New activation method of chloroenaminone quinones for synthesis of polynuclear heterocyclic systems

Article abstract of DOI:10.1080/10426500307929

The chlorine atom of chloroenamineone in the quinonoid compounds 1a-f and 7 was activated by the reaction with benzenesulphonyl chloride to form naphthoquinonid moiety fused with linear or angular heterocyclic systems as carbazoles 2a-c, phenazines 3a,b and 5a-c, phenoxazines 3c phenothiazine 3d, quinoxalinophenazine 6a, quinox-alinophenoxazine 6b, quinoxalinophenthiazine 6c, oxadiazine 8, thiadiazine 9, and pyrazole 10. The mechanism of the latter derivative was discussed. Spectroscopic data of all new products are given. Additionally, the antimicrobial activity of some reported compounds was screened.

Full text of DOI:10.1080/10426500307929

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Phosphorus, Sulfur, and Silicon and the Related
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New Activation Method of Chloroenaminone Quinones
for Synthesis of Polynuclear Heterocyclic Systems
M. A. Berghot a
a Mansoura University , Mansoura, Egypt
Published online: 27 Oct 2010.
To cite this article: M. A. Berghot (2003) New Activation Method of Chloroenaminone Quinones for Synthesis of Polynuclear
Heterocyclic Systems, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:3, 627-637
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:627–637
C
Copyright 2003 Taylor & Francis
1042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390170291
NEW ACTIVATION METHOD OF
CHLOROENAMINONE QUINONES FOR SYNTHESIS
OF POLYNUCLEAR HETEROCYCLIC SYSTEMS
M. A. Berghot
Mansoura University, Mansoura, Egypt
(Received May 10, 2002; accepted July 16, 2002)
The chlorine atom of chloroenamineone in the quinonoid compounds
1a–f and 7 was activated by the reaction with benzenesulphonyl chlo-
ride to form naphthoquinonid moiety fused with linear or angular
heterocyclic systems as carbazoles 2a–c, phenazines 3a,b and 5a–c,
phenoxazines 3c phenothiazine 3d, quinoxalinophenazine 6a, quinox-
alinophenoxazine 6b, quinoxalinophenthiazine 6c, oxadiazine 8, thia-
diazine 9, and pyrazole 10. The mechanism of the latter derivative
was discussed. Spectroscopic data of all new products are given. Ad-
ditionally, the antimicrobial activity of some reported compounds was
screened.
Keywords: Alkylamino naphthoquinones; heterocyclic naphtho-
quinones; sulphonylation reaction
INTRODUCTION
It is well known that the chlorine atom in chloroenaminone quinones
is inert toward nucleophilic substitution reactions.1,2 Kallmayer and
5
Binger3 reported that acylation or nitrosation reactions of the amino
group in this moiety increase the reactivity of the chlorine atom. In
this article, we report a new method for activation of this atom by re-
action of the amino group with benzenesulphonyl chloride. Interesting
heterocyclic quinones containing a sulphonamide group were formed.
8
Analogous quinonoid systems showed excellent anticancer activities.6
On the other hand, the sulphonamide group leads to an increase of the
pharmacological activity of the compounds due to in vivo release of this
13
group by metabolic processes.9
The author thank Dr. Seif-Eldin N. Ayyad for carrying out 13C and 1H-NMR spectra
in the Chemistry Department at Minnesota University, Minnesota, USA.
Address correspondence to M. A. Berghot, Chemistry Department, Faculty of Sciences,
Mansours University, Mansours, Egypt.
627

