Nitric Acid → ethyl (7-hydroxy-8-nitro-1,1-dioxido-4H-1,2,4-benzothiadiazin-3-yl)acetate

HRID 601336ノート

反応式

HRID 601336 の反応式
[OH:1][C:2]1[CH:19]=[CH:18][C:5]2[NH:6][C:7]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N:8][S:9](=[O:11])(=[O:10])[C:4]=2[CH:3]=1.[N+:20]([O-])([OH:22])=[O:21].[N+]([O-])(O)=O.C(O)(=O)C>C(O)(=O)C.O>[OH:1][C:2]1[CH:19]=[CH:18][C:5]2[NH:6][C:7]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N:8][S:9](=[O:11])(=[O:10])[C:4]=2[C:3]=1[N+:20]([O-:22])=[O:21]

参加物

6

反応物 3

HCID 944Nitric AcidHCID 46942308Ethyl (7-hydroxy-1,1-dioxido-4H-1,2,4-benzothiadiazin-3-yl)acetateHCID 86584207Acetic acid nitric acid

生成物 1

HCID 86594015ethyl (7-hydroxy-8-nitro-1,1-dioxido-4H-1,2,4-benzothiadiazin-3-yl)acetate収率 41%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒2 回HCID 962Water溶媒

実験手順

A suspension of the product of Example 352C (100 mg, 0.352 mmol) in glacial acetic acid (3 mL) was treated at room temperature with a solution of concentrated nitric acid in glacial acetic acid (1.43 M, 0.305 mL, 0.436 mmol) and stirred at this temperature for 19 hours. Added additional 1.43 M nitric acid/acetic acid (0.020 mL, 0.029 mmol) and let stir for 1.5 hours. The reaction was diluted with water (30 mL) and extracted with ethyl acetate (2×50 mL). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel eluting with 8% methanol/dichloromethane to give the title compound as a light yellow solid (47 mg, 41%). MS (ESI−) m/z 328 (M−H)−. 1H NMR (300 MHz, PYRIDINE-d5) δ 0.98 (t, J=7.17 Hz, 3 H) 3.86 (s, 2 H) 4.01 (q, J=7.23 Hz, 2 H) 7.11 (d, J=8.82 Hz, 1 H) 7.22 (d, J=8.82 Hz, 1 H).

後処理

  1. stirringlet stir for 1.5 hours
  2. extractionextracted with ethyl acetate (2×50 mL)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel eluting with 8% methanol/dichloromethane

出典と根拠

ORDレコード
ord-cc58910d51e0423fb046a5285055f6a0
出典データセット
uspto-grants-2011_03
特許番号
US07902203B2

反応ノート

読み込み中…