4'-Chlorovalerophenone → tert-Butyl 4-(1-(4-chlorophenyl)-1-oxopentan-2-yl)benzoate

HRID 2408148

반응식

HRID 2408148 반응식
CC([O-])(C)C.[Na+].CC1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1.[Cl:57][C:58]1[CH:63]=[CH:62][C:61]([C:64](=[O:69])[CH2:65][CH2:66][CH2:67][CH3:68])=[CH:60][CH:59]=1.Br[C:71]1[CH:83]=[CH:82][C:74]([C:75]([O:77][C:78]([CH3:81])([CH3:80])[CH3:79])=[O:76])=[CH:73][CH:72]=1.C([O-])(O)=O.[Na+]>CCCCCCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1COCC1>[Cl:57][C:58]1[CH:59]=[CH:60][C:61]([C:64](=[O:69])[CH:65]([C:71]2[CH:83]=[CH:82][C:74]([C:75]([O:77][C:78]([CH3:79])([CH3:80])[CH3:81])=[O:76])=[CH:73][CH:72]=2)[CH2:66][CH2:67][CH3:68])=[CH:62][CH:63]=1

참가 물질

9

반응물 5

HCID 906864'-ChlorovalerophenoneHCID 516892Sodium BicarbonateHCID 4189906(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1, 1'-binaphthylHCID 11334366Tert-butyl 4-bromobenzoateHCID 23676156Sodium t-butoxide

생성물 1

HCID 58349443tert-Butyl 4-(1-(4-chlorophenyl)-1-oxopentan-2-yl)benzoate

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 8028Tetrahydrofuran용매HCID 8900Heptane용매

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온도
60 °C

실험 절차

A 3-neck flask was charged with NaOtBu (2.85 g, 28.6 mmol) and dry THF (50 mL) under nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (0.26 g, 0.28 mmol) and (S)-Tol-Binap (0.47 g, 0.69 mmol) were then added under nitrogen. After stirring for 15 min, 1-(4-chlorophenyl)pentan-1-one (4.21 g, 21.0 mmol) was added, followed by tert-butyl 4-bromobenzoate (5.0 g, 19.1 mmol) under nitrogen. The mixture was heated at 60° C. for 8 hours. The mixture was diluted with heptane (100 mL) and poured into a solution of saturated NaHCO3 (aq) (60 mL) and ice (40 g). The resulting layers were separated, and the aqueous phase was back-extracted with methyl tert-butyl ether (50 mL). The combined organics were washed with saturated NaHCO3 (aq) then 10% NaCl (aq). The organic solution was filtered through a bed of silica 60 (84 g, wetted with 1:1 methyl tert-butyl ether/heptane), and washed with 1:1 methyl tert-butyl ether/heptane (600 mL). The combined filtrate was concentrated to afford an orange oil that was used directly for the next step: 1H NMR (500 MHz, CDCl3): δ 7.91 (d, J=8.1 Hz, 2H); 7.86 (d, J=8.4 Hz, 2H); 7.35 (d, J=8.4 Hz, 2H); 7.32 (d, J=8.2 Hz, 2H); 4.53 (1, J=7.2 Hz, 1H); 2.19-2.09 (m, 1H); 1.85-1.76 (m, 1H); 1.56 (s, 9H); 1.35-1.18 (m, 2H); 0.91 (t, J=7.3 Hz, 3H); LC3: 1.35 min. (M-tBu+H)+ 317.

후처리

  1. customThe resulting layers were separated
  2. extractionthe aqueous phase was back-extracted with methyl tert-butyl ether (50 mL)
  3. washThe combined organics were washed with saturated NaHCO3 (aq)
  4. filtrationThe organic solution was filtered through a bed of silica 60 (84 g, wetted with 1:1 methyl tert-butyl ether/heptane)
  5. washwashed with 1:1 methyl tert-butyl ether/heptane (600 mL)
  6. concentrationThe combined filtrate was concentrated
  7. customto afford an orange oil that
  8. custom1.35 min.

출처 및 근거

ORD 기록
ord-c7f06e237f2d4c0e8d9b6b01c0f027cd
출처 데이터셋
uspto-grants-2014_08
특허 번호
US08809579B2

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