Terminal selective metathesis of polyenes derived from natural oil
Methods of carrying out metathesis reactions of natural oil-derived polyenes (e.g., dienes and trienes), including functionalized polyenes, are generally disclosed herein. In some embodiments, the dienes or trienes contain a terminal carbon-carbon double bond, and the metathesis reaction is selective toward reaction of the terminal carbon-carbon double bonds in the polyene. Compounds made by such methods are also generally disclosed herein.
1. A method for forming a dimer by olefin metathesis, the method comprising:
providing a reactant composition comprising a compound of formula (Ia):
and a compound of formula (Ib):
and
reacting the compound of formula (Ia) with the compound of formula (Ib) in the presence of a metathesis catalyst to form a product composition comprising a compound of formula (II):
wherein:
Z 1 is —(CH 2 ) 7 —, or —CH 2 —CH═CH—(CH 2 ) 4 —;
R 1 is an organic group; and
R 2 is a hydrogen atom or an organic group;
provided that the compound of formula (Ia) is derived from a natural oil.
2. The method of claim 1 , wherein the reacting step generates the compound of formula (II) in a yield of at least 30%.
3. The method of claim 1 , wherein the metathesis catalyst is a ruthenium-based first-generation Grubbs catalyst.
4. The method of claim 1 , wherein the metathesis catalyst is a molybdenum- or tungsten-based alkylidene catalyst.
5. The method of claim 1 , wherein Z 1 is —(CH 2 ) 7 —.
6. The method of claim 1 , wherein Z 1 is —CH 2 —CH═CH—(CH 2 ) 4 —.
7. The method of claim 1 , wherein R 1 is methyl.
8. The method of claim 1 , wherein R 1 is a carboxylic acid group, an ester group, an amide group, a carboxylate salt group, an aldehyde group, a ketone group, an acyl halide group, a —CH 2 —OH group, or a —CN group.
9. The method of claim 8 , wherein R 1 is —C(═O)—O—(C 1-12 alkyl).
10. The method of claim 9 , wherein R 1 is —C(═O)—O—CH 3 or —C(═O)—O—CH 2 —CH 3 .
11. The method of claim 1 , wherein R 2 is a hydrogen atom.
12. The method of claim 1 , wherein R 2 is an organic group.
13. The method of claim 12 , wherein R 2 is C 1-12 alkyl or C 2-12 alkenyl.
14. The method of claim 13 , wherein R 2 is —CH 2 —CH═CH—(CH 2 ) 4 —CH 3 , —CH 2 —CH═CH—CH 2 —CH 3 , or —CH 2 —CH═CH—CH 2 —CH═CH—CH 2 —CH 3 .
15. The method of claim 12 , wherein R 2 is —(CH 2 ) 7 —R 3 , —CH 2 —CH═CH—(CH 2 ) 7 —R 3 , or —CH 2 —CH═CH—CH 2 —CH═CH—(CH 2 ) 7 —R 3 ; wherein R 3 is a carboxylic acid group, an ester group, an amide group, a carboxylate salt group, an aldehyde group, a ketone group, an acyl halide group, a —CH 2 —OH group, or a —CN group.
16. The method of claim 15 , wherein R 2 is —(CH 2 ) 7 —R 3 , and R 3 is —C(═O)—O—(C 1-12 alkyl).
17. The method of claim 16 , wherein R 2 is —(CH 2 ) 7 —C(═O)—O—CH 3 .
18. The method of claim 15 , wherein R 2 is —CH 2 —CH═CH—(CH 2 ) 7 —R 3 , and R 3 is —C(═O)—O—(C 1-12 alkyl).
19. The method of claim 18 , wherein R 2 is —CH 2 —CH═CH—(CH 2 ) 7 —C(═O)—O—CH 3 .
20. The method of claim 15 , wherein R 2 is —CH 2 —CH═CH—CH 2 —CH═CH—(CH 2 ) 7 —R 3 , and R 3 is —C(═O)—O—(C 1-12 alkyl).