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

HRID 514393노트

반응식

HRID 514393 반응식
[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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 176Acetic Acid용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-9200489db5bb4663af329ed15a58889a
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09107916B2

반응 노트

불러오는 중…