反応 #3998

ord-582897d5e0ee4beea88f45c69a6bdd13

反応方程式

ClCc1cccc2c1CC2
4-chloromethylbenzocyclobutene
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
CCOCC
diethyl ether
C1=Cc2cc(C[P+](c3ccccc3)(c3ccccc3)c3ccccc3)ccc21.[Cl-]
tripheny(4-benzocyclobutenyl)methyl phosphonium chloride

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    温度at reflux for 24 h
  2. 2
    ろ過followed by filtration

実験手順

A solution of 4-chloromethylbenzocyclobutene (24.4 g, 160 mmol) and triphenylphosphine (41.9 g, 160 mmol) in 120 ml of chloroform was heated at reflux for 24 h. Addition of diethyl ether followed by filtration gave tripheny(4-benzocyclobutenyl)methyl phosphonium chloride as a white powder: 1H NMR (CDCl3) δ3.03 (m, 4H), 5.36 (d, 2H), 6.82 (m, 3H), 7.6-7.8 (m, 15H). To a solution of the phosphonium salt in 500 ml of 37% formaldehyde in water was added dropwise 75 ml of 50% aqueous sodium hydroxide. The mixture was stirred at ambient temperature for 2 h and then extracted with diethyl ether. The ether extract was washed with brine and dried over magnesium sulfate. Fractional distillation gave 14.5 g of 90% pure 4-vinylbenzocyclobutene: bp 63°-66° C. (6 torr); 1H NMR (CDCl3) δ3.11 (s, 4 H), 5.11 (d, 1H), 5.63 (d, 1H), 6.66 (dd, 1H), 6.95 (d, 1H), 7.10 (s, 1H), 7.18 (d, 1H); 13C NMR (CDCl3) δ29.29, 29.44, 112.27, 119.87, 122.52, 125.70, 136.72, 137.97, 146.66, 146.01. ##STR6##

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US04722974uspto-grants-1988_02