反応 #2033

反応方程式

triphenylphosphine

Br2

4,7-decadien-1-ol

NaHCO3

→

(4Z,7Z)-1-bromo-4,7-decadiene

収率 32.0%

溶媒

CH2Cl2

CH2Cl2

CH2Cl2

water

反応条件

後処理

1. 1
   その他Into the slightly yellow suspension that formed
2. 2
   workup.ADDITIONthe crude mixture of 4
3. 3
   workup.STIRRINGAfter stirring for 1 hour
4. 4
   抽出The mixture was extracted with pentane
5. 5
   workup.WAITwere stored overnight in a freezer
6. 6
   その他In this way, triphenylphosphine oxide could be crystallized
7. 7
   その他removed by filtration
8. 8
   workup.DISTILLATIONColumn chromatography followed by distillation at reduced pressure
9. 9
   その他afforded 5 (3.48 g, 32% yield
10. 10
    その他=80°-85° C./2.5 torr

実験手順

A solution of triphenylphosphine (20.9 g, 80 mmol) in CH2Cl2 (100 ml) was treated with Br2 (7.8 g, 49 mmol) in CH2Cl2 (15 mL, 0° C.) and the mixture was stirred at room temperature for 20 min. Into the slightly yellow suspension that formed, the crude mixture of 4 and 4Z,7Z)-4,7-decadien-1-ol (12.4 g) in CH2Cl2 (15 ml) was added dropwise. After stirring for 1 hour, a solution of saturated NaHCO3 (50 mL) and water (50 ml) were added. The mixture was extracted with pentane and combined extracts were stored overnight in a freezer. In this way, triphenylphosphine oxide could be crystallized and removed by filtration. Column chromatography followed by distillation at reduced pressure afforded 5 (3.48 g, 32% yield based on 1 of b.p. =80°-85° C./2.5 torr. 1H NMR (200 MHz) δ: 5.37 (m, 4H, CH=CH), 3.41 (t, J=6.6, 6.6 Hz, 2H, CH2 --Br), 2.80 (dd, J=6.4, 6.5 Hz, 2H, =CH--CH2 --CH=), 2.21 (dt, J=7.0, 6.9, 6.8, 6.9 Hz, 2H, CH2 -3), 2.07 (dq, J=7.4 Hz, CH2 -9), 1.91 (tt, J=6.7, 6.6, 7.0, 7.0, 2H, CH2 -2), 0.97 (t, J=7.5, 7.5 Hz, 3H, CH3). 13C NMR (100.6 MHz) δ: 132.1 (8), 129.8 (5), 127.6 (7), 127.0 (4), 33.4 (1), 32.5 (2), 25.6 (3), 25.5 (6), 20.6 (9), 14.3 (10). MS [EI, m/z (%)] 218 (M+, 15), 216 (17), 137 (6), 109 (13), 107 (18), 96 (14), 95 (78), 82 (18), 81 (74), 79 (22), 68 (27), 67 (100), 55 (17), 53 (15), 42 (11), 41 (38), 40 (40).

出典