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

HRID 2306509Notes

Reaction equation

HRID 2306509 reaction equation
[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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-86b1837b61cc44d395500016d9cd6fed
Source dataset
uspto-grants-2002_08
Patent number
US06441212B1

Reaction notes

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