Halogenated heteroalkenyl- and heteroalkyl-functionalized organic compounds and methods for preparing same - Patents.com

Abstract

Trifluoropropenyl ether-substituted aromatic compounds are provided. [Solution] This problem is solved by a trifluoropropenyl ether-substituted aromatic compound selected from the group consisting of 4-chlorophenyl-3,3,3-trifluoropropenyl ether, 1,4-bis(3,3,3-trifluoropropenyloxy)benzene, 4-methylphenyl-3,3,3-trifluoropropenyl ether, 3-cyanophenyl-3,3,3-trifluoropropenyl ether, 2-fluorophenyl-3,3,3-trifluoropropenyl ether, 3-nitrophenyl-3,3,3-trifluoropropenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoropropenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4-(3,3,3-trifluoropropenyl)phenyl sulfate, and the like.

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to synthetic methods for introducing halogenated heteroalkenyl-containing functional groups (e.g., trifluoropropenyl-containing functional groups such as trifluoropropenyl ethers, trifluoropropenyl thioethers, trifluoropropenyl amine substituents, etc.) and halogenated heteroalkyl-containing functional groups into organic compounds, and the reaction products resulting from such methods. [Background technology]

[0002] Related Technology Background The preparation of novel organic compounds containing various types of substituents, particularly those containing functional groups capable of further reactions (e.g., polymerization or derivatization) or capable of imparting desired physical or chemical properties to the organic compounds, continues to be of great interest in the chemical, advanced materials (including electronic materials and coatings), agricultural and pharmaceutical industries. As is well known, substituted or functionalized organic compounds have many different end uses, such as solvents, monomers, synthetic intermediates, active pharmaceutical ingredients, pesticides, herbicides, complexing agents, etc.

[0003] One type of organic substituent of particular interest would be a substituent containing a halogenated (e.g., fluorinated) alkenyl or halogenated alkyl moiety, such as a trifluoropropenyl moiety (e.g., a trifluoro-1-propenyl moiety corresponding to the structure F3C-CH=CH-, or a trifluoro-2-propenyl moiety corresponding to the structure F3C-C(-)=CH2). Also of interest are substituents having heteroatoms (O, N, S) attached to the halogenated (e.g., fluorinated) alkenyl or halogenated (e.g., fluorinated) alkyl moieties. Exemplary substituents of this type include trifluoropropenyl ether, trifluoropropenyl thioether, and trifluoropropenyl amine substituents. For example, such a substituent can correspond to the structure F3C-CH=CH-X- (cis or trans form) or F3C-C(-X-)=CH2, where X is O (oxygen), S (sulfur), or NR (where N is nitrogen and R is hydrogen or an organic moiety such as an alkyl group, which may be substituted). Summary of the Invention [Means for solving the problem]

[0004] Summary of the Invention Various aspects of the present invention can be summarized, without being limited thereto, as follows. Aspect 1: A method for producing a halogenated organic compound, comprising reacting an active hydrogen-containing organic compound selected from the group consisting of alcohols, primary amines, secondary amines, and thiols with a halogenated olefin having a carbon-carbon double bond to produce the halogenated organic compound, wherein at least one carbon of the carbon-carbon double bond is substituted with at least one substituent selected from the group consisting of halogens and halogenated alkyl groups. Aspect 2: The method of embodiment 1, wherein the halogenated olefin contains 1, 2, 3, 4 or more fluorine atoms. Aspect 3: The method of any one of the preceding claims, wherein the halogenated organic compound is a halogenated heteroalkenyl-functionalized organic compound (e.g., a fluorinated heteroalkenyl-functionalized organic compound, a chlorinated heteroalkenyl-functionalized organic compound, or a chlorinated / fluorinated heteroalkenyl-functionalized organic compound). Aspect 4: The method of any one of the preceding claims, wherein the halogenated organic compound is a halogenated heteroalkyl-functionalized organic compound (e.g., a fluorinated heteroalkyl-functionalized organic compound, a chlorinated heteroalkyl-functionalized organic compound, or a chlorinated / fluorinated heteroalkyl-functionalized organic compound). Aspect 5: A method according to any one of aspects 1 to 4, wherein the halogenated olefin has one carbon of a carbon-carbon double bond substituted with a fluorinated alkyl group. Aspect 6: A method according to any one of aspects 1 to 5, wherein the halogenated olefin has one carbon of a carbon-carbon double bond substituted with a perfluoroalkyl group. Aspect 7: The method of any one of aspects 1 to 6, wherein the halogenated olefin has a structure of formula (1): CX 1 X 2 =CX 3 X 4 (1) In the formula, X 1 , X 2 , X 3 and X 4 are independently hydrogen (H), chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and halogenated and non-halogenated C1-C 20 alkyl groups, with the proviso that X 1 , X 2 , X 3 and X 4 One or more of X is selected from the group consisting of chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and a halogenated alkyl group. In another embodiment, particularly when the active hydrogen-containing compound is an aliphatic alcohol, X 1 , X 2 , X 3 Or X4 In another embodiment, X is Br. 1 , X 2 , X 3 Or X 4 At least one of is Cl, and the halogenated olefin further comprises 1, 2, 3, 4 or more fluorine atoms. Aspect 8: The halogenated olefin may be CClF=CH2 (VCF), CH2=CF2 (VDF), CFH=CH2, CF2=CHF, CF3CF=CH2, CF2=CF2 (TFE), CH2=CHCl, CHCl=CHCl, CH2=CCl2, CF2=CFCl; CF2=CHCl, CF3CCl=CH2, CF3CCl=CClH, CF3CH=CCl2, CF3CF=CCl2, CF3CF=CClH, CF3CCl=CFH, CF3 8. The method of any one of aspects 1 to 7, wherein the CF3CF is selected from the group consisting of CCl=CF2, CF3CCl=CFCl, CF3CF=CFCl, CF3CH=CHCl, CF3CF=CFH, CF3CH=CF2, CF3CF=CF2, CF3CH2CF=CH2, CF3CH=CFCH3, CF3CF=CHCF3, CF3CCl=CHCF3, CF2HCH2CF=CH2, CF2HCH2CF=CHCl and CF2HCH=CFCH2Cl. Aspect 9: A method according to any one of the preceding aspects, wherein the halogenated olefin is reacted with a phenolic compound. Aspect 10: The method according to any one of the preceding aspects, wherein the halogenated olefin is reacted with an aliphatic alcohol. Aspect 11: A method according to any one of the first to eighth aspects, wherein the halogenated olefin is reacted with an aliphatic polyhydric alcohol (polyol). Aspect 12: 9. The method of any of the preceding aspects, wherein the halogenated olefin is reacted with a masked aliphatic polyalcohol, which is an aliphatic polyol having multiple hydroxyl groups, in which at least one hydroxyl group is blocked and at least one hydroxyl group is a free hydroxyl group. Aspect 13: A method according to any one of the preceding aspects, wherein the halogenated olefin is reacted with a primary or secondary amine. Aspect 14: The method of any one of aspects 1 to 8, wherein the halogenated olefin is reacted with a thiol. Aspect 15: A method according to any one of aspects 1 to 14, wherein the reaction is carried out under basic conditions. Aspect 16: 16. The method according to any one of the preceding aspects, wherein the reaction is carried out in the presence of an inorganic base. Aspect 17: 17. The method of embodiment 16, wherein the inorganic base is selected from the group consisting of alkali metal hydroxides and alkali metal carbonates. Aspect 18: A method according to any one of the preceding aspects, wherein the reaction is carried out in a liquid medium. Aspect 19: 20. The method of embodiment 18, wherein the liquid medium is comprised of one or more organic solvents. Aspect 20: 20. The method of embodiment 19, wherein the one or more organic solvents are selected from the group consisting of polar aprotic organic solvents. Aspect 21: 20. The method according to aspect 19, wherein the one or more organic solvents are polar aprotic organic solvents having a dielectric constant from 2 to 190. Aspect 22: 22. The method according to any one of the preceding aspects, wherein the reaction is carried out in the presence of a phase transfer catalyst. Aspect 23: The phenolic compound has the structure Ar(OH) x wherein Ar is an optionally substituted aromatic moiety and x is an integer equal to or greater than 1. Aspect 24: 24. The method of embodiment 23, wherein x is 1, 2 or 3. Aspect 25: 25. The method of any one of embodiments 23 to 24, wherein Ar is selected from the group consisting of optionally substituted phenyl, optionally substituted naphthyl, and optionally substituted anthryl. Aspect 26: 26. The method of any one of aspects 23-25, wherein Ar is an aromatic moiety substituted with one or more substituents selected from the group consisting of halogen, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted alkoxy, optionally substituted aroxy, optionally substituted aryl, optionally substituted heteroaryl, cyano, optionally substituted carboxyl, sulfate, nitrile, and nitro. Aspect 27: 27. The method according to any one of aspects 1 to 26, wherein the active hydrogen-containing organic compound and the halogenated olefin are reacted at a temperature of about 5° C. to about 200° C., or about 20° C. to about 120° C., for about 0.5 hours to about 120 hours. Aspect 28: The method according to any one of aspects 1 to 27, wherein the active hydrogen-containing organic compound and the halogenated olefin are reacted in a stoichiometric ratio of (moles of active hydrogen-containing organic compound) / x:moles of halogenated olefin, where x is the number of active hydrogens per mole of the active hydrogen-containing organic compound, from about 1:8 to about 8:1. Aspect 29: A trifluoropropenyl ether substituted aromatic compound of formula (I): Ar(OCR 1 =CHR 2 ) x (I) where Ar is an optionally substituted aromatic moiety, x is an integer equal to or greater than 1, and R 1 is CF3, R 2 is H or R 1 is H and R 2 is either CF3 or Aspect 30: 30. The trifluoropropenyl ether substituted aromatic compound according to embodiment 29, wherein x is 1, 2 or 3. Aspect 31: The trifluoropropenyl ether substituted aromatic compound according to any one of embodiments 29 to 30, wherein Ar is selected from the group consisting of an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted anthryl group. Aspect 32: The trifluoropropenyl ether substituted aromatic compound according to any one of aspects 29 to 31, wherein Ar is an aromatic moiety substituted with one or more substituents selected from the group consisting of halogen, alkyl, cyano, sulfate, nitrile, and nitro. Aspect 33: The trifluoropropenyl substituted aromatic compound may be 4-chlorophenyl-3,3-trifluoropropenyl ether, 1,4-bis(3,3,3-trifluoropropenyloxy)benzene, 4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4-methylphenyl-3,3,3-trifluoropropenyl ether, 3-cyanophenyl-3,3,3-trifluoropropenyl ether, 2-fluorophenyl-3,3,3-trifluoropropenyl ether, 3-nitrophenyl-3,3,3-trifluoropropenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoropropenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4-(3,3,3-trifluoropropenyl)phenyl sulfate, 4-fluorophenyl-3,3,3-trifluoro-2-propenyl 33. The trifluoropropenyl-substituted aromatic compound according to any one of embodiments 29 to 32, wherein the trifluoropropenyl-substituted aromatic compound is selected from the group consisting of phenyl ether, 3-nitrophenyl-3,3,3-trifluoro-2-propenyl ether, 2-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, 4-methylphenyl-3,3,3-trifluoro-2-propenyl ether, 4-chlorophenyl-3,3,3-trifluoro-2-propenyl ether, 3-cyanophenyl-3,3,3-trifluoro-2-propenyl ether, 1,4-bis(3,3,3-trifluoro-2-propenyl)phenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoro-2-propenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, and 4-(3,3,3-trifluoro-2-propenyl)phenyl sulfate sodium salt. Aspect 34: Haloalkyl ether (meth)acrylates corresponding to the following general structure (I): X 1 X 2 HC-CX 3 X 4 -OROC(=O)-CR 1 =CH2(I) where R is an organic moiety and X 1 , X 2 , X3 and X 4 are independently selected from hydrogen, halogen, alkyl, or haloalkyl, with the proviso that X 1 , X 2 , X 3 Or X 4 At least one of R is a halogen or haloalkyl group; 1 is hydrogen, methyl or fluorine. Aspect 35: X 1 , X 2 , X 3 Or X 4 35. The haloalkyl ether (meth)acrylate according to embodiment 34, wherein at least two of are selected from the group consisting of halogen and a haloalkyl group. Aspect 36: X 1 , X 2 , X 3 Or X 4 36. The haloalkyl ether (meth)acrylate according to any one of claims 34 to 35, wherein at least two of are selected from the group consisting of fluorine and a fluoroalkyl group. Aspect 37: X 1 , X 2 , X 3 Or X 4 37. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 36, wherein at least one of is fluorine or a fluoroalkyl group. Aspect 38: X 1 , X 2 , X 3 and X 4 38. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 37, wherein each of is a halogen or a haloalkyl group. Aspect 39: X 1 , X 2 , X 3 Or X 4 39. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 38, wherein one of said groups is a C1 to C8 haloalkyl group. Aspect 40: X 1, X 2 , X 3 Or X 4 40. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 39, wherein one of the groups is a C1 to C8 fluoroalkyl group. Aspect 41: (a)X 1 is chlorine and X 2 , X 3 and X 4 is fluorine, or (b) X 3 is chlorine and X 1 , X 2 and X 4 35. The haloalkyl ether (meth)acrylate according to embodiment 34, wherein is fluorine. Aspect 42: 42. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 41, wherein R is an alkylene segment or a poly(oxyalkylene) segment. Aspect 43: 43. The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 42, wherein R is an ethylene segment or a poly(oxyethylene) segment. Aspect 44: R is -[CH2CH2O] n The haloalkyl ether (meth)acrylate according to any one of embodiments 34 to 43, wherein n is 0 or an integer of 1 to 10. Aspect 45: Part X 1 X 2 HC-CX 3 X 4 45. The haloalkyl ether (meth)acrylate of any one of embodiments 34 to 44, wherein -ORO- has a molecular weight of 900 Daltons or less. Aspect 46: 46. ​​The haloalkyl ether (meth)acrylate of any one of embodiments 34 to 45, wherein R is a non-halogenated organic moiety. Aspect 47: 47. The haloalkyl ether (meth)acrylate of any one of embodiments 34 to 46, wherein R is an aliphatic organic moiety which may contain one or more oxygen atoms. Aspect 48: 48. The haloalkyl ether (meth)acrylate of any one of embodiments 34 to 47, wherein R is a saturated aliphatic organic moiety that may contain one or more ether oxygen atoms. Aspect 49: Haloalkenyl ether (meth)acrylates corresponding to the following general structure (II): X 1 X 2 C=CX 3 -OROC(=O)-CR 1 =CH2(II) where R is an organic moiety and X 1 , X 2 , X 3 are independently selected from hydrogen, halogen, alkyl, or haloalkyl, with the proviso that X 1 , X 2 , or X 3 At least one of R is a halogen or haloalkyl group; 1 is hydrogen, methyl or fluorine. Aspect 50: X 1 , X 2 , X 3 Or X 4 50. The haloalkyl ether (meth)acrylate of embodiment 49, wherein at least two of are selected from the group consisting of halogen and haloalkyl groups. Aspect 51: X 1 , X 2 , X 3 Or X 4 51. The haloalkyl ether (meth)acrylate according to any one of claims 49 to 50, wherein at least two of are selected from the group consisting of fluorine and a fluoroalkyl group. Aspect 52: X 1 , X 2 , X 3 Or X 4 52. The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 51, wherein at least one of is fluorine or a fluoroalkyl group. Aspect 53: X 1 , X 2, X 3 and X 4 53. The haloalkyl ether (meth)acrylate of any one of embodiments 49 to 52, wherein each of is a halogen or a haloalkyl group. Aspect 54: X 1 , X 2 , X 3 Or X 4 54. The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 53, wherein one of the groups is a C1 to C8 haloalkyl group. Aspect 55: X 1 , X 2 , X 3 Or X 4 55. The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 54, wherein one of the groups is a C1 to C8 fluoroalkyl group. Aspect 56: (a)X 1 is chlorine and X 2 , X 3 and X 4 is fluorine, or (b) X 3 is chlorine and X 1 , X 2 and X 4 50. The haloalkyl ether (meth)acrylate according to embodiment 49, wherein is fluorine. Aspect 57: 57. The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 56, wherein R is an alkylene segment or a poly(oxyalkylene) segment. Aspect 58: 58. The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 57, wherein R is an ethylene segment or a poly(oxyethylene) segment. Aspect 59: R is -[CH2CH2O] n The haloalkyl ether (meth)acrylate according to any one of embodiments 49 to 58, wherein the haloalkyl ether (meth)acrylate is -CH2CH2-, and n is 0 or an integer from 1 to 10. Aspect 60: Part X 1 X 2 HC-CX3 X 4 60. The haloalkyl ether (meth)acrylate of any one of embodiments 49 to 59, wherein -ORO- has a molecular weight of 900 Daltons or less. Aspect 61: 61. The haloalkyl ether (meth)acrylate of any one of embodiments 49 to 60, wherein R is a non-halogenated organic moiety. Aspect 62: 62. The haloalkyl ether (meth)acrylate of any one of embodiments 49 to 61, wherein R is an aliphatic organic moiety that may contain one or more oxygen atoms.

