Jour nal of the Chi nese Chem i cal So ci ety, 2002, 49,

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1 Jour nal of the Chi nese Chem i cal So ci ety, 2002, 49, Syn the sis and Vis i ble Spec tral Behaviour of Some ew -bridgehead Heterocyclic Cyanine Dyes n cor po rating Pyrazolo (4,5-b) ndolizine (Benzoindolizine).. M. Koraiem,. M. bd El-al and. S. Mo ham med* Chem is try De part ment, swan Fac ulty of Sci ence, South Val ley Uni ver sity, swan, Egypt The new un sym met ri cal -bridgehead, apo (zeromethine), mono-methine, dimethine, meso sub sti tuted tetramethine and styryl cyanine dyes in cor po rat ing pyrazolo (4,5-b) indolizine (benzoindolizine) nu clei were pre pared. Struc tural con fir ma tion was car ried out by el e men tal anal y ses,, 1 H-M, mass spec tra and 13 C-M with the aid of car bon DEPT spec tral data. The vis i ble ab sorp tion spec tra for the newly syn the sized cyanines were ex am ined in 95% eth a nol. T DUC T Cyanine dyes are among the most ver sa tile of func - tional dyes. 1 Be sides their use as colorants, 2 they have con - sid er able potetial for ap pli ca tion in en ergy con ver sion, 3 as la - ser dyes, 4 and as op to el ec tronic and photonic de vices. 5 More - over, some cyanine and re lated dyes show strong in ter ac tions with nu cleic ac ids with ef fi cient in ter ac tion and photo - damage of D. 6 lso, methine dyes play a vi tal role in many bi o log i cal pro cess as in hib i tors for cell growth and di - vi sion 7 or as anticancer agents. 8 Many syn thetic mem bers are im por tant as vul ca niz ing ac cel er a tor agents, pho to graphic sta bi liz ers 9 and photosensitizers in blue green light. 10 E SULTS D DS CUS S Syn the sis The syn the sis of the de sired -bridgehead heterocyclic cyanine dyes in cor po rat ing pyrazolo (4,5-b) indolizine (benzoindolizine) nu clei started by pyrazolo (4,5-b) in - dolizine (benzoindolizine) ylide io dide salts 3a,b which were pre pared by re ac tion of 3-methyl-1-phenyl pyrazol-5-one 1, 11 io dine and -picoline (and/or quinaldine) in ab so lute meth a - nol to give the in ter me di ate com pounds 3-methyl-1- phenyl- 4- (2-methyl--pyridine (quinaldine)-1-ium io dide) pyra - zol- 5- one 2a,b which un der piperidine ca tal y sis and eth a nol as sol vent achieved the key re ac tion in ter me di ates namely pyrazolo (4,5-b) indolizinium (and/or benzoindolizinium) ylide io dide salts 3a,b; 12 Scheme. chem i cal con fir ma tion of the key re ac tion in ter me di ates 3a,b was con ducted via treat ment of ethanolic so lu tion of the re ported 1-methyl pyrazolo (4,5-b) pyrolo (1,2-a) pyridinium/quinolinium bro - mides 13 with a sat u rated so lu tion of K. e ac tion of equi - molar ra tios of 3a,b and -methyl (pyridinium, quinolinium, isoquinolinium) io dide and/or -methyl 2(4)-methyl (pyri - dinium, quinolinium) io dide in eth a nol/piperidine con di tion af forded the cor re spond ing 8-methyl-6-phenyl pyrazolo (4,5-b) indolizine (benzoindolizine) apo (zeromethine)- 5[4(1)] cyanine dyes 4a-e and/or the mono-3[2(4)] methine cyanine dyes 5a-d; Scheme. Chem i cal con fir ma tion takes place via re ac tion of equimolar ra tios of 3a and - quino - linium p-toluene sulphonate salt in eth a nol/piperidine af - forded the com pound 4e. Treament of an ethanolic so lu tion of the lat ter com pound with a sat u rated so lu tion of K fol - lowed by sol u bil ity of the re sult ing pre cip i tated p-toluene io - dide com pound with conc. H 2 S 4 re sulted in lib er a tion of io - dine vapour on warm ing. This is a cri te rion for the pres ence of io dine an ion in volv ing of the six membered pyridine (quinoline) ring in the formed dyes, Scheme. e ac tion of the com pounds 3a,b and equimolar ra tios of ar o matic al de - hydes un der ther mal piperidine ca tal y sis re sulted in 8- meth - yl- 6-phenyl pyrazolo (4,5-b) indolizine (benzoindolizine)- 5(1) styryl cyanine dyes 6a-d. The lat ter com pounds 6a-d un - dergo fur ther re ac tion with -methyl-2-methyl quinolinum io dide in equimolar ra tios in eth a nol/piperidine re sult ing in 8-methyl-6-phenyl pyrazolo (4,5-b) indolizine (benzoindo - lizine)- 5(1) styryl-mono-3(2) methine cyanine dyes 7a-d; Scheme. lso, re ac tion of equimolar ra tios of com pounds 3a,b and benzalacetophenone de riv a tives 11 and/or 4- aryl - ideno- 3-methyl-1-phenyl pyrazol-5-one de riv a tives 14,15,16,17 {chalkone com pounds} un der ace tic acid af forded the in ter - me di ate com pounds 8a-f and/or 9a-d. n the pres ence of ZnCl 2/200 C 18 (or eth a nol/piperidine) con di tions, 8a-f and/or 9a-d com pounds un dergo an intermediacy of the Micheal ad - di tion re ac tion to give the cor re spond ing -bridgehead heterocyclic styryl dyes re lated to cyanines 10a-f and/or 11a-d; Scheme. e ac tion of equimolar amounts of com -

