Dimethyl Sulfide → Methyl 2-hydroxy-7-nitro-2,3-dihydrobenzofuran-4-carboxylate

HRID 354052ノート

反応式

HRID 354052 の反応式
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[C:6]([OH:13])[C:5]=1[CH2:14][CH:15]=C.[O:18]=[O+][O-].CSC>ClCCl.CO>[CH3:1][O:2][C:3]([C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[C:6]2[O:13][CH:15]([OH:18])[CH2:14][C:5]=12)=[O:17]

参加物

6

反応物 3

HCID 1068Dimethyl SulfideHCID 24823OzoneHCID 59768300Methyl 2-allyl-3-hydroxy-4-nitro-benzoate

生成物 1

HCID 20738652Methyl 2-hydroxy-7-nitro-2,3-dihydrobenzofuran-4-carboxylate

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
-70 °C

実験手順

Into a solution of 2-allyl-3-hydroxy-4-nitro-benzoic acid methyl ester (6.11 g 25.6 mmol) in dichloromethane (100 mL) and methanol (10 mL) at −78° C. was bubbled with ozone for 40 minutes. After stirring for another 20 min at −70° C., a stream of nitrogen gas was passed through the reaction mixture. Dimethyl sulfide (5 mL, 68.1 mmol) was added at −78° C. The reaction solution was allowed to warm up gradually to room temperature overnight. The reaction mixture was partitioned between dichloromethane and water. The aqueous layer was further extracted twice with dichloromethane. The organic extract was washed with brine, dried (anhydrous sodium sulfate), and concentrated under reduced pressure to give 2-hydroxy-7-nitro-2,3-dihydro-benzofuran-4-carboxylic acid methyl ester as a yellow solid (6.0 g). 1H NMR (CDCl3) δ: 3.51-3.74 (m, 2H), 3.96 (s, 3H), 6.43 (dd, 1H, J=6.4 Hz, 2.6 Hz), 7.63 (d, 1H, J=8.8), 8.01 (d, 1H, J=8.9 Hz).

後処理

  1. temperatureto warm up gradually to room temperature overnight
  2. customThe reaction mixture was partitioned between dichloromethane and water
  3. extractionThe aqueous layer was further extracted twice with dichloromethane
  4. extractionThe organic extract
  5. washwas washed with brine
  6. dry with materialdried (anhydrous sodium sulfate)
  7. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-ea4e5a4680974f7da94754d1a6747285
出典データセット
uspto-grants-2004_06
特許番号
US06756395B2

反応ノート

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