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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 [email protected] (T. Ahmad), [email protected] (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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