EM. R ES. I ESE U. 2004, 20 (2), 216 220 Syn theses of Som e rgan ic Fluorescen t D yes for Secur ity Tickers 3 L I Jun2fen, BA I Guan, L I Pei2hua, T IA M ei2lin, D G huan 3 3 and L I D u2x in D ep a rtm en t of hem istry, S hanx i U n iversity, T a iy uan 030006, P. R. h ina R eceived ov. 22, 2003 F ive o rganic fluo rescence dyes w ere synthesized by tw o2 o r th ree2step reactionṡ T hese synthetic m eth2 ods have an advantage of the simp le p rocesses, low co sts and h igh yields. T he compo sitions of the five com 2 pounds are characterized by IR, 1 M R, elem ental analyses and fluo rescence spectro scop ies. T he quantum yields of fluo rescence w ere m easured. Ke yw o rds rganic fluo rescence dye, Security sticker, Synthesis A rtic le ID 100529040 (2004) 2022216205 In troduction T he chem ical fakep roof is a new techno logy of secu rity tickerṡ T here are tw o k inds of chem ical m aterials u sed fo r fakep roof. ne k ind is ther2 moch rom atic m aterials of w h ich the co lo r w ill change w hen hea ted to d iscern the rea l; the o ther k ind is fluo rescence m aterials w h ich give off fluo2 rescence w hen irradiated by specific w avelength u l2 travio let ligh t [1, 2 ]. T he fluo rescence dyes, fo r in2 stance, as fakep roof m aterials, have m any advan2 tages, such a s the ab ility to g ive rich2co lo r ligh t and to be m ade in to co lo r design. Besides all these, they are also co lo rless o r w ith ligh t co lo r, very sta2 b le, conven ien t to be p rin ted, co sting little and easy to be distingu ished. Pyrazo line derivatives are excellen t o rgan ic fluo rescence dyes. T he syn thetic m ethods of th is k ind of compounds have been re2 po rted [3 7 ]. In th is study, five new fluo rescence dyes: 1, 32diphenyl252(42ch lo ro) phenyl222pyrazo line (1), 1, 52diphenyl232b iphenyl222pyrazo line (2), 2ethyl2 32acetyl2carbazo le (3), 2ethyl carbazo lidene (32yl) b iphenyl acetone (4), 2vinyl carbazo lidene (32yl) b iphenyl acetone (5) w ere syn thesized. T he charac2 terization of these compounds w ere carried ou t by m ean s of IR, 1 M R, elem en tal analysis and flu2 o rescence spectrom etries. Exper im en ta l 1 Syn thesis of 1, 3-D iphenyl-5- (4-chloro) -phenyl- 2-pyrazol ine (1) T he syn thesis rou te of compound 1 is given in Schem e 1. l 3 3 l l 2 l Scheme 1 Syn thesis of 1, 3-diphengl-5- (4-chloro) phenyl-2-pyrozoline T he reaction p roduct w as filtrated, dried and re2 crysta llized from ethano l. Yellow need le crysta l2 lo id (3 g) w as ob tained (70%, m. p. 111 112 1. 2 S y n thesis of 1, 32D ip heny l252( 42ch loro ) 1. 1 S y n thesis of B enz ol2ch lorop heny l2acetone A cco rding to the m ethod from reference [ 8 ], p 2ch lo robenzaldehyde (2. 3 g) w as disso lved in 50 ml of ab so lu te alcoho l in an ice bath w ith 2 ml of a m ass fraction 15% a aqueou s so lu tion being added dropw ise. A cetophenone (3 ml ) w as added and it w as stirred fo r 3 h at am b ien t temperatu re. 1 p heny l222py roz oline Benzo l2ch lo rophenyl2acetone ( 1 g ) w as dis2 so lved in 20 ml of glyco l monoethyl ether w ith a 3 Suppo rted by the ational atural Science Foundation of h ina ( o. 20275022) and the atural Science Foundation of Shanxi P rovince. 3 3 To w hom co rrespondence should be addressed.
