Method for producing fluorinated organic compounds
View Patent ↗Disclosed is a method for producing fluorinated organic compounds, including hydrofluoropropenes, which preferably comprises converting at least one compound of formula (I): CF 3 CF n CH m X a-m (I) to at least one compound of formula (II) CF 3 CZCHZ (II). where each X is independently Cl, F, I or Br; each Z is independently H or F; n is 1 or 2; m is 1, 2 or 3, provided that when n is 1, m is 1 or 2; a is 2 or 3, and a-m≧0. Certain embodiments include the step of reacting fluorinated C 2 olefin, such as tetrafluoroethylene, with a Cl addition agent under conditions effective to produce a compound of formula (I).
1. A method of preparing fluorinated organic compounds comprising
(a) reacting at least one fluorinated C2 olefin with at least one addition agent under conditions effective to produce a compound of formula (I),
CF 3 CF n CH m X a-m (I)
where each X is independently Cl, I or Br; n is 1 or 2; m is 1, 2 or 3, a is 2 or 3, and a-m ≧0, provided that when n is 1, m is 1 or 2 and provided that valence of each carbon atom is satisfied, wherein at least one fluorinated C2 olefin comprises a compound of formula III
CY 2 ═CY 2 (III)
where each Y is independently F, Cl, I or Br, provided that there is at least one F on each carbon atom, and wherein at least one addition agent comprises a compound of formula (IV)
CH m Y a-m (IV)
where m is 1, 2 or 3; a is 4, and a-m≧0;
(b) dehydrohalogenating the at least one compound of formula (I) to at least one compound of formula (II)
CF 3 CZ═CHZ (II)
in the presence of hydrogen as a reducing agent that reduces at least one compound of formula (I) to at least one compound of formula (II), wherein each Z is independently H or F and where at least one compound of formula I is not the same as at least one compound of formula II.
2. The method of claim 1 wherein said compound of formula (III) comprises as compound of formula (IIIA) CF 2 ═CY 2 (IIIA) where each Y is independently F or Cl, and the compound of formula (IV) comprises a compound of formula CH 2 FCl.
3. The method of claim 1 wherein said fluorinated C2 olefin comprises tetrafluoroethylene.
4. The method of claim 1 wherein said step of reacting a compound of formula (III) is carried out under conditions effective to convert at least about 15% of said compound of formula (III).
5. The method of claim 1 wherein said step of reacting a compound of formula (III) is carried out under conditions effective to provide selectivity to compound(s) of formula (I) of at least about 50%.
6. The method of claim 1 wherein said step of reacting a compound of formula (III) is carried out under conditions effective to provide a selectivity to compound(s) of formula (I) of at least about 70%.
7. The method of claim 1 wherein said dehydrohalogenating step is carried out under conditions effective to provide a formula (I) conversion of at least about 40%.
8. The method of claim 1 wherein said dehydrohalogenating step is carried out under conditions effective to provide a formula (I) conversion of at least about 90%.
9. The method of claim 6 wherein said dehydrohalogenating step is carried out under conditions effective to provide a formula (II) selectivity of at least about 40%.
10. The method of claim 1 wherein said dehydrohalogenating step is carried out under conditions effective to provide a formula (II) selectivity of at least about 90%.
11. The method of claim 1 wherein said reacting step comprises introducing said compounds of formulas (III) and (IV) to a reactor containing catalyst.
12. The method of claim 11 wherein said catalyst is selected from the group consisting of carbon, activated carbon, palladium, palladium on carbon, palladium on aluminum oxides, ruthenium, and ruthenium on aluminum oxides.
13. The method of claim 1 wherein at least one of said reacting step or said dehydrohalogenating step is a continuous process.
14. The method of claim 1 , wherein the compound of formula (II) is 2,3,3,3-tetrafluoropropene.
15. The method of claim 1 wherein said dehydrohalogenating step is in a gas phase.
16. A method of preparing fluorinated organic compounds comprising dehydrohalogenating at least one compound of formula:
CF 3 CF 2 CH 3
to at least one compound of the following formula
CF 3 CZ═CH 2
in the presence of a reducing agent, where each Z is independently H or F.
17. A method of preparing fluorinated organic compounds comprising:
(a) reacting fluorinated C2 olefin with an addition agent under conditions effective to produce at least one compound of formula (I)
CF 3 CF n CH m X a-m (I) wherein said compound of formula (I) is not CF 3 CF 2 CH 3 ;
(b) converting at least one compound of said formula I to CF 3 CF 2 CH 3 and
(c) dehydrohalogenating at least one of CF 3 CF 2 CH 3 to at least one compound of the following formula
CF 3 CZ═CH 2 ,
wherein steps (b) and (c) are in the presence of a reducing agent where each X is independently Cl, I or Br; each Z is independently H or F; n is 1 or 2; m is 1, 2 or 3, a is 2 or 3, and a-m ≧0, provided that when n is 1, m is 1 or 2and provided that valence of each carbon atom is satisfied.
18. A method of preparing fluorinated organic compounds comprising dehydrohalogenating at least one compound of formula (I):
CF 3 CF n CH m X a-m (I); and
to at least one compound of formula (II)
CF 3 CZ═CHZ (II)
in the presence of hydrogen as a reducing agent that reduces at least one compound of formula (I) to at least one compound of formula (II), where each X is independently Cl, I or Br; each Z is independently H or F; n is 1 or 2; m is 1, 2 or 3, a is 2 or 3, and a-m ≧0, provided that when n is 1, m is 1 or 2and provided that valence of each carbon atom is satisfied, and wherein said dehydrohalogenating step is carried out under conditions effective to provide a formula (II) selectivity of at least about 90%.
19. The method of claim 18 further comprising forming said compound of formula (I) by a method comprising reacting fluorinated C2 olefin with an addition agent under conditions effective to produce a compound of formula (I).
20. The method of claim 19 wherein said fluorinated C2 olefin comprises a compound of formula (III) CY 2 ═CY 2
where each Y is independently F, Cl, I or Br, provided that there is at least one F on each carbon atom, and wherein said addition agent is a compound of formula (IV)
CH m Y a-m (IV)
where m is 1, 2 or 3; a is 4, and a-m ≧0.
21. The method of claim 20 wherein said compound of formula (III) comprises as compound of formula (IIIA) CF 2 ═CY 2 (IIIA) where each Y is independently F or Cl, and the compound of formula (IV) comprises a compound of formula CH 2 FCl.
22. The method of claim 20 wherein said fluorinated C2 olefin comprises tetrafluoroethylene.
23. The method of claim 18 wherein at least one of said reacting step or said dehydrohalogenating step is a continuous process.
24. The method of claim 18 , wherein the compound of formula (II) is 2,3,3,3-tetrafluoropropene.