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

HRID 229128

反応式

HRID 229128 の反応式
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

参加物

9

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
85 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-5ba1f222dbff451289313246ad3add99
出典データセット
uspto-grants-2009_07
特許番号
US07560589B2

関連ノート

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