Dimethyl oxalate → HCID 22315365、化合物

HRID 1274281ノート

反応式

HRID 1274281 の反応式
[CH3:1][C:2]([C:4]1[CH:9]=[C:8]([F:10])[C:7]([O:11][CH3:12])=[C:6]([F:13])[CH:5]=1)=[O:3].[C:14](OC)(=[O:19])[C:15]([O:17][CH3:18])=[O:16].C[O-].[Na+]>CO.C(Cl)Cl>[F:13][C:6]1[CH:5]=[C:4]([C:2](=[O:3])[CH2:1][C:14](=[O:19])[C:15]([O:17][CH3:18])=[O:16])[CH:9]=[C:8]([F:10])[C:7]=1[O:11][CH3:12]

参加物

6

反応物 3

HCID 11120Dimethyl oxalateHCID 27369833',5'-Difluoro-4'-methoxyacetophenoneHCID 10942334Sodium Methoxide

生成物 1

HCID 22315365HCID 22315365、化合物

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒

実験手順

To a stirred solution of 3,5-difluoro-4-methoxyacetophenone from Step 1 (6.46 g, 34.70 mmol) and dimethyl oxalate (6.15 g, 52.05 mmol) in methanol (80 mL), was added sodium methoxide solution (13.4 mL of 25% solution, 58.99 mmol) in one portion and the reaction stirred overnight. The crude reaction was diluted with methylene chloride, washed with potassium bisulfate (0.1N solution), brine, dried over MgSO4, filtered, and concentrated in vacuo yielding methyl 4-(3,5-difluoro-4-methoxyphenyl)-2,4-dioxo-butanoate as an off white crystalline solid which was used as is. A mixture of 4-(3,5-difluoro-4-methoxyphenyl)-2,4-dioxo-butanoate and 4-sulfonamidophenylhydrazine hydrochloride salt (7.76 g, 34.70 mmol) dissolved in methanol was warmed to reflux for 9 hours. Upon allowing the clear reaction to cool to room temperature, a crystalline precipitate formed which was collected by vacuum filtration yielding 5.45 g, (37% based upon the 3,5-difluoro-4-methoxyacetophenone) of methyl 1-(4-aminosulfonylphenyl)-5-(3,5-difluoro-4-methoxyphenyl)-1-H-pyrazole-3-carboxylate as an off-white solid: mp 185-190° C.; 1H NMR (CDCl3 /300 mHz) 7.95 (d, J=8.86, 2H), 7.49 (d, J=8.86, 2H), 7.02 (s, 1H), 6.77 (m, 2H), 4.99 (s, 2H), 4.04 (s, 3 H), 3.98 (s, 3H); 19F NMR (CDCl3 /300 mHz) -126.66. Anal. Calc'd for C17H13F2N3O3S: C, 51.06; H, 3.57; N, 9.92. Found: C, 51.06; H, 3.54, N, 9.99.

後処理

  1. customThe crude reaction
  2. washwashed with potassium bisulfate (0.1N solution), brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-7b9e286783d44e66ba1d1b87247e81e3
出典データセット
uspto-grants-2000_12
特許番号
US06156781

反応ノート

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