628
M. A. Berghot
RESULTS AND DISCUSSION
2-Chloro-3-(N-arylamino)-1,4-naphthoquinones 1a–f14 were used as
starting materials. Compounds 1a–c were smoothly stirred with ben-
zenesulphonyl chloride in the presence of a catalytic amount of tri-
ethylamine at room temperature for 5 h to afford the carbazole deriva-
tives 2a–c with about 80–90% yield. Moreover, linear polynuclear
heterocyclic systems as phenazines 3a,b, phenoxazine 3c and phenoth-
iazine 3d were immediately achieved by treatment of 1d–f with ben-
zenesulphonyl chloride in triethylamine respectively (Scheme 1). IR
spectra of the products 2a–c and 3a,c,d revealed the absence of NH
and C Cl bands, in addition to the appearance of a sulphonamide band
at 1330–1320 cm 1. The IR spectrum of 3b revealed the absence of a
1
C Cl bond only and the clear appearance of an NH band at 3310 cm
.
The 1H NMR spectra of 2a–c and 3a,c,d do not contain signals charac-
teristic for amino groups. The 1H NMR spectrum of 3b showed a singlet
signal at 8.11 ppm due to an NH group. The mass spectra of 2a,b and
3a–c supported the reported structures. The 13C NMR spectrum of 3b
was also consistent with its structure (cf. Experimental part). On the
other hand, the cyclized compounds 2d–f and 3e–g were not formed
when 1a–f were refluxed for 24 h with triethylamine only. Moreover, 1d
was stirred with concentrated sulfuric acid for 15 h to give the angular
phenazine product 4a, which was reacted subsequently with benzene-
sulphonyl chloride in triethylamine to give 4b. The structure of 4a fol-
lows from its IR spectrum which shows an NH band at 3330 cm 1 and a
strong C Cl band at 730 cm 1. The NH band in the IR spectrum of 4b
disappeared. Instead strong bands at 1330, 1220, and 1630 cm 1 due to
sulphonamide and C N groups appeared. The 13C and 1H NMR spectra
confirmed the structure of 4a. The mass spectrum of 4b supported the
structure (cf. Experimental part).
Compound 4b was reacted quickly with o-phenylenediamine, o-
aminophenol and o-aminothiophenol in absolute ethanol and a cat-
alytic amount of freshly fused sodium acetate to afford 5a–c respec-
tively; while 4a failed to react with these amines under all conditions.
The 1H-NMR spectra of 5a–c showed amino protons centered at 10.11–
10.54 ppm as singlet signals. Also, the IR spectra of 5a–c exhibited
bands at 3330–3310 due to NH2 groups. The mass spectrum of 5c
showed a molecular ion peak at 509 [M+] and an additional peak of
low intensity at 513 [(M + 4), 2%].
Cyclization reactions of 5a–c with concentrated sulfuric acid gave
polynuclear heterocyclic quinones 6a–c. 6d was obtained from 6a under
1
similar conditions as used for the preparation of 4b from 4a. The H
NMR spectra of 6a–c are consistent with the reported structures. The

Heterocyclic Naphthoquinones
629
SCHEME 1
13C NMR spectrum of 6a and the mass spectrum of 6b supported also
the reported structures (Scheme 2).
Finally, 1,3,4-oxadiazine derivative 8 was accomplished by stirring
of the hydrazide derivative 715 with benzenesulphonyl chloride in the
presence of triethylamine for 10 h at room temperature. Refluxing of 7
with triethylamine only for 15 h failed to give 8. Instead the starting
material was recovered.

630
M. A. Berghot
SCHEME 2
Compound 8 was subjected to react with phosphorus pentasulfide in
xylene for 3 h to give 1,3,4-thiadiazine 9 and the unexpected pyrazole
derivative 10. The formed product 10 can be interpreted in terms of the
formation of a 1,3,4-thiadiazine ring with subsequent sulfur-extrusion
reaction as shown in the mechanistic consideration (Scheme 3). A sim-
ilar synthesis type has been reported.16 The molecular ion peaks in
the mass spectra of 8,9 and 10 appeared at m/e 430, 446, and 414

Heterocyclic Naphthoquinones
631
SCHEME 3
respectively. The IR spectra of the three compounds 8,9 and 10 revealed
the absence of NH and C Cl bonds. Also, the 1H NMR spectra of 8–10
showed only the multiplet signals of aromatic protons. The 13C NMR
spectrum of 9 showed a signal at 165.1 due to C2 of the oxadiazine
ring while 10 showed a signal at 134.6 due to C3 of the pyrazole ring
(cf. Experimental part).
The above results showed clearly that the formation of 2,3,5,8 and
10 are understandable only in terms of the increasing reactivity of the
chlorine atom in the chloroenaminone moiety of the starting material
by sulphonylation of the NH group.