[0005] In a particular embodiment of the present invention, the synthesis of trifluoropropenyl ether-containing compounds can be achieved by reacting an appropriate alcohol with a base in the presence of 1-chloro-3,3,3-trifluoro-1-propene (hereinafter referred to as 12333zd). The alcohol can be an aliphatic alcohol (e.g., an aliphatic monoalcohol or an aliphatic polyalcohol) or an aromatic alcohol (e.g., a phenolic compound). A representative example for the preparation of substituted phenyl-3,3,3-trifluoropropenyl ethers is provided by the following general formula (1), where X can be hydrogen or a substituent such as halo, alkyl, alkoxy, cyano, sulfate, nitrile, nitro, etc.: [ka]

[0006] In this general example, the reaction of the substituted phenol X-ArOH with trans-(E)-1233zd in the presence of potassium carbonate (K2CO3) in DMSO solvent at elevated temperature affords the substituted phenyl 3,3,3,3-trifluoropropenyl ether X-Ar-O-CH=CH-CF3 (where Ar is phenyl), and cis-(Z)-1233zd is an effective source of the trifluoropropenyl moiety as well.

[0007] In another embodiment of the present invention, 2-chloro-3,3,3-trifluoro-1-propene is used as the source of the trifluoropropene moiety, and the product is the corresponding 3,3,3,3-trifluoro-2-propene phenyl ether. A representative example is given below in general formula (2). [ka]

[0008] The halogenated heteroalkenyl- and heteroalkyl-functionalized organic compounds prepared according to the methods of the present invention are useful in many applications, including as synthetic intermediates and monomers (where the halogenated compound contains at least one functional group, such as a vinyl group, a vinylidene group, a (meth)acrylate group, or an active hydrogen-containing functional group (e.g., hydroxyl) that can participate in a curing or polymerization reaction to form a polymer). Such applications are described in more detail in concurrently filed U.S. provisional applications under Attorney Docket Nos. IR4328A, IR4328B, and IR4328C, the disclosures of each of which are incorporated herein by reference in their entirety for all purposes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Detailed Description of Certain Aspects of the Invention Halogenated Olefins The process of the present invention employs halogenated olefins (e.g., fluorinated olefins) as reactants. As used herein, the term "halogenated olefin" refers to an organic compound that contains at least one carbon-carbon double bond and at least one halogen atom (Cl, F, Br, I). As used herein, the term "fluorinated olefin" refers to an organic compound that contains at least one carbon-carbon double bond and at least one fluorine atom (and optionally one or more halogen atoms other than fluorine, particularly one or more chlorine atoms).

[0010] The halogenated olefin may contain one, two, three or more halogen atoms, such as bromine, chlorine, fluorine, iodine, or a combination thereof (e.g., at least one fluorine atom and at least one chlorine atom). In certain embodiments, the halogenated olefin has at least one halogen atom substituted on at least one of the carbon atoms participating in the carbon-carbon double bond present in the halogenated olefin. However, in other embodiments, the halogenated olefin does not contain a halogen atom bonded to any of the carbon atoms participating in the carbon-carbon double bond, but at least one of the carbon atoms participating in the carbon-carbon double bond is substituted with at least one halogenated alkyl group. Suitable fluorinated olefins include olefins containing one, two, three or more fluorine (F) atoms. The fluorine atoms may be substituted on one or both of the carbon atoms participating in the carbon-carbon double bond and / or may be present as a substituent on a moiety, such as an alkyl group, bonded to one or both of the carbon atoms participating in the carbon-carbon double bond. For example, the fluorinated olefin may contain one or more fluoroalkyl (e.g., perfluoroalkyl) groups, such as fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, perfluoroethyl, fluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, and the like, and analogs thereof, where some of the fluorine atoms and / or one or more of the hydrogen atoms are replaced with other halogen atoms (e.g., Cl). The fluorinated olefin may contain one or more halogen atoms other than fluorine, in particular one or more chlorine (Cl), iodine (I) and / or bromine (Br) atoms. In certain embodiments of the present invention, the halogenated or fluorinated olefin may have at least one chlorine atom substituted at a carbon atom participating in a carbon-carbon double bond. In further embodiments of the present invention, the halogenated or fluorinated olefin may have at least one hydrogen atom substituted at a carbon atom participating in a carbon-carbon double bond.As the halogenated olefin reactant in the present invention, for example, all of fluoroolefins, hydrofluoroolefins, chloroolefins, hydrochloroolefins, chlorofluoroolefins, and hydrochlorofluoroolefins can be used. Suitable types of fluorinated olefins include fluoroethylene, chlorofluoroethylene, fluoropropene, chlorofluoropropene, fluorobutene, chlorofluorobutene, fluoropentene, chlorofluoropentene, fluorohexene, and chlorofluorohexene. Other suitable fluorinated olefins include cyclofluorobutene, cyclochlorofluorobutene, cyclofluoropentene, cyclochlorofluoropentene, cyclofluorohexene, and cyclochlorofluorohexene, such as 1-chloro-2,3,3-trifluorocyclobutene, 1,2-dichlorotetrafluorocyclobutene, hexafluorocyclobutene, 1H-heptafluorocyclopentene, 1-chloro-3,3,4,5,5,5-hexafluorocyclopentene, 1-chloroheptafluorocyclopentene, octafluorocyclopentene, 1,2-dichlorohexafluorocyclopentene, 1,2,3-trichloropentafluorocyclopentene, perfluorocyclohexene, 1,2-dichlorooctafluorocyclohexene, 1H-perfluorocyclohexene, and the like. In various embodiments of the present invention, the halogenated olefin comprises 2, 3, 4, 5, 6 or more carbon atoms, for example, 2 to 20 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms.

[0011] According to a particular embodiment of the present invention, the halogenated olefin can have the structure of formula (1): CX 1 X 2 =CX 3 X 4 (1) In the formula, X 1 , X 2 , X 3 and X 4 are independently hydrogen (H), chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and halogenated and non-halogenated C1-C20 alkyl groups, with the proviso that X 1 , X 2 , X 3 and X 4 At least one of the following is selected from the group consisting of chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and halogenated alkyl groups (e.g., C1-C 20 The halogenated olefin is intended to be selected from the group consisting of halogenated alkyl groups, particularly halogenated alkyl groups containing one, two, three, four or more halogen atoms, particularly F and / or Cl, e.g., chlorinated alkyl groups, fluorinated alkyl groups such as trifluoromethyl, and chlorinated / fluorinated alkyl groups. In one embodiment, the halogenated olefin has no carbon atoms participating in the carbon-carbon double bond substituted with bromine atoms. In another embodiment, the halogenated olefin has carbon atoms participating in the carbon-carbon double bond substituted with bromine atoms and carbon atoms participating in the carbon-carbon double bond substituted with one or more halogen atoms other than bromine atoms.

[0012] Specific representative examples of halogenated olefins suitable for use in the present invention include, but are not limited to, the following: CClF=CH2 (sometimes called VCF) CH2=CF2 (sometimes called VDF) CFH=CH2 CF2=CHF CF3CF=CH2 CF2=CF2 (sometimes called TFE) CF2=CHCl CF3CCl=CH2 CF3CH=CHCl CF3CF=CFH CF3CH=CF2 CF3CF=CF2 CF3CH2CF=CH2 CF3CH=CFCH3 CF3CF=CHCF3 CF3CCl=CHCF3 CF2HCH2CF=CH2 CF2HCH2CF=CHCl CF2HCH=CFCH2Cl CH2=CHCl CHCl=CHCl CH2=CCl2 CF2 = CFCl; CF3CCl=CH2 CF3CCl=CClH CF3CH=CCl2 CF3CF=CCl2 CF3CF=CFCl CF3CF=CClH CF3CCl=CFH CF3CCl=CF2 CF3CCl=CFCl.

[0013] All possible isomers of the halogenated olefins (eg, E or Z isomers) can be used.

[0014] In one embodiment, chloro-substituted trifluoropropenyl compounds are used as halogenated olefins.Suitable chloro-substituted trifluoropropenyl compounds include 1-chloro-3,3,3-trifluoro-1-propene (also known as 1233zd) and 2-chloro-3,3,3-trifluoro-1-propene.Can use either cis or trans isomer of 1-chloro-3,3,3-trifluoro-1-propene (i.e., trans-(E)-1233zd or cis-(Z)-1233zd).

[0015] In various embodiments of the present invention, the halogenated olefin reactant may have a purity (calculated as weight percent) of at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or even 100%. Methods for producing and purifying such halogenated olefins are well known in the art. Moreover, suitable halogenated olefins are available from commercial sources, such as The Arkema Group.

[0016] Active hydrogen-containing organic compounds The active hydrogen-containing organic compound utilized in the method of the present invention can be selected from the group consisting of alcohols, primary amines, secondary amines, and thiols. The active hydrogen-containing organic compound can contain one or more active hydrogens per molecule (e.g., 1, 2, 3, 4, 5 or more active hydrogens per molecule). Such active hydrogens can be in the form of hydroxyl groups (-OH), thiol groups (-SH), and / or primary or secondary amine groups (-NH2 or -NH-, where each open bond is to a carbon atom). It should be noted that under certain reaction conditions (e.g., when the reaction is catalyzed or promoted by a base), the active hydrogen-containing organic compound can be in a deprotonated or partially deprotonated form (e.g., -O - , -S - ). The active hydrogen-containing organic compound can be monomeric, oligomeric, or polymeric. Although there is no particular known limit as to the number of carbon atoms that may be present in the active hydrogen-containing organic compound, in various embodiments of the present invention, the active hydrogen-containing organic compound may be comprised of 1 to 30 or 2 to 20 carbon atoms.

[0017] The term "alcohol" refers to an organic compound in which the organic moiety is substituted with at least one hydroxyl group (-OH). The term "thiol" refers to an organic compound in which the organic moiety is substituted with at least one thiol group (-SH). The term "primary amine" refers to an organic compound in which the organic moiety is substituted with at least one -NH2 group. The term "secondary amine" refers to an organic compound that contains at least one -NH- group, either as a substituent on an organic moiety or as part of a cyclic organic structure (where the nitrogen atom is bonded to two carbon atoms).

[0018] The organic portion of the active hydrogen-containing organic compound is not particularly limited, and can be, for example, an optionally substituted alkyl group, an optionally substituted heteroalkyl group, an optionally substituted alkylene group, an optionally substituted heteroalkylene group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, or an optionally substituted heterocycloalkyl group.

