Sodium Cyanide → 3-Chloro-2-cyanomethylbenzoic acid methyl ester

HRID 915356ノート

反応式

HRID 915356 の反応式
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([Cl:10])[C:5]=1[CH2:11]Br.[C-:14]#[N:15].[Na+]>CN(C=O)C.CCOCC.O>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([Cl:10])[C:5]=1[CH2:11][C:14]#[N:15]

参加物

6

反応物 2

HCID 8929Sodium CyanideHCID 110327262-Bromomethyl-3-chloro-benzoic acid methyl ester

生成物 1

HCID 668839793-Chloro-2-cyanomethylbenzoic acid methyl ester収率 65%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
55 °C

実験手順

To a solution of crude 2-bromomethyl-3-chlorobenzoic acid methyl ester (30.4 mmol) in DMF (60 mL), was added finely powdered sodium cyanide (2.22 g, 45 mmol). The reaction mixture turned brown rapidly, and became warm. The dark suspension was then immersed in an oil bath held at 55° C. The reaction mixture was allowed to stir at 55° C. for 1.5 hours, at which time heating was discontinued, and the reaction was allowed to cool to ambient temperature. After stirring at ambient temperature for 16 hours, the reaction was diluted with ether (300 mL) and water (200 mL). The layers were separated, the aqueous was extracted with ether (3×75 mL), and the combined organic extracts were washed with water (3×50 mL). The organic layer was then washed with brine (100 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure to afford a yellow oil. The crude oil was purified by flash chromatography eluting with a gradient from 0% to 16% ethyl acetate/hexane to afford 3-chloro-2-cyanomethylbenzoic acid methyl ester (3.9 g, 65% yield over two steps) as a white solid: 1H-NMR (400 MHz, CDCl3): δ 7.96 (1H, dd, J=8.1 Hz, 1.3 Hz), 7.65 (1H, dd, J=8.1, 1.3), 7.4 (1H, t, J=7.9Hz), 4.35 (2H, s), 3.97 (3H, s) ppm.

後処理

  1. temperaturebecame warm
  2. customThe dark suspension was then immersed in an oil bath
  3. customheld at 55° C
  4. temperatureheating
  5. temperatureto cool to ambient temperature
  6. stirringAfter stirring at ambient temperature for 16 hours
  7. customThe layers were separated
  8. extractionthe aqueous was extracted with ether (3×75 mL)
  9. washthe combined organic extracts were washed with water (3×50 mL)
  10. washThe organic layer was then washed with brine (100 mL)
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure
  14. customto afford a yellow oil
  15. customThe crude oil was purified by flash chromatography
  16. washeluting with a gradient from 0% to 16% ethyl acetate/hexane

出典と根拠

ORDレコード
ord-b0172cedec4c4ee5946b2440c35b1599
出典データセット
uspto-grants-2007_09
特許番号
US07265131B2

反応ノート

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