Cesium carbonate → 2-Chloro-8-[4-(dimethyl-phosphinoyl)-phenyl]-[1,2,4]triazolo[1,5-a]pyridine

HRID 472499ノート

反応式

HRID 472499 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]3[N:10]([N:14]=[C:15]([Cl:17])[N:16]=3)[CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1.[CH3:18][PH:19]([CH3:21])=[O:20].CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[Cl:17][C:15]1[N:16]=[C:9]2[C:8]([C:5]3[CH:6]=[CH:7][C:2]([P:19]([CH3:21])([CH3:18])=[O:20])=[CH:3][CH:4]=3)=[CH:13][CH:12]=[CH:11][N:10]2[N:14]=1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 674814248-(4-Bromo-phenyl)-2-chloro-[1,2,4]triazolo[1,5-a]pyridineHCID 178503022methylphosphonoylmethane

生成物 1

HCID 674814912-Chloro-8-[4-(dimethyl-phosphinoyl)-phenyl]-[1,2,4]triazolo[1,5-a]pyridine

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

198 b) To an oven dried tube was added 8-(4-bromo-phenyl)-2-chloro-[1,2,4]triazolo[1,5-a]pyridine (0.90 g, 2.9 mmol), methylphosphinoylmethane (0.24 g, 3.1 mmol) (prepared as described in WO2005/009348), palladium acetate (13.5 mg, 0.0601 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (36.0 mg, 0.0622 mmol), cesium carbonate (1422.0 mg, 4.3644 mmol) and 1,4-dioxane (9 mL). The tube was evacuated, carefully, and backflushed with nitrogen. The tube was sealed and heated at 90° C. for 24 hours then cooled to room temperature, diluted with dichloromethane (30 mL), filtered through a plug of diatomaceous earth and evaporated. The residue was purified via chromatography using an ISCO automated purification apparatus (silica gel column 40 g and 0%→7% dichloromethane:methanol). 2-Chloro-8-[4-(dimethyl-phosphinoyl)-phenyl]-[1,2,4]triazolo[1,5-a]pyridine was isolated as a white solid (0.303 g, 34%). MP=220-223° C. 1H NMR (400 MHz, CDCl3, δ, ppm): 8.55 (d, J=6.9 Hz, 1H), 8.11 (d, J=7.7 Hz, 2H), 7.94-7.86 (m, 2H), 7.77 (t, J=7.4 Hz, 1H), 7.21 (t, J=6.9 Hz, 1H), 1.80 (s, 3H), 1.77 (s, 3H). MS=306, 308 (MH)+.

後処理

  1. custom198 b) To an oven dried tube
  2. customThe tube was evacuated
  3. customThe tube was sealed
  4. temperaturethen cooled to room temperature
  5. additiondiluted with dichloromethane (30 mL)
  6. filtrationfiltered through a plug of diatomaceous earth
  7. customevaporated
  8. customThe residue was purified via chromatography
  9. custompurification apparatus (silica gel column 40 g and 0%→7% dichloromethane:methanol)

出典と根拠

ORDレコード
ord-f43e6ce1a04e4139900f29d6b795c6f5
出典データセット
uspto-grants-2014_01
特許番号
US08633173B2

反応ノート

読み込み中…