Vinyl Chloride → 1,1,3,3-Tetrachloropropane-1-phosphonic dichloride

HRID 1438903Notes

Reaction equation

HRID 1438903 reaction equation
[CH:1]([Cl:3])=[CH2:2].[Cl:4][C:5]([Cl:11])(Cl)[P:6]([Cl:9])([Cl:8])=[O:7].[Cl-:12].C([NH+](CC)CC)C>C(#N)C.C1(C(C(C2C=CC=CC=2)O)=O)C=CC=CC=1>[Cl:4][C:5]([Cl:11])([P:6]([Cl:9])([Cl:8])=[O:7])[CH2:2][CH:1]([Cl:12])[Cl:3]

Participants

6

Reactant 3

HCID 6338Vinyl ChlorideHCID 277422(Trichloromethyl)phosphonic dichlorideHCID 12698378Triethylazanium chloride

Product 1

HCID 213996861,1,3,3-Tetrachloropropane-1-phosphonic dichlorideYield 926.1%

Reagents, catalysts & solvents 2

HCID 8400BenzoinCatalystHCID 6342AcetonitrileSolvent

Procedure

6.25 g (0.1 mole) vinyl chloride, 23.6 g (0.1 mole) trichloromethane phosphonic dichloride, 540 mg (2 mmole) ferric chloride hexahydrate, 412 mg (3 mmole) triethylammonium chloride, and 424 mg (2 mmole) benzoin were heated in 30 ml acetonitrile in an ampoule at 100° during 15 hours. After opening of the ampoule, and evaporating unconverted vinyl chloride, the reaction product was diluted with methylene chloride, washed twice with ice-cold 1N aqueous hydrochloric acid and dried on calcium chloride. The solvent was distilled at atmospheric pressure, and unconverted phosphonic dichloride sublimed at 25 mm and 120°. The remainder was fractionated in vacuo, giving 8.3 g 1,1,3,3-tetrachloropropane-1-phosphonic dichloride, bp/0.1: 66°-67°; containing 70.3% Cl (Calc. for C3H3Cl6OP: 71.0%).

Workup

  1. customevaporating unconverted vinyl chloride
  2. additionthe reaction product was diluted with methylene chloride
  3. washwashed twice with ice-cold 1N aqueous hydrochloric acid
  4. customdried on calcium chloride
  5. distillationThe solvent was distilled at atmospheric pressure, and unconverted phosphonic dichloride
  6. customsublimed at 25 mm and 120°

Sources & evidence

ORD record
ord-c0c8d4aa3a0b416aadc30656de867739
Source dataset
uspto-grants-1977_11
Patent number
US04057579

Reaction notes

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