tert-Butyldimethylsilyl chloride → 4-Bromo-2-(((tert-butyldimethylsilyl)oxy)methyl)pyridine

HRID 1807623Notes

Reaction equation

HRID 1807623 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([CH2:8][OH:9])[CH:3]=1.[C:10]([Si:14](Cl)([CH3:16])[CH3:15])([CH3:13])([CH3:12])[CH3:11]>C(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([CH2:8][O:9][Si:14]([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:16])[CH3:15])[CH:3]=1

Participants

4

Reactant 2

HCID 28928tert-Butyldimethylsilyl chlorideHCID 14761462(4-Bromopyridin-2-yl)methanol

Product 1

HCID 583550294-Bromo-2-(((tert-butyldimethylsilyl)oxy)methyl)pyridineYield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirring solution of (4-bromopyridin-2-yl)methanol (1.50 g, 8.0 mmol) in DCM (4 mL) was added tert-butylchlorodimethylsilane (1.20 g, 8.0 mmol) following by TEA (1.60 g, 12.0 mmol). The reaction mixture was stirred at room temperature for 12 h then washed with brine and EA. The combined organic layers were dried over MgSO4, filtered, and concentrated to yield an amber liquid. The crude product was purified by chromatography (EA/Hexanes) to produce 1.67 g (70%) of 4-bromo-2-((tert-butyldimethylsilyloxy)methyl)pyridine INT-70 as a light yellow liquid. LCMS-ESI (m/z) calculated for C12H20BrNOSi: 302.3; found 303.0 [M+H]+, tR=4.87 min (Method 1). 1H NMR (400 MHz, CDCl3) δ 8.30 (d, J=5.3, 1H), 7.68 (dd, J=1.9, 0.7, 1H), 7.35-7.24 (m, 1H), 4.80 (s, 2H), 0.99-0.86 (m, 9H), 0.16-0.06 (m, 6H).

Workup

  1. washthen washed with brine and EA
  2. dry with materialThe combined organic layers were dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customto yield an amber liquid
  6. customThe crude product was purified by chromatography (EA/Hexanes)

Sources & evidence

ORD record
ord-f3a416223ac74137813bc630e39d70fc
Source dataset
uspto-grants-2013_01
Patent number
US08357706B2

Reaction notes

Loading…