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

HRID 1505238ノート

反応式

HRID 1505238 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 4.2) (1.57 g) in tetrahydrofuran/water (3:1) (20 ml) was added sodium acetate (0.67 g) and N-methyl-hydroxylamine 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-77a0e418616143299f8a38005119bced
出典データセット
uspto-grants-2015_12
特許番号
US09216973B2

反応ノート

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