Cesium carbonate → 1-Methyl-5-(3-methyl-2-nitro-phenylamino)-1H-pyrazole-4-carboxylic Acid Ethyl Ester

HRID 220940

反応式

HRID 220940 の反応式
C(=O)([O-])[O-].[Cs+].[Cs+].[NH2:7][C:8]1[N:12]([CH3:13])[N:11]=[CH:10][C:9]=1[C:14]([O:16][CH2:17][CH3:18])=[O:15].Br[C:20]1[C:21]([N+:27]([O-:29])=[O:28])=[C:22]([CH3:26])[CH:23]=[CH:24][CH:25]=1>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[CH2:17]([O:16][C:14]([C:9]1[CH:10]=[N:11][N:12]([CH3:13])[C:8]=1[NH:7][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH3:26])[C:21]=1[N+:27]([O-:29])=[O:28])=[O:15])[CH3:18]

参加物

7

反応物 3

HCID 10796Cesium carbonateHCID 142929Benzene, 1-bromo-3-methyl-2-nitro-HCID 271299Ethyl 5-amino-1-methyl-1H-pyrazole-4-carboxylate

生成物 1

HCID 575553391-Methyl-5-(3-methyl-2-nitro-phenylamino)-1H-pyrazole-4-carboxylic Acid Ethyl Ester収率 54.8%

試薬・触媒・溶媒 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒2 回

実験手順

Cesium carbonate (35.2 g, 108 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.4 g, 0.7 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.2 g, 0.2 mmol) were added to a solution of ethyl 5-amino-1-methylpyrazole-4-carboxylate (15.3 g, 90 mmol) in dioxan (50 ml) under an inert atmosphere. A solution of 3-bromo-2-nitrotoluene (16.2 g, 75 mmol) in dioxane (10 ml) was added and the mixture was stirred for 30 min at room temperature then heated at reflux for 72 h. The suspension was filtered through Celite® filter agent, washed with EtOAc and the filtrate was concentrated in vacuo. The residue was purified by flash chromatography on silica gel (eluant; 50% EtOAc:50% pet. ether) then recrystallised from EtOAc/pet. ether to yield the title compound (12.5 g, 45%).

後処理

  1. temperaturethen heated
  2. temperatureat reflux for 72 h
  3. filtrationThe suspension was filtered through Celite®
  4. filtrationfilter agent
  5. washwashed with EtOAc
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe residue was purified by flash chromatography on silica gel (eluant; 50% EtOAc:50% pet. ether)
  8. customthen recrystallised from EtOAc/pet. ether

出典と根拠

ORDレコード
ord-7f6ea4725ee44fed822d4114be08db03
出典データセット
uspto-grants-2012_06
特許番号
US08202858B2

関連ノート

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