2-Aryl-4H-naphtho[2′,3′:4,5]thieno+- [2,3-d][1,3]oxazine-4,5, 10-triones

Full text of DOI:10.1007/s10593-008-0131-4

Chemistry of Heterocyclic Compounds, Vol. 44, No. 7, 2008
2-ARYL-4H-NAPHTHO[2',3':4,5]THIENO+-
[2,3-d][1,3]OXAZINE-4,5,10-TRIONES
M. V. Stasevych, S. I. Sabat, M. I. Semenyuk,
R. Ya. Musyanovych, and V. P. Novikov
Keywords: 2-amino-3-ethoxycarbonylnaphtho[2,3-b]thiophene-4,9-dione, 2-aryl-4H-naphtho[2',3':4,5]-
thieno[2,3-d][1,3]oxazine-4,5,10-trione.
The synthetic potential of 2-amino-3-ethoxycarbonylnaphtho[2,3-b]thiophene-4,9-dione (1) has been
little studied until now [1, 2]. We have carried out the reaction of dione 1 with equimolar quantities of aroyl
chlorides in dioxane in the presence of triethylamine (70-80°C, 5 h) and have obtained 2-aroylamino-3-ethoxy-
carbonylnaphtho[2,3-b]thiophene-4,9-diones 2a,b. Reaction of compounds 2a,b with dichlorotriphenyl-
phosphorane in the presence of triethylamine in toluene gave the previously undescribed 2-aryl-4H-
naphtho[2',3':4,5]thieno[2,3-d][1,3]oxazine-4,5,10-triones 3a,b in yields of 74-78%.
O
O
O
O
N
COOEt
NH2
COOEt
RCOCl/Et3N
Ph3P / C2Cl6 / Et3N
O
.
.
– Et3N HCl
S
.
S
N
H
– Et3N HCl
S
R
O
O
R
O
O
3a,b
1
2а,b
a R = n-ClC6H4; b R = n-MeC6H4
1H NMR spectra of DMSO-d6 solutions with TMS as internal standard were recorded with a Bruker
MSL-400 (400 MHz) spectrometer at 25°C.
2-(4-Chlorobenzoylamino)-3-ethoxycarbonylnaphtho[2,3-b]thiophene-4,9-dione (2a).
1
Yield 61%; mp 184-185°C. H NMR spectrum, δ, ppm (J, Hz): 7.82-7.77 (2H, dd, J = 0.4, J = 7.3, CHarom);
8.23-8.09 (2H, m, CHarom); 3.30 (1H, s, NH); 7.37-7.82 (4H, dd, J = 2.3, J = 2.1, CHarom); 4.24-4.30 (2H, q,
J = 7, CH2); 1.35 (3H, t, J = 2.9, CH3). Found, %: C 59.95; H 2.99; Cl 8.00; N 3.25; S 7.38. C22H14ClNSO5.
Calculated, %: C 60.07; H 3.21; Cl 8.06; N 3.18; S 7.29.
2-(4-Methylbenzoylamino)-3-ethoxycarbonylnaphtho[2,3-b]thiophene-4,9-dione (2b).
1
Yield 64%; mp 180-181°C. H NMR spectrum, δ, ppm (J, Hz): 7.81-7.75 (2H, m, CHarom); 8.21-8.08 (2H, dd,
J = 7.3, J = 0.4, CHarom); 3.30 (1H, s, NH); 7.30 (2H, d, J = 2.3, CHarom); 7.03 (2H, d, J = 2.2, CHarom); 4.24-4.30
(2H, q, J = 6.9, CH2); 2.35 (3H, s, CH3); 1.35 (3H, t, J = 2.8, CH3). Found, %: C 65.97; H 4.15; N 3.20; S 7.38.
C23H17NSO5. Calculated, %: C 65.86; H 4.09; N 3.34; S 7.64.
__________________________________________________________________________________________
Lviv Polytechnic National University "Lviv Polytechnic", Lviv 79013, Ukraine; e-mail:
vnovikov@polynet.lviv.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1112-1113, July,
2008. Original article submitted January 28, 2008.
0009-3122/08/4407-0897©2008 Springer Science+Business Media, Inc.
897

2-(4-Chlorophenyl)-4H-naphtho[2',3':4,5]thieno[2,3-d][1,3]oxazine-4,5,10-trione (3a). Yield 74%;
mp 292-293°C. 1H NMR spectrum, δ, ppm (J, Hz): 8.14-7.75 (2H, m, CHarom); 8.47-8.41 (2H, t, J = 7.5, CHarom);
7.46 (2H, d, J = 2.1, CHarom); 8.03 (2H, d, J = 3.3, CHarom). Found, %: C 59.94; H 2.10; Cl 8.90; N 3.61; S 8.21.
C21H11NO4S. Calculated, %: C 61.00; H 2.05; Cl 9.00; N 3.56; S 8.14.
2-(4-Methylphenyl)-4H-naphtho[2',3':4,5]thieno[2,3-d][1,3]oxazine-4,5,10-trione (3b). Yield 75%;
mp 292-293°C. 1H NMR spectrum, δ, ppm (J, Hz): 8.16-7.74 (2H, t, J = 7.5, CHarom); 8.47-8.41 (3H, m, CHarom);
7.21 (2H, d, J = 3.3, CHarom); 8.23 (2H, d, J = 2.2, CHarom); 2.39 (3H, s, CH3). Found, %: C 67.71; H 3.02;
N 7.02; S 8.40. C21H11NSO4. Calculated, %: C 67.55; H 2.97; N 3.75; S 8.59.
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