Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives

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1 AASCIT Journal of Chemistry 2015; 2(2): Published online April 10, 2015 ( Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives Thawra Ahmad 1, *, Farouk Kandil 1, Chahid Moustapha 2 1 Chemistry Department, Faculty of Science, Damascus University, Damascus, Syria 2 Chemistry Department, Faculty of Science, Tishreen University, Lattakia, Syria address thawra.ahmad.a@gmail.com (T. Ahmad), farouk-k@windowslive.com (F. Kandil) Keywords Schiff Bases, Fluorene, Azo Dye, Azomethine Dye, Azolidine-2-One, and Tiazolidin-4-One Received: February 2, 2015 Revised: March 24, 2015 Accepted: March 25, 2015 Citation Thawra Ahmad, Farouk Kandil, Chahid Moustapha. Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives. AASCIT Journal of Chemistry. Vol. 2, No. 2, 2015, pp Abstract A series of Schiff bases and their fluorene derivatives have been synthesized. Primary amines were condensed with aromatic keton, 2-acetyl fluorene in DMF (dimethyl formamide) in the presence of conc. HCl acid as catalyst to yield the Schiff bases (I, IV). The Schiff base (I) was treated with diazotised p-sulphanilic acid to give Azomethine Dye compound (II), and The Schiff base (I) was treated with benzenediazonium salt solution to give Azo Dye compound (III), The Schiff bases (V,VI and VII) were prepared from the reaction of Schiff base (IV) with 2-hydroxy-5-methyl-1,3- benzenedicarboxaldehyde and 2,5-dihydroxy benzaldehyde respectively. The Schiff base (VII) was treated with mono-chloro acetyl choride to give 1-{p-[1-(2-fluorenyl) ethylideneamino]phenyl}-3-chloro-4-(2,5-dihydroxyphenyl)-2- azetidinone (VIII). And with α-mercaptoacetic acid gave 3-{p-[(1-(2-Fluorenyl) ethylidene amino] phenyl}-2- (2,5-dihydroxy phenyl)-1,3- thiazolidin-4-one (IX). The structures of synthesized compounds have been established based on their spectral (FT-IR, MS, 1 H-NMR and 13 C- NMR) data and elemental analysis. TLC confirmed the purity of the prepared compounds. 1. Introduction Azo dyes constitute one of the largest and most varied groups of synthetic organic dyes in use today 1. Azo compounds are highly important, well- known and widely used substances in the textile, paper, coloring agents for foods and cosmetics industries. Other applications include emerging technologies like liquid crystals, organic photoconductors and non-linear optics. Azo compounds serve as important analytical tools by providing a strongly chromophoric label, the concentration of which is easily determined by colorimetric, spectrophotometric or spectrofluorimetric methods. Besides, azo compounds are important analytical aid compounds serving as ph indicators, complexometric indicators and to a lesser extent, pre-concentration reagents. The pharmacological use of azo compounds originates from the discovery of the antibacterial action of Prontosil on streptococcal infections by Dogmagk. Furthermore, azo compounds were reported to show a variety of biological activities including antibacterial, antifungal, pesticidal, antiviral and anti-inflammatory activities 1-6. Fluorene-based aromatic compounds are of increasing interest as building blocks for the production of drugs and pharmaceuticals and as fine chemicals of industrial relevance, including applications in the production of thermosetting plastics and

