Potassium Phosphate, Tribasic → 5-methyl-1-(4-vinylphenyl)-1H-pyrazole-4-carboxylic acid

HRID 1748440ノート

反応式

HRID 1748440 の反応式
C([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:12]2[CH:17]=[CH:16][C:15](Br)=[CH:14][CH:13]=2)[C:10]=1[CH3:11])=[O:5])C.[CH:19]1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCC[CH2:20]1.C(B1OC(C)(C)C(C)(C)O1)=C.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.O1CCCC1>[CH3:11][C:10]1[N:9]([C:12]2[CH:13]=[CH:14][C:15]([CH:19]=[CH2:20])=[CH:16][CH:17]=2)[N:8]=[CH:7][C:6]=1[C:4]([OH:3])=[O:5]

参加物

8

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 3470813ethyl 1-(4-bromophenyl)-5-methyl-1H-pyrazole-4-carboxylateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

生成物 1

HCID 866924095-methyl-1-(4-vinylphenyl)-1H-pyrazole-4-carboxylic acid収率 461.5%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
100 °C

実験手順

Tetrahydrofuran (10 ml) was added to 1-(4-bromophenyl)-5-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (1.5 g) described in Reference Example 26(1), palladium (II) acetate (108 mg), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos) (198 mg), vinylboronic acid pinacol ester (1.04 g) and tripotassium phosphate (2.6 g), and stirred at 100° C. for 7 hours. Water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The resulting residue was purified with silica gel column chromatography (n-hexane/ethyl acetate). 4N Aqueous solution of sodium hydroxide (4 ml) and ethanol (10 ml) were added to the purified yellow oily product, stirred at 80° C. for two hours and the reaction solution was washed with ethyl acetate. 1N Hydrochloric acid aqueous solution was added to the aqueous layer at 0° C., and the precipitated solid was washed with diethyl ether and water to give 5-methyl-1-(4-vinylphenyl)-1H-pyrazole-4-carboxylic acid (508 mg).

後処理

  1. extractionextracted with ethyl acetate
  2. washthe organic layer was washed with water and saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe resulting residue was purified with silica gel column chromatography (n-hexane/ethyl acetate)
  6. addition4N Aqueous solution of sodium hydroxide (4 ml) and ethanol (10 ml) were added to the purified yellow oily product
  7. stirringstirred at 80° C. for two hours
  8. washthe reaction solution was washed with ethyl acetate
  9. addition1N Hydrochloric acid aqueous solution was added to the aqueous layer at 0° C.
  10. washthe precipitated solid was washed with diethyl ether and water

出典と根拠

ORDレコード
ord-4e321b0293e84de78c5f033c550adcf7
出典データセット
uspto-grants-2015_10
特許番号
US09150555B2

反応ノート

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