Oxazole → Methyl 4-butyl-8-(1,3-oxazol-2-yl)-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate

HRID 348979

反応式

HRID 348979 の反応式
[O:1]1[CH:5]=[CH:4][N:3]=[CH:2]1.C([Li])CCC.[CH2:11]([N:15]1[C:20]2[CH:21]=[C:22]([C:26]([O:28][CH2:29]C)=[O:27])[CH:23]=[C:24](I)[C:19]=2[O:18][CH2:17][CH2:16]1)[CH2:12][CH2:13][CH3:14]>O1CCCC1.C(OCC)(=O)C.[Cl-].[Zn+2].[Cl-]>[CH2:11]([N:15]1[C:20]2[CH:21]=[C:22]([C:26]([O:28][CH3:29])=[O:27])[CH:23]=[C:24]([C:2]3[O:1][CH:5]=[CH:4][N:3]=3)[C:19]=2[O:18][CH2:17][CH2:16]1)[CH2:12][CH2:13][CH3:14]

参加物

7

反応物 3

HCID 9255OxazoleHCID 21086105ethyl 4-butyl-8-iodo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 21086201Methyl 4-butyl-8-(1,3-oxazol-2-yl)-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate収率 71.7%

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-70 °C

実験手順

To a −70° C. solution of oxazole (227 mg) in tetrahydrofuran (10 mL) was added n-butyllithium (2.5 M in hexanes, 2 mL). After stirred at −70° C. for 30 min, zinc chloride (1 M in ethyl ether, 13 mL) was added. The mixture was warmed to 0° C. for 1 h. To this mixture was then added ethyl 4-butyl-8-iodo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate (600 mg, 1.6 mmol) in THF (5 mL) followed by tetrakis triphenylphosphine palladium (0) (115 mg). The mixture was heated at reflux for 3 h, diluted with ethyl acetate (300 mL) and washed with water followed by brine. The organic solution was dried (sodium sulfate) and concentrated under reduced pressure. Purification by silica gel plug (1:1 acetate/hexanes) provided 363 mg of the title compound: 1H NMR (300 MHz, CDCl3) δ 7.96, 7.73, 7.40, 7.28, 4.44, 3.90, 3.43, 3.34, 1.61, 1.41, 0.98.

後処理

  1. temperatureThe mixture was warmed to 0° C. for 1 h
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 3 h
  4. washwashed with water
  5. dry with materialThe organic solution was dried (sodium sulfate)
  6. concentrationconcentrated under reduced pressure
  7. customPurification by silica gel plug (1:1 acetate/hexanes)

出典と根拠

ORDレコード
ord-e3cba9d18d30480a81c2788dd1582291
出典データセット
uspto-grants-2007_02
特許番号
US07176242B2

関連ノート

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