2 AASCIT Journal of Chemistry 2015; 2(2): lubricating materials. In addition, fluorene-based polymers and copolymers are of interest owing to their unusual optical and electrical properties and are for that reason commonly used in organic light-emitting diodes, flat panel displays and in solar cells 7. Some Schiff bases bearing aryl groups or heterocyclic residues possess excellent biological activities, which has attracted many researcher s attention in recent year. They have been reported to use as analgesic, antibacterial, antituberculer, anti-rheumatoid arthritis, anti-viral, antiinflammatory, anti-hypertensive, anti-microbial and anticancer. Fluorene derivatives introduced in 1960 for use in relief of the pain, fluorene is homologous ring. fluorene compounds have medical and biological important and they have medicinal and pharmaceutical application Among the wide chemical derivatives are a heteropolymer, which have activity and effectiveness against cancer they also have effective against malaria and bacteria, found that some fluorene derivative is considered a medical drug against some diseases In this paper we have synthesized new Schiff bases, azo compounds and heterocyclic derivatives from 2-acetyl fluorene with primary amine because these compounds have many applications in medicine and industry. 2. Material and Methods 2.1. General Procedures Melting points were determined in open glass capillaries on Aagallenkamp apparatus and are uncorrected. TLC was performed to assess the reactions and the purity of the products. IR spectra were recorded in KBr (pellet forms) on anicolet-avatar-330 FT-IR spectrophotometer and noteworthy absorption values (cm -1 ) alone are listed. 1 H and 13 C-NMR Spectra were recorded at 400 MHZ Bruker AMX using CDCl 3 as solvent. The ESI+ve MS spectra were recorded on a Bruker Daltonics LC-MS Spectrometer. Satisfactory microanalysis was obtained on Carlo Erba 1106 CHN analyzer Chemical and Starting Materials 2-acetyl fluorine, 2-hydroxy-5-methyl-1,3- benzenedicarboxaldehyde, 2,5-dihydroxy benzaldehyde, monochloroacetyl chloride, α-mercaptoacetic acid, Ρ-amino phenol, Ρ-phenylenediamine, dioxane, p-sulphanilic acid, aniline, sodium nitrite and zinc chloride (all from Aldrich) were used as supplied, without further purification General Procedure for Synthesis of Schiff Bases and their Derivatives p-[1-(2-fluorenyl)ethylideneamino]phenol. (I) p-[1-(2-fluorenyl)ethylideneamino]aniline. (IV) Schiff bases (I, IV) were prepared by the reaction of two primary amines (Ρ-amino phenol, Ρ-phenylenediamine) respectively, (0.02 mol) with 2-acetyl fluorine (0.02 mol), in 50 ml DMF (dimethyl form amide) and few drops of conc. HCl acid. This mixture was refluxed for 12hrs. The mixture was cooled, filtered and recrystallized from absolute ethanol 11, Preparation of Azo Compounds Hydroxy-5-[1-(2-Fluorenyl) Ethylideneamino]-4'-Sulfo-Azobenzene. (II) p-sulphanilic acid ( 0.69 g, mol) was dissolved in dilute hydrochloric acid, stirred vigorously while being cooled to 0 C. A solution of sodium nitrite (0.28 g, mol) in distilled water was added dropwise to the reaction mixture and the solution was kept below 0 C. KOH (0.224 g, mol) was dissolved in methanol and was added Shiff base (1.3 g, mol) with constant stirring. This solution was added dropwise to diazotised p-sulphanilic acid. The solution was cooled to 0 C. The dye (azo compound II) was extracted from the reaction mixture by treating with dichloromethane. The dichloromethane layer was washed repeatedly 3-4 times with 20 ml of distilled water and evaporated to dryness Hydroxy-5-[1-(2-Fluorenyl) Ethylideneamino]-Azobenzene. (III) (i) Preparation of the Diazonium Salt Solution 50 g ice, 20 ml water and 5 ml conc. hydrochloric acid were filled in a 100 ml Erlenmeyer flask with magnetic stirring bar and internal thermometer. To this mixture 0.93 g (0.01 mol) aniline were added. Under ice cooling and stirring and at an