Formaldehyde → 2,6-Dimethyl-4-isopropylbenzaldehyde

HRID 1595448ノート

反応式

HRID 1595448 の反応式
N([O-])=O.[Na+].Cl.[CH3:6][C:7]1[CH:13]=[C:12]([CH:14]([CH3:16])[CH3:15])[CH:11]=[C:10]([CH3:17])[C:8]=1N.[C:18]([O-])(=[O:20])C.[K+].C=O.Cl.NO.[Na]>O.Cl.S([O-])([O-])(=O)=O.[Cu+2]>[CH3:6][C:7]1[CH:13]=[C:12]([CH:14]([CH3:16])[CH3:15])[CH:11]=[C:10]([CH3:17])[C:8]=1[CH:18]=[O:20]

参加物

10

反応物 6

HCID 712Formaldehyde2 回HCID 443297Hydroxyamine hydrochlorideHCID 517044Potassium Acetate3 回HCID 5360545SodiumHCID 217050592,6-Dimethyl-4-(propan-2-yl)aniline hydrochlorideHCID 23668193Sodium Nitrite

生成物 1

HCID 154807002,6-Dimethyl-4-isopropylbenzaldehyde収率 16.3%

試薬・触媒・溶媒 3

HCID 24462Copper Sulfate触媒HCID 313Hydrochloric Acid溶媒2 回HCID 962Water溶媒3 回

反応条件

温度
0 °C

実験手順

A solution of NaNO2(1.75 g, 25 mmol) in water (4 mL) was added to a stirred solution of 2,6-dimethyl-4-isopropylaniline hydrochloride (Schubert, W. M. et al. J. Amer. Chem. Soc. 1954, 76:1) (5 g, 25 mmol) in concentrated HCl (4.5 mL) at 0° C. The mixture was allowed to stir at 0° C. for 1.5 hours. Potassium acetate (6 g) was then added. At the same time, a solution of paraformaldehyde (1.15 g), hydroxylamine hydrochloride (2.63 g, 37.84 mmol) and potassium acetate (5.1 g) in water (17 mL) was heated under reflux for 15 min. To this solution, cooled to 10-15° C., was added potassium acetate (16.5 g) in water (18 mL), copper sulfate (0.625 g) and sodium suffite (0.1 g). The neutral diazonium solution was then added immediately to the paraformaldehyde mixture and the resulting solution was allowed to stir at room temperature for 2 hours. The mixture was acidified with 20 mL of concentrated HCl and heated at reflux for 2 hours. The cooled mixture was extracted with ether (3×30 mL) and the solvent was removed under reduced pressure. The yellow liquid was purified by column chromatography using as eluent hexane-EtOAc (97:3) to give 0.72 g (16%) of the title compound as a white liquid.

後処理

  1. temperatureunder reflux for 15 min
  2. temperatureTo this solution, cooled to 10-15° C.
  3. stirringto stir at room temperature for 2 hours
  4. temperatureheated
  5. temperatureat reflux for 2 hours
  6. extractionThe cooled mixture was extracted with ether (3×30 mL)
  7. customthe solvent was removed under reduced pressure
  8. customThe yellow liquid was purified by column chromatography

出典と根拠

ORDレコード
ord-9299cdb0773944499e1e19c67afaddb7
出典データセット
uspto-grants-2001_09
特許番号
US06288101B1

反応ノート

読み込み中…