Synthesis of arylnaphthoquinones and their reactions with o-substituted primary aromatic amines

Article abstract of DOI:10.1002/jccs.200100113

Cycloaddition reaction of 2-aryl-1,4-benzoquinones 1a-d with a number of different dienes, namely 2,3-dimethylbutadiene; 1,4-diphenylbutadiene and anthracene yield 2-aryl-6,7-dimethyl-1,4-naphthoquinones 3a,b; 2,5,8-triphenyl-1,4-naphthoquinone 4 and 2-aryl-1,4,9,10-tetrahydro-9,10-o-benzoanthracene-1,4-dione 5, respectively were investigated. In addition, the cycloaddition reaction of 2-aryl-1,4-benzoquinones 1d,e with 2,3-dimethylbutadiene was also investigated to yield 2-aryl-5,8-dihydro-6,7-dimethyl-1,4-naphthohydroquinones 2a,b. Cyclocondensation reactions of Diels-Alder adducts 2b, 3b, 5a with ethylenediamine, o-substituted primary aromatic amines gave quinoxaline, phenazine, phenoxazine and phenothiazine ocyclic derivatives 6-14.

Full text of DOI:10.1002/jccs.200100113

JournaloftheChineseChemicalSociety, 2001, 48, 795-800
795
Synthesis of Arylnaphthoquinones and Their Reactions with o-Substituted
PrimaryAromaticAmines
Ragab F. Fandya*, Hessan H. Abbasa, Ayman S. Al-Hussainia and Ahmed S. Hammamb
aChemistryDepartment,FacultyofScience,SouthValleyUniversity,Qena,Egypt
bChemistryDepartment,FacultyofScience,AssiutUniversity,Assiut,Egypt
Cycloadditionreactionof2-aryl-1,4-benzoquinones 1a-d with a num ber of dif fer ent dienes, namely 2,3-
dimethylbutadiene; 1,4-diphenylbutadiene and anthracene yield 2-aryl-6,7-dimethyl-1,4- naphthoquinones
3a,b; 2,5,8-triphenyl-1,4-naphthoquinone 4 and 2-aryl-1,4,9,10-tetrahydro-9,10-o-benzoanthracene-1,4-
dione5,respectivelywereinvestigated.Inaddition,thecycloadditionreactionof2-aryl-1,4-benzoquinones
1d,e with 2,3-dimethylbutadiene was also investigated to yield 2-aryl-5,8-dihydro-6,7-dimethyl-1,4-
naphthohydroquinones2a,b. Cyclocondensation re ac tions of Diels-Alder ad ducts 2b, 3b, 5a with ethyl-
enediamine, o-substitutedprimaryaromaticaminesgavequinoxaline,phenazine,phenoxazineandphenothi-
azineocyclicderivatives6-14.
INTRODUCTION
Incontinuationofourstudyforthesynthesisofhetero-
butadiene in dry ben zene was ob tained in an ox i dized state as
2,5,8-triphenyl-1,4-naphthoquinone 4. The cycloaddition re-
ac tion of 1a-d with anthracene pro ceeded also in hot gla cial
ace tic acid, af forded the ad ducts 5a-d, namely 2-aryl- 1,4,9,10-
tetrahydro-9,10-o-benzoanthracene-1,4-diones (Scheme I).
The struc tures of these prod ucts 2-5were sup ported by
their an a lyt i cal and spec tral data (IR, NMR and MS) which
were in full agree ment with the pro posed struc tures (cf. Ta-
bles 1 and 2).
Treat ment of Diels-Alder ad ducts, 6,7-dimethyl-2-(p-
nitrophenyl)-1,4-naphthoquinone 3b with ethylenediamine
at room tem per a ture and at 80 C in ab so lute eth a nol gave
8,9-dimethyl-5-(p-nitrophenyl)-2,3,4,6-tetrahydrobenzo[f]-
quinoxalin-6-one 6 and 2,3-dihydro-8,9-dimethyl-5-(p-nitro-
phenyl)benzo[f]quinoxalin-6-ol 7, re spec tively (Scheme II).