internal temperature of 0-5 C. A solution of mg (0.01 mol) sodium nitrite in 20 ml water was added slowly by using a pipette, so that an excess of nitric acid is avoided. The test for HNO 2 was carried out with potassium iodide starch test strips by dropping a sample of the reaction solution with a pipette on a test strip. A blue coloured paper shows HNO 2. So much sodium nitrite solution was added, that a proof is positive still 5 minutes after the last addition of nitrite. Excessive nitric acid was removed by addition of a small amount of urea. (ii) Azocoupling g (0.006 mol) Schiff base compound (I) are dissolved in (0.1) M sodium hydroxide solution in a 250 ml Erlenmeyer flask. The solution was cooled. Under strong stirring and ice cooling, the ice cooled benzenediazonium salt solution is added in portions. Towards the end of addition the ph value of the solution is controlled. To keep the solution in the alkaline range, a (0.1 M) sodium hydroxide solution was added dropwise by means of a pipette, if necessary. After the addition is finished, the mixture was stirred for 30 minutes at 0-5 C. (iii) Work Up The dark brown color precipitated product was sucked off

3 26 Thawra Ahmad et al.: Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives over a Buchner funnel and repeatedly washed with water. The product was dried in the vacuum desiccator until weight constancy. According to the vacuum and drying agent, the drying procedure can last up to a few days. The crude product was recrystallized from 50 ml ethanol and then dried in the vacuum desiccator Preparation of Schiff Base Azomethine Dye (V), and Schiff Base (VI) 3,5-Bis{p-[1-(2-fluorenyl)ethylideneamino]- phenylimino}cresol. (V) 3-{p-[1-(2-Fluorenyl)ethylideneamino]phenylimino}-2- hydroxy-5-methyl benzaldehyde (VI) Schiff bases (V, VI) were prepared from the reaction of Schiff base (IV) (0.004 mol), with 2-hydroxy-5-methyl-1,3- benzenedicarboxaldehyde (0.002 mol), in 50 ml absolute ethanol and few drops of conc. HCl acid. This mixture was refluxed for 24hrs. The mixture was cooled; precipitate was formed and recrystallized from ethanol absolute, the precipitate was compound (VI), the filtrate was evaporated by rotary evaporator and green yellow powder was formed. This powder recrystallized from a mixture of acetone and ether. The obtained compound was (V) Preparation of Schiff Base (VII) 2-{p-[1-(2-Fluorenyl)ethylideneamino] phenylimino} hydroquinone. (VII) Schiff base (VII) was prepared from the reaction of Schiff base (IV) (0.002 mol), with 2,5-dihydroxy benzaldehyde, (0.002 mol), in 50 ml absolute ethanol and few drops of conc. HCl acid. This mixture was refluxed for 24hrs. The mixture was cooled filtered and recrystallized from absolute ethanol Preparation of 1-{p-[1-(2-Fluorenyl) Ethylideneamino] Phenyl}-3-Chloro-4-(2,5- Dihydroxyphenyl)-2-Azetidinone (VIII) A solution of Schiff base compound (VII) ( mol) in dioxane (50 ml) was added to a well- stirred mixture of monochloroacetyl chloride ( mol, 0.31 ml) and triethyl amine ( mol, 0.50 ml) in dioxane (20 ml) at 0-5 ºC. The mixture was refluxed for (10-12) hrs. and kept for 2 days at room temperature. The reaction mixture was then poured into crushed ice, filtered and washed with water. The solid product was dried and recrystallized from ethanol and water Preparation of 3-{p-[(1-(2- Fluorenyl)Ethylideneamino]Phenyl}-2- (2,5-Dihydroxy Phenyl)-1,3-Thiazolidin-4- one (IX) To a mixture of Schiff base compound (VII) ( mol) and mercaptoacetic acid (0.018 mol) dissolved in dioxane (50 ml), anhydrous zinc chloride (0.003 mol) was added and refluxed for 12 hrs. The reaction mixture was cooled, filtered, washed with 