Dimethylformamide → HCID 10613913, compound

Participants

Reaction Steps

A solution of 4 (5.15 g, 19.1 mmol) in DMF (6.1 mL) and CH2Cl2 (140 mL) under argon was cooled to 0° C. and then POCl3 (2.11 mL, 22.6 mmol) was added dropwise. After 1 h, the flask was warmed to room temperature and stirred overnight. The reaction was quenched at 0° C. with 2.5 M NaOH (100 mL). The mixture was poured into water (500 mL), extracted with CH2Cl2, and the combined organic layers were washed with water, brine, dried (Na2SO4), and the solvent was removed in vacuo. 1H NMR spectroscopy showed two regioisomers in a ˜6:1 ratio. The minor isomer exhibited signals at δ7.21 and 7.39 ppm, compared with signals at δ6.42 and 7.14 for the major isomer. The most downfield signal (7.39 ppm) is assigned to the proton adjacent to a formyl group, which occurs in the 2-formyl-4-aryl substituted pyrrole. Recrystallization from ethyl acetate afforded an orange solid corresponding to the major aldehyde (2.25 g). The mother liquor was concentrated and purified by flash column chromatography [silica, hexanes/ethyl acetate (3:1)]. The first fraction corresponded to the major aldehyde (1.25 g). The total yield of the title compound was 3.50 g (62%): mp 153-154° C.; 1H NMR δ6.42 (m, 1H), 7.14 (m, 1H), 7.22 (m, 2H), 7.76 (m 2H), 9.59 (s, 1H), 10.72 (br, 1H); 13C NMR δ93.5, 104.3, 111.4, 125.8, 128.6, 130.8, 133.1, 137.8, 179.4; FAB-MS obsd 296.9663, calcd 296.9651; Anal. Calcd for C10H8INO: C, 44.5; H, 2.7; N, 4.7. Found: C, 44.4; H, 2.7; N, 4.6.

Provenance & Evidence