Synthesis and absorption properties of some 4-thioaryl-1,8-naphthalimides and 4-thioaryl-7H-benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-7-one derivatives

Article abstract of DOI:10.1080/10426500600758373

A series of novel 4-thioaryl-1,8-naphthalimide derivatives were synthesized using 4-chloro-1,8-naphthalic anhydrid and arylthioles as starting materials. 4-thioaryl-1,8-naphthalic anhydride was treated with different primary amines and o-phenylene diamine

Full text of DOI:10.1080/10426500600758373

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Synthesis and Absorption
Properties of Some 4-
Thioaryl-1,8-naphthalimides
and 4-Thioaryl-7H-
benzimidazo-[2,1-a]-benz-
[d,c]-isoquinolin-7-one
Derivatives
R. Hekmatshoar a , S. Y. S. Beheshtiha a & F. Soltani a
a Department of Chemistry , Alzahra University ,
Vanak, Tehran, Iran
Published online: 01 Feb 2007.
To cite this article: R. Hekmatshoar , S. Y. S. Beheshtiha & F. Soltani (2006)
Synthesis and Absorption Properties of Some 4-Thioaryl-1,8-naphthalimides and
4-Thioaryl-7H-benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-7-one Derivatives,
Phosphorus, Sulfur, and Silicon and the Related Elements, 181:11, 2535-2540, DOI:
10.1080/10426500600758373
To link to this article: http://dx.doi.org/10.1080/10426500600758373
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Phosphorus, Sulfur, and Silicon, 181:2535–2540, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500600758373
Synthesis and Absorption Properties of Some
4-Thioaryl-1,8-naphthalimides and 4-Thioaryl-7H-
benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-7-one
Derivatives
R. Hekmatshoar
S. Y. S. Beheshtiha
F. Soltani
Department of Chemistry, Alzahra University, Vanak, Tehran, Iran
A
series of novel 4-thioaryl-1,8-naphthalimide derivatives were synthesized
using 4-chloro-1,8-naphthalic anhydrid and arylthioles as starting materi-
als. 4-thioaryl-1,8-naphthalic anhydride was treated with different primary
amines and o-phenylene diamine or 1,2-diaminoethene to produce 4-thioaryl-
1,8-naphthalimides and 4-thioaryl-7 H-benzimidazo-[2,1-a]-benz-[d,c]-isoquinolin-
7-one derivatives, respectively. The UV/VIS absorption properties are discussed.
Keywords 1,2-Diaminoethene; 4-chloro-1,8-naphthalic anhydride; arylthiol; o-
phenylene diamine
INTRODUCTION
Derivatives of 4-substituted-1,8-naphthalimides have found applica-
tion in a number of areas, including fluorescent dyes,1−12 laser active
media,13,14 liquid crystal displays,15 analgetics in medicine,16−18 fluo-
rescent markers in biology,19 and light emitting diodes.20−22 The use of
1,8-naphthalimid derivatives in electronic devices has become increas-
ingly popular due to the good light stability and high quantum yield of
suitably substituted derivatives.
In this article, we present the synthesis and the UV/VIS absorption
properties of a number of 4-thioaryl-1,8-naphthalimides and 4-thioaryl-
7H-benzimidazo[2.1-a]-benz-[d,c]-isoquinolin-7-one derivatives.
RESULTS AND DISCUSSION
In continuation of our ongoing research to develop the synthesis of 1,8-
naphthalimides23 with the aim to prepare 4-thioaryl-1,8-naphthalimide
Received January 10, 2006; accepted April 7, 2006.
Address correspondence to R. Hekmatshoar, Alzahra University, Department of
Chemistry, Faculty of Science, Vanak, Tehran, Iran. E-mail: rhekmatus@yahoo.com
2535

2536
R. Hekmatshoar et al.
derivatives, we reacted 4-chloro-1,8-naphthalic anhydride 1 with thio-
phenoles 2a,b in the presence of sodium hydrogen carbonate in boiling
DMF24 (Scheme 1). After the completion of the reaction, the solution was
acidified, and the solid products 3a,b were filtered off. For the prepa-
ration of the different imides and imidazols, 4-thioaryl-1,8-naphthalic
anhydride was reacted with the corresponding amines and 1,2-diamines
(Schemes 2–4).
SCHEME 1
SCHEME 2