10% w/v sodium bicarbonate solution, vacuum dried and recrystallised using absolute ethanol Results and Discussion The present work involved three steps. First step: includes preparation of new five Schiff bases (I, II, III, IV, V, VI, VII) were prepared by reaction of two primary amines with 2-acetyl fluorene. The synthesis of these compounds was carried out lined in Scheme (1,2,3) and the physical properties for Schiff bases including melting point range of (89-265) and % yield were range of (79-98) and these compounds were identified by FT-IR Spectroscopy, LC-MS, 1 H, 13 C-NMR. FT-IR spectrum of compound (II) showed characteristic absorption bands ( ) cm -1, (3065.3) cm -1,( ) cm -1, ( ) cm -1, ( ) cm -1, (1543.9) cm -1, ( ) cm -1 due to v(c=n)str, v(c-h) aromatic, v(c-h)aliphatic, v(c=c)aromatic, v(oh), v(n=n)azo group, v(so 3 ), respectively. As shown in table (3). 1 H-NMR spectrum of compounds (II) showed multiplet signals at ( ) ppm due to aromatic protons and singlet signal at (4.98)ppm due to (OH) group proton and singlet signal at (3.21) ppm due to (CH 2 ) group protons of fluorene ring, in addition to singlet signal at (0.95) due to (CH 3 ) methyl group protons. 13 C-NMR of compounds (II) showed multiplet signal at ( ) ppm due to aromatic carbons, signal at (41.99) ppm due to (CH 2 ) carbon of fluorene ring, signal at (159.34) ppm due to (C=N) carbon, in addition to signal at (15.13) ppm due to (CH 3 ) due to methyl group carbon. The physical properties (melting points, yields, elemental analysis and spectral data) of these compounds are included in tables (1, 2), and the Spectroscopy data included in table (3) Second step: The second step include preparation of new Lactam derivative (VIII) which prepared by reaction of Schiff bases (VII) in (First step) with monochloroacetyl chloride in dioxane. The synthesis of this compound was carried out lined in scheme (3). And the physical properties for lactam derivative (VIII) including melting point is (155) C and % Yield is (88) and this compound was identified by FT-IR, LC-MS and 1 H, 13 C-NMR. FT-IR spectrum of compound (VIII) showed clear absorption bands at ( ) cm -1 due to the v(c=o) of lactam ring, (636.98) cm -1 due to the v(c-cl) of lactam ring, ( ) cm -1 due to the v(c-h) aromatic, ( , ) cm -1 due to the v(oh), ( ) cm -1 due to the v(c=n). The 1 H-NMR spectrum of compound (VIII), showed multiplet signals at ( ) ppm due to aromatic protons and a singlet signal at (5.55) ppm due to N-CH group proton of lactam ring, a singlet signal at (4.56) ppm due to Cl-CH group proton of lactam ring and a singlet signal at (4.84) ppm due to proton of (OH) group and a singlet signal at (0.83) ppm due to (CH 3 ) methyl group protons. 13 C-NMR spectrum of compound (VIII) showed signals at ( ) ppm due to aromatic carbons and signal at (177.23) ppm due to (C=O) carbon of lactam, and signals at (49.04) ppm due to (HC-Cl) carbon of lactam, signals at (59.74) ppm due to (N-CH) carbon of lactam, and signals at (159.51) ppm due to (C=N) carbon. The signal at (13.86) ppm due to (CH 3 ) methyl group carbon. The physical properties (melting points, yieldes, elemental

