ꢁꢀꢀꢀ
Y. Shimotori et al.: Synthesis and evaluation of antibacterial properties of dibenzothiazepinesꢂ
ꢂ7
+
2-Amino-5-methoxyphenyl
2-cyano-4-nitrophenyl
sulfide
145.9 (C-2′), 150.7 (C-4). HRMS (FD). Calcd for C13H8N3O2SCl, [M] : m/z
305.0026. Found: m/z 305.0025.
(4e)ꢁYield 75%; orange solid; mp 149–150°C; Rf 0.28 (hexane-AcOEt,
3:1); IR: 3466 (N-H), 3375 (N-H), 2229 (C≡N), 1570 (ArNO2, (N=O)2),
1498 (Ar, C=C), 1454 (Ar, C=C), 1348 (ArNO2, (N=O)2), 1299 (C-O-C),
2-Nitrodibenzo[b,f][1,4]thiazepine (7a)ꢁYield 67%; yellow solid;
mp 148–149°C; Rf 0.50 (hexane-AcOEt, 3:1); IR: 3051 (Ar, C-H), 1599
(Ar, C=C), 1567 (ArNO2, (N=O)2), 1520 (Ar, C=C), 1460 (Ar, C=C), 1345
(ArNO2, (N=O)2), 1058 (Ar-S-Ar), 945 (Ar, C-H), 914 (ArNO2, C-N), 845
(Ar, C-H), 778 cm−1 (Ar, C-H); 1H NMR: δ 7.31 (m, 2H, H-8, H-9), 7.47 (m,
2H, H-6, H-7), 7.73 (d, Jꢀ=ꢀ8.6 Hz, 1H, H-4), 8.28 (t, Jꢀ=ꢀ5.6 Hz, 1H, H-3),
8.50 (d, Jꢀ=ꢀ2.6 Hz, 1H, H-1), 9.04 (s, 1H, H-11); 13C NMR: δ 125.4 (C-1),
126.7 (C-3), 127.1 (C-5a), 127.2 (C-9), 128.4 (C-8), 130.7 (C-7), 133.2 (C-4),
133.5 (C-6), 137.8 (C-11a), 146.7 (C-4a), 148.1 (C-2), 148.5 (C-9a), 161.5
1032 (Ar-S-Ar), 914 cm−1 (ArNO2, C-N); H NMR (600 MHz, CDCl3): δ
1
3.77 (s, 3H, ArOCH3), 4.02 (s, 2H, NH2), 6.86 (d, Jꢀ=ꢀ8.6 Hz, 1H, H-3′),
6.91 (d, Jꢀ=ꢀ9.2 Hz, 1H, H-6), 6.99 (dd, Jꢀ=ꢀ2.9, 8.0 Hz, 1H, H-4′), 7.02
(d, Jꢀ=ꢀ2.9 Hz, 1H, H-6′), 8.16 (dd, Jꢀ=ꢀ2.3, 8.9 Hz, 1H, H-5), 8.47 (d,
Jꢀ=ꢀ2.6 Hz, 1H, H-3); 13C NMR (CDCl3): δ 55.9 (ArOCH3), 109.4 (C-1′), 110.1
(C-2), 114.8 (-C≡N), 117.5 (C-3′), 120.6 (C-4′, C-6′), 126.3 (C-6), 127.3 (C-5),
128.5 (C-3), 143.3 (C-2′), 144.8 (C-1), 151.6 (C-4), 152.8 (C-5′). HRMS (FD).
+
Calcd for C14H11N3O3S, [M] : m/z 301.0521. Found: m/z 301.0530.
+
(C-11). HRMS (FD). Calcd for C13H8N2O2S, [M] : m/z 256.0306. Found:
2-Amino-5-fluorophenyl
2-cyano-4-nitrophenyl
sulfide
m/z 256.0315.
