Sodium Cyanide → Ethyl 3-(cyanomethyl)-5-[(dipropylamino)carbonyl)benzoate

HRID 348818

反応式

HRID 348818 の反応式
Br[CH2:2][C:3]1[CH:4]=[C:5]([CH:11]=[C:12]([C:14]([N:16]([CH2:20][CH2:21][CH3:22])[CH2:17][CH2:18][CH3:19])=[O:15])[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7].[C-:23]#[N:24].[Na+]>CS(C)=O>[C:23]([CH2:2][C:3]1[CH:4]=[C:5]([CH:11]=[C:12]([C:14]([N:16]([CH2:20][CH2:21][CH3:22])[CH2:17][CH2:18][CH3:19])=[O:15])[CH:13]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:24]

参加物

4

反応物 2

HCID 8929Sodium CyanideHCID 21086099Ethyl 3-(bromomethyl)-5-[(dipropylamino)carbonyl]benzoate

生成物 1

HCID 21086102Ethyl 3-(cyanomethyl)-5-[(dipropylamino)carbonyl)benzoate

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

実験手順

A mixture of ethyl 3-[(dipropylamino)carbonyl]-5-(hydroxymethyl)benzoate (1.5 g) and phosphorous tribromide (0.95 mL) is stirred in dichloromethane (10 mL) and heated at 50 degrees C. for 4 hours and then cooled and partitioned between dichloromethane and water. The organic phase is separated and washed with aqueous sodium bicarbonate and then dried over magnesium sulfate and taken to dryness to give ethyl 3-(bromomethyl)-5-[(dipropylamino)carbonyl]benzoate, high resolution MS MH+=370.1020. Ethyl 3-(bromomethyl)-5-[(dipropylamino)carbonyl]benzoate (1.4 g) and sodium cyanide (0.2 g) are stirred in dry DMSO (25 mL) at 20–25 degrees C. for 3.5 hours and the mixture is then partitioned between ethyl acetate, water and saline. The organic layer is separated and dried over magnesium sulfate and taken to dryness under reduced pressure to give ethyl 3-(cyanomethyl)-5-[(dipropylamino)carbonyl]benzoate. Ethyl 3-(cyanomethyl)-5-[(dipropylamino)carbonyl]benzoate (0.6 g) is hydrolyzed with lithium hydroxide monohydrate (0.1 g) in ethanol and water at 20–25 degrees C. overnight and then added to water (50 mL). The pH is adjusted to 4 using concentrated hydrochloric acid and the mixture is partitioned between ethyl acetate, water, and saline. The organic phase is separated and dried over magnesium sulfate and taken to dryness under reduced pressure to give 3-(cyanomethyl)-5-[(dipropylamino)carbonyl]benzoic acid, MS M+H=287.2.

後処理

  1. customthe mixture is then partitioned between ethyl acetate, water and saline
  2. customThe organic layer is separated
  3. dry with materialdried over magnesium sulfate

出典と根拠

ORDレコード
ord-2e14a7470aba42bfb510a8538dbde8ba
出典データセット
uspto-grants-2007_02
特許番号
US07176242B2

関連ノート

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