Ammonia → HCID 135899475, compound

HRID 1669153Notes

Reaction equation

HRID 1669153 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][N:17]([CH3:35])[CH2:18][CH2:19][NH:20][C:21]1[N:22]=[N+:23]([O-:34])[C:24]2[CH:30]=[C:29]3[CH2:31][CH2:32][O:33][C:28]3=[CH:27][C:25]=2[N:26]=1.C(O)(C(F)(F)F)=O.N>C(Cl)Cl.C(Cl)(Cl)Cl>[O-:34][N+:23]1[C:24]2[CH:30]=[C:29]3[CH2:31][CH2:32][O:33][C:28]3=[CH:27][C:25]=2[N+:26]([O-:4])=[C:21]([NH:20][CH2:19][CH2:18][N:17]([CH3:35])[CH3:16])[N:22]=1

Participants

8

Reactant 5

HCID 222AmmoniaHCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25140917HCID 25140917, compound

Product 1

HCID 135899475HCID 135899475, compoundYield 53.4%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 0.18 mL, ca. 3.6 mmol) was added dropwise to a stirred solution of TFAA (0.51 mL, 3.6 mmol) in DCM (6 mL) at 0° C. The solution was stirred at 20° C. for 10 min, then cooled to 0° C., added to a solution of 1-oxide 207 (100 mg, 0.36 mmol) and TFA (0.06 mL, 0.78 mmol) in CHCl3 (6 mL) at 0° C. and the solution stirred at 20° C. for 4.5 h. The solution was cooled to 0° C., made basic with dilute aqueous NH3 solution and extracted with CHCl3 (3×10 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (5-16%) of MeOH/DCM to give 1,4-dioxide 208 (56 mg, 53%) as an orange solid: mp 186-189° C.; 1H NMR δ 8.13 (t, J=1.6 Hz, 1H, H-9), 7.48 (br s, 2H, H-5, NH), 4.81 (t, J=8.3 Hz, 2H, H-7), 3.62 (t, J=6.0 Hz, 2H, CH2N), 3.37 (dt, J=8.3, 1.6 Hz, 2H, H-8), 2.62 (t, J=8.3 Hz, 2H, CH2N), 2.30 [s, 6H, N(CH3)2]; 13C NMR δ 167.2, 149.9, 140.6, 132.0, 117.9, 93.8, 87.9, 73.4, 57.5, 45.2 (2), 38.8, 28.5. HRMS (FAB+) calcd for C13H18N5O3 (MH+) m/z 292.1410, found 292.1409.

Workup

  1. temperaturecooled to 0° C.
  2. stirringthe solution stirred at 20° C. for 4.5 h
  3. temperatureThe solution was cooled to 0° C.
  4. extractionextracted with CHCl3 (3×10 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (5-16%) of MeOH/DCM

Sources & evidence

ORD record
ord-535ba9e03a394550963efbce41f0b4e9
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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