HALOGENATED HETEROALKENYL- AND HETEROALKYL-FUNCTIONALIZED ORGANIC COMPOUNDS AND METHODS FOR PREPARING SUCH COMPOUNDS

Abstract

A method for synthesizing halogenated organic compounds, such as halogenated alkenyl group-containing and halogenated alkyl group-containing compounds having a heteroatom (e.g., O,N.S) coupled to a carbon atom of a halogenated alkenyl or halogenated alkyl group, involves reacting a halogenated olefin such as a chloro-substituted trifluoropropenyl compound with an active hydrogen-containing organic compound such as an alcohol (e.g., an aliphatic monoalcohol, aliphatic polyalcohol, or a phenolic compound), a primary amine, a secondary amine or a thiol.

Claims

1. A method of making 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 containing a carbon-carbon double bond, 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, to produce the halogenated organic compound.

2. The method of claim 1, wherein the halogenated olefin contains one or more fluorine atoms.

3. The method of claim 1, wherein the halogenated organic compound is a halogenated heteroalkenyl-functionalized organic compound.

4. The method of claim 1, wherein the halogenated organic compound is a halogenated heteroalkyl-functionalized organic compound.

5. The method of claim 1, wherein the halogenated olefin has a fluorinated alkyl group substituted on one carbon of the carbon-carbon double bond.

6. The method of claim 1, wherein the halogenated olefin has a perfluorinated alkyl group substituted on one carbon of the carbon-carbon double bond.

7. The method of claim 1, wherein the halogenated olefin has a structure in accordance with formula (1):
CX.sup.1X.sup.2CX.sup.3X.sup.4(1) wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.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-C20 alkyl groups, subject to the proviso that one or more of X.sup.1, X.sup.2, X.sup.3 and X.sup.4 is selected from the group consisting of chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and halogenated alkyl groups.

8. The method of claim 1, wherein the halogenated olefin is selected from the group consisting of CFClCH.sub.2, CH.sub.2CF.sub.2, CFHCH.sub.2, CF.sub.2CHF, CF.sub.3CFCH.sub.2, CF.sub.2CF.sub.2, CFCHCl, CF.sub.3CClCH.sub.2, CF.sub.3CHCHCl, CF.sub.3CFCFH, CF.sub.3CHCF.sub.2, CF.sub.3CFCF.sub.2, CF.sub.3CH.sub.2CFCH.sub.2, CF.sub.3CHCFCH.sub.3, CF.sub.3CFCHCF.sub.3, CF.sub.3CClCHCF.sub.3, CF.sub.2HCH.sub.2CFCH.sub.2, CF.sub.2HCH.sub.2CFCHCl and CF.sub.2HCHCFCH.sub.2Cl.

9. The method of claim 1, wherein the halogenated olefin is reacted with a phenolic compound.

10. The method of claim 1, wherein the halogenated olefin is reacted with an aliphatic alcohol.

11. The method of claim 1, wherein the halogenated olefin is reacted with an aliphatic polyalcohol.

12. The method of claim 1, wherein the halogenated olefin is reacted with a masked aliphatic polyalcohol which is an aliphatic polyol having a plurality of hydroxyl groups wherein at least one hydroxyl group is blocked and at least one hydroxyl group is a free hydroxyl group.

13. The method of claim 1, wherein the halogenated olefin is reacted with a primary or secondary amine.

14. The method of claim 1, wherein the halogenated olefin is reacted with a thiol.

15. The method of claim 1, wherein the reacting is carried out under basic conditions.

16. The method of claim 1, wherein the reacting is carried out in the presence of an inorganic base.

17. The method of claim 16, wherein the inorganic base is selected from the group consisting of alkali metal hydroxides and alkali metal salts of carbonic acid.

18. The method of claim 1, wherein the reacting is carried out in a liquid medium.

19. The method of claim 18, wherein the liquid medium is comprised of one or more organic solvents.

20. The method of claim 19, wherein the one or more organic solvents are selected from the group consisting of polar, non-protic organic solvents.

21. The method of claim 19, wherein the one or more organic solvents are polar, non-protic organic solvents having dielectric constants of from 2 to 190.

22. The method of claim 1, wherein the reacting is carried out in the presence of a phase transfer catalyst.

23. The method of claim 2, wherein the phenolic compound has structure Ar(OH).sub.x, wherein Ar is an optionally substituted aromatic moiety and x is an integer of 1 or more.

24. The method of claim 23, wherein x is 1, 2 or 3.

25. The method of claim 23, wherein Ar is selected from the group consisting of optionally substituted phenyl groups, optionally substituted naphthyl groups, and optionally substituted anthryl groups.

26. The method of claim 23, wherein Ar is an aromatic moiety substituted with one or more substituents selected from the group consisting of halogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heterocycloalkyl, optionally substituted alkoxy, optionally substituted aroxy, optionally substituted aryl, optionally substituted heteroaryl, cyano, optionally substituted carboxyl, sulfate and nitro.

27. The method of claim 1, wherein the active hydrogen-containing organic compound and the halogenated olefin are reacted at a temperature of from about 200 C. to about 200 C. for a time of from about 0.5 hours to about 120 hours.

28. The method of claim 1, wherein the active hydrogen-containing organic compound and the halogenated olefin are reacted in a stoichiometric ratio of (moles active hydrogen-containing organic compound)/x:moles halogenated olefin, wherein x=number of active hydrogens per molecule of the active hydrogen-containing organic compound, of from about 1:8 to about 8:1.