Thioaryl Naphthalimides
2537
SCHEME 3
SCHEME 4
EXPERIMENTAL
Melting points were determined with an electrothermal 9100 appa-
ratus and are uncorrected. UV spectra were recorded on a UNICAM
8700 series UV/VIS spectrometer. The FTIR spectra were obtained on
a Philips 9800 Fourier transform infrared spectrometer. 4-chloro-1,8-
naphthalic anhydride was obtained from Aldrich; the other chemicals
were obtained from Merck and were used without further purification.
TABLE I Spectroscopic Data and Physical Properties of
1,8-Naphthalic Anhydride and Its Derivatives
Compound
λ
nm
M.P.◦C
Yield (%)
Color
max
1,8-naphtalic anhydride
1
3a
3b
330.2
338.2
386.9
390.2
256–267
216–217
159–160
179–180
—
—
90
93
Pale yellow
White
Dark yellow
Dark yellow

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R. Hekmatshoar et al.
TABLE II Spectroscopic Data and Physical Properties of 4a–i
Compound
Rꢀꢀ
M.P.◦C Yield (%)
λ
nm log ε
Color
max
4a
4b
4c
4d
4e
4f
4g
4h
4i
PhCH2
188–189
178–179
186–187
177–178
192–193
241–243
181–182
194–196
86
76
75
83
88
81
82
84
87
395
4.08 Yellow
4.11 Yellow
4.12 Yellow
4.10 Yellow
4.10 Pale yellow
4.11 Greenish yellow
4.09 Greenish yellow
4.14 Bright yellow
4.12 Greenish yellow
p-NO2C6H4
o-NO2C6H4
p-CH3C6H4
Ph
p-NH2C6H4
p-OHC6H4
p-HO2C-C6H4
395.2
394.5
394.4
392
394
394.5
393.9
397.6
p-CH3-CONH-C6H4 182–183
The Synthesis of 4-Thiophenyl-1,8-naphtalic Anhydride (3a)
and 4-(4-Methylphenyl) thio-1,8-naphthalic Anhydride (3b)
2.32 g (10 mmol) of 4-chloro-1,8-naphtalic anhydride, 15 mmol of the
thiophenol, and 0.84 g (10 mmol) of sodium bicarbonate were refluxed
in 30 mL of DMF for 7 h. The progress of the reaction was monitored
by TLC. The solution was cooled down to an ambient temperature and
acidified with 5% aqueous HCl to form a yellow precipitate, which was
filtered and recrystallized from ethanol. For spectroscopic data and
physical properties, see Table I.
The Synthesis of 4-Thioaryl-N-substituted
1,8-Naphthalimides 4a–i and 5a–i
0.01 mol of 4-thioaryl-1,8-naphthalic anhydride and 0.01 mol of the
amine was dissolved in 20 mL of 2-methoxyethanol, and the solution
was refluxed for 5 h. The progress of the reaction was monitored by TLC.
After cooling to r.t. the liquor was poured into 50 mL of distilled water to
TABLE III Spectroscopic Data and Physical Properties of 5a–i
λ
max
Compound
Rꢀꢀ
M.P.◦C Yield (%)
nm
log ε
Color
5a
5b
5c
5d
5e
5f
5g
5h
5i
PhCH2
152–153
175–177
199–200
202–204
162–163
262–263
256–257
81
84
85
78
78
87
85
87
95
391.2 4.08 Yellow
391.4 4.13 Yellow
389.8 4.12 Yellow
389.6 4.04 Pale yellow
388.8 4.11 Greenish yellow
390.4 4.13 Yellow
396.6 4.13 Bright yellow
397.2 4.14 Greenish yellow
397 4.14 Bright yellow
p-O2NC6H4
p-H3CC6H4
Ph
p-H2NC6H4
p-HOC6H4
p-HO2CC6H4
p-CH3CONH-C6H4 240–243
H2N 196–197

Thioaryl Naphthalimides
2539
TABLE IV Spectroscopic Data and Physical Properties
of Compounds 6–9
Compounds
R
M.P.◦C
Yield (%)
λMax nm
log ε
Color
6a, 7a
8a, 9a
6b, 7b
8b, 9b
H
H
Me
Me
196–197
193–194
192–193
194–195
93
85
91
81
418
4.15
4.14
4.11
4.09
Orange
Orange
Orange
Orange
438.1
414.9
441.9
form a yellow precipitate. The resulting precipitate was filtered off, and
the crude product was recrystallized from ethanol. For spectroscopic
data and physical properties, see Tables II and III.
The Synthesis of 4-Thioaryl-7H-benzimidazo[1,2-a]-benz-[d,c]-
isoquinolin-7-one Derivatives 6–9
0.01 mol of 4-thioaryl-1,8-naphthalic anhydride was reacted with 0.02
mol of 1,2-diamine in 10 mL of boiling acetic acid for 3 h. After cool-
ing to r.t., 100 mL of distilled water was added to the solution, and
the resulting precipitate was filtered off. Recrystallization of the crude
product from DMF gave the final products 6–9. For spectroscopic data
and physical properties, see Table IV.
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