(1,1'-Biphenyl)-2,2'-diol → Dibenzo(d,f)(1,3,2)dioxaphosphepin, 6-chloro-

HRID 479870

反応式

HRID 479870 の反応式
[C:1]1([OH:14])[C:2]([C:7]2[C:8]([OH:13])=[CH:9][CH:10]=[CH:11][CH:12]=2)=[CH:3][CH:4]=[CH:5][CH:6]=1.[P:15](Cl)(Cl)[Cl:16]>>[P:15]1([Cl:16])[O:13][C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=2[O:14]1

参加物

3

反応物 2

HCID 15731(1,1'-Biphenyl)-2,2'-diolHCID 24387Phosphorus trichloride

生成物 1

HCID 612102Dibenzo(d,f)(1,3,2)dioxaphosphepin, 6-chloro-収率 81%

実験手順

A solution of 2,2′-biphenol (28.1 g, 0.151 mol) in 49 mL phosphorus trichloride was heated at reflux for 2 hours. The excess PCl3 was removed by distillation. The residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg) to give 30.70 g (81% yield) 1,1′-biphenyl-2,2′-diyl phosphorochloridite (as a clear viscous oil which solidified to a white solid upon standing at room temperature in an inert atmosphere for an extended period of time). 31P{1H}NMR (121.4 MHz, d8-toluene): δ 180.1 (s), 85% H3PO4 external reference. To a solution containing 1.018 g (2.84 mmoles) of 2,2′-dihydroxy-3,3′-di-t-butyl-5,5′-dimethoxy-1,1′-biphenyl and 0.575 g (5.68 mmoles) of NEt3 in 15 ml of tetrahydrofuran (THF) was added 1.412 g (5.68 mmoles) of 1,1′-biphenyl-2,2′-diyl phosphorochloridite in 5 ml of THF. The mixture was stirred overnight at room temperature. The mixture was filtered through celite, washed with THF and solvent removed to give 2.2 g of white solid. 31P{1H} nmr (121.4 MHz, C6D6): 145.15 s and 138.5 s. 1H nmr (300 MHz, C6D6): singlet at 3.15 and 1.3 along with aromatic resonances.

後処理

  1. temperatureat reflux for 2 hours
  2. customThe excess PCl3 was removed by distillation
  3. distillationThe residue was purified by vacuum distillation (140-143° C. at 0.5 mm Hg)

出典と根拠

ORDレコード
ord-cb7cab976ca24474a4ddcb78a4c38f4c
出典データセット
uspto-grants-2003_11
特許番号
US06646148B1

関連ノート

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