Ammonium Chloride → HCID 131723391, compound

HRID 2228403Notes

Reaction equation

HRID 2228403 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][O:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][O:11]2)=[CH:4][N:3]=1.[CH2:16]([Li])[CH2:17][CH2:18]C.[CH2:21]([Si:24](Cl)(C)[CH3:25])C=C.[NH4+].[Cl-]>C1COCC1>[CH2:16]([C:2]1[C:7]([SiH:24]([CH3:25])[CH3:21])=[CH:6][C:5]([CH2:8][O:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][O:11]2)=[CH:4][N:3]=1)[CH:17]=[CH2:18]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 77646AllylchlorodimethylsilaneHCID 18469682HCID 18469682, compoundHCID 178418339Butyllithium

Product 1

HCID 131723391HCID 131723391, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-[(2-bromopyridin-5-yl)methoxy]tetrahydro-2H-pyran. (5 Scheme 27, 5.1 g, 18.7 mmol) in dry THF (200 mL) at −78° C. was added n-butyllithium (7.5 mL, 2.5 M solution in hexanes, 18.7 mmol). After being stirred for 10 min −78° C., allylchlorodimethylsilane (2.5 g, 18.7 mmol) was added dropwise over a period of 20 min. The reaction mixture was stirred further for 1 h and warmed to room temperature. Concentrated NH4Cl (5 mL) was added to the solution, and the reaction mixture was concentrated. The resulting yellow oil was concentrated, extracted with ethyl acetate/water, and the organic layer was dried, concentrated, and purified by column chromatography (1:7 ethyl acetate/hexanes) to give the desired compound as a liquid (3 g, 55%) 1H NMR (300 MHz, CDCl3) δ 0.31 (s, 6 H), 1.45-1.68(6 H), 1.82 (d, J=8.40 Hz, 2 H), 3.54 (m, 1 H), 3.87 (m, 1 H), 4.47 (d, J=12.30 Hz, 1 H), 4.70 (t, J=3.45 Hz, 1 H), 4.77 (d, J=12.30 Hz, 1 H), 4.80-4.87 (2 H), 7.75 (m, 1 H), 7.46 (d, J=7.50 Hz, 1 H), 7.58 (dd, J=7.50, 1.80 Hz, 1 H), 8.76 (1 H); 13C NMR (75 MHz, CDCl3) −3.8 (2C), 19.4, 22.9, 25.8, 30.6, 62.3, 66.7, 98.1, 113.8, 129.1, 133.0, 133.6, 134.6, 149.9, 165.9. HRMS (EI) calcd for C16H25NO2Si 291.1654, found 291.1556.

Workup

  1. additionwas added dropwise over a period of 20 min
  2. concentrationthe reaction mixture was concentrated
  3. concentrationThe resulting yellow oil was concentrated
  4. extractionextracted with ethyl acetate/water
  5. customthe organic layer was dried
  6. concentrationconcentrated
  7. custompurified by column chromatography (1:7 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-9b97984585f641a68966c7778c5c0058
Source dataset
uspto-grants-2002_07
Patent number
US06416861B1

Reaction notes

Loading…