Iodoethane → Ethyl 3,6-dichloro-2-methylbenzoate

HRID 577497ノート

反応式

HRID 577497 の反応式
[Cl:1][C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[Cl:12]N1C(=O)CCC1=O.C(=O)([O-])[O-].[Cs+].[Cs+].I[CH2:27][CH3:28]>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OC)(C)(C)C.O>[Cl:1][C:2]1[C:3]([CH3:11])=[C:4]([C:8]([Cl:12])=[CH:9][CH:10]=1)[C:5]([O:7][CH2:27][CH3:28])=[O:6]

参加物

9

反応物 4

HCID 6340IodoethaneHCID 10796Cesium carbonateHCID 31398ChlorosuccinimideHCID 820103-Chloro-2-methylbenzoic acid

生成物 1

HCID 86723723Ethyl 3,6-dichloro-2-methylbenzoate収率 81.4%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
110 °C

実験手順

A mixture of 3-chloro-2-methylbenzoic acid (100 g, 0.58 mol), N-chlorosuccinimide (90 g, 0.67 mol) and palladium (II) acetate (14.7 g, 65.7 mmol) in N,N-dimethylformamide (1 L) was stirred at 110° C. under a nitrogen atmosphere overnight. After cooling to room temperature, cesium carbonate (378 g, 1.16 mol) and iodoethane (317 g, 2.03 mol) were added and stirring continued at room temperature for 1.5 hours. The reaction mixture was poured into a mixture of water (1 L) and methyl tert-butyl ether (800 mL). Solids were removed by filtration, and the filtrate layers separated. The aqueous layer was extracted with more methyl tert-butyl ether (600 mL). The combined organic extracts were washed with saturated aqueous sodium chloride solution (1.2 L), dried over sodium sulfate, and concentrated in vacuo. The residue was purified by silica gel chromatography (eluting with 50:1 petroleum ether/ethyl acetate), affording ethyl 3,6-dichloro-2-methylbenzoate (253b, 110 g, ˜80% pure, 80% yield) as a yellow oil.

後処理

  1. temperatureAfter cooling to room temperature
  2. stirringstirring
  3. waitcontinued at room temperature for 1.5 hours
  4. customSolids were removed by filtration
  5. customthe filtrate layers separated
  6. extractionThe aqueous layer was extracted with more methyl tert-butyl ether (600 mL)
  7. washThe combined organic extracts were washed with saturated aqueous sodium chloride solution (1.2 L)
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by silica gel chromatography (eluting with 50:1 petroleum ether/ethyl acetate)

出典と根拠

ORDレコード
ord-2320b05f59a5491186425a6b53f48a54
出典データセット
uspto-grants-2015_05
特許番号
US09040515B2

反応ノート

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