Dimethyl nitromalonate → Methyl 4-isobutyl-5-phenylisoxazole-3-carboxylate

HRID 1804456

反応式

HRID 1804456 の反応式
[CH3:1][CH:2]([CH3:12])[CH2:3][C:4]#[C:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[N+:13]([CH:16](C(OC)=O)[C:17]([O:19][CH3:20])=[O:18])([O-])=[O:14].F[P-](F)(F)(F)(F)F.C([N+]1C=CN(C)C=1)CCC>C1(C)C=CC=CC=1>[CH2:3]([C:4]1[C:16]([C:17]([O:19][CH3:20])=[O:18])=[N:13][O:14][C:5]=1[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH:2]([CH3:12])[CH3:1]

参加物

5

反応物 3

HCID 226085Dimethyl nitromalonateHCID 27341741-Butyl-3-methylimidazolium hexafluorophosphateHCID 12861410(4-Methylpent-1-ynyl)benzene

生成物 1

HCID 58537171Methyl 4-isobutyl-5-phenylisoxazole-3-carboxylate収率 30.2%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

A solution of (4-methylpent-1-ynyl)benzene (0.247 g, 1.56 mmol), dimethyl 2-nitromalonate (0.421 mL, 3.12 mmol), 1-butyl-3-methylimidazoliumhexafluorophosphate (0.032 mL, 0.156 mmol) in toluene (5 mL) was subjected to the microwave at 170° C. for 150 min. By HPLC, the reaction was ˜40-50% complete and resubjected to the microwave conditions for 360 min. (170° C.). The toluene was decanted off leaving a dark gum which was triturated several times with ethyl acetate. The combined organic layers were concentrated under reduced pressure. The residue was purified by flash silica gel chromatography using 5% ethyl acetate in hexane to give methyl 4-isobutyl-5-phenylisoxazole-3-carboxylate (0.122 g, 0.470 mmol, 30.2% yield) as a clear, colorless oil. The compound had an HPLC ret. time=2.96 min.−Column: CHROMOLITH® SpeedROD 4.6×50 mm (4 min.); Solvent A=10% MeOH, 90% H2O, 0.1% TFA; Solvent B=90% MeOH, 10% H2O, 0.1% TFA. LC/MS M+1=259.9. 1H NMR (500 MHz, chloroform-d) δ ppm 0.88 (s, 3H), 0.89 (s, 3H), 1.89 (dt, J=13.75, 6.87 Hz, 1H), 2.80 (d, J=7.15 Hz, 2H), 4.00 (s, 3H), 7.45-7.53 (m, 3H), 7.73 (d, J=6.60 Hz, 2H).

後処理

  1. custom(170° C.)
  2. customThe toluene was decanted off
  3. customleaving a dark gum which
  4. customwas triturated several times with ethyl acetate
  5. concentrationThe combined organic layers were concentrated under reduced pressure
  6. customThe residue was purified by flash silica gel chromatography

出典と根拠

ORDレコード
ord-8ac02dc5c15a4ae0a89da84895155186
出典データセット
uspto-grants-2013_01
特許番号
US08354398B2

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