632
M. A. Berghot
Some newly prepared compounds 2b,2c,3a,4b,6a, and 6b were
tested in vitro for their antimicrobial activity. The microorganisms and
the minimum inhibitory concentrations (MIC) in g/ml are the follow-
ing: Escherichia coli 2a 32.2, 2b 33.1, 3a 21.7, 3c 22.8, 4b 18.1, 6a 6.3,
and 6b 6.3. A perusal of the literature reveals that, the compounds have
a low value of MIC with gram negative bacteria recorded to have an-
titumor activity.17 Therefore, the antitumor activity of the compounds
6a,b was investigated in tumor bearing mice. The results shows that
these compounds have a relative high toxicity. Maximum tolerance dose
is (MTD) = 70, 69 mg/kg body weight respectively.
EXPERIMENTAL
The purity of the prepared compounds was checked by thin layer
chromatography. Melting points were determined using Fisher-Johns
apparatus and are not corrected. Infra-red spectra (KBr) were recorded
on an SP 2000 Pye-Unicam Spectrophotometer (¯/cm 1). 1H NMR spec-
tra were recorded on Varian EM 360 spectrophotometer at 90 MHz
using TMS as an internal standard, in CDCl3 or Me2SO-d6, chemical
shifts in values (ppm) 13C NMR spectra at 75 MHz in CDCl3, chemical
shifts in values (ppm). Mass spectra were performed on a Varian 111
spectrometer (70 eV). Microanalytical data were determined at micro-
analytical laboratories in Cairo and Tanta Universities.
2-Alkyl-5-benzenesulphonyl-benzo[b]-5H-carbazole-
6,11-dione (2a c)
To a stirred mixture of 1a–c (0.01 mmol) and triethylamine (5 ml),
benzenesulphonyl chloride (3 ml) was added dropwise with continous
smooth stirring for 5 h, cooled, and poured into ice water. The solid that
separated was filtered off, washed with water, dried and recrystallized
from dioxane to give 2.
2a: m.p. >360 C, 80% yield. IR spectrum (¯/cm 1): 1660, 1645
(2C O), 1610 (C C), 1325 (NSO2Ph), 1220 ( SO2 ). 1H-NMR spec-
trum ( /ppm): 7.36–7.78 (br, 13H, Ar). Mass spectrum m/e: 387 [M+]
C22H13NO4S (387.4), Calc. C 68.21, H 3.38, N 8.28, S 3.61. Found C
68.38, H 3.51, N 8.16, S 3.48.
2b: m.p. 310 C, 90% yield. IR spectrum (¯/cm 1): 1660, 1650 (2C O),
1600 (C C), 1330 (NSO2Ph), 1210 ( SO2 ). 1H-NMR spectrum ( /ppm):
1.62 (s, 3H, CH3), 7.15–7.63 (m, 12H, Ar). Mass spectrum m/e: 401 [M+],
C23H15NO4S (401.4), Calc. C 68.81, H 3.77, N 3.49, S 7.99. Found C
68.69, H 3.99, N 3.22, S 8.21.

Heterocyclic Naphthoquinones
633
2c: m.p. 360 C, 85% yield. IR spectrum (¯/cm 1): 1650, 1640 (2C O),
1625 (C C), 1320 (NSO2Ph), 1200 ( SO2 ). 1H-NMR spectrum ( /ppm):
7.22–7.73 (br, 12H, Ar). C22H12ClNO4S (421.86), Calc. C 62.63, H 2.87,
N 3.32, S 7.60. Found C 62.92, H 3.11, N 3.19, S 7.88.
5,12-Dibenzenesulphonyl-benzo[b]-5,12-dihydro-
phenazine-6,11-dione (3a), 12-Benzenesulphonylbenzo-
[b]-5,12-dihydro-phenazine-6,11-dione (3b),
12-Benzenesulphonylbenzo[b]-12H-phenoxazine-
6,11-dione (3c) and 12-Benzenesulphonylbenzo[b]-
12H-phenothia-zine-6,11-dione (3d)
To a stirred mixture of 1d–f (0.02 mmol) and triethylamine (5 ml), ben-
zenesulphonyl chloride (3 ml) was added dropwise at room temperature.
The formed gummy products were column chromatographed over silica
gel using a mixture of benzene and ethyl acetate (5:1) as an eluent to
give 3a and 3b from reaction of 1d. Both 3c and 3d were obtained as
sole products from reaction of 1e and 1f respectively.
3a: m.p. 285 C, 80% yield. IR spectrum (¯/cm 1): 3005 (aromatic
CH), 1680, 1675 (2C O), 1580 (C C), 1320 (NSO2Ph), 1210 ( SO2 ).
1H-NMR spectrum ( /ppm): 7.11–7.56 (m, 8H, H1-H10), 7.62–798 (br,
10H, SO2Ph). Mass spectrum m/e: 542 [M+]. C28H18N2O6S2 (542.6),
Calc. C 61.98, H 3.34, N 5.17, S 11.82. Found C 62.12, H 3.53, N 4.93,
S 12.12.
3b: m.p. 260 C, 10% yield. IR spectrum (¯/cm 1): 3310 (NH), 3000
(aromatic CH), 1675, 1670 (2C O), 1580 (C C), 1315 (NSO2Ph), 1220
1
(SO2), 1100 (C N C). H-NMR spectrum ( /ppm): 7.21–7.46 (m, 8H,
H1-H10), 7.58–7.87 (br, 5H, SO2Ar), 8.11 (s, 1H, NH). 13C-NMR
( /ppm): 186.3, 186.1, 149.9, 149.7, 146.7, 146.7, 145.9, 133.4, 131.8,
131.2, 130.8, 124.6, 124.4, 123.5, 123.1, 122.6, 122.3, 121.9, 121.3,
121.0, 120.8. Mass spectrum m/e: 402 [M+]. C22H14N2O4S2 (402.4),
Calc. C 65.66, H 3.51, N 6.96, S 7.97. Found C 65.36, H 3.69, N 7.23,
S 8.19.
3c: m.p. 246 C, 85% yield. IR spectrum (¯/cm 1): 3010 (aromatic
C H), 1680, 1670 (2C O), 1580 (C C), 1330 (NSO2Ph), 1220 ( SO2 ),
1220 (C N C), 1050 (cyclic C O C). Mass spectrum m/e: 403 [M+].
C22H13NO5S (403.4), Calc. C 65.50, H 3.25, N 3.47, S 7.95. Found C
65.39, H 3.50, N 3.32, S 8.20.
3d: m.p. 239 C, 80% yield. IR spectrum (¯/cm 1): 3000 (aromatic
C H), 1675, 1670 (2C O), 1575 (C C), 1320 (NSO2Ph), 1210 ( SO2 ),
1110 (C S C). 1H-NMR spectrum ( /ppm): 7.20–7.51 (br, 8H, H1-H10),
7.61–7.89 (br, 5H, SO2Ph). C22H13NO4S2 (419.5), Calc. C 62.99, H 3.12,
N 3.34, S 15.29. Found C 63.19, H 2.93, N 3.56, S 15.08.

