Triphenylphosphine → 3-(2,6-Dichloro-3-fluoro-benzyloxy)-2-nitro-pyridine

HRID 1766730Notes

Reaction equation

HRID 1766730 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.[Cl:32][C:33]1[C:38]([F:39])=[CH:37][CH:36]=[C:35]([Cl:40])[C:34]=1[CH:41]([OH:43])C.O[C:45]1[C:46]([N+:51]([O-:53])=[O:52])=[N:47][CH:48]=[CH:49][CH:50]=1>C1(C)C=CC=CC=1.C1COCC1>[Cl:32][C:33]1[C:38]([F:39])=[CH:37][CH:36]=[C:35]([Cl:40])[C:34]=1[CH2:41][O:43][C:45]1[C:46]([N+:51]([O-:53])=[O:52])=[N:47][CH:48]=[CH:49][CH:50]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 270573-Hydroxy-2-nitropyridineHCID 5462977Diethyl azodicarboxylateHCID 167700681-(2,6-Dichloro-3-fluorophenyl)ethan-1-ol

Product 1

HCID 211113993-(2,6-Dichloro-3-fluoro-benzyloxy)-2-nitro-pyridineYield 100%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of triphenyl phosphine (8.2 g, 0.03 mol) and DEAD (13.65 mL of a 40% solution in toluene) in THF (200 mL) at 0° C. was added a solution of 1-(2,6-dichloro-3-fluoro-phenyl)-ethanol (4.55 g, 0.021 mol) and 3-hydroxy-nitropyridine (3.35 g, 0.023 mol) in THF (200 mL). The resulting bright orange solution was stirred under a nitrogen atmosphere at ambient temperature for 4 hours at which point all starting materials had been consumed. The solvent was removed, and the crude material was dry loaded onto silica gel, and eluted with ethyl acetate-hexanes (20:80) to yield 3-(2,6-dichloro-3-fluoro-benzyloxy)-2-nitro-pyridine (6.21 g, 0.021 mol, 98%) as a pink solid. 1H NMR (CDCl3, 300 MHz) δ1.8–1.85 (d, 3H), 6.0–6.15 (q, 1H), 7.0–7.1 (t, 1H), 7.2–7.21 (d, 1H), 7.25–7.5 (m, 2H), 8.0–8.05 (d, 1H).

Workup

  1. customhad been consumed
  2. customThe solvent was removed
  3. dry with materialthe crude material was dry
  4. washeluted with ethyl acetate-hexanes (20:80)

Sources & evidence

ORD record
ord-6bc00f98d9d7489ca20fd86c1fbbd938
Source dataset
uspto-grants-2007_06
Patent number
US07230098B2

Reaction notes

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