2 572 J. Chin. Chem. Soc., Vol. 49, o. 4, 2002 Koraiem et al. Scheme (1) 2 MeH (2a,b) (2a,b): = 2-methyl--pyridine ylide io dide (a); = 2-methyl--quinoline ylide io dide (b). (3a,b): = indolizinium ylide io dide (a); = benzoindolizinium ylide io dide (b). (3a,b) C H 3 ' X ' ' X (4a-e) H (4a-e): = indolizine, = pyridine-4-ium, X = methiodide (a); = indolizine, = quinoline-4-ium, X = methiodide (b); = indolizine, = quinoline-1-ium, X = methiodide (c); = benzoindolizine, = quinoline-4-ium, X = methiodide (d); = indolizine, = quinoline-4-ium, X = p-toluene sulphonate (e). (5a-d): = indolizine, = pyridine-2-ium methiodide (a); = indolizine, = quinoline-2-ium methiodide (b); = indolizine, = pyridine-4-ium methiodide (c); = benzoindolizine, = quinoline-2-ium methiodide (d). Fusion/pip. CH (5a-d) ' (6a-d), (7a-d): = H, = indolizine (a); = p.h, = indolizine (b); = p. 2, = indolizine (c); = H, = benzoindolizine (d). CH (6a-d) CH C H 3 (7a-d) pounds 8a-f and/or 9a-d and -2 (4) methyl qua ter nary salts of -methyl-2 (4) methyl (pyridinium, quinolinium) io dide in eth a nol/piperidine af forded the cor re spond ing 8-methyl- 6- phenyl pyrazolo (4,5-b) indolizine (benzoindolizine) tetra- 5[2(4)]-disubstituted methine cyanine dyes 12a-f and/or 13a-d; Scheme. n the other hand, com pounds 3a,b treated with phos - pho rus oxy chlo ride in dimethylformamide at room tem per a - ture 19 af forded the cor re spond ing com pounds 5-formyl-8- methyl- 6-phenyl pyrazolo (4,5-b) indolizinium (benzoindo - lizinium) io dide 14a,b. e ac tion of equimolar ra tios of 14a,b and -methyl-2 (4) methyl (pyridinium, quinolinium) io dide in eth a nol/piperidine ca tal y sis gave the cor re spond ing com - pounds 8-methyl-6-phenyl pyrazolo (4,5-b) indolizine (ben - zoindolizine) di-5[2(4)] methine cyanine dyes 15a-d. e ac - tion of equimolar ra tios of 5-formyl-8-methyl-6-phenyl pyr - azolo (4,5-b) indolizinium (benzoindolizinium) io dide 14a,b and acetophenone de riv a tives in the pres ence of piperidine af forded the in ter me di ate com pounds 16a-d. Com pounds 16a-d re acted with -methyl (pyridine, quinoline) io dide in the pres ence of piperidine as ba sic cat a lyst af forded the cor - re spond ing 8-methyl-6-phenyl pyrazolo (4,5-b) indolizine

3 Syn the sis and Spec tra of -bridgehead Heterocyclic Cyanine Dyes J. Chin. Chem. Soc., Vol. 49, o. 4, Scheme (3a,b) ' ch ch (8a-f) ' (9a-d) ZnCl 2 /200 C or (10a-f) ' (11a-d) ZnCl 2 /200 C or C H 3 ' ' (12a-f) ' (13a-f ) ' C H 3 ' (8a-f), (10a-f): = = H, = indolizinium io dide (a); = p.h, = H, = indolizinium io dide (b); = p.cl, = H, = indolizinium io dide (c); = o. 2, = H, = indolizinium io dide (d); = H, = H 2, = indolizinium io dide (e); = p.h, = H, = benzoindolizinium io dide (f). (9a-d), (11a-d): = H, = indolizinium io dide (a); = p.h, = indolizinium io dide (b); = p. 2, = indolizinium io dide (c); = p.h, = benzoindolizinium io dide (d). (12a-f): = p.h, = H, = indolizine, = pyridine-2-ium methiodide (a); = p.h, = H, = indolizine, = quinoline-2-ium methiodide (b); = p.h, = H, = indolizine, = pyridine-4-ium methiodide (c); = H, = H, = indolizine, = quinoline-2-ium methiodide (d); = p. 2, = H, = indolizine, = quinoline-2-ium methiodide (e); = p.h, = H, =benzoindolizine, = quinoline-2-ium methiodide (f). (13a-f): = p.h, = indolizine, = pyridine-2-ium methiodide (a); = p.h, = indolizine, = quinoline-2-ium methiodide (b); = p.h, = indolizine, = pyridine-4-ium methiodide (c); = H, = indolizine, = quinoline-2-ium methiodide (d); = p. 2, = indolizine, = quinoline-2-ium methiodide (e); = p.h, = benzoindolizine, = quinoline-2-ium methiodide (f).

4 574 J. Chin. Chem. Soc., Vol. 49, o. 4, 2002 Koraiem et al. Scheme DMF / PCl 3 (14a,b): = indolizinium io dide (a); = benzoindolizinium io dide (b). CH (3a,b) (14a,b) H ' 3 C ' (15a-d ) CH 3 C Fusion/pip. (16a-d) H 3 C ' (15a-d): = indolizine, = pyridine-2-ium methiodide (a); = indolizine, = quinoline-2-ium methiodide (b); = indolizine, = pyridine-4-ium methiodide (c); = benzoindolizine, = quinoline-2-ium methiodide (d). (16a-d): = H, = indolizinium io dide (a); = p.ch 3, = indolizinium io dide (b); = p. 2, = indolizinium io dide (c); = H, = benzoindolizinium io dide (d). (17a-f): = H, = indolizine, = pyridine-2-ium methiodide (a); = H, = indolizine, = quinoline-2-ium methiodide (b); = H, = indolizine, = pyridine-4-ium methiodide (c); = p.ch 3, = indolizine, = quinoline-2-ium methiodide (d); = p. 2, = indolizine, = quinoline-2-ium methiodide (e); = H, = benzoindolizine, = quinoline-2-ium methiodide (f). ' (17a-f ) (benzoindolizine)-tetra-5[2(4)]-mono-substituted methine cyanine dyes 17a-f; Scheme. Gen eral Characterization The struc ture of the syn the sized com pounds was con - firmed by el e men tal anal y ses,, 1 H-M, 13 C-M with the aid of car bon DEPT spec tral data and mass spec tra. The syn the sized cyanine dyes are highly col oured com pounds rang ing from brown ish-violet to in tense vi o let. They are eas - ily (par tially) sol u ble in po lar (non) or ganic sol vents ex hib it - ing col oured so lu tions (red/vi o let) con com i tant with slight or in tense green ish/red flu o res cence. They are sol u ble in con - cen trated H 2S 4 acid lib er at ing io dine vapour on acid i fi ca - tion. They pos sess an in ter change able colours so lu tion (brown ish- vi o let/in tense vi o let yel low) in ba sic and acidic me dium. Spec tral Be hav iour The elec tronic ab sorp tion spec tral fea tures ( max and max val ues) of novel syn the sized cyanine dyes in ethanolic so lu tion are de picted af ter the ex per i men tal sec tion. The elec - tronic ab sorp tion spec tra of apo (zeromethine), mono meth - ine, disubstituted-tetramethine, dimethine and mono -sub sti - tuted-tetramethine cyanines 4a-e, 5a-d, 12a-f, 13a-f, 15a-d and 17a-f showed ab sorp tion bands un dergo batho (hypso) chromically shifts de pend ing on the na ture of heterocyclic (), heterocyclic qua ter nary res i due ( ) and their link age po si tion. Thus, the elec tronic ab sorp tion spec tra (for ex am - ple) of dye 4a (5a) = indolizine, = pyridine-4(2)-ium methiodide showed max at 460 (464) nm max 1750 (4000) cm 2 mol -1. Sub sti tu tion of = pyridine-4(2)-ium meth - iodide in dye 4a (5a) by = quinoline-4(2)-ium meth - iodide in dye 4b (5b) re sulted in a bathochromic shift by 15 (52) nm con com i tant with the in creas ing num ber of ab sorp - tion bands for (5b). This is due to the more ex ten sive - delocalisation and ex tra con ju ga tion within the ex tra phenyl ring in the quinolinium ring in dye 4b (5b). d di tionally, chang ing the link age po si tion from 4(2)-ium in 4b (5a) =

