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

HRID 722307노트

반응식

HRID 722307 반응식
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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매2회HCID 3283Diethyl Ether용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-54ba110f70484f6aa98b3300006c61d5
출처 데이터셋
uspto-grants-2006_11
특허 번호
US07138411B2

반응 노트

불러오는 중…