[0019] As used herein, the term "alkyl" is defined to include saturated aliphatic hydrocarbons, including straight (linear) and branched chains. In some embodiments, an alkyl group has 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms. An alkyl group may be optionally substituted with one or more (e.g., 1-5) suitable substituents. Heteroatoms such as oxygen, sulfur, phosphorus, and nitrogen (in the form of a tertiary amine moiety) may be present in an alkyl group to provide a heteroalkyl group (e.g., an alkyl group containing one or more ether, thioether, or amino linkages). Illustrative examples of heteroalkyl groups include -CH2CH2N(CH3)2 and -CH2CH2OCH2CH2CH3.

[0020] As used herein, the term "alkenyl" refers to an aliphatic hydrocarbon having at least one carbon-carbon double bond, including straight and branched chains having at least one carbon-carbon double bond. In some embodiments, the alkenyl group has 2-20 carbon atoms, 2-10 carbon atoms, 2-6 carbon atoms, 3-6 carbon atoms, or 2-4 carbon atoms. The alkenyl group may be optionally substituted with one or more (e.g., 1-5) suitable substituents. When the active hydrogen-containing organic compound contains an alkenyl group, the alkenyl group may be present in a pure E form, a pure Z form, or any mixture thereof. Heteroatoms such as oxygen, sulfur, and nitrogen (in the form of tertiary amine moieties) may be present in the alkylene group to provide a heteroalkylene group (e.g., an alkylene group containing one or more ether, thioether, or amino linkages).

[0021] As used herein, the term "cycloalkyl" refers to a saturated or unsaturated, non-aromatic, monocyclic or polycyclic (e.g., bicyclic, etc.) hydrocarbon ring (e.g., monocyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, etc., or bicyclic, such as spiro, fused, bridged, etc. systems). A cycloalkyl group can have 3 to 15 carbon atoms. In some embodiments, a cycloalkyl can optionally contain one, two or more non-cumulative non-aromatic double or triple bonds and / or one to three oxo groups. Also included within the definition of cycloalkyl are moieties in which one or more aromatic rings (including aryl and heteroaryl) are fused to a cycloalkyl ring. A cycloalkyl group can be optionally substituted with one or more (e.g., one to five) suitable substituents.

[0022] As used herein, the term "aryl" refers to an all-carbon monocyclic or fused ring polycyclic aromatic group having a conjugated π-electron system. The aryl group may have, for example, 6, 10, or 14 carbon atoms in the ring. Examples of suitable aryl groups include phenyl, naphthyl, and anthryl. Examples of compounds containing one or more aryl groups include 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 3-allyl-4-hydroxyacetophenone, and 4-methacryloxy-2-hydroxybenzophenone. The aryl group may be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0023] As used herein, the term "heteroaryl" refers to a monocyclic or fused-ring polycyclic aromatic heterocyclic group having in at least one ring one or more heteroatom ring members (ring-forming atoms) each independently selected from O, S, and N. A heteroaryl group can have 5 to 14 ring-forming atoms, including 1 to 13 carbon atoms, and 1 to 8 heteroatoms selected from O, S, and N. A heteroaryl group can be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0024] As used herein, the term "heterocycloalkyl" refers to a monocyclic or polycyclic [spiro, fused or bridged systems, e.g., containing two or more rings fused together, including bicyclic ring systems] saturated or unsaturated non-aromatic 4-15 membered ring system containing 1 to 14 ring-forming carbon atoms and 1 to 10 ring-forming heteroatoms independently selected from O, S and N. A heterocycloalkyl group can be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0025] Suitable types of groups which may be present as substituents on any of the above organic moieties include one or more of the following: halo (F, Cl, Br, I), alkyl, aryl, alkoxy, cyano (-CN), carboxyl (-C(=O)R where R is an organic substituent such as alkyl, aryl, etc.), carboxylic acid (-C(=O)OH), cycloalkoxy, aryloxy, tertiary amino, sulfate (-SO3M where M is an alkali metal or ammonium), oxo, nitrile, and the like.

[0026] As used herein, the term "halo" or "halogen" group is defined to include fluorine, chlorine, bromine, or iodine.

[0027] As used herein, the term "alkoxy" refers to an -O-alkyl group. An alkoxy group may be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0028] As used herein, the term "cycloalkoxy" or "cycloalkyloxy" refers to an -O-cycloalkyl group. The cycloalkoxy or cycloalkyloxy group may be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0029] As used herein, the term "aryloxy" refers to an -O-aryl group. An example of an aryloxy group is -O-phenyl [i.e., phenoxy]. An aryloxy group can be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0030] As used herein, the term "oxo" refers to =O. When oxo is substituted on a carbon atom, they are combined to form a carbonyl moiety [-C(=O)-]. When oxo is substituted on a sulfur atom, they are combined to form a sulfinyl moiety [-S(=O)-]. When two oxo groups are substituted on a sulfur atom, they are combined to form a sulfonyl moiety [-S(=O)2-].

[0031] As used herein, the term "optionally substituted" refers to optional substitution, and therefore includes both unsubstituted and substituted atoms or moieties. "Substituted" atoms or moieties indicate that any hydrogen on the specified atom or moiety can be replaced with a selection from the specified substituents (up to the limit that all hydrogen atoms on the specified atom or moiety are replaced with a selection from the specified substituents), provided that any hydrogen on the specified atom or moiety does not exceed the normal valence of the specified atom or moiety, and the replacement results in a stable compound. For example, if a phenyl group (-CH) is optionally substituted, then up to five hydrogen atoms on the phenyl ring can be replaced with a substituent.

[0032] In certain embodiments of the present invention, the active hydrogen-containing organic compound has the general structure Q(YH): x where Q is a substituted or unsubstituted organic moiety (e.g., alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and substituted variations thereof), Y is O, S, or NR (where R is H or a substituted or unsubstituted organic moiety such as an alkyl group, which may be substituted), and x is an integer equal to or greater than 1 (e.g., 1-10, 1-5, or 1-3). In such compounds, an oxygen, sulfur, or nitrogen atom of each Y moiety is bonded to a carbon atom of Q. When x is an integer equal to or greater than 2, the Y moieties can be the same or different from one another.

[0033] For example, the active hydrogen-containing organic compound can correspond to the following general formula: Ar(OH) x wherein Ar is a substituted or unsubstituted aromatic group, and x is an integer equal to or greater than 1 (e.g., 1, 2, or 3). In certain embodiments, Ar is selected from the group consisting of phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthryl, and substituted anthryl. Ar may also be an aromatic moiety, such as a phenyl group, substituted with one or more substituents at any position of the aromatic ring, where the substituents may be selected from the group consisting of, for example, halogen, alkyl, cyano, sulfate, and nitro, although any of the above additional types of substituents may also be used (alone or in combination).

[0034] In another embodiment of the invention, the active hydrogen-containing organic compound can be an aliphatic polyalcohol, i.e., an aliphatic alcohol having two or more hydroxyl groups per molecule (e.g., 2-6 hydroxyl groups per molecule), which may also be referred to as a "polyol." By controlling the reaction conditions (e.g., the stoichiometry of the aliphatic polyalcohol and the halogenated olefin), all of the hydroxyl groups may be reacted, or only a portion of the hydroxyl groups may be reacted. Partially reacted products may be of interest when it is desired to obtain products that contain at least one halogenated (e.g., fluorinated) alkenyl or alkyl group, but that are still available for further reaction (e.g., reaction with hydroxyl-reactive compounds other than the halogenated olefin, such as isocyanates or carboxylic acids or anhydrides) or that can participate in hydrogen bonding, etc. (thereby changing the properties of the product). Examples of suitable aliphatic polyalcohols include C2-C 18These include, but are not limited to, aliphatic diols (including glycols and oligomeric glycols such as diethylene glycol and triethylene glycol), sugars, sugar alcohols, glycerol, pentaerythritol, aliphatic triols (e.g., trihydroxybutane and trihydroxypentane), trimethylolpropane, trimethylolethane, dipentaerythritol, and alkoxylated derivatives thereof (e.g., when any of the aliphatic polyalcohols is reacted with 1 to 750 moles (e.g., 1 to 30 moles) of an alkylene oxide, such as ethylene oxide and / or propylene oxide, per mole of the aliphatic polyalcohol).

[0035] According to another aspect of the present invention, the active hydrogen-containing organic compound may contain two or more active hydrogen-containing functional groups, where at least one active hydrogen-containing functional group is masked / blocked and at least one active hydrogen-containing functional group remains in unprotected form and can participate in the desired reaction with the halogenated olefin. Alternatively, the unprotected active hydrogen-containing functional group may first be reacted with another reactant to obtain an intermediate containing active hydrogen (e.g., in the form of a hydroxyl group) which is then reacted with the halogenated olefin. For example, the unprotected active hydrogen-containing functional group may be reacted with one or more equivalents of an alkylene oxide (e.g., ethylene oxide, propylene oxide) to form an alkoxylated intermediate containing a hydroxyl group which is then reacted with the halogenated olefin.

[0036] Following such a reaction, the masked / blocked active hydrogen-containing functional group can be optionally deprotected, thereby generating at least one active hydrogen-containing functional group. Any method known in the art can be utilized to remove the masking or blocking group. For example, an acetal or ketal protecting group can be removed by treating the intermediate with aqueous acid. As another example, a benzyl protecting group can be removed using hydrogenation.

[0037] The regenerated active hydrogen-containing functional group can be further reacted, if desired, with, for example, a reactant that contains at least one functional group that is reactive with the active hydrogen-containing functional group. In another embodiment, at least one active hydrogen-containing functional group is masked / blocked to introduce a reactive functional group (e.g., (meth)acrylate, (meth)acrylamide or allyl functional group) into the active hydrogen-containing organic compound. The reactive functional group can be left in place after reaction with the halogenated olefin to provide a curable or polymerizable site, such as, for example, (meth)acrylate, (meth)acrylamide, allyl group, etc.

[0038] Examples of mask / block polyols include (2,2-dimethyl-1,3-dioxolan-4-yl)methanol (also known as solketal), 4-hydroxymethyl-1,3-dioxolan-2-one (also known as glycerol carbonate), hydroxyethyl methacrylate (HEMA), poly(ethoxyethyl methacrylate), e.g., HEMA-10, 2-hydroxyethyl or HEA acrylate, hydroxypolyethoxyallyl ethers such as hydroxypolyethoxy(10)allyl ether, hydroxypropyl methacrylate, hydroxypropyl acrylate, 3-phenoxy-2-hydroxypropyl methacrylate. , pentaerythritol triacrylate, poly(propylene glycol) methacrylates such as poly(propylene glycol) 300 methacrylate, 1,1,1,1-trimethylolpropane diallyl ether (pure or mono / di / triallyl mixture), 1,1,1-trimethylolpropane monoether, glycerol monomethacrylate, N-(2-hydroxypropyl) methacrylamide, hydroxypolyethoxyallyl ethers, sodium 1-allyloxy-2-hydroxypropyl sulfonate, N-hydroxyethyl acrylamide, polyols partially esterified with carboxylic acids, and the like.

[0039] In certain embodiments of the present invention, an aliphatic polyalcohol is employed in which one or more of the hydroxyl groups are masked or blocked, with one or more of the hydroxyl groups remaining free for reaction with the halogenated olefin. After the blocked / masked polyalcohol is reacted with the halogenated olefin, the blocking / masking group (sometimes called a protecting group) may be optionally removed to generate one or more free hydroxyl groups. Any blocking or masking reagent or technique known in the art of organic chemistry suitable for masking hydroxyl groups can be employed in the present invention. However, it will typically be desirable to employ a blocking or masking group that remains stable (i.e., is not removed to a significant extent) under the conditions used to react the masked aliphatic polyalcohol with the halogenated olefin. For example, if a basic catalyst is used during the masked aliphatic polyalcohol / halogenated olefin reaction, the blocking / masking group should be resistant to deblocking or unmasking under such basic conditions. Examples of suitable blocking / masking groups include, but are not limited to, silyl ether groups, acetal groups, ketal groups, benzyl groups, and the like. A specific example of a blocked / masked aliphatic polyhydric alcohol is solketal, in which two hydroxyl groups of glycerol are blocked via ketal groups, and the other hydroxyl group is free to react with halogenated olefins according to the present invention. Other examples of suitable protecting groups for hydroxyl functions include, but are not limited to, acetyl (Ac), benzoyl (Bz), β-methoxyethoxymethyl ether (MEM), dimethoxytrityl (DMT), methoxymethyl ether (MOM), methoxytrityl (MMT), p-methoxybenzyl ether (PMB), methylthiomethyl ether, pivaloyl (Piv), tetrahydropyranyl (THP), tetrahydrofuryl (THF), trityl (triphenylmethyl, Tr), silyl ether, methyl ether, tertiary alkyl ether, and ethoxyethyl ether (EE).In one embodiment of the present invention, an aliphatic polyalcohol containing three or more hydroxyl groups per molecule is reacted with an aldehyde or ketone to form an acetal or ketal, where two of the hydroxyl groups of the aliphatic polyalcohol, separated by two or three carbon atoms, react with the aldehyde or ketone to form a structure containing a cyclic acetal or ketal.

[0040] Similarly, other types of active hydrogen-containing functional groups (e.g., thiol groups, primary amine groups, secondary amine groups) that may be present in the active hydrogen-containing compounds used as starting materials in the present invention may be masked or blocked using any masking / blocking technique known in the art. One or more unblocked active hydrogen-containing functional groups still present can then be reacted with a halogenated olefin to provide a halogenated intermediate, which can then be deblocked (demasked) to provide one or more active hydrogen-containing functional groups (which can then be utilized for further reaction or derivatization). Suitable amine protecting groups include, for example, carbobenzyloxy (Cbz), p-methoxybenzylcarbonyl (Moz or MeOZ), t-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl (Ac), benzoyl (Bz), benzyl (Bn), carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMPM), p-methoxyphenyl (PMP), tosyl (Ts), trichloroethyl chloroformate (Troc), sulfonamide (e.g., nosyl and Nps) groups, and the like.

