Ethyl 3-(4-pyridyl)-3-oxopropionate → 1,1'-(2-Hydroxy-5-methyl-1,3-phenylene)di(ethan-1-one)

HRID 253044

反応式

HRID 253044 の反応式
O=[C:2](C1C=CN=CC=1)CC(OCC)=O.[OH:15][C:16]1[C:21]([CH2:22][O:23]C)=[CH:20][C:19]([CH3:25])=[CH:18][C:17]=1[C:26](=[O:28])[CH3:27].CC(C)([O-])C.[K+]>C1COCC1.C(OCC)(=O)C.Cl[Pd]Cl>[C:26]([C:17]1[C:16]([OH:15])=[C:21]([C:22](=[O:23])[CH3:2])[CH:20]=[C:19]([CH3:25])[CH:18]=1)(=[O:28])[CH3:27]

参加物

7

反応物 3

HCID 2735202Ethyl 3-(4-pyridyl)-3-oxopropionateHCID 132292322'-Hydroxy-5'-methyl-3'-methoxymethylacetophenoneHCID 23665647Potassium tert-butoxide

生成物 1

HCID 23050491,1'-(2-Hydroxy-5-methyl-1,3-phenylene)di(ethan-1-one)

試薬・触媒・溶媒 3

HCID 24290Palladium Chloride触媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A mixture of a bromo derivative 1 (324 mg, 1 mmol), (R)-(+)-α-methylbenzylamine 2 (122 mg, 1 mmol), potassium t-butoxide (225 mg, 2 mmol) and PdCl2 (dppf) (35 mg, 0.05 mmol) in THF was stirred at refluxing temperature for 20 hours over a nitrogen atmosphere. The reaction mixture was cooled and diluted with ethyl acetate. The organic layer was washed with water, brine and dried over Na2SO4. The ethyl acetate layers was concentrated in vacuo and the residue was subjected to column chromatography (silica gel, ethylacetate) to give the required product 3. 1H NMR (300 MHz, CDCl3), δ 8.78 (br s, 2H), 8.21 (s, 1H), 7.92 (d, J=5.9 Hz, 2H), 7.4-7.26 (m, 5H), 6.90 (s, 1H), 6.50 (d, J=5.5 Hz, 1H, —NH), 6.27 (s, 1H), 4.60 (m, 1H), 2.23 (s, 3H), 1.71 (d, J=6.9 Hz, 3H). MS (m/z)=357.13 (m+1).

後処理

  1. temperatureat refluxing temperature for 20 hours over a nitrogen atmosphere
  2. temperatureThe reaction mixture was cooled
  3. washThe organic layer was washed with water, brine
  4. dry with materialdried over Na2SO4
  5. concentrationThe ethyl acetate layers was concentrated in vacuo

出典と根拠

ORDレコード
ord-d92d745f475c4858b305487e4cd31f5c
出典データセット
uspto-grants-2011_01
特許番号
US07872011B2

関連ノート

読み込み中…