IR spec tra of com pound6 re vealed the pres ence of CO at
1710 cm-1 and the pres ence of NH band at 3350 cm-1. But IR
spectra of com pound 7 revealed the absence of CO of
quinone and pres ence of OH band at 3400-3450 cm-1; an a-
lyt i cal and spec tro scopic data of these com pounds are listed
in Ta bles 1 and 2. On the other hand the re ac tions of 3b with
o-substitutedaromaticamines,namely o-phenylenediamine;
4,5-dimethyl-o-phenylenediamine; o-aminothiophenol and
o-aminophenol gave 2,3-dimethyl-6-(p-nitrophenyl)-5- hy-
droxybenzo[a]phenazine 8; 2,3-dimethyl-5H-6-(p-nitro-
phenyl)benzo[a]phenothiazin-5-one 9 and 2,3-dimethyl-
5H-6-(p-nitrophenyl)benzo[a]phenoxazin-5-one 10, re spec-
tively (Scheme II).
cyclicnitrogendervatives,1-6 we were in ter ested in the re ac-
tion of arylnaphthoquinones with thioglycolic acid and pri-
mary ar o matic amines giv ing two types of the con den sa tion
products.6 Thequinoxaline,4,7-14 phenazine,15-18 phenoxazine15,19
andphenothiazine,20,21 ring sys tems have been ex ten sively
stud ied and many such com pounds have now be come com-
mercially avail able and are widely used in med i cal prac-
tice22,23 and in the dye in dus try.24 This led us to syn the size
some new re lated com pounds. In this work, 5-arylbenzo-
[f]quinoxalin-6-one 6, 5-arylbenzo[f]quinoxalin-6-ol 7, 6-
aryl-5-hydroxybenzo[a]phenazine 8, 6-arylbenzo[a]pheno-
thiazin-5-one 9 and 6-arylbenzo[a]phenoxazin-5-one 10
were pre pared by the reactions of the synthesizedDiels-
Alderadducts, arylnaphthoquinoneswithethylenediamine
and/or o-substitutedprimaryaromaticamines.
RESULTSANDDISCUSSION
Treat ment of 2-(p-carboxyphenyl)-1,4-benzoquinone
1d and/or 2-(p-nitrophenyl)-1,4-benzoquinone 1e with 2,3-
dimethylbutadiene in glacial acetic acid yields colorless
com pounds of 2-aryl-5,8-dihydro-6,7-dimethyl-1,4- naph-
thohydroquinones 2a,b. The ox i da tion of com pounds2a,b
with aque ous so lu tion of chro mium tri ox ide in hot gla cial
ace tic acid gives yel low com pounds of 2-aryl-6,7-dimethy-
1,4-naphthoquinones3a,b. Diels-Alder adduct from the re ac-
tion of 2-phenyl-1,4-benzoquinone 1a with 1,4-diphenyl-
The chemical structures of these compounds were
basedonspectralandelementalanalyses(cf.Tables1and2).
The re ac tion be tween2b, 5a and o-substitutedprimaryaro-

796 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Fandy et al.
Scheme I
Scheme II
NO2
NO2
OH
N
O
H3C
H3C
H3C
NH2(CH2)2NH2
NH2(CH2)2NH2
80 0C
25 0C
N
H3C
NH
N
NO2
O
O
6
7
H3C
H3C
NO2
OH
3b
NO2
H3C
O
N
R
R
NH2
NH2
XH
H3C
H3C
N
NH2
N
H3C
X
R = H, CH
3
X = S, O
8
a, R = H
b, R = CH3
R
9, X = S
10, X = O
R
matic amines pro duced 11-14 in a sim i lar man ner to that de-
ter. The 1H-NMR spectra were recorded by a 300 MHz
Varian NMR spec trom e ter; chem i cal shifts are re ported in
ppm with TMS as an in ter nal stan dard and are given in
units. Elec tron im pact mass spec tra were ob tained at 70 eV
usingaGCMSsp. 1000Shimadzu. Elementalanalyseswere
car ried out at the Microanalysis Unit at Cairo Uni ver sity.
scribed above (Scheme III). Thechemicalstructuresofthese
com pounds were based on spec tral and el e men tal anal y ses
(cf. Ta bles 1 and 2).