5 Syn the sis and Spec tra of -bridgehead Heterocyclic Cyanine Dyes J. Chin. Chem. Soc., Vol. 49, o. 4, quinoline (pyridine)-4(2)-ium methiodide to 1(4)-ium in dye 4c (5c) = quinoline (pyridine)-1(4)-ium methiodide causes a hypso (batho) chro mic shift by 20 (16) nm. This is due to the ex ten sive -delocalisation within 4(4)-ium rather than 1(2)-ium link age po si tion. lso, sub sti tu tion of hetero - cyclic ( = indolizine) in dye 4b (5b) by (= benzo indo - lizine) in dye 4d (5d) causes a bathochromic shift of the ab - sorp tion band by 5 (4) nm. This is due to the more ex ten sive -delocalisation within the phenyl ring in dye 4d (5d). n the other hand, on com par i son of the elec tronic ab sorp tion spec - tra of apo (zeromethine) 4d, monomethine 5d, dimethine 15d and tetramethine 17f cyanine dyes, it was ob vi ous that there is an in creas ing num ber of ab sorp tion bands con com i tant with strong red shifts in the elec tronic spec tra of the tetra - methine dye 17f more than apo (zero methine) dye 4d, mono - methine dye 5d and dimethine dye 15d (ex per i men tal sec - tion). This is due to the in crease of the con ju ga tion ac cord ing to in crease of the num ber of methine groups. The elec tronic ab sorp tion spec tra of styryl and styrylmonomethine cyanines 6a-d, 7a-d showed ab sorp tion bands batho (hypso) chromically shifted de pend ing on the na ture of aryl sub stitu ents () and heterocyclic (). Thus, the ab sorp - tion spec tra of dye 6a (7a) [ = H, = indolizine] ex hibit max at 400 (512, 592) nm [ max 800 (8267, 1667) cm 2 mol -1 ]. Sub sti tu tion of ( = H) in dye 6a (7a) by ( = p.h) in dye 6b (7b) re sulted in a bathochromic shift of (64 nm) con com i tant with the ap pear ance of a new shorter ab sorp tion band lo cated at max (350 nm) for dye 6b and hypsochromic shift of the shorter (lon ger) wave length by 22 (12) nm for dye 7b. This is due to the elec tron do nat ing char ac ter of the hydroxyl group. d di tionally, sub sti tu tion of ( = p.h ) in dye 6b (7b) by ( = p. 2) in dye 6c (7c) re sulted in a hypso (batho) chro mic shift of the lon ger [shorter (lon ger)] wave length by 44 [15 (10, 10)] nm con com i tant with the dis ap pear ance of the other bands (ap pear ance of new ab sorp tion bands lo cated at 630, 550 nm). This is due to the elec tron with draw ing char ac ter of the 2 group for dye 6c the par tial mix ing of the lone pair of orbitals of ni tro gen with sys tem of the heterocyclic ring leads to a mod i fied set of en ergy lev els and this moves the band to the lon ger wave length for dye 7c]. n the other hand, sub sti tu tion of ( = indolizine) in dye 7b by ( = benzo - indolizine) in dye 7d causes a bathochromic shift of the shorter (lon ger) wave length by 30 (20) nm. This is due to the more ex ten sive -con ju ga tion in the phenyl ring in 7d. lso, on com par i son be tween the elec tronic ab sorp tion spec tra of styryl 6b and styryl-monomethine 7b cyanine dyes, as a rep - re sen ta tive ex am ple, it was ob vi ous that dye 7b showed a strong bathochromic shift con com i tant with an in creas ing num ber of ab sorp tion bands if com pared with styryl cyanine dye 6b. This is due to the in crease of con ju ga tion through the new monomethine group and heterocyclic quinolinium methiodide in dye 7b. The elec tronic ab sorp tion spec tra of -bridgehead styryl re lated to cyanines 10a-f, 11a-d, disubstituted a cy clic (cy clic)-tetramethine 12a-f, 13a-f and monosubstitutedtetra methine 17a-f cyanine dyes, showed ab sorp tion bands batho (hypso) chromically shifted de pend ing on the na ture of heterocyclic and aryl sub stitu ents (, ). Thus, the elec - tronic ab sorp tion spec tra (for ex am ple) of dye 10a (11a), = indolizinium io dide, = = H showed max at 429 (494) nm max 1620 (1512) cm 2 mol -1. Sub sti tu tion of ( = H) in dye 10a (11a) by ( = p.h) in dye 10b (11b) by = p.cl and/or o. 2 (p. 2) in dyes 10c and/or 10d (11c) causes a hypsochromic shift by 51 and/or 6 (35) nm]. This is due to the elec tron with draw ing char ac ter of the Cl and 2 groups. Finally, on com par i son be tween the elec tronic ab sorp tion spec tra of disubstituted-tetramethine acy clic and cy clic cya - nines 12b and 13b, as a rep re sen ta tive ex am ple, it was ob vi - ous that dye 12b showed a strong bathochromic shift ac com - pa nied by an in creas ing num ber of ab sorp tion bands if com - pared with the cor re spond ing cy clic dye 13b. This may be at - trib uted to the eas ier charge trans fer within acy clic one 12b rather than the other cy clic 13b. EX PE ME TL ll melt ing points are un cor rected. El e men tal anal y ses were car ried out at the Mi cro n a lyt i cal Cen ter (Cairo Uni - ver sity). The spec tra (oily film, CHCl 3) were taken on a Perkin Elmer FT--spectrometer. 1 H- and 13 C-M spec tra were re corded with a Bruker MX-250 spec trom e ter. Mass spec tra were re corded on a HpMs 6988 spec trom e ter (Cairo Uni ver sity). The vis i ble spec tra re corded within the wave length range ( ) on UV-visible re cord ing spec trom e - ter UV-160. (Fac ulty of Sci ence, swan). Syn the sis of 3-methyl-1-phenyl-4-(2-methyl--pyridine (quinoline)-1-ium io dide)pyrazolo-5-one 2a,b Equimolar ra tios of 3-methyl-1-phenyl pyrazol-5-one 1, io dine and -picoline (quinaldine) (0.01 mol) were refluxed in ab so lute meth a nol for 4-5 hs., fil tered hot, con - cen trated, cooled and the prod ucts were col lected, washed with eth a nol and crys tal lized from aque ous eth a nol to give 2a,b, re spec tively. 2a, red dish brown crys tals, m.p. = 125 C, yield 85%; Mol. For mula, C 16H 16 3 (393) Calcd %: C,

