# US 9,518,002 B2 · Terminal selective metathesis of polyenes derived from natural oil

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- Number: US 9,518,002 B2
- Document ID: US9518002B2
- Status: Granted
- Kind: B2
- Application number: 14/886,951
- Filed: 2015-10-19
- Published: 2016-05-05
- Granted: 2016-12-13
- Earliest claimed: 2014-10-31
- Assignees: Elevance Renewable Sciences, Inc.
- Applicants: Elevance Renewable Sciences, Inc.
- Inventors: Keith M. Wampler; Jane Uy; Steven A. Cohen
- Web page: https://patentgrep.com/patent/US9518002B2

## CPC

- C07C 67/475: by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules
- C11C 1/04: by hydrolysis
- C11C 3/14: by isomerisation {(isomerisation induced by hydrogenation C11C3/12)}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM

## Abstract

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.

## Claims

### Claim 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:
Z1 is —(CH2)7—, or —CH2—CH═CH—(CH2)4—;
R1 is an organic group; and
R2 is a hydrogen atom or an organic group;
provided that the compound of formula (Ia) is derived from a natural oil.

### Claim 2 (depends on 1)

The method of claim 1, wherein the reacting step generates the compound of formula (II) in a yield of at least 30%.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metathesis catalyst is a ruthenium-based first-generation Grubbs catalyst.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metathesis catalyst is a molybdenum- or tungsten-based alkylidene catalyst.

### Claim 5 (depends on 1)

The method of claim 1, wherein Z1 is —(CH2)7—.

### Claim 6 (depends on 1)

The method of claim 1, wherein Z1 is —CH2—CH═CH—(CH2)4—.

### Claim 7 (depends on 1)

The method of claim 1, wherein R1 is methyl.

### Claim 8 (depends on 1)

The method of claim 1, wherein R1 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 —CH2—OH group, or a —CN group.

### Claim 9 (depends on 8)

The method of claim 8, wherein R1 is —C(═O)—O—(C1-12 alkyl).

### Claim 10 (depends on 9)

The method of claim 9, wherein R1 is —C(═O)—O—CH3 or —C(═O)—O—CH2—CH3.

### Claim 11 (depends on 1)

The method of claim 1, wherein R2 is a hydrogen atom.

### Claim 12 (depends on 1)

The method of claim 1, wherein R2 is an organic group.

### Claim 13 (depends on 12)

The method of claim 12, wherein R2 is C1-12 alkyl or C2-12 alkenyl.

### Claim 14 (depends on 13)

The method of claim 13, wherein R2 is —CH2—CH═CH—(CH2)4—CH3, —CH2—CH═CH—CH2—CH3, or —CH2—CH═CH—CH2—CH═CH—CH2—CH3.

### Claim 15 (depends on 12)

The method of claim 12, wherein R2 is —(CH2)7—R3, —CH2—CH═CH—(CH2)7—R3, or —CH2—CH═CH—CH2—CH═CH—(CH2)7—R3; wherein R3 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 —CH2—OH group, or a —CN group.

### Claim 16 (depends on 15)

The method of claim 15, wherein R2 is —(CH2)7—R3, and R3 is —C(═O)—O—(C1-12 alkyl).

### Claim 17 (depends on 16)

The method of claim 16, wherein R2 is —(CH2)7—C(═O)—O—CH3.

### Claim 18 (depends on 15)

The method of claim 15, wherein R2 is —CH2—CH═CH—(CH2)7—R3, and R3 is —C(═O)—O—(C1-12 alkyl).

### Claim 19 (depends on 18)

The method of claim 18, wherein R2 is —CH2—CH═CH—(CH2)7—C(═O)—O—CH3.

### Claim 20 (depends on 15)

The method of claim 15, wherein R2 is —CH2—CH═CH—CH2—CH═CH—(CH2)7—R3, and R3 is —C(═O)—O—(C1-12 alkyl).