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

HRID 1669081Notes

Reaction equation

HRID 1669081 reaction equation
OO.C(O[C:10]([C:12](F)(F)F)=[O:11])(C(F)(F)F)=O.CN(C)CCNC1N=[N+:23]([O-:35])[C:24]2[CH:33]=[C:32]3[C:28]([CH2:29][CH:30](C)[CH2:31]3)=[CH:27][C:25]=2[N:26]=1.C(O)(C(F)(F)F)=[O:38]>C(Cl)Cl.N>[N+:23]([C:24]1[CH:33]=[C:32]2[C:28]([CH2:29][CH2:30][CH2:31]2)=[CH:27][C:25]=1[NH:26][C:10](=[O:11])[CH3:12])([O-:35])=[O:38]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11952179N1,N1-Dimethyl-N2-(7-methyl-1 oxido-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-yl)-1,2-ethanediamine

Product 1

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

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.65 mL, ca. 12.9 mmol) was added dropwise to a stirred solution of TFAA (1.8 mL, 12.9 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 stirred solution of 1-oxide 96 (371 mg, 1.3 mmol) and TFA (0.50 mL, 6.5 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 20° C. for 6 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with CHCl3 (4×30 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-10%) of MeOH/DCM, to give (i) starting material 96 (181 mg, 49%) and (ii) 1,4-dioxide 97 (103 mg, 26%) as a red solid: mp (MeOH/DCM) 149-151° C.; 1H NMR δ 8.09 (s, 1H, H-9), 8.07 (s, 1H, H-5), 7.52 (br s, 1H, NH), 3.58-3.64 (m, 2H, CH2N), 3.14-3.27 (m, 2H, CH2), 2.63-2.75 (m, 3H, CH, CH2), 2.59 (br t, J=6.0 Hz, 2H, CH2), 2.28 [s, 6H, N(CH3)2], 1.18 (d, J=6.2 Hz, 3H, CH3); 13C NMR δ 155.6, 149.4, 145.5, 138.0, 128.9, 115.8, 111.8, 57.4, 45.0 (2), 41.4, 40.4, 38.7, 34.8, 20.1. Anal. calcd for C15H21N5O2.½CH2Cl2: C, 54.6; H, 6.3; N, 19.9. Found: C, 54.4; H, 6.0; N, 19.8%.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° C. for 6 h
  4. extractionextracted with CHCl3 (4×30 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-0176cb7eaa754047a8cc9d388187c127
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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