5-Nitro-2-(pyridin-2-ylmethoxy)benzaldehyde → 2-[(4-Nitro-2-vinylphenoxy)methyl]pyridine

HRID 550419Notes

Reaction equation

HRID 550419 reaction equation
[Li][CH2:2]CCC.[N+:6]([C:9]1[CH:10]=[CH:11][C:12]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=2)=[C:13]([CH:16]=1)[CH:14]=O)([O-:8])=[O:7]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1.CC(N(C)C)=O>[N+:6]([C:9]1[CH:10]=[CH:11][C:12]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=2)=[C:13]([CH:14]=[CH2:2])[CH:16]=1)([O-:8])=[O:7]

Participants

6

Reactant 2

HCID 167691365-Nitro-2-(pyridin-2-ylmethoxy)benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 670206782-[(4-Nitro-2-vinylphenoxy)methyl]pyridineYield 37.3%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolventHCID 31374DimethylacetamideSolvent

Procedure

Methyltriphenylphosphonium bromide (4.97 g, 13.9 mmol) was dissolved in dry THF (30 ml) and a solution of n-BuLi (1.6 M in hexane, 8.69 ml, 13.9 mmol) was added drop-wise. After 15 minutes, 5-nitro-2-(pyridin-2-ylmethoxy)benzaldehyde (3.0 g, 11.6 mmol) dissolved in dry DMA was added. After 1 hour, the reaction was quenched with saturated sodium bicarbonate and the mixture was extracted with ethyl acetate. After evaporation, the crude material was purified on silica gel (20% EtOAc/petroleum ether) to give 2-[(4-nitro-2-vinylphenoxy)methyl]pyridine (1.11 g, 37%); NMR Spectrum: 5.40 (s, 2H), 5.48 (d, 1H), 6.06 (d, 1H), 7.05 (dd, 1H), 7.34 (d, 1H), 7.38 (dd, 1H), 7.55 (d, 1H), 7.87 (t, 1H), 8.18 (dd, 1H), 8.37 (d, 1H), 8.60 (d, 1H); Mass Spectrum: 257 (MH+).

Workup

  1. additionwas added
  2. waitAfter 1 hour
  3. customthe reaction was quenched with saturated sodium bicarbonate
  4. extractionthe mixture was extracted with ethyl acetate
  5. customAfter evaporation
  6. customthe crude material was purified on silica gel (20% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-4e72a687233b4f16b7504857d5f69372
Source dataset
uspto-grants-2011_05
Patent number
US07947676B2

Reaction notes

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