NJC
Paper
128.9, 136.5, 139.2, 141.7, 143.7, 146.1; HRMS (ESI): m/z calcd 131.5, 131.7, 132.6, 140.8, 142.8, 150.6; HRMS (ESI): m/z calcd
for C21H14F5N4O2 [M ꢀ H]ꢀ: 449.1043, found: 449.1066.
for C21H17BrN3O3 [M ꢀ H]ꢀ: 438.0459; found: 438.0461.
2,5-Bis(2-nitro-1-(1H-pyrrol-2-yl)ethyl)-1H-pyrrole (5f)
2-(1-(Furan-2-yl)-2-nitroethyl)-5-((4-methoxyphenyl)-
(1H-pyrrol-2-yl)methyl)-1H-pyrrole (5i)
Dark brown viscous; yield: %6; Rf = 0.39 (EtOAc : hexane, 1 : 3);
1H NMR (400 MHz, CDCl3) d: 4.78(d, J = 7.2 Hz, 4H), 4.88–4.92 Dark brown viscous; yield: %62; Rf = 0.40 (EtOAc : hexane, 1 : 3);
(m, 2H), 6.04 (s, 4H), 6.16 (s, 2H), 6.70 (s, 2H), 7.88 (bs, 1H), 7.99 1H NMR (400 MHz, CDCl3) (ppm) d: 3.79 (s, 3H), 4.74–4.94 (m,
(bs, 2H); 13C NMR (100 MHz, CDCl3) d: 36.4, 78.7, 106.4, 106.5, 3H), 5.35 (s, 1H), 5.77 (s, 1H), 5.87 (bs, 1H), 5.99 (bs, 1H),
107.0, 107.3, 109.1, 109.1, 118.5, 128.2; HRMS (ESI): m/z calcd 6.14 (s, 2H), 6.30 (s, 1H), 6.69 (s, 1H), 6.84 (d, J = 8.6 Hz, 2H),
for C16H16N5O4 [M ꢀ H]ꢀ: 342.1208, found: 342.1267.
5,50-(Phenylmethylene)bis(2-(2-nitro-1-(1H-pyrrol-2-yl)et-hyl)-
1H-pyrrole) (6a)
7.07–7.13 (m, 2H), 7.35 (s, 1H), 7.91 (bs, 1H), 7.98 (bs, 1H);
13C NMR (100 MHz, CDCl3) (ppm) d: 37.1, 43.1, 55.3, 77.8,
106.9, 106.9, 107.1, 107.7, 108.4, 110.6, 114.0, 117.3, 125.6,
129.4, 132.6, 133.6, 133.8, 142.7, 150.8, 158.6; HRMS (ESI):
Dark brown viscous; yield: %15; Rf = 0.073 (EtOAc : hexane, m/z calcd for C22H20N3O4 [M ꢀ H]ꢀ: 390.1459; found: 390.1464.
1 : 4); 1H NMR (400 MHz, CDCl3) d: 4.68–4.74 (m, 4H), 4.82 (bs,
2-((1H-Pyrrol-2-yl)(p-tolyl)methyl)-5-(1-(furan-2-yl)-2-nitroethyl)-
1H-pyrrole (5j)
2H), 5.19 (s, 1H), 5.65–5.69 (m, 2H), 5.89 (bs, 2H), 5.94 (s, 2H),
6.08 (s, 2H), 6.62 (s, 2H), 7.03 (d, J = 7.3 Hz, 2H), 7.18–7.24 (m,
3H), 7.73 (bs, 2H), 8.03 (bs, 2H); 13C NMR (100 MHz, CDCl3) d: Dark brown viscous; yield: %95; Rf = 0.58 (EtOAc : hexane, 1 : 3);
36.5, 43.8, 79.0, 106.2, 106.7, 108.0, 108.9, 118.2, 127.2, 127.3, 1H NMR (400 MHz, CDCl3) (ppm) d: 2.36 (s, 3H), 4.74–4.94 (m,
127.3, 128.2, 128.7, 133.0, 141.3; HRMS (ESI): m/z calcd for 3H), 5.37 (s, 1H), 5.80 (bs, 1H), 5.90 (bs, 1H), 6.01 (bs, 1H),
C
27H25N6O4 [M ꢀ H]ꢀ: 497.1943, found: 497.1964.
6.16 (bs, 2H), 6.32 (s, 1H), 6.69 (bs, 1H), 7.09 (d, J = 7.8 Hz, 2H),
7.15 (d, J = 7.8 Hz, 2H), 7.37 (s, 1H), 7.91 (bs, 1H), 7.98 (bs, 1H);
13C NMR (100 MHz, CDCl3) (ppm) d: 21.1, 37.1, 43.6, 77.8,
106.9, 107.1, 107.7, 107.8, 108.4, 110.6, 117.3, 125.7, 128.3,
General procedure for the synthesis of tripyrranes 5g–l and
bilanes 6b–e
Nitrovinylarenes 2 or 3 (1 eq., 0.900 mmol), dipyrromethane 129.4, 132.4, 133.5, 136.7, 138.8, 142.7, 150.8; HRMS (ESI):
(6 eq., 5.40 mmol) and iodine (0.05 eq., 0.045 mmol) were m/z calcd for C22H20N3O3 [M ꢀ H]ꢀ: 374.1510; found: 374.1516.