6 576 J. Chin. Chem. Soc., Vol. 49, o. 4, 2002 Koraiem et al ; H, 4.07;, 10.68; Found %: C, 48.89; H, 4.11;, 10.72; ( KBr cm -1 ) 1497 (C=), 1594 (C=C), 1711 (C=), 2919 ( - - ); 1 H-M (MeH, 250 MHz) (m, 9H, r.het), 2.6 (s, 1H, CH-C=), 2.2 (s, 3H, CH 3 of pyridine), 2.0 (s, 3H, CH 3 of pyrazol); 13 C-M with the aid of car bon DEPT (CD 3D, 250 MHz) (d, 9CH = r.het), 12.4, 16.4 (q, 2CH 3 ), 19.9 (d, CH of pyrazol), (s, C=), 161.7, (s, 2C=), (s, rcq); m/z 394 (M1). 2b, deep red dish brown, m.p. = 130 C, yield 89%; Mol. For mula, C 20 H 18 (443) Calcd %: C, 54.17; H, 4.06;, 9.48; Found %: C, 54.20; H, 4.10;, indolizinium (benzoindolizinium) ylide io dide salts 3a,b ac cord ing to ef. 12 The in ter me di ate com pounds 2a,b were dis solved in eth a nol (30 ml) and piperidine (3-5 drops) was added. The re ac tion mix ture was refluxed for 4-5 hs., fil tered hot, con - cen trated, cooled and acid i fied with ace tic acid. The pre cip i - tated prod ucts af ter di lu tion with wa ter were col lected and crys tal lized from aque ous eth a nol to give 3a,b, re spec tively. 3a, deep brown crys tals, m.p. = 160 C, yield 79%; Mol. For - mula, C 16H 14 3 (375) Calcd %: C, 51.20; H, 3.73;, 11.20; Found %: C, 51.90; H, 3.82;, b, deep red dish brown crys tals, m.p. = 168 C, yield 75%; Mol. For mula, C 20 H 16 3 (425) Calcd %: C, 56.47; H, 3.76;, 9.88; Found %: C, 56.52; H, 3.85;, 9.95; ( KBr cm -1 ) for 3a and 3b: 1497 (C=), 1594 (C=C), (CH 2 ), 2921 ( - - ); 1 H-M (CD 3 D, 250 MHz) 3a and 3b: 2.08 (s, 3H, CH 3), 2.27 (s, 2H, CH 2), for 3a (m, 9H, rhet) and for 3b (m, 11H, r.het). 3a, 13 C-M with the aid of car bon DEPT (CD 3D, 250 MHz) 12.1 (q, CH 3), 22.1 (t, CH 2), (d, 9CH = rhet), 147.2, 152, 153.1, 161.6, (s, 5q car bons); m/z 375 (M). indolizine (benzoindolizine) apo (zero) 5 4(1) methine cyanine dyes 4a-e n ethanolic so lu tion of 3a,b was refluxed with - methyl (pyridine, quinoline, isoquinoline) methiodide in pres ence of piperidine for 6-8 hs. The re ac tion mix ture was fil tered hot, con cen trated, cooled and acid i fied with ace tic acid. The pre cip i tated prod ucts af ter di lu tion with wa ter were col lected and crys tal lized from aque ous eth a nol to af ford the cor re spond ing 4a-d. 4a, red dish brown crys tals, m.p. = 130 C, yield 40%; Mol. For mula, C 22 H 19 4 (466) Calcd %: C, 56.65; H, 4.08;, 12.02; Found %: C, 56.70; H, 4.19;, 12.11; max (nm) 460 max (cm 2 mol -1 ) b, red dish vi o let crys tals, m.p. = 160 C, yield 55%; Mol. For mula, C 26 H2 1 4 (516) Calcd %: C, 60.46; H, 4.07;, 10.85; Found %: C, 60.51; H, 4.12;, 10.89; max (nm) 475 max (cm 2 mol -1 ) 4000; ( KBr cm -1 ) 1497 (C=), 1594 (C=C), 2924 (Me); 1 H- M (CD 3 D, 250 MHz) 1.52, 2.1 (2s, 6H, 2CH 3 ), (m, 15H, r.het); 13 C-M (CD 3D, 250 MHz) (s, 2CH 3 pyrazolquinolinium car bons), (15CH, r.quinolinium car bons). 4c, deep brown crys tals, m.p. = 135 C, yield 42%; Mol. For mula, C 26H 21 4 (516) Calcd %: C, 60.46; H, 4.07;, 10.85; Found %: C, 60.55; H, 4.15;, 10.92; max (nm) 455 max (cm 2 mol -1 ) d, in tense vi o let crys tals, m.p. = 140 C, yield 62%; Mol. For mula, C 30H 23 4 (566) Calcd %: C, 63.60; H, 4.06;, 9.89; Found %: C, 63.68; H, 4.12;, 9.94; max (nm) 480 max (cm 2 mol -1 ) 4500; ( KBr cm -1 ) 1492 (C=), 1595 (C=C), 2921 (Me); 1 H-M (CDCl 3, 250 MHz) 1.24, 2.62 (2s, 6H,CH 3 ), (m, 17H, r.het). indolizine (benzoindolizine) mono-3 2(4) methine cyanine dyes 5a-d Equimolar ra tios of 3a,b and methyl qua ter nary salts of ( )-picoline, quinaldine (0.01 mol) were dis solved in eth a - nol (30 ml), then piperidine (3-5 drops) was added. The re ac - tion mix ture was refluxed for 6-8 hs., fil tered hot, con cen - trated, cooled and acid i fied with ace tic acid. The pre cip i tated prod ucts af ter di lu tion with wa ter were col lected and recrys - tallized from eth a nol to give 5a-d. 5a, brown ish vi o let crys - tals, m.p. = 135 C, yield 44%; Mol. For mula, C 23 H 21 4 (480) Calcd %: C, 57.62; H, 4.37;, 11.66; Found %: C, 57.62; H, 4.40;, 11.68; max (nm) 464 max (cm 2 mol -1 ) 4000; 5b, in tense vi o let crys tals, m.p. = 160 C, yield 86%; Mol. For mula, C 27H 23 4 (530) Calcd %: C, 61.13; H, 4.34;, 10.56; Found %: C, 61.19; H, 4.39;, 10.64; max (nm): 516, 380 max (cm 2 mol -1 ): 13200, 9900; ( KBr cm -1 ) 1497 (C=), 1595 (C=C), 2920 (Me), 3060 (=CH); 1 H-M (CD 3D, 250 MHz) 1.52, 2.22 (2s, 6H, 2CH 3), 2.5 (s, 2H, CH 2 ), (m, 15H, r.hetch); 13 C-M with the aid of car bon DEPT (CD 3D, 250 MHz) (s, 2CH 3), (s, CH 2), (15 car bon sig nals, CH, r.hetch). 5c, red dish vi o let crys tals, m.p. = 148 C, yield 52%; Mol. For mula, C 23H 21 4 (480) Calcd %: C, 57.50; H, 4.37;, 11.66; Found %: C, 57.59; H, 4.24;, 11.73; max (nm) 480 max (cm 2 mol -1 ) d, in tense vi o let crys tals, m.p. = 155 C, yield 90%; Mol. For mula, C 31H 25 4 (580) Calcd %: C, 64.13; H, 4.31;, 9.65; Found %: C, 64.15; H, 4.49;, 9.70; max (nm): 520, 344 max (cm 2 mol -1 ): 1500, 1800; ( KBr cm -1 ) 1498 (C=), 1595 (C=C), 2923 (Me), 3058 (=CH); 1 H-M (CDCl 3, 250 MHz) 1.25 (s, 6H, 2CH 3 ), 2.64 (s, 2H, CH 2 ), (m, 17H, r.hetch).

