Methoxymethyl-triphenylphosphonium chloride → 1-(2,6-dichloro-phenyl)-4-isopropyl-5-[4-(2-methoxy-vinyl)-3-methyl-phenoxymethyl]-1H-pyrazole

HRID 2261757노트

반응식

HRID 2261757 반응식
[CH3:1][C:2](C)([O-:4])C.[K+].[Cl-].[CH3:8]OC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cl:30][C:31]1[CH:36]=[CH:35][CH:34]=[C:33]([Cl:37])[C:32]=1[N:38]1[C:42]([CH2:43][O:44][C:45]2[CH:52]=[CH:51][C:48](C=O)=[C:47]([CH3:53])[CH:46]=2)=[C:41]([CH:54]([CH3:56])[CH3:55])[CH:40]=[N:39]1>C1COCC1>[Cl:30][C:31]1[CH:36]=[CH:35][CH:34]=[C:33]([Cl:37])[C:32]=1[N:38]1[C:42]([CH2:43][O:44][C:45]2[CH:52]=[CH:51][C:48]([CH:1]=[CH:2][O:4][CH3:8])=[C:47]([CH3:53])[CH:46]=2)=[C:41]([CH:54]([CH3:55])[CH3:56])[CH:40]=[N:39]1

참가 물질

5

반응물 3

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 23665647Potassium tert-butoxideHCID 866354624-[2-(2,6-Dichloro-phenyl)-4-isopropyl-2H-pyrazol-3-ylmethoxy]-2-methyl-benzaldehyde

생성물 1

HCID 675279671-(2,6-dichloro-phenyl)-4-isopropyl-5-[4-(2-methoxy-vinyl)-3-methyl-phenoxymethyl]-1H-pyrazole수율 73%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To an ambient temperature suspension of potassium tert-butoxide (668 mg, 5.96 mmol) in THF (20 mL) is added (methoxymethyl)triphenyl phosphonium chloride (2.04 g, 5.96 mmol) and is stirred at room temperature for 20 min. Solid 4-[2-(2,6-Dichloro-phenyl)-4-isopropyl-2H-pyrazol-3-ylmethoxy]-2-methyl-benzaldehyde (400 mg, 0.992 mmol) is added and the reaction is stirred at room temperature overnight. The reaction is quenched with sat. aq. NH4Cl and concentrated. The residue is partitioned between Et2O and water. The aqueous layer is extracted with Et2O and the combined organic layers are washed with brine, dried (MgSO4), filtered, concentrated and chromatographed (SiO2 120 g, 0% to 30% EtOAC/Hex) to yield the title compound (302 mg, 73%) as a mix of E/Z isomers. 1H NMR (400 MHz, CDCl3) (major isomer) δ 7.70 (s, 1H), 7.43-7.38 (m, 2H), 7.33-7.26 (m, 1H), 7.08 (d, 1H, J=8.4 Hz), 6.72 (d, 1H, J=12.8 Hz), 6.60-6.52 (m, 2H), 5.82 (d, 1H, J=12.8 Hz), 4.78 (s, 2H), 3.66 (s, 3H), 3.00 (sept, 1H, J=7.0 Hz), 2.22 (s, 3H), 1.30 (d, 6H, J=7.0 Hz).

후처리

  1. stirringthe reaction is stirred at room temperature overnight
  2. customThe reaction is quenched with sat. aq. NH4Cl
  3. concentrationconcentrated
  4. customThe residue is partitioned between Et2O and water
  5. extractionThe aqueous layer is extracted with Et2O
  6. washthe combined organic layers are washed with brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customchromatographed (SiO2 120 g, 0% to 30% EtOAC/Hex)

출처 및 근거

ORD 기록
ord-4f485ba2f0bb4e0e9d4e85aab549bc5a
출처 데이터셋
uspto-grants-2010_12
특허 번호
US07846960B2

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