AASCIT Journal of Chemistry 2015; 2(2): 24-31

Published online April 10, 2015 (http://www.aascit.org/journal/chemistry)

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

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

Thawra Ahmad1, *

, Farouk Kandil1, Chahid Moustapha

2

1Chemistry Department, Faculty of Science, Damascus University, Damascus, Syria

2Chemistry Department, Faculty of Science, Tishreen University, Lattakia, Syria

Email address thawra.ahmad.a@gmail.com (T. Ahmad), farouk-k@windowslive.com (F. Kandil)

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. 24-31.

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, 1H-NMR and

13C-

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 today1. 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

AASCIT Journal of Chemistry 2015; 2(2): 24-31 25

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, anti-

tuberculer, anti-rheumatoid arthritis, anti-viral, anti-

inflammatory, anti-hypertensive, anti-microbial and anti-

cancer. 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

diseases8-10

.

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. 1H and

13C-NMR Spectra were recorded at 400 MHZ Bruker AMX

using CDCl3 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.

2.2. 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.

2.3. 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 11,12

.

2.4. Preparation of Azo Compounds

2.4.1. 2-Hydroxy-5-[1-(2-Fluorenyl)

Ethylideneamino]-4'-Sulfo-Azobenzene.

(II)

p-sulphanilic acid ( 0.69 g, 0.004 mol) was dissolved in

dilute hydrochloric acid, stirred vigorously while being

cooled to 0 °C. A solution of sodium nitrite (0.28 g, 0.004

mol) in distilled water was added dropwise to the reaction

mixture and the solution was kept below 0 °C. KOH (0.224 g,

0.004 mol) was dissolved in methanol and was added Shiff

base (1.3 g, 0.004 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 13

.

2.4.2. 2-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 0.759

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 HNO2 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 HNO2. 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

1.794 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

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 14

.

2.4.3. 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) 15

.

2.4.4. 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.

2.5. 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) (0.0036 mol) in

dioxane (50 ml) was added to a well- stirred mixture of

monochloroacetyl chloride (0.0036 mol, 0.31 ml) and triethyl

amine (0.0036 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 16

.

2.6. 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) (0.0036 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 17

.

3. 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, 1H,

13C-NMR. FT-IR spectrum of compound (II)

showed characteristic absorption bands (1679.69) cm-1

,

(3065.3) cm-1

,( 2997.8) cm-1

, (1600.04) cm-1

, (3338.18) cm-1

,

(1543.9) cm-1

, (1265.07) 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(SO3), respectively. As shown in table

(3). 1H-NMR spectrum of compounds (II) showed multiplet

signals at (7.11 - 7.86) 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 (CH2) group protons of

fluorene ring, in addition to singlet signal at (0.95) due to

(CH3) methyl group protons. 13

C-NMR of compounds (II)

showed multiplet signal at (114 - 156) ppm due to aromatic

carbons, signal at (41.99) ppm due to (CH2) carbon of

fluorene ring, signal at (159.34) ppm due to (C=N) carbon, in

addition to signal at (15.13) ppm due to (CH3) 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 1H,

13C-NMR. FT-IR

spectrum of compound (VIII) showed clear absorption bands

at (1689.69) cm-1

due to the v(C=O) of lactam ring, (636.98)

cm-1

due to the v(C-Cl) of lactam ring, (3025.26) cm-1

due to

the v(C-H) aromatic, (3365.97, 3265.73) cm-1

due to the

v(OH), (1653.34) cm-1

due to the v(C=N). The 1H-NMR

spectrum of compound (VIII), showed multiplet signals at

(6.94 - 7.87) 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 (CH3)

methyl group protons. 13

C-NMR spectrum of compound

(VIII) showed signals at (115 – 147) 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 (CH3) methyl group carbon.

The physical properties (melting points, yieldes, elemental

AASCIT Journal of Chemistry 2015; 2(2): 24-31 27

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) C0 and %Yield was (94) and this compound was

identified by FT-IR, LC-MS and 1H,

13C-NMR. FT-IR

spectrum of compound (IX) showed clear absorption bands at

(1683.76) cm-1

due to the v(C=O) of thiazolidinone-4 ring,

(3029.28) cm-1

due to the v(C-H)aromatic, (3404.71-3304.9)

cm-1

due to the v(OH), (1643.77) cm-1

due to the v(C=N),

(1564.87) cm-1 due to the v(C=C) aromatic, (1226.57,

1265.07) cm-1 due to the v(C-O). The 1H-NMR spectrum of

compound (IX), showed multiplet signals at (6.93 -7.88) 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 (CH2) 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 (CH3) methyl group protons. 13

C-NMR spectrum

of compound (IX) showed signals at (116 - 149) 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 (CH2) carbon of thiazolidinone-4. in addition to signal at

(15.02) ppm due to (CH3) 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

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 (0C) Colour Rf (eter: hexan) (1:3)

