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

HRID 1062488

반응식

HRID 1062488 반응식
[CH2:1]([Si:5]([CH:18]1[S:23][CH2:22][CH2:21][CH2:20][S:19]1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH2:2][CH:3]=[CH2:4].C([Li])CCC.Br[CH2:30][CH:31]([CH3:33])[CH3:32]>C1COCC1>[CH2:1]([Si:5]([C:18]1([CH2:30][CH:31]([CH3:33])[CH3:32])[S:19][CH2:20][CH2:21][CH2:22][S:23]1)([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[CH2:2][CH:3]=[CH2:4]

참가 물질

5

반응물 3

HCID 65551-Bromo-2-methylpropaneHCID 15349849(3-Buten-1-yl)(1,3-dithian-2-yl)diphenylsilaneHCID 178418339Butyllithium

생성물 1

HCID 22287058(3-Buten-1-yl) [2-(2-methyl-1-propyl)-1,3-dithian-2-yl]diphenylsilane수율 92.5%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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 (ME+−1). found: 412.1727. Anal. Calcd for C24H32S2Si: C, 69.84; H, 7.82. Found: C, 70.08; H, 8.07.

후처리

  1. stirringthe mixture was stirred for 2 h at −78° C. and overnight at rt
  2. customThe reaction mixture was quenched with water (10 mL)
  3. customthe excess organic solvent was removed under reduced pressure
  4. extractionThe crude mixture was extracted with three 100-mL portions of EtOAc
  5. washThe combined organic extracts were washed with saturated aqueous NaCl
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated

출처 및 근거

ORD 기록
ord-1549adfb46b440c4924763e9e18b721b
출처 데이터셋
uspto-grants-2005_11
특허 번호
US06960678B2

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