2,3,5,6-Tetrabromo-4-methyl-4-nitro-2,5-cyclohexadien-1-one → 7-amino-9a-butyl-6-fluoro-4-methyl-8-nitro-1,2,9,9a-tetrahydro-3H-fluoren-3-one

HRID 1372515Notes

Reaction equation

HRID 1372515 reaction equation
[NH2:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[C:11]([CH2:15][CH2:16][CH2:17][CH3:18])([CH2:12]2)[CH2:10][CH2:9][C:8](=[O:19])[C:7]=3[CH3:20])=[CH:4][C:3]=1[F:21].BrC1C(=O)C(Br)=C(Br)C(C)([N+:30]([O-:32])=[O:31])C=1Br>FC(F)(F)C(O)=O.CCOC(C)=O>[NH2:1][C:2]1[C:14]([N+:30]([O-:32])=[O:31])=[C:13]2[C:5]([C:6]3[C:11]([CH2:15][CH2:16][CH2:17][CH3:18])([CH2:12]2)[CH2:10][CH2:9][C:8](=[O:19])[C:7]=3[CH3:20])=[CH:4][C:3]=1[F:21]

Participants

5

Reactant 2

HCID 27245472,3,5,6-Tetrabromo-4-methyl-4-nitro-2,5-cyclohexadien-1-oneHCID 98355697-amino-9a-butyl-6-fluoro-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one

Product 1

HCID 99236627-amino-9a-butyl-6-fluoro-4-methyl-8-nitro-1,2,9,9a-tetrahydro-3H-fluoren-3-one

Reagents, catalysts & solvents 2

HCID 6422Trifluoroacetic acidSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 7-amino-9a-butyl-6-fluoro-4-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (243 mg, 0.845 mmol) in trifluoroacetic acid (1.7 mL) was treated with 2,3,5,6-tetrabromo-4-methyl-4-nitro-2,5-cyclohexadien-1-one (396 mg, 0.845 mmol). The resulting mixture was placed under a N2 atmosphere, sonicated briefly, and stirred at room temperature for 3 hours. The mixture was diluted with EtOAc (50 mL), washed successively with water, 5% NaHCO3 and brine, dried over MgSO4, filtered, and evaporated under vacuum to a brown oil (659 mg). The crude product was purified by flash chromatography on a Biotage 40S KP-Sil column, eluting with 10:1 hexanes-EtOAc. The product containing fractions were evaporated under vacuum to an orange gum (113 mg, 40%) which was lyophilized from benzene to provide 7-amino-9a-butyl-6-fluoro-4-methyl-8-nitro-1,2,9,9a-tetrahydro-3H-fluoren-3-one as an amorphous solid.

Workup

  1. customsonicated briefly
  2. washwashed successively with water, 5% NaHCO3 and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customevaporated under vacuum to a brown oil (659 mg)
  6. customThe crude product was purified by flash chromatography on a Biotage 40S KP-Sil column
  7. washeluting with 10:1 hexanes-EtOAc
  8. additionThe product containing fractions
  9. customwere evaporated under vacuum to an orange gum (113 mg, 40%) which

Sources & evidence

ORD record
ord-4c66fc401a2d4ecda4e87f89e776a331
Source dataset
uspto-grants-2007_01
Patent number
US07157604B2

Reaction notes

Loading…