4 AASCIT Journal of Chemistry 2015; 2(2): analysis and spectral data) of this compound are included in tables (1, 2), and the Spectroscopy data included in table (3) Third step: The third step includes preparation of new thiazolidinone-4 derivatives (IX) which prepared by reaction of Schiff base (VII) in (First step) with mercaptoacetic acid in dioxane. The synthesis of this compound was carried out lined in scheme (3). And the physical properties or Thiazolidinone-4 derivative (IX) including melting point was (143) C 0 and %Yield was (94) and this compound was identified by FT-IR, LC-MS and 1 H, 13 C-NMR. FT-IR spectrum of compound (IX) showed clear absorption bands at ( ) cm -1 due to the v(c=o) of thiazolidinone-4 ring, ( ) cm -1 due to the v(c-h)aromatic, ( ) cm -1 due to the v(oh), ( ) cm -1 due to the v(c=n), ( ) cm-1 due to the v(c=c) aromatic, ( , ) cm-1 due to the v(c-o). The 1 H-NMR spectrum of compound (IX), showed multiplet signals at ( ) ppm due to aromatic protons and a singlet signal at (5.95) ppm due to (N-CH) group proton of thiazolidinone-4 ring, a singlet signal at (2.94) ppm due to (CH 2 ) group protons of Thiazolidinone-4 ring, and a singlet signal at (4.89) ppm due to (-OH) group proton in addition to singlet signal at (0.69) ppm due to (CH 3 ) methyl group protons. 13 C-NMR spectrum of compound (IX) showed signals at ( ) ppm due to aromatic carbons and signals at (177.35) ppm due to (C=O) carbon of thiazolidinone-4, and signal at (66.33) ppm due to (HC-N) carbon of thiazolidinone-4, signal at (34.56) ppm due to (CH 2 ) carbon of thiazolidinone-4. in addition to signal at (15.02) ppm due to (CH 3 ) methyl group carbon. The physical properties (melting points, yields, elemental analysis and spectral data) of this compound are included in tables (1, 2), and the Spectroscopy data included in table (3) Scheme 1. Synthesis of Schiff base and azo Dyes Scheme 2. Synthesis of Schiff base and Azomethine Dyes

5 28 Thawra Ahmad et al.: Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives Scheme 3. Synthesis of Schiff base and fluorene Heterocyclic derivatives Table 1. Melting points, yield, molecular formula (M. F.), molecular weight (M. Wt.), colour and Rf of compounds [I-IX] Comp. R M.Wt. M.F. Yield (%) M.P ( 0 C) Colour Rf (eter: hexan) (1:3) I 299 C 21NOH rotten 0.63 II 403 C 27N 3OH grey 0.58 III 483 C 27N 3O 4SH oily 0.28 IV 298 C 21N 2H rotten 0.34 V 724 C 51N 2OH lime yellow 0.42 VI 444 C 30N 4O 2H brown 0.38 VII 418 C 28N 2O 2H oily 0.46 VIII C 30N 2O 3Cl H grey 0.36 IX 492 C 30N 2O 3S H black 0.52

6 AASCIT Journal of Chemistry 2015; 2(2): Compound R Table 2. Depicted elemental analysis (C.H.N) of synthesis compounds [I-IX] Found Calculated C% H% N% S% C% H% N% S% I II III IV V VI VII VIII IX Table 3. Spectroscopial data of Synthesized Schiff Base of fluorene derivatives Comp. NO I Spectroscopy data IR(KBr, cm -1 ): 3465,46 [(OH)], [(C-H) Ar], 2995 [(C-H)Alipha], [(C=N)], [(C=C) Ar], [(C-O)]. LC-MS: m/z = H-NMR (400 MHz, CDCl 3, ppm)δh: 5.25 (S, 1H, OH), 3.48 (S, 2H, CH 2 fluorene ring), 0.59 (S, 3H, -CH 3), (m, 11H, aromatic ring). 13 C-NMR(400MHz,CDCl 3,ppm)δC: (C=N), 41,87(CH 2 fluorene ring), 15.93(CH 3), (aromatic ring). II IR (KBr, cm -1 ): [(OH)], [(C-H) Ar], [(C-H)Alipha], [(C=N)], [(C=C) Ar], [(C- O)], [(N=N)], [(SO 3)]. LC-MS: H NMR (400 MHz, CDCl 3, ppm) δh: (S, 1H, OH), 3. 21(S, 2H, CH 2 fluorene ring), 0.95 (S, 3H, CH 3), (m, 14H, aromatic ring). 13 C-NMR(400MHz, CDCl 3, ppm)δc: (C=N), 41, 99(CH 2 fluorene ring), (CH3), (aromatic ring). III IR(KBr, cm -1 ): [(OH)], [(C-H) Ar], [(C-H)Alipha],1682,9 [(C=N)], [(C=C) Ar], [(C- O)], [(N=N)],. LC-MS: HNMR(400 MHz, CDCl 3, ppm)δh: (S, 1H, OH), 3. 24(S, 2H, CH 2 fluorene ring), 0.76 (S, 3H, CH 3), (m, 15H, aromatic ring). 13 C-NMR:(400MHz,CDCl 3,ppm)δC: (C=N), 41, 98 (CH 2 fluorene ring), (CH3), (aromatic ring). IV IR(KBr,cm -1 ):(3451, 3351)[(NH)], [(C-H) Ar], [(C-H)Alipha], [(C=N)], 1588 [(C=C) Ar]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh: 5.15(S, 1H, NH), 3.56(S, 2H, CH 2 fluorene ring), 0.97 (S, 3H, CH 3), (m, 11H, aromatic ring). 13 C-NMR:(400MHz, CDCl 3, ppm)δc: (C=N), 41,84 (CH 2 fluorene ring), (CH 3), (aromatic ring).

