Water → 2-[2-[[(1,1-Dimethylethyl)diphenylsilyl]oxy]ethoxy]-5-nitropyridine

HRID 1587824Notes

Reaction equation

HRID 1587824 reaction equation
[OH:1][CH2:2][CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][N:6]=1.[H-].[Na+].[C:16]([Si:20](Cl)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([CH3:19])([CH3:18])[CH3:17].O>CN(C)C=O>[Si:20]([O:1][CH2:2][CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][N:6]=1)([C:16]([CH3:19])([CH3:18])[CH3:17])([C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 94078tert-ButyldiphenylchlorosilaneHCID 5879372-[(5-Nitropyridin-2-yl)oxy]ethan-1-ol

Product 1

HCID 197564132-[2-[[(1,1-Dimethylethyl)diphenylsilyl]oxy]ethoxy]-5-nitropyridineYield 40.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

2-(2-Hydroxyethoxy)-5-nitropyridine (obtained as described in Annalen der Chemie., 1936, 521, 286) (114 g) was added portionwise to an ice-cooled, stirred suspension of sodium hydride (60% dispersion in mineral oil; 24.8 g) in N,N-dimethylformamide (DMF) (600 ml), at such a rate that the temperature did not exceed 10° C. The solution was stirred at 0° C. for 10 minutes, and then tert-butylchlorodiphenylsilane (171 g) was added dropwise at such a rate that the temperature did not exceed 10° C. The solution was stirred for 72 hours and then added to water (2 l). The mixture was extracted with ethyl acetate (2 ×1 l), and the extracts were washed with water (1 l) and saturated sodium chloride solution (500 ml), and then dried (MgSO4). Volatile material was removed by evaporation, and the residue was purified by flash chromatography, eluting with hexane to give 2-[2-(t-butyldiphenylsilyl)oxyethoxy]-5-nitropyridine (B) (106 g), as an oil which solidified on standing, m.p. 63°-64° C. (from hexane); NMR (d6 -DMSO): 1.0(s,9H), 4.0(t,2H), 4.55(t,2H), 7.0(d,1H), 7.3-7.5(m,6H), 7.55-7.75(m,4H), 8.45(dd,1H), 9.0(d,1H).

Workup

  1. temperaturecooled
  2. customdid not exceed 10° C
  3. stirringThe solution was stirred at 0° C. for 10 minutes
  4. customdid not exceed 10° C
  5. stirringThe solution was stirred for 72 hours
  6. extractionThe mixture was extracted with ethyl acetate (2 ×1 l)
  7. washthe extracts were washed with water (1 l) and saturated sodium chloride solution (500 ml)
  8. dry with materialdried (MgSO4)
  9. customVolatile material was removed by evaporation
  10. customthe residue was purified by flash chromatography
  11. washeluting with hexane

Sources & evidence

ORD record
ord-617ea54423ca44e1a2c5323d76806e75
Source dataset
uspto-grants-1993_06
Patent number
US05219863

Reaction notes

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