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

HRID 1505238노트

반응식

HRID 1505238 반응식
[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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 21881883Oxolane--water (1/1)용매

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온도
50 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-77a0e418616143299f8a38005119bced
출처 데이터셋
uspto-grants-2015_12
특허 번호
US09216973B2

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