Allyl Alcohol → 2-(Allyloxy)-5-chloro-3-nitropyridine

HRID 1373767Notes

Reaction equation

HRID 1373767 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([OH:8])=[N:6][CH:7]=1.[CH:12]1[CH:17]=CC(COC(/N=N/C(OCC2C=CC=CC=2)=O)=O)=C[CH:13]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(O)C=C>C1COCC1>[CH2:17]([O:8][C:5]1[C:4]([N+:9]([O-:11])=[O:10])=[CH:3][C:2]([Cl:1])=[CH:7][N:6]=1)[CH:12]=[CH2:13]

Participants

6

Reactant 4

HCID 7858Allyl AlcoholHCID 11776TriphenylphosphineHCID 5387121Dibenzyl azodicarboxylateHCID 178526657HCID 178526657, compound

Product 1

HCID 210753722-(Allyloxy)-5-chloro-3-nitropyridineYield 16.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 5-chloro-3-nitro-pyridin-2-ol (0.600 g, 3.4 mmol), DBAD (1.19 g, 5.16 mmol), triphenylphosphine-polymer supported (3 mmol/g, 1.70 g, 5.16 mmol) in THF (18 mL) was added allyl alcohol (0.42 mL, 6.12 mmol). The reaction mixture was stirred at room temperature overnight, filtered through celite, and concentrated. The residue was purified by flash chromatography eluting with hexane/ethyl acetate (95:5 to 1:1) to give 0.120 g (15%) of the desired product. MS (DCI/NH3) m/z: 214.9 (M+H)+; 1H NMR (300 MHz, CDCl3) δ ppm 5.01 (ddd, J=5.34, 1.40, 1.40 Hz, 2 H) 5.32 (dd, J=10.51, 1.36 Hz, 1 H) 5.49 (dd, J=17.12, 1.53 Hz, 1 H) 6.06 (m, 1 H) 8.28 (d, J=2.37 Hz, 1 H) 8.34 (d, J=2.37 Hz, 1 H).

Workup

  1. filtrationfiltered through celite
  2. concentrationconcentrated
  3. customThe residue was purified by flash chromatography
  4. washeluting with hexane/ethyl acetate (95:5 to 1:1)

Sources & evidence

ORD record
ord-0fa675ad2edc4d09a2be2e8ea6a94f23
Source dataset
uspto-grants-2007_01
Patent number
US07163939B2

Reaction notes

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