634
M. A. Berghot
6-Chloro-benzo[a]-7H-phenazine-5-one (4a)
To 1d (0.01 mmol) concentrated sulfuric acid (6 ml, d 1.84) was added
with stirring for 15 h. The resulting solution was poured into crushed
ice and brought to pH 5 by addition of ammonia. The solid was collected,
washed with water, and recrystallized from benzene to give 4a.
m.p. 250–252 C, 60% yield. IR spectrum (¯/cm 1): 3330 (NH), 1680
(C O), 1630 (C N), 730 (C Cl). 1H-NMR spectrum ( /ppm): 7.11–7.45
(m, 4H, CH8 CH11), 7.53–7.99 (m, 4H, CH1 CH4), 10.54 (s, 1H, NH)
slowly exchanged with D2O. 13C NMR ( /ppm): 186.3, 152.9, 148.4,
144.6, 135.2, 134.4, 133.1, 132.7, 130.6, 130.2, 125.5, 125.3, 124.6, 117.3,
116.4, 104.5. C16H9ClN2O (280.71), Calc. C 68.46, H 3.23, N 9.98. Found
C 68.17, H 3.39, N 10.21.
7-Benzenesulphonyl-6-chloro-benzo[a]-7H-phenazine-
5-one (4b)
To a mixture of 4a (0.01 mmol) and triethylamine (5 ml), benzenesulpho-
nyl chloride (3 ml) was added dropwise at room temperature with stir-
ring for 3 h. The reaction mixture was left to stand overnight, then
poured into ice-cold water. The precipitated solid was filtered off and
crystallized from benzene to give 4b.
m.p. 275 C, 50% yield. IR spectrum (¯/cm 1): 1680 (C O), 1630
(C N), 1330 (NSO2Ph), 1220 ( SO2 ), 1200 (C N C). 1H-NMR
( /ppm): 7.13–7.48 (br, 8H, H1 CH11), 7.67–7.96 (m, 5H, SO2 Ar H).
Mass spectrum m/e: 421 [M+]. C22H13ClN2O3S (420.87), Calc. C 62.78,
H 3.11, N 6.66, S 7.62. Found C 62.87, H 3.32, N 6.41, S 7.55.
7-Benzenesulphonyl-6-[substituted]-benzo[a]-
7H-phenazine-5-one (5a c)
To a stirred mixture of 4b (0.01 mmol) and anhydrous sodium ac-
etate (0.02 mmol) in absolute ethanol (50 ml), an arylamine derivative
(0.01 mmol) was added with continuous stirring. When the color of the
reaction mixture turned dark, it was heated under reflux for 4 h cooled,
and left overnight. The solid was filtered, washed well with hot wa-
ter, and finally with aqueous ethanol, and crystallized from ethanol to
give 5.
5a: m.p. 272 C, 60% yield. IR spectrum (¯/cm 1): 3330, 3310 (NH2,
NH), 1670 (C O), 1660 (C N), 1320 (NSO2Ph), 1210 ( SO2 ), 1200
(C N C). 1H-NMR spectrum ( /ppm): 7.01–7.46 (m, 12H, NAr H),
7.62–7.85 (br, 5H, SO2Ar H), 10.54 (br, 3H, NH2, NH). C28H20N4O3S
(492.48), Calc. C 68.28, H 4.08, N 11.37, S 6.53. Found C 68.07, H 3.89,
N 11.51, S 6.39.

