31Н25ВГШ5О 53.93 3.65 10.14 65 167—170 Brownish violet 530 2720 690.38 54.25 3.52 9.91 XIV С31Н25ВГШ5О 53.93 3.65 10.14 63 207—210 Red 525 2800 690.38 53.87 3.88 10.43 (VIb and Vllb).
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