Ethylene → 4-Bromo-3-chloro-3,4,4-trifluorobut-1-ene

HRID 590637

Reaction equation

HRID 590637 reaction equation
C=C.C(F)(F)=C(Cl)F.C(OOC(C)(C)C)(=O)C(C)(C)C.C(OOC(C)(CCC(OOC(C)(C)C)(C)C)C)(C)(C)C.[Br:41][C:42]([C:45]([CH2:48][CH2:49]Br)([Cl:47])[F:46])([F:44])[F:43]>FC(F)(F)CC(F)(F)C>[Br:41][C:42]([C:45]([CH:48]=[CH2:49])([Cl:47])[F:46])([F:44])[F:43]

Participants

7

Reactant 5

HCID 6325EthyleneHCID 65452,5-Dimethyl-2,5-di-(tert-butylperoxy)hexaneHCID 6594ChlorotrifluoroethyleneHCID 61238tert-BUTYL PEROXYPIVALATEHCID 1362211,4-Dibromo-2-chloro-1,1,2-trifluorobutane

Product 1

HCID 1362174-Bromo-3-chloro-3,4,4-trifluorobut-1-ene

Reagents, catalysts & solvents 1

HCID 678841,1,1,3,3-PentafluorobutaneSolvent

Procedure

A supply of BCTFB was obtained by reacting ethylene with dibrominated CTFE in 1,1,1,3,3-pentafluorobutane at 120° C. for 4 hours using a mixture of tert-butyl peroxypivalate (TBPPi, 3 mol %) and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (Trigonox 101, 4.5 mol %) as radical initiators, with the resulting structure being Br—CF2—CFCl—CH2—CH2—Br after distillation under vacuum. This was dehydrochlorinated with KOH in refluxing methanol for 15 hours, forming Br—CF2—CFCl—CH═CH2 (BCTFB). Successful radical copolymerization of CTFE (96 mol % in the feed) with BCTFB initiated by TBPPi (2 mol % with respect to both monomers) was carried out at 74° C. in a 100 mL autoclave. The 19F NMR spectrum of the obtained polymer is shown in FIG. 7.

Workup

  1. customA supply of BCTFB was obtained
  2. customat 120° C.
  3. customfor 4 hours
  4. distillationafter distillation under vacuum
  5. temperaturein refluxing methanol for 15 hours

Sources & evidence

ORD record
ord-1bac611b9d77408f8d1b37e1104a652a
Source dataset
uspto-grants-2016_01
Patent number
US09234062B2

Linked notes

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