Claims
- 1. A process for obtaining a stereospecific nerolidol at the .DELTA..sup.6 position thereof and having the formula: ##STR20## which comprises rectifying a mixture of .DELTA..sup.6 -cis-nerolidol and .DELTA..sup.6 -trans-nerolidol in a rectification column having from 10 to 100 theoretical plates with a reflux ratio of from 2 to 200 at a temperature below 230.degree. C. under reduced pressure of from 0.1 to 5 mm Hg at the top of said column to separate each stereospecific nerolidol from said mixture.
- 2. The process according to claim 1, wherein one of the components or a mixture containing the same obtained by the rectification is heated in the presence of an isomerization catalyst, and the resulting isomerization reaction mixture is re-rectified to recover the other component of the stereospecific nerolidols.
- 3. The process for obtaining .DELTA..sup.6 -cis-nerolidol according to claim 1, wherein said rectification of a mixture comprising .DELTA..sup.6 -cis- and .DELTA..sup.6 -trans-nerolidols is conducted in the presence of an isomerization catalyst to isomerize the trans-isomer to the cis-isomer.
- 4. The process according to claim 1, wherein said rectification is conducted with a rectification column having from 2 to 60 theoretical plates with a reflux ratio of from 5 to 30.
- 5. The process according to claim 2, wherein said isomerization catalyst is a compound of a transition metal of Group VI, VII or VIII of the Periodic Table, or an organic sulfur compound.
- 6. The process according to claim 5, wherein said isomerization catalyst is a ruthenium compound.
- 7. The process according to claim 5, wherein said isomerization catalyst is a tungsten compound.
- 8. The process according to claim 5, wherein said isomerization catalyst is an organic sulfur compound.
- 9. A process for preparing a stereospecific nerolidol at the .DELTA..sup.6 -position thereof and having the formula: ##STR21## which comprises (1) rectifying a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone having the formula: ##STR22## to obtain each isomer thereof, and (2) subjecting said cis- or trans-isomer to vinylation.
- 10. The process according to claim 9, which comprises
- heating the residual component obtained by the rectification of a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone, in the presence of an isomerization catalyst to enrich each one of the isomers,
- re-rectifying the resulting reaction product to recover each stereo-isomeric geranylacetone, and
- subjecting each stereo-generic geranylacetone to vinylation.
- 11. The process according to claim 10, wherein said isomerization catalyst is a compound of a transition metal of Group VI, VII or VIII of the Periodic Table, or an organic sulfur compound.
- 12. The process according to claim 9, wherein said rectification is conducted in a rectification column having from 10 to 100 theoretical plates with a reflux ratio of from 2 to 200 at a temperature below 230.degree. C. under reduced pressure.
- 13. The process according to claim 11, wherein said rectification is conducted with a rectification column having from 20 to 60 theoretical plates with a reflux ratio of from 5 to 30.
- 14. The process for preparing .DELTA..sup.6 -cis-nerolidol according to claim 9, which comprises rectifying a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone in the presence of an isomerization catalyst to isomerize the trans-isomer to the cis-isomer.
- 15. A process for preparing a stereospecific nerolidol at the .DELTA..sup.6 -position thereof and having the formula: ##STR23## which comprises (1) rectifying a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone having the formula: ##STR24## to obtain each isomer thereof, and (2) ethynylating said cis- or trans-isomer and partially hydrogenating the resulting reaction product, .DELTA..sup.6 -cis-nerolidol being so formed from .DELTA..sup.5 -cis-geranylacetone and .DELTA..sup.6 -trans-nerolidol being so formed from .DELTA..sup.5 -trans-geranylacetone.
- 16. The process according to claim 15, which comprises
- heating the residual component obtained by rectification of a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone, in the presence of an isomerization catalyst to enrich each one of the isomers,
- re-rectifying the resulting reaction product to recover each stereo-isomeric geranylacetone, and
- subjecting each stereo-isomeric geranylacetone to (2).
- 17. The process according to claim 16, wherein said isomerization catalyst is a compound of a transition metal of Group VI, VII or VIII of the Periodic Table, or an organic sulfur compound.
- 18. The process according to claim 15, wherein said rectification is conducted in a rectification column having from 10 to 100 theoretical plates with a reflux ratio of from 2 to 200 at a temperature below 230.degree. C. under reduced pressure.
- 19. The process according to claim 18, wherein said rectification is conducted with a rectification column having from 20 to 60 theoretical plates with a reflux ratio of from 5 to 30.
- 20. The process for preparing .DELTA..sup.6 -cis-nerolidol according to claim 15, which comprises rectifying a mixture of .DELTA..sup.5 -cis- and .DELTA..sup.5 -trans-geranylacetone in the presence of an isomerization catalyst to isomerize the trans-isomer to the cis-isomer.
Priority Claims (8)
Number |
Date |
Country |
Kind |
49-100631 |
Sep 1974 |
JPX |
|
49-100632 |
Sep 1974 |
JPX |
|
49-100633 |
Sep 1974 |
JPX |
|
49-100634 |
Sep 1974 |
JPX |
|
49-100635 |
Sep 1974 |
JPX |
|
49-104062 |
Sep 1974 |
JPX |
|
49-119797 |
Oct 1974 |
JPX |
|
49-119798 |
Oct 1974 |
JPX |
|
RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 605,455, filed Aug. 18, 1975, now U.S. Pat. No. 4,028,385.
US Referenced Citations (5)
Non-Patent Literature Citations (2)
Entry |
Bates, J. Org. Chem., vol. 28, pp. 1086-1089 (1963). |
Eliel, Stereochemistry of Carbonyl Compounds, pp. 326-346 (1962). |
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
605455 |
Aug 1975 |
|