Isopropanol → 2-Fluoro-4-isopropoxy-1-nitrobenzene

HRID 2064075Notes

Reaction equation

HRID 2064075 reaction equation
[F:1][C:2]1[C:3]([N+:9]([O-:11])=[O:10])=[CH:4][CH:5]=[C:6]([OH:8])[CH:7]=1.[CH3:12][CH:13](O)[CH3:14].C1(P(C2C=CC=CC=2)C2C=CC=CN=2)C=CC=CC=1.N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O.Cl.C(OCC)C>O1CCCC1>[F:1][C:2]1[CH:7]=[C:6]([O:8][CH:13]([CH3:14])[CH3:12])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10]

Participants

7

Reactant 5

HCID 3776IsopropanolHCID 97268Di-tert-butyl azodicarboxylateHCID 5209483-Fluoro-4-nitrophenolHCID 6218932-PyridyldiphenylphosphineHCID 10953452Ether hydrochloride

Product 1

HCID 135386522-Fluoro-4-isopropoxy-1-nitrobenzeneYield 69.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 5-fluoro-4-nitrophenol (314 mg, 2.0 mmol), propan-2-ol (120 mg, 2.0 mmol), diphenyl-2-pyridylphosphine (789 mg, 3.0 mmol) and di-tert-butyl azodicarboxylate (691 mg, 3.0 mmol) in tetrahydrofuran (15 ml) was stirred at room temperature under argon for 22 hrs. The mixture was treated with 1M HCl/diethyl ether (15 ml) and stirred at room temperature for 2 hrs, then concentrated under vacuum and the residue dissolved in diethyl ether (10 ml), treated with 5M HCl acid and stirred for 2 hrs. The organic layer was separated, washed with 5M HCl acid (15 ml), then 10% Na2CO3 solution (2×10 ml), dried (MgSO4) and concentrated under vacuum. The residue was purified by chromatography on silica gel eluting with 5-70% ethyl acetate/60-80 petrol ether to afford the title compound as a yellow oil (276 mg, 69%).

Workup

  1. stirringstirred at room temperature for 2 hrs
  2. concentrationconcentrated under vacuum
  3. dissolutionthe residue dissolved in diethyl ether (10 ml)
  4. additiontreated with 5M HCl acid
  5. stirringstirred for 2 hrs
  6. customThe organic layer was separated
  7. washwashed with 5M HCl acid (15 ml)
  8. dry with material10% Na2CO3 solution (2×10 ml), dried (MgSO4)
  9. concentrationconcentrated under vacuum
  10. customThe residue was purified by chromatography on silica gel eluting with 5-70% ethyl acetate/60-80 petrol ether

Sources & evidence

ORD record
ord-a4066224525d4eabbcd421d089daec3a
Source dataset
uspto-grants-2012_10
Patent number
US08288413B2

Reaction notes

Loading…