Dimethylformamide → 3-Tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylate

HRID 717855

反応式

HRID 717855 の反応式
[Cl:1][C:2]1[CH:3]=[N:4][C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[CH:13]=2)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[NH2:19]OS(C1C(C)=CC(C)=CC=1C)(=O)=O.[C:33]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])(=[O:36])[C:34]#[CH:35].CN(C)C=O.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.C(OCC)(=O)C>[Cl:1][C:2]1[C:3]2[N:4]([N:19]=[CH:35][C:34]=2[C:33]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C:5]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[CH:13]=2)=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:11]=1

参加物

8

反応物 5

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 543038tert-Butyl propiolateHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 58515983Methyl 5-chloro-2-(3-fluorophenyl)nicotinate

生成物 1

HCID 585159563-Tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylate収率 30.2%

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

The methyl 5-chloro-2-(3-fluorophenyl)nicotinate (1.00 g, 3.76 mmol) was combined with freshly prepared 2-[(aminooxy)sulfonyl]-1,3,5-trimethylbenzene (0.972 g, 4.52 mmol) ether solution in acetonitrile (20.0 mL) at room temperature. The reaction was stirred for 24 hours and became a tan colored slurry. The slurry was added portion wise to a vigorously stirring suspension of tert-butyl propiolate (1.55 mL, 11.3 mmol), N,N-dimethylformamide (20.0 mL, 258 mmol) and potassium carbonate (2.60 g, 18.8 mmol) open to the air. After stirring for 15 minutes, the reaction was a dark red brown suspension. This was allowed to stir for 5 hours at room temperature. The reaction was taken up in ethyl acetate and decanted from the solids. The organic layer was washed with water, brine, dried over magnesium sulfate and concentrated to give the crude product as a reddish brown oil. The product was purified on silica gel eluting hexane:ethyl acetate gradient to give 3-tert-butyl 6-methyl 4-chloro-7-(3-fluorophenyl)pyrazolo[1,5-a]pyridine-3,6-dicarboxylate (0.46 g, 30%) as a semi-solid residue. LCMS calculated for C20H19ClFN2O4 (M+H)+: m/z=405.1. found: 404.9.

後処理

  1. additionThe slurry was added portion wise to
  2. stirringa vigorously stirring
  3. stirringAfter stirring for 15 minutes
  4. stirringto stir for 5 hours at room temperature
  5. customdecanted from the solids
  6. washThe organic layer was washed with water, brine
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. customto give the crude product as a reddish brown oil
  10. customThe product was purified on silica gel
  11. washeluting hexane

出典と根拠

ORDレコード
ord-aff6d0b51c2548fd9183c0ac89b78443
出典データセット
uspto-grants-2015_11
特許番号
US09193721B2

関連ノート

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