[0041] Particular suitable phenolic compounds that can be used as starting materials include the phenolic compounds described in the Examples.Particular suitable secondary amines that can be used as starting materials include the secondary amines described in the Examples.Amino acids are also useful as active hydrogen-containing organic compounds.

[0042] After reaction with the halogenated olefin, one or more active hydrogens of the active hydrogen-containing organic compound (i.e., one or more of the hydrogens of the -YH moiety) are replaced with an alkenyl or alkyl group (e.g., -CF=CH2, -CF2CFHCF3, -CF2CFClH, -CF2CClH2, -CF2CF2H, -CH=CHCF3, or -C(CF3)=CH2). In certain embodiments, all of the active hydrogens of the active hydrogen-containing organic compound are replaced with an alkenyl or alkyl group. In such embodiments, the resulting halogenated organic compound has the general structure Q(Y-Alk): n where Q, Y and n have the same meanings as above, and Alk is a halogenated alkenyl or alkyl group. In other embodiments (n=2 or more), not all of the active hydrogens in the active hydrogen-containing organic compound are replaced with halogenated alkenyl or alkyl groups. In such embodiments, the resulting halogenated organic compound has the formula Q(YH) n-m (Y-Alk) m where Q, Y, and n have the same meanings as above, m is an integer from 1 to n-1, and Alk is a halogenated alkenyl group or a halogenated alkyl group. In embodiments where Y is NH, the hydrogen atom of NH may or may not be substituted with a halogenated alkenyl group or a halogenated alkyl group in turn.

[0043] Without wishing to be limited by theory, it is believed that the reaction of the present invention proceeds by the addition of an active hydrogen-containing functional group of an active hydrogen-containing organic compound across the double bond of the halogenated olefin. Such a reaction forms an alkyl halide group (i.e., the halogenated olefin is converted to an alkyl halide group present in the product formed). Typically, the heteroatom of the active hydrogen-containing functional group (e.g., the oxygen atom of a hydroxyl group) preferably becomes bonded to the "halogen-heavy" carbon atom (i.e., the carbon with the greatest number of halogen atoms bonded to it) among the carbons participating in the carbon-carbon double bond of the halogenated olefin. In certain cases, a mixture of different products is obtained, in which the heteroatom of the active hydrogen-containing functional group becomes bonded to each of the carbon atoms participating in the carbon-carbon double bond. The alkenyl group is obtained by elimination of the hydrohalide from the alkyl halide group. Such elimination may be advantageous in that it increases the basicity of the reaction medium.

[0044] The above transformation can be generally exemplified as follows: Initial reaction: R-OH+ZXC=CZ2→(RO)ZXC-CZ2 Removal:(RO-)ZXC-CHZ2→(RO-)ZC=CZ2+HX R=organic moiety (e.g., alkyl, aryl) X=halogen (e.g., F, Cl) Z=hydrogen, halogenated or non-halogenated organic moiety, halogen.

[0045] The present invention allows, for example, the preparation of trifluoropropenyl ether substituted aromatic compounds of formula (I): Ar(OCR 1 =CHR 2 ) x (I) where Ar is a substituted or unsubstituted aromatic moiety, x is an integer equal to or greater than 1 (e.g., 1, 2, or 3), and R 1 is CF3 and R 2 is H or R 1 is H and R2 is CF3.

[0046] Ar can be selected from the group consisting of phenyl, substituted phenyl, naphthyl, substituted naphthyl, anthryl, and substituted anthryl. Ar can also be an aromatic moiety such as phenyl substituted with one or more substituents, for example, phenyl substituted with one or more substituents selected from the group consisting of halogen, alkyl, alkoxy, cyano, sulfate, and nitro. Such one or more substituents can be attached to any of the carbon atoms of the aromatic ring other than the carbon atom attached to the oxygen atom of the trifluoropropenyl group. Here, Ar is a substituted phenyl group, x=1, and for example, the substituents can be at the 2-, 3-, 4-, 5-, and / or 6-positions of the phenyl ring (the trifluoropropenyl group is at the 1-position of the phenyl ring).

[0047] Specific examples of halogenated organic compounds which may be produced according to the present invention include, but are not limited to, halogenated organic compounds which are the reaction products of active hydrogen-containing organic compounds selected from the group consisting of solketal, glycerol carbonate, aminoethanol, hydroxyethyl acrylate, hydroxyethyl methacrylate, poly(ethoxyethyl methacrylate), hydroxypropyl methacrylate, pentaerythritol triacrylate, N-(2-hydroxypropyl) methacrylamide, and glycerol monomethacrylate with halogenated olefins selected from the group consisting of CF2=CH2, CFCl=CH2, CF2=CHCl, CF2=CFCl, CF2=CF2, CF3CF=CF2, CF3CF=CH2, CF3CH=CFH, CF3CCl=CH2, and CF3CH=CHCl.

[0048] Specific examples of trifluoropropenyl ether substituted aromatic compounds according to the present invention include, but are not limited to, 4-chlorophenyl-3,3,3-trifluoropropenyl ether, 1,4-bis(3,3,3-trifluoropropenyloxy)benzene, 4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4-methylphenyl-3,3,3-trifluoropropenyl ether, 3-cyanophenyl-3,3,3-trifluoropropenyl ether, 2-fluorophenyl-3,3,3,3-trifluoropropenyl ether, 3-nitrophenyl-3,3,3-trifluoropropenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoropropenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4- ...-trifluoropropenyl ether, 3-nitrophenyl-3,3,3-trifluoropropenyl ether, 2 4-(3,3,3-trifluoro-2-propenyl)phenyl sulfate, 4-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, 3-nitrophenyl-3,3,3-trifluoro-2-propenyl ether, 2-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, 4-methylphenyl-3,3,3-trifluoro-2-propenyl ether, 4-chlorophenyl-3,3,3-trifluoro-2-propenyl ether, 3-cyanophenyl-3,3,3-trifluoro-2-propenyl ether, 1,4-bis(3,3,3-trifluoro-2-propenyl)phenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoro-2-propenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, and 4-(3,3,3-trifluoro-2-propenyl)phenyl sulfate sodium salt.

[0049] The method of the present invention is also useful for the synthesis of haloalkyl ether (meth)acrylates and haloalkylene ether (meth)acrylates. Haloalkyl (meth)acrylates can be characterized as organic compounds that contain a haloalkyl moiety and an organic spacer moiety (in that order) attached to a (meth)acrylate functional group via an ether bond. Haloalkyl ether (meth)acrylates and haloalkenyl ether (meth)acrylates are sometimes referred to collectively herein as "haloalkyl / haloalkenyl ether (meth)acrylates." As used herein, the term "(meth)acrylate" refers to acrylate (-C(=O)CH=CH2) and methacrylate (-C(=O)C(CH3)=CH2) functional groups. As used herein, the term "haloalkyl" refers to an alkyl group substituted with one or more halogen atoms, which may be the same or different from each other when one or more halogen atoms are present. As used herein, the term "haloalkenyl" refers to an alkenyl group substituted with one or more halogen atoms, which may be the same or different from each other when more than one halogen atom is present. When a haloalkyl or haloalkenyl group contains two or more carbon atoms, the halogen may be substituted on any or all of the carbon atoms. Each carbon atom in a haloalkyl or haloalkenyl group may be substituted with one, two or three halogen atoms, which may be the same or different from each other. In addition to the halogen, each carbon atom in a haloalkyl or haloalkenyl group may be substituted with one or more hydrogen atoms. When a haloalkyl or haloalkenyl group contains two or more carbon atoms, one or more carbon atoms may be unhalogenated, provided that at least one carbon atom is halogenated. As used herein, the term "alkyl" refers to a paraffinic hydrocarbon group that can be derived from an alkane by dropping one hydrogen therein, such as ethyl (CH3CH2-).As used herein, the term "alkenyl" refers to an unsaturated hydrocarbon group having at least one carbon-carbon double bond that can be derived from an alkene by removing a hydrogen therefrom, such as propenyl (CHCH=CH- or CH=C(CH)-). As used herein, the term halogen refers to fluorine (F), chlorine (Cl), bromine (BR) or iodine (I).

[0050] In certain embodiments, the haloalkyl ether (meth)acrylate corresponds to the following general structure (I): X 1 X 2 HC-CX 3 X 4 -OROC(=O)-CR 1 =CH2(I) where R is an organic moiety and X 1 , X 2 , X 3 and X 4 are independently selected from hydrogen, halogen, or haloalkyl, with the proviso that X 1 , X 2 , X 3 Or X 4 At least one of R is a halogen or haloalkyl group; 1 is hydrogen or methyl. According to a particular embodiment of the invention, X 1 , X 2 , X 3 Or X 4 At least two of X are selected from the group consisting of halogen and haloalkyl groups. 1 , X 2 , X 3 Or X 4 At least two of X are selected from the group consisting of fluorine and fluoroalkyl groups. 1 , X 2 , X 3 Or X 4 At least one of X is fluorine or a fluoroalkyl group. 1 , X 2 , X 3 and X4 Each of X is a halogen or a haloalkyl group. 1 , X 2 , X 3 Or X 4 One of these may be a C1-C8 haloalkyl group, particularly a C1-C8 fluoroalkyl group such as a C1-C8 perfluoroalkyl group (eg, trifluoromethyl).

[0051] In other embodiments, the haloalkenyl ether (meth)acrylate corresponds to the following general structure (IA): X 1 X 2 C=CX 3 -OROC(=O)-CR 1 =CH2(IA) where R is an organic moiety and X 1 , X 2 and X 3 are independently selected from hydrogen, halogen, or haloalkyl, with the proviso that X 1 , X 2 Or X 3 At least one of R is a halogen or haloalkyl group; 1 is hydrogen or methyl. According to a particular embodiment of the invention, X 1 , X 2 Or X 3 At least two of X are selected from the group consisting of halogen and haloalkyl groups. 1 , X 2 Or X 3 At least two of X are selected from the group consisting of fluorine and fluoroalkyl groups. 1 , X 2 Or X 3 At least one of X is fluorine or a fluoroalkyl group. 1 , X 2 and X 3 Each of X is a halogen or a haloalkyl group. 1 , X 2 Or X 3One of these may be a C1-C8 haloalkyl group, particularly a C1-C8 fluoroalkyl group such as a C1-C8 perfluoroalkyl group (eg, trifluoromethyl).

[0052] Illustrative examples of suitable haloalkyl ether moieties include, but are not limited to, the following: CH3-CF2-O- CH3-CFH-O- CH2F-CF2-O- CF3CF(CH3)-O- CF2H-CF2-O- CH2Cl-CF2-O- CH3C(CF3)Cl-O- CH2Cl-CH(CF3)-O- CFH2-CF(CF3)-O- CF3CH2-CF2-O- CF3CFH-CF2-O- CH3-CF(CH2CF3)-O- CF3-CH2-CF(CH3)-O- CF3-CH2-CF(CF3)-O- CF3-CH2-CCl(CF3)-O- CH3CF(CH2CF2H)-O- CH2Cl-CF(CH2CF2H)-O- CF2H-CH2-CF(CH2Cl)-O- CH3CHCl-O- CH2Cl-CHCl-O- CH3CCl2-O- CFClH-CF2-O- CH3-CCl(CF3)-O- CClH2-CCl(CF3)-O- CF3-CH2-CCl2-O- CCl2H-CF(CF3)-O- CFClH-CF(CF3)-O- CClH2-CF(CF3)-O- CFH2-CCl(CF3)-O- CF3-CHCl-CF2-O- CF3-CHCl-CFCl-O-.

[0053] Illustrative examples of suitable haloalkenyl ether moieties include, but are not limited to, moieties similar to the haloalkyl ether moieties described above, but in which the hydrohalide has been removed to form a carbon-carbon double bond between the carbon attached to the ether oxygen and the adjacent carbon atom. The haloalkyl ether (meth)acrylates of the present invention comprise: (a) X 1 is chlorine and X 2 , X 3 and X 4 is fluorine, or (b) X 3 is chlorine and X 1 , X 2 and X 4 It can correspond to the general structure (I) in which

[0054] In certain aspects of the invention, R may be an alkylene segment or a poly(oxyalkylene) segment. As used herein, the term "alkylene" refers to a paraffinic hydrocarbon group that can be derived from an alkane by dropping two hydrogens in the formula, such as ethylene (-CH2CH2-). The term "oxyalkylene" refers to an alkylene group attached to an ether oxygen, such as oxyethylene (-CH2CHO-). Thus, in various aspects of the invention, haloalkyl / haloalkenyl ether (meth)acrylates corresponding to the general structure (I) or (IA) are provided, where R is an ethylene segment or a poly(oxyethylene) segment. For example, R is -[CH2CHO] nR may be -CH2CH2-, where n is 0 or an integer from 1 to 10 or more. R may be a substituted or heteroatom-containing organic moiety, such as an oxygen-containing organic moiety, although in certain embodiments R is not halogenated (i.e., does not contain halogen atoms). R may be, for example, aliphatic (including linear or branched aliphatic or cycloaliphatic), aromatic, or contains both aliphatic and aromatic structural units, although in certain embodiments R is aliphatic and does not contain aromatic structural units. In particular, R may be a saturated aliphatic organic moiety that may contain one or more oxygen atoms, such as an ether oxygen atom (an oxygen atom that forms an ether linkage).

[0055] According to a particular embodiment, the moiety X 1 X 2 HC-CX 3 X 4 -ORO- or X 1 X 2 C=CX 3 -ORO- can have a molecular weight of 900 daltons or less, 800 daltons or less, or 700 daltons or less.

