反応 #1914847

反応方程式

18-crown-6

Chloride

1-Chloro-3,6,9-trioxadecane

p-hydroxybenzaldehyde

K2CO3

→

604

収率 71.2%

p-(1,4,7,10-Tetraoxaundecyl)benzaldehyde

収率 71.2%

溶媒

THF

water

反応条件

後処理

1. 1
   温度at reflux for 48 h
2. 2
   抽出The product was extracted with 3×350 mL portions of ethyl acetate
3. 3
   その他the combined organic layers were dried
4. 4
   濃縮concentrated
5. 5
   洗浄eluted with a 1:9 mixture of ethyl acetate/hexane
6. 6
   洗浄finally washed with ethyl acetate

実験手順

Chloride 603 (26 g, 0.14 mol, 1.3 equiv) and p-hydroxybenzaldehyde (13 g, 0.11 mol, 1 equiv) were dissolved in dry THF (40 mL). K2CO3 (15 g, 0.11 mol, 1 equiv) was added followed by 18-crown-6 (3.0 g, 11 mmol, 0.11 equiv) and KI (0.20 g, 1.2 mmol, 0.01 equiv). The reaction mixture was stirred at reflux for 48 h. The resulting mixture was cooled to room temperature, and water (200 mL) was added. The product was extracted with 3×350 mL portions of ethyl acetate and the combined organic layers were dried and concentrated. The oil was loaded onto a silica gel column and eluted with a 1:9 mixture of ethyl acetate/hexane, followed by a ratio of 1:4, 3:7, 4:1 of ethyl acetate/hexane and finally washed with ethyl acetate to afford 21 g (70%) of 604 as a clear oil. IR (cm−1): 1697 (s), 1165 (s). 1H NMR (400, CDCl3): δ 3.36 (s, 3), 3.54 (t, 2, J=4.6), 3.63–3.68 (m, 4), 3.72–3.75 (m, 2), 3.88 (t, 2, J=4.8), 4.20 (t, 2, J=4.8), 7.01 (d, 2, J=8.8), 9.87 (s, 1). 13C NMR (CDCl3): δ 58.86, 67.59, 69.29, 70.40, 70.47, 70.71, 71.73, 114.71, 129.84, 13.1.76, 163.69, 190.63. Calcd: [M+H]+ (C14H21O5) m/z=269.13889. Found FAB-HRMS: [M+H]+ m/z=269.134487. Anal. Calcd. for C14H20O5: C, 62.67; H, 7.51. Found: C, 62.47; H, 7.74.

出典