反应 #6530

反应方程式

allyl bromide

Methyl 2-(nicotinoyl)acetate

sodium

Allyl bromide

→

methyl-2-nicotinoyl-4-pentenoate

溶剂

methanol

反应条件

后处理

1. 1
   workup.STIRRINGstirring
2. 2
   workup.WAITwas continued overnight
3. 3
   workup.STIRRINGthe mixture was stirred for 48 hours
4. 4
   浓缩concentrated
5. 5
   其他The residual oil was partitioned between water and ether
6. 6
   萃取the aqueous layer was extracted three times with ether
7. 7
   洗涤The combined extracts were washed with saturated brine
8. 8
   干燥dried (MgSO4)
9. 9
   浓缩concentrated
10. 10
    其他The residue was purified by flash column chromatography
11. 11
    洗涤eluting with a mixture of petroleum ether (b.p. 60°-80°) and ethyl acetate (1:1

实验过程

Methyl 2-(nicotinoyl)acetate (17.9 g, prepared by the method of E. Wenkert el al. J. Org. Chem., 1983, 48, 5006) was added under argon to a solution of sodium metal (2.3 g) in methanol (200 ml) and the resulting mixture was stirred at 25° C. for 30 mins. Allyl bromide (12.0 g) was then added and stirring was continued overnight. A further amount (about 2 g) of allyl bromide was added, the mixture was stirred for 48 hours, and then concentrated. The residual oil was partitioned between water and ether and the aqueous layer was extracted three times with ether. The combined extracts were washed with saturated brine, dried (MgSO4) and concentrated. The residue was purified by flash column chromatography, eluting with a mixture of petroleum ether (b.p. 60°-80°) and ethyl acetate (1:1, v/v) to give methyl-2-nicotinoyl-4-pentenoate (A) as a pale yellow oil (13.8 g); NMR 2.6-2.9 (2H,m), 3.7 (3H,s), 4.4 (1H,m), 4.9-5.2 (2H,m), 5.5-6.0 (1H,m), 7.2-7.5 (1H,m), 8.1-8.3 (1H,m), 8.7-8.8 (1H,m) and 9.1-9.2 (1H,m).

来源