I OH

299 C21NOH17 89 95-97 rotten 0.63

II OH

403 C27N3OH21 86 89-91 grey 0.58

III OH

483 C27N3O4SH21 79 122-124 oily 0.28

IV NH2

298 C21N2H18 93 105 rotten 0.34

V NH2

724 C51N2OH40 98 263-265 lime yellow 0.42

VI NH2

444 C30N4O2H24 95 102 brown 0.38

VII NH2

418 C28N2O2H22 97 116 oily 0.46

VIII NH2

494.5 C30N2O3Cl H23 88 155 grey 0.36

IX NH2

492 C30N2O3S H24 94 143 black 0.52

AASCIT Journal of Chemistry 2015; 2(2): 24-31 29

Table 2. Depicted elemental analysis (C.H.N) of synthesis compounds [I-IX]

Compound R Found Calculated

C% H% N% S% C% H% N% S%

I OH

84.37 5.89 4.56 0.00 84.28 5.69 4.68 0.00

II OH

67.33 4.42 8.75 6.71 67.08 4.35 8.69 6.63

III OH

80.42 5.30 10.36 0.00 80.39 5.21 10.42 0.00

IV NH2

84.63 6.12 9.41 0.00 84.56 6.04 9.39 0.00

V NH2

84.49 5.55 7.69 0.00 84.53 5.52 7.73 0.00

VI NH2

81.11 5.38 6.23 0.00 81.08 5.41 6.31 0.00

VII NH2

80.29 5.31 6.72 0.00 80.38 5.26 6.69 0.00

VIII NH2

72.77 4.69 5.70 0.00 72.80 4.65 5.66 0.00

IX NH2

73.19 4.91 5.67 6.48 73.17 4.88 5.69 6.50

Table 3. Spectroscopial data of Synthesized Schiff Base of fluorene derivatives

Comp. NO Spectroscopy data

I

IR(KBr, cm-1): 3465,46 [�(OH)], 3017. 69 [�(C-H)Ar], 2995 [�(C-H)Alipha],1680. 66 [(C=N)], 1557. 89 [�(C=C)Ar], 1228.43 [�(C-O)]. LC-MS: m/z =299.13. 1H-NMR (400 MHz, CDCl3, ppm)δH: 5.25 (S, 1H, OH), 3.48 (S, 2H, CH2 fluorene ring), 0.59 (S, 3H, -CH3), 7.03-7.78 (m, 11H, aromatic ring). 13C-NMR(400MHz,CDCl3,ppm)δC: 159.53(C=N), 41,87(CH2 fluorene ring), 15.93(CH3), 115-155(aromatic ring).

II

IR (KBr, cm-1): 3338.18 [(OH)] , 3065.3 [�(C-H)Ar], 2997.8[�(C-H)Alipha], 1679.69 [�(C=N)], 1600.04 [�(C=C)Ar], 1226.5 [�(C-

O)],1453.9 [�(N=N)], 1265.07 [�(SO3)].

LC-MS:483. 13 1H NMR (400 MHz, CDCl3, ppm) δH: 4. 98 (S, 1H, OH), 3. 21(S, 2H, CH2 fluorene ring), 0.95 (S, 3H, CH3), 7.11 - 7.86 (m, 14H, aromatic ring). 13C-NMR(400MHz, CDCl3, ppm)δC: 159.34 (C=N), 41, 99(CH2 fluorene ring), 15.13 (CH3),114 -156(aromatic ring).

III

IR(KBr, cm-1): 3455.76 [�(OH)], 3022.93 [�(C-H)Ar], 2993.98[�(C-H)Alipha],1682,9 [�(C=N)], 1587. 33[�(C=C)Ar],1246.04 [�(C-

O)],1458.11 [�(N=N)],. LC-MS:403.17 1HNMR(400 MHz, CDCl3, ppm)δH: 4. 81 (S, 1H, OH), 3. 24(S, 2H, CH2 fluorene ring), 0.76 (S, 3H, CH3), 7.12 -7.86 (m, 15H, aromatic ring). 13C-NMR:(400MHz,CDCl3,ppm)δC: 159.63 (C=N), 41, 98 (CH2 fluorene ring), 14.98 (CH3), 115.8-155.5(aromatic ring).

IV

IR(KBr,cm-1):(3451, 3351)[�(NH)], 3029.68[�(C-H)Ar], 2996.93[�(C-H)Alipha], 1674. 73[(C=N)], 1588 [�(C=C)Ar]. LC-MS:298.15 1H-NMR(400MHz, CDCl3, ppm)δH: 5.15(S, 1H, NH), 3.56(S, 2H, CH2 fluorene ring) , 0.97 (S, 3H, CH3), 6.75 -7. 77(m, 11H, aromatic ring). 13C-NMR:(400MHz, CDCl3, ppm)δC: 159.34 (C=N), 41,84 (CH2 fluorene ring), 15.36 (CH3), 116-147(aromatic ring).

