تفاعل #2034

معادلة التفاعل

5

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

1-(tetrahydropyran-2-yloxy)-3-butyne

n-butyllithium hexane

→

(8Z,11Z)-1-(tetrahydropyran-2-yloxy)-8,11-tetradecadien-3-yne

المردود 55.0%

المذيبات

—

1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H)-pyrimidine

THF

ظروف التفاعل

المعالجة

1. 1
   workup.WAITthe mixture was kept at room temperature for 30 min
2. 2
   أخرىat room temperature and quenched with saturated NH4Cl solution (30 ml)
3. 3
   أخرىThe product (6) was removed with ether (3×50 ml)
4. 4
   أخرىpurified by silica-gel flash chromatography (2.2 g, 55% yield)

الإجراء التجريبي

A solution of 1-(tetrahydropyran-2-yloxy)-3-butyne (2.25 g, 14 mmol) in dry THF (15 ml) was treated at -50° C. with n-butyllithium hexane solution (11 ml, 17.5 mmol). After 15 min at -30° C., the mixture was kept at room temperature for 30 min. The mixture was then treated at 0° C. with 5 (3.0 g, 13.8 mmol) dissolved in 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H)-pyrimidine (DMPU) (15 mL) during 30 min. The reaction mixture was stirred 12 hr. at room temperature and quenched with saturated NH4Cl solution (30 ml). The product (6) was removed with ether (3×50 ml) and purified by silica-gel flash chromatography (2.2 g, 55% yield). 1H NMR (200 MHz) δ5.36 (m, 4H, CH=CH), 4.64 (m, 1H, CH-2'), 3.81 (m, 2H, CH2 -6' and 1), 3.54 (m, 2H, CH2 -6' and 1), 2.78 (dd, J=6.0, 6.0 Hz, 2H, =CH--CH2 --CH=), 2.47 (m, 4H, CH2 -2, and -5), 2.15 (m, 4H, CH2 -7, and -13), 1.8-1.4 (m, 8H, CH2 -6, -3', -4', and -5'), 0.96 (t, J=7.5, 7.6 Hz, 3H, CH3). 13C NMR (100.6 MHz) δ: 131.8 (12), 128.9 (9, 11), 127.2 (8), 98.7 (2'), 81.0 (3), 76.6 (4), 66.2 (1), 62.2 (6'), 33.4 (2), 30.6 (3'), 28.9 (7), 26.2 (6), 25.5 (14), 25.4 (4'), 20.5 (5), 20.2 (13), 18.3 (5'), 14.3 (10). MS [EI, m/z (%)] 159 (7), 131 (9), 119 (8), 117 (9), 105 (8), 93 (11), 91 (16), 86 (12), 85 (100), 79 (18), 77 (11), 67 (36), 57 (16), 55 (15), 43 (29), 42 (16), 41 (51), 40 (24).

المصدر