7 Syn the sis and Spec tra of -bridgehead Heterocyclic Cyanine Dyes J. Chin. Chem. Soc., Vol. 49, o. 4, indolizine (benzoindolizine)-5(1) styryl cyanine dyes 6a-d Equimolar ra tios of 3a,b and ar o matic al de hydes (0.01 mol) were fused in the pres ence of a few drops of piperidine (3-5 drops) for 5-10 min utes. The re ac tion mix ture was ex - tracted by ethyl al co hol, fil tered hot, con cen trated, cooled and acid i fied with ace tic acid. The pre cip i tated prod ucts af ter di lu tion with wa ter were col lected and crys tal lized from the proper sol vent to give 6a-d. 6a, brown ish vi o let crys tals, m.p. = 130 C, yield 33%; Mol. For mula, C 23 H 18 3 (463) Calcd %: C, 59.61; H, 3.89;, 9.07; Found %: C, 59.67; H, 3.92;, 9.12; max (nm) 400 max (cm 2 mol -1 ) 800; ( KBr cm -1 ) 1498 (C=), 1595 (C=C), 2923 ( - - ), 3060 (=CH); 1 H-M (CDCl 3, 250 MHz) 1.24 (s, 3H, CH 3), (m, 15H, r.hetch); 13 C-M with the aid of car bon DEPT (CDCl 3, 250 MHz) (s, CH 3 ), (15 car - bon of r.hetch). 6b, deep brown ish vi o let crys tals, m.p. = 135 C, yield 45%; Mol. For mula, C 23H 18 3 (479) Calcd %: C, 57.62; H, 3.76;, 8.77; Found %: C, 57.68; H, 3.82;, 8.79; max (nm): 464, 350 max (cm 2 mol -1 ) 1218, c, deep brown crys tals, m.p. = 128 C, yield 39%; Mol. For - mula, C 23 H (508) Calcd %: C, 54.33; H, 3.35;, 11.02; Found %: C, 54.39; H, 3.42;, 11.09; max (nm) 420 max (cm 2 mol -1 ) 667; 6d, vi o let crys tals, m.p. = 135 C, yield 48%; Mol. For mula, C 27 H 20 3 (513) Calcd %: C, 63.13; H, 3.89;, 8.19; Found %: C, 63.20; H, 3.97;, 8.28; max (nm) 450 max (cm 2 mol -1 ) 333. indolizine (benzoindolizine)-5(1) styryl-mono-3(2) methine cyanine dyes 7a-d Equimolar ra tios of 6a-d and 2-methyl quinolinium methiodide (0.01 mol) were dis solved in eth a nol (30 ml), and then piperidine (3-5 drops) was added. The re ac tion mix - ture was refluxed for 6-8 hs., fil tered hot, con cen trated, cooled, acid i fied with ace tic acid, treated by wa ter where the pre cip i tated prod ucts were fil tered off, washed with wa ter, dried and crys tal lized from aque ous eth a nol. 7a, deep vi o let crys tals, m.p. = 124 C, yield 75%; Mol. For mula, C 34H 27 4 (618) Calcd %: C, 66.01; H, 4.37;, 9.06; Found %: C, 66.11; H, 4.39;, 9.12; max (nm): 592, 512, 312 max (cm 2 mol -1 ): 1667, 8267, 3902; ( KBr cm -1 ) 1497 (C=), 1595 (C=C), 2923 (Me), 3060 (=CH); 1 H-M (CDCl 3, 250 MHz) 1.24, (s, 6H, 2CH 3), (m, 21H, r.het 2CH); 13 C-M with the aid of car bon DEPT (CDCl 3, 250 MHz) (s, CH 3, pyrazol), (s, CH 3, CH 3 - ), (21CH, r.het2ch). 7b, deep vi o let crys - tals, m.p. = 130 C, yield 80%; Mol. For mula, C 34H 27 4 (634) Calcd %: C, 64.35; H, 4.25;, 8.83; Found %: C, 64.42; H, 4.32;, 8.92; max (nm): 580, 490, 450, 312 max (cm 2 mol -1 ): 3500, 6000, 7000, c, deep vi o let crys - tals, m.p. = 190 C, yield 45%; Mol. For mula, C 34H (663) Calcd %: C, 61.53; H, 3.92;, 10.55; Found %: C, 61.60; H, 3.99;, 10.62; max (nm): 630, 590, 550, 500, 465, 312 max (cm 2 mol -1 ): 2000, 3000, 4000, 6000, 7500, d, in tense vi o let crys tals, m.p. = 120 C, yield 62%; Mol. For mula, C 38H 29 4 (668) Calcd %: C, 68.26; H, 4.34;, 8.38; Found %: C, 68.32; H, 4.39;, 8.42; max (nm): 600, 520 max (cm 2 mol -1 ): 1000, indolizinium (benzoindolizinum) io dide styryl re lated to cyanine dyes 10a-f, 11a-d Type (), Step (1) Equimolar ra tios of 3a,b and benzalacetophenone de - riv a tives (0.01 mol) were refluxed in ace tic acid (30 ml) for 3-4 hs. The mix ture was then con cen trated, cooled and prod - ucts were col lected af ter di lu tion with wa ter and crys tal lized from aque ous eth a nol to give the in ter me di ate com pounds 8a-f. 8a, yel low ish brown crys tals, m.p. = 120 C, yield 52%; Mol. For mula, C 31 H 24 3 (581) Calcd %: C, 64.03; H, 4.13;, 7.23; Found %: C, 64.09; H, 4.19;, b, brown crys - tals, m.p. = 130 C, yield 48%; Mol. For mula, C 31H (597) Calcd %: C, 62.31; H, 4.02;, 7.04; Found %: C, 62.42; H, 4.10;, 7.09; ( KBr cm -1 ) 1498 (C=), 1594 (C=C), 2923 ( - - ), 3065 (H); 1 H-M (CDCl 3, 250 MHz) 1.23 (s, 3H, CH 3, pyrazol), (m, 18H, r.het) the dou blet at 7.4 and 9.03 (J = 8 Hz) ortho cou - pling in di cate the pres ence of 1,4-disubstituted ben zene, 10.2 (H); 13 C-M with the aid of car bon DEPT (CDCl 3, 250 MHz) (s, CH 3), (s, CH 2), (18CH, r.het). 8c, pale brown crys tals, m.p. = 90 C, yield 42%; Mol. For mula, C 31 H 23 3 Cl (615.5) Calcd %: C, 60.44; H, 3.74;, 6.82; Found %: C, 60.49; H, 3.80;, d, brown crys tals, m.p. = 100 C, yield 51%; Mol. For mula, C 31 H (626) Calcd %: C, 59.42; H, 3.67;, 8.95; Found %: C, 59.52; H, 3.69;, e, red dish brown crys - tals, m.p. = 120 C, yield 59%; Mol. For mula, C 31H 25 4 (569) Calcd %: C, 62.42; H, 4.19;, 9.40; Found %: C, 62.49; H, 4.25;, f, deep brown crys tals, m.p. = 138 C, yield 55%; Mol. For mula, C 35H (647) Calcd %: C, 64.90; H, 4.02;, 6.49; Found %: C, 64.98; H, 4.09;, Step (2) suit able amount of com pounds 8a-f was re acted in a way sim i lar to that de scribed in ef. 18 to give styryl com - pounds re lated to cyanine dyes 10a-f. 10a, brown ish vi o let crys tals, m.p. = 115 C, yield 44%; Mol. For mula, C 31H 22 3 (563) Calcd %: C, 66.07; H, 3.91;, 7.46; Found %: C,

