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

HRID 1715988ノート

反応式

HRID 1715988 の反応式
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

参加物

9

反応物 4

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

生成物 1

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

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
75 °C

実験手順

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).

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 (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)

出典と根拠

ORDレコード
ord-e7250f4984334123bdf919f21c4f6832
出典データセット
uspto-grants-2010_09
特許番号
US07799828B2

反応ノート

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