Methanol → HCID 135899513, compound

HRID 1669140Notes

Reaction equation

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

Participants

Reactant 2

HCID 887Methanol

HCID 25140757HCID 25140757, compound

Product 1

HCID 135899513HCID 135899513, compound

Procedure

H2O2 (70%, 0.31 mL, ca. 6.2 mmol) was added dropwise to a stirred solution of TFAA (0.9 mL, 6.2 mmol) in DCM (10 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 188 (186 mg, 0.6 mmol) and TFA (0.24 mL, 3.1 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 20° C. for 16 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with CHCl3 (4×50 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 188 (43 mg, 23%) and (ii) 1,4-dioxide 189 (82 mg, 42%) as a red solid: mp (MeOH) 131-133° C.; 1H NMR δ 8.03 (s, 1H, H-11), 7.99 (s, 1H, H-5), 7.36 (br s, 1H, NH), 3.63 (br t, J=6.0 Hz, 2H, CH2N), 2.98-3.03 (m, 2H, CH2), 2.91-2.95 (m, 2H, CH2), 2.60 (br t, J=6.0 Hz, 2H, CH2N), 2.30 [s, 6H, N(CH3)2], 1.82-1.89 (m, 2H, H-8), 1.68-1.76 (m, 4H, H-7, H-9); 13C NMR δ 154.4, 149.7, 144.7, 137.1, 128.7, 119.8, 115.9, 57.5, 45.2 (2), 38.9, 37.0, 36.2, 31.8, 28.4, 28.2. Anal. calcd for C16H23N5O2.¼CH3OH: C, 60.0; H, 7.4; N, 21.5. Found: C, 59.9; H, 7.0; N, 21.5%.

Sources & evidence

ORD record: ord-6c0e75fb818648d2b352158946bd65bc
Source dataset: uspto-grants-2011_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07989451B2

Reaction notes

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