N,N-Diethylaniline → 2-Chloro-4,5,6-trimethylpyrimidine
反応式
O[C:2]1[N:7]=[C:6]([CH3:8])[C:5]([CH3:9])=[C:4]([CH3:10])[N:3]=1.N(C1C=CC=CC=1)(CC)CC.O=P(Cl)(Cl)[Cl:24]>>[Cl:24][C:2]1[N:7]=[C:6]([CH3:8])[C:5]([CH3:9])=[C:4]([CH3:10])[N:3]=1参加物
4
実験手順
0.8489 g (6.15 mmol) of the compound of part (a) was suspended in POCl3 (5 ml) and heated under reflux under a Drierite guard tube. Complete dissolution did not occur after 11/2 hours and so Et2NPh (0.5 ml) was added and the reflux was continued for an additional 11/2 hours. Complete solution had occurred to give a wine colored solution. This was concentrated in vacuo to ~2 ml and then added dropwise to ice-H2O (50 ml). The pH of the mixture was adjusted to 3-4 (pH paper) with NH4OH and the solution was extracted with CH2Cl2 (2×50 ml). The pooled organic phases were dried (MgSO4), filtered, and evaporated to an off-white residue. This solid was dissolved in CH2Cl2 -MeOH and adsorbed onto a little silica gel by evaporation. The solid was placed atop a dry-packed silica gel 60 column (2.5×33.0 cms) and development was initiated with EtOAc:hexanes 1:3 (500 ml). Then, EtOAc:hexanes 1:1 was utilized; fractions containing the required product, were pooled and evaporated to dryness in vacuo to give the title compound as crystalline plates. NMR (CDCl3, δ from TMS): 2.23 (S, 5-CH3), 2.50 (S, 4.6-CH3 'S).