Heterocyclic Naphthoquinones
635
5b: m.p. 228 C, 50% yield. IR spectrum (¯/cm 1): 3320 (NH2), 1680
(C O), 1640 (C N), 1330 (NSO2Ph), 1220 ( SO2 ), 1200 (C O C).
1H-NMR spectrum ( /ppm): 7.23–7.64 (br, 12H, NAr H), 7.81–7.93
(m, 5H, SO2Ar H), 10.51 (s, 2H, NH2). C28H19N3O4S (493.50), Calc.
C 68.14, H 3.88, N 8.51, S 6.50. Found C 68.40, H 4.02, N 8.32, S 6.31.
5c: m.p. 236 C, 70% yield. IR spectrum (¯/cm 1): 3310 (NH2), 1680
(C O), 1630 (C N), 1320 (NSO2Ph), 1210 ( SO2 ), 1210 (C S C).
1H-NMR spectrum ( /ppm): 7.76–7.89 (m, 5H, SO2Ar H), 10.11 (s, 2H,
NH2). Mass spectrum m/e: 509 [M+]. C28H19N3O3S2 (509.58), Calc. C
65.99, H 3.76, N 8.25, S 12.58. Found C 66.21, H 3.68, N 8.35, S 12.72.
6-Benzenesulphonyl-benzo[a]-6H-quinoxalino-
[3,2-c]phenazine (6a), 6-Benzenesulphonyl-6H-benzo-
[a]quinoxalino[3,2-c]phenoxazine (6b) and
6-Benzenesulphonylbenzo[a]6H-quinoxalino[3,2-c]-
phenothiazine (6c)
A mixture of 5a–c (0.01 mmol) and concentrated sulfuric acid (10 ml)
was stirred for 4 h. The mixture was treated with sodium bicarbonate
solution, the precipitated solid was filtered. The residue was washed
with water and crystallized from benzene to give 6a–c.
6a: m.p. 360 C, 40% yield. IR spectrum (¯/cm 1): 3310 (NH), 2900
(Ar CH), 1630, 1620 (2C N), 1600 (C C), 1380 (C N C), 1320
(NSO2Ph). 1H-NMR spectrum ( /ppm): 7.05–7.23 (br, 12H, Ar H), 7.35–
8.14 (m, 5H, SO2Ph), 10.33 (s, 1H, NH). 13C-NMR ( /ppm): 149.8, 149.3,
146.7, 146.3, 142.7, 142.1, 136.4, 136.2, 134.8, 134.5, 134.1, 131.2, 130.6,
130.2, 130.0, 125.8, 125.7, 125.5, 124.9, 121.3, 121.1, 120.8, 125.3, 124.7,
124.6, 122.7. C28H18N4O2S (474.52), Calc. C 70.87, H 3.82, N 11.81, S
6.76. Found C 71.07, H 4.09, N 12.03, S 6.92.
6b: m.p. 256 C, 60% yield. IR spectrum (¯/cm 1): 2880 (Ar CH),
1
1640, 1625 (2C N), 1600 (C C), 1330 (NSO2Ph), 1200 (C O C). H-
NMR ( /ppm): 7.12–7.43 (br, 12H, Ar H), 7.55–7.91 (m, 5H, SO2Ar H).
Mass spectrum m/e: 476 [M+]. C28H17N3O3S (475.51), Calc. C 70.72, H
3.61, N 8.84, S 6.74. Found C 70.59, H 3.88, N 9.02, S 6.51.
6c: m.p. 287 C, 35% yield. IR spectrum (¯/cm 1): 2995 (Ar CH), 1635,
1
1630 (2C N), 1610 (C C), 1320 (NSO2Ph), 1205 (C S C). H-NMR
( /ppm): 7.23–7.45 (br, 12H, Ar H), 7.49-7.92 (m, 5H, SO2Ar H).
C28H17N3O2S2 (491.57), Calc. C 68.40, H 3.49, N 8.55, S 13.05. Found
C 68.23, H 3.68, N 8.80, S 12.79.
6,7-Dibenzenesulphonyl-6,7-dihydro-
benzo[a]quinoxalino[3,2-c]phenazine (6d)
6d was prepared as mentioned above in the preparation of 4b.

