Synthesis and absorption properties of some new 4-thio-1,8-naphthylimides and 4-(thio)-7H-benzimidazo [2,1-A] benz [D,E] isoquinolin-7-one derivatives

Article abstract of DOI:10.1080/10426500490466328

A series of new 1,8-naphthylimide and 4-(thio)-7H-benzimidazo[2,1-a]benz[d, e]isoquinolin-7-one derivatives has been synthesized, and the UV/Vis absorptioin characteristics discussed. Substituents' effect on the UV/Vis absorption characteristics have been investigated.

Full text of DOI:10.1080/10426500490466328

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SYNTHESIS AND ABSORPTION PROPERTIES OF SOME
NEW 4-THIO-1,8-NAPHTHYLIMIDES AND 4-(THIO)-7H-
BENZIMIDAZO [2,1-A] BENZ [D,E] ISOQUINOLIN-7-ONE
DERIVATIVES
a
a
a
S. Y. S. Beheshtiha , R. Hekmatshoar & F. Soltani
a
Department of Chemistry, Faculty of Science, Alzahra University , Vanak, Tehran, Iran
Published online: 16 Aug 2010.
To cite this article: S. Y. S. Beheshtiha , R. Hekmatshoar & F. Soltani (2004) SYNTHESIS AND ABSORPTION PROPERTIES OF
SOME NEW 4-THIO-1,8-NAPHTHYLIMIDES AND 4-(THIO)-7H-BENZIMIDAZO [2,1-A] BENZ [D,E] ISOQUINOLIN-7-ONE DERIVATIVES,
Phosphorus, Sulfur, and Silicon and the Related Elements, 179:9, 1723-1729, DOI: 10.1080/10426500490466328
To link to this article: http://dx.doi.org/10.1080/10426500490466328
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Phosphorus, Sulfur, and Silicon, 179:1723–1729, 2004
Copyright ꢀC Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490466328
SYNTHESIS AND ABSORPTION PROPERTIES
OF SOME NEW 4-THIO-1,8-NAPHTHYLIMIDES
AND 4-(THIO)-7H-BENZIMIDAZO [2,1-A] BENZ [D,E]
ISOQUINOLIN-7-ONE DERIVATIVES
S. Y. S. Beheshtiha, R. Hekmatshoar, and F. Soltani
Department of Chemistry, Faculty of Science,
Alzahra University, Vanak, Tehran, Iran
(
Received November 25, 2003; accepted January 6, 2004)
A series of new 1,8-naphthylimide and 4-(thio)-7H-benzimidazo[2,1-
a]benz[d,e]isoquinolin-7-one derivatives has been synthesized, and the
UV/Vis absorptioin characteristics discussed. Substituents’ effect on
the UV/Vis absorption characteristics have been investigated.
Keywords: 1,8-Naphthylimides; 4-(thio)-7H-benzimidazo [2,1-a] benz
[d,e]isoquinolin-7-one derivatives
INTRODUCTION
During recent years, 4-substituted-1,8-naphthylimide derivatives
and
4-substituted-7H-benzimidazo[2,1-a]benz[d,e]isoquinolin-7-one
derivatives have aroused scientific interest because of their potential
1
use as excellent yellow, orange and red dye stuffs for synthetic fibers
and as polymerizable fluorophores for synthetic polymers. A series
2
−6
of fluorescent polymerizable 1,8-naphthylimide
were synthesized
and their ability to polymerize with styrene, methyl methacrylate or
7
−12
acrylonitrile, obtaining copolymers with intensive fluorescence,
was studied.
Recently, 1,8-naphthylimide dyes have been examined with regards
to their use in nematic liquid crystals for guest-host–type electro-
optical displays.1
3,14
Fluorescent 1,8-naphthylimide derivatives are
very interesting in view of their usage as fluorescent dyes, solar en-
1
5
16
ergy collectors, organic light-emitting diodes, markers in molecular
1
7
18,19
20
biology, in laser active media,
and in medicine as antitumours
Address correspondence to R. Hekmatshoar, Department of Chemistry, Faculty of
Science, Alzahra University, Vanak, Tehran, Iran. E-mail: rhekmatus@yahoo.com
1
723

1
724
S. Y. S. Beheshtiha et al.
and analgesics.21 Recently, some 3-brominated compounds of 1,8-
2
2
naphthylimide have been proposed for the photoinactivation of HIV.
The present work concerns the synthesis of new 1,8-naphthylimides
and 4-(thio)-7H-benzimidazo [2,1-a] benz [d,e] isoquinolin-7-one deriva-
tives that have different substituents at the C-4 position in the 1,8-
naphthalic anhydride structure; some of their absorption properties
are also investigated.
RESULT AND DISCUSSIONS
The first step is the synthesis of new thioethers from 4-chloronaphthalic
anhydride. This reaction is SN2, the convenient solvent is DMF or
2
-methoxy ethanol, and NaHCO3 as a base is used too. DMF is bet-
◦
ter than 2-methoxy ethanol but in temperatures higher than 190 C it
will decompose. Thiols are highly nucleophilic compounds and other
solvents can be used, such as 2-methoxy ethanol, for their reaction
with 4-chloronaphthalic anhydride. The ratio of nucleophile to sub-
strate is important. We found that the best ratio according to different
SCHEME 1

