p-Toluenesulfonic acid → (2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol

HRID 521873

반응식

HRID 521873 반응식
[CH3:1][N:2]1[C:6]([CH:7]=[O:8])=[C:5]([N+:9]([O-:11])=[O:10])[CH:4]=[N:3]1.[OH:12][CH2:13][CH:14]([CH2:17]O)[CH2:15][OH:16].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[CH3:1][N:2]1[C:6]([CH:7]2[O:12][CH2:13][CH:14]([CH2:15][OH:16])[CH2:17][O:8]2)=[C:5]([N+:9]([O-:11])=[O:10])[CH:4]=[N:3]1

참가 물질

5

반응물 3

HCID 6101p-Toluenesulfonic acidHCID 78432TrimethylolmethaneHCID 598129402-Methyl-4-nitro-pyrazole-3-carbaldehyde2회

생성물 1

HCID 86713821(2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

To a solution of 2-methyl-4-nitro-pyrazole-3-carbaldehyde (718 mg, 4.63 mmol, intermediate 3) in toluene (100 mL) was added 2-(hydroxymethyl)propane-1,3-diol (700 mg, 6.73 mmol) followed by p-toluenesulfonic acid (88 mg, 0.463 mmol). The reaction mixture was heated at reflux for 18 hr whilst azeotropically removing the water. The mixture was cooled to room temperature and concentrated under reduced pressure. The residue was diluted with DCM (50 mL) and washed with a saturated aqueous NaHCO3 (50 mL). The organic layer was washed with water (20 mL) and brine (20 mL), separated, dried over Na2SO4 and concentrated under reduced pressure. Purification via silica gel column chromatography (0-100% EtOAc/isohexane) gave (2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol (trans isomer) as the first eluting isomer as a colourless solid (220 mg, 20%). 1H NMR (400 MHz, CDCl3) δ 8.02 (s, 1H), 6.42 (s, 1H), 4.34 (dd, J=11.6, 4.7 Hz, 2H), 4.12 (s, 3H), 3.81 (t, J=11.5 Hz, 2H), 3.56 (t, J=5.1 Hz, 2H), 2.53-2.38 (m, 1H), 1.67 (t, J=4.6 Hz, 1H).

후처리

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 18 hr
  3. customwhilst azeotropically removing the water
  4. concentrationconcentrated under reduced pressure
  5. additionThe residue was diluted with DCM (50 mL)
  6. washwashed with a saturated aqueous NaHCO3 (50 mL)
  7. washThe organic layer was washed with water (20 mL) and brine (20 mL)
  8. customseparated
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated under reduced pressure
  11. customPurification via silica gel column chromatography (0-100% EtOAc/isohexane)

출처 및 근거

ORD 기록
ord-8f2176cc1ef84bb0854f4fee4986bedc
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09328106B2

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