Hydrochloric Acid → 2-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate

HRID 879267Notes

Reaction equation

HRID 879267 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:11])[C:3]=1[OH:12].CCN(CC)CC.[O:20](S(C(F)(F)F)(=O)=O)[S:21]([C:24]([F:27])([F:26])[F:25])(=O)=[O:22].Cl>C(Cl)Cl>[F:25][C:24]([F:27])([F:26])[S:21]([O:12][C:3]1[C:4]([CH3:11])=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[Br:1])(=[O:22])=[O:20]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 67749Trifluoromethanesulfonic anhydrideHCID 203754122-Bromo-6-methyl-4-nitrophenol

Product 1

HCID 866997872-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonateYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-70 °C

Procedure

To a solution of 2-bromo-6-methyl-4-nitrophenol (110.0 g, 0.474 mol) in DCM (950 mL) at −70° C. was added Et3N (62.3 g, 0.616 mol) and Tf2O (147.1 g, 0.521 mol). The resulting solution was stirred at −70° C. for 20 min. TLC showed the reaction was complete. Aqueous HCl (0.5 M, 1 L) was added to quench the reaction. The DCM layers were separated, dried over anhydrous Na2SO4, filtered, concentrated in vacuo and purified by silica gel column (Petroleum Ether→Petroleum Ether:EtOAc (20:1)) to afford desired 2-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate (146.7 g, 85%) as yellow solid. 1H-NMR: 400 MHz, (CDCl3) δ: 8.41 (d, J=2.0 Hz, 1H), 8.16 (d, J=2.8 Hz, 1H), 2.59 (s, 3H).

Workup

  1. customto quench
  2. customthe reaction
  3. customThe DCM layers were separated
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. custompurified by silica gel column (Petroleum Ether→Petroleum Ether:EtOAc (20:1))

Sources & evidence

ORD record
ord-26f825af12814bed84002ab7f91fbe4e
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

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