Cesium carbonate → Trifluoromethanesulfonate

HRID 339691ノート

反応式

HRID 339691 の反応式
[F:1][C:2]([F:27])([F:26])[S:3]([O:6][C:7]1[CH:8]=[CH:9][CH:10]=[C:11]2[C:16]=1[N:15]=[C:14]([C:17]1[N:21]3[CH:22]=[CH:23][CH:24]=[CH:25][C:20]3=[N:19][N:18]=1)[CH:13]=[CH:12]2)(=[O:5])=[O:4].[CH3:28][CH:29]1[CH2:34][CH2:33][CH2:32][NH:31][CH2:30]1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[N:19]1[N:18]=[C:17]([C:14]2[CH:13]=[CH:12][C:11]3[C:16](=[C:7]([N:31]4[CH2:32][CH2:33][CH2:34][CH:29]([CH3:28])[CH2:30]4)[CH:8]=[CH:9][CH:10]=3)[N:15]=2)[N:21]2[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=12.[O-:6][S:3]([C:2]([F:27])([F:26])[F:1])(=[O:5])=[O:4]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 790813-MethylpiperidineHCID 634876Binap, (A+-)-HCID 866543542-([1,2,4]Triazolo[4,3-a]pyridin-3-yl)quinolin-8-yl trifluoromethanesulfonate

生成物 2

HCID 2758875TrifluoromethanesulfonateHCID 461789032-([1,2,4]Triazolo[4,3-a]pyridin-3-yl)-8-(3-methylpiperidin-1-yl)quinoline

試薬・触媒・溶媒 1

HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
92 °C

実験手順

2-([1,2,4]Triazolo[4,3-a]pyridin-3-yl)quinolin-8-yl trifluoromethanesulfonate (0.040 g, 0.10 mmol), 3-methylpiperidine (0.016 mL, 0.13 mmol), cesium carbonate (0.050 g, 0.15 mmol), Pd2dba3 (0.005 g, 0.005 mmol) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.006 g, 0.01 mmol) were added to minimal degassed toluene and heated to 92° C. overnight in a sealed tube. After stirring overnight, DCM was added, and solids removed through filtration (Waters filter), followed by concentration in vacuo. The crude mixture was then purified by flash column chromatography (gradient elution of 6% NH4 in MeOH/DCM). The desired product was isolated, along with triflate starting material. The mixture was then treated with 3 N HCl aqueous at 95° C. overnight. The reaction was then cooled and solids removed by filtration. The filtrate was purified by flash column chromatography (gradient elution of 6% NH4 in MeOH/DCM (Rf˜0.1 in 6% NH4 in MeOH (5%) and DCM (95%)). The desired product was isolated as a yellow solid, 0.005 g (15% yield). MS ESI (+) m/z 344.3 (M+1) detected.

後処理

  1. customto minimal degassed toluene
  2. additionDCM was added
  3. customsolids removed through filtration (Waters filter)
  4. concentrationfollowed by concentration in vacuo
  5. customThe crude mixture was then purified by flash column chromatography (gradient elution of 6% NH4 in MeOH/DCM)

出典と根拠

ORDレコード
ord-ddb9d29ae283448ba8feb601878ed577
出典データセット
uspto-grants-2014_11
特許番号
US08895550B2

反応ノート

読み込み中…