(4f)ꢁYield 89%; yellow solid; mp 160–161°C; Rf 0.20 (hexane-AcOEt,
3:1); IR: 3452 (N-H), 3357 (N-H), 2237 (C≡N), 1631 (Ar, C=C), 1567
(ArNO2, (N=O)2), 1494 (Ar, C=C), 1454 (Ar, C=C), 1342 (ArNO2, (N=O)2),
7-Methyl-2-nitrodibenzo[b,f][1,4]thiazepine (7b)ꢁYield 60%;
yellow solid; mp 133–134°C; Rf 0.51 (hexane-AcOEt, 3:1); IR: 3045 (Ar,
C-H), 2923 (CH3), 2850 (CH3), 1601 (Ar, C=C), 1569 (ArNO2, (N=O)2),
1525 (Ar, C=C), 1468 (Ar, C=C), 1347 (ArNO2, (N=O)2), 941 (Ar, C-H), 915
(ArNO2, C-N), 741 cm−1 (Ar, C-H); 1H NMR: δ 2.26 (s, 3H, ArCH3), 7.18 (d,
Jꢀ=ꢀ8.0 Hz, 1H, H-9), 7.23 (d, Jꢀ=ꢀ8.3 Hz, 1H, H-8), 7.26 (s, 1H, H-6), 7.69 (d,
Jꢀ=ꢀ8.6 Hz, 1H, H-4), 8.25 (dd, Jꢀ=ꢀ2.3, 8.6 Hz, 1H, H-3), 8.45 (d, Jꢀ=ꢀ2.6 Hz,
1H, H-1), 8.96 (s, 1H, H-11); 13C NMR: δ 20.5 (ArCH3), 125.3 (C-1), 126.6
(C-3), 127.2 (C-5a), 131.4 (C-9), 133.1 (C-8), 133.6 (C-7), 137.9 (C-4), 138.4
(C-6), 146.2 (C-11a), 146.5 (C-4a), 148.1 (C-2, C-9a), 160.1 (C-11). HRMS
1
1301 (ArNH2, C-N), 913 cm−1 (ArNO2, C-N); H NMR (CDCl3): δ 4.19 (s,
2H, NH2), 6.85 (q, Jꢀ=ꢀ4.5 Hz, 1H, H-3′), 6.92 (d, Jꢀ=ꢀ8.9 Hz, 1H, H-6), 7.13
(t, Jꢀ=ꢀ6.9 Hz, 1H, H-4′), 7.20 (d, Jꢀ=ꢀ7.7 Hz, 1H, H-6′), 8.17 (d, Jꢀ=ꢀ8.9 Hz,
1H, H-5), 8.47 (s, 1H, H-3); 13C NMR (CDCl3): δ 109.5 (C-1′) 110.5 (C-2),
114.6 (-C≡N), 116.9 (C-3′), 120.6 (C-4′), 122.9 (C-6′), 126.4 (C-6), 127.3
(C-5), 128.6 (C-3), 145.1 (C-1), 145.8 (C-4), 150.6 (C-2′), 154.5 (C-5′). HRMS
+
(FD). Calcd for C13H8N3O2SF, [M] : m/z 289.0321. Found: m/z 289.0316.
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2-Amino-4-fluorophenyl
2-cyano-4-nitrophenyl
sulfide
(FD). Calcd for C14H10N2O2S, [M] : m/z 270.0463. Found: m/z 270.0458.
