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

HRID 521872

반응식

HRID 521872 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.[CH2:12]([C:14]([CH2:19]O)([CH2:17][OH:18])[CH2:15][OH:16])[CH3:13].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[CH2:12]([C:14]1([CH2:17][OH:18])[CH2:15][O:16][CH:7]([C:6]2[N:2]([CH3:1])[N:3]=[CH:4][C:5]=2[N+:9]([O-:11])=[O:10])[O:8][CH2:19]1)[CH3:13]

참가 물질

5

반응물 3

HCID 6101p-Toluenesulfonic acidHCID 6510TrimethylolpropaneHCID 598129402-Methyl-4-nitro-pyrazole-3-carbaldehyde2회

생성물 1

HCID 86713820(5-ethyl-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 (370 mg, 2.39 mmol, intermediate 3) in toluene (50 mL) was added 2-ethyl-2-(hydroxymethyl)propane-1,3-diol (315 mg, 2.35 mmol) followed by p-toluenesulfonic acid (20 mg, 0.10 mmol). The reaction mixture was heated at reflux for 36 hr whilst azeotropically removing the water. The mixture was cooled to room temperature and concentrated under reduced pressure. Purification via silica gel column chromatography (0-100% EtOAc/isohexane) gave (5-ethyl-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 (244 mg, 38%). 1H NMR (400 MHz, CDCl3) δ 8.02 (s, 1H), 6.38 (s, 1H), 4.16 (s, 3H), 4.02 (d, J=11.5 Hz, 2H), 3.97 (d, J=5.2 Hz, 2H), 3.42 (d, J=3.8 Hz, 2H), 1.90 (m, 3H), 0.99 (t, J=7.6 Hz, 3H).

후처리

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 36 hr
  3. customwhilst azeotropically removing the water
  4. concentrationconcentrated under reduced pressure
  5. customPurification via silica gel column chromatography (0-100% EtOAc/isohexane)

출처 및 근거

ORD 기록
ord-336fc74a336b40bca70b3094d68a10ee
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09328106B2

연결된 노트

불러오는 중…