Acetonitrile → 2-Chloromethyl-3,5,6-trimethyl-[1,4]benzoquinone

HRID 63806

反応式

HRID 63806 の反応式
[Cl:1][CH2:2][C:3]1[C:8]([CH3:9])=[C:7]([O:10]C)[C:6]([CH3:12])=[C:5]([CH3:13])[C:4]=1[O:14]C.C(#N)C.O=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+]>O>[Cl:1][CH2:2][C:3]1[C:4](=[O:14])[C:5]([CH3:13])=[C:6]([CH3:12])[C:7](=[O:10])[C:8]=1[CH3:9]

参加物

5

反応物 3

HCID 6342AcetonitrileHCID 180504Ceric ammonium nitrateHCID 108789291-(Chloromethyl)-2,5-dimethoxy-3,4,6-trimethylbenzene

生成物 1

HCID 110526102-Chloromethyl-3,5,6-trimethyl-[1,4]benzoquinone収率 81%

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
0 °C

実験手順

A flask was charged with 1-chloromethyl-2,5-dimethoxy-3,4,6-trimethyl-benzene (Ex-1B-3) (6.37 g, 27.9 mmol) and ACN (10 mL) then cooled to 0° C. A solution of CAN (31.3 g, 57.1 mmol) in water (10 mL) was added to the flask. After 1 h the reaction mixture was extracted with MTBE (3×50 mL). The combined MTBE layers were then washed with water (50 mL), dried over MgSO4, filtered and concentrated by rotary evaporation. Trituration of the crude product with MeOH yielded 4.49 g of 2-chloromethyl-3,5,6-trimethyl-[1,4]benzoquinone (Ex-1B-4) (81%) as a bright orange-yellow solid. 1H NMR (400 MHz, CDCl3) δ (ppm): 4.77 (s, 2H), 2.17 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H).

後処理

  1. extractionAfter 1 h the reaction mixture was extracted with MTBE (3×50 mL)
  2. washThe combined MTBE layers were then washed with water (50 mL)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation

出典と根拠

ORDレコード
ord-b1bb2187f6bf4db9b69e81d6345ac86a
出典データセット
uspto-grants-2016_09
特許番号
US09447006B2

関連ノート

読み込み中…