29. A trifluoropropenylether-substituted aromatic compound of formula (I):
Ar(OCR.sup.1CHR.sup.2).sub.x(I) wherein Ar is an optionally substituted aromatic moiety, x is an integer of 1 or more, and either R.sup.1 is CF.sub.3 and R.sup.2 is H or R.sup.1 is H and R.sup.2 is CF.sub.3.

30. The trifluoropropenylether-substituted aromatic compound of claim 29, wherein x is 1, 2 or 3.

31. The trifluoropropenylether-substituted aromatic compound of claim 29, wherein Ar is selected from the group consisting of optionally substituted phenyl groups, optionally substituted naphthyl groups, and optionally substituted anthryl groups.

32. The trifluoropropenylether-substituted aromatic compound of claim 29, wherein Ar is an aromatic moiety substituted with one or more substituents selected from the group consisting of halogen, alkyl, cyano, sulfate and nitro.

33. The trifluoropropenylether-substituted aromatic compound of claim 29, wherein the trifluoropropenylether-substituted aromatic compound is selected from the group consisting of 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-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-trifluoroprop-2-enyl ether, 3-nitrophenyl-3,3,3-trifluoroprop-2-enyl ether, 2-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether, 4-methylphenyl-3,3,3-trifluoroprop-2-enyl ether, 4-chlorophenyl-3,3,3-trifluoroprop-2-enyl ether, 3-cyanophenyl-3,3,3-trifluoroprop-2-enyl ether, 1,4-bis(3,3,3-trifluoroprop-2-enyl)phenyl ether, 2,4-dichlorophenyl-3,3,3-trifluoroprop-2-enyl ether, 2-chloro-4-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether, and 4-(3,3,3-trifluoroprop-2-enyl)phenyl sulfate, sodium salt.

34. A haloalkyl ether (meth)acrylate corresponding to general structure (I):
X.sup.1X.sup.2HCCX.sup.3X.sup.4OROC(O)CR.sup.1CH.sub.2(I) wherein R is an organic moiety, X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently selected from hydrogen, halogen, alkyl or haloalkyl, subject to the proviso that at least one of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 is halogen or a haloalkyl group, and R.sup.1 is hydrogen or methyl or fluorine.

35. The haloalkyl ether (meth)acrylate of claim 34, wherein at least two of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 are selected from the group consisting of halogens and haloalkyl groups.

36. The haloalkyl ether (meth)acrylate of claim 34, wherein at least two of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 are selected from the group consisting of fluorine and fluoroalkyl groups.

37. The haloalkyl ether (meth)acrylate of claim 34, wherein at least one of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 is fluorine or a fluoroalkyl group.

38. The haloalkyl ether (meth)acrylate of claim 34, wherein each of X.sup.1, X.sup.2, X.sup.3 and X.sup.4 is halogen or a haloalkyl group.

39. The haloalkyl ether (meth)acrylate of claim 34, wherein one of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 is a C1-C8 haloalkyl group.

40. The haloalkyl ether (meth)acrylate of claim 34, wherein one of X.sup.1, X.sup.2, X.sup.3 or X.sup.4 is a C1-C8 fluoroalkyl group.

41. The haloalkyl ether (meth)acrylate of claim 34, wherein a) X.sup.1 is chlorine and X.sup.2, X.sup.3 and X.sup.4 are fluorine or b) X.sup.3 is chlorine and X.sup.1, X.sup.2 and X.sup.4 are fluorine.

42. The haloalkyl ether (meth)acrylate of claim 34, wherein R is an alkylene segment or a poly(oxyalkylene) segment.

43. The haloalkyl ether (meth)acrylate of claim 34, wherein R is an ethylene segment or a poly(oxyethylene) segment.

44. The haloalkyl ether (meth)acrylate of claim 34, wherein R is [CH.sub.2CH.sub.2O].sub.nCH.sub.2CH.sub.2 and n is 0 or an integer of from 1 to 10.

45. The haloalkyl ether (meth)acrylate of claim 34, wherein the moiety X.sup.1X.sup.2HCCX.sup.3X.sup.4ORO has a molecular weight not greater than 900 daltons.

46. The haloalkyl ether (meth)acrylate of claim 34, wherein R is a non-halogenated organic moiety.

47. The haloalkyl ether (meth)acrylate of claim 34, wherein R is an aliphatic organic moiety, optionally containing one or more oxygen atoms.

48. The haloalkyl ether (meth)acrylate of claim 34, wherein R is a saturated aliphatic organic moiety, optionally containing one or more ether oxygen atoms.

49-62. (canceled)

Description

EXAMPLES

Example 1: Preparation of 4-chlorophenyl-3,3,3-trifluoropropenyl ether

[0167] A 100 ml four-neck (14/20) flask was set up in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell that contained a thermocouple that was connected to a temperature controller and a dry-ice condenser with 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). ,,-Trifluorotoluene (0.5196 g/0.0036 mol) was added as an internal standard. The reaction mixture was stirred while trans-(E)-1233zd (6.16 g/0.047 mol) was added subsurface through a septum over a 40 minute period. Following the addition of the 1233zd, the reaction mixture was heated to 70-90 C. for nine hours. Following the specified time, the reaction mixture was analyzed by NMR spectroscopy and the yield (based on internal standard) was 82% of the trans (E) isomer, 4-chlorophenyl-(E)-3,3,3-trifluoropropenyl ether, together with 4% of the cis (Z) isomer, 4-chlorophenyl-(Z)-3,3,3-trifluoropropenyl ether.

[0168] The reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. The amount of product isolated was 6.63 g. NMR analysis revealed a product with an isomer distribution of 94% trans-(E)-isomer and 6% cis-(Z)-isomer. There were identified about 3% impurities and, thus, the isolated yield was about 6.43 g, representing a 69% isolated yield (based on starting phenol).

