Ammonium Chloride → Methyl 4-[(4E)-5-(5-fluoro-2-hydroxyphenyl)-3-{2-[4-(methoxycarbonyl)phenyl]ethyl}pent-4-en-1-yl]benzoate

HRID 1015932ノート

反応式

HRID 1015932 の反応式
C([Li])CCC.[Br-].[F:7][C:8]1[CH:9]=[CH:10][C:11]([OH:34])=[C:12]([CH:33]=1)[CH2:13][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH:35]([CH:37]([CH2:50][CH2:51][C:52]1[CH:61]=[CH:60][C:55]([C:56]([O:58][CH3:59])=[O:57])=[CH:54][CH:53]=1)[CH2:38][CH2:39][C:40]1[CH:49]=[CH:48][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:42][CH:41]=1)=O.[Cl-].[NH4+]>CCCCCC.C1COCC1.O.C(OCC)(=O)C>[F:7][C:8]1[CH:9]=[CH:10][C:11]([OH:34])=[C:12](/[CH:13]=[CH:35]/[CH:37]([CH2:38][CH2:39][C:40]2[CH:41]=[CH:42][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:48][CH:49]=2)[CH2:50][CH2:51][C:52]2[CH:61]=[CH:60][C:55]([C:56]([O:58][CH3:59])=[O:57])=[CH:54][CH:53]=2)[CH:33]=1

参加物

9

反応物 4

HCID 25517Ammonium ChlorideHCID 59397497Dimethyl 4,4'-(3-formylpentane-1,5-diyl)dibenzoateHCID 86638793(5-Fluoro-2-hydroxybenzyl)(triphenyl)phosphonium bromideHCID 178418339Butyllithium

生成物 1

HCID 59397498Methyl 4-[(4E)-5-(5-fluoro-2-hydroxyphenyl)-3-{2-[4-(methoxycarbonyl)phenyl]ethyl}pent-4-en-1-yl]benzoate

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

At 0° C., 2.95 ml (7.39 mmol) of a 2.5 M solution of n-butyllithium in hexane are slowly added dropwise to a solution of 1479 mg (3.2 mmol) of (5-fluoro-2-hydroxybenzyl)-(triphenyl)phosphonium bromide in 40 ml of THF. The reaction mixture is stirred at this temperature for another 45 min. At 0° C., 1080 mg (2.64 mmol) of dimethyl 4,4′-(3-formylpentane-1,5-diyl)dibenzoate in 10 ml of THF are then slowly metered in. The reaction solution is stirred at 0° C. for 5 h, saturated ammonium chloride solution is then added and the mixture is diluted with water and ethyl acetate. The organic phase is separated off, and the aqueous phase is extracted two more times with ethyl acetate. The combined organic phases are dried over sodium sulfate and filtered, and the solvent is removed to dryness. The crude product obtained is purified by flash chromatography on silica gel (mobile phase:cyclohexane/ethyl acetate 4:1). This gives 529 mg (1.11 mmol, 42% of theory) of a colorless oil.

後処理

  1. customAt 0° C.
  2. stirringThe reaction solution is stirred at 0° C. for 5 h
  3. customThe organic phase is separated off
  4. extractionthe aqueous phase is extracted two more times with ethyl acetate
  5. dry with materialThe combined organic phases are dried over sodium sulfate
  6. filtrationfiltered
  7. customthe solvent is removed to dryness

出典と根拠

ORDレコード
ord-315d7318a7824748af71fcf9ba3f55d7
出典データセット
uspto-grants-2011_07
特許番号
US07985876B2

反応ノート

読み込み中…