反应 #69217

反应方程式

dimethyl (2E)-pent-2-enedioate

4-(1H-Pyrazol-4-yl)-7-[2-(trimethylsilyl)ethoxy]methyl-7H-pyrrolo[2,3-d]pyrimidine

ACN

DBU

→

dimethyl 3-[4-(7-{[2-(trimethylsilyl)ethoxy]methyl}-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]pentanedioate

收率 64.0%

溶剂

ethyl acetate

反应条件

后处理

1. 1
   温度to cool to room temperature
2. 2
   浓缩was concentrated in vacuo
3. 3
   其他to give a dark oil
4. 4
   其他The oil was partitioned between ethyl acetate and water
5. 5
   洗涤The organic layer was washed with 1.0 N HCl, brine
6. 6
   干燥dried over magnesium sulfate
7. 7
   浓缩concentrated
8. 8
   其他to give a dark oil
9. 9
   其他The viscous oil was triturated with ethyl ether 3×500 mL
10. 10
    其他to give a dark precipitate
11. 11
    其他to form a solid
12. 12
    其他The solids were collected
13. 13
    洗涤washed with ethyl ether
14. 14
    其他dried

实验过程

4-(1H-Pyrazol-4-yl)-7-[2-(trimethylsilyl)ethoxy]methyl-7H-pyrrolo[2,3-d]pyrimidine (31.0 g, 0.0983 mol) was suspended in ACN (620 mL, 12 mol), and DBU (9.3 mL, 0.062 mol) was added under nitrogen. The reaction was heated to 65° C. and dimethyl (2E)-pent-2-enedioate (16 mL, 0.12 mol) was added in 5 mL portions over 2 h. After stirring overnight, the reaction was complete. The reaction was allowed to cool to room temperature and was concentrated in vacuo to give a dark oil. The oil was partitioned between ethyl acetate and water. The organic layer was washed with 1.0 N HCl, brine, dried over magnesium sulfate, and then concentrated to give a dark oil. The viscous oil was triturated with ethyl ether 3×500 mL to give a dark precipitate. The oil was taken up in ethyl acetate to form a solid. The solids were collected, washed with ethyl ether and dried to give dimethyl 3-[4-(7-{[2-(trimethylsilyl)ethoxy]methyl}-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]pentanedioate as a white powder (29.5 gm, 64%), LC/MS (M+H)+: 474, 1H NMR (DMSO-d6) δ 9.1 (s,1H), 9.02 (s,1H), 8.65 (s, 1H), 8.11 (d, 1H), 7.42(d, 1H), 5.78(s, 2H), 5.27(m, 1H), 3.65(m, 8H), 3.15(m, 4H), 0.95(t, 2H), 0.1(s, 9H).

来源