[0056] The method of the present invention also includes 1 X 2 HC-CX 3 X 4 OCH2CH2OX 3 X 4 C-CX 1 X 2 H(X 1 , X 2 , X 3 and X 4 The present invention is also useful for the synthesis of haloalkyl diethers according to the general structure of (wherein A is fluorine or chlorine). The haloalkyl diethers of the present invention are generally electrochemically stable and therefore suitable as solvents and / or additives for Li batteries utilizing LiPF6, LiTFSI, LiFSI, LiTDI, and other lithium-sulfur based batteries. Examples of haloalkyl diethers of the present invention are FClHC-CF2-O-CH2CH2CH2-O-CF2CFClH, HF2C-CF2-O-CH2CH2CH2-OCF2-CF2H, etc.

[0057] Reaction conditions The active hydrogen-containing organic compound and the halogenated olefin are contacted with each other for a time and at a temperature effective to achieve the desired degree of reactivity between the starting materials, thereby producing the desired halogenated organic compound.

[0058] The reaction can be carried out in any suitable manner and using any suitable equipment, apparatus or system, which will vary depending on the reactants and reaction conditions selected. For example, the reaction can be carried out batchwise, continuously, semi-continuously, or in stages or stepwise. If one or more of the reactants are relatively volatile (e.g., if the reactants have boiling points lower or slightly higher than the desired reaction temperature), it may be advantageous to carry out the reaction in a closed or pressurized vessel and / or to provide a means for recovering any volatile reactants that may distill from the reaction mixture (e.g., using a reflux condenser) and returning such reactants to the reaction mixture. The reaction vessel can be equipped with suitable heating, cooling and / or stirring means, as well as lines for introducing and / or withdrawing materials.

[0059] In one embodiment of the present invention, the reaction is carried out at elevated pressure, i.e., pressure greater than atmospheric pressure, for example pressures between atmospheric and 50 bar can be utilized.

[0060] The active hydrogen-containing organic compound may be reacted directly with the halogenated olefin. An excess of one of the reactants may be utilized substantially as a solvent. In another embodiment, a reaction medium such as a solvent or combination of solvents may be used to solubilize or disperse the reactants and / or the reaction product. According to certain aspects of the invention, one or more organic solvents are used for miscibility with the reactants. In particular, sulfoxides (e.g., DMSO), amides (e.g., dimethylformamide (DMF), dimethylacetamide, diethylacetamide, hexamethylphosphoramide (HMPA), hexamethyltriamide (HMPT)), nitriles (e.g., acetonitrile, benzonitrile, benzonitrile), sulfolane, esters (e.g., ethyl acetate), ethers (THF), N-methyl-2-pyrrolidinone (NMP), nitrobenzene, nitromethane, ketones (e.g., acetone, methyl ethyl ketone), carbonates such as 4-fluoro-1,3-dioxolan-2-one (FEC), cis-4,5-difluoro- Polar aprotic organic solvents such as 1,3-dioxolan-2-one (cis-DFEC), trans-4,5-difluoro-1,3-dioxolan-2-one (trans-DFEC), 4,4-difluoro-1,3-dioxolan-2-one (gem-DFEC), 4-fluoromethyl-1,3-dioxolan-2-one (FPC), 4-trifluoromethyl-1,3-dioxolan-2-one (TFPC), ethylene carbonate (EC), propylene carbonate (PC), transbutylene carbonate (t-BC), dimethyl carbonate (DMC), and the like, and combinations thereof, can be used. Polar protic solvents such as alcohols and aminoalcohols (e.g., 2-aminoethanol) can also be used, at least under certain reaction conditions, e.g., when the active hydrogen-containing organic compound is more reactive with the halogenated olefin than the polar protic solvent. In the present invention, an organic solvent or a mixture of organic solvents having a dielectric constant between 2 and 190, preferably between 4 and 120, more preferably between 13 and 92 under ambient conditions (25° C.) may be used.Water may also be present, provided that the desired product is not readily converted to undesired products in the presence of water along with one or more organic solvents (which may be water-miscible or water-immiscible). For example, when potassium hydroxide is used, the water content is preferably less than about 24% by weight, more preferably less than about 15% by weight, and even more preferably less than about 10% by weight. Thus, the liquid reaction medium may comprise a mixture of water and one or more organic solvents.

[0061] In order to promote the desired reaction between the active hydrogen-containing organic compound and the halogenated olefin, it may be advantageous to contact the reactants under basic conditions. For example, one or more bases may be present in the reaction mixture, and the base may be present in a soluble or insoluble form. The base may be a weak or strong base, provided that it is not so strong as to cause undesirable side reactions of the halogenated organic compound, which is the target product. Inorganic bases may be used, particularly alkali metal hydroxides (e.g., NaOH, KOH) and alkali metal salts of carbonate (e.g., potassium carbonate, sodium carbonate, cesium carbonate). Organic bases may also be used, particularly tertiary amines such as trialkylamines and pyridine. Basic ion exchange resins may also be used. The amount of base may be appropriately changed depending on the reactants and base used and other reaction conditions (temperature, solvent), but in one embodiment, it is approximately equimolar to the number of moles of the active hydrogen-containing organic compound used. Furthermore, more basic conditions (i.e., the use of a strong base or high pH) typically serve to promote the formation of the alkenyl-containing product, which is believed to result from the removal of hydrohalide from the initially formed haloalkyl-containing product.

[0062] Optionally, a phase transfer catalyst (PTC) may also be additionally used to promote the desired reaction between the halogenated olefin and the active hydrogen-containing organic compound. Any suitable phase transfer catalyst known in the field of organic chemistry may be used, such as ammonium compounds (e.g., quaternary ammonium compounds such as tetraalkylammonium halides or hydroxides), phosphonium compounds, crown ethers, cryptands (also called cryptates), polyethylene glycols (PEGs) and their ethers, and other organic complexing agents. The phase transfer catalyst may be water-soluble or soluble in an organic solvent. Typically, when a phase transfer catalyst is used in combination with a base, the molar amount of the phase transfer catalyst may be, for example, 0.1 to 5% of the molar amount of the base.

[0063] Suitable exemplary quaternary ammonium salts include benzyl dimethyl tetradecyl ammonium chloride hydrate, benzyl cetyl dimethyl ammonium chloride hydrate, benzalkonium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium iodide, benzyl trimethyl ammonium chloride, benzyl tributyl ammonium bromide, benzyl tributyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride dihydrate, benzyl trimethyl ammonium bromide, benzyl dodecyl dimethyl ammonium bromide, bis (2-hydroxyethyl) dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, decyl trimethyl ammonium chloride, decyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, 4-dimethylamino-1-neopentyl pyridinium chloride, dilauryl dimethyl ammonium bromide, dimethyl dioctadecyl ammonium bromide, diallyl dimethyl ammonium chloride, dimethyl dipalmityl ammonium bromide, dimethyl dimyristyl ammonium bromide, didecyl dimethyl ammonium bromide, dimethyl dioctadecyl ... Octylammonium, dimethyldioctadecylammonium iodide, didodecyldimethylammonium chloride, ethyltrimethylammonium iodide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexyltrimethylammonium bromide, triethylmethylammonium chloride, triethylphenylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, trimethylphenylammonium tribromide, trimethylstearylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, tetrapropylammonium iodide, tetrapropylammonium bromide, trioctylmethylammonium, tetradecyltrimethylammonium bromide, trimethyltetradecylammonium chloride, tetrahexylammonium iodide, tetramethylammonium acetate,Examples of the ammonium bromide include tetra(decyl)ammonium bromide, tetra-n-octylammonium iodide, tetramethylammonium sulfate, tetrabutylammonium triiodide, methyltri-n-octylammonium chloride, tetraheptylammonium iodide, tetramethylammonium acetate, tetraamylammonium bromide, tetraamylammonium chloride, tetrahexylammonium bromide, tetraheptylammonium bromide, tetra-n-octylammonium bromide, tetrapropylammonium chloride, trimethyl[2-[(trimethylsilyl)methyl]benzyl]ammonium iodide, tetrabutylammonium acetate, trimethylnonylammonium bromide, trimethylpropylammonium bromide, tributylmethylammonium, and tetraethylammonium nitrate. Examples of suitable phosphonium salts include trans-2-butene-1,4-bis(triphenylphosphonium chloride), tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, tributyl-n-octylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, tetraphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium sulfate, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride, tetra-n-octylphosphonium bromide, tetraethylphosphonium hexafluorophosphate, tetraethylphosphonium, tetrafluoroborate, tetrabutylphosphonium tetrafluoroborate, and tetrabutylphosphonium hexafluorophosphate. Suitable crown ethers include, for example, 12-crown-4, 15-crown-5, 18-crown-6, and their complexes.

[0064] The reaction temperature can vary, for example, from about 5° C. to about 200° C., for example, from about 10° C. to about 150° C., or from about 20° C. to about 120° C., and the pressure in the reactor is between atmospheric pressure and 50 bar, preferably between atmospheric pressure and 20 bar. The pressure can be the autogenous pressure of the solution, or an inert, for example nitrogen, can be added to increase the pressure. Typically, the reaction time ranges from about 0.5 hours to about 72 hours, for example, from about 4 hours to about 12 hours.

[0065] The reactants can be mixed all at once and then reacted. Alternatively, one or both of the active hydrogen-containing organic compound and the halogenated olefin can be added to the reaction mixture continuously or partially or stepwise. When the active hydrogen-containing organic compound contains two or more active hydrogen-containing functional groups and it is desired to obtain a product in which at least one of the active hydrogen-containing functional groups remains unreacted, it may be preferable to incrementally add the halogenated olefin to the active hydrogen-containing organic compound while reacting the two reactants to favor the formation of the desired product.

[0066] In certain embodiments of the present invention, approximately stoichiometric amounts of the active hydrogen-containing organic compound and the halogenated olefin are used, although in other embodiments a stoichiometric excess of one reactant may be used.

[0067] For example, the active hydrogen-containing organic compound and the halogenated olefin can be reacted in a stoichiometric ratio of (number of moles of active hydrogen-containing organic compound) / x: number of moles of halogenated olefin (wherein x=number of active hydrogens per mole of active hydrogen-containing organic compound of about 1:8 to about 8:1, about 1:7 to about 7:1, about 1:6 to about 6:1, about 1:5 to about 5:1, about 1:4 to about 4:1, about 1:3 to about 3:1, about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.1 to about 1.1:1).

[0068] When the active hydrogen-containing organic compound contains two or more active hydrogen-containing functional groups per molecule (for example, when the active hydrogen-containing organic compound is an aliphatic polyhydric alcohol), and when it is desired to obtain a product containing one or more free (unreacted) active hydrogen-containing functional groups per molecule after reaction with a halogenated olefin, it may be preferable to use a stoichiometric excess of the active hydrogen-containing organic compound relative to the halogenated olefin, so that the production of the product is more favorable than the product in which all of the active hydrogen-containing functional groups have reacted with the halogenated olefin. In such a case, the active hydrogen-containing organic compound and the halogenated olefin may be reacted in a stoichiometric ratio of (moles of active hydrogen-containing organic compound) / x:moles of halogenated olefin, where x is the number of active hydrogens per mole of the active hydrogen-containing organic compound, and is about 1x:1 to about 12x:1, about 1.5x:1 to about 10x:1, or about 2x:1 to about 8x:1.

[0069] purification After the reaction of the active hydrogen-containing organic compound with the halogenated olefin has been carried out for a desired period of time (e.g., to a predetermined conversion of the starting materials), the resulting reaction mixture can be subjected to one or more additional processing and / or purification steps to isolate the desired halogenated organic compound from other components of the reaction mixture (e.g., solvent, unreacted starting materials, undesired by-products, base, etc.). Any of the purification techniques known in the organic chemistry art, or any combination of such techniques, can be used, and the particular method selected will be influenced by various parameters such as the volatility, crystallizability, solubility, polarity, acidity / basicity, and other properties of the components of the reaction mixture. Suitable isolation and purification techniques include, but are not limited to, distillation (including fractional distillation), extraction, filtration, washing, neutralization, chromatographic separation, adsorption / absorption, treatment with ion exchange resins, crystallization, recrystallization, trituration, sublimation, precipitation, dialysis, membrane separation, filtration, centrifugation, decolorization, drying, and combinations thereof. By application of such techniques, halogenated organic compounds can be obtained in purities of at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or even 100% (by weight).

[0070] In other embodiments of the invention, the reaction mixture is not purified, but instead is used as is (or only partially purified) in one or more subsequent reaction steps in which the halogenated organic compounds present in the reaction mixture are converted to one or more other compounds.

[0071] Further reactions of halogenated organic compounds The halogenated organic compound produced according to the present invention can be further reacted one or more times to convert the halogenated organic compound into another compound of interest.Thus, the halogenated organic compound obtained by the process described herein can serve as a synthetic intermediate.For example, one or more functional groups on the halogenated organic compound can be converted or transformed into other types of functional groups using reagents and conditions known in the art of organic chemistry.

[0072] In one embodiment, the carbon-carbon double bonds in the halogenated organic compounds may be reacted, e.g., hydrogenated to give saturated species, hydrohalogenated and / or halogenated to introduce additional halogens into the halogenated organic compounds, oxidized, reacted with dienes to give Diels-Alder adducts, or polymerized.

[0073] In another embodiment, a free active hydrogen-containing group (e.g., a hydroxyl group, a thiol group, a secondary amino group, or a primary amino group) in a halogenated organic compound may be reacted with a compound containing an active hydrogen-reactive functional group (e.g., an isocyanate group, a carboxylic acid group, an anhydride group, a carboxylic acid ester group, or an acyl halide group) that may also contain at least one other functional group (e.g., a (meth)acrylate group). This chemistry may be employed as a method of introducing one or more desired functional groups into the halogenated organic compounds of the present invention.

