2-Methylbenzenesulfonic acid → Methyl 4-(5-cyano-7-methyl-1,3-benzoxazol-2-yl)benzoate

HRID 2093624ノート

反応式

HRID 2093624 の反応式
C1(C)C(S(O)(=O)=O)=CC=CC=1.[NH2:12][C:13]1[CH:14]=[C:15]([CH:18]=[C:19]([CH3:22])[C:20]=1[OH:21])[C:16]#[N:17].Cl[C:24]([C:26]1[CH:35]=[CH:34][C:29]([C:30]([O:32][CH3:33])=[O:31])=[CH:28][CH:27]=1)=O>O1CCOCC1>[C:16]([C:15]1[CH:18]=[C:19]([CH3:22])[C:20]2[O:21][C:24]([C:26]3[CH:35]=[CH:34][C:29]([C:30]([O:32][CH3:33])=[O:31])=[CH:28][CH:27]=3)=[N:12][C:13]=2[CH:14]=1)#[N:17]

参加物

5

反応物 3

HCID 69252-Methylbenzenesulfonic acidHCID 81850Methyl 4-(chlorocarbonyl)benzoateHCID 57917192HCID 57917192、化合物

生成物 1

HCID 59586084Methyl 4-(5-cyano-7-methyl-1,3-benzoxazol-2-yl)benzoate収率 67.3%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

To a solution of 117 mg of toluenesulfonic acid in 40 ml of dioxane was added 3-amino-4-hydroxy-5-methylbenzonitrile (101 mg) and methyl 4-(chlorocarbonyl)benzoate (149 mg) The mixture was heated to reflux under N2 for 15 h. The mixture was then cooled to room temperature and the dioxane was removed in vacuo. To the residue was added 80 ml of toluene and the solution was heated to reflux overnight (15 h). Purification by flash chromatography (Rf in 2/1 hexanes/ethyl acetate=0.58) on a Biotage Horizon, 65i column, eluting with 1 column volume of 30% ethyl acetate in hexanes, followed by a linear gradient of ethyl acetate in hexanes from 30 to 100% over 10 column volumes provided 134 mg (67%) of the title compound. Mass spectrum (ESI) 293.0 (M+1). 1H NMR (500 MHz, CDCl3): δ 8.35 (d, J=8.2 Hz, 2H), 8.22 (d, J=8.4 Hz, 2H), 7.95 (s, 1H), 7.49 (s, 1H), 3.98 (s, 3H), 2.65 (s, 3H).

後処理

  1. temperaturewas heated
  2. temperatureto reflux under N2 for 15 h
  3. customthe dioxane was removed in vacuo
  4. additionTo the residue was added 80 ml of toluene
  5. temperaturethe solution was heated
  6. temperatureto reflux overnight (15 h)
  7. customPurification by flash chromatography (Rf in 2/1 hexanes/ethyl acetate=0.58) on a Biotage Horizon, 65i column
  8. washeluting with 1 column volume of 30% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-a07b4b57b0ca4943aef172ae60b98432
出典データセット
uspto-grants-2013_05
特許番号
US08445480B2

反応ノート

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