4
Tetrahedron
ACCEPTED MANUSCRIPT
4.1.1.
5-Acetyl-3-thiophen-2-yl-1,2,4-triazine (2a): 0.05 g
Hz, J2 = 4.0 Hz, 1H, Th), 7.24 (d, J1 = 4.0 Hz, J2 = 5.2 Hz, 1H,
(12 %), mp 107-108 ºC. Rf (99 % CH2Cl2/acetone) 0.68. IR
Th), 6.86 (d, J1 = 4.0 Hz, J2 = 5.2 Hz 1H, Th), 6.52 (d, J1 = 1.2
Hz, J2 = 4.0 Hz, 1H, Th), 3.33 (q, J = 7.2 Hz, 2H, CH2CH3), 1.27
(t, J = 7.2 Hz, 3H, CH2CH3), 2.32 (s, 3H, Me). 13C NMR (100
MHz, CDCl3) δ: 202.1, 161.2, 157.9, 153.1, 149.8, 148.8, 147.5,
142.5, 139.2, 132.2, 131.1, 129.9, 129.2, 128.9, 128.7, 127.9,
121.4, 31.3, 20.2, 7.9. Anal. Calcd for C20H16N4OS2: C; 61.22, H;
4.08, N; 14.28. Found: C; 60.98, H; 4.41 N; 14.28.
(KBr) cm-1: 1712 (C=O), 1076 (C-S-C). H NMR (400 MHz,
1
CDCl3) δ: 9.52 (s, 1H, triazine), 8.25 (dd, J1 = 1.2 Hz, J2 = 4.0
Hz, 1H, Th), 7.66 (dd, J1 = 1.2 Hz, J2 = 5.2 Hz, 1H, Th), 6.25 (dd,
J1 = 1.2 Hz, J2 = 5.2 Hz, 1H, Th), 2.01 (s, 3H, Me).13C NMR (100
MHz, CDCl3) δ: 199.5, 161.9, 148.4, 142.9, 139.1,132.6, 131.6,
129.2, 25.7. Anal. Calcd for C9H7N3OS: C; 52.68, H; 3.41, N;
20.49. Found: C; 52.65, H; 3.26, N; 20.21.
4.1.7.
5-Propanoyl-3-furan-2-yl-1,2,4-triazine (2d): 0.15 g
4.1.2.
5-[6-Acetyl-2-(thiophen-2-yl)pyridin-3-yl-3-thiophen-2-
(42 %), 107-108 ºC. Rf (99 % CH2Cl2/acetone) 0.40. IR (KBr)
cm-1: 1707 (C=O), 1099 (C-O-C). 1H NMR (400 MHz, CDCl3) δ:
9.53 (s, 1H, triazine), 7.76 (dd, J1 = 0.8 Hz, J2 = 1.6 Hz, 1H, Fu),
7.60 (dd, J1 = 0.8 Hz, J2 = 3.6 Hz, 1H, Fu), 6.68 (dd, J1 = 1.6 Hz,
J2 = 3.6 Hz, 1H, Fu), 3.31 (q, J = 7.2 Hz, 2H, CH2CH3), 1.27 (t, J
= 7.2 Hz, 3H, CH2CH3). 13C NMR (100 MHz, CDCl3) δ : 201.7,
157.7, 149.1, 148.1, 146.8, 142.6, 116.4, 112.8, 31.2, 7.2. Anal.
Calcd for C10H9N3O2: C; 59.11, H; 4.43, N; 20.69. Found: C;
59.05, H; 4.47, N; 20.53.
yl]-1,2,4-triazine-(3a): 0.15 g (40 %), mp 142-143 ºC. Rf (99 %
CH21Cl2/acetone) 0.88. IR (KBr) cm-1: 1700 (C=O), 1062 (C-S-
C). H NMR (400 MHz, CDCl3) δ: 8.95 (s, 1H, triazine), 8.25
(dd, J1 = 0.8 Hz, J2 = 3.6 Hz, 1H, Th), 8.19 (d, J = 8.0 Hz, 1H,
Py), 8.09 (d, J = 8.0 Hz, 1H, Py), 7.65 (dd, J1 = 1.2 Hz, J2 = 5.2
Hz, 1H, Th), 7.50 (dd, J1 = 0.8 Hz, J2 = 5.2 Hz, 1H, Th), 7.24 (dd,
J1 = 4.0 Hz, J2 = 5.2 Hz, 1H, Th), 6.97 (dd, J1 = 3.6 Hz, J2 = 4.8
Hz, 1H, Th), 6.87 (dd, J1 = 1.2 Hz, J2 = 4.0 Hz, 1H, Th), 2.81 (s,
3H, Me). 13C NMR (100 MHz, CDCl3) δ: 199.1, 161.4, 157.2,
153.8, 150.4, 146.6, 141.4, 140.5, 139.1, 132.0, 130.9, 130.8,
129.7, 129.4, 128.7, 128.1, 119.5, 25.7. Anal. Calcd for
C18H12N4OS2: C; 59.30, H; 3.30, N; 15.40. Found: C; 59.30, H;
3.22, N; 15.32.