EXPERIMENTAL
Synthesis of 2-aryl-5,8-dihydro-6,7-dimethyl-1,4-
naphthohydroquinones 2a,b
Melting points were de ter mined on an elec tric melt ing
point ap pa ra tus (Gallenkamp) and were un cor rected. The IR
spec tra (KBr) were re corded on a Shimadzu 408 spec trom e-
A so lu tion of 2-(p-carboxyphenyl)-1,4-benzoquinone
1d (0.005 mol) or 2-(p-ni trophenyl)-1,4-benzoquinone1e

SynthesisofHeterocycliesfromArylnaphthoquinones
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 797
Table 1. Physical Data of Compounds 2-14
Comp.
No.
Ar
Cryst.
Solvent
Yield
%
Appearance
M.P.
C
Molecular
Formula
2a
2b
3a
3b
4
p-C6H4CO2H
p-C6H4NO2
p-C6H4CO2H
p-C6H4NO2
C6H5
acetic acid
67
74
63
71
70
88
92
63
70
80
64
60
66
43
30
40
52
56
39
62
66
colorless needles
257
265-8
270-2
256-8
103-5
157-8
115-6
139-140
148
C19H18O4
(310.34)
C18H17NO4
(311.33)
C19H14O4
(306.32)
C18H13NO4
(307.30)
C28H18O2
(386.45)
C26H16O2
(360.41)
C27H18O2
(374.44)
C26H15O2Cl
(394.86)
C27H16O4
(404.42)
C20H17N3O3
(347.34)
C20H17N3O3
(347.34)
C24H17N3O3
(395.42)
C26H21N3O3
(423.47)
C24H16N2SO3
(412.47)
C24H16N2O4
(396.40)
C24H18N2SO3
(414.48)
C24H19N3O3
(397.43)
C26H23N3O3
(425.49)
C32H19NSO
(465.56)
C32H20N2O
(448.51)
C34H24N2O
(476.58)
acetic acid
colorless needles
acetic acid
yellow flakes
acetic acid
yellow flakes
petroleum ether (60-80)
aqueous ethanol
aqueous ethanol
aqueous ethanol
aqueous ethanol
ethanol/petr. ether
aqueous ethanol
acetone
yellowish orange needles
yellowish brown crystals
yellowish orange crystals
pale brown fine crystals
gray fine crystals
5a
5b
5c
5d
6
C6H5
p-C6H4CH3
p-C6H4Cl
p-C6H4CO2H
brown crystals
184
-
7
yellowish gray micro crystals
orange red crystals
red flakes
128-130
320-2
346-8
326-8
324-5
310
-
-
8a
8b
9
acetone
-
-
-
-
acetone
cherry red needles
brownish yellow flakes
red micro crystals
red micro crystals
red micro crystals
dark brown crystals
brownish orange crystals
deep brown crystals
10
11
12a
12b
13
14a
14b
methanol
chloroform/pet. ether
ethanol/pet. ether
ethanol/pet. ether
benzene/pet. ether
aqueous ethanol
aqueous ethanol
270-2
> 360
170
-
-
-
-
-
182
168
and (0.41 g; 0.005 mol) of 2,3-dimethylbutadiene in 20 mL
gla cial ace tic acid was left for 12 hours in a closed ves sel at
roomtemperature.Thereactionmixturewasheatedunderre-
flux for 3-5 hours and cooled. The solid prod uct so formed
was col lected by fil tra tion and recrystallized from the ap pro-
pri ate sol vent to yield the de sired col or less prod ucts2a,b;
yields, meltingpoints, analyticalandspectroscopicdataare
listed in Ta bles 1 and 2.
Synthesis of 2-aryl-6,7-dimethyl-1,4-naphthoquinones
3a,b
To a hot so lu tion of 2a or 2b (0.005 mol) in 25 mL gla-
cial ace tic acid was grad u ally added a so lu tion of chro mic
acid (1.35 g of chro mium tri ox ide in 3 mL dis tilled wa ter).

798 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Fandy et al.
Table 2. Analytical and Spectroscopic Data of Compounds 2-14
Elemental Analysis
Found/Calcd.
MS
m/e
base peak
Ar
IR
1H-NMR
Comp.
No.
