Potassium Carbonate → Methyl 6-iodo-2-phenylpyrazolo[1,5-a]pyridine-3-carboxylate

HRID 44020

反応式

HRID 44020 の反応式
[I:1][C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C1(C)C=C(C)C=C(C)C=1S(O[NH2:20])(=O)=O.[C:22]1([C:28]#[C:29][C:30]([O:32][CH3:33])=[O:31])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(=O)([O-])[O-].[K+].[K+]>ClCCl.CN(C)C=O.C(OCC)C>[I:1][C:2]1[CH:7]=[CH:6][C:5]2[N:4]([N:20]=[C:28]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:29]=2[C:30]([O:32][CH3:33])=[O:31])[CH:3]=1

参加物

8

反応物 4

HCID 11430Potassium CarbonateHCID 707143-IodopyridineHCID 138378Phenylpropynoic acid methyl esterHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamine

生成物 1

HCID 59233743Methyl 6-iodo-2-phenylpyrazolo[1,5-a]pyridine-3-carboxylate収率 12%

試薬・触媒・溶媒 3

HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒2 回

実験手順

Dichloromethane (10 mL) and 3-Iodopyridine (928 mg, 4.53 mmol) were charged to a 100 mL round-bottomed flask equipped with a magnetic stir bar. This colorless solution was cooled on an ice bath and O-(mesitylsulfonyl)hydroxylamine (975 mg, 4.53 mmol) in dichloromethane (10 mL) was added dropwise over 5 minutes. After to stirring at room temperature for 30 minutes, the solvent was removed by rotory evaporation to give a white solid. Methyl phenylpropiolate (1000 mg, 6.24 mmol) was added in dimethylformamide (9 mL). Potassium carbonate (2504 mg, 18.12 mmol) was added. Reaction slowly turned dark green. After stirring at room temp for 2 hours, the reaction was poured into diethyl ether (300 mL and extracted 8×25 mL water. The solvent was removed from the organic portion by rotory evaporation. The crude product was dissolved in a minimum amount of dichloromethane and charged to a 90 g “Single Sep” silica gel cartridge and eluted with 0 to 40% ethyl acetate in hexanes over 1000 mL. The title compound (200 mg, 12%) was isolated as an orange solid. 1H NMR (500 MHz, CHLOROFORM-D) δ ppm 3.83 (s, 3H) 7.46 (m, 3H) 7.59 (dd, J=9.16, 1.53 Hz, 1H) 7.75 (m, 2H) 8.00 (dd, J=9.31, 0.76 Hz, 1H) 8.82 (s, 1H). LCMS: 2.4 minutes, M+1=379.

後処理

  1. customequipped with a magnetic stir bar
  2. temperatureThis colorless solution was cooled on an ice bath
  3. customthe solvent was removed by rotory evaporation
  4. customto give a white solid
  5. customReaction slowly turned dark green
  6. stirringAfter stirring at room temp for 2 hours
  7. extractionextracted 8×25 mL water
  8. customThe solvent was removed from the organic portion by rotory evaporation
  9. dissolutionThe crude product was dissolved in a minimum amount of dichloromethane
  10. additioncharged to a 90 g “Single Sep” silica gel cartridge
  11. washeluted with 0 to 40% ethyl acetate in hexanes over 1000 mL

出典と根拠

ORDレコード
ord-ff7fe275eebd4045805f1f10b307a03c
出典データセット
uspto-grants-2013_09
特許番号
US08536338B2

関連ノート

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