Phosphorus tribromide → Ethyl 3-(bromomethyl)-5-[(dipropylamino)carbonyl]benzoate

HRID 1350974

反応式

HRID 1350974 の反応式
[CH2:1]([N:4]([CH2:20][CH2:21][CH3:22])[C:5]([C:7]1[CH:8]=[C:9]([CH:15]=[C:16]([CH2:18]O)[CH:17]=1)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:6])[CH2:2][CH3:3].P(Br)(Br)[Br:24]>ClCCl>[Br:24][CH2:18][C:16]1[CH:15]=[C:9]([CH:8]=[C:7]([C:5]([N:4]([CH2:20][CH2:21][CH3:22])[CH2:1][CH2:2][CH3:3])=[O:6])[CH:17]=1)[C:10]([O:12][CH2:13][CH3:14])=[O:11]

参加物

4

反応物 2

HCID 24614Phosphorus tribromideHCID 21086103Ethyl 3-[(dipropylamino)carbonyl]-5-(hydroxymethyl)benzoate

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
50 °C

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. temperaturecooled
  2. custompartitioned between dichloromethane and water
  3. customThe organic phase is separated
  4. washwashed with aqueous sodium bicarbonate
  5. dry with materialdried over magnesium sulfate

出典と根拠

ORDレコード
ord-fe4ffce519514c9f9fef80a676f22802
出典データセット
uspto-grants-2007_05
特許番号
US07214715B2

関連ノート

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