8 578 J. Chin. Chem. Soc., Vol. 49, o. 4, 2002 Koraiem et al ; H, 4.02;, 7.49; max (nm) 429 max (cm 2 mol -1 ) b, deep vi o let crys tals, m.p. = 145 C, yield 49%; Mol. For - mula, C 31H 22 3 (579) Calcd %: C, 64.25; H, 3.79;, 7.25; Found %: C, 64.29; H, 3.85;, 7.31; max (nm) 469 max (cm 2 mol -1 ) 1920; ( KBr cm -1 ) 1498 (C=), 1596 (C=C), 2924 ( - - ), 3400 (H); 1 H-M (CDCl 3, 250 MHz) 1.23, (s, 3H, CH 3, pyrazol), (m, 18H, r.het), 9.8 (s, 1H, H). 10c, vi o let crys tals, m.p. = 100 C, yield 52%; Mol. For - mula, C 31H 21 3Cl (597.5) Calcd %: C, 62.26; H, 3.51;, 7.03; Found %: C, 62.32; H, 3.59;, 7.11; max (nm) 418 max (cm 2 mol -1 ) d, vi o let crys tals, m.p. = 110 C, yield 55%; Mol. For mula, C 31H (608) Calcd %: C, 61.18; H, 3.45;, 9.21; Found %: C, 61.25; H, 3.52;, 9.30; max (nm) 463 max (cm 2 mol -1 ) e, brown ish vi o let crys tals, m.p. = 122 C, yield 56%; Mol. For mula, C 31H 23 4 (578) Calcd %: C, 64.36; H, 3.98;, 9.69; Found %: C, 64.39; H, 4.05;, 9.72; max (nm) 458 max (cm 2 mol -1 ) f, vi o let crys tals, m.p. = 150 C, yield 56%; Mol. For mula, C 35H 24 3 (629) Calcd %: C, 66.77; H, 3.82;, 6.68; Found %: C, 66.82; H, 3.90;, 6.73; max (nm) 487 max (cm 2 mol -1 ) Type (B) Step (1) Equimolar ra tios of 3a,b and 4-arylideno-3- methyl- 1- phenyl pyrazol-5-one de riv a tives (0.01 mol) were refluxed in ace tic acid (30 ml) for 3-4 hs. The mix ture was then fil tered hot, con cen trated, cooled and prod ucts were col lected af ter di lu tion with wa ter and crys tal lized from aque ous eth a nol to give the in ter me di ate com pounds 9a-d. 9a, deep brown crys - tals, m.p. = 145 C, yield 62%; Mol. For mula, C 33 H 26 5 (635) Calcd %: C, 62.36; H, 4.09;, 11.02; Found %: C, 62.45; H, 4.15;, b, brown crys tals, m.p. = 190 C, yield 65%; Mol. For mula, C 33 H (651) Calcd %: C, 60.83; H, 3.99;, 10.75; Found %: C, 60.92; H, 4.05;, 10.85; ( KBr cm -1 ) 691 (ben zene monosubstituted), 839 (ben zene disubstituted), 1499 (C=), 1597 (C=C), 1726 (C=), 2959 ( - - ), 3441 (H); 1 H-M (CD 3D, 250 MHz) 1.0 (s, 3H, CH 3, pyrazoloindolizinium), 2.07 (s, 3H, CH 3, pyrazolone), 2.21 (s, CH, pyrazolone), (m, 18H, r.het) the dou blet at 6.49 and 8.27 (J = 7 Hz) ortho cou pling in di cated the oc cur rence of 1,4-disubstituted ben - zene, (m, 18H, r.het); (CH and Cq of r.het). 9c, deep brown crys tals, m.p. = 140 C, yield 60%; Mol. For mula, C 33H (680) Calcd %: C, 58.24; H, 3.68;, 12.35; Found %: C, 58.30; H, 3.77;, d, pale brown crys tals, m.p. = 190 C, yield 72%; Mol. For mula, C 37H (701) Calcd %: C, 63.34; H, 3.99;, 9.99; Found %: C, 63.45; H, 4.10;, 10.08; ( KBr cm -1 ) 668 (ben zene monosubstituted), 829 (ben zene disubstituted), 3441 (H), 2959 ( - - ); 1 H-M (CDCl 3, 250 MHz) 2.27 (s, 3H, CH 3, pyrazol), 2.37 (s, 3H, CH 3, pyrazol sub sti tuted), (m, 21H, r.heth), the dou blet at 6.83 and 8.45 (J = 7 Hz) ortho cou pling in di cate the pres ence of 1,4- disubstituted ben zene. Step (2) suit able amount of com pounds 9a-d was re acted in a way sim i lar to that de scribed in ef. 18 to give an other kind of styryl com pound re lated to cyanine dyes 11a-d. 11a, brown ish vi o let crys tals, m.p. = 150 C, yield 58%; Mol. For - mula, C 33H 24 5 (617) Calcd %: C, 64.18; H, 3.89;, 11.35; Found %: C, 64.24; H, 3.92;, 11.42; max (nm) 494 max (cm 2 mol -1 ) b, deep red dish vi o let crys tals, m.p. = 165 C, yield 59%; Mol. For mula, C 33H 24 5 (633) Calcd %: C, 62.56; H, 3.79;, 11.06; Found %: C, 62.62; H, 3.86;, 11.13; max (nm) 499 max (cm 2 mol -1 ) 1366; ( KBr cm -1 ) 1122 (C--C cy clic) 1499 (C=), 1596 (C=C), 2959 ( - - ), 3430 (H); 1 H-M (CDCl 3, 250 MHz) 1.22 (s, 6H, 2CH 3), (m, 17H, r.het.). 11c, deep brown crys tals, m.p. = 140 C, yield 62%; Mol. For mula, C 33H 23 6 (662) Calcd %: C, 59.82; H, 3.47;, 12.69; Found %: C, 59.90; H, 3.52;, 12.77; max (nm) 469 max (cm 2 mol -1 ) d, yel - low ish brown crys tals, m.p. = 190 C, yield 65%; Mol. For - mula, C 37 H 26 5 (683) Calcd %: C, 65.01; H, 3.81;, 10.25; Found %: C, 65.09; H, 3.92;, 10.35; max (nm) 494 max( cm 2 mol -1 ) indolizine (benzoindolizine) tetra-5 2(4) disubstituted methine cyanine dyes 12a-f and/or 13a-f Equimolar ra tios of 8a-f and/or 9a-d and methyl qua - ter nary salts of ( )-picoline, quinaldine (0.01 mol) were dis solved in eth a nol (30 ml), then piperidine (3-5 drops) was added. The re ac tion mix ture was refluxed for 6-8 hs., fil tered hot, con cen trated, cooled and acid i fied with ace tic acid. The pre cip i tated prod ucts af ter di lu tion with wa ter were col lected and recrystallized from eth a nol to give 12a-f. and/or 13a-f. 12a, deep brown crys tals, m.p. = 170 C, yield 35%; Mol. For mula, C 38 H 32 4 (687) Calcd %: C, 66.38; H, 4.66;, 8.15; Found %: C, 66.45; H, 4.75;, 8.22; max (nm) 465 max (cm 2 mol -1 ) b, in tense vi o let crys tals, m.p. = 165 C, yield 52%; Mol. For mula, C 42 H 34 4 (737) Calcd %: C, 68.38; H, 4.61;, 7.59; Found %: C, 68.48; H, 4.71;, 7.66; max (nm): 670, 580, 507 max (cm 2 mol -1 ): 5000, 11000, 27600; ( KBr cm -1 ) 1166 (C--C cy clic), 1498 (C=), 1596 (C=C), 2924 (Me), 3421 (H); 1 H-M (CDCl 3, 250 MHz) 1.24, 2.6 (2s, 6H, 2CH 3 of pyrazolch 3- ), (m, 21H, r.het2ch), 9.72 (H). 12c, brown ish vi o let crys tals, m.p. = 195 C, yield 52%; Mol. For mula, C 38H 32 4 (687) Calcd %: C, 66.38; H, 4.66;,8.15; Found %: C, 66.49; H, 4.72;, 8.75; max (nm) 480 max (cm 2 mol -1 ) d,