4.1.8. 5-[4-Methyl-(6-propanoyl-2-furan-2-yl)pyridin-3-yl-3-
furan-2-yl]-1,2,4-triazine (3d): 0.04 g (13 %), oil. Rf (99 %
CH2Cl2/acetone) 0.78. IR (KBr) cm-1: 1701 (C=O). 1H NMR (400
MHz, CDCl3) δ: 8.95 (s, 1H, triazine), 7.88 (s, 1H, Py), 7.74 (dd,
J1 = 0.8 Hz, J2 = 1.6 Hz, 1H, Fu), 7.58 (dd, J1 = 0.4 Hz, J2 = 3.2
Hz, 1H, Fu), 7.16 (dd, J1 = 0.4 Hz, J2 = 1.6 Hz, 1H, Fu), 7.10 (dd,
J1 = 0.8 Hz, J2 = 3.2 Hz, 1H, Fu), 6.66 (dd, J1 = 2.0 Hz, J2 = 3.6
Hz, 1H, Fu), 6.43 (dd, J1 = 2.0 Hz, J2 = 3.6 Hz, 1H, Fu), 3.33 (q,
J = 7.2 Hz, 2H, CH2CH3), 2.28 (s, 3H, Me), 0.92 (t, J = 7.2 Hz,
3H, CH2CH3). 13C NMR (100 MHz, CDCl3) δ: 202.2, 158.1,
157.2, 153.3, 152.4, 149.5, 148.5, 147.6, 146.5, 146.0, 144.2,
128.8, 121.2, 115.8, 112.7, 112.7, 111.9, 31.5, 20.1, 7.9. HRMS
(EI) m/z calcd. for C20H16N4O3, 360.12224 (M+). Found
360.12166.
4.1.3.
5-Acetyl-3-furan-2-yl-1,2,4-triazine (2b): 0.08 g (21 %),
mp. 99-100 ºC. Rf (99 % CH2Cl2/acetone) 0.62. IR (KBr) cm-1:
1702 (C=O), 1070 (C-O-C). 1H NMR (400 MHz, CDCl3) δ: 9.53
(s, 1H, triazine), 7.77 (dd, J1 = 0.8 Hz, J2 = 1.6, 1H, Fu), 7.61 (dd,
J1 = 0.4 Hz, J2 = 3.2, 1H, Fu), 6.68 (dd, J1 = 2.0 Hz, J2 = 3.6, 1H,
Fu), 2.01 (s, 3H, Me). 13C NMR (100 MHz, CDCl3) δ: 199.1,
157.8, 148.1, 146.9, 146.9, 142.4, 116.5, 112.8, 25.3. Anal. Calcd
for C9H7N3O2: C; 57.14, H; 3.70, N; 22.22. Found: C; 57.10, H;
3.80, N; 22.11.
4.1.4.
5-[6-(Acetyl-2-furan-2-yl)pyridin-3-yl-3-furan-2-yl]-
4.1.9.
5-Butanoyl-3-thiophen-2-yl-1,2,4-triazine (2e): 0.06 g
1,2,4-triazine (3b): 0.087 g (26 %), mp. 153-155 ºC. Rf (99 %
CH2Cl2/acetone) 0.20, IR (KBr) cm-1: 1710 (C=O). 1H NMR (400
MHz, CDCl3) δ: 9.53 (s, 1H, triazine), 8.17 (d, J = 8.0 Hz, 1H,
Py), 8.07 (d, J = 8.0 Hz, 1H, Py), 7.75 (d, J = 0.8 Hz, 1H, Fu),
7.58 (d, J = 3.2 Hz, 1H, Fu), 7.31 (d, J = 0.8 Hz, 1H, Fu), 7.24 (d,
J = 3.6 Hz, 1H, Fu), 6.66 (dd, J1 = 1.6 Hz, J2 = 3.2 Hz, 1H, Fu),
6.55 (dd, J1 = 1.6 Hz, J2 = 3.2 Hz, 1H, Fu), 2.81 (s, 3H, Me).13C
NMR (100 MHz, CDCl3) δ: 199.1, 156.4, 154.1, 152.0, 146.5,
146.3, 145.1, 144.5, 142.4, 140.4, 132.0, 128.4, 119.5, 116.5,
(16 %), mp. 89-90 ºC. Rf (99 % CH2Cl2/acetone) 0.62, IR (KBr)
cm-1: 1705 (C=O), 1070 (C-S-C). 1H NMR (400 MHz, CDCl3) δ:
9.53 (s, 1H, triazine), 8.24 (dd, J1 = 1.2 Hz, J2 = 3.6 Hz, 1H, Th),
7.65 (dd, J1 = 1.2 Hz, J2 = 4.8 Hz, 1H, Th), 7.24 (dd, J1 = 1.6 Hz,
J2 = 5.2 Hz, 1H, Th), 3.24 (t, J = 7.2 Hz, 2H, CH2CH2CH3), 1.82
(sek, J = 7.2 Hz, 2H, CH2CH2CH3), 1.05 (t, J = 7.2 Hz, 3H,
CH2CH2CH3). 13C NMR (100 MHz, CDCl3) δ: 201.3, 149.1,
148.1, 142.6, 138.8, 132.3, 131.2, 128.9, 39.5, 16.9, 13.7. Anal.
