Methyl 4-(4-methylphenyl)-2,4-dioxobutanoate → methyl 1-(4-cyanopyridin-2-yl)-5-(4-methylphenyl)-1H-pyrazole-3-carboxylate

HRID 514393ノート

反応式

HRID 514393 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH2:9][C:10](=O)[C:11]([O:13][CH3:14])=[O:12])=[CH:4][CH:3]=1.Cl.[NH:18]([C:20]1[CH:25]=[C:24]([C:26]#[N:27])[CH:23]=[CH:22][N:21]=1)[NH2:19]>CC(O)=O>[C:26]([C:24]1[CH:23]=[CH:22][N:21]=[C:20]([N:18]2[C:8]([C:5]3[CH:6]=[CH:7][C:2]([CH3:1])=[CH:3][CH:4]=3)=[CH:9][C:10]([C:11]([O:13][CH3:14])=[O:12])=[N:19]2)[CH:25]=1)#[N:27]

参加物

4

反応物 2

HCID 308119Methyl 4-(4-methylphenyl)-2,4-dioxobutanoateHCID 867254842-Hydrazinylpyridine-4-carbonitrile hydrochloride salt

生成物 1

HCID 86725519methyl 1-(4-cyanopyridin-2-yl)-5-(4-methylphenyl)-1H-pyrazole-3-carboxylate収率 85%

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

実験手順

A solution of methyl 4-(4-methylphenyl)-2,4-dioxobutanoate (500 mg, 22.7 mmol) and 2-hydrazinylpyridine-4-carbonitrile hydrochloride salt (500 mg, 24.2 mmol, PREPARATION 3) in AcOH (10 mL) was heated at 100° C. for 30 min and cooled to rt. The solution was concentrated to an oily residue which was partitioned between EtOAc (50 mL) and water (50 mL). The pH was adjusted to pH=8 using a saturated aq. Na2CO3 solution. The organics were dried (MgSO4), filtered, and concentrated to give a solid which was triturated with MTBE/hexanes (1:1) and filtered to give the title compound (613 mg, 85%) as a yellow solid. 1H NMR (400 MHz, CD3OD): δ 2.48 (3H, s), 3.92 (3H, s), 7.01 (1H, s), 7.08-7.21 (4H, m), 7.71 (1H, d, J=4.8 Hz), 8.12 (1H, s), 8.48 (1H, d, J=4.8 Hz), 8.00 (1H, s), 8.48 (1H, d, J=8 Hz).

後処理

  1. concentrationThe solution was concentrated to an oily residue which
  2. customwas partitioned between EtOAc (50 mL) and water (50 mL)
  3. dry with materialThe organics were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a solid which
  7. customwas triturated with MTBE/hexanes (1:1)
  8. filtrationfiltered

出典と根拠

ORDレコード
ord-9200489db5bb4663af329ed15a58889a
出典データセット
uspto-grants-2015_08
特許番号
US09107916B2

反応ノート

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