N,N-Dimethylethylenediamine → N1,N1-Dimethyl-N2-(1-oxido-8,9-dihydro-7H-indeno[5,4-e][1,2,4]triazin-3-yl)-1,2-ethanediamine

HRID 1668999Notes

Reaction equation

HRID 1668999 reaction equation
[CH3:1][N:2]([CH3:6])[CH2:3][CH2:4][NH2:5].Cl[C:8]1[N:9]=[N+:10]([O-:21])[C:11]2[C:20]3[CH2:19][CH2:18][CH2:17][C:16]=3[CH:15]=[CH:14][C:12]=2[N:13]=1>COCCOC>[CH3:1][N:2]([CH3:6])[CH2:3][CH2:4][NH:5][C:8]1[N:9]=[N+:10]([O-:21])[C:11]2[C:20]3[CH2:19][CH2:18][CH2:17][C:16]=3[CH:15]=[CH:14][C:12]=2[N:13]=1

Participants

4

Reactant 2

HCID 66053N,N-DimethylethylenediamineHCID 119505673-Chloro-8,9-dihydro-7H-indeno[5,4-e][1,2,4]triazine 1-Oxide

Product 1

HCID 11950568N1,N1-Dimethyl-N2-(1-oxido-8,9-dihydro-7H-indeno[5,4-e][1,2,4]triazin-3-yl)-1,2-ethanediamineYield 91.9%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

N,N-Dimethyl-1,2-ethanediamine (0.28 mL, 2.5 mmol) was added to a stirred solution of chloride 5 (187 mg, 0.8 mmol) in DME (30 mL), and the solution stirred at reflux temperature for 2 h. The solvent was evaporated and the residue was partitioned between DCM (100 mL) and dilute aqueous NH3 solution (50 mL). The 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 1-oxide 6 (201 mg, 88%) as a pale yellow solid: mp (MeOH/EtOAc) 186-190° C.; 1H NMR δ 7.54 (d, J=8.4 Hz, 1H, H-6), 7.37 (d, J=8.4 Hz, 1H, H-5), 5.80 (br s, 1H, NH), 3.63 (br t, J=7.3 Hz, 2H, H-9), 3.52-3.57 (m, 2H, CH2N), 2.96 (br t, J=7 Hz, 2H, H-7), 2.57 (t, J=6.0 Hz, 2H, CH2N), 2.29 [s, 6H, N(CH3)2], 2.12-2.21 (m, 2H, H-8); 13C NMR δ 158.5, 149.0, 142.0, 137.3, 132.2, 129.2, 124.7, 57.6, 45.0 (2), 38.7, 35.3, 32.9, 24.8. Anal. calcd for C14H19N5O.¼H2O: C, 60.5; H, 7.1; N, 25.2. Found: C, 60.6; H, 6.6; N, 25.4%.

Workup

  1. temperatureat reflux temperature for 2 h
  2. customThe solvent was evaporated
  3. customthe residue was partitioned between DCM (100 mL) and dilute aqueous NH3 solution (50 mL)
  4. customThe organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-bef3954e30e747e1a1aa10858942cf9d
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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