# US 8,569,560 B2 · Synthesis of terminal alkenes from internal alkenes via olefin metathesis

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- Number: US 8,569,560 B2
- Document ID: US8569560B2
- Status: Granted
- Kind: B2
- Application number: 13/622,613
- Filed: 2012-09-19
- Published: 2013-02-07
- Granted: 2013-10-29
- Earliest claimed: 2006-10-13
- Assignees: Elevance Renewable Sciences, Inc.
- Applicants: Elevance Renewable Sciences, Inc.
- Inventors: Yann Schrodi; Richard L. Pederson; Hiroki Kaido; Michael J. Tupy
- Web page: https://patentgrep.com/patent/US8569560B2

## CPC

- B01J 31/2278: {Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts}
- C07C 6/04: at a carbon-to-carbon double bond
- C07C 67/333: by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32)
- 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
- B01J 2231/54: Metathesis reactions, e.g. olefin metathesis
- B01J 2531/821: Ruthenium
- C07C 2531/22: Organic complexes
- C07C 2531/24: Phosphines
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

This disclosure 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 an olefin metathesis catalyst. According to one aspect, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting, in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C. The methods, compositions, reactions and reaction systems herein disclosed have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

## Claims

### Claim 1

A method for synthesizing a terminal olefin, the method comprising: contacting, in the presence of a metathesis catalyst, an olefinic substrate comprising a mixture of internal olefins with a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C., and wherein the internal olefins are selected from the group consisting of:
monoqlycerides, diglycerides, triglycerides, and combinations thereof.

### Claim 2 (depends on 1)

The method of claim 1, wherein the reaction conditions effective to ensure that the olefinic substrate and the cross-metathesis partner are in liquid form.

### Claim 3 (depends on 1)

The method of claim 1, wherein the olefinic substrate is an oil or a compound derived from an oil.

### Claim 4 (depends on 1)

The method of claim 1, wherein the olefinic substrate is a fatty acid ester.

### Claim 5

A method for synthesizing 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 a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C., wherein the olefinic substrate is a seed oil or a compound derived from a seed oil.

### Claim 6 (depends on 5)

The method of claim 5, wherein the olefinic substrate is selected from the group consisting of: canola oil, soybean oil, sunflower oil, safflower oil, cottonseed oil, castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil, sesame oil, grapeseed oil, fatty acid esters thereof, and combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the alpha olefinic reactant is selected from the group consisting of: mono-substituted olefins, di-substituted olefins, and combinations thereof.

### Claim 8 (depends on 7)

The method of claim 7, wherein the alpha olefinic reactant contains one or two substituents each having 1 to about 10 carbon atoms.

### Claim 9 (depends on 8)

The method of claim 8, wherein the alpha olefinic reactant is a mono-substituted olefin having 1 to about 10 carbon atoms.

### Claim 10 (depends on 9)

The method of claim 9, wherein the alpha olefinic reactant is selected from the group consisting of: 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and combinations thereof.

### Claim 11 (depends on 1)

The method of claim 1, wherein the alpha olefinic reactant has a solubility of at least 0.25 M in the olefinic substrate.

### Claim 12 (depends on 1)

The method of claim 1, wherein the contacting is carried out in an atmosphere and/or solution selected from the group consisting of: an oxygen containing atmosphere, an inert atmosphere, or an oxygen free atmosphere and solution.

### Claim 13

A method for synthesizing 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 a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C., wherein the method provides a terminal olefin having a turnover number of at least twice the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefinic reactant.

### Claim 14 (depends on 13)

The method of claim 13, wherein the turnover number at least five times the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefinic reactant.

### Claim 15 (depends on 1)

The method of claim 1, wherein the metathesis catalyst is a ruthenium alkylidene metathesis catalyst which has the structure of formula (II):
wherein:
M is ruthenium;
n is 0 or 1;
m is 0, 1, or 2;
L1, L2 and L3 are neutral electron donor ligands;
X1 and X2 are anionic ligands;
R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
wherein any two or more of X1, X2, L1, L2, L3, R1, and R2 can be taken together to form a cyclic group, and further wherein any one of X1, X2, L1, L2, L3, R1, and R2 can be attached to a support.

