BACKGROUND

Synthesis of a variety of polyfluoroallyl ethers is reported in U.S. Pat. No. 4,349,650 (Krespan) and U.S. Pat. No. 4,273,729 (Krespan). The polyfluoroallyl ethers are made by the reaction of a polyfluorocarbonyl compound such as a polyfluoroketone or polyfluorocarboxylic acid fluoride with fluoride ion and a polyfluoroallyl chloride, polyfluoroallyl bromide, or polyfluoroallyl fluorosulfate. Most commonly, polyfluoroallyl ethers are synthesized by substitution of the fluorosulfate group in CF2═CF—CF2—OSO2F (perfluoroallyl fluorosulfate or PFAFS) by alkoxides.

Perfluoroallyl fluorosulfate is obtained by the reaction of hexafluoropropylene with SO3and BF3. While effective in the reaction to make perfluoroallyl fluorosulfate, BF3is reported to be dangerous and difficult to handle (see, e.g., Wlassics et al. in “Perfluoro Allyl Fluorosulfate (FAFS): A Versatile Building Block for New Fluoroallylic Compounds”Molecules2011, 16, 6512-6540.

SUMMARY

The present disclosure provides synthetic methods for making polyfluoroallyl ethers that do not require the use of BF3and synthetic intermediates associated with these methods. By comparison to BF3, BCl3is much easier to handle, less toxic, less corrosive, and less expensive.

In one aspect, the present disclosure provides a method of making a compound having at least one perfluorinated allyl ether group. The method includes combining first components including at least one of CF2═CF—CF2—OSO2Cl or CF2═CF—CF2—OSO2CF3, a polyfluorinated compound comprising at least one ketone or carboxylic acid halide, and fluoride ion.

In another aspect, the present disclosure provides a method of making CF2═CF—CF2—OSO2Cl. The method includes combining second components including B(OSO2Cl)3and hexafluoropropylene to provide CF2═CF—CF2—OSO2Cl.

In another aspect, the present disclosure provides a compound represented by formula CF2═CF—CF2—OSO2Cl.

In another aspect, the present disclosure provides a method of making CF2═CF—CF2—OSO2CF3, the method comprising combining second components comprising M(OSO2CF3)3and hexafluoropropylene at a temperature greater than 0° C. to provide CF2═CF—CF2—OSO2CF3, wherein M is Al or B.

In this application:

Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terms “a”, “an”, and “the” are used interchangeably with the term “at least one”.

The phrase “comprises at least one of” followed by a list refers to comprising any one of the items in the list and any combination of two or more items in the list. The phrase “at least one of” followed by a list refers to any one of the items in the list or any combination of two or more items in the list.

“Alkyl group” and the prefix “alk-” are inclusive of both straight chain and branched chain groups and of cyclic groups. Unless otherwise specified, alkyl groups herein have up to 20 carbon atoms. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.

The terms “aryl” and “arylene” as used herein include carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring optionally substituted by up to five substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo), hydroxy, or nitro groups. Examples of aryl groups include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.

“Alkylene” is the multivalent (e.g., divalent or trivalent) form of the “alkyl” groups defined above. “Arylene” is the multivalent (e.g., divalent or trivalent) form of the “arll” groups defined above.

“Arylalkylene” refers to an “alkylene” moiety to which an aryl group is attached. “Alkylarylene” refers to an “arylene” moiety to which an alkyl group is attached.

The terms “perfluoro” and “perfluorinated” refer to groups in which all C—H bonds are replaced by C—F bonds.

The phrase “interrupted by at least one —O— group”, for example, with regard to a perfluoroalkyl or perfluoroalkylene group refers to having part of the perfluoroalkyl or perfluoroalkylene on both sides of the —O— group. For example, —CF2CF2—O—CF2—CF2— is a perfluoroalkylene group interrupted by an —O—.

All numerical ranges are inclusive of their endpoints and nonintegral values between the endpoints unless otherwise stated (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

