反応 #600259

反応方程式

(6-chloro-4-iodo-pyridin-3-yl)-carbamic acid tert-butyl ester

1-butyne

triethylamine

→

tert-butyl 4-(but-1-ynyl)-6-chloropyridin-3-ylcarbamate

収率 74.0%

溶媒

toluene

water

反応条件

後処理

1. 1
   ろ過The solid was filtered off
2. 2
   洗浄washed with ethyl acetate (60 mL×3)
3. 3
   その他The filtrate was evaporated under reduced pressure
4. 4
   その他the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10/1)

実験手順

To a deoxygenated solution of (6-chloro-4-iodo-pyridin-3-yl)-carbamic acid tert-butyl ester (6.0 g, 16.9 mmol), 1-butyne (9 g, 169 mmol), CuI (160.1 mg, 0.84 mmol) and triethylamine (3.4 g, 33.2 mmol) in toluene (40 mL) and water (14 mL) was added Pd(PPh3)2Cl2 (592 mg, 0.84 mmol) under N2 in a autoclave. The mixture was heated to 70° C. and stirred for 24 h. The solid was filtered off and washed with ethyl acetate (60 mL×3). The filtrate was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 10/1) to give tert-butyl 4-(but-1-ynyl)-6-chloropyridin-3-ylcarbamate (3.5 g, 74%). 1H-NMR (CDCl3, 300 MHz) δ 9.13 (s, 1H), 7.22 (s, 1H), 6.98 (s, 1H), 2.53 (q, J=7.5 Hz, 2H), 1.54 (s, 9H), 1.29 (t, J=7.5 Hz, 3H).

出典