Nitric Acid → 5,6-Dihydro-6-hydroxy-5,5-dimethyl-2-nitro-7-(4-nitrobenzamido)-7H-thieno[3,2-b]pyran

HRID 257213노트

반응식

HRID 257213 반응식
[OH:1][CH:2]1[C:7]([CH3:9])([CH3:8])[O:6][C:5]2[CH:10]=[CH:11][S:12][C:4]=2[CH:3]1[NH:13][C:14](=[O:24])[C:15]1[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=1.[N+:25]([O-])([OH:27])=[O:26].[K+].[Br-]>C(O)(=O)C>[OH:1][CH:2]1[C:7]([CH3:8])([CH3:9])[O:6][C:5]2[CH:10]=[C:11]([N+:25]([O-:27])=[O:26])[S:12][C:4]=2[CH:3]1[NH:13][C:14](=[O:24])[C:15]1[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=1

참가 물질

5

반응물 3

HCID 944Nitric AcidHCID 253877Potassium BromideHCID 149864905,6-Dihydro-6-hydroxy-5,5-dimethyl-7-(4-nitrobenzamido)-7H-thieno[3,2-b]pyran

생성물 1

HCID 149865005,6-Dihydro-6-hydroxy-5,5-dimethyl-2-nitro-7-(4-nitrobenzamido)-7H-thieno[3,2-b]pyran

시약·촉매·용매 1

HCID 176Acetic Acid용매

실험 절차

5,6-Dihydro-6-hydroxy-5,5-dimethyl-7-(4-nitrobenzamido)-7H-thieno[3,2-b]pyran (1.5 g, 4.30 mmol) was treated with 90% nitric acid (2.5 mL, 53.5 mmol) in acetic acid (25 mL) and stirred at 15°-20° C. for 0.5 h. The resultant solution was poured into ice water 100 mL and extracted with 10% isopropanol in dichloromethane. The dichloromethane solution was washed with saturated aqueous sodium bicarbonate and dried over magnesium sulfate. The solvent was evaporated in vacuo and the residue was purified by medium pressure chromatography using 2% methanol in dichloromethane as the eluant, to give the product, 0.489 g (29%), as a yellow solid: mp 221°-225° C. dec; IR (KBr): 3345, 1647 and 1602 cm-1 ; MS: m/z 394 (MH+); 1H NMR (DMSO-d6): δ 1.26 (s, 3H), 1.45 (s, 3H), 3.90 (dd, J= 8.8 Hz and J=5.9 Hz, 1H, simplifies to d, J=8.8 Hz with D2O), 4.98 (dd, J=7.6 Hz and J=8.8 Hz, 1H, simplifies to d, J=8.8 Hz with D2O), 6.01 (d, J=5.9 Hz, 1H exchanges with D2O), 7.75 (s, 1H), 8.14 (d, J=8.8 Hz, 2H) 8.37 (d, J=8.8 Hz, 2H) and 9.38 (d, J=7.6 Hz, 1H, exchanges with D2O).

후처리

  1. extractionextracted with 10% isopropanol in dichloromethane
  2. washThe dichloromethane solution was washed with saturated aqueous sodium bicarbonate
  3. dry with materialdried over magnesium sulfate
  4. customThe solvent was evaporated in vacuo
  5. customthe residue was purified by medium pressure chromatography
  6. customto give the product, 0.489 g (29%)

출처 및 근거

ORD 기록
ord-19b9871e406548b1af89efd31b3d22f2
출처 데이터셋
uspto-grants-1993_11
특허 번호
US05260453

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