Direct oxidation of olefins to oxygenated species

Patent metadata

Field	Value
Publication number	US-10858301-B2
Application number	US-201816616626-A
Country	US
Kind code	B2
Filing date	May 25, 2018
Priority date	May 25, 2017
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

Provided is a process for oxidizing an alkene. The process comprises contacting an alkene, and either an oxidizing electrophile comprising a main group element in oxidized form or 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 oxygenate and a reduced form of the oxidizing electrophile. The process optionally further comprises separating the oxygenate and the reduced form of the oxidizing electrophile. The oxygenate can be further hydrolyzed to form an alcohol, diol, or polyol.

First claim

The invention claimed is:

1. A process for oxidizing an alkene, comprising:
(a) contacting an alkene, and
(i) an oxidizing electrophile comprising a main group element selected from lead, antimony, mercury, tin, selenium, tellurium, arsenic, iodine, and bismuth 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, without the need for molecular oxygen, an oxygenate and a reduced form of the oxidizing electrophile; and
(b) optionally separating the oxygenate and the reduced form of the oxidizing electrophile.

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

3. The process of claim 1 , further comprising (c) hydrolyzing the oxygenate to form an alcohol, a diol, a polyol with three or more hydroxyl groups, or a combination thereof.

4. The process of claim 3 , wherein the hydrolysis step takes place in the presence of an acid.

5. The process of claim 3 , wherein the hydrolysis step takes place in the presence of a base.

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

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

8. The process of claim 7 , 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.

9. The process of claim 7 , wherein the oxidizing electrophile further comprises at least one ligand with at least one electron-withdrawing group.

10. The process of claim 9 , wherein the ligand with at least one electron-withdrawing group is selected from

11. 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 an 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.

12. The process of claim 1 , wherein the oxidizing electrophile comprising a main group element in oxidized form is present in less than stoichiometric quantities relative to the oxygenate and acts as a catalyst.

13. The process of claim 12 , further comprising (d) contacting the reduced form of the oxidizing electrophile and an oxidizing regeneration reagent to regenerate the oxidizing electrophile.

14. The process of claim 13 , wherein the oxidizing regeneration reagent is a quinone, molecular oxygen, air, a peroxide, nitric oxide, nitrous oxide, nitric acid, a nitroxide, sulfur trioxide, ozone, or a combination thereof.

15. The process of claim 13 , wherein step (d) is an electrochemical process.

16. The process of claim 14 , 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.

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

18. 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.

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

20. 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 non-oxidizable liquid is substantially inert in the presence of the oxidizing electrophile.

21. The process of claim 1 , 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, or 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

• C07F5/00

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title

• C07C69/63

  of saturated acids · CPC title

• C07C67/30

  by modifying the acid moiety of the ester, such modification not being an introduction of an ester group · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• Y02P30/40

  Ethylene production · CPC title