Oxidizing liquid media for chemical transformations

Patent metadata

Field	Value
Publication number	US-11814348-B2
Application number	US-201816616604-A
Country	US
Kind code	B2
Filing date	May 25, 2018
Priority date	May 25, 2017
Publication date	Nov 14, 2023
Grant date	Nov 14, 2023

Abstract

Provided is an oxidizing composition, in which a liquid medium is substantially inert in the presence of an oxidizing electrophile contained in the liquid medium. The composition comprises (a) an oxidizing electrophile comprising a main group element in oxidized form and at least one conjugate anion of an oxygen acid; (b) a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, and a combination thereof; and (c) optionally one or more salt additives. Further provided are a method of using the oxidizing composition to oxidize a substrate and a method of generating and/or regenerating an oxidizing electrophile comprising a main group element.

First claim

The invention claimed is:

1. An oxidizing composition comprising:
(a) an oxidizing electrophile comprising a main group element in oxidized form and at least one conjugate anion of an oxygen acid;
(b) a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, compound (I), and a combination thereof;
wherein
the deactivated arene and deactivated heteroarene comprise at least one electron withdrawing group selected from the group consisting of —NO 2 , fluoro-C 1-8 alkyl, —F, —OOCR, —COOH, —OH 2 + , —CONH 2 , —COOR, —NR 3 + , —CN, —SO 3 H, —SO 3 R, —SO 3 W, and a combination thereof,
the deactivated aliphatic and deactivated heteroaliphatic comprise at least one electron withdrawing group selected from the group consisting of —NO 2 , —CONH 2 , —NR 3 + , —CN, —SO 3 H, —SO 3 R, —SO 3 W, and a combination thereof, provided that the deactivated aliphatic and deactivated heteroaliphatic are not methanesulfonic acid,
R is hydrogen or any aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted with halo, hydroxyl, cyano, nitro, alkoxy, amino, aryl, heteroaryl, alkyl, heteroalkyl, oxo, or a combination thereof, and W is a cation comprising a metal selected from boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, an alkali metal, and an alkaline earth metal, and
compound (I) is selected from trifluoromethanol, trifluoromethyl 2,2,2-trifluoroacetate, 2,2,2-trifluoroethan-1-ol, 2,2,2-trifluoroethyl 2,2,2-trifluoroacetate, perfluoroethyl 2,2,2-trifluoroacetate, 1,1,2,2,2-pentafluoroethan-1-ol, trifluoro(nitro)methane, 1,1,2,2-tetrafluoroethane-1,2-diol, 1,1,2,2-tetrafluoro-2-hydroxyethyl 2,2,2-trifluoroacetate, perfluoroethane-1,2-diyl bis(2,2,2-trifluoroacetate), 1,1,2,2,3,3-hexafluoropropane-1,3-diol, propane-1,2,3-triyl tris(2,2,2-trifluoroacetate), oxalic acid, 1,1,1,4,4,4-hexafluorobutane-2,3-dione, methyl 2,2,3,3,3-pentafluoropropanoate, trifluoromethyl 2,2,3,3,3-pentafluoropropanoate, trifluoromethyl acetate, 1,1-difluoroethyl acetate, 2,2,2-trifluoroethyl acetate, perfluoroethyl acetate, perfluoropropan-2-yl acetate, 1,1,1,3,3,3-hexafluoropropan-2-yl acetate, 1,1,2,2-tetrafluoro-2-hydroxyethyl acetate, perfluoroethane-1,2-diyl diacetate, ethane-1,2-diyl diacetate, propane-1,2,3-triyl trisacetate, perfluoropropane-1,2,3-triyl triacetate, 1,1,3,3-tetrafluoropropane-1,2,3-triyl triacetate, 1,1-difluoroethane-1,2-diyl diacetate, trifluoro(trifluoromethoxy)methane, 1,1,1,2,2-pentafluoro-2-(trifluoromethoxy)ethane, 1,1,1,2,2-pentafluoro-2-(perfluoroethoxy)ethane, tris(trifluoromethyl)amine, 1,1,2,2,2-pentafluoro-N-(perfluoroethyl)-N-(trifluoromethyl)ethan-1-amine, tris(perfluoroethyl)amine, 2,2,2-trifluoro-N,N-bis(trifluoromethyl)acetamide, NN-bis(trifluoromethyl)formamide, 2,2,2-trifluoroacetamide, perfluoropyrrolidine, perfluoropyrroline, perfluoropyran, perfluoropiperidine, perfluorodioxane, perfluoromorpholine, perfluoropiperazine, pyrrolidine carboxylic acid, pyrroline carboxylic acid, pyran carboxylic acid, piperidine carboxylic acid, dioxane carboxylic acid, morpholine carboxylic acid, piperazine carboxylic acid, and a combination thereof, and
(c) optionally one or more salt additives 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; and
wherein the non-oxidizable liquid is substantially inert in the presence of the oxidizing electrophile.

2. The oxidizing composition of claim 1 , 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.

3. The oxidizing composition of claim 1 , comprising one or more salt additives of formula Q a Z b .

4. The oxidizing composition of claim 1 , wherein the oxidizing electrophile comprises thallium, lead, antimony, mercury, tin, selenium, tellurium, arsenic, iodine, or bismuth.

5. The oxidizing composition 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.

6. The oxidizing composition of claim 5 , further comprising an oxidizing regeneration reagent to generate and/or regenerate the oxidizing electrophile of the formula M +n X p L q , 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.

7. The oxidizing composition of claim 6 , further comprising an oxidative regeneration catalyst to generate and/or regenerate the oxidizing electrophile of the formula M +n X p L q .

8. The oxidizing composition of claim 7 , wherein the oxidative regeneration catalyst comprises copper, silver, iron, cobalt, manganese, nickel, chromium, vanadium, or a combination thereof.

9. The oxidizing composition of claim 3 , 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.

10. The oxidizing composition of claim 3 , wherein Q is a proton, a cation of an alkali metal, a cation of an alkaline earth metal, a cation of a rare-earth metal, a main group element cation, or a combination thereof.

11. The oxidizing composition of claim 3 , wherein the salt additive is an oxygen acid selected from the group consisting of 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, and a mixture thereof.

12. A process for oxidizing a substrate, comprising:
(a) contacting a substrate and the oxidizing composition of claim 1 to provide an oxidized substrate and a reduced form of the oxidizing electrophile; and
(b) optionally separating the oxidized substrate and the reduced form of the oxidizing electrophile.

13. The process of claim 12 , wherein the oxidizing composition 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

Assignees

• Univ Florida
• Hyconix Inc

Inventors

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

Classifications

• C07C5/50 Primary

  with an organic compound as an acceptor · CPC title

• C07C29/132

  by reduction of an oxygen containing functional group · CPC title

• C07C29/50

  with molecular oxygen only · CPC title

• C07C67/30

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

• C07F5/00

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