Direct oxidative amination of hydrocarbons

Patent metadata

Field	Value
Publication number	US-2020377448-A1
Application number	US-201816767831-A
Country	US
Kind code	A1
Filing date	Nov 30, 2018
Priority date	Dec 1, 2017
Publication date	Dec 3, 2020
Grant date	—

Abstract

Provided is a process for converting a hydrocarbon comprising at least one C—H bond to a nitrogen-functionalized product. The process comprises contacting a hydrocarbon and (i) an oxidizing electrophile comprising (a) a main group element or transition metal in oxidized form and (b) at least one nitrogen-containing ligand, or (ii) an oxidant and a reduced form of an oxidizing electrophile comprising (a) a main group element or transition metal and (b) at least one nitrogen-containing ligand, in a solvent to provide the nitrogen-functionalized product and an electrophile reduction product. Further provided is an oxidizing composition comprising the oxidizing electrophile with at least one nitrogen-containing ligand and a non-oxidizable liquid.

First claim

1 . A process for converting a hydrocarbon comprising at least one C—H bond to a nitrogen-functionalized product, comprising
contacting the hydrocarbon and
(i) an oxidizing electrophile comprising (a) a main group element or transition metal in oxidized form and (b) at least one nitrogen-containing ligand, or
(ii) an oxidant and a reduced form of an oxidizing electrophile comprising (a) a main group element or transition metal and (b) at least one nitrogen-containing ligand,
in a solvent to provide the nitrogen-functionalized product and an electrophile reduction product; and
optionally separating the nitrogen-functionalized product and the electrophile reduction product.

2 . The process of claim 1 , comprising separating the nitrogen-functionalized product and the electrophile reduction product.

3 . The process of claim 1 , further comprising contacting the nitrogen-functionalized product with a compound of the formula H-Nu to form an amine, wherein Nu is a nucleophilic group that enables the formation of the amine

4 . The process of claim 3 , wherein Nu is oxide, hydroxide, alkoxide, aryloxide, carboxylate, thiolate, bisulfide, optionally protected amide, or optionally protected azanide.

5 . The process of claim 3 , wherein Nu is —O, —OR 1 , —CO 2 R 1 , —S, —SR 1 , —NR 1 , —NHR 1 , or —NR 1 R 2 , in which R 1 and R 2 are the same or different and each is hydrogen, aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

6 . (canceled)

7 . (canceled)

8 . (canceled)

9 . The process of claim 3 , wherein the amine comprises a monoamine, a diamine, or both a monoamine, and a diamine

10 . The process of claim 1 , further comprising contacting the electrophile reduction product and an oxidizing regeneration reagent to regenerate the oxidizing electrophile.

11 . (canceled)

12 . The process of claim 1 , wherein the hydrocarbon is selected from alkane, alkene, alkyne, cycloalkane, cycloalkene, heterocycloalkane, heterocycloalkene, arene, and heteroarene, each of which is optionally substituted.

13 . (canceled)

14 . The process of claim 1 , wherein the oxidizing electrophile comprises the element mercury, thallium, lead, antimony, selenium, tellurium, bismuth, iodine, gold, platinum, palladium, silver, iridium, rhodium, osmium, or rhenium.

15 . The process of claim 1 , wherein the at least one nitrogen-containing ligand has the formula —NH n Y 2-n , wherein Y is an electron withdrawing group and n is 0 or 1.

16 . The process of claim 15 , wherein Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

17 . The process of claim 16 , wherein Y is —COR, —C(O)OR, —C(O)NRR′, or —SO 2 R, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

18 . The process of claim 1 , wherein the oxidizing electrophile is of the formula M m (NH n Y 2-n ) p , wherein
M is a main group or transition metal cation, Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic, m is the formal oxidation state of M, n is 0 or 1, and p is 1 to m.

19 . The process of claim 18 , wherein m is 1-8.

20 . The process of claim 1 , wherein the solvent is a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, a compound of the formula HNY 2 or H 2 NY, and any combination thereof, wherein Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, and R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

21 . (canceled)

22 . An oxidizing composition comprising
(a) an oxidizing electrophile comprising a main group element or transition metal in oxidized form and at least one nitrogen-containing ligand; (b) a non-oxidizable liquid selected from the group consisting of a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, a compound of the formula HNY 2 or H 2 NY, and a combination thereof, wherein Y is an electron-withdrawing group; and (c) optionally one or more additives of the formula Z a (NH n Y 2-n ) p , wherein Z is a cation, Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, in which R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic, a is 1 to 5, n is 0 or 1, and p is 1 to 5.

23 . The oxidizing composition of claim 22 , wherein the oxidizing electrophile comprises the element mercury, thallium, lead, antimony, selenium, tellurium, bismuth, iodine, gold, platinum, palladium, silver, iridium, rhodium, osmium, or rhenium.

24 . The oxidizing composition of claim 22 , wherein the at least one nitrogen-containing ligand has the formula —NH n Y 2-n , wherein Y is an electron withdrawing group and n is 0 or 1.

25 . The process of claim 24 , wherein Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 S 2 O, —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

26 . (canceled)

27 . The oxidizing composition of claim 22 , wherein the oxidizing electrophile is of the formula M m (NH n Y 2-n ) p , wherein
M is a main group or transition metal cation, Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic, m is the formal oxidation state of M, n is 0 or 1, and p is 1 to m.

28 . The oxidizing composition of claim 27 , wherein m is 1-8.

29 . The oxidizing composition of claim 22 , wherein the composition further comprises an oxidizing regeneration reagent.

30 . (canceled)

31 . The oxidizing composition of claim 22 , wherein at least one additive of the formula Z a (NH n Y 2-n ) p is present.

Assignees

• Scripps Research Inst
• Hyconix Inc

Inventors

• Periana Roy A
• Hashiguchi Brian G
• Park Sae Hume
• Gunsalus Niles Jensen

Classifications

• C07B43/06

  of amide groups · CPC title

• C07B43/04

  of amino groups · CPC title

• C07B43/00

  Formation or introduction of functional groups containing nitrogen · CPC title

• C07C209/62

  by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds (C07C209/24 takes precedence) · CPC title

• C07C303/40 Primary

  by reactions not involving the formation of sulfonamide groups · CPC title