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): (3446.17)[�(OH)], 3028.25[�(C-H)Ar], 2998.68, 2975.62, 2918.73 [�(C-H)Aliph], 1677.77 [�(HC=N)], 1565.42

[�(C=C)Ar], 1225.54 [�(C-O)]. LC-MS:724.32 1H-NMR(400MHz, CDCl3, ppm)δH: 9.79(S,1H,HC=N), 6. 18 (S, 1H, OH), 2.84 (S, 2H, CH2 fluorene ring), 1.79 (S, 6H, CH3(a,b)), 0.84 (S, 3H, CH3(c)), 7,44 -8,11(m, 24H, aromatic ring). 13C-NMR(400MHz, CDCl3, ppm)δC: 160.81(HC=N), 158.29(C=N), 41,88(CH2, fluorene ring), 19.97 (CH3(c)), 13.39 (CH3(a,b)), 115-153(aromatic ring).

VI

IR (KBr, cm-1):(3336.25)[�(OH)], 3048. 91[�(C-H)Ar], 2966.95, 2911.02 [�(C-H) Aliph], 2861.84, 2791.46 [�(C-H)Aldehydic], 1708

[�(C=O)], 1675.48 [�(HC=N)], 1606.41 [�(C=C)Ar], 1223.61 [�(C-O)]. LC-MS:444.18 1H-NMR(400MHz, CDCl3, ppm)δH:9.65(S,1H,HC=N), 8.44(S,1H, CHO), 4.91 (S, 1H, OH), 3.23(S, 2H, CH2,fluorine ring), 2.24 (S, 3H, CH3(b)), 0.98 (S, 3H, CH3(c)), 7.93 -7.58(m, 13H, aromatic ring). 13C-NMR(400MHz,CDCl3,ppm)δC: 191.71(CHO), 161.57(HC=N), 157.14(C=N), 41,85(CH2, fluorene ring), 19.81(CH3(b)), 13.53 (CH3(a)), 116 -154(aromatic ring).

VII

IR (KBr, cm-1):(3375.12, 3275.16)[�(OH)], 3038 [�(C-H)Ar], 2906.2 �(C-H)Alipha], 1676.8 [�(HC=N)], 1606.9 [�(C=C)Ar], 1267.97,

1226.62 [�(C-O)]. LC-MS:418.17 1H-NMR(400MHz, CDCl3, ppm)δH: 8.68(S,1H,HC=N), 5.03 (S, 1H, OH), 3.42(S, 2H, CH2,fluorine ring), 0.79 (S, 3H, CH3), 6.93 - 7.86 (m, 13H, aromatic ring). 13C-NMR(400MHz,CDCl3,ppm)δC:160.86 (HC=N), 158.24(C=N), 41,87 (CH2, fluorene ring), 14.37 (CH3), 117-148 (aromatic ring).

VIII

IR(KBr,cm-1):(3365.97,3265.73)[�(OH)], 3035.26[�(C-H)Ar], 2898.49[�(C-H)Alipha], 1689.69 [�(C=O)Lactam], 1653. 34 [�(C=N)], 1566.

88 [�(C=C)Ar], 1266.04, 1227. 37 [�(C-O)], 636.98 [�(C-Cl)]. LC-MS:494.14 1H-NMR(400MHz, CDCl3, ppm)δH: : 5.55(S,1H, N-CH), 4.84 (S, 1H, OH), 4.56(S,1H, Cl-CH), 3.24(S, 2H, CH2,fluorene ring), 0.83 (S, 3H, CH3), 6.94 - 7.87 (m, 14H, aromatic ring). 13C-NMR(400MHz, CDCl3, ppm)δC: 177.23(C=O)lactam, 159.51(C=N), 59.74(N-CH), 49.04(Cl-CH), 41,97 (CH2, fluorene ring), 13.86 (CH3), 115-1147(aromatic ring).

IX

IR(KBr,cm-1):(3404.71, 3304.9)[�(OH)],3029.28[�(C-H)Ar],2964.59[�(C-H)Alipha] , 1683.79 [�(C=O)], 1643.77 [�(C=N)], 1564.87

[�(C=C)Ar], 1265.07,1226. 57 [�(C-O)]. LC-MS:492.15 1H-NMR(400MHz, CDCl3, ppm)δH: 5.95 (S, 1H,N-CH thiazolidinone), 4.89 (S, 1H, OH), 3.43(S, 2H, CH2,fluorene ring), 2.94 (S, 2H, CH2 thiazolidinone), 0.69 (S, 3H, CH3), 6. 93 -7. 88(m, 14H, aromatic ring). 13C-NMR(400MHz,CDCl3,ppm)δC: 177.35 (C=O thiazolidinone),159.17(C=N), 66.33(N-CH thiazolidinone),41,98(CH2 fluorene ring),

34.56(CH2 thiazolidinone), 15.02 (CH3) ,116-149 (aromatic ring).

AASCIT Journal of Chemistry 2015; 2(2): 24-31 31

4. 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, 1H-NMR,

13C-

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 1H-NMR,

13C-NMR and

LC-MS spectra.

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