7 30 Thawra Ahmad et al.: Preparation and Characterization of Some New Azo Dyes, Azomethine Dyes and Heterocyclic -Schiff Bases Derivatives Comp. NO Spectroscopy data V IR (KBr, cm -1 ): ( )[(OH)], [(C-H) Ar], , , [(C-H)Aliph], [(HC=N)], [(C=C) Ar], [(C-O)]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh: 9.79(S,1H,HC=N), (S, 1H, OH), 2.84 (S, 2H, CH 2 fluorene ring), 1.79 (S, 6H, CH 3(a,b)), 0.84 (S, 3H, CH 3(c)), 7,44-8,11(m, 24H, aromatic ring). 13 C-NMR(400MHz, CDCl 3, ppm)δc: (HC=N), (C=N), 41,88(CH2, fluorene ring), (CH 3(c)), (CH 3(a,b)), (aromatic ring). VI IR (KBr, cm -1 ):( )[(OH)], [(C-H) Ar], , [(C-H) Aliph], , [(C-H)Aldehydic], 1708 [(C=O)], [(HC=N)], [(C=C) Ar], [(C-O)]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh:9.65(s,1h,hc=n), 8.44(S,1H, C), 4.91 (S, 1H, OH), 3.23(S, 2H, CH 2,fluorine ring), 2.24 (S, 3H, CH 3(b)), 0.98 (S, 3H, CH 3(c)), (m, 13H, aromatic ring). 13 C-NMR(400MHz,CDCl 3,ppm)δC: (C), (HC=N), (C=N), 41,85(CH 2, fluorene ring), 19.81(CH 3(b)), (CH 3(a)), (aromatic ring). VII IR (KBr, cm -1 ):( , )[(OH)], 3038 [(C-H) Ar], (C-H)Alipha], [(HC=N)], [(C=C) Ar], , [(C-O)]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh: 8.68(S,1H,HC=N), 5.03 (S, 1H, OH), 3.42(S, 2H, CH 2,fluorine ring), 0.79 (S, 3H, CH 3), (m, 13H, aromatic ring). 13 C-NMR(400MHz,CDCl 3,ppm)δC: (HC=N), (C=N), 41,87 (CH 2, fluorene ring), (CH 3), (aromatic ring). VIII IR(KBr,cm -1 ):( , )[(OH)], [(C-H) Ar], [(C-H)Alipha], [(C=O)Lactam], [(C=N)], [(C=C) Ar], , [(C-O)], [(C-Cl)]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh: : 5.55(S,1H, N-CH), 4.84 (S, 1H, OH), 4.56(S,1H, Cl-CH), 3.24(S, 2H, CH 2,fluorene ring), 0.83 (S, 3H, CH 3), (m, 14H, aromatic ring). 13 C-NMR(400MHz, CDCl 3, ppm)δc: (C=O)lactam, (C=N), 59.74(N-CH), 49.04(Cl-CH), 41,97 (CH 2, fluorene ring), (CH 3), (aromatic ring). IX IR(KBr,cm -1 ):( , )[(OH)], [(C-H) Ar], [(C-H)Alipha], [(C=O)], [(C=N)], [(C=C) Ar], , [(C-O)]. LC-MS: H-NMR(400MHz, CDCl 3, ppm)δh: 5.95 (S, 1H,N-CH thiazolidinone), 4.89 (S, 1H, OH), 3.43(S, 2H, CH 2,fluorene ring), 2.94 (S, 2H, CH 2 thiazolidinone), 0.69 (S, 3H, CH3), (m, 14H, aromatic ring). 13 C-NMR(400MHz,CDCl 3,ppm)δC: (C=O thiazolidinone),159.17(c=n), 66.33(N-CH thiazolidinone),41,98(ch 2 fluorene ring), 34.56(CH 2 thiazolidinone), (CH 3), (aromatic ring).

