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

HRID 521872

反応式

HRID 521872 の反応式
[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]

参加物

5

反応物 3

HCID 6101p-Toluenesulfonic acidHCID 6510TrimethylolpropaneHCID 598129402-Methyl-4-nitro-pyrazole-3-carbaldehyde2 回

生成物 1

HCID 86713820(5-ethyl-2-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,3-dioxan-5-yl)methanol

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-336fc74a336b40bca70b3094d68a10ee
出典データセット
uspto-grants-2016_05
特許番号
US09328106B2

関連ノート

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