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

HRID 229131

反応式

HRID 229131 の反応式
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

参加物

10

反応物 5

HCID 8471Triethylamine2 回HCID 15458tert-Butyl acrylate2 回HCID 80271Tri-o-tolylphosphine2 回HCID 23287334II acetateHCID 686545334-[(4-Bromophenyl)(cyclohexylidene)methyl]phenol

生成物 1

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

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
75 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-f359ffa4632b4065ab9c7d0065dff03c
出典データセット
uspto-grants-2009_07
特許番号
US07560589B2

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