Molecules 2016, 21, 864
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(Z)-N
'
-(Isonicotinoyloxy)picolinimidamide (
6
). Solvent: CHCl3; R.T.: 5 h; amine: DIPEA; white crystals,
˝
yield 77%, mp 161.1 C (ethyl acetate); IR (KBr): 3493, 3380, 3054, 1732, 1632 cm´1 1H-NMR
;
(
CDCl3 + DMSO-d6
1H), 8.00 (dd, J = 4.5, 1.5 Hz, 2H), 7.76 (dt, J = 7.2, 1.6 Hz, 1H), 7.40 (ddd, J = 7.4, 4.9, 0.9 Hz, 1H), 6.82
(br s, 2H) ppm; 13C-NMR (CDCl3 + DMSO-d6)
161.2, 153.5, 149.1, 147.2, 146.5, 135.6, 135.4, 124.4,
121.7, 119.9 ppm; HRMS (ESI) Calc C12H11N4O2 [M + H]+ 243.0877; found 243.0876.
) δ 8.72 (dd, J = 4.5, 1.5 Hz, 2H), 8.56 (d, J = 4.6 Hz, 1H), 8.07 (d, J = 8.0 Hz,
δ
(Z)-N -(Isonicotinoyloxy)nicotinimidamide ( ). Solvent: CHCl3; R.T.: 3 h; amine: DIPEA; white crystals,
yield 73%, mp 155.9 C (ethyl acetate); IR (KBr): 3445, 3313, 3166, 1726, 1634 cm´1; 1H-NMR (500 MHz,
CDCl3 + DMSO-d6) 8.93 (s, 1H), 8.73 (d, J = 4.7 Hz, 2H), 8.63 (d, J = 3.3 Hz, 1H), 8.08 (d, J = 7.9 Hz,
1H), 8.02 (d, J = 5.5 Hz, 2H), 7.37 (dd, J = 7.6, 4.9 Hz, 1H), 7.00 (br s, 2H) ppm; 13C-NMR (125 MHz,
CDCl3 + DMSO-d6) 161.0, 154.5, 149.8, 148.9, 146.6, 135.2, 133.3, 126.2, 121.7, 121.5 ppm; HRMS (ESI)
Calc C12H11N4O2 [M + H]+ 243.0877; found 243.0872.
(Z)-N -(Isonicotinoyloxy)isonicotinimidamide ( ). Solvent: CHCl3; R.T.: 3 h; amine: Et3N; column
chromatography (10% MeOH in ethyl acetate); Light yellow crystals, yield 70%, mp 155 ˝C (ethyl
acetate); IR (KBr): 3459, 3366, 1731, 1627 cm´1; 1H-NMR (DMSO-d6)
8.82 (dd, J = 4.2, 1.3 Hz, 2H),
8.72 (dd, J = 4.4, 1.3 Hz, 2H), 8.09 (dd, J = 4.4, 1.6 Hz, 2H), 7.74 (dd, J = 4.5, 1.6 Hz, 2H), 7.32 (br s, 2H)
ppm; 13C-NMR (DMSO-d6)
162.4, 155.7, 150.6, 150.1, 139.0, 136.3, 122.9, 121.2 ppm; HRMS (ESI) Calc
C12H11N4O2 [M + H]+ 243.0877; found 243.0872.
(Z)-N -(Isonicotinoyloxy)-4-methoxybenzimidamide (
crystals, yield 87%, mp 165.8 C (ethyl acetate); IR (KBr): 3492, 3366, 1728, 1618 cm´1; H-NMR
CDCl3 + DMSO-d6 8.49 (d, J = 5.9 Hz, 2H), 7.66 (d, J = 6.0 Hz, 2H), 7.45 (d, J = 8.9 Hz, 2H), 6.63 (d,
'
7
˝
δ
δ
'
8
δ
δ
'
9). Solvent: THF; R.T.: 7 h; amine: Et3N; white
˝
1
(
) δ
J = 8.9 Hz, 2H), 5.88 (bs, 2H), 3.55 (s, 3H) ppm; 13C-NMR (CDCl3 + DMSO-d6)
δ 162.1, 161.0, 157.3,
149.8, 136.4, 127.9, 122.7, 122.1, 113.1, 54.7 ppm; HRMS (ESI) Calc C14H14N3O3 [M + H]+ 272.1030;
found 272.1032.
