1004
A. A. Aly et al. · Syntheses of New Pyridoxazines, Benzoxa(thia)azines, and Benzoxa(thia)azepines
tonitrile). – UV/vis (CH3CN): λmax(lgε) = 390 nm (3.80). (qC), 124.20, 124.98, 126.70 (Ar-CH), 126.90, 127.70,
˜
– IR (film): ν = 3050 – 2990 (Ar-CH), 1680 (CO), 1580 128.20, 128.98, 134.30, 134.80, 137.40 (qC), 137.60, 139.10,
(C=N) cm−1. – 1H NMR (400.134 MHz, CDCl3): 7.40 – 140.70, 152.20 (Ar-C-O), 156.40, 164.20, 164.50 (Ar-C=N).
1
7.26 (m, 3 H), δ = 7.80 – 7.70 (m, 1 H). – 13C{ H} NMR – MS (EI, 70 eV): m/z (%) = 439 (100) [M+], 314 (60),
(100.6 MHz, CDCl3): δ = 118.00 (qC-Cl), 120.00, 128.90 281 (16), 247 (80), 186 (12), 174 (52), 136 (14), 124 (80),
(Ar-CH), 130.28, 130.90 (qC), 132.00, 134.20 (Ar-CH), 97 (62), 76 (30), 55 (85). – C24H13N3S3 (439.58): calcd.
135.00, 136.00 (qC), 150.90 (Ar-C-O), 152.00 (C=N), C 65.58, H 2.98, N 9.56, S 21.88; found C 65.40, H 2.90,
182.00 (CO). – MS (EI, 70 eV): m/z (%) = 300 (100) [M+], N 9.45, S 21.71.
298 (80), 296 (54), 294 (22), 264 (40), 228 (20), 192 (24),
144 (30), 108 (18), 72 (20). – C12H4Cl3NO2 (300.53): calcd.
C 47.96, H 1.34, Cl 35.39, N 4.66; found C 47.78, H 1.30,
Cl 35.28, N 4.60.
15,16-Dioxa-5,10-diazahexaphene (13a): (0.48 g, 72%)
as green crystals (EtOH), m. p. 210 – 212 ◦C. – UV/vis
˜
(CH3CN): λmax(lgε) = 428 nm (4.18). – IR (film): ν =
3060 – 3020 (Ar-CH), 1640 (C=N) cm−1. – 1H NMR
(400.134 MHz, DMSO-d6): δ = 7.40 – 7.10 (m, 8 H, Ar-H),
2,3,4-Trichlorophenothiazine-1-one (11b): (0.23 g, 73%)
as orange crystals (Rf 0.4, CH2Cl2), m. p. 140 – 142 ◦C
(EtOH). – UV/vis (CH3CN): λmax(lgε) = 400 nm (3.90).
1
7.90 – 7.78 (m, 4 H, Ar-H). – 13C{ H} NMR (100.6 MHz,
DMSO-d6): δ = 120.90 (2Ar-CH), 122.70 (2Ar-CH),
124.80 (2Ar-CH), 127.70 (2Ar-CH), 129.10 (2qC), 132.80
(2Ar-CH), 134.90 (2Ar-CH), 137.50 (2qC), 148.70 (2qC),
150.20 (2qC), 164.50 (2qC=N). – C22H12N2O2 (336.35):
calcd. C 78.56, H 3.60, N 8.33; found C 78.43, H 3.54,
N 8.21.
˜
– IR (film): ν = 3060 – 2994 (Ar-CH), 1682 (CO), 1584
(C=N) cm−1. – 1H NMR (400.134 MHz, CDCl3): δ = 7.44 –
1
7.22 (m, 3 H), 7.84 – 7.72 (m, 1 H). – 13C{ H} NMR
(100.6 MHz, CDCl3): δ = 118.60 (qC-Cl), 120.40, 128.80
(2Ar-CH), 130.20, 131.10 (qC), 132.40, 134.40 (2Ar-CH),
135.20, 136.20 (qC), 150.60 (Ar-C-O), 152.40 (C=N),
182.80 (CO). – MS (EI, 70 eV): m/z (%) = 316 (100) [M+],
314 (78), 312 (52), 310 (20), 284 (20), 282 (24), 280 (34),
244 (30), 210 (18), 208 (24), 124 (14), 108 (22), 72 (24). –
C12H4Cl3NOS (316.59): calcd. C 45.53, H 1.27, Cl 33.59,
N 4.42; found C 45.40, H 1.22, Cl 33.52, N 4.40.
15,16-Dithia-5,10-diazahexaphene◦(13b): (0.56 g, 76%)
as green crystals (EtOH), m. p. 260 C (decop.). – UV/vis
˜
(CH3CN): λmax(lgε) = 424 nm (4.20). – IR (film): ν =
3060 – 3020 (Ar-CH), 1648 (C=N) cm−1. – 1H NMR
(400.134 MHz- DMSO-d6): δ = 7.44 – 7.18 (m, 8 H, Ar-H),
1
8.05 – 7.84 (m, 4 H, Ar-H). – 13C{ H} NMR (100.6 MHz,
DMSO-d6): δ = 122.00 (2Ar-CH), 122.90 (2Ar-CH),
125.00 (2Ar-CH), 127.90 (2Ar-CH), 129.60 (2qC), 132.90
(2Ar-CH), 134.94 (2Ar-CH), 137.62 (2qC), 148.90 (2qC),
150.40 (2qC), 164.00 (2qC=N). – C22H12N2S2 (368.48):
calcd. C 71.71, H 3.28, N 7.60; found C 71.58, H 3.20,
N 7.55.
