Oxidation of alkane to alkene

Patent metadata

Field	Value
Publication number	US-11078136-B2
Application number	US-201816616615-A
Country	US
Kind code	B2
Filing date	May 25, 2018
Priority date	May 25, 2017
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

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.

First claim

The invention claimed is:

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.

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

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

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

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

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

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

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

9. 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.

10. The process of claim 1 , wherein the oxidizing electrophile has a formula M +n X p L q , 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.

11. 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.

12. 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.

13. 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.

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

15. 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.

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

17. 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.

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

19. 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.

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

21. The process of claim 20 , wherein the liquid medium comprises a salt additive of formula Q a Z b , 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.

22. 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.

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

Assignees

• Scripps Research Inst
• Hyconix Inc

Inventors

• Periana Roy A
• Hashiguchi Brian G
• Konnick Michael M

Classifications

• Y02P30/40

  Ethylene production · CPC title

• C07C29/03

  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) · CPC title

• C07C5/42 Primary

  by dehydrogenation with a hydrogen acceptor · CPC title

• C07C2531/04

  containing carboxylic acids or their salts · CPC title

• C07C29/50

  with molecular oxygen only · CPC title