Trifluoroacetic acid → Ethyl[2-oxo-5-[(trifluoromethyl)oxy]-1,3-benzoxazol-3(2H)-yl]acetate

HRID 2354404ノート

反応式

HRID 2354404 の反応式
[F:1][C:2]([F:15])([F:14])[O:3][C:4]1[CH:5]=[CH:6][C:7]2[O:11][C:10](=[O:12])[NH:9][C:8]=2[CH:13]=1.[H-].[Na+].Br[CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21].FC(F)(F)C(O)=O>O1CCCC1.CC#N.O>[CH2:23]([O:22][C:20](=[O:21])[CH2:19][N:9]1[C:8]2[CH:13]=[C:4]([O:3][C:2]([F:1])([F:14])[F:15])[CH:5]=[CH:6][C:7]=2[O:11][C:10]1=[O:12])[CH3:24]

参加物

7

反応物 4

HCID 6422Trifluoroacetic acidHCID 7748Ethyl bromoacetateHCID 24758Sodium hydrideHCID 574186752(3H)-Benzoxazolone, 5-(trifluoromethoxy)-

生成物 1

HCID 57488864Ethyl[2-oxo-5-[(trifluoromethyl)oxy]-1,3-benzoxazol-3(2H)-yl]acetate収率 62%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 18373917Acetonitrile--water (1/1)溶媒

実験手順

A solution of 5-[(trifluoromethyl)oxy]-1,3-benzoxazol-2(3H)-one (1.12 g, 5.1 mmol) dissolved in 6 mL of anhydrous tetrahydrofuran was added drop-wise to a mixture of sodium hydride (60% by weight in mineral oil, 0.22 g, 5.6 mmol) suspended in 11 mL of anhydrous tetrahydrofuran under argon. The mixture was allowed to stir at room temperature for 10 minutes and then ethyl bromoacetate (0.68 mL, 6.1 mmol) was added to the mixture and stirred vigorously for 18 hours before it was determined to be complete by LCMS (two Aquasil C18, 20×1 mm columns were run in sequence, 4 minutes at 0.1 mL/min, 1-99% CH3CN/H2O with 0.018% trifluoroacetic acid, ES) Rt=2.8 min and m/e 306 [M+1]+. The reaction was quenched by adding 5 mL of a 4 M solution of hydrochloric acid in dioxane. After allowing the mixture to stir for one hour, all of the volatiles were removed by rotary evaporation, and the crude residue was purified by silica gel chromatography (40 g Redisep column, silica, 40 um, 60 Å, 35 mL/min, A: methylene chloride, B: methanol, B: 0% to 35% over 30 min; detection at 214 nm) to give ethyl[2-oxo-5-[(trifluoromethyl)oxy]-1,3-benzoxazol-3(2H)-yl]acetate (0.96 g, 3.0 mmol, 62%) of a pink oil. MS (ES) m/e 306 [M+1]+.

後処理

  1. additionwas added drop-wise
  2. stirringstirred vigorously for 18 hours before it
  3. customThe reaction was quenched
  4. additionby adding 5 mL of a 4 M solution of hydrochloric acid in dioxane
  5. stirringto stir for one hour
  6. customall of the volatiles were removed by rotary evaporation
  7. customthe crude residue was purified by silica gel chromatography (40 g Redisep column, silica, 40 um, 60 Å, 35 mL/min
  8. waitA: methylene chloride, B: methanol, B: 0% to 35% over 30 min

出典と根拠

ORDレコード
ord-6fce3a561b8a4e2aadf206ffa4943740
出典データセット
uspto-grants-2010_07
特許番号
US07749998B2

反応ノート

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