Cesium carbonate → N-(4-(benzylthio)-2-nitrophenyl)-4'-chloro-2-fluoro-5-methoxy-3'-methyl-[1,1'-biphenyl]-4-amine

HRID 1504386

反応式

HRID 1504386 の反応式
[CH2:1]([S:8][C:9]1[CH:15]=[CH:14][C:12]([NH2:13])=[C:11]([N+:16]([O-:18])=[O:17])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([C:26]2[CH:31]=[C:30]([O:32][CH3:33])[C:29](I)=[CH:28][C:27]=2[F:35])=[CH:22][C:21]=1[CH3:36].COC1CCCC1.C(=O)([O-])[O-].[Cs+].[Cs+]>CCOC(C)=O.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].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH2:1]([S:8][C:9]1[CH:15]=[CH:14][C:12]([NH:13][C:29]2[C:30]([O:32][CH3:33])=[CH:31][C:26]([C:23]3[CH:24]=[CH:25][C:20]([Cl:19])=[C:21]([CH3:36])[CH:22]=3)=[C:27]([F:35])[CH:28]=2)=[C:11]([N+:16]([O-:18])=[O:17])[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

8

反応物 4

HCID 10796Cesium carbonateHCID 138539Cyclopentyl methyl etherHCID 135509934-(Benzylthio)-2-nitroanilineHCID 1177369494'-Chloro-2-fluoro-4-iodo-5-methoxy-3'-methyl-1,1'-biphenyl

生成物 1

HCID 117737265N-(4-(benzylthio)-2-nitrophenyl)-4'-chloro-2-fluoro-5-methoxy-3'-methyl-[1,1'-biphenyl]-4-amine収率 72.8%

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 8857Ethyl Acetate溶媒

実験手順

A RBF was charged with 4-(benzylthio)-2-nitroaniline (1.80 g, 6.91 mmol), 4′-chloro-2-fluoro-4-iodo-5-methoxy-3′-methyl-1,1′-biphenyl (2.86 g, 7.61 mmol), xantphos (0.200 g, 0.346 mmol), Pd2(dba)3 (0.158 g, 0.173 mmol), CPME (13.83 ml) and cesium carbonate (3.15 g, 9.68 mmol). A reflux condenser was attached and the flask was lowered into a 110° C. heating for 3 hours. The mixture was cooled to room temperature, diluted with EtOAc, and filtered through celite with the aid of EtOAc. The filtrate was concentrated. The oily residue was purified using Biotage and eluting with 0-50% EtOAc/Heptane to give N-(4-(benzylthio)-2-nitrophenyl)-4′-chloro-2-fluoro-5-methoxy-3′-methyl-[1,1′-biphenyl]-4-amine (2.56 g, 5.03 mmol, 72.7% yield) as a bright-yellow solid. m/z (ESI) 509.1 (M+H)+.

後処理

  1. customA reflux condenser was attached
  2. customwas lowered into a 110° C.
  3. temperatureheating for 3 hours
  4. filtrationfiltered through celite with the aid of EtOAc
  5. concentrationThe filtrate was concentrated
  6. customThe oily residue was purified
  7. washeluting with 0-50% EtOAc/Heptane

出典と根拠

ORDレコード
ord-3d1ba1a0155f4a3591f6978a9be3688e
出典データセット
uspto-grants-2015_12
特許番号
US09212182B2

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