Triethylamine → 3-pyridyl-N-t-butyl nitrone

HRID 993314

反応式

HRID 993314 の反応式
Cl.[C:2]([NH:6][OH:7])([CH3:5])([CH3:4])[CH3:3].[N:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH:14]=O)[CH:9]=1.[O-]S([O-])(=O)=O.[Mg+2].CCN(CC)CC.N(CC)(CC)CC.Cl>CCOC(C)=O.C1(C)C=CC=CC=1>[C:2]([N+:6]([O-:7])=[CH:14][C:10]1[CH:9]=[N:8][CH:13]=[CH:12][CH:11]=1)([CH3:5])([CH3:4])[CH3:3]

参加物

8

反応物 5

HCID 8471TriethylamineHCID 103713-PyridinecarboxaldehydeHCID 11130Triethylamine hydrochlorideHCID 24083Sulfuric acid magnesium salt (1:1)HCID 2777896N-tert-butylhydroxylamine hydrochloride

生成物 1

HCID 1534193-pyridyl-N-t-butyl nitrone

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
105 °C

実験手順

To a mixture of N-tert-butylhydroxylamine hydrochloride (2.512 g, 20.0 mmo 1), pyridine-3 -carboxaldehyde (2.144 g, 20.0 mmol), and MgSO4 (2.889 g, 22.0 mmol) was added 100 mL of anhydrous toluene followed by 2.024 g (20.0 mmol/2.79 mL) of Et3N. The reaction mixture was heated to 100-110° C. under argon atmosphere, and the reaction course was followed by t.l.c. and GC/MS. After 3-5 hours, the reaction was cooled to room temperature, Mg SO4 was filtered off, and the solvent was evaporated under reduced pressure to yield a dark yellow-green mixture of product and Et3N.HCl. The crystals were dissolved in EtOAc and the solution was subsequently washed with saturated aqueous NaHCO3, water and saturated aqueous NaCl, dried (MgSO4 or Na2SO4, ca. 30 min), filtered, and evaporated under reduced pressure. The crude product was purified by passing through a short plug of silica gel (1:1 EtOAc/hexanes) to yield after evaporation 3.00 g (84%) of a pale yellow solid. TLC (1:9 EtOAc/hexanes): Rf=0.61; GC: Rt: 3.92 min; MS: 178 (M+.), 147, 122 (b.p.), 106, 79, 57; 1H NMR (300 MHZ, CDCl3): D=1.54 (s, 9H, C(CH3)3), 7.31 (dd, J=8.1,4.8 Hz, 1H, C(5)-H), 7.56 (s, 1H, HC=N), 8.53 (dd, J=4.8,1.8 Hz, 1H, C(6)-H), 8.93 (d, J=1.8 Hz, 1H, C(2)-H), 9.06 (dt, J=8.4,1.8 Hz, 1H, C(4)-H) ppm; 13C NMR (75 MHZ, CDCl3): D=28.24 71.43, 123.40, 126.91, 127.49, 134.57, 150.09, 150.20 ppm.

後処理

  1. temperaturethe reaction was cooled to room temperature
  2. filtrationMg SO4 was filtered off
  3. customthe solvent was evaporated under reduced pressure
  4. customto yield
  5. washthe solution was subsequently washed with saturated aqueous NaHCO3, water and saturated aqueous NaCl
  6. dry with materialdried (MgSO4 or Na2SO4, ca. 30 min)
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe crude product was purified
  10. customto yield
  11. customafter evaporation 3.00 g (84%) of a pale yellow solid

出典と根拠

ORDレコード
ord-7f91afe567ff4d56b13a4f54bd889ee0
出典データセット
uspto-grants-2002_10
特許番号
US06472486B2

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