# US 11,078,136 B2 · Oxidation of alkane to alkene

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- Number: US 11,078,136 B2
- Document ID: US11078136B2
- Status: Granted
- Kind: B2
- Application number: 16/616,615
- Filed: 2018-05-25
- Published: 2020-03-26
- Granted: 2021-08-03
- Earliest claimed: 2017-05-25
- Assignees: The Scripps Research Institute; Hyconix, Inc.
- Applicants: The Scripps Research Institute; Hyconix, Inc.
- Inventors: Roy A. Periana; Brian G. Hashiguchi; Michael M. Konnick
- Web page: https://patentgrep.com/patent/US11078136B2

## CPC

- C07C 5/42: by dehydrogenation with a hydrogen acceptor
- C07C 5/50: with an organic compound as an acceptor
- C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C 29/03: by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 (by simultaneous introduction of -OH groups and halogens C07C29/64)
- C07C 29/132: by reduction of an oxygen containing functional group
- C07C 29/50: with molecular oxygen only
- C07C 67/30: by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07F 5/00: Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07C 31/202: {Ethylene glycol}
- C07C 31/205: {1,3-Propanediol; 1,2-Propanediol}
- C07C 69/63: of saturated acids
- C07C 2523/18: Arsenic, antimony or bismuth
- C07C 2531/04: containing carboxylic acids or their salts
- Y02P 30/20: using bio-feedstock
- Y02P 30/40: Ethylene production
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided is a process for converting an alkane to an alkene. The process comprises (a) contacting the alkane and either (i) an oxidizing electrophile comprising a main group element in oxidized form, or (ii) an oxidant and a reduced form of the oxidizing electrophile, in a liquid medium comprising an oxygen acid and optionally one or more additives selected from a non-oxidizable liquid, a salt additive, a Lewis acid, and water, to provide an oxidized intermediate and a reduced form of the oxidizing electrophile; (b) optionally separating the oxidized intermediate and the reduced form of the oxidizing electrophile; and (c) performing an elimination reaction on the oxidized intermediate to provide the alkene and the oxygen acid.

## Claims

### Claim 1

A process for converting an alkane to an alkene, comprising
(a) contacting the alkane and
(i) an oxidizing electrophile comprising a main group element selected from gallium, germanium, arsenic, tin, thallium, lead, antimony, bismuth, and iodine, each in oxidized form or
(ii) an oxidant and a reduced form of the oxidizing electrophile,
in a liquid medium comprising an oxygen acid and optionally one or more additives selected from a non-oxidizable liquid, a salt additive, a Lewis acid, and water, to provide an oxidized intermediate and a reduced form of the oxidizing electrophile;
(b) optionally separating the oxidized intermediate and the reduced form of the oxidizing electrophile; and
(c) performing an elimination reaction on the oxidized intermediate to provide the alkene and the oxygen acid.

### Claim 2 (depends on 1)

The process of claim 1, comprising (b) separating the oxidized intermediate and the reduced form of the oxidizing electrophile.

### Claim 3 (depends on 1)

The process of claim 1, wherein (c) takes place in the presence of an acid catalyst.

### Claim 4 (depends on 1)

The process of claim 1, wherein (c) takes place in the presence of a base catalyst.

### Claim 5 (depends on 1)

The process of claim 1, further comprising (d) separating the alkene and the oxygen acid.

### Claim 6 (depends on 5)

The process of claim 5, wherein the separated oxygen acid is recycled for use in step (a).

### Claim 7 (depends on 1)

The process of claim 1, wherein the oxidizing electrophile comprises arsenic, antimony, or bismuth.

### Claim 8 (depends on 1)

The process of claim 1, wherein the oxidizing electrophile comprises at least one conjugate anion of an oxygen acid.

### Claim 9 (depends on 8)

The process of claim 8, wherein the conjugate anion of the oxygen acid is an aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, or a mixture thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein the oxidizing electrophile has a formula M+nXpLq, wherein M is a main group element cation in an oxidation state of n, X is the conjugate anion of the oxygen acid, L is a ligand, n is an integer from 2 to 6, p is an integer from 1 to 6, and q is an integer from 0 to 5.

### Claim 11 (depends on 1)

The process of claim 1, wherein the oxidizing electrophile is present in less than stoichiometric quantities relative to the alkane and acts as a catalyst.

### Claim 12 (depends on 11)

The process of claim 11, further comprising (e) contacting the reduced form of the oxidizing electrophile and an oxidizing regeneration reagent to regenerate the oxidizing electrophile.

### Claim 13 (depends on 12)

The process of claim 12, wherein the oxidizing regeneration reagent is a quinone, molecular oxygen, air, ozone, a peroxide, nitric oxide, nitrous oxide, nitric acid, a nitroxide, sulfur trioxide, or a combination thereof.

### Claim 14 (depends on 12)

The process of claim 12, wherein step (e) is an electrochemical process.

### Claim 15 (depends on 12)

The process of claim 12, wherein the reduced form of the oxidizing electrophile and the oxidizing regeneration reagent are contacted to regenerate the oxidizing electrophile in the presence of an oxidative regeneration catalyst.

### Claim 16 (depends on 15)

The process of claim 15, wherein the oxidative regeneration catalyst comprises copper, silver, iron, cobalt, manganese, nickel, chromium, vanadium, or a combination thereof.

### Claim 17 (depends on 1)

The process of claim 1, wherein the oxygen acid is aliphatic carboxylic acid, heteroaliphatic carboxylic acid, aromatic carboxylic acid, heteroaromatic carboxylic acid, aliphatic sulfonic acid, heteroaliphatic sulfonic acid, aromatic sulfonic acid, heteroaromatic sulfonic acid, aliphatic phosphonic acid, heteroaliphatic phosphonic acid, aromatic phosphonic acid, heteroaromatic phosphonic acid, boric acid, aliphatic boronic acid, heteroaliphatic boronic acid, aromatic boronic acid, heteroaromatic boronic acid, or a mixture thereof.

### Claim 18 (depends on 1)

The process of claim 1, wherein all or a portion of the oxygen acid is added as an anhydride of the oxygen acid.

### Claim 19 (depends on 1)

The process of claim 1, wherein the liquid medium comprises a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, or a combination thereof, wherein the liquid is substantially inert in the presence of the oxidizing electrophile.

### Claim 20 (depends on 1)

The process of claim 1, wherein the liquid medium comprises a salt additive.

### Claim 21 (depends on 20)

The process of claim 20, wherein the liquid medium comprises a salt additive of formula QaZb, wherein Q is a cation, Z is a bridging oxide, a terminal oxide, a hydroxide, or a conjugate anion of an oxygen acid, a is an integer from 1 to 5, and b is an integer from 1 to 5, wherein a and b are the same or different and balance the oxidation states of Q and Z.

### Claim 22 (depends on 21)

The process of claim 21, wherein Z is a conjugate anion of an oxygen acid that is one or more selected from an aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, and a mixture thereof.

### Claim 23 (depends on 1)

The process of claim 1, wherein the liquid medium comprises a Lewis acid.