Ethanol → ethyl 6-[(hydroxyimino)methyl]-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

HRID 722307ノート

反応式

HRID 722307 の反応式
Cl.[NH2:2][OH:3].[CH:4]([C:6]1[CH:7]=[CH:8][C:9]2[O:14][CH:13]([C:15]([F:18])([F:17])[F:16])[C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][C:10]=2[CH:24]=1)=O.C([O-])(=O)C.[Na+].C(O)C>O.C(OCC)C>[OH:3][N:2]=[CH:4][C:6]1[CH:7]=[CH:8][C:9]2[O:14][CH:13]([C:15]([F:18])([F:17])[F:16])[C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][C:10]=2[CH:24]=1

参加物

7

反応物 4

HCID 702EthanolHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 21883688ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

生成物 1

HCID 73852042ethyl 6-[(hydroxyimino)methyl]-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate収率 55%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 3283Diethyl Ether溶媒

実験手順

A 50 mL round bottom flask was charged with hydroxylamine HCl (0.255 g, 3.67 mmol), ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate (Example 75, Step 1) (1.00 g, 3.34 mmol), sodium acetate (0.301 g, 3.67 mmol), ethanol (10 mL), and H2O (2 mL). The reaction was stirred at room temperature for 18 hours, then diluted with H2O and diethyl ether. The layers were separated and the organic phase washed with H2O, brine, dried over MgSO4, filtered, and concentrated in vacuo yielding an orange semi-crystalline mass. Recrystallization of this solid from hot ethyl acetate and isooctane yielded the oxime (0.578 g, 55%): mp 113.0–116.2° C. 1H NMR (acetone-d6/300 MHz) 10.46 (s, ca.1 exch.), 8.11 (s, 2H), 7.92 (s, 1H), 7.72 (d, 1H, J=2 Hz)), 7.68 (dd, 1H, J=8.5, 2.0 Hz), 7.07 (d, 1H, J=8.5 Hz), 5.89 (q, 1H, J=7.1 Hz), 4.43−4.22 (m, 2H), 1.34 9t, 3H, J=7.3 Hz). FABLRMS m/z 316 (M+H). EIHRMS m/z 315.0719 (M+, Calc'd 315.0733). Anal. Calc'd for C14H12F3N1O4: C, 53.34; H, 3.84; N 4.44. Found: C, 53.85; H, 3.90; N, 4.19.

後処理

  1. customThe layers were separated
  2. washthe organic phase washed with H2O, brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customyielding an orange semi-crystalline mass
  7. customRecrystallization of this solid from hot ethyl acetate and isooctane

出典と根拠

ORDレコード
ord-54ba110f70484f6aa98b3300006c61d5
出典データセット
uspto-grants-2006_11
特許番号
US07138411B2

反応ノート

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