Water → 1-[6-amino-4-oxo-3-(2-trimethylsilanyl-ethoxymethyl)-3,4-dihydro-quinazolin-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester

HRID 1428873ノート

反応式

HRID 1428873 の反応式
[Cl-].[NH4+].O.[CH2:4]([O:6][C:7]([C:9]1[CH:10]=[N:11][N:12]([C:14]2[N:23]([CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])[C:22](=[O:32])[C:21]3[C:16](=[CH:17][CH:18]=[C:19]([N+:33]([O-])=O)[CH:20]=3)[N:15]=2)[CH:13]=1)=[O:8])[CH3:5]>CC(C)=O.[Zn]>[CH2:4]([O:6][C:7]([C:9]1[CH:10]=[N:11][N:12]([C:14]2[N:23]([CH2:24][O:25][CH2:26][CH2:27][Si:28]([CH3:31])([CH3:30])[CH3:29])[C:22](=[O:32])[C:21]3[C:16](=[CH:17][CH:18]=[C:19]([NH2:33])[CH:20]=3)[N:15]=2)[CH:13]=1)=[O:8])[CH3:5]

参加物

6

反応物 3

HCID 962WaterHCID 25517Ammonium ChlorideHCID 684879631-[6-nitro-4-oxo-3-(2-trimethylsilanyl-ethoxymethyl)-3,4-dihydro-quinazolin-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester

生成物 1

HCID 684879131-[6-amino-4-oxo-3-(2-trimethylsilanyl-ethoxymethyl)-3,4-dihydro-quinazolin-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester収率 89.5%

試薬・触媒・溶媒 2

HCID 23994Zinc触媒HCID 180Acetone溶媒

実験手順

Ammonium chloride (4.10 g, 76.6 mmol) and water (9.1 mL) were added to a solution of 1-[6-nitro-4-oxo-3-(2-trimethylsilanyl-ethoxymethyl)-3,4-dihydro-quinazolin-2-yl]-1H-pyrazole-4-carboxylic acid ethyl ester (5.92 g, 85% pure, 10.9 mmol) in acetone (46 mL). Zinc dust (5.01 g, 76.6 mmol) was then added in portions with vigorous stirring. Stirring was continued for 45 min, at which point the reaction mixture was filtered through diatomaceous earth. The filter cake was rinsed thoroughly with EtOAc (100 mL). The filtrate was concentrated and the residue was dissolved in EtOAc (75 mL), decanting from the remaining salts. The organic layer was washed with brine (45 mL), dried (MgSO4), and concentrated. The residue was purified by FCC (2-70% EtOAc/hexanes) to yield the titled compound (4.19 g, 89% yield). MS (ESI/Cl): mass calcd. for C20H27N5O4Si, 430.2; m/z found, 429.2 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.56 (d, J=0.6 Hz, 1H), 8.15 (d, J=0.6 Hz, 1H), 7.53 (d, J=8.6 Hz, 1H), 7.49 (d, J=2.6 Hz, 1H), 7.13 (dd, J=8.6, 2.8 Hz, 1H), 5.78 (s, 2H), 4.35 (q, J=7.1 Hz, 2H), 4.09 (s, 2H), 3.57-3.43 (m, 2H), 1.37 (t, J=7.1 Hz, 3H), 0.86-0.74 (m, 2H), -0.08 (s, 9H).

後処理

  1. filtrationwas filtered through diatomaceous earth
  2. washThe filter cake was rinsed thoroughly with EtOAc (100 mL)
  3. concentrationThe filtrate was concentrated
  4. dissolutionthe residue was dissolved in EtOAc (75 mL)
  5. customdecanting from the remaining salts
  6. washThe organic layer was washed with brine (45 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customThe residue was purified by FCC (2-70% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-1227b33f2614497f8d1811f368052f35
出典データセット
uspto-grants-2015_01
特許番号
US08937078B2

反応ノート

読み込み中…