Ammonia → N-(6-nitro-2,3-dihydro-1H-inden-5-yl)acetamide

HRID 1669057Notes

Reaction equation

HRID 1669057 reaction equation
[OH:1]O.C(O[C:10]([C:12](F)(F)F)=[O:11])(C(F)(F)F)=O.[N+:16]1([O-:29])[C:21]2[CH:22]=[C:23]3[C:27](=[CH:28][C:20]=2[N:19]=CN=1)[CH2:26][CH2:25][CH2:24]3.N>C(Cl)Cl>[N+:16]([C:21]1[CH:22]=[C:23]2[C:27]([CH2:26][CH2:25][CH2:24]2)=[CH:28][C:20]=1[NH:19][C:10](=[O:11])[CH3:12])([O-:29])=[O:1]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 784Hydrogen PeroxideHCID 9845Trifluoroacetic anhydrideHCID 11951640HCID 11951640, compound

Product 1

HCID 10751392N-(6-nitro-2,3-dihydro-1H-inden-5-yl)acetamide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 1.1 mL, ca. 21 mmol) was added dropwise to a stirred solution of TFAA (3.0 mL, 21 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 0° C. for 5 min, warmed to 20° C. for 10 min, then cooled to 0° C. and added to a solution of 1-oxide 64 (0.40 g, 2.1 mmol) in DCM (20 mL) at 0° C. and the solution was stirred at 20° C. for 4 h. Dilute aqueous NH3 solution (10 mL) was added and the mixture stirred vigorously for 30 min and then extracted with DCM (4×50 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (10-30%) of EtOAc/DCM, to give (i) starting material 64 (68 mg, 17%) and (ii) 1,4-dioxide 65 (213 mg, 49%) as a tan solid: mp (EtOAc/pet. ether) 179-181° C.; 1H NMR δ 8.81 (s, 1H, H-3), 8.31 (s, 1H, H-9), 8.28 (s, 1H, H-5), 3.13-3.22 (m, 4H, H-6, H-8), 2.26 (p, J=7.5 Hz, 2H, H-7); 13C NMR δ 155.2, 152.0, 141.0, 139.1, 134.5, 116.1, 114.1, 33.4, 33.0, 25.5. Anal. calcd for C10H9N3O2: C, 59.1; H, 4.5; N, 20.7. Found: C, 58.9; H, 4.6; N, 20.5%.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringthe solution was stirred at 20° C. for 4 h
  4. stirringthe mixture stirred vigorously for 30 min
  5. extractionextracted with DCM (4×50 mL)
  6. customThe combined organic fraction was dried
  7. customthe solvent evaporated
  8. customThe residue was purified by chromatography
  9. washeluting with a gradient (10-30%) of EtOAc/DCM

Sources & evidence

ORD record
ord-9518f088c97a41079fb5a9a1dd912962
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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