Characterization Data: 4-chlorophenyl-3,3,3-trifluoropropenyl ether

[0169] .sup.1H NMR (CDCl.sub.3): 5.38 ppm (doq, 1H, .sup.3J.sub.H-H=13 Hz, .sup.3J.sub.H-F=7 Hz); 7.21 ppm (doq, 1H, .sup.3J.sub.H-H=13 Hz, .sup.4J.sub.H-F=2 Hz); 6.90-7.40 ppm (m, 4H).

[0170] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.60 (dod, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz).

[0171] cis-isomer 58.13 (d, 3F, .sup.3J=9 Hz). nD.sub.20=1.4842.

[0172] Following the procedure described in Example 1, other derivatives were prepared from 1233zd in a similar fashion and the results are summarized in Table 1:

TABLE-US-00001 TABLE 1 Summary of Results from Examples 1-10 Example Phenol Product (g) Isolated Yield (%) 1 4-Cl 6.43 69 2 4-OH 5.04 61 3 4-F 6.99 81 4 4-CH.sub.3 8.28 83 5 3-CN 7.65 84 6 2-F 6.65 73 7 3-NO.sub.2 8.11 92 8 2,4-dichloro 7.46 83 9 2-chloro-4-fluoro- 7.22 77 10 4-SO.sub.3.sub. 4.65 49 Na.sup.+

Characterization Data, Examples 2-10

Example 2: 1,4-bis(3,3,3-trifluoropropenyloxy)benzene

[0173] .sup.1H NMR (CDCl.sub.3): 5.35 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.22 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 7.06 ppm (s, 4H).

[0174] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.73 (dod, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz).

[0175] cis-isomer 58.29 (d, 3F, .sup.3J=9 Hz). nD.sub.20=1.4516.

Example 3: 4-fluorophenyl-3,3,3-trifluoropropenyl ether

[0176] .sup.1H NMR (CDCl.sub.3): 5.32 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.21 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 7.04 ppm (m, 4H).

[0177] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.65 (dod, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=3 Hz).

[0178] cis-isomer 58.23 (d, 3F, .sup.3J=8 Hz). nD.sub.20=1.4434.

Example 4: 4-methylphenyl-3,3,3-trifluoropropenyl ether

[0179] .sup.1H NMR (CDCl.sub.3): 2.35 (s, 3H); 5.31 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.24 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 7.17 ppm (m, 4H).

[0180] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.51 (d, 3F, .sup.3J.sub.F-H=6 Hz).

[0181] cis-isomer 58.12 (d, 3F, .sup.3J=9 Hz). nD.sub.20=1.4624.

Example 5: 3-cyanophenyl-3,3,3-trifluoropropenyl ether

[0182] .sup.1H NMR (CDCl.sub.3): 5.51 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.27 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 7.30-7.57 ppm (m, 4H).

[0183] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.95 (d, 3F, .sup.3J.sub.F-H=5 Hz).

[0184] cis-isomer 58.35 (d, 3F, .sup.3J=8 Hz). nD.sub.20=1.4915.

Example 6: 2-fluorophenyl-3,3,3-trifluoropropenyl ether

[0185] .sup.1H NMR (CDCl.sub.3): 5.30 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.00-7.30 ppm (m, 4H).

[0186] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.66 (d, 3F, .sup.3J.sub.F-H=6 Hz).

[0187] cis-isomer 58.16 (d, 3F, .sup.3J=8 Hz); 131.80 (m, 1F). nD.sub.20=1.4421.

Example 7: 3-nitrophenyl-3,3,3-trifluoropropenyl ether

[0188] .sup.1H NMR (CDCl.sub.3): 5.53 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.28 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 7.35-8.10 ppm (m, 4H).

[0189] .sup.19F NMR (CDCl.sub.3): trans-isomer 61.28 (d, 3F, .sup.3J.sub.F-H=7 Hz).

[0190] cis-isomer 58.71 (d, 3F, .sup.3J=8 Hz). nD.sub.20=1.4977.

Example 8: 2,4-dichlorophenyl-3,3,3-trifluoropropenyl ether

[0191] .sup.1H NMR (CDCl.sub.3): 5.31 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.17 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 6.92-7.48 ppm (m, 3H).

[0192] .sup.19F NMR (CDCl.sub.3): trans-isomer 61.07 (dod, 3F, .sup.3J.sub.F-H=6 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 58.61 (d, 3F, .sup.3J=8 Hz). nD.sub.20=1.4979.

[0193] HRMS [M].sup.+=255.9669 m/z (observed); 255.9670 m/z (calc).

Example 9: 2-chloro-4-fluorophenyl-3,3,3-trifluoropropenyl ether

[0194] .sup.1H NMR (CDCl.sub.3): 5.23 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.16 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.4J.sub.H-F=2 Hz); 6.96-7.26 ppm (m, 3H).

[0195] .sup.19F NMR (CDCl.sub.3): trans-isomer 60.74 (d, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 58.33 (d, 3F, .sup.3J=8 Hz); Aromatic-F 114.92 (m, 1F). nD.sub.20=1.4633.

[0196] HRMS [M].sup.=239.9960 m/z (observed); 239.9960 m/z (calc).

Example 10: 4-(3,3,3-trifluoropropenyl)phenyl sulfate, sodium salt

[0197] .sup.1H NMR (CDCl.sub.3): trans 5.79 ppm (doq, 1H, .sup.3J.sub.H-H=12 Hz, .sup.3J.sub.H-F=7 Hz); 7.6 not fully resolved; 7.06-7.64 ppm (m, 4H). cis 5.32 ppm (doq, 1H, .sup.3J.sub.H-F=8 Hz, .sup.3J.sub.H-H=7 Hz); 7.21 ppm (d, 1H, .sup.3J.sub.H-H=7 Hz).