8 AASCIT Journal of Chemistry 2015; 2(2): Conclusions The main aim of the present study is to synthesize Schiff bases and new heterocyclic derivatives containing, fluorene moiety, and new azo, azomethine dyes containing fluorene ring from new Shiff bases containing fluorene moiety also, Nine new heterocyclic with fluorine substituted compounds were synthesized, and characterized by IR, 1 H-NMR, 13 C- NMR and LC-MS spectral methods and elemental analysis. The yields were excellent and the reactions times were acceptable. We hope from our research to discover new structures serving as potential broad-spectrum antimicrobials and anti-corrosion agents. Acknowledgments We are grateful to Department of Chemistry, Faculty of Sciences, Damascus University, Syria and Syrian Atomic Energy Commission for recording 1 H-NMR, 13 C-NMR and LC-MS spectra. References [1] Xu, H. & Zeng, X. (2010) "Synthesis of diaryl-azo derivatives as potential antifungal agents". Bioorg. Med. Chem. Lett., 20, [2] Tonelli, M., Vazzana, I., Tasso, B., Boido, V., Sparatore, F., Fermeglia, M., Paneni, M. S., Posocco, P., Pricl, S., Colla, P., Ibba, C., Secci, B., Collu, G. & Loddo, R. (2009) "Antiviral and cytotoxic activities of aminoarylazo compounds and aryltriazene derivatives". Bioorg. Med. Chem., 17, [3] Jarrahpour, A. & Zarei, M. (2010) "Efficient one- pot synthesis of 2-azetidinones from acetic acid derivatives and imines using methoxymethylene- N,N-dimethyliminium salt". Tetrahedron, 66, " [4] Jarrahpour, A. & Zarei, M. (2009) DMF-dimethyl sulfate as a new reagent for the synthesis of β-lactams". Tetrahedron Lett. 50, [5] Zarei, M. & Mohamadzadeh, M. (2011)" 3- Thiolated 2- azetidinones: synthesis and in vitro antibacterial and antifungal activities". Tetrahedron, 67, [6] Zhao, X., Li, C., Zeng, S. & Hu, W. (2011) "Discovery of highly potent agents against influenza A virus". Eur. J. Med. Chem., 46, [7] Salam. J. J. Titnchi, Fadhil. S. Kamounah, Hanna. S. Abbo, and ole Hammerich, (2008) "the synthesis of mano and diacetyl -, H- fluorenes. Reactivity and selectivity in the lewis acid catalyzed Friedel Grafts acetylation of, 9H-fluorine", arkivoc, Xiii, [8] K. Venkatesan;S. Dhivya;J. Rethavathi and S. Narasimhan; (2012)" Preparation of various Schiff, s bases of 9- fluorenone and its biological application", J. Chem. pharm. Res. 4(10), [9] M. C. Sharma;D. V. Kohli;S. Sharma;A. D. Sharma; (2010)"Synthesis and antihypertensive activity of 4'-{2-[4-[2- (substituted-phenyl)-4-oxo-thiazolidin-3-yl]-benzoimidazol-1- yl methyl}-biphenyl-2-carboxylic acids", Der pharmacia Sinica, 1(1), [10] Iranpoor, N., Firouzabadi, H., Khalili, D. & Motevalli, S. " Easily prepared azopyridines as potent and recyclable reagents for facile esterification reactions: an efficient modified Mitsunobu reaction". J. Org. Chem., 73, , [11] Tidwell, T. T. Hugo (Ugo) Schiff, (2008) Schiff bases, and a century of β-lactam synthesis. Angew. Chem. Int. Ed., 47, [12] Vazzana, I.E. ;Terranova, F. ; Mattioli and F. Sparatore, (2004) Aromatic Schiff Bases and 2,3- Disubstituted 1,3- Thiazolidin-4-one Derivatives as Anti-inflammatory agents ARKIVOC, V, ,. [13] Park, J. & Koh, J. (2009) "The synthesis and spectral properties of an encapsulated aminoazobenzene dye ". Dyes Pigm., 82, [14] Kumarand, H.; Chaudhary, R. (2010) "Biological studies of a novel azo based Heterocyclic Schiff base and its transition metal complexes "; Der. Chem. Sin. 1, [15] S. Gopalakrishnan, N. T. Nevaditha and C. V. Mythili, (2011) "Antibacterial activity of azo compounds synthesized from the natural renewable source, cardanol", J. Chem. Pharm. Res., 3(4): [16].Jubie S, Gowramma B, Nitin K Muthal, Elango K. (2009) "Synthesis and antimicrobial evaluation of some 2- azetidinone derivatives". Int. J of ChemTech Res; 1(2): [17] Deepak Pareek, Manish Chaudhary, (2011) Synthesis and biological evaluation of thiazolidinone derivatives incorporating benzothiazole moiety". Der Pharmacia Sinica. ; 2(1):