1,4-Dioxane → 2-amino-4-ethyl-5-(2-methyl-2H-pyrazol-3-yl)-benzoic acid methyl ester

HRID 906602

反応式

HRID 906602 の反応式
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[C:8](I)[C:7]([CH2:11][CH3:12])=[CH:6][C:5]=1[NH2:13].[CH3:15][N:16]1[C:20]([Sn](CCCC)(CCCC)CCCC)=[CH:19][CH:18]=[N:17]1.O1CCOCC1>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CCOC(C)=O>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[C:8]([C:20]2[N:16]([CH3:15])[N:17]=[CH:18][CH:19]=2)[C:7]([CH2:11][CH3:12])=[CH:6][C:5]=1[NH2:13]

参加物

6

反応物 3

HCID 312751,4-DioxaneHCID 218674551-Methyl-5-(tributylstannyl)-1H-pyrazoleHCID 53424411Methyl 2-amino-4-ethyl-5-iodobenzoate

生成物 1

HCID 591644712-amino-4-ethyl-5-(2-methyl-2H-pyrazol-3-yl)-benzoic acid methyl ester収率 68.3%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
100 °C

実験手順

2-Amino-5-iodo-4-ethyl-benzoic acid methyl ester (280 mg, 0.92 mmol) and 1-methyl-5-tributylstannanyl-1H-pyrazole (409 mg, 1.2 equiv) were weighed in air and added to a flame-dried flask. [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium (75 mg, 0.1 equiv) was added and the flask was closed by a septum. Dioxane (1 mL) was added and the mixture was stirred at 100° C. for 18 h (TLC control). The mixture was dissolved with EtOAc, filtered and evaporated to dryness. The crude product was purified by flash chromatography (hexanes to EtOAc/hexanes (4:6)) to yield 2-amino-4-ethyl-5-(2-methyl-2H-pyrazol-3-yl)-benzoic acid methyl ester (163 mg, 68% yield) as a yellow solid. ESI-MS: m/z 260.3 [M+H]+, rt 6.37 min.

後処理

  1. additionadded to a flame-dried flask
  2. customthe flask was closed by a septum
  3. filtrationfiltered
  4. customevaporated to dryness
  5. customThe crude product was purified by flash chromatography (hexanes to EtOAc/hexanes (4:6))

出典と根拠

ORDレコード
ord-139aa7e9fc524e31ab2a94840ad9736e
出典データセット
uspto-grants-2011_09
特許番号
US08012988B2

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