9 Syn the sis and Spec tra of -bridgehead Heterocyclic Cyanine Dyes J. Chin. Chem. Soc., Vol. 49, o. 4, deep brown crys tals, m.p. = 152 C, yield 56%; Mol. For - mula, C 42H 34 4 (721) Calcd %: C, 69.90; H, 4.72;, 7.76; Found %: C, 69.98; H, 4.79;, 7.83; max (nm): 665, 501 max (cm 2 mol -1 ): 6000, e, in tense vi o let crys tals, m.p. = 150 C, yield 56%; Mol. For mula, C 42H (766) Calcd %: C, 65.79; H, 4.31;, 9.14; Found %: C, 65.85; H, 4.39;, 9.20; max (nm) 525 max (cm 2 mol -1 ) f, in tense vi o let crys tals, m.p. = 170 C, yield 68%; Mol. For mula, C 46H 36 4 (787) Calcd %: C, 70.14; H, 4.57;, 7.12; Found %: C, 70.23; H, 4.63;, 7.19; max (nm): 675, 580, 507 max (cm 2 mol -1 ): 666, 1888, a, red dish brown crys tals, m.p. = 180 C, yield 48%; Mol. For mula, C 40H 34 6 (741) Calcd %: C, 64.77; H, 4.59;, 11.34; Found %: C, 64.82; H, 4.68;, 11.45; max (nm) 380 max (cm 2 mol -1 ) b, in tense vi o let crys tals, m.p. = 215 C, yield 50%; Mol. For mula, C 44 H 36 6 (791) Calcd %: C, 66.75; H, 4.55;, 10.62; Found %: C, 66.82; H, 4.55;, 10.73; max (nm) 505 max (cm 2 mol -1 ) 1179; ( KBr cm -1 ) 1156 (C--C cy clic), 1498 (C=), 1595 (C=C), 2923 (Me), 3420 (H); 1 H-M (CDCl 3, 250 MHz) 1.24, (s, 3H, CH 3 of pyrazolo (4,5-b) indolizine), 2.03 (s, 3H, CH 3 of pyrazolo), 2.5 (s, 3H, CH 3-), (m, 23H, r.hetch), 9.7 (H). 13, brown ish vi o - let crys tals, m.p. = 195 C, yield 52%; Mol. For mula, C 40H 34 6 (741) Calcd %: C, 64.77; H, 4.59;, 11.34; Found %: C, 64.82; H, 4.68;, 11.45; max (nm) 400 max (cm 2 mol -1 ) d, in tense vi o let crys tals, m.p. = 180 C, yield 59%; Mol. For mula, C 44H 36 6 (775) Calcd %: C, 68.13; H, 4.65;, 10.83; Found %: C, 68.25; H, 4.71;, 10.92; max (nm) 510 max (cm 2 mol -1 ) e, deep vi o let crystals, m.p. = 175 C, yield 54%; Mol. For mula, C 44H (820) Calcd %: C, 64.39; H, 4.27;, 11.95; Found %: C, 64.42; H, 4.31;, 12.08; max (nm) 490 max (cm 2 mol -1 ) f, deep vi o let crys tals, m.p. = 200 C, yield 65%; Mol. For - mula, C 48 H 38 6 (841) Calcd %: C, 68.49; H, 4.52;, 9.99; Found %: C, 68.55; H, 4.62;, 10.09; max (nm) 500 max (cm 2 mol -1 ) Syn the sis of 5-formyl 8-methyl-6-phenyl pyrazolo (4,5-b) indolizinium (benzoindolizinium) io dide 14a,b These com pounds 14a,b were pre pared in a way sim i lar to that de scribed in ef a, brown crys tals, m.p. = 120 C, yield 45%; Mol. For mula, C 17H 14 3 (403) Calcd %: C, 50.62; H, 3.47;, 10.42; Found %: C, 50.72; H, 3.54;, 10.49; ( KBr cm -1 ) 1498 (C=), 1594 (C=C), 2922 ( - - ); 1 H-M (CDCl 3, 250 MHz) 1.23 (s, 3H, CH 3), (d, 1H, CH), (m, 9H, r.het). 14b, brown crys tals, m.p. = 135 C, yield 48%; Mol. For mula, C 21H 16 3 (453) Calcd %: C, 55.63; H, 3.53;, 9.27; Found %: C, 55.71; H, 3.59;, 9.35; 1 H-M (CDCl 3, 250 MHz) 1.24, (s, 3H, CH 3 ), 2.37 (s, 1H, CH), (m, 11H, r.het), 8.56 (CH); 13 C-M (CDCl 3, 250 MHz) (s, CH 3), (s, CH), 205 (s, C=), (18 car bons of CH, Cq, r.het). indolizine (benzoindolizine) di-5 2(4) methine cyanine dyes 15a-d Equimolar ra tios of 14a,b and 2(4)-methyl qua ter nary salts of ( )-picoline, quinaldine (0.01 mol) were dis solved in eth a nol (30 ml) and piperidine (3-5 drops) was added. The re ac tion mix ture was refluxed for 6-8 hs., fil tered hot, con - cen trated, cooled and acid i fied with ace tic acid. The pre cip i - tated prod ucts af ter di lu tion with wa ter were col lected and crys tal lized from aque ous eth a nol. 15a, brown ish vi o let crys - tals, m.p. = 120 C, yield 50%; Mol. For mula, C 24 H 21 4 (492) Calcd %: C, 58.54; H, 4.27;, 11.38; Found %: C, 58.63; H, 4.32;, 11.45; max (nm) 380 max (cm 2 mol -1 ) b, in tense vi o let crys tals, m.p. = 160 C, yield 70%; Mol. For mula, C 28H 23 4 (542) Calcd %: C, 61.99; H, 4.24;, 10.33; Found %: C, 62.09; H, 4.30;, 10.42; max (nm) 580, 505 max (cm 2 mol -1 ) 6250, 9000; ( KBr cm -1 ) 1498 (C=), 1596 (C=C), (Me); 1 H-M (CDCl 3, 250 MHz) 1.23 (s, 3H, CH 3 of pyrazol), 2.39 (s, 3H, CH 3) (m, 17H, r.hetch=ch). 15c, red dish vi o let crys tals, m.p. = 140 C, yield 65%; Mol. For mula, C 24H 21 4 (492) Calcd %: C, 58.54; H, 4.27;, 11.38; Found %: C, 58.54; H, 4.35;, 11.45; max (nm): 462, 382 max (cm 2 mol -1 ): 2500, d, in tense vi o let crys tals, m.p. = 150 C, yield 72%; Mol. For mula, C 32H 25 4 (592) Calcd %: C, 64.86; H, 4.22;, 9.20; Found %: C, 64.93; H, 4.32;, 9.28; max (nm) 520 max (cm 2 mol -1 ) indolizine (benzoindolizine) tetra-5 2(4) mono-substituted methine cyanine dyes 17a-f Step () Equimolar ra tios of 14a,b and acetophenone de riv a - tives (0.01 mol) were dis solved in eth a nol (30 ml) and piperidine (3-5 drops) was added. The re ac tion mix ture was refluxed in a wa ter bath 2-4 hs., fil tered hot, con cen trated, cooled and acid i fied with ace tic acid. The pre cip i tated prod - ucts af ter di lu tion with wa ter were col lected and crys tal lized from aque ous eth a nol to give the in ter me di ate com pounds 16a-d. 16a, deep brown crys tals, m.p. = 105 C, yield 48%; Mol. For mula, C 25 H 20 3 (505) Calcd %: C, 59.41; H, 3.96;, 8.32; Found %: C, 59.48; H, 4.05;, 8.38; ( KBr cm -1 ) 1497 (C=), 1595 (CH=CH),1715 (C=), 2924 ( - - ); 1 H- M (MeH, 250 MHz) 1.02 (s, 3H, CH 3 of pyrazol),

