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

HRID 1169701Notes

Reaction equation

HRID 1169701 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) 1.8-1.85 (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-afcafc2f33574f0ea765659bf2794d97
Source dataset
uspto-grants-2010_11
Patent number
US07825137B2

Reaction notes

Loading…