[0074] For example, a hydroxyl-functionalized halogenated organic compound can be reacted with (meth)acrylic anhydride to give a (meth)acrylate-functionalized halogenated organic compound. This synthetic route can be illustrated by the following general reaction scheme: HO-R-OH+CX 1 X 2 =CX 3 X 4 →HO-RO-CX 1 X 2 -CX 3 X 4 H HO-RO-CX 1 X 2 -CX 3 X 4 +CH2=CHR 1 -C(=O)-OC(=O)-CHR 1 =CH2→CH2=CHR 1 -C(=O)-ORO- CX 1 X 2 -CX 3 X 4 H. where R is an organic moiety and R 1 is H or CH3, and X 1 , X 2 , X 3 and X 4 are independently selected from the group consisting of hydrogen (H), chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and halogenated and non-halogenated C1-C8 alkyl groups, with the proviso that X 1 , X 2 , X 3 and X 4 At least one of X is a halogen selected from the group consisting of chlorine (Cl), fluorine (F), bromine (Br) and iodine (I); 1 , X 2 , X 3 Or X 4 One of X is a halogen and the other X 1 , X 2 , X 3 and X 4is a substituent other than halogen, the halogenated olefin contains at least one halogenated alkyl group. In one aspect of this approach, one of the hydroxyl groups in the active hydrogen-containing compound starting material may be blocked (masked) during the reaction of the halogenated olefin with the active hydrogen-containing compound, and this blocking (masking group) is removed prior to reacting the intermediate halogenated organic compound with (meth)acrylic anhydride.

[0075] Further description of processing conditions Exemplary processes according to the present invention are further described below.

[0076] Product: Halogenated olefins are reacted with alcohols (e.g., aliphatic alcohols, aliphatic polyalcohols, phenols, etc.) to produce halogenated alkenyl ethers in a deuterated solvent and catalyzed by a base.

[0077] Process overview: The halogenated olefin and alcohol are added to a solvent, e.g. DMSO, NMP, in the presence of a base, e.g. KOH, NaOH, etc., such as acetonitrile. The reaction proceeds at a temperature between ambient and 200°C, typically between 20°C and 100°C, for 1 hour to 24 hours, typically 2 hours to 4 hours. The pressure in the reactor is between atmospheric and 50 bar, preferably between atmospheric and 20 bar. The pressure may be the autogenous pressure of the solution or an inert gas, e.g. nitrogen, may be added to increase the pressure. The reaction product is then purified. The purification methods may be distillation, crystallization, and / or extraction, either by themselves or together. If necessary, the solvent may be recycled for the next batch or remixed in a feed vessel in a continuous process.

[0078] Process description: The process can be carried out either continuously, semi-continuously, or batchwise. For purposes of illustration, a batch reactor will be described. However, a batch reactor is not required and is used only to illustrate the process.

[0079] A typical feed mixture may be 1300 kg halogenated olefin, 1300 kg alcohol, 8580 kg solvent, and 800 kg potassium hydroxide powder. In this example, DMSO is employed. In this example, an excess of alcohol is used. Alternatively, equimolar amounts of halogenated olefin and alcohol, or an excess of halogenated olefin, may be used. The feeds may be premixed or added directly to the reactor.

[0080] The reaction can be carried out in a stirred tank reactor. Coils and / or jackets within the reactor are used to cool or heat the reactor. Stirring is preferred. Other reactor configurations can be used, such as loops, tubular elements with internal or external heat exchange. An optional static mixer may also be used. The reactor may be a pressurized reactor to facilitate carrying out the reaction at temperatures above the boiling points of the reactants and solvent (if present).

[0081] The reactor is heated between ambient temperature and 200°C, preferably between 20°C and 100°C. The reaction can be carried out at atmospheric pressure or above, especially if one or both of the reactants have significant volatility at the reaction temperature (e.g., if the reactants have a boiling point at atmospheric pressure lower than the reaction temperature employed). The pressure in the reactor is between atmospheric pressure and 50 bar, preferably between atmospheric pressure and 20 bar. The pressure can be the autogenous pressure of the solution or an inert gas, such as nitrogen, can be added to increase the pressure. The pressure in the reactor in which the halogenated olefin and the alcohol are reacting can be generated by the reactants and any solvent that may be present, or even by external pressure (e.g., pressurizing the headspace above the liquid phase in the reactor with an inert gas such as nitrogen).

[0082] The reaction is typically carried out for 0.25 hours to 24 hours. After the reaction, the contents may be pumped out of the reactor or may be retained in the reactor for processing. After the reaction, the reactor contents (i.e., the reaction mixture produced) may contain about 2300 kg of halogenated alkenyl ether, 300 kg of excess alcohol, 8580 kg of solvent, and salt (KCl or KF, depending on the particular halogenated olefin used).

[0083] Purification of the halogenated alkenyl ether can be accomplished by filtration, distillation or extraction, or any other means known in the art. Filtration is used to remove the solids, which may be unreacted potassium hydroxide, potassium chloride or potassium fluoride, depending on the particular halogenated olefin used. If distillation is used, the reactor is heated, optionally under vacuum or pressure, to drive off the alcohol and halogenated alkenyl ether. A portion of the solvent may be distilled. This operation does not have to be carried out in the same reactor, but may be carried out in a separate vessel or distillation column.

[0084] Continuing with this example, 102,000 kg of methylene chloride and 7,020 kg of water cooled to ambient or near 0° C. are added to the mixture in a continuous countercurrent Karr column. The aqueous stream product from the top of the column contains 7,020 kg of water, 560 kg of KCl, and about 7,680 kg of the solvent DMSO. The organic phase is composed of 2,300 kg of halogenated alkenyl ether, 300 kg of excess alcohol, and about 3,900 kg of DMSO in 93,500 kg of CH2Cl2.

[0085] The organic phase is distilled to separate the extraction solvent from the heavier components. Distillation is also used to remove light alcohols, 99.5% or more pure halogenated alkenyl ethers, and solvents for recycle. Distillation can be accomplished using any distillation technique known in the art, including, but not limited to, tray columns, packed columns, structured packed columns, divided wall columns, and the like.

[0086] The aqueous layer is subjected to distillation and crystallization or precipitation, either together or sequentially. The stream is distilled to remove water. At the same time, salts are precipitated, for example in a falling film crystallizer, or crystallized and filtered. In this way, the solvent may be recovered and recycled.

[0087] Within this specification, embodiments are described in a manner that enables a clear and concise specification to be written, but it is intended and understood that the embodiments can be combined or separated in various ways without departing from the invention, for example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0088] In some embodiments, the invention may be construed to exclude any component or process step that does not materially affect the basic and novel characteristics of the composition or process. Further, in some embodiments, the invention may be construed to exclude any component or process step not specified herein.

[0089] Although the invention has been illustrated and described herein with reference to specific embodiments, the invention is not limited to the details shown, but rather, various modifications may be made to the details within the scope and range of equivalence of the claims without departing from the invention. EXAMPLES

[0090] Example 1: Preparation of 4-chlorophenyl-3,3,3-trifluoropropenyl ether A 100 ml four-neck flask (14 / 20) was placed on a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell containing a thermocouple connected to a temperature controller and a dry ice condenser with an outlet connected to a nitrogen source. The reaction flask was charged with 4-chlorophenol (5.39 g / 0.0419 mol), potassium carbonate 6.40 g / 0.0463 mol, and DMSO (40.17 g / 0.5129 mol). α,α,α-trifluorotoluene (0.5196 g / 0.0036 mol) was added as an internal standard. While the reaction mixture was stirred, trans-(E)-1233zd (6.16 g / 0.047 mol) was added subsurface through a septum over a period of 40 minutes. After the addition of 1233zd, the reaction mixture was heated to 70-90 °C for 9 hours. After the specified time, the reaction mixture was analyzed by NMR spectroscopy, which showed that the yield (based on an internal standard) was 82% of the trans (E) isomer, 4-chlorophenyl-(E)-3,3,3-trifluoropropenyl ether, and 4% of the cis (Z) isomer, 4-chlorophenyl-(Z)-3,3,3-trifluoropropenyl ether.

[0091] The reaction mixture was mixed with 150 mL of water and 100 mL of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and allowed to stand for 15 minutes after which two immiscible layers formed. The resulting layers were separated and the bottom organic layer was washed twice with 100 mL of water. The organic layers were separated and the product was isolated by removing the solvent under reduced pressure. The amount of isolated organic layer was 6.63 g. NMR analysis revealed a product with an isomer distribution of 94% trans (E) isomer and 6% cis (Z) isomer. Approximately 3% of an impurity was identified, therefore the isolated yield was approximately 6.43 g, which represents an isolated yield of 69% (based on starting phenol).

[0092] Characterization Data: 4-Chlorophenyl-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.38ppm(doq,1H, 3 J H-H =13Hz,3 J H-F = 7Hz); δ 7.21ppm (doq, 1H, 3 J H-H =13Hz, 4 J H-F = 2Hz); δ 6.90-7.40ppm (m, 4H). 19 F NMR(CDCl3): trans isomer δ-60.60(dod,3F, 3 J F-H =7Hz, 4 J F-H =2Hz). Cis isomer δ-58.13 (d,3F, 3 J=9Hz).nD 20 =1.4842.

[0093] Other derivatives were similarly prepared from 1233zd following the procedure described in Example 1. The results are summarized in Table 1.

[0094] Table 1: Summary of results for Examples 1-10 [Table 1]

[0095] Characterization data, examples 2-10. Example 2: 1,4-Bis(3,3,3-trifluoropropenyloxy)benzene. 1 H NMR(CDCl3):δ5.35ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.22ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 7.06ppm (s, 4H). 19 F NMR(CDCl3): trans isomer δ-60.73 (dod, 3F, 3 J F-H =7Hz, 4 J F-H =2Hz). Cis isomer δ-58.29 (d,3F, 3 J=9Hz).nD 20 =1.4516.

[0096] Example 3: 4-Fluoro-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.32ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.21ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 7.04ppm (m, 4H). 19 F NMR(CDCl3): trans isomer δ-60.65(dod,3F, 3 J F-H =7Hz, 4 J F-H =3Hz). Cis isomer δ-58.23 (d,3F, 3 J=8Hz). nD 20 =1.4434.

[0097] Example 4: 4-Methylphenyl-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ2.35(s,3H);δ5.31ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.24ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 7.17ppm (m, 4H). 19 F NMR(CDCl3): trans isomer δ-60.51 (d,3F, 3 J F-H =6Hz). Cis isomer δ-58.12 (d,3F, 3 J=9Hz). nD20 =1.4624.

[0098] Example 5: 3-Cyanophenyl-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.51ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.27ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 7.30-7.57ppm (m, 4H). 19 F NMR(CDCl3): trans isomer δ-60.95 (d, 3F, 3 J F-H =5Hz). Cis isomer δ-58.35 (d,3F, 3 J=8H.nD 20 =1.4915.

[0099] Example 6: 2-Fluoro-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.30ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.00-7.30ppm (m, 4H). 19 F NMR(CDCl3): trans isomer δ-60.66 (d, 3F, 3 J F-H =6Hz). Cis isomer δ-58.16 (d,3F, 3 J=8Hz);δ-131.80(m,1F). nD 20 =1.4421.

[0100] Example 7: 3-Nitrophenyl-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.53ppm(doq,1H,3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.28ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz);δ7.35-8.10ppm(m,4H). 19 F NMR(CDCl3): trans isomer δ-61.28 (d,3F, 3 J F-H =7Hz). Cis isomer δ-58.71 (d,3F, 3 J=8Hz). nD 20 =1.4977.

[0101] Example 8: 2,4-Dichlorophenyl-3,3,3-trifluoropropenyl ether 1 H NMR(CDCl3):δ5.31ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7 Hz); δ 7.17 ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 6.92-7.48ppm (m,3H). 19 F NMR(CDCl3): trans isomer δ-61.07 (dod, 3F, 3 J F-H =6Hz, 4 J F-H = 2Hz). cis isomer - 58.61 (d, 3F, 3 J=8Hz). nD 20 =1.4979. HRMS[M · ] + = 255.9669 m / z(observed); 255.9670 m / z(calc).

[0102] Example 9: 2-Chloro-4-fluoro-3,3,3-trifluoropropenyl ether 1H NMR(CDCl3):δ5.23ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.16ppm (doq, 1H, 3 J H-H =12Hz, 4 J H-F = 2Hz); δ 6.96-7.26ppm (m,3H). 19 F NMR(CDCl3): trans isomer δ-60.74 (d, 3F, 3 J F-H =7Hz, 4 J F-H =2Hz) cis isomer δ-58.33 (d,3F, 3 J=8Hz);Aromatic-Fδ-114.92(m,1F). nD 20 =1.4633. HRMS[M · ] - = 239.9960 m / z(observed); 239.9960 m / z(calc).

[0103] Example 10: 4-(3,3,3-trifluoropropenyl)phenyl sulfate sodium salt 1 H NMR(CDCl3):transδ5.79ppm(doq,1H, 3 J H-H =12Hz, 3 J H-F = 7Hz); δ 7.6 not fully resolved; δ 7.06-7.64ppm (m, 4H). cis δ 5.32ppm (doq, 1H, 3 J H-F =8Hz, 3 J H-H = 7Hz); δ 7.21ppm (d, 1H, 3 J H-H =7Hz). 19 F NMR(CDCl3): trans isomer δ-57.69 (d,3F, 3 J F-H =7Hz, 4 J F-H =2Hz). Cis isomer δ-55.45 (d,3F,3 J=8Hz).