o. 2 L I Jun2fen et al. 217 lit t le hyd roch lo ric acid being added d ropw ise. Phenyl hydrazine (1 g) w as added and it w as stirred at am b ien t temperatu re fo r 3 h. Som e w ater w as added to the reaction liqu id. T he yellow p recip itate app ea red a t once. R ecrysta llized from ethano l, 1. 1 g of ligh t yellow crystallo id w as ob tained (yield 80%, m. p. 152 153 2 Syn thesis of 1, 5-D iphenyl-3-biphenyl-2-pyrazol ine (2) T he syn thesis rou te of compound ( 2) is de2 scribed as Schem e 2. 2. 1 S y n thesis of p 2P heny lacetop henone A cco rding the m ethod from reference [ 9 ], b iphenyl(6 g), 28 ml of n itrobenzene, 5 g of A l2 l3 w ere added in a 32necked flask and stirred w ith 2. 8 ml of acyl ch lo ride being dropped at am b ien t temperatu re. T he reaction lasted fo r 4 h. i2 trobenzone w as removed by steam distillation. T he residue w as recrystallized from ethano l, 4 g of yel2 3 l A l l3 low crystals (yield 52. 4%, m. p. 120 121 ) w as ob tained. 2. 2 S y n thesis of B enz a l2bip heny lacetop henone p 2Phenylacetophenone (30 g) w as disso lved in ab so lu te ethano l w ith stirring. Benzaldehyde (1. 2 ml ) and 0. 5 ml of a 15% K aqueou s so2 lu tion w as added at am b ien t temperatu re. T he re2 action w as kep t fo r 1 h. A yellow pow der (30 g, yield 69%, m. p. 153 154 ) w as ob tained. 2. 3 S y n thesis of 1, 52D ip heny l232bip heny l222py ra2 z oline To a 32necked fla sk equ ipp ed w ith a st irrer w ere added 15 g of benzal2b iphenylacetophenone, 300 ml of g lyco l m onoethyl ether, a lit t le hy2 droch lo ric acid, and 9 ml of phenyl hydrazine and the m ix tu re w as stirred fo r 2 h at am b ien t tempera2 tu re. A yellow needle crystals w ere ob tained (24 g, 62%, m. p. 196 198 2 3 K l 2 Scheme 2 Syn thesis of 1, 5-diphenyl-3-biphenyl-2-pyrazoline. 3 Syn thesis of -ethyl-3-acetyl arbazole (3) T he syn thesis rou te of com pound 3 can be seen from Schem e 3. 3. 1 S y n thesis of 2E thy l a rbaz ole A m ix tu re of 100 g of ca rbazo le, 10 g of K, and 500 ml of DM S w as stirred at 80 85 fo r 2 h, and 80 ml of 3 2B r w as added dropw ise to iṫ T he reaction m ix tu re w as distilled at reduced p ressu re ( 1. 06 10 4 Pa T he crude p roduct w as recrystallized from ethano l and 90 g of w h ite needle crystals w as ob tained (yield 80%, m. 2 5B r DM S 4 Syn thesis of -ethyl arbazolidene ( 3-yl ) - b iphenylacetone (4) T he syn thesis rou te of compound ( 4) is p re2 sen ted in Schem e 4. p. 67 68 3. 2 S y n thesis of 2E thy l232acety l a rbaz ole To a 32necked flask w ere added 5 g of 2ethyl carbazo le, 18 ml of benzene, 3. 4 g of A l l3 and st irred w ith 2 ml of acyl ch lo ride being added dropw ise at am b ien t temperatu re. T he reaction lasted fo r 4 h. Benzene w as removed by steam dis2 t illa t ion. T he residu re w a s recrysta llized from ethano l, and 4. 6 g of yellow g reen crysta ls w a s ob tained (yidld 75%, m. p. 114 3 l A l l3 2 5 2 5 3 Scheme 3 Syn thesis of -ethhl-3-acetyl carbazole. 3 4. 1 S y n thesis of p 2P heny lacetop henone T he syn thesis m ethod of p 2p henylace2 tophenone w as sim ilar to that of section 2. 1. 4. 2 S y n thesis of 2E thy l a rbaz ole