[0198] .sup.19F NMR (CDCl.sub.3): trans-isomer 57.69 (d, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 55.45 (d, 3F, .sup.3J=8 Hz).

Example 11: Preparation of 4-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0199] Following a similar procedure to that described in Example 1, with the exception that 1233xf was used in place of 1233zd, 5.23 g (46.7 mmol) of 4-fluorophenol together with 7.54 g (54.6 mmol) potassium carbonate in 45.05 g (520.5 mmol) DMSO was reacted with 9.90 g (75.9 mmol) 1233xf at 70-90 C. over 8 hours. After aqueous work-up 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 titled product was 8.37 g=87.0%.

Characterization Data: 4-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0200] .sup.1H NMR (CDCl.sub.3): 5.00 ppm (doq, 1H, .sup.3J.sub.H-H=8 Hz, .sup.3J.sub.H-F=8 Hz); 6.66 ppm (d, 1H, .sup.3J.sub.H-H=8 Hz). 7.02-7.25 ppm (m, 4H).

[0201] .sup.19F NMR (CDCl.sub.3): 58.07 (d, 3F, .sup.3J.sub.F-H=8 Hz). nD.sub.20=1.4983.

[0202] Following the procedure described in Example 11, other derivatives were prepared from 1233xf in a similar fashion. The results obtained are summarized in Table 2:

TABLE-US-00002 TABLE 2 Summary of Results from Examples 11-20. Example Phenol Product (g) Isolated Yield (%) 11 4-F 8.37 87 12 3-NO.sub.2 5.00 61 13 2-F 4.62 55 14 4-CH.sub.3 7.69 68 15 4-Cl 7.97 85 16 3-CN 7.60 81 17 4-OH 5.64 70 18 2,4-dichloro 5.37 63 19 2-chloro-4-fluoro- 4.57 49 20 4-SO.sub.3.sub.Na.sup.+ 7.44 79

Characterization Data, Examples 12-20

Example 12: 3-nitrophenyl-3,3,3-trifluoroprop-2-enyl ether

[0203] .sup.1H NMR (CDCl.sub.3): 5.21 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.82 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 7.42 ppm (m, 1H); 7.58 ppm (t, 1H, J.sub.H-H=8 Hz); 7.91 ppm (t, 1H, J.sub.H-H=2 Hz); 8.05 ppm (m, 1H).

[0204] .sup.19F NMR (CDCl.sub.3): 58.42 (d, 3F, .sup.4J.sub.F-H=8 Hz). nD.sub.20=1.5123.

[0205] HRMS [MH].sup.=232.0233 m/z (observed); 232.0227 m/z (calc).

Example 13: 2-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0206] .sup.1H NMR (CDCl.sub.3): 5.02 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.65 ppm (dod, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=2 Hz); 7.05 to 7.25 ppm (m, 4H).

[0207] .sup.19F NMR (CDCl.sub.3): 58.42 (d, 3F, .sup.4J.sub.F-H=8 Hz). Aromatic-F 133.40 (m, 1F). nD.sub.20=1.4505.

[0208] HRMS [MH].sup.=205.0280 m/z (observed); 205.0282 m/z (calc).

Example 14: 4-methylphenyl-3,3,3-trifluoroprop-2-enyl ether

[0209] .sup.1H NMR (CDCl.sub.3): 4.93 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.67 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 2.30 ppm (s, 3H); 6.88 to 7.13 ppm (m, 4H).

[0210] .sup.19F NMR (CDCl.sub.3): 58.11 (d, 3F, .sup.4J.sub.F-H=8 Hz). nD.sub.20=1.4721.

[0211] HRMS [M].sup.+=202.0602 m/z (observed); 206.0600 m/z (calc).

Example 15: 4-chlorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0212] .sup.1H NMR (CDCl.sub.3): 5.03 ppm (doq, 1H, .sup.2J.sub.H-H=8 Hz, .sup.4J.sub.H-F=8 Hz); 6.67 ppm (d, 1H, .sup.2J.sub.H-H=8 Hz); 6.95 to 7.35 ppm (m, 4H).

[0213] .sup.19F NMR (CDCl.sub.3): 58.30 (d, 3F, .sup.4J=8 Hz). nD.sub.20=1.4896.

[0214] HRMS [M].sup.+=222.0057 m/z (observed); 222.0054 m/z (calc).

Example 16: 3-cyanophenyl-3,3,3-trifluoroprop-2-enyl ether

[0215] .sup.1H NMR (CDCl.sub.3): 5.17 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.73 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 7.29 to 7.54 ppm (m, 4H).

[0216] .sup.19F NMR (CDCl.sub.3): 58.50 (d, 3F, .sup.4J=8 Hz). nD.sub.20=1.4963.

[0217] HRMS [MH].sup.=212.0334 m/z (observed); 212.0329 m/z (calc).

Example 17: 1,4-bis(3,3,3-trifluoroprop-2-enyl)phenyl ether

[0218] .sup.1H NMR (CDCl.sub.3): 5.03 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.68 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 7.07 ppm (s, 4H).

[0219] .sup.19F NMR (CDCl.sub.3): 58.28 (d, 3F, .sup.4J=8 Hz); nD.sub.20=1.4434.

[0220] HRMS [M].sup.+=298.0430 m/z (observed); 298.0423 m/z (calc).

Example 18: 2,4-dichlorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0221] .sup.1H NMR (CDCl.sub.3): 5.09 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.57 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 7.00-7.50 ppm (m, 3H). .sup.19F NMR (CDCl.sub.3): 58.41 (d, 3F, .sup.4J.sub.F-H=8 Hz). nD.sub.20=1.5124.

