Benzoyl Peroxide → Ethyl 2-(bromomethyl)-5-chlorobenzoate

HRID 1640006ノート

反応式

HRID 1640006 の反応式
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([CH:12]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8].[Br:14]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>ClCCCl>[Br:14][CH2:13][C:5]1[CH:4]=[CH:3][C:2]([Cl:1])=[CH:12][C:6]=1[C:7]([O:9][CH2:10][CH3:11])=[O:8]

参加物

5

反応物 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 21269135Ethyl 5-chloro-2-methylbenzoate

生成物 1

HCID 13272463Ethyl 2-(bromomethyl)-5-chlorobenzoate収率 69.2%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒

反応条件

温度
75 °C

実験手順

A mixture of ethyl 5-chloro-2-methylbenzoate (3.20 g, 16.1 mmol), N-bromosuccinimide (3.15 g, 17.7 mmol) and benzoyl peroxide (0.39 g, 1.61 mmol) in 1,2-dichloroethane (90 mL) was heated to 75° C. in an oil bath for 4 h. After this time, the mixture was cooled to room temperature and the organic layer was washed with water (45 mL) and brine (45 mL). The organic layer was then dried over magnesium sulfate and concentrated under reduced pressure. Purification by flash chromatography (silica, 1:20 ethyl acetate/hexanes) afforded ethyl 2-(bromomethyl)-5-chlorobenzoate (3.09 g, 68%) as a clear oil: 1H NMR (500 MHz, CDC13) 7.94 (d, J=2.5 Hz, 1H), 7.46 (dd, J=8.5, 2.5 Hz, 1H), 7.40 (d, J=8.0 Hz, 1H), 4.91 (s, 2H), 4.42 (q, J=7.0 Hz, 2H), 1.43 (t, J=7.0 Hz, 3H); ESI MS m/z 279 [(M+2)+H]+.

後処理

  1. temperatureAfter this time, the mixture was cooled to room temperature
  2. washthe organic layer was washed with water (45 mL) and brine (45 mL)
  3. dry with materialThe organic layer was then dried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customPurification by flash chromatography (silica, 1:20 ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-df0590a0be1340c3a625f52c44e55cf8
出典データセット
uspto-grants-2012_02
特許番号
US08110681B2

反応ノート

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