Ethyl Acetate → 1-Nitroso-4-propylbenzene

HRID 522518Notes

Reaction equation

HRID 522518 reaction equation
[CH2:1]([C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[CH:6][CH:5]=1)[CH2:2][CH3:3].[OH:11]OS([O-])=O.[K+].C(OCC)(=O)C>ClCCl.O>[N:8]([C:7]1[CH:9]=[CH:10][C:4]([CH2:1][CH2:2][CH3:3])=[CH:5][CH:6]=1)=[O:11]

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 759084-PropylanilineHCID 23707502Potassium hydroxy sulfite

Product 1

HCID 136411781-Nitroso-4-propylbenzene

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 4-propylaniline (541 μl, 3.7 mmol) in dichloromethane (12.5 ml) was added a solution of oxone (4.55 g, 7.4 mmol) in H2O (50 ml). The biphasic mixture was stirred vigorously under nitrogen for 1 h, at which time the color had become deep aqua green and the reaction was judged as complete by TLC (1:1 hexanes:ethyl acetate; Rf=0.83). The mixture was transferred to a separatory funnel and the organic layer was removed. The aqueous layer was extracted twice with dichloromethane (20 ml). The combined organics were subsequently washed with 20 ml each of 1M HCl, sat. NaHCO3, H2O, and brine and then dried over Na2SO4, filtered and removed of solvent in vacuo to provide nitrosyl-4-propylbenzene as a green oil. The crude product was immediately dissolved in glacial acetic acid (30 ml) and stirred under nitrogen, followed by the addition of 1,4-diaminobenzene (400 mg, 3.7 mmol) in dry DMSO (10 ml). The reaction was allowed to stir for 48 hrs, during which time the color turned orange-brown. The mixture was transferred to a separatory funnel containing 100 ml brine and extracted five times with ethyl acetate (50 ml). The combined organics were then washed with dilute NaCl (50 ml) six times to remove the DMSO and then dried of Na2SO4, filtered removed of solvent in vacuo. Silica gel chromatography through a wide column (40% ethyl acetate in hexanes) provided S6 as an orange solid (432 mg, 1.8 mmol, 49% yield): 1H (MeOD, 500 MHz): 0.95 (t, 3H, J=7.5); 1.66 (q, 2H, J=7.5); 2.62 (t, 2H, J=7.5); 6.74 (d, 2H, J=8.5); 7.26 (d, 2H, J=8) 7.70 (d, 4H, J=8.5). 13C (MeOD, 125 MHz): 12.7, 24.2, 37.4, 113.8, 121.7, 124.6, 128.7, 144.3, 144.4, 151.2, 151.8. HRMS (FAB+): calc'd for C15H18N3+—240.1495. found—240.1500 (MH+).

Workup

  1. customThe mixture was transferred to a separatory funnel
  2. customthe organic layer was removed
  3. extractionThe aqueous layer was extracted twice with dichloromethane (20 ml)
  4. washThe combined organics were subsequently washed with 20 ml each of 1M HCl, sat. NaHCO3, H2O, and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customremoved of solvent in vacuo

Sources & evidence

ORD record
ord-7e052487552b442f824e74695cfb5723
Source dataset
uspto-grants-2016_05
Patent number
US09334231B2

Reaction notes

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