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

HRID 229131

반응식

HRID 229131 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:21][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:22]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])(=[O:25])[CH:23]=[CH2:24].C(N(CC)CC)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.II.CC(O)=O>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:24]=[CH:23]/[C:22]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])=[CH:3][CH:4]=2)[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1

참가 물질

10

반응물 5

HCID 8471Triethylamine2회HCID 15458tert-Butyl acrylate2회HCID 80271Tri-o-tolylphosphine2회HCID 23287334II acetateHCID 686545334-[(4-Bromophenyl)(cyclohexylidene)methyl]phenol

생성물 1

HCID 689777101,1-Dimethylethyl(2E)-3-{4-[cyclohexylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate수율 76%

시약·촉매·용매 4

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 6342Acetonitrile용매2회HCID 8857Ethyl Acetate용매

반응 조건

온도
75 °C

실험 절차

To a round-bottomed flask were added 4-[(4-bromophenyl)(cyclohexylidene)methyl]phenol (6) (0.465 g, 1.35 mmol), tert-butyl acrylate (0.58 mL, 0.508 g, 3.96 mmol, 2.9 eq), Pd(OAc)2 (0.03 g, 0.134 mmol, 0.1 eq), triethylamine (0.54 mL, 0.39 g, 3.87 mmol, 2.9 eq), P(o-tolyl)3 (0.08 g, 0.26 mmol, 0.19 eq), and CH3CN (6 mL). The reaction mixture was heated overnight at 75° C. with stirring under a nitrogen atmosphere. Thin layer chromatography indicated the reaction was not complete. To the reaction mixture were added P(o-tolyl)3 (0.087 g, 0.29 mmol, 0.21 eq), tert-butyl acrylate (0.58 mL, 0.51 g, 3.96 mmol, 2.9 eq), paladium II acetate (0.033 g, 0.147 mmol), triethylamine (0.54 mL, 0.39 g, 3.87 mmol), and CH3CN (2 mL). The reaction mixture was heated at 75° C. with stirring under a nitrogen atmosphere for three days. The reaction mixture was allowed to cool to room temperature and transferred to a separatory funnel with the aid of EtOAc and H2O. The layers were separated and the organic phase was washed with brine. The organic solution was dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product as an oil. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 50:50) to give 0.40 g (76%) of compound 7 as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 1.45 (s, 9H), 1.52 (m, 6H), 2.14 (m, 4H), 6.43 (d, J=15.9 Hz, 1H), 6.66 (d, J=8.5 Hz, 2H), 6.84 (d, J=8.4 Hz, 2H), 7.05 (d, J=8.1 Hz, 2H), 7.48 (d, J=15.9 Hz, 1H), 7.57 (d, J=8.1 Hz, 2H), 9.31 (s, 1H). The sample was silated prior to EI analysis. HRMS (EI) Calcd for C29H38O3Si: 462.2590 (M+.). Found: 462.2592.

후처리

  1. temperatureThe reaction mixture was heated at 75° C.
  2. stirringwith stirring under a nitrogen atmosphere for three days
  3. temperatureto cool to room temperature
  4. customThe layers were separated
  5. washthe organic phase was washed with brine
  6. dry with materialThe organic solution was dried over MgSO4
  7. filtrationfiltered
  8. concentrationthe filtrate was concentrated
  9. customto give the crude product as an oil
  10. 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-f359ffa4632b4065ab9c7d0065dff03c
출처 데이터셋
uspto-grants-2009_07
특허 번호
US07560589B2

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