Imidazole → 6-[2-(Tert-butyl-dimethyl-silanyloxy)-ethylsulfanyl]-2-methyl-3-nitro-pyridine

HRID 1811572Notes

Reaction equation

HRID 1811572 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([S:8][CH2:9][CH2:10][OH:11])[CH:5]=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].N1C=CN=C1.[C:20]([Si:24](Cl)([CH3:26])[CH3:25])([CH3:23])([CH3:22])[CH3:21]>CN(C=O)C>[C:20]([Si:24]([CH3:26])([CH3:25])[O:11][CH2:10][CH2:9][S:8][C:6]1[N:7]=[C:2]([CH3:1])[C:3]([N+:12]([O-:14])=[O:13])=[CH:4][CH:5]=1)([CH3:23])([CH3:22])[CH3:21]

Participants

5

Reactant 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 114244292-(6-Methyl-5-nitro-pyridin-2-ylsulfanyl)-ethanol

Product 1

HCID 586715856-[2-(Tert-butyl-dimethyl-silanyloxy)-ethylsulfanyl]-2-methyl-3-nitro-pyridineYield 79.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 2-(6-methyl-5-nitro-pyridin-2-ylsulfanyl)-ethanol (60% pure, 3.25 g, 9.1 mmol), 1H-imidazole (1.24 g, 18.2 mmol), and tert-butylchlorodimethylsilane (2.75 g, 18.2 mmol) in 20 mL DMF was stirred at room temperature for 4 h. Solution was concentrated and residue was extracted with water and CH2Cl2. Organic phases were dried over MgSO4, filtered, and concentrated. Residue was purified by column chromatography (hexane/AcOEt 30:1) to give 6-[2-(tert-butyl-dimethyl-silanyloxy)-ethylsulfanyl]-2-methyl-3-nitro-pyridine as a yellow oil (2.39 g, 48%). 1HNMR (CDCl3, 400 MHz) δ 0.8 (s, 6H), 0.90 (s, 9H), 2.85 (s, 3H), 3.39-3.42 (t, J=6.7 Hz, 2H), 3.85-3.89 (t, J=6.7 Hz, 2H), 7.13-7.15 (d, J=8.7 Hz, 1H), 8.10-8.13 (d, 1H). Exact mass calculated for C14H24N2O3SSi 328.13 found 329.1 (MH+).

Workup

  1. concentrationSolution was concentrated
  2. extractionresidue was extracted with water and CH2Cl2
  3. dry with materialOrganic phases were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customResidue was purified by column chromatography (hexane/AcOEt 30:1)

Sources & evidence

ORD record
ord-471ed5acf9b8437a843f2dbc9981f25f
Source dataset
uspto-grants-2013_01
Patent number
US08362248B2

Reaction notes

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