Cesium carbonate → HCID 10162554、化合物

HRID 896082ノート

反応式

HRID 896082 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([O:25][CH3:26])=[C:6]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([NH:16][C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][C:18]=3[F:24])=[CH:12][CH:11]=2)=[O:9])[CH:7]=1.[CH3:27][N:28]1[CH2:33][CH2:32][N:31]([CH2:34][C:35]#[CH:36])[CH2:30][CH2:29]1.C([O-])([O-])=O.[Cs+].[Cs+].C(N(CC)C(C)C)(C)C>COCCOCCOC.CC(OC)(C)C.Cl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[F:24][C:18]1[CH:19]=[C:20]([F:23])[CH:21]=[CH:22][C:17]=1[NH:16][C:13]1[CH:14]=[CH:15][C:10]([C:8]([C:6]2[CH:7]=[C:2]([C:36]#[C:35][CH2:34][N:31]3[CH2:32][CH2:33][N:28]([CH3:27])[CH2:29][CH2:30]3)[CH:3]=[CH:4][C:5]=2[O:25][CH3:26])=[O:9])=[CH:11][CH:12]=1

参加物

10

反応物 4

HCID 10796Cesium carbonateHCID 81531DiisopropylethylamineHCID 135140911-Methyl-4-(prop-2-yn-1-yl)piperazineHCID 22349575(5-Bromo-2-methoxy-phenyl)-[4-(2,4-difluoro-phenylamino)-phenyl]-methanone

生成物 1

HCID 10162554HCID 10162554、化合物収率 32%

試薬・触媒・溶媒 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 313Hydrochloric Acid溶媒HCID 8150Diglyme溶媒HCID 15413tert-Butyl methyl ether溶媒

実験手順

(5-Bromo-2-methoxy-phenyl)-[4-(2,4-difluoro-phenylamino)-phenyl]-methanone (0.5 g; 1.18 mmol), 1-methyl-4-prop-2-ynyl-piperazine (0.33 g; 2.37 mmol), PdCl2(PPh3)2 (0.158 g; 0.22 mmol), Cs2CO3 (1.0 g; 3.1 mmol) and CuI (50 mg; 0.26 mmol) are dissolved in diethylene glycol dimethyl ether (10 ml) and N,N-diisopropylethylamine (5 ml) and heated to 140° C. for 1 hour. The reaction mixture is diluted with TBME, filtered, evaporated and purified by chromatography (SiO2, EtOAc/MeOH/NH3conc 100/0/0>90/10/1) to yield the crude title compound as brown foam. The latter is dissolved in 2N HCl, washed with EtOAc, Na2CO3 added to the aqueous phase and extracted with EtOAc. The organic phase is filtered through Alox and evaporated to give the pure product as yellow foam (177 mg; 32%).

後処理

  1. filtrationfiltered
  2. customevaporated
  3. custompurified by chromatography (SiO2, EtOAc/MeOH/NH3conc 100/0/0>90/10/1)
  4. customto yield the crude title compound as brown foam
  5. washwashed with EtOAc, Na2CO3
  6. additionadded to the aqueous phase
  7. extractionextracted with EtOAc
  8. filtrationThe organic phase is filtered through Alox
  9. customevaporated

出典と根拠

ORDレコード
ord-c4d1e256d6fb4a36ba975b88c3925956
出典データセット
uspto-grants-2005_07
特許番号
US06919336B2

反応ノート

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