636
M. A. Berghot
m.p. >360 C, 30% yield. IR spectrum (¯/cm 1): 2930 (Ar CH), 1630,
1
(C N), 1600 (C C), 1320 (NSO2Ph), 1210 ( SO2 ). H-NMR ( /ppm):
7.11–7.34 (m, 12H, Ar H), 7.55–8.26 (m, 10H, SO2Ar H). Mass spec-
trum m/e: 615 [M+]. C34H22N4O4S2 (614.68), Calc. C 66.43, H 3.61,
N 9.12, S 10.43. Found C 66.29, H 3.82, N 8.97, S 10.32.
4-Benzenesulphonyl-2-phenyl-naphtho[2,3-e]-
1,3,4-oxadiazine-5,10-dione (8)
To a solution of 7 (0.01 mmol) in DMF (20 ml), triethylamine (5 ml), and
benzenesulphonyl chloride (3 ml) were added dropwise. The mixture
was refluxed with stirring for 10 h and left overnight. The precipitated
solid was filtered, washed well with water, dried, and recrystallized
from ethanol to give 8.
m.p. 241–243 C, 65% yield. IR spectrum (¯/cm 1): 1680, 1660
(2C N), 1320 (NSO2Ph), 1210 ( SO2 ), 1200 (C O C). 1H-NMR
( /ppm): 7.12–8.13 (br, 14H, Ar H). Mass spectrum ( /ppm): 430 [M+].
C23H14N2O5S (430.43), Calc. C 64.18, H 3.27, N 6.51, S 7.45. Found C
63.97, H 3.38, N 6.40, S 7.63.
4-Benzenesulphonyl-2-phenyl-naphtho[2,3-e]-
1,3,4-thiadiazine-5-,10-dione (9), 1-Benzenesulphonyl-
3-phenylnaphtho[2,3-d]pyrazole-4,9-dione (10)
To a solution of 8 (0.01 mmol) in xylene (50 ml), phosphorus pentasulfide
(0.02 mmol) was added. The mixture was boiled under reflux for 3 h,
and the mixture was then filtered while hot and allowed to cool. The
solid was filtered off, dried, and crystallized from xylene to give 9. The
filtrate was concentrated by evaporation. The solid that separated was
crystallized from dioxane to give 10.
9: m.p. >360 C, 40% yield. IR spectrum (¯/cm 1): 1680, 1660 (2C N),
1330 (NSO2Ph), 1260 (C S C). 13C NMR ( /ppm): 186.3, 186.1, 165.1,
149.8, 149.6, 146.5, 145.9, 133.2, 130.2, 129.7, 128.8, 128.6, 128.3, 128.2,
127.6, 127.2, 126.9, 126.5, 125.8, 125.5, 125.1. Mass spectrum m/e: 446
[M+]. C23H14N2O4S2 (446.49), Calc. C 61.87, H 3.16, N 6.28, S 14.36.
Found C 61.69, H 3.36, N 6.09, S 14.18.
10: m.p. 210 C, 30% yield. IR spectrum (¯/cm 1): 1660 (C O), 1620
1
(C N), 1580 (C C), 1320 (NSO2Ph). H-NMR ( /ppm): 7.00–7.56 (m,
14H, Ar H). 13C NMR ( /ppm): 186.5, 186.2, 149.9, 149.6, 146.4, 145.8,
134.6, 132.7, 130.2, 130.0, 129.8, 128.7, 128.4, 128.3, 128.1, 127.8,
127.5, 127.1, 126.7, 125.9, 124.8, 124.5. Mass spectrum m/e: 414 [M+].
C23H14N2O4S (414.43), Calc. C 66.65, H 3.40, N 6.76, S 7.74. Found
C 66.91, H 3.62, N 7.01, S 7.52.

Heterocyclic Naphthoquinones
637
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