Synthesis and absorption properties of some 4-mercapto-1,8-naphthalimides, 4-mercapto-7H-benzimidazo[2,1-a]benz[d,e] isoquinolin-7-one, and 4-mercapto-7H-benzimidazo [2,1-a]benz[d,e]isoquinoline-7-one

Article abstract of DOI:10.1080/10426500500269497

The reaction of 4-chloro-1,8-naphthalic anhydride with sulfur and sodium sulfide in boiling ethanol lead to 4-mercapto-1,8-naphthalic anhydride. The condensation of a later compound with amines produced 4-mercapto-1,8- naphthalimides and with ethylenediam

Full text of DOI:10.1080/10426500500269497

This article was downloaded by: [Gebze Yuksek Teknoloji Enstitïsu ]
On: 25 December 2014, At: 20:40
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
Synthesis and Absorption
Properties of Some
4-Mercapto-1,8-
naphthalimides, 4-
Mercapto-7H-benzimidazo[2,1-
a]benz[d,e] Isoquinolin-7-
one, and 4-Mercapto-7H-
benzimidazo [2,1-a]Benz[d,
e]isoquinoline-7-one
R. Hekmatshoar a , S. Y. S. Beheshtiha a , A. Nazari a
& F. Faridbod 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 , A. Nazari & F. Faridbod
(2006) Synthesis and Absorption Properties of Some 4-Mercapto-1,8-naphthalimides,
4-Mercapto-7H-benzimidazo[2,1-a]benz[d,e] Isoquinolin-7-one, and 4-Mercapto-7H-
benzimidazo [2,1-a]Benz[d, e]isoquinoline-7-one, Phosphorus, Sulfur, and Silicon and
the Related Elements, 181:7, 1521-1526, DOI: 10.1080/10426500500269497
To link to this article: http://dx.doi.org/10.1080/10426500500269497
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.

However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 181:1521–1526, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500269497
Synthesis and Absorption Properties of Some
4-Mercapto-1,8-naphthalimides,
4-Mercapto-7H-benzimidazo[2,1-a]benz[d,e]
Isoquinolin-7-one, and 4-Mercapto-7H-benzimidazo
[2,1-a]Benz[d, e]isoquinoline-7-one
R. Hekmatshoar
S. Y. S. Beheshtiha
A. Nazari
F. Faridbod
Department of Chemistry, Alzahra University, Vanak, Tehran, Iran
The reaction of 4-chloro-1,8-naphthalic anhydride with sulfur and sodium sulfide
in boiling ethanol lead to 4-mercapto-1,8-naphthalic anhydride. The condensation
of a later compound with amines produced 4-mercapto-1,8-naphthalimides and
with ethylenediamine and orthophenylenediamine, respectively, led to 4-mercapto-
7H-imidazo[2,1-a]benz[d,e]isoquinoline-7-one and 4-mercapto-7H-imidazo[2,1-
a]benz[d,e]isoquinoline-7-one in good to fairly high yields.
Keywords
4-Chloro-1,8-naphthalic anhydrides; 4-mercapto-1,8-naphthalimides;
ethylendiamine; orthophenylendiamine
INTRODUCTION
4-substituted-1,8-naphthalimide derivatives have scientific interest be-
cause of their potential use as polymerizable fluorophores for syn-
thetic polymers,1−6 fluorescent dyes for solar energy collectors,7 or-
ganic light emitting diodes,8 markers in molecular biology,9 in laser
active media,10,11 in medicine as antitumors,12 and as an analgesic.13
Recently, some 3-brominated-1,8-naphthalimides have been proposed
for the photoinactivation of HIV.14 In this study, we report the synthe-
sis of fluorophores that have a mercapto group at the C4 position in the
1,8-naphthalimide structure, and their absorption properties are also
investigated.
Received April 12, 2005; accepted May 10, 2005.
Address correspondence to R. Hekmatshoar, Alzahra University, Department of
Chemistry, Faculty of Science, Vanak, Tehran, Iran. E-mail: rhekmatus@yahoo.com
1521

