Process for synthesis of fluorinated olefins

Abstract

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.

What is claimed is: 
     
         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 formula (I) comprises HF. 
     
     
         3 . The process of  claim 2  wherein formula (II) comprises a compound of formula (IIA)
   CH 2 X 2 CX 2 ═CX 2 X 2    (IIA)
 
 
       and wherein said reaction step (a) produces a reaction product comprising a compound of formula (IIIB)
   CF 3 CHFCH 2 Z 2    (IIIB),
 
 wherein Z 2  is Cl or F. 
 
     
     
         4 . The process of  claim 3  wherein said compound of formula (II) is CH 2 ClCCl═CCl 2 . 
     
     
         5 . The process of  claim 3  wherein compound of formula (IIIB) is CF 3 CHFCH 2 Cl. 
     
     
         6 . The process of  claim 3  wherein compound of formula (IIIB) is CF 3 CHFCH 2 F. 
     
     
         7 . The process of  claim 1  wherein said compound of formula (IV) is CF 3 CF═CH 2 . 
     
     
         8 . The process of  claim 5  wherein said compound of formula (IV) is CF 3 CF═CH 2 . 
     
     
         9 . The process of  claim 6  wherein said compound of formula (IV) is CF 3 CF═CH 2 . 
     
     
         10 . The process of  claim 1  wherein said reacting step (a) is a catalyzed liquid phase reaction. 
     
     
         11 . The process of  claim 10  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. 
     
     
         12 . The process of  claim 11  wherein said catalyst comprises SbCl 5 . 
     
     
         13 . 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. 
     
     
         14 . The process of  claim 13  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. 
     
     
         15 . 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. 
     
     
         16 . The process of  claim 15  wherein said metal-based catalyst is at least one of Pd or Ni on a carbon substrate. 
     
     
         17 . The process of  claim 16  wherein said exposing step is at least partially conducted at a temperature of from about 200° C. to about 500° C. 
     
     
         18 . 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. 
     
     
         19 . 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.