반응 #8635

반응 방정식

1-bromo-2-methylpropane

32

(3-Buten-1-yl)(1,3-dithian-2-yl)diphenylsilane

n-butyllithium

→

26

수율 92.5%

(3-Buten-1-yl) [2-(2-methyl-1-propyl)-1,3-dithian-2-yl]diphenylsilane

수율 92.5%

용매

THF

반응 조건

후처리

1. 1
   workup.STIRRINGthe mixture was stirred for 2 h at −78° C. and overnight at rt
2. 2
   기타The reaction mixture was quenched with water (10 mL)
3. 3
   기타the excess organic solvent was removed under reduced pressure
4. 4
   추출The crude mixture was extracted with three 100-mL portions of EtOAc
5. 5
   세척The combined organic extracts were washed with saturated aqueous NaCl
6. 6
   건조dried over Na2SO4
7. 7
   농축concentrated

실험 절차

To a solution of 32 (4.68 g, 13.1 mmol) in THF (100 mL) at −78° C. was added dropwise over 10 min n-butyllithium (1.6 M in hexanes, 18.4 mmol). After 3 h of stirring under argon, 1-bromo-2-methylpropane (2.14 mL, 19.7 mmol) was added dropwise over 5 min, and the mixture was stirred for 2 h at −78° C. and overnight at rt. The reaction mixture was quenched with water (10 mL) and the excess organic solvent was removed under reduced pressure. The crude mixture was extracted with three 100-mL portions of EtOAc. The combined organic extracts were washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated. Flash chromatography over silica gel (1/9 EtOAc:hexane) gave pure 26 as a colorless solid (5.0 g, 92%): Rf=0.75 (1/9 EtOAc:hexane); mp 67–69° C.; 1H NMR (300 MHz, CDCl3) δ 7.83 (d, J=6.0 Hz, 4H), 7.41 (m, 6H), 5.88 (m, 1H), 4.97 (dd, J=17.1, 1.7 Hz, 1H), 4.88 (dd, J=10.1, 1.7 Hz, 1H), 3.04 (m, 2H), 2.49 (t. J=4.3 Hz 1H), 2.44 (t, J=4.1 Hz, 1H), 2.08 (d, J=5.1 Hz, 2H), 1.98 (m, 4H), 1.79 (m, 1H), 1.54 (m, 2H), 0.82 (d, J=6.7 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 141.5, 136.7, 132.9, 129.9, 127.7, 113.0, 45.7, 39.9, 28.3, 27.2, 24.6, 24.3, 24.2, 11.0; IR (film) 3068 (m), 3043 (m), 2951 (s), 2912 (s), 2863 (m), 1432 (s), 1274 (w), 1113 (s), 997 (m), 913 (m), 738 (s), 705 (s) cm−1; MS (EI) m/e (rel. intensity) 289 (M+-123, 3), 237 (8), 183 (72), 175 (100), 159 (32), 143 (17), 119 (16), 105 (35); HRMS (FAB) calcd for C24H32S2Si: 412.1715 (MH+-1), found: 412.1727. Anal. Calcd for C24H32S2Si: C, 69.84; H, 7.82. Found: C, 70.08; H, 8.07.

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