1. A process for synthesizing camptothecin derivatives having the formula I:
where A is \u2014(CH2)m\u2014;
m is 1 to 6; and R1, R2, and R3 are individually lower alkyl or aryl substitutent groups; the process comprising:
a) providing a quantity of substantially pure camptothecin, and dissolving said camptothecin in a solution of a strong acid;
b) providing a quantity of a compound having the formula II: R3R2R1Si-Am-X (II),
wherein X is 1,3-dioxolane and dissolving (II) in an organic-based solution; and
c) mixing the solutions from steps a) and b) for a sufficient period of time to allow them to react to form the formula I compound.
2. The process of claim 1, wherein the strong acid is sulfuric acid, and the organic-based solution is a lower alcohol or benzyl alcohol.
3. The process of claim 1, wherein step a) includes adding a quantity of a metal hydrate catalyst and a strong oxidizing agent to the strong acid solution.
4. The process of claim 1 wherein R1, R2 and R3 are methyl.
5. (canceled)
6. The process of claim 3, wherein the metal hydrate is ferrous sulfate and the strong oxidizing agent is hydrogen peroxide.
7. The process of claim 1, wherein m is 1 to 4, and each of R1, R2 and R3 is individually a methyl, tert-butyl or phenyl substituent group.
8. The process of claim 1, wherein m is 1 and each of R1, R2 and R3 is a methyl substituent group.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A stable and liquid olein fraction made by fractionation of high oleic, high saturated sunflower oil, wherein;
a. less than 8.6% of the TAG species of said olein fraction have the general formula SMS;
b. at least 26% of TAG species of said olein fraction have the general formula SMM; and
c. the olein fraction has a cloud point lower than \u22124\xb0 C.;
wherein S represents a saturated fatty acid and M represents a monoenoic fatty acid, and wherein said olein fraction is obtainable by:
fractionation of a high oleic high saturated sunflower oil; and
collecting the liquid fraction.
2. A stable and liquid olein fraction as claimed in claim 1, wherein the fractionation is a low temperature dry fractionation, comprising the following steps:
decreasing the temperature of the oil to or below 12\xb0 C.; and
separating the olein from the solid fraction.
3. A stable and liquid olein fraction as claimed in claim 2, wherein the low temperature fractionation further contains the step of fractionating the resulting olein again at or below 2.5\xb0 C.
4. A stable and liquid olein fraction as claimed in claim 1, wherein the fractionation is a low temperature dry fractionation, consisting of the following steps:
decreasing the temperature of the oil to or below 12\xb0 C.; and
separating the olein from the solid fraction.
5. A stable and liquid olein fraction as claimed in claim 4 wherein the low temperature fractionation further contains the step of fractionating the resulting olein again at or below 2.5\xb0 C. to obtain a less saturated olein fraction.
6. A stable and liquid olein fraction as claimed in claim 1, wherein the fractionation is a low temperature solvent fractionation, comprising the following steps:
mixing the oil with an organic solvent;
decreasing the temperature of the oil solution to or below 0\xb0 C.; and
separating the olein from the solid fraction.
7. A stable and liquid olein fraction as claimed in claim 6, wherein the fractionation further comprises the step of recovering the olein by removing the solvent from the supernatant.
8. A stable and liquid olein fraction as claimed in claim 6, wherein the organic solvent comprises a solvent selected from the group consisting of acetone, hexane and ethyl ether.
9. A stable and liquid olein fraction as claimed in claim 1, wherein the fractionation is a low temperature solvent fractionation, consisting of the following steps:
mixing the oil with an organic solvent;
decreasing the temperature of the oil solution to or below 0\xb0 C.; and
separating the olein from the solid fraction.
10. A stable and liquid olein fraction as claimed in claim 9, wherein the fractionation further contains the step of recovering the olein by removing the solvent from the supernatant.
11. A stable and liquid olein fraction as claimed in claim 10, wherein the solvent is removed from the supernatant by distillation at vacuum.
12. A stable and liquid olein fraction as claimed in claim 9, wherein the organic solvent comprises a solvent selected from the group consisting of acetone, hexane and ethyl ether.