(4g)ꢁYield 75%; yellow solid; mp 126–127°C; Rf 0.36 (hexane-AcOEt,
3:1); IR: 3451 (N-H), 3353 (N-H), 1632 (Ar, C=C), 1569 (ArNO2, (N=O)2),
1452 (Ar, C=C), 1342 (ArNO2, (N=O)2), 1145 (Ar, C-F), 914 cm−1 (ArNO2,
C-N); 1H NMR (CDCl3): δ 4.43 (s, 2H, NH2), 6.58 (m, 2H, H-3′, H-5′), 6.88
(d, Jꢀ=ꢀ8.9 Hz, 1H, H-6), 7.42 (t, Jꢀ=ꢀ7.3 Hz, 1H, H-6′), 8.16 (dd, Jꢀ=ꢀ2.3,
8.9 Hz, 1H, H-5), 8.46 (d, Jꢀ=ꢀ2.6 Hz, 1H, H-3); 13C NMR (CDCl3): δ 102.6
(C-3′), 104.4 (C-1′), 107.2 (C-5′), 110.3 (C-2), 114.7 (-C≡N), 126.1 (C-6), 127.3
(C-5), 128.6 (C-3), 139.6 (C-6′), 145.0 (C-1), 151.0 (C-2′), 151.5 (C-4), 164.8
9-Methyl-2-nitrodibenzo[b,f][1,4]thiazepine (7c)ꢁYield 63%;
dark yellow solid; mp 137–138°C; Rf 0.59 (hexane-AcOEt, 3:1); IR: 3043
(Ar, C-H), 2925 (CH3), 2852 (CH3), 1598 (Ar, C=C), 1566 (ArNO2, (N=O)2),
1449 (Ar, C=C), 1373 (Ar, C-N), 1339 (ArNO2, (N=O)2), 1005 (Ar-S-Ar),
1
943 (Ar, C-H), 916 (ArNO2, C-N), 773 (Ar, C-H), 699 cm−1 (Ar, C=C); H
NMR: δ 2.27 (s, 3H, ArCH3), 7.13 (t, Jꢀ=ꢀ7.6 Hz, 1H, H-6), 7.26 (m, 2H, H-7,
H-8), 7.68 (d, Jꢀ=ꢀ8.6 Hz, 1H, H-4), 8.22 (dd, Jꢀ=ꢀ2.6, 8.6 Hz, 1H, H-3), 8.42
(d, Jꢀ=ꢀ2.6 Hz, 1H, H-1), 9.06 (s, 1H, H-11); 13C NMR: δ 19.0 (ArCH3), 124.9
(C-1), 126.4 (C-3), 127.4 (C-5a), 128.1 (C-9), 131.1 (C-8), 132.1 (C-7), 133.1
(C-4), 135.1 (C-6), 137.9 (C-11a), 146.6 (C-4a), 147.0 (C-2), 148.1 (C-9a),
+
(C-4′). HRMS (FD). Calcd for C13H8N3O2SF, [M] : m/z 289.0321. Found:
m/z 289.0321.
+
2-Amino-5-chlorophenyl
2-cyano-4-nitrophenyl
sulfide
160.5 (C-11). HRMS (FD). Calcd for C14H10N2O2S, [M] : m/z 270.0463.
(4h)ꢁYield 83%; orange-colored solid; mp 146–147°C; Rf 0.25
(hexane-AcOEt, 3:1); IR: 3456 (N-H), 3358 (N-H), 2242 (C≡N), 1629
(Ar, C=C), 1515 (Ar, C=C), 1455 (Ar, C=C), 1340 (ArNO2, (N=O)2), 1299
(ArNH2, C-N), 1152 (Ar, C-Cl), 1053 (Ar-S-Ar), 794 (Ar, C-H), 726 cm-1
(Ar, C=C); 1H NMR (CDCl3): δ 4.33 (s, 2H, NH2), 6.82 (d, Jꢀ=ꢀ8.6 Hz, 1H,
H-3′), 6.92 (d, Jꢀ=ꢀ9.2 Hz, 1H, H-6), 7.32 (dd, Jꢀ=ꢀ2.3, 8.6 Hz, 1H, H-4′),
7.45 (d, Jꢀ=ꢀ2.3 Hz, 1H, H-6′), 8.18 (dd, Jꢀ=ꢀ2.3, 8.9 Hz, 1H, H-5), 8.47 (d,
Jꢀ=ꢀ2.3 Hz, 1H, H-3); 13C NMR (CDCl3): δ 110.2 (C-1′), 110.5 (C-2), 114.6
(-C≡N), 117.1 (C-3′), 123.5 (C-5′), 126.4 (C-6), 127.4 (C-5), 128.6 (C-3), 133.2
(C-4′), 136.5 (C-6′), 145.1 (C-1), 147.9 (C-2′), 150.5 (C-4). HRMS (FD).
Found: m/z 270.0456.
