Claims
- 1. A process for the preparation of a composition for the reduction of organic substrates, comprising adding at least one active hydride to a slurry comprising at least one Lewis base and at least one additive under conditions sufficient to form a reduction composition having reducing properties.
- 2. The process of claim 1, further comprising adding said at least one Lewis base to said at least one additive to form a slurry thereof prior to the step of adding at least one active hydride to said slurry.
- 3. The process of claim 1, wherein the step of adding at least one active hydride to said Lewis base/additive slurry comprises adding a slurry of said at least one active hydride in a hydrocarbon solvent to said Lewis base/additive slurry.
- 4. The process of claim 1, wherein said reduction composition comprises a slurry.
- 5. The process of claim 1, further comprising heating the slurry after the step of adding at least one active hydride to said slurry.
- 6. The process of claim 1, wherein said at least one additive is selected from the group consisting of lithium chloride, lithium bromide, aluminum trichloride, titanium tetrachloride, titanium tetrabromide, lithium alkoxides, lithium alkoxides of chiral alcohols, lithium dialkylamides, lithium dialkyl amides of chiral amines, and mixtures thereof.
- 7. The process of claim 6, wherein said at least one additive comprises lithium chloride.
- 8. The process of claim 1, wherein said at least one active hydride is selected from the group consisting of sodium aluminum hydride, trisodium aluminum hexahydride, and mixtures thereof.
- 9. The process of claim 8, wherein said at least one active hydride comprises sodium aluminum hydride.
- 10. The process of claim 1, wherein said at least one Lewis base is selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, dibutyl ether, methyl t-butyl ether (MTBE), 1,2-diethoxyethane, 1,2-dimethoxyethane, triethylamine, tributylamine, N, N, N′, N′-tetramethylethylenediamine (TMEDA), diisopropylethylamine, and mixtures thereof.
- 11. The process of claim 10, wherein said at least one Lewis base comprises tetrahydrofuran.
- 12. The process of claim 2, wherein:
the step of adding at least one Lewis base to at least one additive comprises adding 45 to 80 mole % Lewis base to 5 to 20 mole % additive; and the step of adding at least one active hydride comprises adding 5 to 20 mole % active hydride.
- 13. A process for the preparation of a composition for the reduction of organic substrates, comprising:
adding 45 to 80 mole % tetrahydrofuran to 5 to 20 mole % lithium chloride to form a slurry thereof; and adding 5 to 20 mole % of a slurry of sodium aluminum hydride in a hydrocarbon solvent to said tetrahydrofuran/lithium chloride slurry.
- 14. A composition for the reduction of organic substrates, comprising a composition prepared by the process of:
adding at least one Lewis base to at least one additive to form a slurry thereof; and adding at least one active hydride to said slurry under conditions sufficient to produce a reduction composition having reducing properties.
- 15. The composition of claim 14, wherein the step of adding at least one active hydride to said Lewis base/additive slurry comprises adding a slurry of said at least one active hydride in a hydrocarbon solvent to said Lewis base/additive slurry.
- 16. The composition of claim 14, wherein said at least one Lewis base comprises tetrahydrofuran, said at least one additive comprises lithium chloride and said at least one active hydride comprises sodium aluminum hydride, and wherein said reduction composition comprises a slurry.
- 17. A composition for the reduction of organic substrates, comprising a composition prepared by the process of:
adding 45 to 80 mole % tetrahydrofuran to 5 to 20 mole % lithium chloride to form a slurry thereof; and adding 5 to 20 mole % of a slurry of sodium aluminum hydride in a hydrocarbon solvent to said tetrahydrofuran/lithium chloride slurry.
- 18. A composition for the reduction of organic substrates, comprising a composition prepared from at least one Lewis base, at least one additive, and at least one active hydride, said composition exhibiting substantially stable rate acceleration/runaway behavior until heated above 300° C.
- 19. The composition of claim 18, further comprising about 10 to about 11.5% Na, about 10 to about 11.5% Al, about 9 to about 10% Li and about 9 to about 10% Cl.
- 20. A process for reducing at least one functional group of an organic substrate, comprising contacting said organic substrate with a reduction composition prepared by adding at least one Lewis base to at least one additive to form a slurry thereof; and adding at least one active hydride to said slurry.
- 21. A process for the reduction of organic substrates having at least one functional group with in situ generated, unfiltered hydride reducing agents capable of reducing said at least one functional group, which process comprises contacting an organic substrate to be reduced with sodium aluminum hydride in an organic solvent in the presence of an additive comprising 0.01 to 5 equivalents of a lithium compound selected from the group consisting of lithium halides, lithium alkoxides and lithium organoamides.
- 22. The process of claim 21, wherein the organic substrate is (+/−) trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione.
- 23. The process of claim 21, wherein the organic substrate is (+/−) trans 3-methoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione.
- 24. The process of claim 21, wherein the organic substrate is (−) trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione.
- 25. The process of claim 21, wherein the organic substrate is (−) trans 3-methoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione.
- 26. The process of claim 21, wherein said organic solvent is toluene, said additive comprises more than 0.01 equivalents of lithium halide in tetrahydrofuran, and further wherein said additive is added before, during or after the contact between the sodium aluminum hydride and the organic substrate.
- 27. A process for the reduction of organic substrates having at least one functional group with in situ generated hydride reducing agents capable of reducing said at least one functional group, comprising contacting an organic substrate to be reduced with sodium aluminum hydride in an organic solvent, the sodium aluminum hydride being reacted with more than 0.01 equivalents of lithium halide before, during or after the contact between the sodium aluminum hydride and the organic substrate.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application of commonly owned copending U.S. application Ser. No. 08/817,003, filed Mar. 31, 1997, the entire disclosure of which is hereby incorporated by reference, and is related to commonly owned provisional application Serial No. 60/001,857, filed Aug. 3, 1995 and claims the benefit of the earlier filing date of this application under 35 USC §119(e), and is also a continuation-in-part application of commonly owned U.S. application Ser. No. 09/051,813, filed Apr. 15, 1998, the entire disclosure of which is incorporated by reference, which is related to commonly owned copending provisional application Serail No. 60/026,552, filed Sep. 24, 1996, and claims the benefit of the earlier filing date of this application under 35 U.S.C. §119(e).
Provisional Applications (2)
|
Number |
Date |
Country |
|
60001857 |
Aug 1995 |
US |
|
60026552 |
Sep 1996 |
US |
Continuation in Parts (2)
|
Number |
Date |
Country |
Parent |
08817003 |
Mar 1997 |
US |
Child |
09262093 |
Mar 1999 |
US |
Parent |
09051813 |
Apr 1998 |
US |
Child |
09262093 |
Mar 1999 |
US |