### Claim 16 (depends on 15)

The method of claim 15, wherein n and m are 0; R1 is hydrogen, and R2 is selected from C1-C20 alkyl, C2-C20 alkenyl, and aryl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy and phenyl; L2 is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pylidine, substituted pylidine, imidazole, substituted imidazole, pyrazine, and thieother; and X1 and X2 are independently selected from hydrogen, halide, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, C2-C20 acyl, C2-C20 acyloxy, C1-C20 alkylsulfonato, C5-C20 arylsulfonato, C1-C20 alkylsulfanyl, C5-C20 arylsulfanyl, C1-C20 alkylsulfinyl, or C5-C20 arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl.

### Claim 17 (depends on 15)

The method of claim 15, wherein L1 has the structure of formula (III)
in which:
X and Y are heteroatoms selected from N, O, S, and P;
p is zero when X is O or S, and p is 1 when X is N or P;
q is zero when Y is O or S, and q is 1 when Y is N or P;
Q1, Q2, Q3, and Q4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group;
w, x, y, and z are independently zero or 1; and
R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatomcontaining hydrocarbyl,
such that the transition metal complex is a ruthenium carbene complex having the structure of formula (IV)
wherein any two or more of X1, X2, L2, L3, R1, R2, R3, R3A, R4, an R4A can be taken together to form a cyclic group, and further wherein any one of X1, X2, L2, L3, R1, R2, R3, R3A, R4, and R4A can be attached to a support.

### Claim 18

A method for synthesizing 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 a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C., wherein the metathesis catalyst is a ruthenium alkylidene metathesis catalyst that has the structure of formula (VI)
wherein:
n is 0 or 1;
L2 and L3 are neutral electron donor ligands;
X1 and X2 are anionic ligands;
R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;
R3 and R4 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatomcontaining hydrocarbyl,
wherein any two or more of X1, X2, L2, L3, R1, and R2 can be taken together to form a cyclic group, and further wherein any one of X1, X2, L2, L3, R1, and R2 can be attached to a support; and
wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.

### Claim 19 (depends on 18)

The method of claim 18, wherein Q has the structure —CR11R12—CR13R14— or —CR11═CR13—, wherein R11, R12, R13, and R14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, and or wherein any two of R11, R12, R13, and R14 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring.

### Claim 20 (depends on 19)

The method of claim 19, wherein R1 is hydrogen, and R2 is selected from C1-C20 alkyl, C2-C20 alkenyl, and aryl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy and phenyl, L2 is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pylidine, substituted pylidine, imidazole, substituted imidazole, pyrazine, and thioether; X1 and X2 are independently selected from hydrogen, halide, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, C2-C20 acyl, C2-C20 acyloxy, C1-C20 alkylsulfonato, C5-C20 arylsulfonato, C1-C20 alkylsulfanyl, C5-C20 arylsulfanyl, C1-C20 alkylsulfinyl, or C5-C20 arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl; R3 and R4 are aromatic, substituted aromatic, heteroaromatic, substituted heteroaromatic, alicyclic, substituted alicyclic, heteroatom-containing alicyclic, or substituted heteroatom-containing alicyclic, composed of from one to about five lings; and R12 and R14 are hydrogen, and R11 and R13 are selected from hydrogen, lower alkyl and phenyl, or are linked to form a cyclic group.

### Claim 21

A method for synthesizing a terminal olefin, the method comprising: providing an olefinic substrate having at least one internal olefin; providing an alpha olefin having at least 3 carbon atoms; and contacting the olefinic substrate with the alpha olefin in the presence of less than approximately 1000 ppm of a metathesis catalyst relative to the number of olefinic substrate double bonds, under reaction conditions effective to allow cross-metathesis to occur; wherein the contacting yields a product having at least 0.2 wt% 9DA, and the catalyst has a TON9DA of approximately 100 or greater.

### Claim 22 (depends on 21)

The method of claim 21, wherein the contacting occurs in the presence of approximately 100 ppm or less of the catalyst.

### Claim 23 (depends on 21)

The method of claim 21, wherein the contacting occurs in the presence of approximately 50 ppm or less of the catalyst.

### Claim 24 (depends on 21)

The method of claim 21, wherein the contacting occurs in the presence of approximately 10 ppm or less of the catalyst.

### Claim 25 (depends on 21)

The method of claim 21, wherein the contacting yields a product having at least about 5 wt % 9DA.

### Claim 26 (depends on 21)

The method of claim 21, wherein the TON9DA is approximately 1000 or greater.