Calcd for C11H11N3OS: C; 56.65, H; 4.72, N; 18.02. Found: C;
56.67, H; 4.80, N;17.87.
113.0, 112.8, 112.4, 25.7. HRMS (ESI) m/z
calcd for
C18H14N4O3 (M+H)+: 334.10157. Found 334.10143.
4.1.10. 5-[4-Ethyl-6-butanoyl-2-thiophen-2-yl)pyridin-3-yl-3-
thiophen-2-yl]-1,2,4-triazine (3e): 0.015 g (4 %), 154-155 ºC, Rf
(99 % CH2Cl2/acetone) 0.88, IR (KBr) cm-1: 1697 (C=O), 1055
4.1.5.
5-Propanoyl-3-thiophen-2-yl-1,2,4-triazine (2c): 0.10 g
(17 %), mp 112-113 ºC. Rf (99 % CH2Cl2/acetone) 0.65, IR
(KBr) cm-1: 1708 (C=O), 1062 (C-S-C). H NMR (400 MHz,
(C-S-C). H NMR (400 MHz, CDCl3) δ: 8.84 (s, 1H, triazine),
1
1
CDCl3) δ: 9.51 (s, 1H, triazine), 8.23 (d, J1 = 1.2 Hz, J2 = 3.6 Hz,
1H, Th), 7.65 (d, J1 = 1.2 Hz, J2 = 4.8 Hz, 1H, Th), 7.24 (dd, J1 =
4.0 Hz, J2 = 5.6 Hz, 1H, Th), 3.30 (q, J = 7.2 Hz, 2H, CH2CH3),
1.28 (t, J = 7.2Hz, 3H, CH2CH3). 13C NMR (100 MHz, CDCl3) δ:
201.7, 161.9, 147.9, 142.6, 138.8, 132.2, 131.1, 128.8, 31.2, 7.3.
Anal. Calcd for C10H9N3O2: C; 59.11, H; 4.43, N; 20.69. Found:
C; 59.05, H; 4.47, N; 20.53.
7.96 (s, 1H, Py), 8.24 (dd, J1 = 1.2 Hz, J2 = 3.6 Hz, 1H, Th), 7.65
(dd, J1 = 1.2 Hz, J2 = 4.8 Hz, 1H, Th), 7.38 (dd, J1 = 1.2 Hz, J2 =
5.2 Hz, 1H, Th), 7.25 (dd, J1 = 1.2 Hz, J2 = 5.2 Hz, 1H, Th), 6.86
(dd, J1 = 4.0 Hz, J2 = 5.2 Hz, 1H, Th), 6.49 (dd, J1 = 1.2 Hz, J2 =
4.0 Hz, 1H, Th), 3.26 (t, J = 2.8 Hz, 2H, CH2CH2CH3), 2.57 (q, J
= 7.6 Hz, 2H, CH2CH3), 1.84 (qui, J = 7.6 Hz, 2H, CH2CH2CH3),
1.23 (t, J = 7.6 Hz, 3H, CH2CH2CH3), 1.06 (t, J = 7.2 Hz, 3H,
CH2CH3).13C NMR (100 MHz, CDCl3) δ: 201.7, 161.1, 157.8,
154.5, 153.5, 149.9, 147.7, 142.7, 139.3, 132.1, 131.1, 129.5,
129.2, 128.9, 128.8, 127.9, 119.7, 39.8, 26.5, 17.7, 14.6, 13.9.
Anal. Calcd for C22H20N4OS2: C; 62.86, H; 4.76, N; 13.33.
Found: C; 62.72, H; 4.52, N;13.30.
4.1.6.
5-[4-(Methyl-6-propanoyl-2-thiophen-2-yl)pyridin-3-yl-
3-thiophen-2-yl]-1,2,4-triazine (3c): 0.16 g (27 %), 144-145 ºC.
Rf (99 % CH2Cl2/acetone) 0.80. IR (KBr) cm-1: 1697 (C=O),
1058 (C-S-C). 1H NMR (400 MHz, CDCl3) δ: 8.84 (s, 1H,
triazine), 7.91 (s, 1H, Py), 8.22 (d, J1 = 1.2 Hz, J2 = 3.6 Hz, 1H,
Th) 7.64 (d, J1 = 1.2 Hz, J2 = 4.8 Hz, 1H, Th), 7.37 (d, J1 = 1.2