7,8-Dimethyl-2-nitrodibenzo[b,f][1,4]thiazepine (7d)ꢁYield 49%;
yellow solid; mp 210–211°C; Rfꢀ=ꢀ 0.59 (hexane-AcOEt, 3:1); IR: 3056
(Ar, C-H), 2919 (CH3), 2857 (CH3), 1597 (Ar, C=C), 1567 (ArNO2, (N=O)2),
1525 (Ar, C=C), 1464 (Ar, C=C), 1344 (ArNO2, (N=O)2), 1023 (Ar-S-Ar),
1
942 (Ar, C-H), 912 (ArNO2, C-N), 879 (Ar, C-H), 769 cm−1 (Ar, C-H); H
NMR (600 MHz, DMSO-d6): δ 2.17 (s, 3H, ArCH3), 2.19 (s, 3H, ArCH3),
7.09 (s, 1H, H-9), 7.22 (s, 1H, H-6), 7.69 (d, Jꢀ=ꢀ8.6 Hz, 1H, H-4), 8.25 (dd,
Jꢀ=ꢀ2.6, 8.6 Hz, 1H, H-3), 8.45 (d, Jꢀ=ꢀ2.6 Hz, 1H, H-1), 8.96 (s, 1H, H-11); 13C
NMR: δ 18.3 (ArCH3), 18.8 (ArCH3), 122.8 (C-1), 124.6 (C-3), 125.9 (C-9),
127.4 (C-4), 132.3 (C-5a), 133.2 (C-6), 136.6 (C-8), 137.3 (C-11a), 138.7 (C-7),
145.7 (C-9a), 146.2, 147.4 (C-2, C-4a), 160.1 (C-11). HRMS (FD). Calcd for
+
Calcd for C13H8N3O2SCl, [M] : m/z 305.0026. Found: m/z 305.0022.
2-Amino-3-chlorophenyl
2-cyano-4-nitrophenyl
sulfide
+
(4i)ꢁYield 71%; yellow solid; mp 126–127°C; Rf 0.58 (hexane-AcOEt,
3:1); IR: 3442 (N-H), 3346 (N-H), 2237 (C≡N), 1627 (Ar, C=C), 1512 (Ar,
C=C), 1456 (Ar, C=C), 1344 (ArNO2, (N=O)2), 1304 (ArNH2, C-N), 1147
C15H12N2O2S, [M] : m/z 284.0619. Found: m/z 284.0631.
7-Methoxy-2-nitrodibenzo[b,f][1,4]thiazepine (7e)ꢁYield 68%;
yellow solid; mp 164–165°C; Rf 0.40 (hexane-AcOEt, 3:1); IR: 3007
(Ar, C-H), 2977 (CH3), 2837 (CH3), 1590 (Ar, C=C), 1511 (ArNO2, (N=O)2),
1475 (Ar, C=C), 1344 (ArNO2, (N=O)2), 1236 (C-O-C), 1056 (C-O-C), 1039
(Ar-S-Ar), 945 (Ar, C-H), 912 (ArNO2, C-N), 741 (Ar, C-H), 696 cm−1 (Ar,
1
(Ar, C-Cl), 1058 (Ar-S-Ar), 914 cm−1 (ArNO2, C-N); H NMR (CDCl3): δ
4.75 (s, 2H, NH2), 6.79 (t, Jꢀ=ꢀ7.9 Hz, 1H, H-5′), 6.88 (d, Jꢀ=ꢀ8.9 Hz, 1H,
H-6), 7.40 (d, Jꢀ=ꢀ7.7 Hz, 1H, H-3′), 7.49 (d, Jꢀ=ꢀ7.7 Hz, 1H, H-4′), 8.18 (dd,
Jꢀ=ꢀ2.3, 8.9 Hz, 1H, H-5), 8.48 (d, Jꢀ=ꢀ2.3 Hz, 1H, H-3); 13C NMR (CDCl3):
δ 110.2 (C-1′), 110.4 (C-2), 114.6 (-C≡N), 119.0 (C-5′), 120.2 (C-3′), 126.2
(C-6), 127.4 (C-5), 128.6 (C-3), 133.1 (C-4′), 136.2 (C-6′), 145.0 (C-1),
1
C=C); H NMR: δ 3.76 (s, 3H, ArOCH3), 7.02 (m, 2H, H-6, H-8), 7.24
(d, Jꢀ=ꢀ8.3 Hz, 1H, H-9), 7.70 (d, Jꢀ=ꢀ8.6 Hz, 1H, H-4), 8.27 (dd, Jꢀ=ꢀ2.3,
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