N-methylhydroxylamine hydrochloride → (4-tert-butoxycarbonyl-3-methyl-benzylidene)-N-methyl-nitrone

HRID 874212ノート

反応式

HRID 874212 の反応式
[C:1]([O:5][C:6](=[O:16])[C:7]1[CH:12]=[CH:11][C:10]([CH:13]=O)=[CH:9][C:8]=1[CH3:15])([CH3:4])([CH3:3])[CH3:2].[C:17]([O-])(=O)C.[Na+].Cl.[CH3:23][NH:24][OH:25]>O1CCCC1.O.C(OCC)(=O)C.O>[C:1]([O:5][C:6]([C:7]1[CH:12]=[CH:11][C:10]([CH:13]=[C:23]=[N+:24]([CH3:17])[O-:25])=[CH:9][C:8]=1[CH3:15])=[O:16])([CH3:4])([CH3:3])[CH3:2]

参加物

7

反応物 3

HCID 77906N-methylhydroxylamine hydrochlorideHCID 517045Sodium AcetateHCID 59563495Tert-butyl 4-formyl-2-methylbenzoate

生成物 1

HCID 86658978(4-tert-butoxycarbonyl-3-methyl-benzylidene)-N-methyl-nitrone収率 76.8%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 21881883Oxolane--water (1/1)溶媒

反応条件

温度
50 °C

実験手順

To a solution of 4-formyl-2-methyl-benzoic acid tert-butyl ester (Example I2) (1.57 g) in tetrahydrofuran/water (3:1) (20 ml) was added sodium acetate (0.67 g) and N-methylhydroxylamine hydrochloride (0.69 g). The reaction mixture was stirred at 50° C. for 15 hours. The reaction mixture was diluted with ethyl acetate and water. The phases were separated and the organic layer was washed with water, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: methanol/ethyl acetate 5:5) to give (4-tert-butoxycarbonyl-3-methyl-benzylidene)-N-methyl-nitrone (1.43 g) as yellow oil. 1H-NMR (CDCl3, 400 MHz): 8.10 (s, 1H), 8.02 (d, 1H), 7.85 (d, 1H), 7.35 (s, 1H), 3.90 (s, 3H), 2.60 (s, 3H).

後処理

  1. customThe phases were separated
  2. washthe organic layer was washed with water
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography on silica gel (eluent: methanol/ethyl acetate 5:5)

出典と根拠

ORDレコード
ord-0d68131f35e145e38c5d1b3c4941ca39
出典データセット
uspto-grants-2015_03
特許番号
US08980892B2

反応ノート

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