[0104] Example 11: Preparation of 4-fluoro-3,3,3-trifluoro-2-propenyl ether A similar procedure to that of Example 1 was followed except that 1233xf was used instead of 1233zd. 5.23 g (46.7 mmol) of 4-fluorophenol was reacted with 9.90 g (75.9 mmol) of 1233xf along with a 45.05 g (520.5 mmol) DMSO solution of 7.54 g (54.6 mmol) of potassium carbonate at 70-90 °C for 8 hours. After aqueous workup similar to that described in Example 1, 8.63 g of 97% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the product. The isolated yield of the title product was 8.37 g = 87.0%.

[0105] Characterization data: 4-Fluoro-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.00ppm(doq,1H, 3 J H-H =8Hz, 3 J H-F =8Hz); δ6.66ppm(d,1H, 3 J H-H =8Hz). δ7.02-7.25ppm(m,4H). 19 F NMR(CDCl3): δ-58.07(d,3F, 3 J F-H =8Hz). 20 =1.4983.

[0106] Other derivatives were similarly prepared from 1233xf following the procedure described in Example 11. The results obtained are summarized in Table 2.

[0107] Table 2: Summary of results for Examples 11-20 [Table 2]

[0108] Characterization Data, Examples 12-20: Example 12: 3-Nitrophenyl-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.21ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz); δ6.82ppm(d,1H, 2 J H-H =7Hz);δ7.42ppm(m,1H);δ7.58ppm(t,1H,J H-H = 8Hz); δ 7.91ppm (t, 1H, J H-H = 2Hz); δ 8.05ppm (m, 1H). 19 F NMR(CDCl3): δ-58.42(d,3F, 4 J F-H =8Hz). 20 =1.5123. HRMS[MH] - = 232.0233 m / z(observed); 232.0227 m / z(calc).

[0109] Example 13: 2-Fluoro-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.02ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz);δ6.65ppm(dod,1H, 2 J H-H =7Hz, 4 J H-F = 2 Hz); δ 7.05 ~ 7.25 ppm (m, 4H). 19 F NMR(CDCl3): δ-58.42(d,3F, 4 J F-H =8Hz). Aromatic-Fδ-133.40(m,1F). nD 20 =1.4505. HRMS[MH] -= 205.0280 m / z(observed); 205.0282 m / z(calc).

[0110] Example 14: 4-Methylphenyl-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ4.93ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz); δ6.67ppm(d,1H, 2 J H-H =7Hz);δ2.30ppm(s,3H);δ6.88~7.13ppm(m,4H). 19 F NMR(CDCl3): δ-58.11(d,3F, 4 J F-H =8Hz). 20 =1.4721. HRMS[M · ] + = 202.0602 m / z(observed); 206.0600 m / z(calc).

[0111] Example 15: 4-Chlorophenyl-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.03ppm(doq,1H, 2 J H-H =8Hz, 4 J H-F =8Hz); δ6.67ppm(d,1H, 2 J H-H = 8Hz); δ 6.95~7.35ppm(m,4H). 19 F NMR(CDCl3): δ-58.30(d,3F, 4 J=8Hz). nD 20 =1.4896. HRMS[M · ] + = 222.0057 m / z(observed); 222.0054 m / z(calc).

[0112] Example 16: 3-Cyanophenyl-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.17ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz); δ6.73ppm(d,1H, 2 J H-H = 7 Hz); δ 7.29 ~ 7.54 ppm (m, 4H). 19 F NMR(CDCl3): δ-58.50(d,3F, 4 J=8Hz). nD 20 =1.4963. HRMS[MH] - = 212.0334 m / z(observed); 212.0329 m / z(calc).

[0113] Example 17: 1,4-bis(3,3,3-trifluoro-2-propenyl)phenyl ether 1 H NMR(CDCl3):δ5.03ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz); δ6.68ppm(d,1H, 2 J H-H = 7Hz); δ 7.07ppm(s,4H). 19 F NMR(CDCl3): δ-58.28(d,3F, 4 J=8Hz);nD 20 =1.4434. HRMS[M · ] + = 298.0430 m / z(observed); 298.0423 m / z(calc).

[0114] Example 18: 2,4-Dichlorophenyl-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.09ppm(doq,1H, 2 J H-H =7Hz,4 J H-F =8Hz); δ6.57ppm(d,1H, 2 J H-H = 7Hz); δ 7.00-7.50ppm (m,3H). 19 F NMR(CDCl3): δ-58.41(d,3F, 4 J F-H =8Hz). 20 =1.5124. HRMS[M · ] + = 255.9669 m / z(observed); 255.9670 m / z(calc).

[0115] Example 19: 2-Chloro-4-fluoro-3,3,3-trifluoro-2-propenyl ether 1 H NMR(CDCl3):δ5.05ppm(doq,1H, 2 J H-H =7Hz, 4 J H-F =8Hz); δ6.54ppm(d,1H, 2 J H-H = 7Hz); δ 6.85-7.25ppm (m,3H). 19 F NMR(CDCl3): δ-58.27(d,3F, 4 J F-H =8Hz);Aromatic-Fδ-115.6(m,1F). nD 20 =1.4705.

[0116] Example 20: 4-(3,3,3-trifluoro-2-propenyl)phenyl sulfate sodium salt 1 H NMR(CDCl3):transδ5.38ppm(doq,1H, 4 J H-F =9Hz, 2 J H-H = 7Hz); δ7.27(d,1H, 2 J H-H = 7); δ 7.08-7.65 ppm (m, 4H). 19F NMR(CDCl3): δ-55.45(d,3F, 4 J F-H =9Hz).

[0117] Example 21: Preparation of 1-(3,3,3-trifluoro-1-propenyl)imidazole A similar procedure as described in Example 1 was followed, except that 3.00 g (44.1 mmol) of imidazole was used instead of 4-chlorophenol along with a solution of 6.49 g (47.0 mmol) of potassium carbonate in 45.05 g (512.9 mmol) of DMSO, which was reacted with 10.89 g (83.4 mmol) of 1233zd at 140° C. for 17 hours. After aqueous workup similar to that described in Example 1 and sublimation, 1.19 g of an oily solid of 99% purity was obtained. Analysis by NMR spectroscopy confirmed the identity of the product. The isolated yield of the title product was 1.18 g = 17.0%.

[0118] Characterization Data: 1-(3,3,3-trifluoroprop-1-propenyl)imidazole 1 H NMR (CDCl3): trans isomer δ 5.89 ppm (doq, 1H, 3 J H-H =14Hz, 3 J H-F = 6Hz); δ 7.43ppm (doq, 1H, 3 J H-H =14Hz, 4 J H-F =2Hz). Cis isomer δ 5.42 ppm (doq, 1H, 3 J H-H =11Hz, 3 J H-F = 9Hz); δ 6.96ppm (d, 1H, 3 J H-H =11Hz). Imidazole ring.δ7.16ppm(d,1H,J=1Hz);7.19ppm(t,1H,J=1Hz);δ7.71ppm(s,1H). 19 F NMR(CDCl3): trans isomer δ-62.58 (dod,3F, 3 JF-H =6Hz, 4 J F-H =2Hz). Cis isomer δ-57.95 (d,3F, 3 J=8Hz). HRMS[M+H] + = 163.0472 m / z(observed); 163.0478 m / z(calc).

[0119] Example 22: Preparation of 1-(3,3,3-trifluoro-1-propenyl)imidazole A procedure similar to that described in Example 20 was followed, except that K + The imidazolium salt was preformed and then the resulting salt was treated with 1233zd. 6.88 g (101.1 mmol) of imidazole was treated with 6.89 g (122.8 mmol) of KOH, which was used instead of potassium carbonate, and 102.35 g (1.4194 mol) of THF was used instead of DMSO. 16.78 g (111.2 mmol) of 1233zd was reacted with this mixture at 60° C. for 53 hours. After an aqueous workup similar to that described in Example 19, the crude product was analyzed by NMR spectroscopy to confirm the identity of the product. The isolated yield of the title product was 3.47 g = 21.0%.

[0120] Example 23: Attempted preparation of 1-(3,3,3-trifluoro-2-propenyl)imidazole A similar procedure as described in Example 1 was followed, except that 3.00 g (44.1 mmol) of imidazole was used instead of 4-chlorophenol along with 6.50 g (47.1 mmol) of potassium carbonate in 46.06 g (589.5 mmol) of DMSO, which was reacted with 9.40 g (72.0 mmol) of 1233xf at 140° C. for 24 hours. After a similar aqueous workup as described in Example 1 and distillation at 120-140° C. under 1 Torr vacuum, 0.75 g of 98% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the product to be the same two isomers observed in Example 20 (12333zd was used as the source of the trifluoropropyl moiety). The isolated yield of the title product was 0.74 g = 10.0%.

[0121] Characterization data: 1-(3,3,3-trifluoroprop-1-propenyl)imidazole 1 H NMR (CDCl3): trans isomer δ 5.88 ppm (doq, 1H, 2 J H-H =14Hz, 4 J H-F = 6Hz); δ 7.42ppm (doq, 1H, 2 J H-H =14Hz, 4 J H-F =2Hz). Imidazole ring. δ 7.16 ppm (d, 1H, J = 1 Hz); δ 7.19 ppm (t, 1H, J = 1 Hz); δ7.71ppm(s,1H). Product isomer δ5.42ppm(doq,1H, 2 J H-H =10Hz, 4 J H-F = 9Hz); δ 6.95ppm (d, 1H, 3 J H-H =11 Hz). Imidazole ring. δ 7.13 ppm (d, 1H, J = 1 Hz); δ 7.26 ppm (t, 1H, J = 1 Hz); δ 7.69 ppm (s, 1H). 19 F NMR(CDCl3): trans isomer δ-62.51(dod,3F, 4 J F-H =6Hz, 4 J F-H =2Hz). Cis isomer δ-57.88 (dod,3F, 4 J F-H =9Hz, 4 J F-H =1Hz). HRMS[M+H] + = 163.0473 m / z(observed); 163.0478 m / z(calc).

[0122] Example 24: Preparation of 1-(3,3,3-trifluoro-1-propenyl)pyrazole A similar procedure as described in Example 1 was followed, except that 3.02 g (44.4 mmol) of pyrazole was used instead of 4-chlorophenol along with a solution of 6.56 g (47.5 mmol) of potassium carbonate in 45.72 g (585.2 mmol) of DMSO, which was reacted with 6.33 g (48.5 mmol) of 1233zd at 140° C. for 24 hours. After a similar aqueous workup as described in Example 1 and distillation at 120-140° C. under 1 Torr vacuum, 0.79 g of 98% pure product was obtained. Analysis by NMR spectroscopy confirmed that the desired product was two isomers. The isolated yield of the title product was 0.77 g = 11.0%.

[0123] Characterization Data: 1-(3,3,3-trifluoro-1-propenyl)pyrazole 1 H NMR (CDCl3): trans isomer 6.26 ppm (doq, 1H, 3 J H-H =14Hz, 3 J H-F = 6Hz); δ 7.48ppm (doq, 1H, 3 J H-H =14Hz, 4 J H-F =2Hz). Pyrazole ring δ7.69ppm(s,1H); δ7.59ppm(d,1H,J=3Hz); δ6.43ppm(t,1H,J=2Hz). Product isomer δ5.29ppm(doq,1H, 3 J H-H =10Hz, 4 J H-F = 9Hz); δ 7.22ppm (d, 1H, 3 J H-H =10Hz). 19 F NMR(CDCl3): trans isomer δ-62.25 (dod, 3F, 3 J F-H =7Hz, 4 J F-H =2Hz). Cis isomer δ-57.56 (d,3F, 3 J F-H =9Hz). HRMS[M+H]+ = 163.0474 m / z(observed); 163.0478 m / z(calc).

[0124] Example 25: Attempted preparation of 1-(3,3,3-trifluoro-2-propenyl)pyrazole A similar procedure was followed as described in Example 1, but instead of 4-chlorophenol, 3.23 g (47.4 mmol) of pyrazole was used along with a 46.20 g (591.3 mmol) solution of 7.14 g (51.7 mmol) of potassium carbonate in DMSO, which was reacted with 8.10 g (62.1 mmol) of 1233xf at 140 °C for 19 hours. After a similar aqueous workup as described in Example 1 and distillation at 120-140 °C under 1 Torr vacuum, 0.49 g of 99% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the product to be the same two isomers observed in Example 23 (12333zd was used as the source of the trifluoropropyl moiety). The isolated yield of the title product was 0.49 g = 6.0%.

[0125] Characterization Data: 1-(3,3,3-trifluoroprop-1-propenyl)pyrazole 1 H NMR (CDCl3): trans isomer δ 6.25 ppm (doq, 1H, 2 J H-H =14Hz, 4 J H-F = 7Hz); δ 7.48ppm (doq, 1H, 2 J H-H =14Hz, 4 J H-F =2Hz). Pyrazole ring.δ7.69ppm(s,1H);δ7.59ppm(d,1H,J=2Hz);δ6.43ppm(t,1H,J=2Hz). Product isomer δ5.29ppm(doq,1H, 3 J H-H =11Hz, 4 J H-F = 9Hz); δ 7.21ppm (d, 1H, 3 J H-H =11Hz). 19F NMR(CDCl3): trans isomer δ-62.21 (dod,3F, 4 J F-H =7Hz, 4 J F-H =2Hz). Cis isomer δ-57.53 (dod,3F, 4 J F-H =9Hz, 4 J F-H =1Hz). HRMS[M+H] + = 163.0472 m / z(observed); 163.0478 m / z(calc).

[0126] Example 26: Reaction of 1233zd with hydroxy-functionalized tertiary amines Jeffcat® Z110 [HOCH2CH2CH2N(CH3)CH2CH2N(CH3)2] and 1233zd were mixed and aged for 2 weeks at 50° C. in the presence of potassium hydroxide (KOH). 1 Analysis by 1 H NMR confirmed partial reaction of the starting material according to the following scheme: HOCH2CH2CH2N(CH3)CH2CH2N(CH3)2+CF3CH=CHCl→CF3CH=CHOCH2CH2CH2N(CH3)2.

