Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
View Patent ↗This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.
1. A method for synthesizing a metathesis reaction product having a terminal olefin, the method comprising contacting, in the presence of a metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with ethylene, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the amount of the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (IIa):
wherein:
M is Ru;
X 1 and X 2 are anionic ligands;
R 1 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
Q is selected from the group consisting of heteroatom-containing hydrocarbylene and substituted heteroatom-containing hydrocarbylene, wherein M is connected to a heteroatom, wherein a five or six member ring is formed with M and the heteroatom, and wherein two or more substituents on adjacent atoms within Q may be taken together to form an additional, optionally substituted cyclic structure;
n1 is zero or 1;
L 1 has the structure of formula (IIIb):
L 3 is a neutral electron donating ligand;
wherein Ar 1 is an aryl substituted with at least one group selected from the group consisting of C 2 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 6 -C 12 aralkyl, and C 6 -C 12 alkaryl; α is an optional double bond; and R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein any two or more of Ar 1 , R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 may be taken together to form a cyclic group, and provided that R 14 and R 16 are not present if α is present.
2. The method of claim 1 , wherein Ar 1 has the structure of formula (VIIa):
wherein represents the attachment point to N in formula (IIIb), R 17 and R 18 are independently selected from the group consisting of C 2 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 5 -C 12 aralkyl, and C 5 -C 12 alkaryl, and R 19 , R 20 and R 21 are independently selected from the group consisting of hydrogen, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 6 -C 12 aralkyl, and C 6 -C 12 alkaryl.
3. The method of claim 2 , wherein R 19 , R 20 and R 21 are hydrogen such that Ar 1 has the structure of formula (VIIb):
4. The method of claim 3 , wherein R 17 and R 18 are C 2 -C 12 alkyl.
5. The method of claim 1 , wherein the catalyst has the structure of formula (IIb):
6. The method of claim 1 , wherein at least 50% of the metathesis reaction product comprises the terminal olefins and further wherein at least 50% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
7. The method of claim 1 , wherein the catalyst is present in an amount that is 100 ppm or less relative to the amount of the olefinic substrate, at least 50% of the metathesis reaction product comprises the terminal olefins, and at least 50% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
8. The method of claim 7 , wherein at least 70% of the metathesis reaction product comprises the terminal olefins.
9. The method of claim 7 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
10. The method of claim 7 , wherein at least 90% of the metathesis reaction product comprises the terminal olefins.
11. The method of claim 7 , wherein at least 60% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
12. The method of claim 7 , wherein at least 70% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
13. The method of claim 1 , wherein the catalyst is present in an amount that is 10 ppm or less relative to the amount of the olefinic substrate, at least 50% of the metathesis reaction product comprises the terminal olefins, and at least 40% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
14. The method of claim 13 , wherein at least 70% of the metathesis reaction product comprises the terminal olefins.
15. The method of claim 13 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
16. The method of claim 1 , wherein the catalyst is selected from the group consisting of:
17. The method of claim 16 , wherein the catalyst is present in an amount that is 100 ppm or less relative to the amount of the olefinic substrate, at least 70% of the metathesis reaction product comprises the terminal olefins, and at least 40% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
18. The method of claim 17 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
19. The method of claim 17 , wherein at least 90% of the metathesis reaction product comprises the terminal olefins.
20. The method of claim 17 , wherein at least 50% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
21. The method of claim 17 , wherein at least 60% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
22. The method of claim 17 , wherein at least 70% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
23. The method of claim 1 , wherein the olefinic substrate is selected from the group consisting of seed oils, alkyl esters of unsaturated fatty acids, and aryl esters of unsaturated fatty acids.
24. The method of claim 1 , wherein the olefinic substrate is a seed oil or composition derived from a seed oil.
25. The method of claim 24 , wherein the seed oil is selected from the group consisting of soybean oil and canola oil.
26. The method of claim 1 , wherein the olefinic substrate comprises a mixture of internal olefins selected from the group consisting of monoacylglycerols, diacylglycerols, triacylglycerols, and combinations thereof.
27. The method of claim 26 , wherein the monoacylglycerols, diacylglycerols, and triacylglycerols each contain at least one C 8 -C 24 unsaturated side chain.
28. An olefin metathesis process comprising contacting an olefinic substrate comprising at least one internal olefin and further comprising a mixture of mono-, di-, and tri-glycerides with ethylene in the presence of a ruthenium alkylidene metathesis catalyst under reaction conditions effective to prepare a metathesis product having a terminal olefin, wherein the metathesis catalyst has the structure of formula (IIa):
wherein:
M is Ru;
X 1 and X 2 are anionic ligands;
R 1 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
Q is selected from the group consisting of heteroatom-containing hydrocarbylene and substituted heteroatom-containing hydrocarbylene, wherein M is connected to a heteroatom, wherein a five or six member ring is formed with M and the heteroatom, and wherein two or more substituents on adjacent atoms within Q may be taken together to form an additional, optionally substituted cyclic structure;
n1 is zero or 1;
L 1 has the structure of formula (IIIb):
L 3 is a neutral electron donating ligand;
wherein Ar 1 is an aryl substituted with at least one group selected from the group consisting of C 2 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 6 -C 12 aralkyl, and C 6 -C 12 alkaryl; α is an optional double bond; and R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein any two or more of Ar 1 , R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 may be taken together to form a cyclic group, and provided that R 14 and R 16 are not present if α is present.
