Dimethylformamide → 6-Chloro-5-nitro-1H-isochromen-1-one

HRID 1161185ノート

反応式

HRID 1161185 の反応式
[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[C:3]=1[N+:13]([O-:15])=[O:14].CN(C)C=O.COC(OC)N(C)C.C(OCC)(=O)C>>[Cl:1][C:2]1[C:3]([N+:13]([O-:15])=[O:14])=[C:4]2[C:5](=[CH:10][CH:11]=1)[C:6](=[O:7])[O:8][CH:9]=[CH:12]2

参加物

5

反応物 4

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 78373Dimethylformamide dimethyl acetalHCID 10657064Methyl 4-chloro-2-methyl-3-nitrobenzoate

生成物 1

HCID 595157256-Chloro-5-nitro-1H-isochromen-1-one

反応条件

温度
120 °C

実験手順

A pressure tube was charged with methyl 4-chloro-2-methyl-3-nitrobenzoate (13 g, 57 mmol), N,N-dimethylformamide (10 mL, 200 mmol) and 1,1-dimethoxy-N,N-dimethylmethanamine (26.5 mL, 200 mmol) and the reaction heated to 120° C. for 20 h. The solvents were removed and the resultant brown residue was redissolved in ethyl acetate (600 mL, 6000 mmol) and 130-270 mesh 60A silica gel (500 g, 6000 mmol) was added and the reaction stirred with a mechanical stirrer for 8 h. The silica gel was filtered off, washed with ethyl acetate (400 mL) and the organics were removed under vacuum and the residue purified by flash chromatography (330 g, 2-50% ethyl acetate/hexane) to obtain the two isomers in 14% yields each in almost 98% purity. MS m/z=226.2 (M+H). 1H NMR (400 MHz; DMSO-d6) δ 8.35 (d, J=8.63 Hz, 1H), 7.95 (d, J=8.63 Hz, 1H), 7.76 (d, J=5.91 Hz, 1H), 6.61 (d, J=6.04 Hz, 1H).

後処理

  1. customThe solvents were removed
  2. filtrationThe silica gel was filtered off
  3. washwashed with ethyl acetate (400 mL)
  4. customthe organics were removed under vacuum
  5. customthe residue purified by flash chromatography (330 g, 2-50% ethyl acetate/hexane)
  6. customto obtain the two isomers in 14%
  7. customyields each in almost 98% purity

出典と根拠

ORDレコード
ord-e659516bb4864d4f90fb4357fb133b94
出典データセット
uspto-grants-2010_10
特許番号
US07816371B2

反応ノート

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