[0222] HRMS [M].sup.+=255.9669 m/z (observed); 255.9670 m/z (calc).

Example 19: 2-chloro-4-fluorophenyl-3,3,3-trifluoroprop-2-enyl ether

[0223] .sup.1H NMR (CDCl.sub.3): 5.05 ppm (doq, 1H, .sup.2J.sub.H-H=7 Hz, .sup.4J.sub.H-F=8 Hz); 6.54 ppm (d, 1H, .sup.2J.sub.H-H=7 Hz); 6.85-7.25 ppm (m, 3H).

[0224] .sup.19F NMR (CDCl.sub.3): 58.27 (d, 3F, .sup.4J.sub.F-H=8 Hz); Aromatic-F 115.6 (m, 1F). nD.sub.20=1.4705.

Example 20: 4-(3,3,3-trifluoroprop-2-enyl)phenyl sulfate, sodium salt

[0225] .sup.1H NMR (CDCl.sub.3): trans 5.38 ppm (doq, 1H, .sup.4J.sub.H-F=9 Hz, .sup.2J.sub.H-H=7 Hz); 7.27 (d, 1H, .sup.2J.sub.H-H=7); 7.08-7.65 ppm (m, 4H).

[0226] .sup.19F NMR (CDCl.sub.3): 55.45 (d, 3F, .sup.4J.sub.F-H=9 Hz).

Example 21: Preparation of 1-(3,3,3-trifluoroprop-1-enyl)imidazole

[0227] Following a similar procedure to that described in Example 1, with the exception that imidazole, 3.00 g (44.1 mmol) was used in place of 4-chlorophenol together with 6.49 g (47.0 mmol) potassium carbonate in 45.05 g (512.9 mmol) DMSO, and was reacted with 10.89 g (83.4 mmol) 1233zd at 140 C. over 17 hours. After aqueous work up similar to that described in Example 1 and sublimation, 1.19 g of a 99% pure oily solid was obtained. Analysis by NMR spectroscopy confirmed the identity of the product. The isolated yield of the titled product was 1.18 g=17.0%.

Characterization Data: 1-(3,3,3-trifluoroprop-1-enyl)imidazole

[0228] .sup.1H NMR (CDCl.sub.3): trans-isomer 5.89 ppm (doq, 1H, .sup.3J.sub.H-H=14 Hz, .sup.3J.sub.H-F=6 Hz); 7.43 ppm (doq, 1H, .sup.3J.sub.H-H=14 Hz, .sup.4J.sub.H-F=2 Hz).

[0229] cis-isomer 5.42 ppm (doq, 1H, .sup.3J.sub.H-H=11 Hz, .sup.3J.sub.H-F=9 Hz); 6.96 ppm (d, 1H, .sup.3J.sub.H-H=11 Hz). Imidazole ring. 7.16 ppm (d, 1H, J=1 Hz); 7.19 ppm (t, 1H, J=1 Hz); 7.71 ppm (s, 1H).

[0230] .sup.19F NMR (CDCl.sub.3): trans-isomer 62.58 (dod, 3F, .sup.3J.sub.F-H=6 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 57.95 (d, 3F, .sup.3J=8 Hz).

[0231] HRMS [M+H].sup.+=163.0472 m/z (observed); 163.0478 m/z (calc).

Example 22: Preparation of 1-(3,3,3-trifluoroprop-1-enyl)imidazole

[0232] Following a similar procedure to that described in Example 20, with the exception that the K.sup.+ imidazolium salt was pre-formed and the resulting salt then treated with 1233zd: 6.88 g (101.1 mmol) imidazole was treated with KOH, 6.89 g (122.8 mmol), used in place of potassium carbonate, and THF 102.35 g (1.4194 mol) was used in place of DMSO. 16.78 g (111.2 mmol) of 1233zd was reacted with this mixture at 60 C. over 53 hours. After aqueous work up 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 titled product was 3.47 g=21.0%.

Example 23: Attempted Preparation of 1-(3,3,3-trifluoroprop-2-enyl)imidazole

[0233] Following a similar procedure to that described in Example 1, with the exception that imidazole, 3.00 g (44.1 mmol) was used in place of 4-chlorophenol, together with 6.50 g (47.1 mmol) potassium carbonate in 46.06 g (589.5 mmol) DMSO that was reacted with 9.40 g (72.0 mmol) 1233xf at 140 C. over 24 hours. After aqueous work up similar to that described in Example 1 and distillation under 1 Torr vacuum at 120 to 140 C., 0.75 g of a 98% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the product to be the same two isomers as that observed in Example 20 (using 1233zd as the source of the trifluoropropyl moiety). The isolated yield of the titled product was 0.74 g=10.0%.

Characterization Data

1-(3,3,3-trifluoroprop-1-enyl)imidazole

[0234] .sup.1H NMR (CDCl.sub.3): trans-isomer 5.88 ppm (doq, 1H, .sup.2J.sub.H-H=14 Hz, .sup.4J.sub.H-F=6 Hz); 7.42 ppm (doq, 1H, .sup.2J.sub.H-H=14 Hz, .sup.4J.sub.H-F=2 Hz).

[0235] Imidazole ring. 7.16 ppm (d, 1H, J=1 Hz); 7.19 ppm (t, 1H, J=1 Hz); 7.71 ppm (s, 1H). product isomer 5.42 ppm (doq, 1H, .sup.2J.sub.H-H=10 Hz, .sup.4J.sub.H-F=9 Hz); 6.95 ppm (d, 1H, .sup.3J.sub.H-H.sup.=11 Hz). Imidazole ring. 7.13 ppm (d, 1H, J=1 Hz); 7.26 ppm (t, 1H, J=1 Hz); 7.69 ppm (s, 1H).

