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

HRID 1715988노트

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HRID 1715988 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:22][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:23]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])(=[O:26])[CH:24]=[CH2:25].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:4]=[CH:3][C:2](/[CH:25]=[CH:24]/[C:23]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[CH:7][CH:6]=2)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]1

참가 물질

9

반응물 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 686541254-[(4-Bromophenyl)(cycloheptylidene)methyl]phenol

생성물 1

HCID 689772221,1-Dimethylethyl (2E)-3-{4-[cycloheptylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate수율 98.4%

시약·촉매·용매 4

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

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온도
75 °C

실험 절차

To a round-bottomeded flask were added 4-[(4-bromophenyl)(cycloheptylidene)methyl]phenol (9) (4.0 g, 11.2 mmol), t-butyl acrylate (7.2 mL, 6.3 g, 49.2 mmol, 4.4 eq), Pd(OAc)2 (0.52 g, 2.3 mmol, 0.21 eq), Et3N (9.5 mL, 6.90 g, 68.2 mmol, 6.1 eq), P(o-tolyl)3 (1.3 g, 4.2 mmol, 0.38 eq), and CH3CN (100 mL). The reaction mixture was heated overnight at 75° C. with stirring under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and then transferred to a separatory funnel with the aid of EtOAc and H2O. The layers were separated, and the organic phase was washed with brine, dried (MgSO4), filtered, and the filtrate was concentrated to give the crude product as a red-orange oil. The crude product was purified by flush chromatography on silica gel with hexanes:EtOAc (9:1 to 4:1) to give 4.46 g (98%) of compound 10 as a yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 1.45 (s, 9H), 1.50 (m, 8H), 2.21 (m, 4H), 6.42 (d, J=16.1 Hz, 1H), 6.65 (d, J=8.4 Hz, 2H), 6.90 (d, J=8.4 Hz, 2H), 7.10 (d, J=8.2 Hz, 2H), 7.48 (d, J=15.9 Hz, 1H), 7.57 (d, J=8.1 Hz, 2H), 9.28 (s, 1H).

후처리

  1. temperatureto cool to room temperature
  2. customThe layers were separated
  3. washthe organic phase was washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product as a red-orange oil
  8. customThe crude product was purified
  9. customby flush chromatography on silica gel with hexanes:EtOAc (9:1 to 4:1)

출처 및 근거

ORD 기록
ord-e7250f4984334123bdf919f21c4f6832
출처 데이터셋
uspto-grants-2010_09
특허 번호
US07799828B2

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