17H-5,6,12-Trioxa-11,17,18-triazatrinaphthylene (12a):
(0.70 g, 60%) as blue crystals (EtOH), m. p. 260 –
◦
262 C. – UV/vis (CH3CN): λmax(lgε) = 420 nm (4.10).
˜
– IR (film): ν = 3180 (NH), 3080 – 3000 (Ar-CH), 1620
(C=N) cm−1. – 1H NMR (400.134 MHz, DMSO-d6): δ =
6.40 (dd, J = 8.4 Hz, J = 1.4 Hz, 2 H), 6.70 (dd, J = 8.4 Hz,
J = 1.4 Hz, 2 H), 7.24 – 7.08 (m, 3 H, Ar-H), 7.72 – 7.52
Indene-10-one-yl[b]-1,4-benzoxazepine-11-carbonitrile
(14a): (0.44 g, 80%) as yellow crystals (actetonitrile), m. p.
174 – 176 ◦C. – UV/vis (CH3CN): λmax(lgε) = 390 nm
1
(m, 5 H, Ar-H), 11.82 (br, s, 1 H, NH). – 13C{ H} NMR
(100.6 MHz, DMSO-d6): δ = 115.30 (qC), 116.00 (Ar-CH),
118.60, 118.80, 123.40, 123.60, 123.80 (qC), 124.00, 124.90,
126.60 (Ar-CH), 126.70, 127.50, 128.00, 128.90, 134.00
(Ar-CH), 134.70, 137.00 (qC), 137.50, 138.90 (qC), 140.50,
152.00 (Ar-C-O), 156.00 (Ar-C-O), 164.00, 164.40 (C=N).
– MS (EI, 70 eV): m/z (%) = 391 (100) [M+], 282 (60),
268 (24), 252 (18), 222 (20), 196 (34), 112 (20), 98 (16).
– C24H13N3O3 (391.39): calcd. C 73.65, H 3.35, N 10.74;
found C 73.50, H 3.25, N 10.58.
˜
(3.80). – IR (film): ν = 3056 – 3008 (Ar-CH), 2210 (CN),
1
1695 (CO), 1620 (C=N) cm−1. – H NMR (400.134 MHz,
DMSO-d6): δ = 6.70 (dd, J = 7.4 Hz, J = 1.2 Hz, 1 H,
Ar-H), 7.08 – 6.90 (m, 2 H, Ar-H), 7.40 – 7.24 (m, 2 H,
Ar-H), 7.70 – 7.52 (m, 2 H, Ar-H), 7.80 (dd, J = 7.4 Hz,
1
J = 1.2 Hz, 1 H, Ar-H). – 13C{ H} NMR (100.6 MHz,
DMSO-d6): δ = 98.00 (indenonyl-C-CO), 114.80 (CN),
122.70 (Ar-CH), 124.00, 126.10, 126.60, 127.70, 128.90,
132.00, 132.80, 135.10 (qC), 137.50, 141.70, 148.00
(Ar-C-O), 156.00 (C-11), 160.20 (indenonyl-C-O, C-5a),
186.00 (C-10). – C17H8N2O2 (272.27): C 75.00, H 2.96,
N 10.29; found C 75.20, H 2.90, N 10.34.
17H-5,6,12-Trithia-11,17,18-triazatrinaphthylene (12b):
(0.84 g, 64%) as blue crystals (EtOH), m. p. 300 –
◦
302 C. – UV/vis (CH3CN): λmax(lgε) = 440 nm (4.28).
˜
– IR (film): ν = 3160 (NH), 3070 – 3010 (Ar-CH), 1622
(C=N) cm−1. – 1H NMR (400.134 MHz, DMSO-d6): δ =
Indene-10-one-yl[b]-1,4-benzothiazepine-11-carbonitrile
6.60 (dd, J = 8.4 Hz, J = 1.4 Hz, 2 H), 6.80 (dd, J = (14b): (0.47 g, 82%) as yellow crystals (actetonitrile), m. p.
8.2 Hz, J = 1.4 Hz, 2 H), 7.24 – 7.10 (m, 3 H, Ar-H), 190 – 192 ◦C. – UV/vis (CH3CN): λmax(lgε) = 398 nm
˜
7.70 – 7.48 (m, 5 H, Ar-H), 11.80 (br, s, 1H, NH). – (3.90). – IR (film): ν = 3050 – 3010 (Ar-CH), 2212 (CN),
1
1
13C{ H} NMR (100.6 MHz, DMSO-d6): δ = 115.30 (qC), 1690 (CO), 1618 (C=N) cm−1. – H NMR (400.134 MHz,
118.00 (Ar-CH), 118.90, 120.00, 123.60, 123.80, 123.94 CDCl3): δ = 6.70 (dd, J = 7.4 Hz, J = 1.2 Hz, 1 H, Ar-H),
Unauthenticated
Download Date | 12/7/18 11:54 AM