1522
R. Hekmatshoar et al.
RESULTS AND DISCUSSION
The synthetic route for obtaining the final products is presented
in Schemes 1 and 2. The 4-chloro-1,8-naphthalic anhydride have
been used as conventional starting material for the preparation
of mercaptoimides. 4-mercapto-1,8-naphthalic anhydride were syn-
thesized by an indicated procedure.15 This compound shows a 38-
nm bathochromic displacement compared with 4-chloronapthalic an-
hydride; this phenomenon is for better resonance and a strong
conjugated system, because the thiol group is a better electron
donor than a chlorine atom. This compound has good color and
fluorescent properties. 4-chloronaphthalic anhydride is a pale yel-
low solid and 4-mercaptonaphthalic anhydride is yellow. Spectro-
scopic data and physical properties of 4-mercaptonaphthalimides
and 4-mercapto-7H-imidazo[2,1-a]benz[d,e]isoquinoline-7-one and 4-
mercapto-7H-benzimidazo[2,1-a]benz[d,e]isoquinoline-7-one are sum-
marized in Tables I and II.
EXPERIMENTAL
Melting points were determined with an electrothermal 9100 appa-
ratus and are uncorrected. The infrared spectra were recorded on a
SCHEME 1

Synthesis and Absorption Properties
1523
SCHEME 2
TABLE I Spectroscopic Data and Physical Properties of
4-Mercapto-1,8-Naphthalimide Derivatives
Compound
R
(%)
87
M.P.
λ
max
2a
CH3CH2CH2
−
220–223
374.4
374.4
2b
2c
2d
2e
2f
77
92
78
78
81
260–262
260–263
258–260
261–263
220–222
376
377.5
370.9
382.4

1524
R. Hekmatshoar et al.
TABLE II Spectroscopic Data and Physical
Properties of 3a, 3b, 4a, and 4b
Compound
MP/◦C
(%)
λ
Color
max
2a, 3b
4a, 4b
258–260
203–205
92
63
414.4
435.2
Orange
Orange
Philips PU 9800 FT-IR spectroscopy. UV spectra were obtained on a
UNICAM 8700 series UV/Vis spectrometer, Mass Spectra were recorded
on a Finnigan-Malt 8430 Mass spectrometer operating at an ioniza-
tion potential of 70 eV. Elemental analysis were performed using a
Heraeus CHN-O-Rapid analyzer. The chemicals were obtained from
Fluka (Buchs, Switzerland) and Merck and were used without further
purification.
General Procedure
Synthesis of 4-Mercapto-1,8-naphthalic anhydride
4.65 g (20 mmol) of 4-chloro-1,8-naphthalic anhydride, 2.12 g of sul-
fur, and 6 g (60 mmol) of sodium sulfide were poured into 50 mL of
ethanol, and the mixture was refluxed for 3 h. At the end of reaction,
the cooled, deep red liquid was added to 200 mL of water; the solution
was acidified with glacial acetic acid. A yellow solution was obtained,
which was added to 125 mL of 1% NaOH solution. The surplus sul-
fur was separated and the filtered solution was acidified with glacial
acetic acid. A yellow solid was obtained. The mixture was filtered and
the crude product was recrystallized with chlorobenzene. υmax (KBr):
2350 cm−1(SH),1750–1785 cm−1 (two carbonyl groups),
M.p.: 280–282◦C; Yield: 63%, C12H6O3S: (MW:230).
The Typical Procedure for the Preparation of 2a–f in Table I
0.02 g (0.1 mmol) of 4-mercapto-1,8-naphthalic anhydride with 0.04
g (0.3 mmol) of 4-chloroaniline and 5 mL of glacial acetic acid were
refluxed for 1 h. At the end, the solution was added to 10 mL of distilled
water; a yellow precipitate was obtained; the mixture was filtered, and
the crude product was crystallized with toluene.
The Typical Process for the Preparation of 3a, 3b, 4a,
and 4b in Table II
0.02 g (0.1 mmol) of 4-mercapto-1,8-naphthalic anhydride, 0.02 g
(0.2 mmol) of ortho-phenylenediamine, and 5 mL of glacial acetic acid

