Chloroform → 4-Chloro-2,5-dimethyl-6-(2,4,6-trimethyl-phenoxy)pyridine

HRID 968027ノート

反応式

HRID 968027 の反応式
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[OH:10].[H-].[Na+].Cl[C:14]1[C:19]([CH3:20])=[C:18]([Cl:21])[CH:17]=[C:16]([CH3:22])[N:15]=1.C(Cl)(Cl)Cl>CS(C)=O.CCCCCC>[Cl:21][C:18]1[CH:17]=[C:16]([CH3:22])[N:15]=[C:14]([O:10][C:3]2[C:4]([CH3:9])=[CH:5][C:6]([CH3:8])=[CH:7][C:2]=2[CH3:1])[C:19]=1[CH3:20]

参加物

7

反応物 4

HCID 6212ChloroformHCID 106982,4,6-TrimethylphenolHCID 24758Sodium hydrideHCID 110843982,4-Dichloro-3,6-dimethylpyridine

生成物 1

HCID 99036754-Chloro-2,5-dimethyl-6-(2,4,6-trimethyl-phenoxy)pyridine

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 8058Hexane溶媒

反応条件

温度
130 °C

実験手順

A solution of 2,4,6-trimethylphenol (405 mg, 3.31 mmol) in 2 ml of DMSO was treated with NaH (60% in oil, 180 mg, 4.5 mmol). After 5 min, 2,4-Dichloro-3,6-dimethyl-pyridine (528 mg, 3 mmol) was added. The mixture was heated in the oil bath of 130° C. for 6 hours. The mixture was quenched with water and extracted with EtOAc. The organic layer was dried and concentrated to give 812.5 mg of crude material with two regioisomers. After silica gel column chromatography using 1:1 of CHCl3:hexane as eluent, the title compound was isolated as white crystals (141 mg), mp 57-62° C.; high MS for C16H18ClNO: calc, 275.1072, found 275.70172; IR(KBr) 2951, 2920, 1592, 1564 cm−1; 1H NMR (CDCl3) δ 6.87 (s, 2H), 6.77 (s, 1H), 2.39 (s, 3H), 2.29 (s, 3H), 2.18 (s, 3H), 2.03 (s, 6H) ppm. The regiochemistry was determined by X-ray structural analysis of the undesired regioisomer, 2-chloro-3,6-dimethyl-4-(2,4,6-trimethyl-phenyoxy)-pyridine.

後処理

  1. customThe mixture was quenched with water
  2. extractionextracted with EtOAc
  3. customThe organic layer was dried
  4. concentrationconcentrated
  5. customto give 812.5 mg of crude material with two regioisomers

出典と根拠

ORDレコード
ord-d69dee69bb0a406faddb0b7a4817909f
出典データセット
uspto-grants-2005_10
特許番号
US06956047B1

反応ノート

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