7-Methyl-N-[3-(4-morpholinyl)propyl]-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-amine 1-Oxide → 7-Methyl-N-[3-(4-morpholinyl)propyl]-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-amine 1,4-Dioxide

HRID 1669085Notes

Reaction equation

[CH3:1][CH:2]1[CH2:25][C:24]2[C:4](=[CH:5][C:6]3[N+:11]([O-:12])=[N:10][C:9]([NH:13][CH2:14][CH2:15][CH2:16][N:17]4[CH2:22][CH2:21][O:20][CH2:19][CH2:18]4)=[N:8][C:7]=3[CH:23]=2)[CH2:3]1.C[OH:27].C(Cl)Cl>>[CH3:1][CH:2]1[CH2:25][C:24]2[C:4](=[CH:5][C:6]3[N+:11]([O-:12])=[N:10][C:9]([NH:13][CH2:14][CH2:15][CH2:16][N:17]4[CH2:18][CH2:19][O:20][CH2:21][CH2:22]4)=[N+:8]([O-:27])[C:7]=3[CH:23]=2)[CH2:3]1

Participants

Reactant 2

HCID 119521817-Methyl-N-[3-(4-morpholinyl)propyl]-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-amine 1-Oxide

HCID 21226129Dichloromethane methanol

Product 1

HCID 1355265677-Methyl-N-[3-(4-morpholinyl)propyl]-7,8-dihydro-6H-indeno[5,6-e][1,2,4]triazin-3-amine 1,4-Dioxide

Procedure

H2O2 (70%, 0.72 mL, ca. 14.3 mmol) was added dropwise to a stirred solution of TFAA (2.0 mL, 14.3 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 98 (490 mg, 1.4 mmol) and TFA (0.55 mL, 7.1 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 98 (280 mg, 57%) and (ii) 1,4-dioxide 99 (88 mg, 17%) as a red solid: mp (MeOH/DCM) 161-163 DC; 1H NMR δ 8.30 (br s, 1H, NH), 8.08 (br s, 2H, H-5, H-9), 3.82 (br t, J=4.5 Hz, 4H, 2×CH2O), 3.58-3.63 (m, 2H, CH2N), 3.15-3.25 (m, 2H, CH2), 2.61-2.74 (m, 3H, CH, CH2), 2.57 (br t, J=6.1 Hz, 2H, CH2N), 2.47-2.53 (m, 4H, 2×CH2N), 1.83-1.90 (m, 2H, CH2), 1.18 (d, J=6.2 Hz, 3H, CH3); 13C NMR δ 155.2, 149.5, 145.2, 138.1, 129.5, 115.8, 111.7, 66.9 (2), 57.7, 53.8 (2), 41.6, 41.4, 40.4, 34.9, 24.5, 20.2. Anal. calcd for C18H25N5O3: C, 60.2; H, 7.0; N, 19.5. Found: C, 60.6; H, 7.0; N, 18.3%.

Sources & evidence

ORD record: ord-e7c4a692a0ae40d88fa325224fe5b00d
Source dataset: uspto-grants-2011_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07989451B2

Reaction notes

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