Water → HCID 178440819, compound

HRID 555413Notes

Reaction equation

HRID 555413 reaction equation
[I-].[Na+].[C:3]([C:7]1[CH:24]=[CH:23][CH:22]=[CH:21][C:8]=1[O:9][C:10]1[C:15]([N+:16]([O-:18])=[O:17])=[CH:14][CH:13]=[C:12]([O:19]C)[N:11]=1)([CH3:6])([CH3:5])[CH3:4].[Al].Cl[Si](C)(C)C.O>C(#N)C.N1C=CC=CC=1>[C:3]([C:7]1[CH:24]=[CH:23][CH:22]=[CH:21][C:8]=1[O:9][C:10]1[N:11]=[C:12]([OH:19])[CH:13]=[CH:14][C:15]=1[N+:16]([O-:18])=[O:17])([CH3:6])([CH3:4])[CH3:5]

Participants

8

Reactant 5

HCID 962WaterHCID 5238Sodium IodideHCID 6397ChlorotrimethylsilaneHCID 5359268AluminumHCID 598574032-(2-tert-Butyl-phenoxy)-6-methoxy-3-nitro-pyridine

Product 1

HCID 178440819HCID 178440819, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6342AcetonitrileSolvent

Procedure

Sodium iodide (10.6 g, 71 mmol) was added to a green solution of 2a (4.26 g, 14 mmol) in acetonitrile (80 mL) in a vessel covered with aluminum foil to protect from light, followed by chlorotrimethylsilane (8.9 mL, 71 mmol) and water (0.4 mL, 21 mmol). The yellow-orange mixture was refluxed overnight in the dark. HPLC analysis showed that although some starting pyridine was still present, decomposition also appeared to be occurring. The reaction was quenched with saturated sodium thiosulfate solution (30 mL). The resulting mixture was extracted with ethyl acetate (3×50 mL). The combined organic layer was washed with brine (30 mL), dried over sodium sulfate, and concentrated to give a yellow oil. The oil was purified by SiO2 chromatography (120 g), loaded with CH2Cl2 and eluted using a gradient of ethyl acetate in hexanes to afford 136a (2.34 g, 58% yield) as a yellow waxy solid, HPLC purity 100%, 3.66 min (Method A); [M+H]+=289.17; in 1H NMR (500 MHz, CDCl3) δ ppm 8.42 (d, 1H, J=5.0 Hz), 7.48 (m, 1H), 7.18 (m, 2H), 6.92 (m, 1H), 6.33 (d, 1H, J=10.0 Hz), 1.37 (s, 9H); 13C (125 MHz, CDCl3) δ (ppm), 163.87, 155.70, 150.61, 142.05, 139.87, 127.86, 126.83, 125.98, 122.98, 104.62, 34.68, 30.17.

Workup

  1. temperatureThe yellow-orange mixture was refluxed overnight in the dark
  2. customThe reaction was quenched with saturated sodium thiosulfate solution (30 mL)
  3. extractionThe resulting mixture was extracted with ethyl acetate (3×50 mL)
  4. washThe combined organic layer was washed with brine (30 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated
  7. customto give a yellow oil
  8. customThe oil was purified by SiO2 chromatography (120 g)
  9. washeluted

Sources & evidence

ORD record
ord-1b2bb6d9ea8646f897881ef3a0ffe95b
Source dataset
uspto-grants-2011_11
Patent number
US08053450B2

Reaction notes

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