(cm-1)
C
H
N
2a
2b
3a
p-C6H4CO2H
p-C6H4NO2
p-C6H4CO2H
73.42
73.54
5.94
5.85
1680,
1.75(s, 6H, 2CH3); 3.12(s, 4H, 2CH2); 6.60(s, 1H,
H-3); 7.69; 7.90(2s, 2H, 2 OH) and 7.60; 7.96(2d,
4H, Ar) (f).
1.72(s, 6H, 2CH3); 3.16(s, 4H, 2CH2); 6.68(s, 1H,
H-3); 7.76; 8.14(2s, 2H, 2 OH) and 8.18; 8.36(2d,
4H, Ar) (f).
2925 (b)
3525 (c)
3525 (c)
69.32
69.44
5.41
5.50
4.43
4.50
74.42
74.50
4.56
4.61
306(M+·, 30.8) 1665 (a)
2.52(s, 6H, 2CH3); 7.17(s, 1H, H-3); 7.73; 8.05(2d,
4H, Ar) and 7.80; 7.86 (2s, 2H, H-5, 8) (f).
261(100)
1700,
2925 (b)
1670 (a)
3b
4
p-C6H4NO2
C6H5
70.48
70.35
87.15
87.02
86.58
86.65
86.75
86.60
4.39
4.26
4.82
4.69
4.38
4.47
5.14
4.85
4.58
4.56
2.43(s, 6H, 2CH3); 7.05(s, 1H, H-3); 7.67; 7.78(2s,
2H, H-5, 8) and 7.92; 8.38(2d, 4H, Ar) (e).
6.82(s, 1H, H-3); 6.85-6.92(m, 5H, Ar); and 7.46-
7.58(m, 12H, Ar) (e).
5.88(s, 2H, H-9, 10); 6.67(s, 1H, H-3); 7.04-7.10(m,
5H, Ar) and 7.41-7.50 (m, 8H, Ar) (e).
2.35(s, 3H, CH3); 5.91(s, 2H, H-9,10); 6.72(s, 1H,
H-3); 7.25; 7.33(2d, 4H, Ar) and 7.48-7.52(m, 8H,
Ar) (f).
1630,
1665 (a)
C6H5
360(M+·, 87.8) 1650,
5a
5b
202(100)
1715 (a)
p-C6H4CH3
374(M+·, 100) 1650,
1715 (a)
5c
p-C6H4Cl
79.15
79.09
80.07
80.19
3.71
3.83
3.89
3.99
1650,
1715 (a)
5.89(s, 2H, H-9,10); 6.66(s, 1H, H-3); 7.05;
7.11(2d, 4H, Ar) and 7.36-7.49(m, 8H, Ar) (f).
p-C6H4CO2H
404(M+·, 87.1) 1650 (a); 5.96(s, 2H, H-9,10); 6.78(s, 1H, H-3); 7.42-7.58(m,
5d
202(100)
1690,
12H, Ar) and 10.84(s, 1H, COOH) (f).
3450 (b)
-
-
-
-
-
-
69.09
69.15
4.88
4.93
12.13
12.10
347(M+·,24.9) 1710 (a)
220(100)
2.38; 2.44(2s, 6H, 2CH3); 3.62-3.87(m, 4H, 2CH2);
6.18(m, 1H, NH); 7.15(m, 4H, Ar); 7.92and
8.12(2s, 2H, Ar) (e).
2.41; 2.49(2s, 6H, 2CH3); 3.82(s, 4H, 2CH2);
7.18(m, 4H, Ar); 8.12; 8.86(2s, 2H, Ar) and 9.15(s,
1H, OH) (e).
2.58(s, 6H, 2CH3); 7.80-7.85(m, 4H, Ar); 8.37(s,
2H, H-1, H-4); 8.41-8.42(m, 4H, Ar) and 9.07(s,
1H, OH) (f).
2.48; 2.51; 2.61; 2.66(4s, 12H, 4CH3); 7.62-7.72(m,
4H, Ar); 7.98(s, 2H, Ar); 8.12; 8.33(2s, 2H, Ar) and
9.04(s, 1H, OH) (f).
2.46; 2.52(s, 6H, 2CH3); 7.33-7.55(m, 4H, Ar);
7.58; 8.39(2d, 4H, Ar) and 8.07; 8.68(2s, 2H, H-
1,4) (e).