[0236] .sup.19F NMR (CDCl.sub.3): trans-isomer 62.51 (dod, 3F, .sup.4J.sub.F-H=6 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 57.88 (dod, 3F, .sup.4J.sub.F-H=9 Hz, .sup.4J.sub.F-H=1 Hz).

[0237] HRMS [M+H].sup.+=163.0473 m/z (observed); 163.0478 m/z (calc).

Example 24: Preparation of 1-(3,3,3-trifluoroprop-1-enyl)pyrazole

[0238] Following a similar procedure to that described in Example 1, with the exception that pyrazole, 3.02 g (44.4 mmol) was used in place of 4-chlorophenol, together with 6.56 g (47.5 mmol) potassium carbonate in 45.72 g (585.2 mmol) DMSO that was reacted with 6.33 g (48.5 mmol) 1233zd at 140 C. over 24 hours. After aqueous work up similar to that described in Example 1 and distillation under 1 Torr vacuum at 120 to 140 C., 0.79 g of a 98% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the target product as two isomers. The isolated yield of the titled product was 0.77 g=11.0%.

Characterization Data: 1-(3,3,3-trifluoroprop-1-enyl)pyrazole

[0239] .sup.1H NMR (CDCl.sub.3): trans-isomer 6.26 ppm (doq, 1H, .sup.3J.sub.H-H=14 Hz, .sup.3J.sub.H-F=6 Hz); 7.48 ppm (doq, 1H, .sup.3J.sub.H-H=14 Hz, .sup.4J.sub.H-F=2 Hz).

[0240] Pyrazole ring. 7.69 ppm (s, 1H); 7.59 ppm (d, 1H, J=3 Hz); 6.43 ppm (t, 1H, J=2 Hz).

[0241] Product isomer 5.29 ppm (doq, 1H, .sup.3J.sub.H-H=10 Hz, .sup.4J.sub.H-F=9 Hz); 7.22 ppm (d, 1H, .sup.3J.sub.H-H=10 Hz).

[0242] .sup.19F NMR (CDCl.sub.3): trans-isomer 62.25 (dod, 3F, .sup.3J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 57.56 (d, 3F, .sup.3J.sub.F-H=9 Hz).

[0243] HRMS [M+H].sup.+=163.0474 m/z (observed); 163.0478 m/z (calc).

Example 25: Attempted Preparation of 1-(3,3,3-trifluoroprop-2-enyl)pyrazole

[0244] Following a similar procedure to that described in Example 1, with the exception that pyrazole, 3.23 g (47.4 mmol) was used in place of 4-chlorophenol, together with 7.14 g (51.7 mmol) potassium carbonate in 46.20 g (591.3 mmol) DMSO that was reacted with 8.10 g (62.1 mmol) 1233xf at 140 C. over 19 hours. After aqueous work up similar to that described in Example 1 and distillation under 1 Torr vacuum at 120 to 140 C., 0.49 g of a 99% pure product was obtained. Analysis by NMR spectroscopy confirmed the identity of the product to be the same two isomers as that observed in Example 23 (using 1233zd as the source of the trifluoropropyl moiety). The isolated yield of the titled product was 0.49 g=6.0%.

Characterization Data: 1-(3,3,3-trifluoroprop-1-enyl)pyrazole

[0245] .sup.1H NMR (CDCl.sub.3): trans-isomer 6.25 ppm (doq, 1H, .sup.2J.sub.H-H=14 Hz, .sup.4J.sub.H-F=7 Hz); 7.48 ppm (doq, 1H, .sup.2J.sub.H-H=14 Hz, .sup.4J.sub.H-F=2 Hz).

[0246] Pyrazole ring. 7.69 ppm (s, 1H); 7.59 ppm (d, 1H, J=2 Hz); 6.43 ppm (t, 1H, J=2 Hz).

[0247] Product isomer 5.29 ppm (doq, 1H, .sup.3J.sub.H-H=11 Hz, .sup.4J.sub.H-F=9 Hz); 7.21 ppm (d, 1H, .sup.3J.sub.H-H=11 Hz).

[0248] .sup.19F NMR (CDCl.sub.3): trans-isomer 62.21 (dod, 3F, .sup.4J.sub.F-H=7 Hz, .sup.4J.sub.F-H=2 Hz). cis-isomer 57.53 (dod, 3F, .sup.4J.sub.F-H=9 Hz, .sup.4J.sub.F-H=1 Hz).

[0249] HRMS [M+H].sup.+=163.0472 m/z (observed); 163.0478 m/z (calc).

Example 26: Reaction of 1233zd with Hydroxy-functionalized Tertiary Amine

[0250] Jeffcat Z110 [HOCH.sub.2CH.sub.2N(CH.sub.3)CH.sub.2CH.sub.2N(CH.sub.3).sub.2] and 1233zd were combined and aged for two weeks at 50 C. in the presence of potassium hydroxide (KOH). Analysis by .sup.1H NMR confirmed partial reaction of the starting materials, in accordance with the following scheme:

HOCH.sub.2CH.sub.2N(CH.sub.3)CH.sub.2CH.sub.2N(CH.sub.3).sub.2+CF.sub.3CHCHCl.fwdarw.CF.sub.3CHCHOCH.sub.2CH.sub.2N(CH.sub.3)CH.sub.2CH.sub.2N(CH.sub.3).sub.2

Example 27: Synthesis of 2,2-Dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane, Using Excess Solketal for Solvent

[0251] A 100 ml four-neck (14/20) flask was set up in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell that contained a thermocouple that was connected to a temperature controller and a dry-ice condenser with 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). ,,-trifluorotoluene (0.4985 g/0.0034 mol) was added as an internal standard. The reaction mixture was stirred while 1-chloro-2,2-difluoroethylene (HCFC1122) (5.44 g/0.0552 mol) was added subsurface through a septum over a 10 minute period. The temperature ranged from 17 C. to 33 C. at the end of addition. Following the addition of HCFC1122, the reaction mixture was stirred at ambient temperature for two hours.

