Dimethylformamide → 2,6-Dichloro-4-methylbenzoyl chloride

HRID 280649ノート

反応式

HRID 280649 の反応式
[Cl:1][C:2]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:7]([Cl:12])[C:3]=1[C:4](O)=[O:5].CN(C)C=O.S(Cl)([Cl:20])=O>>[Cl:1][C:2]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:7]([Cl:12])[C:3]=1[C:4]([Cl:20])=[O:5]

参加物

4

反応物 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 136496822,6-Dichloro-4-methylbenzoic acid

生成物 1

HCID 150651842,6-Dichloro-4-methylbenzoyl chloride収率 109%

実験手順

A solution of 2,6-dichloro-4methylbenzoic acid (7.15 g, 34.9 mmol) in thionyl chloride (133 ml) containing dimethylformamide (1.3 ml) was refluxed 3 hours, evaporated under vacuum, and azeotroped twice with benzene. The residue was triturated with petroleum ether (b.p. 30°-60° C., 200 ml) and filtered. The filtrate was evaporated under vacuum to provide 8.5 g (109% of theory) 2,6-dichloro-4-methylbenzoyl chloride, IR (neat): 1785 cm-1. The crude chloride and chlorobenzene (94 g) were stirred in carbon tetrachloride (235 ml), treated in portions with aluminum chloride (5.35 g, 40.1 mmol), kept 30 minutes at ambient temperature, and refluxed 3 hours. The mixture was cooled, quenched by addition of ice and concentrated hydrochloric acid, and extracted three times with dichloromethane. The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The residue was chromatographed on a column of silica gel (400 g) eluted with 3:2 (v/v) dichloromethane-hexane to provide 7.19 g (69%) of 4-(4-chlorobenzoyl)-3,5-dichlorotoluene, m.p. 111.5°-114° C.

後処理

  1. temperaturewas refluxed 3 hours
  2. customevaporated under vacuum
  3. customazeotroped twice with benzene
  4. customThe residue was triturated with petroleum ether (b.p. 30°-60° C., 200 ml)
  5. filtrationfiltered
  6. customThe filtrate was evaporated under vacuum

出典と根拠

ORDレコード
ord-0ba9ff48635c43d2af16db0b3fc42bc5
出典データセット
uspto-grants-1986_05
特許番号
US04590201

反応ノート

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