Ethyl bromopyruvate → Ethyl 2-(4-cyano-7-fluoro-5-methyl-6-phenyl-1,3-benzoxazol-2-yl)-1,3-thiazole-4-carboxylate

HRID 17490

반응식

HRID 17490 반응식
Br[CH2:2][C:3](=O)[C:4]([O:6][CH2:7][CH3:8])=[O:5].[C:10]([C:12]1[C:17]2[N:18]=[C:19]([C:21](=[S:23])[NH2:22])[O:20][C:16]=2[C:15]([F:24])=[C:14]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:13]=1[CH3:31])#[N:11].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])O.[Na+]>O.C1(C)C=CC=CC=1>[C:10]([C:12]1[C:17]2[N:18]=[C:19]([C:21]3[S:23][CH:2]=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[N:22]=3)[O:20][C:16]=2[C:15]([F:24])=[C:14]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:13]=1[CH3:31])#[N:11]

참가 물질

7

반응물 4

HCID 66144Ethyl bromopyruvateHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 860973994-Cyano-7-fluoro-5-methyl-6-phenyl-1,3-benzoxazole-2-carbothioamide

생성물 1

HCID 68584336Ethyl 2-(4-cyano-7-fluoro-5-methyl-6-phenyl-1,3-benzoxazol-2-yl)-1,3-thiazole-4-carboxylate수율 91.3%

시약·촉매·용매 2

HCID 962Water용매HCID 1140Toluene용매

반응 조건

온도
125 °C

실험 절차

Ethyl 3-bromopyruvate (72.2 μl, 0.518 mmol) was added to a toluene (10 ml) solution of 4-cyano-7-fluoro-5-methyl-6-phenyl-1,3-benzoxazole-2-carbothioamide (I-196-1) (124 mg, 0.398 mmol), followed by heating under reflux in an oil bath at 125° C. for 2 hours. After cooling to room temperature, p-toluenesulfonic acid monohydrate (15.2 mg, 0.080 mmol) was added to the reaction liquid, followed by heating under reflux in an oil bath at 125° C. for 15 hours. After cooling to room temperature, an aqueous saturated sodium hydrogencarbonate solution (50 ml) and water (50 ml) were added, followed by extraction with ethyl acetate (50 ml×2). The organic layer was washed with an aqueous saturated sodium hydrogencarbonate solution (50 ml) and saturated brine (50 ml), and dried over anhydrous sodium sulfate. After concentration, the resulting residue was purified by silica gel column chromatography (eluent, chloroform:ethyl acetate=100:1→25:1) to obtain the entitled compound (148 mg, 91.2%) as a pale yellow solid.

후처리

  1. temperatureby heating
  2. temperatureAfter cooling to room temperature
  3. temperatureby heating
  4. temperatureunder reflux in an oil bath at 125° C. for 15 hours
  5. temperatureAfter cooling to room temperature
  6. extractionfollowed by extraction with ethyl acetate (50 ml×2)
  7. washThe organic layer was washed with an aqueous saturated sodium hydrogencarbonate solution (50 ml) and saturated brine (50 ml)
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationAfter concentration
  10. customthe resulting residue was purified by silica gel column chromatography (eluent, chloroform:ethyl acetate=100:1→25:1)

출처 및 근거

ORD 기록
ord-1171c5d92c7945a39487ce52620c7f22
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07737166B2

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