[0127] Example 27: Synthesis of 2,2-dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane using excess solketal as solvent A 100 ml 4-neck flask (14 / 20) was placed in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell containing a thermocouple connected to a temperature controller and a dry ice condenser with an outlet connected to a nitrogen source. The reaction flask was charged with 2,2-dimethyl-1,3-dioxolane-4-methanol (solketal) (30.94 g / 0.2341 mol), tetrabutylammonium bromide (0.15 g / 0.0005 mol) and potassium hydroxide (3.36 g / 0.0599 mol) dissolved in water (6.72 g / 0.3733 mol). α,α,α-trifluorotoluene (0.4985 g / 0.0034 mol) was added as an internal standard. While the reaction mixture was stirred, 1-chloro-2,2-difluoroethylene (HCFC1122) (5.44 g / 0.0552 mol) was added subsurface through a septum over 10 minutes. The temperature at the end of the addition was 17° C.-33° C. After the addition of HCFC1122, the reaction mixture was stirred at ambient temperature for 2 hours.

[0128] The reaction mixture was mixed with 150 ml of water and 100 ml of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and after standing for 15 minutes formed two immiscible layers. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layers were separated and the solvent was removed under reduced pressure to isolate the product. The amount of product isolated was 10.05 g. The major product was 2,2-dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane. The purity was 42 wt % and the yield was 33% based on FNMR internal standard analysis. The ketal blocking groups could be removed from this product to obtain a dihydroxy functionalized compound with -O-CClH-CF2H groups.

[0129] 19 F NMR(CDCl3): δ-79.64(F A ),-79.89(F B )ppm,tq, 2 J Fa-Fb =-140Hz, 3 J H-F =9Hz AB type tetrad to F A and F B The chemical shifts were calculated.

[0130] Example 28: Synthesis of 2,2-dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane using DMSO as solvent A 100 ml 4-neck flask (14 / 20) was placed in a heating mantle and placed on a mechanical stirrer. The flask was equipped with a thermowell containing a thermocouple connected to a temperature controller and a dry ice condenser with an outlet connected to a nitrogen source. The reaction flask was charged with solketal (6.62 g / 0.0500 mol), DMSO (54.22 g / 0.6940 mol), tetrabutylammonium bromide (0.15 g / 0.0005 mol), and potassium hydroxide (2.86 g / 0.0509 mol) dissolved in water (5.72 g / 0.3178 mol). While the reaction mixture was stirred, 1-chloro-2,2-difluoroethylene (HCFC1122) (5.44 g / 0.0552 mol) was added subsurface through a septum over a period of 10 minutes. At the end of the addition, the temperature had risen from 22° C. to 45° C. After addition of HCFC1122 the reaction mixture was stirred at ambient temperature for 16 hours.

[0131] The reaction mixture was mixed with 150 ml of water and 100 ml of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and after standing for 15 minutes formed two immiscible layers. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layers were separated and the product was isolated by removing the solvent under reduced pressure. The amount of product isolated was 9.93 g. The major product was 2,2-dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane. The purity was 52% by weight and the yield was 45% based on FNMR internal standard analysis.

[0132] 19 F NMR(CDCl3): δ-79.64(F A ),-79.89(F B )ppm,tq,2 J Fa-Fb =-140Hz, 3 J H-F =9Hz AB type tetrad to F A and F B The chemical shifts were calculated.

[0133] Example 29: Synthesis of 2,2-dimethyl-4-[(1-fluoroethenyloxy)methyl]-1,3-dioxolane using DMSO as solvent A 100 ml 4-neck flask (14 / 20) was placed in a heating mantle and placed on a mechanical stirrer. The flask was equipped with a thermowell containing a thermocouple connected to a temperature controller and a dry ice condenser with an outlet connected to a nitrogen source. The reaction flask was charged with solketal (5.60 g / 0.0424 mol), DMSO (31.10 g / 0.3989 mol), potassium hydroxide (2.67 g / 0.0476 mol). While the reaction mixture was stirred, 1-chloro-1-fluoroethylene (HCFC1131a) (5.44 g / 0.0552 mol) was added subsurface through a septum over a period of 5 minutes. At the end of the addition, the temperature had risen from 23° C. to 41° C. After the addition of HCFC1131a, the reaction mixture was stirred at ambient temperature for 48 hours.

[0134] The reaction mixture was mixed with 150 ml of water and 100 ml of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and after standing for 15 minutes formed two immiscible layers. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layers were separated and the product was isolated by removing the solvent under reduced pressure. The amount of product isolated was 5.90 g. The major product was 2,2-dimethyl-4-[(1-fluoroethenyloxy)methyl]-1,3-dioxolane. The purity was 72% by weight and the yield was 52% based on FNMR internal standard analysis.

[0135] 19 F NMR(CDCl3):δ-80.62 ppm (d of d, 3 J F-H=41.3Hz (trans), 6.5Hz cis) 1 HNMR(CDCl3):δ3.24-3.40(d of d,1H-trans, 3 J H-F =41.3, 2 J H-H = 4.4); δ 3.60-3.65, (d of d, 1H-cis, 3 J H-F =6.5, 2 J H-H =4.4);δ3.74-3.64(m,3H),δ4.06-4.12(m,1H),δ4.32-4.40(m,1H)

[0136] Example 30: Synthesis of 2,2-dimethyl-4-[(1-fluoroethenyloxy)methyl]-1,3-dioxolane using DMSO as solvent A 100 ml 4-neck flask (14 / 20) was placed in a heating mantle and placed on a mechanical stirrer. The flask was equipped with a thermowell containing a thermocouple connected to a temperature controller and a dry ice condenser with an outlet connected to a nitrogen source. The reaction flask was charged with solketal (5.60 g / 0.0424 mol), DMSO (31.48 g / 0.4029 mol), potassium hydroxide (3.20 g / 0.0520 mol). While the reaction mixture was stirred, 1-chloro-1-fluoroethylene (HCFC1131a) (4.81 g / 0.0598 mol) was added subsurface through a septum over 8 minutes. At the end of the addition, the temperature had risen from 23° C. to 55° C. After the addition of HCFC1131a, the reaction mixture was stirred at ambient temperature for 16 hours.

[0137] Hexane (50 mL) was added and the reaction mixture was heated to 50° C. with stirring for 1 hour. The reaction mixture was cooled to ambient temperature (22° C.) and stirring was stopped. The layers were allowed to settle for 15 minutes. The top hexane layer was removed by siphoning with a syringe. A second 50 mL of hexane was charged to the reaction flask and the mixture was stirred at ambient temperature for 15 minutes. Stirring was stopped and the layers were allowed to settle for 15 minutes. The top hexane layer was removed by siphoning with a syringe. These two hexane extracts were combined and the solvent was removed under reduced pressure to isolate the product. The amount of product isolated was 4.05 g. The major product was 2,2-dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane. The purity was 75% by weight and the yield was 41% based on FNMR internal standard analysis. The remaining reaction mixture was mixed with 150 mL of water and 100 mL of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and allowed to stand for 15 minutes after which two immiscible layers formed. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layers were separated and the product was isolated by removing the solvent under reduced pressure. The amount of product isolated was 3.40 g. The major product was 2,2-dimethyl-4-[(1-fluoroethenyloxy)methyl)]-1,3-dioxolane. The purity was 57% by weight and the yield was 26% based on FNMR internal standard analysis.

[0138] 19 F NMR(CDCl3):δ-80.62ppm(d of d, 3 J F-H =41.3Hz (trans), 6.5Hz cis) 1 HNMR(CDCl3):δ3.24-3.40(d of d,1H-trans, 3 J H-F =41.3, 2 J H-H = 4.4); δ 3.60-3.65, (d of d, 1H-cis, 3 J H-F =6.5, 2 J H-H=4.4);δ3.74-3.64(m,3H),δ4.06-4.12(m,1H),δ4.32-4.40(m,1H)

[0139] Example 31: Reaction of 1,1,1,2-trifluoro-2-chloroethylene (CTFE) with 2-hydroxyethyl methacrylate (HEMA) in 30% acetone and 70% DMSO solvent A 1 L, four-neck (14 / 20) flask equipped with overhead stirring and a dry ice condenser with an outlet connected to a digital thermometer and nitrogen source was used. A prepuncture septum was placed in the remaining neck. The reaction flask was charged with 2-hydroxyethyl methacrylate (80.22 g / 0.6160 mol), DMSO (374.66 g / 4.7953 mol), acetone (161.55 g / 2.7774 mol), potassium carbonate (94.03 g / 0.6803 mol), and benzoquinone (0.76 / 7.03×10 -3 CTFE (78.92 g / 0.676 mol) was added subsurface in aliquots through the septum over a period of 2 days at temperatures between 16 and 21 °C while the reaction mixture was stirred. An internal standard (α,α,α-trifluorotoluene) was added to the reaction mixture and the reaction was followed by FNMR.

[0140] The reaction mixture was charged to a 5 L separatory funnel with 2 L of water and 1 L of dichloromethane and stirred for 10 minutes. Stirring was stopped and after standing for 15 minutes, two immiscible layers formed. The resulting layers were separated and the bottom organic layer was washed twice with 1 L of water. The organic layers were separated and the product was isolated by distilling off the solvent under reduced pressure. The amount of crude 2-chloro-1,1,2-trifluoroethoxy methacrylate product isolated was 120.90 g. The product had a purity of 73% by weight and a yield of 58% by FNMR based on the 2-hydroxy methacrylate starting material.

[0141] The crude material was purified by column chromatography using a 2" x 24" column packed with silica gel. The crude to silica ratio was 15:1. The product was eluted with 10% ethyl acetate / n-hexane. The crude product was purified in multiple batches. The combined product weighed 66.99g and was 97% pure by GC A%. The product was also confirmed by GC / MS and LC / MS. The yield of the purified product was 43% based on the 2-hydroxymethacrylate starting material.

[0142] 19 F NMR(CDCl3): δ-88.26 ppm(F A ),-88.74ppm(F B ) * ,(d of d of q, 2 J Fa-Fb =-141Hz, 3 J Fa-H =3.5Hz, 3 J Fb-H =4.7Hz), δ-154.31(F c )(t's d, 3 J F-F =12Hz, 2 J F-H =48 1 HNMR (CDCl3): δ 1.95 ppm (d of d, 3H); δ 4.20 ppm (d of d of d, 2H); δ 4.40 (d of d of d, 2H); δ 5.60 (m of d, 1H) δ 6.08 ppm (d of d of d, 1H, 2 J H-F =48, 3 J H-Fa =3.5Hz, 3 J H-Fb = 4.7Hz); δ 6.10ppm (md, 1H)

[0143] * AB type tetrad to F A and F B The chemical shifts were calculated.

[0144] Example 32: Reaction of 1,1,2-trifluoro-2-chloroethylene (CTFE) with 2-hydroxyethyl methacrylate (HEMA) in DMSO solvent A 250 mL four-neck (14 / 20) flask equipped with a digital thermometer and a dry ice condenser with the outlet connected to a nitrogen source was placed on a magnetic stirrer. A pre-pierced septum was placed in the remaining neck. The reaction flask was charged with 2-hydroxyethyl methacrylate (20.12 g / 0.1546 mol), DMSO (116.85 g / 1.4956 mol), potassium carbonate (21.84 g / 0.1580 mol), and benzoquinone (0.06 / 5.55×10 -4 1. CTFE (18.8 g / 0.161 mol) was added to the subsurface of the aliquot through the septum over a period of 3 h at temperatures between 17 and 25 °C while the reaction mixture was stirred. An internal standard (α,α,α-trifluorotoluene) was added to the reaction mixture and the reaction was monitored by FNMR.

[0145] The reaction mixture was mixed with 700 ml of water and 200 ml of methylene chloride and stirred for 15 minutes. The resulting mixture was placed in a separatory funnel and after standing for 15 minutes formed two immiscible layers. The resulting layers were separated and the bottom organic layer was washed twice with 200 ml of water. The organic layers were separated and the product was isolated by removing the solvent under reduced pressure. The amount of crude 2-chloro-1,1,2-trifluoroethoxy methacrylate product isolated was 33.34 g. The product had a purity of 74% by weight and a yield of 64% by FNMR based on the 2-hydroxymethacrylate starting material.

[0146] The crude material was purified by short path distillation under a vacuum of about 1 torr. The amount of distillate collected was 27.02 g. The distillate had a purity of 80 wt. % by FNMR and a yield of 57% based on the 2-hydroxymethacrylate starting material.

[0147] 19 F NMR(CDCl3): δ-88.26 ppm(F A ),-88.74ppm(F B ) * ,(d of d of q, 2 J Fa-Fb =-141Hz, 3 J Fa-H=3.5Hz, 3 J Fb-H =4.7Hz), δ-154.31(F c )(t's d, 3 J F-F =12Hz, 2 J F-H =48 1 HNMR (CDCl3): δ 1.95 ppm (d of d, 3H); δ 4.20 ppm (d of d of d, 2H); δ 4.40 (d of d of d, 2H); δ 5.60 (m of d, 1H) δ 6.08 ppm (d of d of d, 1H, 2 J H-F =48, 3 J H-Fa =3.5Hz, 3 J H-Fb = 4.7Hz); δ 6.10ppm (md, 1H)

[0148] * AB type tetrad to F A and F B The chemical shifts were calculated.

Claims

[Claim 1] A trifluoropropenyl-substituted aromatic compound selected from the group consisting of 3-nitrophenyl-3,3,3-trifluoropropenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoropropenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoropropenyl ether, 4-(3,3,3-trifluoropropenyl)phenyl sulfate, 3-nitrophenyl-3,3,3-trifluoro-2-propenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoro-2-propenyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoro-2-propenyl ether, and 4-(3,3,3-trifluoro-2-propenyl)phenyl sulfate sodium salt.

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