Fluorinated compounds containing a -OSF
A process for the preparation of fluorinated compounds having at least one —OSF 5 group, said method comprising the step of reacting SOF 4 with a fluorinated 3- or 4-membered cyclic ether in the presence of a fluoride catalyst.
1. A process for the preparation of fluorinated compounds having at least one —OSF 5 group, said process comprising the step of reacting SOF 4 with a ring-fluorinated 3- or 4-membered cyclic ether in the presence of a fluoride catalyst.
2. The process of claim 1 wherein the ring-fluorinated 3- or 4-membered cyclic ether is selected from those of formula (I-A) or (I-B):
and the corresponding fluorinated compound having at least one —OSF 5 group has formula (II-A) or (II-B):
wherein R 1 and R 2 , equal to or different from each other, are independently selected from the group consisting of F, and C 1 -C 5 fluorinated alkyl, optionally containing Cl atoms and/or optionally containing etheric oxygen atoms in the chain; and wherein R 3 is selected from the group consisting of H, and C 1 -C 3 alkyl, optionally containing F and/or Cl atoms and/or optionally containing etheric oxygen atoms in the chain.
3. The process of claim 2 , said process further comprising the step of reacting the acyl fluoride of formula (II-B) with fluorine to obtain acyl fluoride of formula (II-C):
wherein R 3 F is the fully fluorinated analogue of group R 3 in formula (II-B).
4. The process of claim 2 , further comprising reacting a compound with the acyl fluoride of formulae (II-A) or (II-B),
wherein R 1 is selected from the group consisting of F, C 1 -C 5 fluorinated alkyl, optionally containing Cl atoms and/or optionally containing etheric oxygen atoms in the chain and R 2 ═F, and
wherein R 3 is selected from the group consisting of H, C 1 -C 3 alkyl, optionally containing F and/or Cl atoms and/or optionally containing etheric oxygen atoms in the chain.
5. The process of claim 4 , wherein the acyl fluoride of formula (II-A) wherein R 2 is F or the acyl fluoride of formula (II-B) is reacted with hexafluoropropylene oxide and/or 2,2,3,3-tetrafluorooxethane in the presence of a catalyst, to obtain compounds of formula or (VI-A) (VI-B):
wherein R 1 is selected from the group consisting of F, and C 1 -C 5 fluorinated alkyl, optionally containing Cl atoms and/or optionally containing etheric oxygen atoms in the chain; R 3 is selected from the group consisting of H and C 1 -C 3 alkyl, optionally containing F and/or Cl atoms and/or optionally containing etheric oxygen atoms in the chain; n* is equal to 0 or is an integer from 1 to 15; and m* is equal to 0 or is an integer from 1 to 15.
6. The process of claim 5 , further comprising the step of pyrolyzing the acyl fluoride of formula (VI-A) or (VI-B) wherein m* is 0 and n*=n is an integer from 1 to 15, to give the corresponding fluorovinyl ethers of formula (IV-A) or (IV-B):
7. The process of claim 5 further comprising the step of fluorinating the acyl fluoride of formula (VI-A) or the acyl fluoride of formula (VI-B) to the corresponding fully fluorinated analogue of formula (VII-A):
wherein R 1 F is the fully fluorinated analogue of group R 1 in formula (IV-A).
8. The process of claim 7 further comprising the step of reacting the acyl fluoride of formula (VII-A), in the liquid phase at a temperature of from −150° C. to 0° C., with elemental fluorine and with at least one olefin of formula (VIII):
wherein A 1 , A 2 , A 3 , and A 4 , equal to or different from each other, are independently selected from the group consisting of H, F, Cl, Br, to obtain a compound of formula (IX-A):
9. The process of claim 8 , further comprising the step of further reacting by dehalogenation or dehydrohalogenation the compound of formula (IX-A) to obtain the corresponding vinyl ether of formula (XI-A):
wherein A 5 and A 6 , equal to or different from each other, are independently selected from the group consisting of H, F, Cl, and Br.
10. The process of claim 7 , said process further comprising the step of reacting the acyl fluoride of formula (VII-A) with elemental fluorine in the presence of a fluoride catalyst to obtain the corresponding hypofluorite of formula (XII-A):
11. The process of claim 10 , said process further comprising the step of reacting the hypofluorite of formula (XII-A) with one olefin of formula (VIII) to obtain a compound of formula (IX-A).
12. The process of claim 1 , wherein the fluoride catalyst is selected from the group consisting of alkali metal fluorides, alkali-earth metal fluorides, quaternary ammonium fluorides and silver fluoride.
13. The process of claim 3 , further comprising reacting a compound with the acyl fluoride of formula (II-C):
wherein R 3 F is selected from the group consisting of F and fully fluorinated C 1 -C 3 alkyl, optionally containing etheric oxygen atoms in the chain.
14. The process of claim 13 , wherein the acyl fluoride of formula (II-C) is reacted with hexafluoropropylene oxide and/or 2,2,3,3-tetrafluorooxethane in the presence of a catalyst, to obtain a compound of formula (VI-C):
wherein R 3 F is selected from the group consisting of F and fully fluorinated C 1 -C 3 alkyl, optionally containing etheric oxygen atoms in the chain; n* is equal to 0 or is an integer from 1 to 15; and m* is equal to 0 or is an integer from 1 to 15.
15. The process of claim 14 , further comprising the step of pyrolyzing the acyl fluoride of formula (VI-C) wherein m* is 0 and n*=n is an integer from 1 to 15, to give the corresponding fluorovinyl ether of formula (IV-C):
16. The process of claim 14 , further comprising the step of fluorinating the acyl fluoride of formula (VI-C) to the corresponding fully fluorinated analogue of formula (VII-C):
17. The process of claim 16 , further comprising the step of reacting the acyl fluoride of formula (VII-C), in the liquid phase at a temperature of from −150° C. to 0° C., with elemental fluorine and with at least one olefin of formula (VIII):
wherein A 1 , A 2 , A 3 , and A 4 , equal to or different from each other, are independently selected from the group consisting of H, F, Cl, Br, to obtain a compound of formula (IX-C):
18. The process of claim 17 , further comprising the step of further reacting by dehalogenation or dehydrohalogenation the compound of formula (IX-C) to obtain the corresponding vinyl ether of formula (XI-C):
wherein A 5 and A 6 , equal to or different from each other, are independently selected from the group consisting of H, F, Cl, and Br.
19. The process of claim 16 , said process further comprising the step of reacting the acyl fluoride of formula (VII-C) with elemental fluorine in the presence of a fluoride catalyst to obtain the corresponding hypofluorite of formula (XII-C):
20. The process of claim 19 , said process further comprising the step of reacting the hypofluorite of formula (XII-C) with one olefin of formula (VIII) to obtain a compound of formula (IX-C).