Diisopropylethylamine → (S)-4-acetyl-3-methyl-7-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-carbonyl chloride

HRID 1485739Notes

Reaction equation

HRID 1485739 reaction equation
ClC(Cl)(OC(=O)[O:6][C:7]([Cl:10])(Cl)Cl)Cl.[CH3:13][C@H:14]1[CH2:23][NH:22][C:21]2[C:16](=[CH:17][CH:18]=[C:19]([C:24]3[CH:25]=[N:26][N:27]([CH:29]4[CH2:32][O:31][CH2:30]4)[CH:28]=3)[CH:20]=2)[N:15]1[C:33](=[O:35])[CH3:34].C(N(CC)C(C)C)(C)C>ClCCCl>[C:33]([N:15]1[C:16]2[C:21](=[CH:20][C:19]([C:24]3[CH:25]=[N:26][N:27]([CH:29]4[CH2:32][O:31][CH2:30]4)[CH:28]=3)=[CH:18][CH:17]=2)[N:22]([C:7]([Cl:10])=[O:6])[CH2:23][C@@H:14]1[CH3:13])(=[O:35])[CH3:34]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 94429TriphosgeneHCID 118079419(S)-1-(2-methyl-6-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxalin-1(2H)-yl)ethanone

Product 1

HCID 118079316(S)-4-acetyl-3-methyl-7-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-carbonyl chlorideYield 67%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

Triphosgene (0.048 g, 0.16 mmol) was added slowly to a solution of (S)-1-(2-methyl-6-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-yl)ethanone (0.050 g, 0.16 mmol) and N,N-diisopropylethylamine (0.413 g, 3.20 mmol) in 1,2-dichloroethane (20 mL) at room temperature. The resulting solution was stirred for 1 hour at room temperature and then concentrated under vacuum. The crude product was purified via preparative thin layer chromatography (eluting with 1:1 petroleum ether:ethyl acetate) to afford (S)-4-acetyl-3-methyl-7-(1-(oxetan-3-yl)-1H-pyrazol-4-yl)-3,4-dihydroquinoxaline-1(2H)-carbonyl chloride (0.040 g, 67%) as a yellow solid. 1H-NMR (300 MHz, CDCl3, ppm): δ 7.92-7.80 (m, 3H), 7.41-7.38 (m, 1H), 7.26-7.23 (m, 1H), 5.55-5.45 (m, 1H), 5.13-5.08 (m, 5H), 4.58-4.53 (m, 1H), 3.33-3.20 (m, 1H), 2.23 (s, 3H), 1.10 (d, J=6.3 Hz, 3H). MS (ESI, pos. ion) m/z 375, 377 [M+H]+.

Workup

  1. concentrationconcentrated under vacuum
  2. customThe crude product was purified via preparative thin layer chromatography (eluting with 1:1 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-2068abdb3006482f928c67dc854d940d
Source dataset
uspto-grants-2016_08
Patent number
US09422281B2

Reaction notes

Loading…