Triphenylphosphine → 3-(1-(2,6-Dichloro-3-fluorophenyl)ethoxy)-2-nitropyridine

HRID 1845879Notes

Reaction equation

HRID 1845879 reaction equation
[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH:10]([OH:12])[CH3:11].O[C:14]1[C:15]([N+:20]([O-:22])=[O:21])=[N:16][CH:17]=[CH:18][CH:19]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[CH:10]([O:12][C:14]1[C:15]([N+:20]([O-:22])=[O:21])=[N:16][CH:17]=[CH:18][CH:19]=1)[CH3:11]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 270573-Hydroxy-2-nitropyridineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 167700681-(2,6-Dichloro-3-fluorophenyl)ethan-1-ol

Product 1

HCID 469422963-(1-(2,6-Dichloro-3-fluorophenyl)ethoxy)-2-nitropyridineYield 89.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1-(2,6-dichloro-3-fluorophenyl)ethanol (29.1 g, 139 mmol) and 3-hydroxy-2-nitropyridine (24.1 g, 153 mmol) were dissolved in anhydrous tetrahydrofuran (300 mL), and triphenylphosphine (PPh3, 51.1 g, 195 mmol) was added and the mixture was stirred for 1 h at room temperature. At 0° C., to the reaction liquid was added diisopropyl azodicarboxylate (DIAD, 38.4 mL, 195 mmol) dropwise. The resultant mixture was stirred overnight at room temperature. The resultant mixture was evaporated under reduced pressure to remove solvent, then purified via silica gel column chromatography (petroleum ether:ethyl acetate=3:1) to yield the target product as white crystals (41.2 g, 124 mmol; yield=89%).

Workup

  1. customAt 0° C., to the reaction liquid
  2. customThe resultant mixture was evaporated under reduced pressure
  3. customto remove solvent
  4. custompurified via silica gel column chromatography (petroleum ether:ethyl acetate=3:1)

Sources & evidence

ORD record
ord-1160b45c78014f9d8f2e73309b658bcc
Source dataset
uspto-grants-2015_02
Patent number
US08952002B2

Reaction notes

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