反应详情

To a suspension of 7-chloro-3-(4-chlorophenyl)-2-(2-chlorophenyl)-pyrazolo[1,5-a]pyrimidine (I-13A-1a; 1.72 g, 4.6 mmol) in allyl alcohol (50 ml) at 0° C. was added NaH (60% dispersion in oil, 0.28 g, 6.9 mmol), portionwise over 3 minutes. After warming to room temperature, the reaction was stirred overnight. The resultant allyl ether was then heated at 125° C. for 1.5 hours to facilitate the rearrangement. The reaction was concentrated, in vacuo, to give a residue which was partitioned between ethyl acetate and water adjusted to pH=4 with 1M aqueous HCl. The organic layer which contained dispersed solids was separated, washed with brine, and the solids then collected by vacuum filtration to give product I-15A-1a (1.24 g, 68%) as a solid: +ESI MS (M+1) 396.4; 1H NMR (400 MHz, CD3OD) δ 7.64 (s 1H), 7.52–7.48 (m, 1H), 7.43–7.48 (m, 3H), 7.30 (d, J=8.7 Hz, 2H), 7.15 (d, J=8.7 Hz, 2H), 6.06–5.92 (m, 1H), 5.21–5.14 (m, 1H), 5.12–5.07 (m, 1H).

1. concentrationThe reaction was concentrated, in vacuo
2. customto give a residue which
3. customwas partitioned between ethyl acetate and water
4. additionThe organic layer which contained dispersed solids
5. customwas separated
6. washwashed with brine
7. filtrationthe solids then collected by vacuum filtration
8. customto give product I-15A-1a (1.24 g, 68%) as a solid