Sodium Carbonate → tert-butyl N-(4-chloro-3-(hydroxymethyl)phenyl)carbamate

HRID 38673

反応式

HRID 38673 の反応式
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:10])=[C:6]([CH2:8][OH:9])[CH:7]=1.[C:11](=[O:14])([O-])[O-:12].[Na+].[Na+]>O1CCOCC1.O>[Cl:10][C:5]1[CH:4]=[CH:3][C:2]([NH:1][C:11](=[O:14])[O:12][C:6]([CH3:8])([CH3:7])[CH3:5])=[CH:7][C:6]=1[CH2:8][OH:9]

参加物

5

反応物 2

HCID 10340Sodium CarbonateHCID 13567962(5-Amino-2-chlorophenyl)methanol

生成物 1

HCID 54223790tert-butyl N-(4-chloro-3-(hydroxymethyl)phenyl)carbamate収率 136.9%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 312751,4-Dioxane溶媒

実験手順

To a solution of (5-amino-2-chlorophenyl)methanol (Aldrich, 500 mg, 3.17 mmol) in a mixture of dioxane (7.5 mL), water (7.5 mL) was added sodium carbonate (336 mg, 3.17 mmol) previously dissolved in 4 mL of water. Solution was stirred and cooled in an ice bath. Boc-anhydride (Aldrich, 692 mg, 3.17 mmol) was added in one portion, and stirring was continued at room temperature for 3 h. Dioxane was removed in vacuo conditions and the aqueous layer chilled, covered with a layer of ethyl acetate, and acidified to pH 4 with dilute KHSO4 (10%, aq) (ALDRICH). This was followed by extraction (EtOAc) and purification by chromatographic column 25 g cartridge (ISOLUTE silice) using Hex/EtOAc 100/0 to 50/50, giving 1,1-dimethylethyl [4-chloro-3-(hydroxymethyl)phenyl]carbamate (560 mg, 2.17 mmol, 68%). 1H NMR (300 MHz, DMSO-d6) δ ppm: 9.46 (br s, 1H), 7.72 (s, 1H), 7.21-7.32 (m, 2H), 5.35 (t, 1H), 4.48 (d, 2H), 1.47 (s, 9H).

後処理

  1. temperaturecooled in an ice bath
  2. stirringstirring
  3. customDioxane was removed in vacuo conditions
  4. temperaturethe aqueous layer chilled
  5. extractionThis was followed by extraction (EtOAc) and purification by chromatographic column 25 g cartridge (ISOLUTE silice)

出典と根拠

ORDレコード
ord-178c23a564744a40a216423d55993ca0
出典データセット
uspto-grants-2013_09
特許番号
US08524750B2

関連ノート

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