(Z)-N
'
-(Isonicotinoyloxy)-4-nit˝robenzimidamide (10). Solvent: THF; R.T.: 7 h; amine: Et3N; yellow
crystals, yield 85%, mp 176.2 C (ethyl acetate); IR (KBr): 3536, 3420, 3120, 1730, 1649 cm´1; 1H-NMR
(
CDCl3 + DMSO-d6) δ 8.72 (d, J = 5.9 Hz, 2H), 8.19 (d, J = 8.9 Hz, 2H), 8.00 (d, J = 8.9 Hz, 2H), 7.99 (d,
J = 5.8 Hz, 2H), 6.90 (br s, 2H) ppm; 13C-NMR (CDCl3 + DMSO-d6)
δ 161.4, 155.0, 149.2, 147.8, 136.6,
135.5, 127.3, 122.1, 121.8 ppm; HRMS (ESI) Calc C13H11N4O4 [M + H]+ 287.0775; found 287.0773.
(E)-1-(Pyridin-4-yl)ethan-1-one O-(4-nitrobenzoyl) oxime (11). Prepared according to reference [32].
1H-NMR (CDCl3)
δ 8.75 (d, J = 5.8 Hz, 2H), 8.37 (d, J = 8.7 Hz, 2H), 8.30 (d, J = 8.7 Hz, 2H), 7.70 (d,
J = 5.8 Hz, 2H), 2.55 (s, 3H) ppm.
(E)-1-(Pyridin-4-yl)ethan-1-one O-isonicotinoyl oxime (12). Solvent: THF; R.T.: 24 h; amine: DIPEA; white
˝
crystals, yield 89%, mp 162.8 C (ethyl acetate); IR (KBr): 1753, 1618 cm´1; 1H-NMR (500 MHz, CDCl3)
δ
8.83 (dd, J = 4.7, 1.2 Hz, 2H), 8.71 (dd, J = 4.7, 1.2 Hz, 2H), 7.91 (dd, J = 4.7, 1.4 Hz, 2H), 7.67 (dd,
J = 4.7, 1.4 Hz, 2H), 2.52 (s, 3H) ppm; 13C-NMR (125 MHz, CDCl3)
δ 162.4, 161.9, 150.8, 150.4, 141.7,
135.9, 122.7, 121.0, 14.2 ppm; HRMS (ESI) Calc C13H12N3O2 [M + H]+ 242.0924; found 242.0922.
1
(E)-Picolinaldehyde O-4-nitrobenzoyl oxime (13). Prepared according to reference [30]. H-NMR (CDCl3)
δ
8.71 (d, J = 4.3 Hz, 1H), 8.67 (s, 1H), 8.35 (d, J = 8.9 Hz, 2H), 8.31 (d, J = 8.9 Hz, 2H), 8.18 (d, J = 7.9 Hz,
1H), 7.82 (dt, J = 7.8, 1.3 Hz, 1H), 7.42 (dd, J = 6.6, 4.9 Hz, 1H) ppm.
(E)-Nicotinaldehyde O-4-nitrobenzoyl oxime (14). Prepared according to reference [30]. 1H-NMR
(DMSO-d6)
δ 9.07 (s, 1H), 8.95 (d, J = 1.6 Hz, 1H), 8.76 (dd, J = 4.8, 1.6 Hz, 1H), 8.42 (dd, J = 8.9,
1.8 Hz, 2H), 8.31 (dd, J = 8.9, 1.8 Hz, 2H), 8.24 (dt, J = 8.0, 1.8 Hz, 1H), 7.58 (dd, J = 7.9, 4.9 Hz, 1H) ppm.
(E)-Isonicotinaldehyde O-4-nitrobenzoyl oxime (15). Prepared according to reference [30]. 1H-NMR
(DMSO-d6)
δ 9.03 (s, 1H), 8.76 (d, J = 5.1 Hz, 2H), 8.41 (d, J = 8.5 Hz, 2H), 8.29 (d, J = 8.5 Hz, 2H), 7.75
(d, J = 5.1 Hz, 2H) ppm.