Supporting information A] General Remarks: The 1H NMR (400 MHz

advertisement
Supporting information
A] General Remarks:
The 1H NMR (400 MHz) chemical shifts were measured relative to CDCl3 as the
internal reference. The
13
C NMR (100 MHz) chemical shifts are given using CDCl3 as the
internal standard. The LCMS were taken from ‘Shimatzu LCMS model no. 2010’. And IR of
the entry no. 1 and 2 (table 2) has given.
Unless otherwise noted, all reagents were obtained from commercial suppliers and used
without further purification.
B] Synthesis and analytical data:
1] N-aryl derivatives of 1, 2, 4 -triazoles.
I. General procedure for the N-arylation of 1, 2, 4 –triazoles.
1, 2, 4-Triazoles (3mmol), iodobenzene (3.3mmol), CuO nanoparticles (0.15mmol), K2CO3
(3mmol) and N-N dimethyl formamide (10ml) was taken in a glass reactor. Stirred the
reaction mixture at room temperature and monitored by Co-TLC, till completion of reaction.
After completion of reaction, dilute with 20 ml of water. The entire reaction mixture was
washed with ethyl acetate (2x10 ml). Aqueous layer was centrifuged to recover CuO
nanocatalyst. The combined organic extracts were washed with brine and dried by sodium
sulphate. Solvent was evaporated under reduced pressure and the crude product was purified
by Flash column chromatography on silica gel with Ethyl Acetate: Petroleum Ether (1:9) as
eluent.
Entry no.1a
N
N
N
1-Phenyl-1H-1, 2, 4-triazole
Nature = light yellow oil
1
HNMR 400 MHz (CDCl3): δ 7.26 (s, 2H), 7.34(s, 3H). 8.32 (d, J=8.4Hz, 1H), 8.64 (s, 1H).
CNMR 100MHz (CDCl3): δ 119.20, 123.25, 123.39, 129.34, 129.65, 135.18, 146.34
13
LCMS: (M+1) = 145
N
N
N
N
N
N
Entry no.2a
N
N
N
O2N
1-(4-Nitrophenyl)-1H-1, 2, 4-triazole
Nature: yellow solid. M.p. = 170-173oC
1
HNMR 400 MHz (CDCl3): δ 7.89-7.94 (m, 4H), 8.46 (s, 1H), 8.78(s, 1H).
CNMR 100MHz (CDCl3): δ 124.85, 130.35, 130.45, 138.65, 147.73, 154.71.
13
LCMS: (M+1) = 191.
N
N
N
O2N
N
N
O2N
N
2] N- aryl derivative of imidazole and pyrazole.
II. General procedure for N-arylation of imidazole and pyrazole.
Azole (3mmol), iodobenzene (3.3mmol), CuO nanoparticles (0.15mmol), K2CO3
(3mmol) and N-N dimethyl formamide (10ml) was taken in a glass reactor fitted with a
condenser. Refluxed the mixture and monitored by Co-TLC, till completion of reaction.
Workup procedure and purification of products were performed as described for the 1, 2, 4triozole reactions.
Entry no. 1b
N
N
1-P-Tolyl-1H-benzo[d]imidazole
Nature: oil
1
HNMR 400 MHz (CDCl3): δ 2.43 (s, 3H), 7.26-7.36 (m, 6H), 7.48(d, J= 8Hz, 1H), 7.87 (d,
J= 8Hz, 1H), 8.09 (s, 1H).
CNMR 100MHz (CDCl3): δ 21.14, 110.53, 120.40, 122.79, 123.67, 124.00, 130.59,
13
133.67, 133.79, 138.21, 142.30, 143.58.
LCMS: (M+1) = 209.10
IR (cm-1) = 3054, 3036, 1610, 1515, 1486, 1453, 1375, 1320, 1287, 1227, 1203, 1140, 1109,
1009, 976, 887, 818, 780, 764, 737, 708, 620, 586, 565.
N
N
N
N
Entry no. 2b
N
N
N
1-Phenyl-1H-benzol[d][1,2,3]triazole
Nature: White crystalline solid M.P. = 86-88oC
1
HNMR 400 MHz (CDCl3): δ (t, J= 7.12 Hz, 1H), 7.49-7.57 (m, 2H), 7.61 (t, J= 8.16 Hz,
2H), 7.75-7.80 (m, 3H), 8.15 (d, J= 8.36 Hz, 1H).
13
CNMR 100MHz (CDCl3): 110.39, 120.36, 122.91, 124.42, 128.26, 128.70, 129.89, 132.33,
137.02, 146.53
LCMS: (M+1) =195
IR (KBr cm-1) = 3098, 3040, 2918, 1655, 1595, 1560, 1500, 1458, 1290, 1275, 1244, 1188,
1143, 1126, 1089, 1059, 1010, 924, 785, 762, 708, 694, 659, 572, 517, 434.
N
N
N
N
N
N
Entry no. 3b
N
N
1-Phenyl-1H-imidazole
Nature: Oil
1
HNMR 400 MHz (CDCl3): δ 7.26 (d, J=3.76 Hz, 1H), 7.30 (s, 1H), 7.41 (d, J= 6.96Hz, 3H),
7.51 (t, J= 8.64 Hz, 2H), 8.05 (s, 1H).
CNMR 100MHz (CDCl3): δ 118.53, 121.67, 127.97, 128.93, 130.01, 135.44, 136.99.
13
LCMS (M+1) =145
N
N
N
N
Entry no.4b
N
N
1-Phenyl-1H-pyrazole
Nature: Oil
1
HNMR 400 MHz (CDCl3): δ 6.47 (s, 1H), 7.25-7.30 (m, 1H), 7.45 (t, J= 8.28 Hz, 2H), 7.70
(t, J= 7.68 Hz, 3H), 7.94 (s, 1H).
CNMR 100MHz (CDCl3): δ 107.69, 115.41, 119.27, 120.30, 126.52, 126.91, 129.47,
13
129.59, 140.16, 141.10.
LCMS (M+1) =145
N
N
N
N
Download