Claims
- 1. Method of selectively reacting a free radical X with an olefin, said free radical X being selected from the group consisting of ##STR111## Where R is an alkyl group and R' is a hydrocarbyl or substituted hydrocarbyl group, and said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol, comprising reacting said olefin, a compound selected from the group consisting of ketones, aldehydes, esters, nitriles, sulfoxides, nitroparaffins, thiosulfonic acid esters, alkanesulfonic acids, allkanesulfinic acids, and thiols, and a stoichiometric quantity of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure ##STR112##
- 2. Method of claim 1 wherein said olefin has one double bond.
- 3. Method of claim 2 wherein said olefin has the formula ##STR113## where R" is a group selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, acyl, acyloxy, alkoxy, alkyl sulfide, aldehyde, alkyl aldehyde, amide, alkyl amide, aryloxy, aroyl, aroyloxy, carboxyl, alkyl carboxyl, alkenyl carboxyl, cyanide, alkyl cyanide, alkenyl cyanide, halogen, mercapto, alkyl mercapto, aryl mercapto, alkenyl mercapto, aralkyl mercapto, alkaryl mercapto, isocyanide, nitro, and heterocyclic groups, each R" is the same as or different from the other R", and wherein the dangling valences in said formula may be satisfied by groups that are the same as or different from R" and are selected from the foregoing groups.
- 4. Method of claim 3 wherein said R" groups are organyl groups that are the same or different.
- 5. Method of claim 3 wherein said R" groups are hydrocarbyl groups that are the same or different.
- 6. Method of claim 3 wherein said R" groups are hydrocarbyl-containing groups that are the same or different.
- 7. Method of claim 3 wherein said olefin has one double bond.
- 8. Method of claim 1 wherein said ion is added to the reaction mixture in the form of a compound of a higher-valent form of said metal.
- 9. Method of claim 1 wherein said ion of higher-valent form is produced in situ in the reaction mixture from a compound of the metal of lower-valent form.
- 10. Method of claim 1 wherein said ion is a manganese ion.
- 11. Method of claim 10 wherein said manganese ion is Mn.sup.+.sup.3.
- 12. Method of claim 1 wherein said ion is a cerium ion.
- 13. Method of claim 1 wherein .sup.. X is a carbonyl-containing radical selected from ##STR114##
- 14. Method of claim 1 wherein .sup.. X is a sulfur-containing radical selected from ##STR115##
- 15. Method of claim 1 wherein .sup.. X is an oxy-sulfur-substituted methyl radical selected from ##STR116##
- 16. Method of claim 1 wherein .sup.. X is a nitrogen-containing radical selected from >C-CN and >C-NO.sub.2.
- 17. Method of claim 1 wherein .sup.. X is ##STR117##
- 18. Method of claim 1 wherein .sup.. X is ##STR118##
- 19. Method of claim 1 wherein .sup.. X is ##STR119##
- 20. Method of claim 1 wherein .sup.. X is >C-CN.
- 21. Method of claim 1 wherein .sup.. X is ##STR120##
- 22. Method of claim 1 wherein .sup.. X is ##STR121##
- 23. Method of claim 1 wherein .sup.. X is >C-NO.sub.2.
- 24. Method of claim 1 wherein .sup.. X is >C-SO.sub.2 SR.
- 25. Method of claim 1 wherein .sup.. X is >C-SO.sub.3 H.
- 26. Method of claim 1 wherein .sup.. X is >C-SO.sub.2 H.
- 27. Method of claim 1 wherein .sup.. X is .sup.. SR'.
- 28. Method of reacting a free radical .sup.. X with an olefin comprising heating said olefin with a source of said free radical .sup.. X in the presence of a stoichiometric amount of manganic acetate and in the presence of acetic acid for a time sufficient to form an addition product comprising said olefin and said free radical, said free radical .sup.. X being selected from the group consisting of ##STR122## where R is an alkyl group, and R' is a hydrocarbyl or substituted hydrocarbyl group, said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitorparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol.
- 29. Method of selectively reacting a free radical .sup.. X with an olefin, said free radical .sup.. X being selected from the group consisting of ##STR123## where R is an alkyl group and R' is a hydrocarbyl or substituted hydrocarbyl group, and said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide a thiosulfonic acid ester, and a thiol, comprising reacting said olefin with a compound selected from the group consisting of ketones, aldehydes, esters, nitriles, sulfoxides, nitroparaffins, thiosulfonic acid esters, and thiols, in the presence of a stoichiometric amount of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure, ##STR124##
- 30. Method of selectively reacting a free radical .sup.. X with an olefin, said free radical .sup.. X being selected from the group consisting of >C-SO.sub.3 H, and said free radical being derived respectively from an alkanesulfonic acid and an alkanesulfinic acid, comprising reacting said olefin with a compound selected from the group consisting of alkanesulfonic acids and alkanesulfinic acids, in the presence of a stoichiometric amount of an ion of manganese, vanadium, or cerium having a valence higher than the lowest valence above the zero valent form of the metal to form a product containing the structure, ##STR125##
- 31. Method of claim 1 wherein said ion is a vanadium ion.
