Guanylhydrazones of Aryl Methyl Ketones
911
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C-5, J(C5, H5) 204.7 Hz, J(C5, H4) 10.9 Hz, J(C5, H3) 7.7 Hz), 152.3 (furane C-2), 152.4
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(ArC=N), J(C=N,CH3) 6.6 Hz), 169.6 (COCH3, J(CO, CH3) 6.5 Hz), 169.8 (COCH3, J(CO,
CH3) 6.5 Hz) ppm.
(E)-N,N0-(2-(1-(2-Thienyl)ethylidene)carbohydrazonoyl)bis-(acetamide) ((E)-3d; C11H14N4O2S)
Yield: 75% of yellowish crystals; m.p.: 129±130ꢀC (EtOH); MS: m/z 266 (M , 29%), 224 (59),
209 (66), 167 (74), 165 (24), 140 (22), 110 (100), 99 (24), 98 (22), 69 (47), 66 (51), 58 (34), 45 (51);
1H NMR (DMSO-d6, ꢂ, 300 MHz): 2.05 (s, 3H, COCH3), 2.14 (s, 3H, COCH3), 2.33 (s, 3H, CH3),
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7.10 (dd, J(H3, H4) 3.7 Hz, J(H4, H5) 5.1 Hz, 1H, Th H-4), 7.53 (dd, J(H3, H4) 3.7 Hz,
4J(H3, H5) 1.2 Hz, Th H-3), 7.59 (dd, 3J(H4, H5) 5.1 Hz, 4J(H3, H5) 1.2 Hz, 1H, Th H-5), 9.71
(s, 1H, NH), 10.33 (s, 1H, NH) ppm; 13C NMR (DMSO-d6, ꢂ, 75 MHz): 15.1 (CH3,
1J(CH3) 129.0 Hz), 23.8 (COCH3), 1J(CH3) 128.9 Hz), 24.5 (COCH3, 1J(CH3) 128.9 Hz),
127.5 (Th C-4, 1J(C4, H4) 168.6 Hz), 128.1 (Th C-3, 1J(C3, H3) 167.5 Hz, 2J(C3, H4) 5.9 Hz,
3J(C3,H5) 9.2 Hz), 128.9 (Th C-5, 1J(C5, H5) 186.5 Hz, 2J(C5, H4) 7.2 Hz, 3J(C5,
H3) 10.5 Hz), 143.4 (N=C=N), 143.6 (Th C-2), 156.3 (ArC=N), 169.2 (COCH3), 169.5
(COCH3) ppm.
(E)-N,N0(2-(1-(2-Pyridyl)ethylidene)carbohydrazonoyl)bis-(acetamide) ((E)-3e; C12H15N5O2)
Yield: 38% of colorless crystals; m.p.: 176±177ꢀC (EtOH); MS: m/z 261 (M ,1%), 204 (42), 183
(32), 141 (70), 134 (24), 106 (64), 104 (31), 99 (37), 98 (49), 79 (56), 78 (100), 52 (39), 51 (56); 1H
NMR (DMSO-d6, ꢂ, 300 MHz): 2.10 (s, 3H, COCH3), 2.19 (s, 3H, COCH3), 2.40 (s, 3H, CH3), 7.41
(m, 1H, Py H-5), 7.83 (m, 1H, Py H-4), 8.31 (m, 1H, Py H-3), 8.61 (m, 1H, Py, H-6), 9.96 (s, 1H,
1
NH), 10.46 (s, 1H, NH) ppm; 13C NMR (DMSO-d6, ꢂ, 75 MHz): 13.7 (CH3, J(CH3) 128.9 Hz),
24.0 (COCH3), 24.7 (COCH3), 121.2 (Py C-3), 124.3 (Py C-5), 136.2 (Py C-4), 144.3 (N=C±N),
148.5 (Py C-6), 155.4 (Py C-2), 161.8 (ArC=N), 169.7 (COCH3), 169.8 (COCH3) ppm.
(E)-N,N0-(2-(1-(3-Pyridyl)ethylidene)carbohydrazonoyl)bis-(acetamide) ((E)-3f; C12H15N5O2)
Yield: 60% of yellowish crystals; m.p.: 150±152ꢀC (EtOH-hexane); MS: m/z 261 (M , 0.5%), 218
(38), 204 (30), 176 (43), 162 (25), 134 (100), 106 (31), 105 (28), 104 (39), 79 (33), 78 (80), 77 (42),
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58 (21), 52 (58), 51 (95), 59 (38); H NMR (DMSO-d6, ꢂ, 300 MHz): 2.11 (s, 3H, COCH3), 2.18
(s, 3H, COCH3), 2.37 (s, 3H, CH3), 7.43 (m, 1H, Py H-5), 8.28 (m, 1H, Py H-4), 8.59 (m, 1H, Py
H-6), 9.13 (m, 1H, Py H-2), 9.96 (s, 1H, NH), 10.46 (s, 1H, NH) ppm; 13C NMR (DMSO-d6, ꢂ,
75 MHz): 14.6 (CH3, 1J(CH3) 128.7 Hz), 24.0 (COCH3, 1J(CH3) 128.9 Hz), 24.7 (COCH3,
1J(CH3) 128.9 Hz), 123.2 (Py C-5), 133.5 (Py C-3), 134.1 (Py C-4), 144.4 (N=C±N), 148.1 (Py C-
2), 150.2 (Py C-6), 158.9 (ArC=N), 169.7 (COCH3, 2J(CO, CH3) 6.5 Hz), 169.9 (COCH3,
2J(CO,CH3) 6.5 Hz) ppm.
N-Acetyl-N0-((E)-1-(2-furyl)ethylidene)aminomethanehydrazonamide acetate
((E)-4c Á HOAc; C11H16N4O4)
Compound 4c Á HOAc resulted (besides 3c) from fractional crystallisation of the crude product
obtained upon reaction of 2c with acetic anhydride.
Yield: 10% of yellow crystals; m.p.: 81ꢀC (EtOH); MS: m/z 208 (M -HOAc, 56%), 193 (39),
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151 (51), 95 (28), 94 (55), 67 (20), 66 (100), 58 (24), 55 (22), 45 (35); H NMR (DMSO-d6, ꢂ,
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300 MHz): 1.90 (s, 3H, CH3COO), 2.05 (s, 3H, NCOCH3), 2.20 (s, 3H, CH3), 6.54 (dd, J(H3,
H4) 3.4 Hz, 3J(H4, H5) 1.8 Hz, 1H, furane H-4), 6.87 (dd, 3J(H3, H4) 3.4 Hz, 4J(H3,
H5) 0.7 Hz, furane H-3), 7.60 (broad s, 1H, NH), 7.69 (dd, 3J(H4, H5) 1.8 Hz, 4J(H3,