Process for synthesis of fluorinated olefins

Patent metadata

Field	Value
Publication number	US-2016145176-A1
Application number	US-201514797699-A
Country	US
Kind code	A1
Filing date	Jul 13, 2015
Priority date	Oct 15, 2007
Publication date	May 26, 2016
Grant date	—

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.

First claim

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.

Assignees

• Honeywell Int Inc

Inventors

• Mukhopadhyay Sudip
• Bortz Cheryl L
• Light Barbara A
• Cantlon Cheryl L
• Johnson Robert C

Classifications

• C07C17/21 Primary

  with simultaneous increase of the number of halogen atoms · CPC title

• C07C17/25

  by splitting-off hydrogen halides from halogenated hydrocarbons · CPC title

• C07C17/23

  by dehalogenation · CPC title

• C07C21/18

  containing fluorine · CPC title