Dimethylcarbamoyl Chloride → Dimethyl-carbamic acid 2-cyano-5-fluoro-phenyl ester

HRID 348164

反応式

HRID 348164 の反応式
[F:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([OH:10])[CH:3]=1.[CH3:11][N:12]([CH3:16])[C:13](Cl)=[O:14].C(N(CC)CC)C>ClC(Cl)C>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([F:1])=[CH:3][C:4]=1[O:10][C:13](=[O:14])[N:12]([CH3:16])[CH3:11])#[N:7]

参加物

5

反応物 3

HCID 6598Dimethylcarbamoyl ChlorideHCID 8471TriethylamineHCID 110299014-Fluoro-2-hydroxybenzonitrile

生成物 1

HCID 58777394Dimethyl-carbamic acid 2-cyano-5-fluoro-phenyl ester収率 67%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒2 回

実験手順

Under N2, a stirred solution of intermediate 129, 4-fluoro-2-hydroxybenzonitrile (685 mg, 5.00 mmol), dimethylcarbamoyl chloride, and triethylamine (606 mg, 6 mmol) in dichloroethane (10 mL) was heated at reflux for 20 hrs. The cooled mixture was diluted with dichloroethane (10 mL) washed with water, and brine. The organic layer was separated, dried (Na2SO4), concentrated, and the residue purified by column chromatography (SiO2, 5% ethyl acetate-CH2Cl2) to provide 700 mg (Yield 67%) of the title compound as a white crystalline solid: 1H NMR (CDCl3, 500 MHz) δ ppm: 3.03 (3H, s, NMe), 3.15 (3H, s, NMe), 6.99 (1H, dt, J=2.5 Hz, 8.5 Hz, Ar—H), 7.23 (1H, dd, J=2.5 Hz, 9.5 Hz, Ar—H), 7.61 (1H, dd, J=9 Hz, 6 Hz, Ar—H); 13C NMR (CDCl3, 125.77 Hz) δ ppm: 36.76, 37.06, 102.84, 102.86, 111.59, 111.79, 113.24, 113.42, 114.99, 134.36, 134.45, 152.54, 155.06, 155.16, 164.26, 166.31. HRMS (ESI) calcd for C10H10N2O2F (M+H) 209.0726, found 209.0722.

後処理

  1. temperatureat reflux for 20 hrs
  2. washwashed with water, and brine
  3. customThe organic layer was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customthe residue purified by column chromatography (SiO2, 5% ethyl acetate-CH2Cl2)

出典と根拠

ORDレコード
ord-e4b497e9d72b4493ad07537b4bb8bdd6
出典データセット
uspto-grants-2007_02
特許番号
US07176196B2

関連ノート

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