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Representative procedure – Method A (stepwise): 3-(2-Thienyl)acrylic acid hydrazide (2b) (2.55 g, 15 mmol),
H2O (50 mL) and NaHCO3 (1.28 g, 15 mmol) were placed in a two-necked flask, cooled to 0 C and agitated.
Then, benzoyl chloride (2.17 g, 1.8 mL, 15 mmol) in toluene (50 mL) was added dropwise and the mixture
agitated at a temperature below 10 °C for 2 h (TLC). The precipitated solid was filtered off, dried under air and
recrystallized from EtOH to give N-benzoyl-N-[3-(2-thienyl)acrylo]hydrazine (4i) (2.65 g, 65%) as a white
solid; mp 211-213 °C; Rf (CHCl3/MeOH, 4:1 v/v) 0.68; [Found: C, 61.78; H, 4.39; N, 10.24. C14H12N2O2S
requires C, 61.75; H, 4.44; N, 10.29%]. 1H NMR (400 MHz, DMSO-d6): δ 6.51 (1H, d, J 15.6 Hz, α-CH=), 7.13
(1H, dd, J 3.2 Hz and J 5.2 Hz, C4-H), 7.45 (1H, d, J 3.2 Hz, C3-H), 7.51 (2H, t, J 7.2 Hz, C3-H, C5-H),
7.58 (1H, d, J 7.2 Hz, C4-H), 7.65 (1H, d, J 5.2 Hz, C5-H), 7.73 (1H, d, J 15.6 Hz, β-CH=), 7.91 (2H, d, J 7.2
Hz, C2-H, C6-H), 10.16 (1H, s, NH), 10.51 (1H, s, NH); 13C NMR (400 MHz, DMSO-d6): δ 118.0, 127.3,
127.4, 128.4, 128.5, 131.2, 131.8, 132.4, 133.2, 139.5, 164.2, 165.4; UV-VIS (MeOH): λmax 201.5 nm (·10-3
27.66 cm-1M-1), 224.0 (15.06), 310.5 (25.96); IR (ATR) ν: 3231, 2992, 1644, 1623, 1602, 1579, 1507, 1478,
1305, 1273, 1240, 1221, 1137, 1042, 968, 707 cm-1; HRMS: m/z calcd for C14H12N2O2S (M+H)+: 273.0698.
Found 273.0687.
The intermediate 4i (2.31 g, 8.5 mmol), dry toluene (40 mL) and POCl3 (15 mL, 160 mmol) were heated
under reflux for 2 h (TLC). After cooling, the mixture was concentrated on a rotary evaporator, dissolved in dry
toluene (30 mL) and washed with H2O (30 mL). The organic layer was dried over MgSO4 and then concentrated
under reduced pressure. The crude 5-phenyl-2-[2-(2-thienyl)ethenyl]-1,3,4-oxadiazole (5i) was recrystallized
from AcOH/H2O to yield 1.03 g (48%) of a beige solid; mp 110-113 °C; Rf (CHCl3/MeOH, 4:1 v/v) 0.78;
1
[Found: C, 66.10; H, 3.99; N, 11.01. C14H10N2OS requires C, 66.12; H, 3.96; N, 11.02%]. H NMR (400 MHz,
CDCl3): δ 6.41 (1H, d, J 15.6 Hz, α-CH=), 7.03 (1H, dd, J 3.6 Hz and 5.2 Hz, C4-H), 7.22 (1H, d, J 3.6 Hz, C3-
H), 7.34 (1H, d, J 5.2 Hz, C5-H), 7.45 (2H, t, J 7.6 Hz, C3-H, C5-H), 7.52 (1H, d, J 7.6 Hz, C4-H), 7.83
(1H, d, J 15.6 Hz, β-CH=), 7.86 (2H, d, J 7.6 Hz, C2-H, C6-H); 13C NMR (400 MHz, CDCl3): δ 109.0, 123.9,
126.9, 127.3, 128.1, 128.8, 129.7, 131.5, 132.4, 140.1, 163.9, 164.3; UV-VIS: λmax (MeOH) 202.0 nm (·10-3
17.57 cm-1M-1), 262.5 (11.97), 335.5 (22.62); IR (ATR) ν: 3059, 2163, 1980, 1636, 1550, 1481, 1448, 1013, 958,
775, 716, 687 cm-1; HRMS: m/z calcd for C14H10N2OS (M+H)+: 255.0593. Found 255.0603.
Method B (one-pot): 3-(2-Thienyl)acrylic acid hydrazide (2b, 2.55 g, 15 mmol) and dry toluene (50 mL)
were placed in a two-necked flask equipped with a reflux condenser and dropping funnel and agitated. Benzoyl
chloride (2.17 g, 1.8 mL, 15 mmol) in dry toluene (50 mL) was added dropwise to the resulting suspension and
the mixture was agitated at room temperature for 10 min and finally POCl3 (25 mL, 267 mmol) was introduced.
The mixture was heated under reflux for 2 h (TLC). After cooling, it was concentrated on a rotary evaporator,
dissolved in dry toluene (40 mL) and washed with H2O (40 mL). The organic layer was dried over MgSO4 and
then concentrated under reduced pressure. The crude solid 5i was recrystallized from AcOH/H2O to yield 2.75 g
(72%) of a beige solid; mp 110-113 °C; Rf (CHCl3/MeOH, 4:1 v/v) 0.78.