Granted Patent
B2
US 12,559,448 · App. 17/438,091 · Granted Feb 24, 2026
Methods for functionalization hydrocarbons
Inventors:
Thomas B. Gunnoe (Palmyra, VA); John T. Groves (Princeton, NJ); William A. Goddard, III (Pasadena, CA)
Assignees:
University of Virgina Patent Foundation; The Trustees of Princeton University; California Institute of Technology
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Abstract
In one aspect, the disclosure relates to a method for functionalizing hydrocarbons. In a further aspect, the method involves heating a hydrocarbon with a composition having an acid and an oxidant. In other aspects, the composition can further include an iodine-based compound and/or a compound having formula A a X n . In any of these aspects, the oxidant can be regenerated in situ or in a separate regeneration step. Also disclosed are functionalized hydrocarbons produced by the disclosed method. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.
Claims (21)
1 . A method comprising mixing a hydrocarbon with a composition comprising an acid and an oxidant comprising a manganese compound, to produce a functionalized hydrocarbon, wherein the acid is selected from the group consisting of trifluoroacetic acid, triflic acid, trifluoromethyl phosphonic acid, hexafluorobutyric acid, sulfuric acid, acetic acid, methanesulfonic acid, phosphoric acid, and any combination thereof, and the manganese compound is not Mn 2 O 3 , wherein the manganese compound comprises Mn 2 (TFA) 4 (HTFA) 4 .
2 . The method of claim 1 , wherein the composition further comprises iodine, an iodine-based compound, or a combination thereof.
3 . The method of claim 2 , wherein the iodine-based compound comprises iodate, periodate, iodine oxide, iodosyl (IO + ), trivalent iodine compound, or any combination thereof.
4 . The method of claim 2 , wherein the iodine-based compound is Q(IO 3 ) p , wherein Q is hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH 3 ) 3 ] + ), wherein p is from 1 to 5.
5 . The method of claim 2 , wherein the iodine-based compound is selected from the group consisting of: KlO 3 , Ca(IO 3 ) 2 , Ba(IO 3 ) 2 , Cu(IO 3 ) 2 , NH 4 IO 3 , H 5 IO 6 , KlO 4 , NaIO 4 , NH 4 IO 4 , I(TFA) 3 , I 2 O 5 , [IO] + , [IO 2 ] + , and any combination thereof.
6 . The method of claim 2 , wherein the molar ratio of the oxidant to the iodine or iodine-based compound is from 1:1 to 30:1.
7 . The method of claim 1 , wherein the acid comprises trifluoroacetic acid.
8 . The method of claim 1 , wherein the hydrocarbon and composition are heated at a temperature of from about 100° C. to about 300° C.
9 . The method of claim 1 , wherein the hydrocarbon comprises a linear or branched alkane or a cycloalkane.
10 . The method of claim 1 , wherein the hydrocarbon comprises methane, ethane, or propane.
11 . The method of claim 1 , wherein the hydrocarbon is monofunctionalized.
12 . A method comprising mixing a hydrocarbon with a composition comprising an acid and an oxidant comprising Mn 2 (TFA) 4 (HTFA) 4 to produce a functionalized hydrocarbon.
13 . The method of claim 12 , wherein the acid comprises trifluoroacetic acid, triflic acid, trifluoromethyl phosphonic acid, hexafluorobutyric acid, sulfuric acid, acetic acid, methanesulfonic acid, phosphoric acid, or any combination thereof.
14 . The method of claim 12 , wherein the hydrocarbon comprises a linear or branched alkane or a cycloalkane.
15 . The method of claim 12 , wherein the hydrocarbon comprises methane, ethane, or propane.
16 . The method of claim 12 , wherein the composition further comprises iodine, an iodine-based compound, or a combination thereof.
17 . The method of claim 16 , wherein the iodine-based compound comprises iodate, periodate, iodine oxide, iodosyl (IO + ), trivalent iodine compound, or any combination thereof.
18 . The method of claim 16 , wherein the iodine-based compound is Q(IO 3 ) p , wherein Q is hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, or trimethyl sulfonium ([S(CH 3 ) 3 ] + ), wherein p is from 1 to 5.
19 . The method of claim 16 , wherein the iodine-based compound is selected from the group consisting of: KlO 3 , Ca(IO 3 ) 2 , Ba(IO 3 ) 2 , Cu(IO 3 ) 2 , NH 4 IO 3 , H 5 IO 6 , KlO 4 , NaIO 4 , NH 4 IO 4 , I(TFA) 3 , I 2 O 5 , [IO] + , [IO 2 ] + , and any combination thereof.
20 . The method of claim 12 , wherein the composition further comprises A a X n , wherein A is hydrogen, lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, transition metals, aluminum, gallium, thallium, indium, tin, sulfur, ammonium (NH 4 + ), alkylammonium, phosphonium (PH 4 + ), alkylphosphonium, arylphosphonium, trimethyl sulfonium ([S(CH 3 ) 3 ] + ) or a combination thereof, wherein X is chlorine, wherein subscript “a” is an oxidation state of X and subscript “n” is an oxidation state of A.
21 . The method of claim 20 , wherein AX is HCl, NaCl, KCl, CaCl 2 ), LiCl, ZnCl 2 , BeCl 2 , MgCl 2 , NH 4 Cl, transition metal chlorides, or any combination thereof.
Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded May 23, 2025
From: UNIVERSITY OF VIRGINIA
To: UNIVERSITY OF VIRGINIA PATENT FOUNDATION
Reel/Frame 071205/0124 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded May 23, 2025
From: GUNNOE, THOMAS B.
To: UNIVERSITY OF VIRGINIA
Reel/Frame 071342/0453 →
CONFIRMATORY LICENSE
Recorded Feb 16, 2022
From: UNIVERSITY OF VIRGINIA
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 059168/0277 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Dec 7, 2021
From: GODDARD, WILLIAM A., III
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 058324/0146 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Dec 2, 2021
From: GROVES, JOHN T.
To: THE TRUSTEES OF PRINCETON UNIVERSITY
Reel/Frame 058265/0886 →
Continuity (2)
Provisional Application
62817594
· Mar 13, 2019
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