[0252] The reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layer was separated and the solvent stripped at 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 group could be removed from this product to yield a dihydroxy-functionalized compound bearing a OCClHCF.sub.2H group.

[0253] .sup.19F NMR (CDCl.sub.3): 79.64 (F.sub.A), 79.89 (F.sub.B) ppm, q of t, .sup.2J.sub.Fa-Fb=140 Hz, .sup.3J.sub.H-F=9 Hz

[0254] The chemical shifts of F.sub.A and F.sub.B were calculated from the AB type quartet.

Example 28: Synthesis of 2,2-Dimethyl-4-(2-chloro-1,1-difluoroethoxymethyl)-1,3-dioxolane, Using DMSO for Solvent

[0255] A 100 ml four-neck (14/20) flask was set up in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell that contained a thermocouple that was connected to a temperature controller and a dry-ice condenser with 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). The reaction mixture was stirred while 1-chloro-2,2-difluoroethylene (HCFC1122) (5.44 g/0.0552 mol) was added subsurface through a septum over a 10 minute period. The temperature increased from 22 C. to 45 C. at the end of addition. Following the addition of HCFC1122, the reaction mixture was stirred at ambient temperature for sixteen hours.

[0256] The reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. 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 wt % and the yield was 45% based on FNMR internal standard analysis.

[0257] .sup.19F NMR (CDCl.sub.3): 79.64 (F.sub.A), 79.89 (F.sub.B) ppm, q of t, .sup.2J.sub.Fa-Fb=140 Hz, .sup.3J.sub.H-F=9 Hz

[0258] The chemical shifts of F.sub.A and F.sub.B were calculated from the AB type quartet.

Example 29 Synthesis of 2,2-Dimethyl-4-[(1-fluoroethenyloxy)methyl]-1,3-dioxolane Using DMSO for Solvent

[0259] A 100 ml four-neck (14/20) flask was set up in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell that contained a thermocouple that was connected to a temperature controller and a dry-ice condenser with 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), and potassium hydroxide (2.67 g/0.0476 mol). The reaction mixture was stirred while 1-Chloro-1-fluoroethylene (HCFC1131a) (5.44 g/0.0552 mol) was added subsurface through a septum over a 5 minutes period. The temperature increased from 23 C. to 41 C. at the end of addition. Following the addition of HCFC1131a, the reaction mixture was stirred at ambient temperature for 48 hours.

[0260] The reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. 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 wt % and the yield was 52% based on FNMR internal standard analysis.

[0261] .sup.19F NMR (CDCl.sub.3): 80.62 ppm (d of d, .sup.3J.sub.F-H=41.3 Hz (trans), 6.5 Hz cis)

[0262] .sup.1HNMR (CDCl.sub.3): 3.24-3.40 (d of d, 1H-trans, .sup.3J.sub.H-F=41.3, .sup.2J.sub.H-H=4.4); 3.60-3.65, (d of d,

[0263] 1H-cis, .sup.3J.sub.H-F=6.5, .sup.2J.sub.H-H=4.4); 3.74-3.64 (m, 3H), 4.06-4.12 (m, 1H), 4.32-4.40 (m, 1H)

Example 30 Synthesis of 2,2-Dimethyl-4-[(1-fluoroethenyloxy]methyl)]-1,3-dioxolane Using DMSO for Solvent

[0264] A 100 ml four-neck (14/20) flask was set up in a heating mantle and placed on a magnetic stirrer. The flask was equipped with a thermowell that contained a thermocouple that was connected to a temperature controller and a dry-ice condenser with outlet connected to a nitrogen source. The reaction flask was charged with Solketal (5.69 g/0.0431 mol), DMSO (31.48 g/0.4029 mol), and potassium hydroxide (3.20 g/0.0520 mol). The reaction mixture was stirred while 1-Chloro-1-fluoroethylene (HCFC1131a) (4.81 g/0.0598 mol) was added subsurface through a septum over a 8 minutes period. The temperature increased from 23 C. to 55 C. at the end of addition. Following the addition of HCFC1131a, the reaction mixture was stirred at ambient temperature for 16 hours.

[0265] Hexane (50 ml) was added and the reaction mixture was heated with stirring to 50 C. for one hour. The reaction mixture was cooled to ambient temperature (22 C.) and the 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 for 15 minutes at ambient temperature. The stirring was stopped and the layers were allowed to settle for 15 minutes. The top hexane layer was removed by siphoning with a syringe. The two hexane extractions were combined and the solvent was stripped at 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 wt % and the yield was 41% based on FNMR internal standard analysis. The remaining reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 100 ml of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. 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 wt % and the yield was 26% based on FNMR internal standard analysis.

