# US 2014/0155666 A1 · Palladium-catalyzed decarbonylation of fatty acid anhydrides for the production of linear alpha olefins

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- Number: US 2014/0155666 A1
- Document ID: US20140155666A1
- Status: Published application
- Kind: A1
- Application number: 14/091,466
- Filed: 2013-11-27
- Published: 2014-06-05
- Earliest claimed: 2012-12-05
- Assignees: California Institute of Technology
- Applicants: California Institute of Technology
- Inventors: YIYANG LIU; BRIAN M. STOLTZ; ROBERT H. GRUBBS; ALEXEY FEDOROV; KELLY E. KIM
- Web page: https://patentgrep.com/patent/US20140155666A1

## CPC

- C07C 1/24: by elimination of water
- C07C 1/2078: {by a transformation in which at least one -C(=O)-O- moiety is eliminated}
- C07C 2531/24: Phosphines
- C07C 2531/30: Halides
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The present invention is directed to methods of forming olefins, especially linear alpha olefins from fatty acids or anhydrides, each method comprising: contacting an amount of precursor carboxylic acid anhydride with a palladium catalyst comprising a bidentate bis-phosphine ligand in a reaction mixture so as to form an olefin in a product with the concomittant formation and removal of CO and water from the reaction mixture, either directly or indirectly, wherein the reaction mixture is maintained with a sub-stoichiometric excess of a sacrificial carboxylic acid anhydride, an organic acid, or both, said sub-stoichiometric excess being relative to the amount of the precursor carboxylic acid anhydride. The precursor carboxylic acid anhydride may be added to the reaction mixture directly or formed in situ by the reaction between at least one precursor carboxylic acid with a stoichiometric amount of the sacrificial acid anhydride.

## Claims

### Claim 1

A method for forming olefins, said method comprising: contacting an amount of precursor carboxylic acid anhydride with a palladium catalyst comprising a bidentate bis-phosphine ligand in a reaction mixture so as to form an olefin in a product with the concomittant formation and removal of CO and water from the reaction mixture, wherein the reaction mixture is maintained with a sub-stoichiometric excess of a sacrificial carboxylic acid anhydride, an organic acid, or both, said sub-stoichiometric excess being relative to the amount of the precursor carboxylic acid anhydride.

### Claim 2 (depends on 1)

The method of claim 1, wherein the precursor carboxylic acid anhydride is formed in situ by the reaction between at least one precursor carboxylic acid with a stoichiometric amount of the sacrificial acid anhydride.

### Claim 3 (depends on 1)

The method of claim 1, wherein the sub-stoichiometric excess of the sacrificial acid anhydride is added incrementally during formation of the olefin.

### Claim 4 (depends on 1)

The method of claim 1, wherein the sub-stoichiometric excess of the sacrificial acid anhydride is present in an amount sufficient to favor the presence of the precursor carboxylic acid anhydride with respect to its corresponding precursor carboxylic acid or acids.

### Claim 5 (depends on 1)

The method of claim 1, wherein the sub-stoichiometric excess of the sacrificial acid anhydride is present in an amount ranging from about 0.01 to about 0.9, relative to the original amount of the precursor carboxylic acid anhydride.

### Claim 6 (depends on 1)

The method of claim 1, wherein the sacrificial acid anhydride is converted to its corresponding carboxylic acid.

### Claim 7 (depends on 1)

The method of claim 1, wherein the sacrificial acid anhydride comprises acetic anhydride, benzoic anhydride, isobutyric anhydride, propionic anhydride, or pivalic anhydride.

### Claim 8 (depends on 1)

The method of claim 1, wherein the organic acid comprises a substituted benzoic acid, substituted hydroxybenzamide, substituted phenol, or a substituted bisphenol.

### Claim 9 (depends on 1)

The method of claim 1, wherein the CO and water is removed from the reaction mixture by distillation.

### Claim 10 (depends on 1)

The method of claim 1, wherein the precursor carboxylic acid anhydride is an acid anhydride of at least one fatty acid.

### Claim 11 (depends on 1)

The method of claim 1, wherein the precursor carboxylic acid anhydride is an acid anhydride of at least moiety functionalized by an alkoxycarbonyl, ester, halide, imide, ketone, protected amine, terminal olefin, or substituted aromatic.

### Claim 12 (depends on 1)

The method of claim 1, wherein the olefin in the product comprises at least 80% of alpha olefin, relative to the total olefin formed by the method.

### Claim 13 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

The method of any one of claims 1 to 12, wherein the bidentate bis-phosphine ligand has a bite angle in a range of from about 100 degrees to about 130 degrees.

### Claim 14 (depends on 1)

The method of claim 1, wherein the palladium is present in a range of from about 0.01 mole percent to about 0.5 mole percent, relative to the amount of the precursor carboxylic acid anhydride present in the reaction mixture.

### Claim 15 (depends on 1)

The method of claim 1, wherein the ratio of bidentate phosphine ligand to palladium in the palladium bidentate bis-phosphine catalyst is in a range of from about 0.9 to about 2.

### Claim 16 (depends on 1)

The method of claim 1, wherein the bidentate bis-phosphine ligand comprises a structure of Formulae (I) or (II):
wherein
Q is absent, a bond, or O;
Z is absent; a bond; —O—; —S—; methylene; optionally substituted C-2 alkylene (—C(R)2—); optionally substituted alkenylene; —P(aryl)-; —P(heteroaryl)-; —Si(R)2—; or —N(R)—; provided at least one of Q or Z are not absent;
each R is independently at each occurrence H, short chain alkyl, aryl, or aralkyl; and
X is independently at each occurrence H, F, Cl, C1-3alkyl, or C1-3alkoxide.

### Claim 17 (depends on 16)

The method claim 16, wherein the bidentate bis-phosphine ligand comprises a structure of Formulae (IA):

### Claim 18 (depends on 16)

The method of claim 16, wherein X is independently at each occurrence F, Cl, methyl, or methoxy substituted in the 2 or 4 position.

### Claim 19 (depends on 17)

The method of claim 17, wherein the bidentate bis-phosphine ligand comprises a Xantphos ligand or a DPEphos ligand:

### Claim 20 (depends on 1)

The method of claim 1, wherein the palladium catalyst comprising the bidentate bis-phosphine ligand is generated in situ.

### Claim 21 (depends on 1)

The method claim 1, wherein the reaction mixture further comprises an optionally substituted monodentate triarylphosphine or monodentate tri-heteroarylphosphine ligand.

### Claim 22 (depends on 21)

The method claim 21, wherein the reaction mixture further comprises a triphenylphosphine ligand.

### Claim 23 (depends on 1)

The method of claim 1, wherein the reaction mixture consists essentially of (a) the precursor carboxylic acid anhydride, (b) the palladium catalyst comprising a bidentate bis-phosphine ligand, and (c) the sacrificial acid anhydride, the organic acid, or both the sacrificial acid anhydride and the organic acid.