Triethylamine → 1,1-Dimethylethyl (2E)-3-{4-[cyclopentylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate

HRID 229128

반응식

HRID 229128 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:20][CH2:19][CH2:18][CH2:17]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[C:21]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])(=[O:24])[CH:22]=[CH2:23].CCN(CC)CC.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CC([O-])=O.CC([O-])=O.[Pd+2].O.CCOC(C)=O.CC#N>[C:16]1(=[C:8]([C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)[C:5]2[CH:6]=[CH:7][C:2](/[CH:23]=[CH:22]/[C:21]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[CH:3][CH:4]=2)[CH2:20][CH2:19][CH2:18][CH2:17]1

참가 물질

9

반응물 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 686545024-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol

생성물 1

HCID 689778841,1-Dimethylethyl (2E)-3-{4-[cyclopentylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate수율 74.5%

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 6342Acetonitrile용매HCID 8857Ethyl Acetate용매

반응 조건

온도
85 °C

실험 절차

4-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol (3) (0.351 g, 1.07 mmol), tert-butyl acrylate (0.94 mL, 0.82 g, 6.4 mmol, 6 eq), Pd(OAc)2 (0.051 g, 0.23 mmol, 0.21 eq), Et3N (0.89 mL, 0.65 g, 6.4 mmol, 6 eq), P(o-tolyl)3 (0.139 g, 0.46 mmol, 0.43 eq), and anhydrous CH3CN (16 mL) were combined in a round-bottomed flask and the reaction mixture was heated overnight at 85° C., with stirring, under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and transferred to a separatory funnel with the aid of EtOAc and water. The layers were separated and the organic phase was washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 50:50) to give 0.30 g (74%) of compound 4 as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 1.45 (s, 9H), 1.60 (m, 4H), 2.30 (m, 4H), 6.43 (d, J=15.9 Hz, 1H), 6.67 (d, J=8.6 Hz, 2H), 6.90 (d, J=8.4 Hz, 2H), 7.12 (d, J=8.2 Hz, 2H), 7.49 (d, J=15.9 Hz, 1H), 7.58 (d, J=8.3 Hz, 2H), 9.32 (s, 1H). HRMS (EI) Calcd for C25H28O3: 376.2038 (M+.). Found: 376.2046.

후처리

  1. temperatureto cool to room temperature
  2. customThe layers were separated
  3. washthe organic phase was washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product
  8. customThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 50:50)

출처 및 근거

ORD 기록
ord-5ba1f222dbff451289313246ad3add99
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560589B2

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