2 18 EM. R ES. I ESE U. V o l. 20 T he syn thesis m ethod of 2ethyl ca rbazo le w as sim ilar to that of section 3. 1. 4. 3 S y n thesis of 2E thy l232f orm y l a rbaz ole 2E thyl carbazo le (10 g), 15 ml of dim ethyl fo rm am ide and 100 ml of ch lo robenzene w ere hea ted and st irred w ith 10 ml of P l3 being added dropvise. T he reaction lasted fo r 3 h. A fter reaction ch lo robenzene w as removed by steam dis2 t illa t ion, the residue w a s recrysta llized from ethano l, and 8. 5 g of yellow crystal w as ob tained (yield 75%, m. p. 86 88 2 5B r DM S 3 l A l l3 2 5 3 2 5 4. 4 S y n thesis of 2E thy l a rbaz olid ene (32y l) 2 bip heny lacetone p 2Phenylacetophenone ( 4 g ), 415 g of 2 ethyl232fo rm yl carbazo le w ere disso lved in 50 ml of ab so lu te ethano l in an ice2bath w ith dropp ing 2 ml of 15% (in m ass fraction) a aqueou s so2 lu tion. T he reaction m ix tu re w as stirred at am b i2 en t temperatu re fo r 3 h. R eaction p roduct w as fil2 tered and recrystallized from ethano l, and 6. 3 g of yellow needle crystals w as ob tained ( 81% m. p. 152 153 ) (Schem e 4 Scheme 4 Syn thesis of -ethhl carbazolidene (3-yl) -biphenylacetone. 5 Syn thesis of -V inyl arbazolidene ( 3-yl ) - b iphenylacetone (5) 5. 1 S y n thesis of p 2P heny lacetop henone T he syn thet ic m ethod of p 2p henylacelop he2 none is alike w ith that of section 2. 1. 5. 2 S y n thesis of 2V iny l a rbaz ole arbazo le ( 50 g ) and K ( 2 g ) w ere dis2 so lved in 100 ml of DM S, 2 2 w as passed in to the m ix tu re liqu id at 160. T he react ion la sted fo r 10 h. T he reaction m ix tu re w as distilled under 3 l 3 4 2 5 reduced p ressu re (1. 06 10 4 Pa T he crude p rod2 uct w a s recrysta llized from ethyano l, and 47 g of w h ite slice2like crystals w as ob tained (yield 82%, m. p. 64 65 5. 3 S y n thesis of 2V iny l a rbaz olid ene (32y l) 2 bip heny l A cetone T he syn thetic m ethod of 2vinyl carbazo li2 dene ( 32yl) 2b iphenyl acetone is sim ilar to that of section 4. 4 (Schem e 5 DM S = 2 = 2 Scheme 5 Syn thesis of -V inyl carbazolidene (3-yl) -biphenylacetone. Results and d iscuss ion 1 IR spectra ompound 1: IR, Μ π gcm - 1 : 3030 ( Μ, ), 1595. 0, 1492. 8, 1448 (Μ=, ), 1502. 4 ( Μ=, ), 1394. 4 ( Μ, (Μ, ), 1569. 0 ( Μ=, 5 = 2 ), 1391. 0 ), 762. 0, 700. 0 ( 2, ompound 3: IR, Μ π gcm - 1 : 2871. 8 ( Μ, ), 823. 5 (, l ), 754. 1, 740. 0 (Μ, ompound 2: IR, Μ π gcm - 1 : 3030 ( Μ, ), 1597. 0, 1500. 0, 1457. 0 ( Μ=, 2 ), 1660. 6 ( Μ=, ), 1591. 2, 1492. 8 ( Μ=, ), 1463. 9 (,
o. 2 L I Jun2fen et al. 219 2, 3), 771. 5, 748. 3 (, ompound 4: IR, Μ π gcm - 1 : 3031. 0 ( Μ, ), 2871. 8 (Μ, 2 ) : 1654. 8 (Μ=, 1593. 1 (Μ=, 1328. 9 (Μ=, 2 (, ), 1384. 8 (, 2 3 ), 1625. 9,, ), ), 812. 0, 750. 3, 887., ompound 5: IR, Μ π gcm - 1 : 3039. 0 ( Μ, ), 2868. 8 (Μ, 2 ), 1780. 0 (Μ, 2 1683. 2 (Μ=, 1582. 1 ( Μ=, 1330. 1 (Μ=, 2 1 M R Spectra (1, ( 1, ompound 1, : 3. 85 (2, ) ), 1624. 2,, ), 2 ), 7. 74 6. 79 (14, 3A r ompound 2, : 3. 85 (2, 2 ), 3. 15 ), 3. 22 ), 7. 83 6. 81 ( 19,, ompound 3, : 1. 46 ( 3, 3 ), 2. 74 (3, 7. 26 (7, 3 ), 4. 4 (2, 2 ), 8. 18 ompound 4, : 1. 46 (3, 3), 4. 4 (2, 2 ), 7. 28 (1, ), 7. 91 (1, ), 8. 15 7. 46 (15,, ompound 5, : 6. 06 (1, ), 5. 42 ( 2, 2), 7. 28 (1, ), 7. 