[0266] .sup.19F NMR (CDCl.sub.3): 80.62 ppm (d of d, .sup.3J.sub.F-H=41.3 Hz (trans), 6.5 Hz cis)

[0267] .sup.1HNMR (CDCl.sub.3): 3.24-3.40 (d of d, 1H-trans, .sup.3J.sub.H-F=41.3, .sup.2J.sub.H-H=4.4); 3.60-3.65, (d of d, 1H-cis, .sup.3J.sub.H-F=6.5, .sup.2J.sub.H-H=4.4); 3.74-3.64 (m, 3H), 4.06-4.12 (m, 1H), 4.32-4.40 (m, 1H)

Example 31 Reaction of 1,1,2-Trifluoro-2-chloroethylene (CTFE) with 2-Hydroxyethylmethacrylate (HEMA) in 30% Acetone and 70% DMSO Solvent

[0268] A 1 L four-neck (14/20) flask with overhead stirring and equipped with a digital thermometer and a dry-ice condenser with outlet connected to a nitrogen source. A pre-puncture septum was placed on the remaining neck. The reaction flask was charged with 2-Hydroxyethylmethacrylate (80.22 g/0.6160 mol), DMSO (374.66 g/4.7953 mol), acetone (161.55 g/2.7774 moles), potassium carbonate (94.03 g/0.6803 mol) and benzoquinone (0.76/7.0310.sup.3 mol). The reaction mixture was stirred while CTFE (78.92 g/0.6776 mol) was added subsurface in aliquots through a septum over two days with the temperature ranging from 16-21 C. An internal standard (,,-trifluorotoluene) was added to reaction mixture to follow reaction by FNMR.

[0269] 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. The stirring was stopped and two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 1 L of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. The amount of crude 2-Chloro-1,1,2-trifluoroethoxy methacrylate product isolated was 120.90 g. The product had a purity of 73 wt % and a yield of 58% by FNMR based on 2-Hydroxymethacrylate starting material.

[0270] The crude material was purified by column chromatography using a 224 column packed with silica gel. The ratio of silica to crude material was 15:1. The product was eluted with 10% ethyl acetate/n-hexane. The crude was purified in multiple batches. The combined purified product was 66.99 grams and was 97% pure by GC A %. The product was also confirm by GC/MS and LC/MS. The yield of purified product was 43% based on 2-Hydroxymethacrylate starting material.

[0271] .sup.19F NMR (CDCl.sub.3): 88.26 ppm (F.sub.A), 88.74 ppm (F.sub.B)*, (q of d of d, .sup.2J.sub.Fa-Fb=141 Hz, .sup.3J.sub.Fa-H=3.5 Hz, .sup.3J.sub.Fb-H=4.7 Hz), 154.31 (Fe) (d of t, .sup.3J.sub.F-F=12 Hz, .sup.2J.sub.F-H=48 * The chemical shifts of F.sub.A and F.sub.B were calculated from the AB type quartet.

[0272] .sup.1HNMR (CDCl.sub.3): 1.95 ppm (d of d, 3H); 4.20 ppm (d of d of d, 2H); 4.40 (d of d of d, 2H); 5.60 (d of m 1H) 6.08 ppm (d of d of d, 1H, .sup.2J.sub.H-F=48, .sup.3J.sub.H-Fa=3.5 Hz, .sup.3J.sub.H-Fb=4.7 Hz); 6.10 ppm (d of m, 1H)

Example 32 Reaction of 1,1,2-Trifluoro-2-chloroethylene (CTFE) with 2-Hydroxyethylmethacrylate (HEMA) in DMSO Solvent

[0273] A 250 ml four-neck (14/20) flask was placed on a magnetic stirrer and equipped with a digital thermometer and a dry-ice condenser with outlet connected to a nitrogen source. A pre-puncture septum was placed on the remaining neck. The reaction flask was charged with 2-Hydroxyethylmethacrylate (20.12 g/0.1546 mol), DMSO (116.85 g/1.4956 mol), potassium carbonate (21.84 g/0.1580 mol) and benzoquinone (0.06/5.5510.sup.4 mol). The reaction mixture was stirred while CTFE (18.81 g/0.1615 mol) was added subsurface in aliquots through a septum over three hours with the temperature ranging from 1725 C. An internal standard (,,-trifluorotoluene) was added to reaction mixture to follow reaction by FNMR.

[0274] The reaction mixture was combined 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 where two immiscible layers formed after sitting for 15 minutes. The resulting layers were separated and the bottom organic layer was washed twice with 200 ml of water. The organic layer was separated and the solvent stripped at reduced pressure to isolate the product. The amount of crude 2-Chloro-1,1,2-trifluoroethoxy methacrylate product isolated was 33.34 g. The product had a purity of 74 wt % and a yield of 64% by FNMR based on 2-Hydroxymethacrylate starting material.

[0275] The crude material was purified by short path distillation under a vacuum of approximately 1 torr. The amount of distilled product collected was 27.02 g. The distilled product had a purity of 80 wt % and a yield of 57% by FNMR based on 2-Hydroxymethacrylate starting material.

[0276] .sup.19F NMR (CDCl.sub.3): 88.26 ppm (F.sub.A), 88.74 ppm (F.sub.B)*, (q of d of d, .sup.2J.sub.Fa-Fb=141 Hz, .sup.3J.sub.Fa-H=3.5 Hz, .sup.3J.sub.Fb-H=4.7 Hz), 154.31 (F.sub.c) (d of t, .sup.3J.sub.F-F=12 Hz, .sup.2J.sub.F-H=48 * The chemical shifts of F.sub.A and F.sub.B were calculated from the AB type quartet.

[0277] .sup.1HNMR (CDCl.sub.3): 1.95 ppm (d of d, 3H); 4.20 ppm (d of d of d, 2H); 4.40 (d of d of d, 2H); 5.60 (d of m 1H) 6.08 ppm (d of d of d, 1H, .sup.2J.sub.H-F=48, .sup.3J.sub.H-Fa=3.5 Hz, .sup.3J.sub.H-Fb=4.7 Hz); 6.10 ppm (d of m, 1H)