13. A stable and liquid olein fraction as claimed in claim 1, wherein the high oleic high saturated sunflower oil is a high oleic high stearic sunflower oil obtainable by extracting high oleic high stearic sunflower seeds which are obtainable by crossing CAS-3 (ATCC 75968) and a high thioesterase mutant with the deposit number ATCC PTA-628.
14. A stable and liquid olein fraction as claimed in claim 1, wherein the high oleic high saturated sunflower oil is a high palmitic sunflower oil obtainable by extracting seeds of the sunflower strain IG-1297M, which seeds were deposited on 20 Jan. 1998 under the ATCC accession number ATCC-209591.
15. A stable and liquid olein fraction as claimed in claim 1, wherein the high oleic high saturated sunflower oil is an high oleic high palmitic sunflower oil with low palmitoleic and low asclepic obtainable by extracting seeds of the sunflower strain CAS-25, which seeds are obtainable by crossing IG-1297M (ATCC 209591) and CAS-3 (ATCC 75968).
16. A stable and liquid olein fraction as claimed in claim 1, wherein the total linolenic acid content in said olein fraction is lower than 0.5%.
17. A stable and liquid olein fraction as claimed in claim 1, characterized in that the linoleic acid content in said olein fraction is lower than 15%.
18. A stable and liquid olein fraction as claimed in claim 1, wherein less than 6% of the TAG species of said olein fraction have the general formula SMS.
19. A stable and liquid olein fraction as claimed claim 1, wherein at least 30% of the TAG species of said olein have the general formula SMM.
20. A stable and liquid olein fraction as claimed in claim 19, wherein at least 35% of the TAG species of said olein have the general formula SMM.
21. A stable and liquid olein fraction as claimed in claim 19, wherein at least 45% of the TAG species of said olein have the general formula SMM.
22. A stable and liquid olein fraction as claimed in claim 1, wherein the fraction has less than 8% of saturated fatty acids at position sn-2 of the TAGs that constitute said olein fraction.
23. A stable and liquid olein fraction as claimed in claim 22, wherein the fraction has less than 5% of saturated fatty acids at position sn-2 of the TAGs that constitute said olein fraction.
24. A stable and liquid olein fraction as claimed in claim 22, wherein the fraction has less than 3% of saturated fatty acids at position sn-2 of the TAGs that constitute said olein fraction.
25. A sauce selected from mayonnaise, light mayonnaise, reduced fat mayonnaise, mustard, ketchup and tartar sauce, salad dressings, salad bar bottle, sandwich spreads, pre-cooked food, prepared soup or cream, and ice-cream or ice-cream cake, comprising a stable and liquid olein fraction as claimed in claim 1.
26. A method of frying, baking, cooking or roasting, comprising heating a stable and liquid olein fraction of claim 1 at high temperature conditions of at least 100\xb0 C.
27. A method as claimed in claim 26, wherein the high temperature conditions comprise temperatures of at least 160\xb0 C.
28. A method as claimed in claim 27, wherein the high temperature conditions comprise temperatures of at least 180\xb0 C.
29. An oil mixture comprising a stable and liquid olein fraction as claimed in claim 1.
30. A stable and liquid olein fraction as claimed in claim 1, wherein the fraction has a cloud point lower than 6\xb0 C.
31. A method for preparation of a stable and liquid olein fraction comprising fractionating a high oleic, high saturated sunflower oil, wherein the fractionating includes the steps of:
decreasing the temperature of the oil to or below 12\xb0 C.
separating the olein from the solid fraction, and
fractionating the resulting olein again at or below 2.5\xb0 to obtain a less saturated olein fraction;
and wherein the olein fraction has a cloud point lower than 5\xb0 C.
32. A method as claimed in claim 31, wherein the fractionation is a low temperature solvent fractionation, which includes the following steps:
mixing the oil with an organic solvent;
decreasing the temperature of the oil solution to or below 0\xb0 C.; and
separating the olein from the solid fraction.
33. A method for preparation of a stable and liquid olein fraction as claimed in claim 32, further comprising recovering the olein by removing the solvent from the supernatant by distillation at vacuum.
34. A method for preparation of a stable and liquid olein fraction as claimed in claim 32, wherein the organic solvent comprises a compound selected from the group consisting of acetone, hexane and ethyl ether.