- 32. Method of claim 17 wherein said olefin is an octene.
- 33. Method of claim 32 wherein said ion is a manganese ion.
- 34. Method of claim 32 wherein said ion is a cerium ion.
- 35. Method of claim 32 wherein said ion is a vanadium ion.
- 36. Method of reacting a free radical .sup.. X with an olefin comprising heating said olefin with a source of said free radical .sup.. X in the presence of a stoichiometric amount of manganic propionate and in the presence of propionic acid for a time sufficient to form an addition product comprising said olefin and said free radical, said free radical .sup.. X being selected from the group consisting of ##STR126## where R is an alkyl group, and R' is a hydrocarbyl or substituted hydrocarbyl group, said free radical being derived respectively from a ketone, a ketone, an aldehyde, an ester, a nitrile, a nitroparaffin, a sulfoxide, a sulfoxide, a thiosulfonic acid ester, an alkanesulfonic acid, an alkanesulfinic acid, and a thiol.
- 37. Method of reacting a free radical, ##STR127## derived from a ketone with an octene comprising heating said ketone and said octene in the presence of a stoichiometric amount of manganic acetate and in the presence of acetic acid for a time sufficient to form an unsaturated ketone product of said octene and said free radical and a keto-ester product of said octene, said free radical, and the acetate portion of said manganic acetate.
- 38. Method of claim 1 wherein said free radical .sup.. X is ##STR128## derived from a ketone, said olefin is an enol ester, and said product is a diketone.
- 39. Method of claim 1 wherein said free radical .sup.. X is ##STR129## derived from a ketone, said olefin is an enol ether, and said product is a diketone.
- 40. Method of claim 1 wherein said free radical .sup.. X is ##STR130## derived from an aldehyde, said olefin is an enol ether, and said product is a keto-aldehyde.
- 41. Method of claim 1 wherein said free radical .sup.. X is ##STR131## derived from an aldehyde, said olefin is an enol ester, and said product is a keto-aldehyde.
- 42. Method of claim 1 wherein said free radical .sup.. X is ##STR132## derived from an aldehyde, said olefin is a vinyl ester, and said product is a keto-aldehyde.
- 43. Method of claim 1 wherein said free radical .sup.. X is ##STR133## derived from an aldehyde, said olefin is a vinyl ester, and said product is a keto-aldehyde.
- 44. Method of claim 1 wherein said free radical .sup.. X is ##STR134## derived from an ester, said olefin is an enol ester, and said product is a keto-ester.
- 45. Method of claim 1 wherein said free radical .sup.. X is ##STR135## derived from an ester, said olefin is an enol ether, and said product is a keto-ester.
- 46. Method of claim 1 wherein said free radical .sup.. X is ##STR136## derived from a ketone, said olefin is an aryl substituted olefin, and said product is a dihydrofuran.
- 47. Method of claim 46 wherein said ketone is a diketone.
- 48. Method of claim 47 wherein said diketone is a cyclic diketone.
- 49. Method of claim 48 wherein said diketone is a non-cyclic diketone.
- 50. Method of claim 48 wherein said cyclic diketone is 1,3-cyclo-hexanedione.
- 51. Method of claim 49 wherein said non-cyclic diketone is 2,4-pentanedione.
- 52. Method of claim 46 wherein said ketone is a beta-keto-ester.
- 53. Method of claim 46 wherein said ketone is a beta-keto-nitrile.
- 54. Method of claim 46 wherein said ketone is a beta-keto-amide.
- 55. The method of claim 1 wherein said free radical .sup.. X is ##STR137## derived from a diketone and said product is a dihydrofuran.
- 56. The method of claim 55 wherein said olefin is an aryl-substituted olefin.
- 57. The method of claim 1 wherein said free radical .sup.. X is ##STR138## derived from a cyclic ketone and said olefin is an allyl chloride or sulfide.
- 58. The method of claim 1 wherein said free radical .sup.. X is ##STR139## derived from a ketone and said olefin is an allyl chloride or sulfide.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of our copending application Ser. No. 755,732, filed Aug. 27, 1968 and now abandoned. This latter application was a continuation-in-part of our then copending application Ser. No. 714,447, filed Mar. 20, 1968 and now abandoned.
Foreign Referenced Citations (1)
Number |
Date |
Country |
218,145 |
May 1968 |
SU |
Non-Patent Literature Citations (2)
Entry |
Heiba, et al., JACS vol. 90:4, Feb. 14, 1968, p. 1082-1084. |
Van Helden et al., Chem. Abstr. vol. 55, (1961), 17564i-17565b. |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
755732 |
Aug 1968 |
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