PROCESS FOR SYNTHESIS OF FLUORINATED OLEFINS
Disclosed is a process for the synthesis of fluorinated olefins, and in particularly preferred embodiments tetrafluorinated olefins having F on an unsaturated, non-terminal carbon, such as 2,3,3,3-tetrafluoropropene. The preferred processes of the present invention in accordance with one embodiment generally comprise: (a) reacting a compound of formula (I) X 1 X 2 (I) with a compound of formula (II) CX 1 X 2 X 3 CX 1 ═CX 1 X 2 (II) to produce a reaction product comprising a compound of formula (III) CF 3 CHX 1 CH 2 X 2 (III), and (b) exposing said compound of formula (III) to reaction conditions effective to convert said compound of formula (III) to a compound of formula (IV) CF 3 CZ═CH 2 (IV) wherein X 1 , X 2 , and X 3 are each independently selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, provided that X 1 and X 2 in formula (I) are not both hydrogen and Z is Cl, I, Br, or F.
1 . A process for the synthesis of 2-halo-3,3,3-fluoropropene comprising:
(a) reacting a compound of formula (I)
X 1 X 2 (I)
with a compound of formula (II)
CX 1 X 2 X 3 CX 1 ═CX 1 X 2 (II)
to produce a reaction product comprising a compound of formula (III)
CF 3 CHX 1 CH 2 X 2 (III), and
(b) exposing said compound of formula (III) to reaction conditions effective to convert said compound of formula (III) to a compound of formula (IV)
CF 3 CZ═CH 2 (IV).
wherein X 1 , X 2 , and X 3 are each independently selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, provided that X 1 and X 2 in formula (I) are not both hydrogen and that Z is Cl, I, Br, or F.
2 . The process of claim 1 , wherein compound of formula (IIIB) is CF 3 CHFCH 2 Cl.
3 . The process of claim 1 , wherein compound of formula (IIIB) is CF 3 CHFCH 2 F.
4 . The process of claim 1 wherein said reacting step (a) is a catalyzed liquid phase reaction.
5 . The process of claim 4 wherein said reaction step (a) comprises reacting said HF with said compound of formula (IIA) at a temperature of from about 0° C. to about 250° C. and at a pressure of about 500 to about 1000 psig in the presence of a catalyst.
6 . The process of claim 5 wherein said catalyst comprises SbCl 5 .
7 . The process of claim 1 wherein said exposing step (b) is a liquid phase reaction that involves contacting the compound of formula (III) with a potassium hydroxide solution and, optionally, a Crown ether.
8 . The process of claim 7 wherein said exposing step is at least partially conducted at a temperature of from about 25° C. to about 90° C. and at a pressure of about 100 to about 200 psig.
9 . The process of claim 1 wherein said exposing step (b) is a vapor phase reaction that involves contacting the compound of formula (III) with a metal-based catalyst.
10 . The process of claim 9 wherein said metal-based catalyst is at least one of Pd or Ni on a carbon substrate.
11 . The process of claim 10 wherein said exposing step is at least partially conducted at a temperature of from about 200° C. to about 500° C.
12 . A process for the synthesis of 2,3,3,3 tetrafluoropropene comprising:
(a) reacting a compound of formula (IA)
X 1 X 2 (IA)
with a compound of formula (IIA)
CH 2 X 2 CX 2 ═CX 2 X 2 (IIA)
to produce a reaction product comprising a compound of formula (IIIA)
CF 3 CHFCH 2 Cl (IIIC), and
(b) exposing said compound of formula (IIIC) to reaction conditions effective to convert said compound of formula (IIIC) to a compound of formula (IVA)
CF 3 CF═CH 2 (IVA),
wherein X 1 is selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, and each X 2 is each independently selected from the group consisting of chlorine, bromine, fluorine and iodine.
13 . A process for the synthesis of 2,3,3,3 tetrafluoropropene comprising:
(a) reacting a compound of formula (IA)
X 1 X 2 (IA)
with a compound of formula (IIA)
CH 2 X 2 CX 2 ═CX 2 X 2 (IIA)
to produce a reaction product comprising a compound of formula (IIID)
CF 3 CHFCH 2 F (IIID), and
(b) exposing said compound of formula (IIID) to reaction conditions effective to convert said compound of formula (IIID) to a compound of formula (IVA)
CF 3 CF═CH 2 (IVA),
wherein X 1 is selected from the group consisting of hydrogen, chlorine, bromine, fluorine and iodine, and each X 2 is each independently selected from the group consisting of chlorine, bromine, fluorine and iodine.