2.52; 2.60(s, 6H, 2CH3); 7.30-7.53(m, 4H, Ar);
7.58- 7.99(m, 4H, Ar) and 8.12; 8.58(2s, 2H, H-1,4)
(e).
6
3350 (d)
69.31
69.15
4.85
4.93
12.19
12.10
347(M+·,15.4) 3450 (c)
299(100)
7
72.74
72.90
4.38
4.33
10.38
10.63
395(M+·,100)
3400 (c)
3400 (c)
1665 (a)
1650 (a)
8a
8b
9
73.59
73.74
5.07
4.99
9.97
9.92
69.87
69.89
3.98
3.91
6.64
6.79
10
72.55
72.72
4.13
4.07
6.92
7.07
396(M+·,100)
11
-
-
69.57
69.55
72.31
72.53
4.42
4.38
4.85
4.82
6.72
6.76
10.49
10.57
1665 (a)
3450 (c)
1.65(s, 6H, 2CH3); 3.11(s, 4H, 2CH2); 7.33-7.52(m,
4H, Ar) and 7.57-7.62(m, 4H, Ar) (e).
1.56(s, 6H, 2CH3); 3.08(s, 4H, 2CH2); 7.57-7.68(m,
4H, Ar); 7.72-7.78(m, 4H, Ar) and 8.90(s, 1H, OH)
(e).
12a
12b
-
73.34
73.40
5.51
5.45
9.85
9.88
3500 (c)
1710 (a)
1.66(s, 6H, 2CH3); 2.47; 2.50(2s, 6H, 2CH3);
3.12(s, 4H, 2CH2); 7.57-7.68(m, 4H, Ar); 7.75;
7.79(2s, 2H, H-8,11) and 8.94(s, 1H, OH) (e).
5.89(s, 2H, H-9 , 10 ); 7.06-7.12(m, 5H, Ar) and
13
-
-
-
82.68
82.55
85.56
85.69
85.52
85.69
4.23
4.11
4.54
4.49
5.12
5.07
2.92
3.01
6.20
6.24
5.82
5.87
7.48-7.56(m, 12H, Ar) (f).
448(M+·,4.1)
345(100)
1700 (a)
3350 (d)
1700 (a)
3350 (d)
14a
14b
5.68(s, 2H, H-9 , 10 ); 7.12-7.19(m, 5H, Ar); 7.42-
7.59(m, 12H, Ar) and 8.1(s,1H, NH) (f).
2.60, 2.64(2s, 6H, 2CH3); 5.82(s, 2H, H-9 , 10 );
7.06-7.12(m, 5H, Ar); 7.45-7.51(m, 8H, Ar) and
8.11, 8.18(2s, 2H, Ar) (f).
(a) CO; (b) COOH; (c) OH; (d) NH; (e) CDCl3; (f) d6 -DMSO.

SynthesisofHeterocycliesfromArylnaphthoquinones
J. Chin. Chem. Soc., Vol. 48, No. 4, 2001 799
Scheme III
SH
NO2
R
NH2
NH2
NO2
NO2
O
OH
OH
OH
H3C
H3C
H3C
H3C
NH2
H3C
H3C
R
S
N
R
N
N
2b
11
12
a, R = H
R
b, R = CH3
O
SH
O
N
R
R
NH2
Ph
NH2
O
Ph
S
NH2
Ph
HN
O
N
14
13
a, R = H
5a
R
b, R = CH3
R
When all the ox i dant had been added, the re ac tion so lu tion
washeatedfor20minuteswithoutboilingandcooledtoroom
temperature.Thedepositedyellowprecipitatewasthencol-
lected, washed with ethanol and recrystallized from the
proper sol vent to af ford 3a,b;yields,meltingpoints,analyti-
cal and spec tro scopic data are listed in Ta bles 1 and 2.
The re ac tion mix ture was stirred at room tem per a ture for 16
hours. The solid prod uct so formed was recrystallized to give
6;yield, meltingpoint, spectroscopicandanalyticaldataare
listed in Ta bles 1 and 2.
Synthesis of 2,3-dihydro-8,9-dimethyl-5-(p-nitrophenyl)-
benzo[f]quinoxalin-6-ol 7
Synthesis of 2,5,8-triphenyl-1,4-naphthoquinone 4
To 0.46 g; (0.0025 mol) of 2-phenyl-p-benzoquinone
1a in 25 mL dry ben zene was added 0.515 g; (0.0025 mol) of
1,4-diphenylbutadiene. The re ac tion mix ture was refluxed
for 16 hours (TLC using pe tro leum ether/ben zene 1:1 as
eluent). The sol vent was re moved un der re duced pres sure,
the res i due formed was recrystallized from pe tro leum ether
to af ford 4;yield,meltingpoint,analyticalandspectroscopic
data are listed in Ta bles 1 and 2.
Ethylenediamine (0.13 mL, 0.12 g, 0.002 mol) was
added to 0.62 g, (0.002 mol) of3bin25mLabsoluteethanol.
The re ac tion mix ture was refluxed for 3-4 hours, then con-
centratedandcooled.Theprecipitatedsolidwascollectedby
fil tra tion and recrystallized from the proper sol vents to give
7; yields, melt ing points, spec tro scopic and an a lyt i cal data
are listed in Ta bles 1 and 2.
Synthesis of 2,3-dimethyl-6-(p-nitrophenyl)-5-hydroxy-
benzo[a]phenazine 8; 2,3-dimethyl-5H-6-(p-nitrophenyl)-
benzo[a]phenothiazin-5-one 9 and 2,3-dimethyl-5H-6-(p-
nitrophenyl)benzo[a]phenoxazin-5-one 10
Synthesis of 2-aryl-1,4,9,10-tetrahydro-9,10-o-benzo-
anthracene-1,4-dione 5a-d
To a so lu tion of 0.002 mol of 1a-d in 15 mL gla cial ace-
tic acid was added 0.37 g, (0.002 mol) of anthracene. The re-
ac tion mix ture was refluxed for 10-12 hours then cooled and
di luted with 30 mL of dis tilled wa ter. The re sult ing pre cip i-
tate was fil tered off, dried and recrystallized from the proper
sol vent to give 5a-d; yields, melt ing points, an a lyt i cal and
spec tro scopic data are listed in Ta bles 1 and 2.
General procedure
A sus pen sion of 0.62 g, (0.002 mol) of3b in 25 mL ab-
soluteethanolwastreatedwiththeappropriateo-substituted
aromaticamine(0.002mol).Thereactionmixturewasheated
un der re flux for 70-80 hours. The sol vent was then evap o-
rated un der re duced pres sure. The re sid ual sol ids were pu ri-
fiedonacolumnchromatographyusingethanol/petroleum
ether (2:8) as an eluent. The sol ids were col lected, re crys-
tallized from the ap pro pri ate sol vents to give 8, 9 and 10, re-
spectively;yields,meltingpoints,spectroscopicandanalyti-
cal data are listed in Ta bles 1 and 2.
Synthesis of 8,9-dimethyl-5-(p-nitrophenyl)-2,3,4,6-
tetrahydrobenzo[f]quinoxalin-6-one 6
To 0.307 g, (0.001 mol) of 3b in20mLabsoluteethanol
was added 0.06 mL, (0.06 g, 0.001 mol) of ethylenediamine.

800 J. Chin. Chem. Soc., Vol. 48, No. 4, 2001
Fandy et al.
Synthesis of 2,3-dimethyl-6-(p-nitrophenyl)-1,4,5-tri-
hydrobenzo[a]phenothiazin-5-one 11 and 2,3-dimethyl-
1,4-dihydro-5-hydroxy-6-(p-nitrophenyl)benzo[a]phenazine
12a,b
Bull. of Assiut 1996, 25, 35.
3. Fandy, R. F. Arch. Pharm. Res. 2000, 23(5), 446.
4. Hassan, M. A.; Fandy, R. F.; El-Amine, T. M. J. Hetero-
cyclic Chem. 2001, 38, 179.
5. Atta, A. H.; Abdel-Razik, H. H.; Fandy, R. F. Hetero-
cyclic Comm. 1998, 4(6), 553.
General procedure
To a so lu tion of 2b (0.31 g, 0.001 mol) in 30 mL ab so-
luteethanolwasaddedtheappropriate o-substitutedaromatic
amine (0.001 mol) and heated un der re flux for 7-12 hours.
Thereactionmixturewasconcentratedtoonethirdofitsvol-
ume and cooled. The pre cip i tated prod ucts were col lected
and recrystallized from the proper sol vent to yield 11 and 12;
yields, meltingpoints, spectroscopicandanalyticaldataare
listed in Ta bles 1 and 2.
6. Fandy, R. F.; Abbas, H. H.; Al-Hussaini, A. S.; Hammam,
A. S. Afinidad in press.
7. Kallmayer, H.; Seyfang, K. Arch. Pharm. (Weinheim)
1980, 313, 603.
8. Kallmayer, H.; Seyfang, K. Arch. Pharm. (Weinheim)
1984, 317, 329.
9. Winkelmann, E. Tetrahedron 1968, 25, 2427.
10. Kallmayer, H.; Seyfang, K. Arch. Pharm. (Weinheim)
1984, 317, 743.
Synthesis of 1-phenyl-2H-phenothiazino[3,4-9 ,10 ]-
9 H,10 H-anthracene-2-one 13 and 1-Phenyl-2H,10H-
phenazino[3,4-9 ,10 ]-9 H,10 H-anthracene-2-one 14
11. Kallmayer, H.; Seyfang, K. Arch. Pharm. (Weinheim)
1986, 319, 52.
12. Krapcho, A. P.; Gallagher, C. E.; Hammach, A.; Ellis, M.;
Menta, E.; Oliva, A. J. Heterocyclic Chem. 1997, 34, 27.
13. Krapcho, A. P.; Maresch, M. J.; Helgason, A. L.; Rosner,
K. E.; Hacker, M. P.; Spinelli, S; Menta, E.; Oliva, A. J.
Heterocyclic Chem. 1993, 30, 1597.
14. Cheng, C. C.; Liu, D. F.; Chou, T. C. Heterocycles 1993,
35, 775.
15. Van Allan, J. A.; Reynalds, G. A. J. Org. Chem. 1963, 28,
1019.
General procedure
Toasolutionof5a (0.36g, 0.001mol)inabsoluteetha-
nol was added the ap pro pri ate o-substitutedamine(0.001
mol). The re ac tion mix ture was refluxed for 3-6 hours. The
reactionsolutionwascooledtoroomtemperatureanddiluted
with two vol umes of wa ter. The pre cip i tated prod ucts were
col lected, dried and recrystallized from the proper sol vent to
give 13 and 14a,b; yields, melt ing points, spec tro scopic and
analyticaldataarelistedinTables1and2.
16. Agarwal, N.; Mital, R. J. of Chrom. 1975, 115, 264.
17. Fenyes, J. J. Chem. Soc. (c) 1968, 5.
18. Badger, G.; Pettit, I. J. Chem. Soc. 1952, 1877.
19. Nan’ya, S.; Maekawa, E.; Kang, W.; Ueno, Y. J.
Heterocyclic Chem. 1986, 23, 1697.
Received November 22, 2000.
20. Agarwal, N.; Mital, R. J. Chem. Eng. Data 1975, 20, 199.
21. Kang, W.; Nan’ya, S.; Maekawa, E.; Ueno, Y. J.
Heterocyclic Chem. 1988, 25, 113.
22. Burack, R. In “The New Handbook of Prescription
Drugs”; Ballantine Books, Inc.: New York, 1970; pp
254-256.
Key Words
2-Aryl-1,4-benzoquinones; Dienes;
2-Aryl-1,4-naphthoquinones; Quinoxaline;
Phenazine; Phenoxazine and phenothiazine.
23. Pollitt, J. In “PsychologicalMedicineforStudies”; Chur-
chill Living stone Ltd., (Longman Group Ltd.): Lon don,
1973; Chap ter 20, pp 241-266.
REFERENCES
1. Fandy, R. F.; Atta, A. H.; Hammam, A. S. Afinidad LIV
1997, 471, 401.
24. Venkataraman, K. In “TheChemistryofSyntheticDyes”;
Ac a demic Press: New York, 1952.
2. Atta, A. H.; Fandy, R. F.; Younes, M. I.; Metwally, S. A.