4-Phenoxyphenol → Bis(4-phenoxyphenyl) Benzenephosphonothioate

HRID 273670

反応式

HRID 273670 の反応式
[O:1]([C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:15]1([P:21](Cl)(Cl)=[S:22])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CN(C)C1C=CN=CC=1.N1C=CC=CC=1>[C:15]1([P:21](=[S:22])([O:14][C:11]2[CH:10]=[CH:9][C:8]([O:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)=[CH:13][CH:12]=2)[O:14][C:11]2[CH:10]=[CH:9][C:8]([O:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)=[CH:13][CH:12]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

参加物

5

反応物 2

HCID 132544-PhenoxyphenolHCID 19016Phenylthionophosphonic dichloride

生成物 1

HCID 53954666Bis(4-phenoxyphenyl) Benzenephosphonothioate収率 79%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 1049Pyridine溶媒

実験手順

An oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser carrying a CaCl2 -Drierite drying tube, and a heating mantle, was charged with 4-phenoxyphenol (8.64 g, 46.4 mmol), 4-dimethylaminopyridine (0.57 g, 4.7 mmol), and anhydrous pyridine (40 mL), and the stirred solution was treated slowly with benzenephosphonothioic dichloride (3.6 mL, 23.2 mmol) via syringe. The resulting mixture was stirred at ambient temperature for 64 hours, then was heated at reflux for 1 hour, and allowed to cool. The reaction was monitored periodically by HPLC. Workup consisted of partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL), then washing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine. Drying (MgSO4) filtration and concentration gave a red oily residue. Purification by chromatography on flash-grade silica gel (4"×2" i.d.), eluting with CH2Cl2 , afforded 9.3 g (79 percent yield) of the title compound as a yellow, viscous oil which had a PDSC (O2) onset/extrap (° C.) of 248/324.

後処理

  1. customAn oven-dried 100 mL 3-necked flask equipped with a magnetic stirring bar, a reflux condenser
  2. temperaturewas heated
  3. temperatureat reflux for 1 hour
  4. temperatureto cool
  5. customof partitioning the reaction mixture between CH2Cl2 (100 mL) and water (100 mL)
  6. washwashing the organic phase successively with 100 mL portions of 5 percent NaOH, water, 5 percent HCl, water, and saturated brine
  7. customDrying
  8. filtration(MgSO4) filtration and concentration
  9. customgave a red oily residue
  10. customPurification by chromatography on flash-grade silica gel (4"×2" i.d.)
  11. washeluting with CH2Cl2

出典と根拠

ORDレコード
ord-72f13c08d75a48aaa1bcf3cdb7db414d
出典データセット
uspto-grants-1995_02
特許番号
US05387353

関連ノート

読み込み中…