91 ( 1, ), 8. 15 7. 46 (15,, 3 Elem ena ta l Ana lysis Found ( ca lcd. % ), com pound 1: 75130 (75170), 5114 (5111), 8134 (8142 om pound 2: 87123 ( 87133 ), 6100 (5193), 7121 (7155 om pound 3: 80192 ( 80179 ), 6149 (6172), 5176 (5188 om pound 4: 84101 ( 84129 ), 5152 (5174), 3158 (3149 om pound 5: 87140 ( 87122 ), 5118 (5126), 3138 (3151 4 Fluorescence Spectra Κm ax of fluo rescence ligh t of the five compounds w ere m easu red by m ean s of standard specim en w ith qu in ine su lfate. T he quan tum yields w ere computed by virtue of the fo llow ing fo rm u la: Q m easured= Q standard A standard S m easuredg A m easured S standard Q : quan tum yield, A : ab so rbance of UV, S : area of ab so rpeak tion. T he resu lts can be seen from T ab le 1. Tabel 1 Quan tum y ields of f ive compounds ompound Κexgnm S A Q 1 356 352126. 0 0. 454 0. 56 2 370 354291. 0 0. 472 0. 58 3 336 262685. 6 0. 765 0. 25 4 339 231135. 6 0. 266 0. 19 5 324 104779. 9 0. 277 0. 27 T he fluo rescence spectra ( so lven t: ch lo rofo rm ) of 1, 52dipheny1232b iphenylyl222pyra2 zo line (2) (F ig. 1) show that w ith the increase of the concen tration of 1, 52diphenyl232b iphenylyl222pyra2 zo line, its fluo rescence excitation peak s and em is2 sion p eak s m ove tow a rd s infra2red, and fluo res2 cence em ission in ten sity increa ses. ow ever, it s fluo rescence is ann ih ilated w hen the concen tration
2 20 EM. R ES. I ESE U. V o l. 20 is h igher than 1 10-3 mo lgl becau se dipo lym er, tripo lym er and po lym er w ere fo rm ed the b it mo lecu les. 5 Prepar ing Fluorescence Pa in t T he po lym ethyl m ethacrylate ( PMM A ) w as disso lved in ch lo robenzene fo r p reparing a w (PMM A ) 2% 8% so lu tion. T hen a certain amoun t of fluo rescence dye w as added and stirred. It m ay be directly u sed to sm ear o r p rin ṫ T he in itial test resu lts ( see T ab le 2) indicate that m (D ye) gm (D isperser) = 1 50 is a su itab le condition fo r p rin t comparatively. ompd. g F ig. 1 The f luorescence spectra of 1. 5-diphenyl-3-biphenylyl-2-pyrazoline (2 a. 8. 0 10-7 mo lgl, b. 8. 0 10-6 mo lgl, c. 3. 6 10-5 mo lgl, d. 7. 2 10-5 mo lgl, e. 1. 0 10-3 mo lgl, f. 1. 2 10-2 mo lgl. Table 2 Effect of disperser quan tity on f lnorescen t in ten sity m (D ye) gm (D isperser) 1 10 1 50 1 100 (very intensive) ( intensive) ( o intensive) ompd. g m (D ye) gm (D isperser) 1 10 1 50 1 100 B lue2green fluo rescent light (very intensive) B lue2green ( intensive) ( o intensive) B lue green fluo rescent light Re fe re nce s [ 1 ] L ei G. D., L u Z. Y., Zhu W. G., et a l., hem ica l R e2 search and A pp lication., 1999, 11 (3), 308 [ 2 ] L i D. X., M eng Z. X., J iao. X., et a l., F ine hem icals, 2001, 18 (5), 271 [ 3 ] Sandler S. R., J. hem., P hy ṡ, 1963, 30, 1062 [ 4 ] Bo rsenberger P. M., J. P hy ṡ hem., 1994, 98, 233 [ 5 ] Sano, J ap an A pp l. P hy ṡ, 1995, 34 (1), 3124 [ 6 ] Gao X.., J. M ater. hem., 1999, 9, 1077 [ 7 ] W n S. K., T h in S olid F ilm ṡ, 2000, 371, 40 [ 8 ] Fan. T., D ictionary of rg aic S y nthesis, Beijing U niversi2 ty of Techno logy P ress, Beijing, 1992, 758 [ 9 ] L i D. X., L i J. F., L u F., et al., hem ical R esearch in hinese U niversities, 2002, 18 (3), 34