Dimethyl Sulfate → 2-[1-(Methanesulfonyl)ethyl]-6-(trifluoromethyl)aniline

HRID 325531Notes

Reaction equation

HRID 325531 reaction equation
[OH-].[Na+].COS(OC)(=O)=O.CS(CC1C=CC=C(C(F)(F)F)C=1[N+]([O-])=O)(=O)=O.[CH3:28][S:29]([CH:32]([C:34]1[CH:39]=[CH:38][CH:37]=[C:36]([C:40]([F:43])([F:42])[F:41])[C:35]=1[N+:44]([O-])=O)[CH3:33])(=[O:31])=[O:30]>[Cl-].C([N+](CC)(CC)CC1C=CC=CC=1)C.C(O)(=O)C.[Pd].[C].CCOC(C)=O.CCO.C(Cl)Cl>[CH3:28][S:29]([CH:32]([C:34]1[CH:39]=[CH:38][CH:37]=[C:36]([C:40]([F:41])([F:43])[F:42])[C:35]=1[NH2:44])[CH3:33])(=[O:31])=[O:30]

Participants

10

Reactant 4

HCID 6497Dimethyl SulfateHCID 14798Sodium HydroxideHCID 133182271-[(Methanesulfonyl)methyl]-2-nitro-3-(trifluoromethyl)benzeneHCID 13318228HCID 13318228, compound

Product 1

HCID 133182292-[1-(Methanesulfonyl)ethyl]-6-(trifluoromethyl)anilineYield 62.8%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidCatalystHCID 66133Benzyl triethylammonium chlorideCatalystHCID 178418390HCID 178418390, compoundCatalystHCID 6344DichloromethaneSolventHCID 21584252Ethanol ethylacetateSolvent

Procedure

A mixture of 50% NaOH (50 mL), CH2Cl2 (50 mL), triethylbenzylammonium chloride (30 mg), Me2SO4 (2.50 mL, 26.41 mmol) and 2-methylsulfonylmethyl-6-trifluoromethyl nitrobenzene 3 (6.8 g, 24.01 mmol) was stirred rapidly for 30 min. The mixture was poured onto ice/water (400 mL) and the organic layer separated. The solvent was removed and excess Me2SO4 removed at 60° C. and 0.7 mm, to give a yellow solid which was identified as the same product as in Example 2, i.e., 2-(1-methylsulfonylethyl)-6-trifluoromethyl nitrobenzene. The solid was transferred to a Parr bomb with EtOAc/EtOH (2:1, 100 mL, not all soluble). Five drops of acetic acid and Pd/carbon was added. The mixture was hydrogenated at 60° C. and 60 psi H2 for 15 hrs. The mixture was filtered and the solvent removed to give a brown solid. Washing with ether gave 4.03 g (15.07 mmol, 62.8%) of 2-(1-methylsulfonylethyl)-6-trifluoromethyl aniline as a white solid, mp 153°-5° C.

Workup

  1. additionThe mixture was poured onto ice/water (400 mL)
  2. customthe organic layer separated
  3. customThe solvent was removed
  4. customexcess Me2SO4 removed at 60° C.
  5. custom0.7 mm, to give a yellow solid which
  6. customwas hydrogenated at 60° C.
  7. wait60 psi H2 for 15 hrs
  8. filtrationThe mixture was filtered
  9. customthe solvent removed
  10. customto give a brown solid
  11. washWashing with ether

Sources & evidence

ORD record
ord-fa4b1b4b9c894fba9be2a69b46fe0c8d
Source dataset
uspto-grants-1984_04
Patent number
US04440964

Reaction notes

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