Synthesis and Absorption Properties
1525
were refluxed for 1.5 h. At the end, the solution was added to 10 mL of
distilled water; an orange precipitate was obtained. The mixture was
filtered, and the crude product was crystallized with DMF.
2a: C15H13NO2S: (MW: 271), elemental analysis: Calc.: C: 66.42; H: 4.79;
N: 5.16; O: 11.88. Found: C, 66.11; H: 4.81; N: 5.05, O: 11.94.
υmax (KBr): 1690, 1649 cm−1 (imide carbonyls), 1378cm−1 C N.
2b: C19H13NO2S: (MW: 319), Elemental analysis: Calc.: C: 71.47; H:
4.07; N: 4.38; O: 10.03; S: 10.03. Found: C: 71.25; H: 4.08; N: 4.29; O:
10.13; S: 10.05.
υmax (KBr): 1763 cm−1, 1723 cm−1 (imide carbonyls) C N: 1323 cm−1
.
2c: C19H13NO2S: (MW: 305), Elemental analysis: Calc.: C: 70.81; H:
3.60; N: 4.59; O: 10.49; S: 10.49. Found: C: 71.02; H: 3.62; N: 4.51; O:
10.62; S: 10.48.
υmax (KBr): 1762, 1725 (imide carbonyls) C N: 1323 cm−1
.
2d: C18H10NO2SCl: (MW: 339.5), Elemental analysis: Calc.: C: 63.62;
H: 2.94; N: 4.12; O: 9.42; S: 9.42; Cl: 10.45. Found: C: 63.65; H: 2.98; N:
4.07; O: 9.53.
υmax (KBr): 1764, 1725 (imide carbonyls), 1334 cm−1
.
2e: C18H10N2O4S: (MW: 350), Elemental analysis; Calc: C: 61.71, H:
2.85, N: 8.00, O: 18.28, S: 9.14. Found: C: 61.64, H: 2.89, N: 8.02, O:
18.34, S: 9.23
υmax (KBr): 1762, 1723 cm−1 (imide carbonyls), 1550, 1323 cm−1, NO2
2f: C19H13NO2S: (MW: 319), Elemental analysis; Calc: C: 71.47, H: 4.07,
N: 4.38, O: 10.03, S: 10.03. Found: C: 71.33, H: 4.02, N: 4.43, O: 10.09,
S: 10.12
υmax (KBr): 1689, 1648 cm−1, (imide carbonyls), 1379 cm−1 C N
REFERENCES
[1] T. Konstantinova, P. Meallier, and I. Grabcher, Dyes and Pigments, 22, 191 (1993).
[2] I. Grabchev, T. Konstantinova, P. Mealier, and M. Popova, Dyes and Pigments, 28,
41 (1995).
[3] T. Konstantinova, and I. Grabchev, J. App/Polym Sci., 62, 447 (1996).
[4] T. Filipova, I. Grabchev, and I. Petkov, J. polym. Sci. Chem., 35, 1069 (1997).
[5] I. Grabchev and T. Philipova, Dyes and Pigments, 27, 321 (1995).
[6] T. Konstantinova and I. Grabchev, Polym. In., 43, 39(1997).
[7] X. Qian, K. Zhu, and K. Chen, Dyes and Pigments, 11, 13 (1989).
[8] R. Cacialli, E. Friend, C. M. Bouche, P. Le Barni, H. Facoetti, F. Sayer, and P. Robin,
J. App/Phys., 83, 2343.
[9] K. Dubey, R. Singh, and K. Mizra, Indian J. Chem., 34B, 876 (1995).
[10] E. Martin, R. Weigand, and A. Pardo, J. Lumines, 68, 157 (1996).

1526
R. Hekmatshoar et al.
[11] V. Gruzinski, A. Kukhta, and G. Shakkah, J. App/Spectr, 65, 444 (1998).
[12] R. Middleton, and J. Parrick, J. Hetero. Chem., 22, 1567 (1985).
[13] A. D. Andricopulo, R. A. Yunes, V. Cechinel Filho, R. Correa, A. W. S. Filho, A. R.
Santos, and R. J. Nunes, Acta Farm Bonaercpes., 17, 219 (1998).
[14] S. C. Chang, B. Archer, R. Utech, D. Levis, M. Judy, and J. Matthews, Biorganic
Med. Chem. Lett., 3, 555 (1993).
[15] A. Tpeters and S.Y.S. Beheshtiha, J. Chem. Tech. and Biotech., 319 (1986).