dissolved in dry ether (10 mL) and stirred at room temperature
2-(1-(Furan-2-yl)-2-nitroethyl)-5-((4-nitrophenyl)(1H-pyrrol-2-
yl)methyl)-1H-pyrrole (5k)
for 48 h. The reaction mixture was monitored by TLC. After
completion of the reaction, aqueous sodiumthiosulfate (0.090 mmol)
was added to this mixture and extracted with ethylacetate Dark brown viscous; yield: %44; Rf = 0.19 (EtOAc : hexane, 1 : 3);
(3 ꢁ 50 mL). The extracts were combined and dried over MgSO4. 1H NMR (400 MHz, CDCl3) (ppm) d: 4.74–4.95 (m, 3H), 5.51
The solvent was removed under reduced pressure and the (s, 1H), 5.71–5.74 (m, 1H), 5.84 (s, 1H), 6.01 (s, 1H), 6.16 (s, 2H),
residue was purified by flash column chromatography (Silica 6.32 (s, 1H), 6.75 (s, 1H), 7.28–7.37 (m, 3H), 8.01 (bs, 1H),
gel, EtOAc–hexane, 1 : 8).
8.06 (bs, 1H), 8.15 (d, J = 8.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3) (ppm) d: 37.1, 43.8, 77.8, 107.3, 107.8, 107.9, 108.5,
108.8, 110.7, 118.1, 123.9, 126.6, 129.2, 130.5, 130.5, 142.8,
147.0, 149.2, 150.4; HRMS (ESI): m/z calcd for C21H17N4O5
2-(1-(Furan-2-yl)-2-nitroethyl)-5-(phenyl(1H-pyrrol-2-yl)methyl)-
1H-pyrrole (5g)
Dark brown viscous; yield: %82; Rf = 0.29 (EtOAc : hexane, 1 : 6); [M ꢀ H]ꢀ: 405.1204; found: 405.1225.
1H NMR (400 MHz, CDCl3) (ppm) d: 4.64–4.84 (m, 3H), 5.31
2-(2-Nitro-1-(thiophen-2-yl)ethyl)-5-(phenyl(1H-pyrrol-2-yl)-
methyl)-1H-pyrrole (5l)
(s, 1H), 5.66–5.70 (m, 1H), 5.78 (bs, 1H), 5.91–5.94 (m, 1H),
6.03–6.07 (m, 2H), 6.22 (s, 1H), 6.60 (s, 1H), 7.09–7.27 (m, 6H),
7.81 (bs, 1H), 7.87 (bs, 1H); 13C NMR (100 MHz, CDCl3) (ppm) d: Dark brown viscous; yield: %82; Rf = 0.33 (EtOAc : hexane, 1 : 6);
37.1, 44.0, 77.8, 106.9, 107.3, 107.8, 107.9, 108.5, 110.6, 117.4, 1H NMR (400 MHz, CDCl3) (ppm) d: 4.79 (dd, J = 12.7, 7.8 Hz,
125.8, 127.1, 128.4, 128.7, 132.2, 133.2, 141.7, 142.7, 150.8; 1H), 4.89 (dd, J = 12.7, 7.8 Hz, 1H), 5.10 (dd, J = 7.8, 7.8Hz, 1H),
HRMS (ESI): m/z calcd for C21H18N3O3 [M ꢀ H]ꢀ: 360.1354; 5.38 (s, 1H), 5.78 (s, 1H), 5.86 (s, 1H), 6.01 (s, 1H), 6.13 (s, 1H),
found: 360.1346.
6.68 (s, 1H), 6.89 (s, 1H), 6.94 (t, J = 4.3 Hz, 1H), 7.15–7.17 (m,
2H), 7.22–7.32 (m, 4H), 7.82 (bs, 1H), 7.89 (bs, 1H); 13C NMR
(100 MHz, CDCl3) (ppm) d: 38.3, 43.9, 79.7, 106.2, 107.3,
107.9, 108.4, 117.4, 125.6, 125.8, 127.1, 127.2, 128.0, 128.4,
2-((4-Bromophenyl)(1H-pyrrol-2-yl)methyl)-5-(1-(furan-2-yl)-2-
nitroethyl)-1H-pyrrole (5h)
Dark brown viscous; yield: %51; Rf = 0.22 (EtOAc : hexane, 1 : 6); 128.7, 132.1, 133.3, 141.3, 141.7; HRMS (ESI): m/z calcd for
1H NMR (400 MHz, CDCl3) (ppm) d: 4.74–4.92 (m, 3H), 5.35
(s, 1H), 5.74 (s, 1H), 5.85 (s, 1H), 5.99 (s, 1H), 6.13 (s, 2H), 6.31
(s, 1H), 6.70 (s, 1H), 7.04 (d, J = 8.3 Hz, 2H), 7.38 (s, 1H), 7.42
(d, J = 8.3 Hz, 2H), 7.91 (bs, 1H), 7.97 (bs, 1H); 13C NMR
C
21H18N3O2S [M ꢀ H]ꢀ: 376.1125; found: 376.1107.
5,50-(Phenylmethylene)bis(2-(1-(furan-2-yl)-2-nitroethyl)-1H-
pyrrole) (6b)
(100 MHz, CDCl3) (ppm) d: 37.1, 43.4, 77.9, 107.0, 107.1, Dark brown viscous; yield: %3; Rf = 0.21 (EtOAc : hexane, 1 : 6);
107.5, 107.8, 108.1, 108.6, 110.6, 117.7, 120.9, 126.1, 130.1, 1H NMR (400 MHz, CDCl3) (ppm) d: 4.73–4.92 (m, 6H),
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