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Tert-butyl acetoacetate → 1,1-Dimethylethyl 9,9-bis(4-fluorophenyl)-5-hydroxy-8-(1-methylethyl)-3-oxo-6,8-nonadienoate

HRID 1086065
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HRID 1086065 반응식
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)=[C:9]([CH:14]([CH3:16])[CH3:15])[CH:10]=[CH:11][CH:12]=[O:13])=[CH:4][CH:3]=1.[C:24]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])(=[O:29])[CH2:25][C:26]([CH3:28])=[O:27].[H-].[Na+].C([Li])CCC>O1CCCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([C:17]2[CH:18]=[CH:19][C:20]([F:23])=[CH:21][CH:22]=2)=[C:9]([CH:14]([CH3:16])[CH3:15])[CH:10]=[CH:11][CH:12]([OH:13])[CH2:28][C:26](=[O:27])[CH2:25][C:24]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])=[CH:6][CH:7]=1
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HCID 15538Tert-butyl acetoacetate2회HCID 24758Sodium hydrideHCID 538739495,5-Bis(4-fluorophenyl)-4-(1-methylethyl)-2,4-pentadienalHCID 178418339Butyllithium

생성물 1

HCID 537261511,1-Dimethylethyl 9,9-bis(4-fluorophenyl)-5-hydroxy-8-(1-methylethyl)-3-oxo-6,8-nonadienoate수율 66.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

To a solution of 5,5-bis(4-fluorophenyl)-4-(1-methyl-ethyl)-2,4-pentadienal (0.5 g, 1.6 mmol) in 20 mL tetrahydrafuran at -70° C., was added the dianion of t-butyl acetoacetate (2.1 mL of 1M solution in THF, 2.1 mmol) which was prepared by adding t-butyl acetoacetate (4.0 g, 25 mmol) in 4 mL tetrahydrofuran to a suspension of sodium hydride (1.0 g of 50% in oil, 25 mmol) in 6 mL tetrahydrofuran at -10° C., butyl lithium (11.4 mL of 2.2M solution) 25 mL was added and stirred for 0.5 hrs. After stirring for 2.5 hrs. the reaction was quenched with 2N hydrochloric acid. The mixture was extracted with diethyl ether. The extracts were dried over magnesium sulfate and concentrated in vacuo. The residue was purified by chromatography on silica gel eluting with 1% methanol in methylene chloride to give 0.5 g of the title compound as a clear oil. MS(CI): m/e =370 for M3 ;

후처리

  1. customwas prepared
  2. stirringAfter stirring for 2.5 hrs
  3. customthe reaction was quenched with 2N hydrochloric acid
  4. extractionThe mixture was extracted with diethyl ether
  5. dry with materialThe extracts were dried over magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by chromatography on silica gel eluting with 1% methanol in methylene chloride

출처 및 근거

ORD 기록
ord-facfd26347cf4bd6b0607a1209ee49e2
출처 데이터셋
uspto-grants-1991_04
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05011947

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