Diethyl Ether → HCID 88650869, compound

HRID 255612Notes

Reaction equation

HRID 255612 reaction equation
[Cl:1]C[C:3]1[CH:10]=[CH:9][CH:8]=[C:5]2[CH2:6][CH2:7][C:4]=12.[C:11]1([P:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH2:30](OCC)C>C(Cl)(Cl)Cl>[Cl-:1].[C:24]1([P+:17]([C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH2:30][C:9]2[CH:10]=[CH:3][C:4]3[CH:7]=[CH:6][C:5]=3[CH:8]=2)[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 11776TriphenylphosphineHCID 126177184-Chloromethylbenzocyclobutene

Product 1

HCID 88650869HCID 88650869, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

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, 4H), 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.

Workup

  1. temperatureat reflux for 24 h
  2. filtrationfollowed by filtration

Sources & evidence

ORD record
ord-6d4a866daccc4c669934809c255a6c49
Source dataset
uspto-grants-1987_10
Patent number
US04698394

Reaction notes

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