Water → 4-Acetamidophenyl 4-nitrophenyl carbonate

HRID 571161ノート

反応式

HRID 571161 の反応式
N1C=CC=CC=1.[OH:7][C:8]1[CH:13]=[CH:12][C:11]([NH:14][C:15](=[O:17])[CH3:16])=[CH:10][CH:9]=1.[C:18](Cl)(=[O:29])[O:19][C:20]1[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][CH:21]=1.O>ClCCl>[C:18](=[O:29])([O:19][C:20]1[CH:21]=[CH:22][C:23]([N+:26]([O-:28])=[O:27])=[CH:24][CH:25]=1)[O:7][C:8]1[CH:9]=[CH:10][C:11]([NH:14][C:15](=[O:17])[CH3:16])=[CH:12][CH:13]=1

参加物

6

反応物 4

HCID 962WaterHCID 1049PyridineHCID 1983Acetaminophen3 回HCID 821294-Nitrophenyl chloroformate

生成物 1

HCID 594879154-Acetamidophenyl 4-nitrophenyl carbonate収率 47%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

Adapting a known procedure (P. Pasetto, et al., Anal. Chim. Acta, 2005, 542(1), 66-75), 8.03 mL of anhydrous pyridine (7.84 g, 99.3 mmol; 1.5 eq.) was added at a temperature of about 0° C. (ice bath) to a suspension of 10.00 g N-(4-hydroxyphenyl)acetamide (1) (paracetamol (INN), acetaminophen (USAN) (66.2 mmol; 1.0 eq.) in 300 mL of anhydrous dichloromethane (DCM). The reaction mixture was stirred at the same temperature for about 10 minutes. To this mixture, a solution of 13.97 g (69.5 mmol; 1.05 eq.) of commercially available 4-nitrophenyl carbonochloridate (2) in 20 mL of anhydrous DCM was then added dropwise and the reaction mixture was stirred with gradual warming to room temperature for overnight. Fifty (50) mL of water were added to the reaction mixture. A solid precipitated out of solution. The solid was filtered off and washed successively with diethylether (Et2O) (2×50 mL) and hexane (4×50 mL) to afford 9.92 g (47% yield) of the target compound 3 as a colorless solid after drying in high vacuum. The initial filtrate (DCM and water) was washed with a saturated aqueous solution of sodium chloride (NaCl/brine). The organic layer was dried using anhydrous sodium sulfate (Na2SO4) to afford an additional 7.0 g (33% yield) of the target compound 3. Rf-value: 0.35 (ethyl acetate/hexane=1:1). 1H NMR (DMSO-d6, 300 MHz): δ=10.09 (s, 1H), 8.34 (d, J=9.3 Hz, 2H), 7.68 (d, J=9.3 Hz, 2H), 7.64 (d, J=9.0 Hz, 2H), 7.31 (d, J=8.7 Hz, 2H), 2.05 (s, 3H) ppm. LC/MS (ESI): m/z=317.2 [M+H]+. The analytical data corresponded to the analytical data given in the literature.

後処理

  1. stirringthe reaction mixture was stirred
  2. customA solid precipitated out of solution
  3. filtrationThe solid was filtered off
  4. washwashed successively with diethylether (Et2O) (2×50 mL) and hexane (4×50 mL)

出典と根拠

ORDレコード
ord-ea36f0d8afae49d78d0748c6592de10e
出典データセット
uspto-grants-2015_05
特許番号
US09024055B2

反応ノート

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