10 580 J. Chin. Chem. Soc., Vol. 49, o. 4, 2002 Koraiem et al (d, 1H, CH), (m, 16H, r.hetch=ch); 13 C-M (CD 3D, 250 MHz) (s, CH 3), (s, CH), (22 car bons of CHCq), (C=). 16b, brown ish vi o let crys tals, m.p. = 110 C, yield 45%; Mol. For mula, C 26H (535) Calcd %: C, 58.32; H, 4.11;, 7.85; Found %: C, 58.39; H, 4.18;, 7.89; 1 H-M (CD 3D, 250 MHz) 1.02 (s, 3H, CH 3 ), (d, 1H, CH), 3.06 (s, 3H, CH 3), (m, 15H, r.hetch=ch); 13 C-M (CD 3D, 250 MHz) (s, CH 3), (s, CH), (s, CH 3 ), (22 car bons of CHCq), (C=). 16c, deep brown ish vi o let crys tals, m.p. = 120 C, yield 49%; Mol. For mula, C 35H (550) Calcd %: C, 54.55; H, 3.45;, 10.18; Found %: C, 54.59; H, 3.49;, d, vi o let crys tals, m.p. = 140 C, yield 55%; Mol. For mula, C 29H 22 3 (555) Calcd %: C, 62.70; H, 3.96;, 7.57; Found %: C, 62.76; H, 3.99;, Step B Equimolar ra tios of 16a-d and 2(4)-methyl qua ter nary salts of ( )-picoline, quinaldine (0.01 mol) were dis solved in eth a nol (30 ml) and piperidine (3-5 drops) was added. The re ac tion mix ture was refluxed for 6-8 hs., fil tered hot, con - cen trated, cooled and acid i fied with ace tic acid. The pre cip i - tated prod ucts af ter di lu tion with wa ter were col lected and crys tal lized from aque ous eth a nol. 17a, brown ish vi o let crys - tals, m.p. = 130 C, yield 52%; Mol. For mula, C 32 H 27 4 (594) Calcd %: C, 64.65; H, 4.55;, 9.43; Found %: C, 64.73; H, 4.63;, 9.43; max (nm) 480 max (cm 2 mol -1 ) b, in tense vi o let crys tals, m.p. = 152 C, yield 58%; Mol. For mula, C 36H 29 4 (644) Calcd %: C, 67.08; H, 4.50;, 8.70; Found %: C, 67.15; H, 4.68;, 8.80; max (nm): 559, 520, 480 max (cm 2 mol -1 ) 4100, 4166, 4166; ( KBr cm -1 ) 1499 (C=), 1597 (CH=CH), 2923 (Me); 1 H-M (CDCl 3, 250 MHz) 1.23 (s, 3H, CH 3 of pyrazol), 2.39 (s, 3H, CH 3), (m, 20H, r.hetch=chch). 17c, vi o let crys - tals, m.p. = 140 C, yield 53%; Mol. For mula, C 32H 27 4 (594) Calcd %: C, 64.65; H, 4.55;, 9.43; Found %: C, 64.73; H, 4.62;, 9.51; max (nm) 492 max (cm 2 mol -1 ) d, in tense vi o let crys tals, m.p. = 130 C, yield 67%; Mol. For mula, C 37H 31 4 (690) Calcd %: C, 64.35; H, 4.49;, 8.12; Found %: C, 64.39; H, 4.54;, 8.18; max (nm): 580, 500 max (cm 2 mol -1 ): 4000, e, deep vi o let crys tals, m.p. = 170 C, yield 65%; Mol. For mula, C 36H (689) Calcd %: C, 62.70; H, 4.03;, 10.16; Found %: C, 62.75; H, 4.06;, 10.22; max (nm): 580, 485, 460 max (cm 2 mol -1 ): 4167, 15000, f, deep vi o let crys tals, m.p. = 173 C, yield 69%; Mol. For mula, C 40 H 31 4 (694) Calcd %: C, 69.16; H, 4.47;, 8.07; Found %: C, 69.22; H, 4.53;, 8.13; max (nm): 650, 510 max (cm 2 mol -1 ): 1250, e ceived c to ber 24, Key Words Cyanine dyes; -bridgehead; Syn the sis; Spec tral be hav iour. EF E ECES 1. (a) Tyutyulkov,.; Fa bian, J.; Mehlhorn,.; Dietz, F.; Tadjer,. Polymethine Dyes, Struc ture and Prop erties, St. Kliment hridski Uni ver sity Press, So fia, (b) Zollinger, H. Color Chem is try, VCH, Weinheim Fa bian, J.; Hartman, H. Light b sorp tion of r ganic Colorants, Springer Berlin 1980, ochlitz, J. Chimia 1980, 34, (a) Maeda, M. La ser Dyes. Prop erties of r ganic Com - pounds for Dye La sers; c a demic Press: ew York, (b) Czerney, P.; Graness, G.; Birckner, E.; Vollmer, F.; ettig, W. J. Photochem. Photobiol. : Chem is try 1995, 89, wen, D. J.; Vanderveer, D.; Schuster, G. B. J. m. Chem Soc. 1998, 120, Seifert, J. L.; Connor,. E.; Kushon, S..; Wang, M.; rmitage, B.. J. m. Chem. Soc. 1999, 121, Gilman, P. Jr; Belly,. T.; Koszelak, T. D.; Zigman, S. US Pat. 1980, 4, 232, 121; Chem. bstr. 1981, 97109u, ormura, H.; Kozai, Y.; Minami,. Ger. ffen. 1980, 2, 919, 447, C.., 1980, 92, n. 9. Wiliams, J.; Vandenberghe, V. Chem. bs. 1960, 54, 22657e. 10. Brooker, L. G. S. East man Ko dak Co. US Pat ent 1934, 1, 969, 446; US Pat ent 1939, 2, 143, Vogel,. Text-Book of Prac ti cal r ganic Chem is try n clud - ing Qual i ta tive r ganic nal y sis, third Edi tion 1956, Khrohuke, F. Ber 66B, 1933, bu El-Hamed,. M. Chem. Pa per 1997, 51(2), Sammour,.; Selim, M.. B.; our El, M. M.; bd El-Halim, M. U...J. Chem. 1970, 13, o., El-Maghraby, M..; Koraiem,.. M.; bd El-Latif, F. M. E. J. Chem. Tech. Biotechnol 1985, 35, Koraiem,.. M.; Khalil, Z. H.; bu El-Hamed,. M. J. Chem. Tech. Biotechnol 1968, 36, Koraiem,.. M. Ph. The sis, ssuit Univ., Egypt Curtze, J. Ph.D. The sis Universität Giessen El-Shekeil,.; Babaqi,.; Hassan, M.; Shiba, S. Heterocycl. 1988, 27(11), 2577.