Thionaphthylimides
1725
SCHEME 2
concentration of reactions is (Nu/Su = 2/1), and for the determination
of the best time of reflux and yields we have used TLC.
The infrared (IR) and mass spectra of the products clearly indicated
the formation of the products.
EXPERIMENTAL
Melting points were determined with an electrothermal 9100 appara-
tus and are uncorrected. The IR spectra were obtained on Philips pu
9
800 Fourier transform infrared (FTIR) spectrometer. Ultraviolet (UV)
spectra were recoded on a UNICAM 8700 series UV/Vis spectrometer.
-chloronaphthalic anhydride was obtained from Alderich and the other
4
chemicals were obtained from Merck and were used without further
purification.
SCHEME 3

1
726
S. Y. S. Beheshtiha et al.
SCHEME 4
General Procedure
Typical Synthesis of Products (Table I): 4-(Thioacetic
acid)-1,8-naphthalic Anhydride
First 2.32 g (10 mmol) of 4-chloronaphtalic anhydride, 2.3 g (20 mmol)
of 2-mercaptoacetic acid, and 2.52 g (30 mmol) of sodium bicarbonate
were refluxed in 30 ml of DMF for 1 h (progress of the reaction checked
by TLC). Then the solution was cooled and acidified with HCl 5% to form
TABLE I Spectroseopic Data and Physical Properties of Naphthalic
Anhydride, 4-chloronaphthalic Anhydride, and 4-thio-1,8-naphtalic
Anhydride Derivatives
◦
Entry
Compound
λmax(nm)loge
m.p C
Yield (%)
Color
1
2
3
4
H
Cl
330.2
338.5
384.2
389.3
265–267
216–217
202
—
—
91
90
Pale yellow
White
Yellow
SCH2COOH
SCH2CH2OH
187
Yellow

Thionaphthylimides
1727
TABLE II Spectroseopic Data and Physical Properties of
4-thio-1,8-naphthylimides
◦
Entry
R
Mp ( C)
Yield (%)
Color
Yellow
Yellow
Yellow
Greenish yellow
Bright yellow
Greenish yellow
λmax (nm)
1
2
3
4
5
6
PhCH2
185–186
227
188–189
175–176
198
81
85
87
82
78
88
386.9
390
385.3
386.4
386.1
388.9
p-NO2-Ph
p-CH3-Ph
p-NH2-Ph
p-COOH Ph
p-CH3-CO NH Ph
197
a yellow precipate, which was filtered and recrystallized in ethanol.
◦
m.p., 202 C; yield, 91%.
Typical Synthesis of Products (Table I): 4-(Ethanol
thio)-1,8-naphthalic Anhydride
First 2.32 g (10 mmol) of 4-chloronaphthalic anhydride, 1.17 g
15 mmol) of 2-mercaptoethanol, and 0.84 g (10 mmol) of sodium hy-
(
drogen carbonate in 30 ml of 2-methyoxy ethanol were refluxed for 6 h.
The color of the solution was dark brown during the reaction time (the
end of the reaction was determined with TLC). The solution was cooled
and acidified with HCl 5%; a dark yellow precipate was formed. The
◦
crude product was recrystallized in ethanol. m.p., 187 C; yield, 91%.
−1
−1
−1
IR (3000 cm acidic OH, 2977 cm CH aliphatic, 1750, 1770 cm
anhydride C O group).
Typical Synthesis of Products (Tables II and III):
4
-(Thioacetic acid)-N-benzyl-1,8-naphthylimide
First 0.06 g (0.2 mmol) of 4-(thioacetic acid)naphthalic anhydrid, 1 ml
of benzyl amine, and 10 ml of 2-methoxy ethanol were refluxed for 5 h.
Then the mixture was poured into 10 ml of distillated water. The solid
TABLE III Spectroseopic Data and Physical Properties of
4-thio-1,8-naphthylimides
◦
Entry
R
Mp ( C)
Yield (%)
Color
Yellow
Yellow
Yellow
Greenish yellow
Bright yellow
Greenish yellow
Pale yellow
λmax (nm)
1
2
3
4
5
6
7
PhCH2
180–182
132
172–173
210
133–134
188
218–220
86
62
81
80
78
85
87
394.8
394.8
394.2
396.3
392.9
394.1
399.2
p-NO2-Ph
p-CH3-Ph
p-NH2-ph
p-COOH-Ph
p-CH3-CO-NH-Ph
NH2

1
728
S. Y. S. Beheshtiha et al.
TABLE IV Spectroseopic Data and Physical Properties of 1a–b,
2
a–b, 3a–b, 4a–b
◦
Entry
R
Mp ( C)
Yield (%)
Color
λmax (nm)
1a, 2a
3a, 4a
1b, 2b
3b, 4b
CH2CH2OH
CH2CH2OH
CH2COOH
CH2COOH
149–150
235
285–586
196–197
81
42
86
57
Orange
Orange
Orange
Orange-red
411.4
433.9
413
438.4
obtained after cooling was filtered, dried, and recrystallized in ethanol
◦
−1
to give yellow crystals. m.p., 85–186 C; yield, 81%. IR (3400 cm
−
1
−1
broad alcholic OH, 2900 cm CH aliphatic, 1720, 1760 cm anhydride
carbonyl).
Typical Synthesis of Products (Table IV): 3,4-(Thioacetic
acid)-7H-benzimidazo (a-1,2)benz[dee]iso quindine-7-one
First 0.05 g (0.15 mmol) of 4-(thioacetic acide)naphthalic anhydride
and 0.017 g (0.15 mmol) of orthophenylendiamin in 10 ml of glacial
acetic acid were refluxed for 2 h. The solution was cooled and filtered,
◦
and the crude product was recrystallized in ethanol. m.p., 285 C; yield,
85%.
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