29. The method of claim 28 , wherein the catalyst is selected from the group consisting of:
30. The method of claim 28 , wherein the catalyst is present in an amount that is 100 ppm or less relative to the amount of the olefinic substrate, wherein at least 50% of the metathesis reaction product comprises the terminal olefins and further wherein at least 50% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
31. The method of claim 30 , wherein at least 70% of the metathesis reaction product comprises the terminal olefins.
32. The method of claim 30 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
33. The method of claim 30 , wherein at least 90% of the metathesis reaction product comprises the terminal olefins.
34. The method of claim 30 , wherein at least 60% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
35. The method of claim 30 , wherein at least 70% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
36. An olefin metathesis process comprising contacting an olefinic substrate comprising a seed oil or a composition derived from a seed oil and further comprising at least one internal olefin, with ethylene in the presence of a ruthenium alkylidene metathesis catalyst under reaction conditions effective to prepare a metathesis product having a terminal olefin, wherein the metathesis catalyst has the structure of formula (IIa):
wherein:
M is Ru;
X 1 and X 2 are anionic ligands;
R 1 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
Q is selected from the group consisting of heteroatom-containing hydrocarbylene and substituted heteroatom-containing hydrocarbylene, wherein M is connected to a heteroatom, wherein a five or six member ring is formed with M and the heteroatom, and wherein two or more substituents on adjacent atoms within Q may be taken together to form an additional, optionally substituted cyclic structure;
n1 is zero or 1;
L 1 has the structure of formula (IIIb):
L 3 is a neutral electron donating ligand;
wherein Ar 1 is an aryl substituted with at least one group selected from the group consisting of C 2 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 6 -C 12 aralkyl, and C 6 -C 12 alkaryl; α is an optional double bond; R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein any two or more of Ar 1 , R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 may be taken together to form a cyclic group, and provided that R 14 and R 16 are not present if α is present; and
wherein at least about 50% of the metathesis reaction products comprise a terminal olefin and further wherein at least about 50% of the internal olefins initially present in the reaction mixture are converted to terminal olefins.
37. The method of claim 36 , wherein the catalyst is selected from the group consisting of:
38. The method of claim 36 , wherein the catalyst is present in an amount that is less than 1000 ppm relative to the amount of the olefinic substrate.
39. The method of claim 36 , wherein the catalyst is present in an amount that is 100 ppm or less relative to the amount of the olefinic substrate.
40. The method of claim 39 , wherein at least 70% of the metathesis reaction product comprises the terminal olefins.
41. The method of claim 39 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
42. The method of claim 39 , wherein at least 90% of the metathesis reaction product comprises the terminal olefins.
43. The method of claim 39 , wherein at least 60% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
44. The method of claim 39 , wherein at least 70% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
45. A method for synthesizing a metathesis product having a terminal olefin, the method comprising contacting, in the presence of a metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with ethylene, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the amount of the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (XII):
wherein:
t is zero;
M is Ru;
X 1 and X 2 are anionic ligands;
R 1 and R 2 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl;
Z 3 is a cationic moiety selected from the group consisting of P(R 2 ) 3 and N(R 2 ) 3 ;
Y is a non-coordinating anion; and
L 1 is a carbene ligand with the structure of formula (IIIb):
wherein Ar 1 is an aryl substituted with at least one group selected from the group consisting of C 2 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 5 -C 12 aryl, C 6 -C 12 aralkyl, and C 6 -C 12 alkaryl; α is an optional double bond; and R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, wherein any two or more of Ar 1 , R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 may be taken together to form a cyclic group, and provided that R 14 and R 16 are not present if α is present.
46. The method of claim 45 , wherein the catalyst is:
47. The method of claim 45 , wherein at least 50% of the metathesis reaction product comprises the terminal olefins and further wherein at least 50% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
48. The method of claim 47 , wherein the catalyst is present in an amount that is 100 ppm or less relative to the amount of the olefinic substrate.
49. The method of claim 48 , wherein at least 80% of the metathesis reaction product comprises the terminal olefins.
50. The method of claim 48 , wherein at least 90% of the metathesis reaction product comprises the terminal olefins.
51. The method of claim 48 , wherein at least 60% of the internal olefins initially present in the reaction mixture are converted to the terminal olefins.
52. The method of claim 51 , wherein the catalyst is: