Decomposition of organic peroxides and hydrogen peroxide by the iron thiolates and related complexes

Patent metadata

Field	Value
Publication number	US-11242296-B2
Application number	US-201916514423-A
Country	US
Kind code	B2
Filing date	Jul 17, 2019
Priority date	Jul 18, 2018
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

Disclosed herein is a method of reducing or disproportionating peroxide, comprising combining an organic chalcogenide, an iron salt, and the peroxide in the presence of an additional reductant, which can be the organic chalcogenide. The method can be used to, e.g., prepare alcohols from peroxides and to disproportionate hydrogen peroxide into water and oxygen.

First claim

What is claimed is:

1. A method of decomposing a peroxide of Formula I:
R 1 —O—O—R 2   (Formula I)

wherein:
each of R 1 and R 2 is independently selected from the group consisting of:
(i) hydrogen;
(ii) C 1-10 alkyl optionally substituted with 1-4 R a ;
(iii) C 3-10 alkenyl optionally substituted with 1-4 R a ;
(iv) C 3-10 alkynyl optionally substituted with 1-4 R a ;
(v) C 6-10 aryl optionally substituted with 1-4 R a ;
(vi) 5-10 membered heteroaryl including 5-10 ring atoms, wherein 1-4 ring atoms are each independently selected from the group consisting of N, NH, O, and S, wherein the heteroaryl is optionally substituted with 1-4 R a ;
(vii) C 3-10 cycloalkyl that is optionally substituted with 1-4 R a ;
(vii) 5-10 membered heterocyclyl including 3-10 ring atoms, wherein 1-3 ring atoms are each independently selected from the group consisting of N, NH and O, wherein the heterocyclyl is optionally substituted with 1-4 R a ;
(viii) —C(O)R b ;
(ix) —CO 2 R b ;
(x) —Si(R′) 3 ;

each occurrence of R a is independently selected from the group consisting of:
(i) C 1-8 alkyl substituted with 1-3 R b ;
(ii) (C 0-6 alkylene)-C 3-10 cycloalkyl, wherein the cycloalkyl is optionally substituted with from 1-4 R b ;
(iii) (C 0-6 alkylene)-heterocyclyl including 3-10 ring atoms, wherein 1-3 ring atoms are each independently selected from the group consisting of NH, O, and S, wherein the heterocyclyl is optionally substituted with 1-4 R b ;
(iv) (C 0-6 alkylene)-(C 6-10 aryl), wherein the aryl is optionally substituted with 1-5 R b ; or
(v) (C 0-6 alkylene)-heteroaryl including 5-10 ring atoms, wherein 1-4 ring atoms are each independently selected from the group consisting of N, NH, O, and S, wherein the heteroaryl is optionally substituted with 1-3 R b ;
(vi) C 1-4 alkoxy optionally substituted with 1-3 R b ;
(vii) C 1-4 haloalkoxy;
(viii) —COH;
(ix) —CO 2 R b ;
(x) —CONR b R b ;
(xi) cyano;
(xii) —NR b R b ;
(xiii) —NR b C(O)NR b R b ;
(xiv) —NR b C(O)OR b ;
(xv) —NR b C(O)R b ;
(xvi) C 1-4 thioalkoxy;
(xvii) —N 3 ;
(xviii) —CO 2 H;
(xix) —C(O)R b ;
(xx) —SO 1-2 (R b );
(xxi) —O n P(O) n Y 2 , wherein n is independently 0 or 1, and wherein each Y is independently selected from —OR b and C 1-6 alkyl;
(xxii) —O—O—R c ;
(xxiii) —(O—O—CH 2 CH 2 ) m —O—OR′″, wherein m is an integer from 1-1000; and

alternatively, any two R a , taken together with the atoms they are bonded to and any atoms that intervene the atoms they are bonded to, form a ring selected from:
(i) a C 3-10 cycloalkyl, wherein the a C 3-10 cycloalkyl is optionally substituted with 1-6 R b ;
(ii) a 5-10-membered heterocyclyl comprising 1-6 heteroatoms selected O, S, and N, wherein the heterocyclyl is optionally substituted with 1-6 R b ;
(iii) a C 6-10 aryl, wherein the aryl is optionally substituted with 1-6 R b ; and
(iv) a 5-10 membered heteroaryl comprising 1-6 heteroatoms selected O, S, and N, wherein the heteroaryl is optionally substituted with 1-6 R b ; and
5-10-membered heterocyclyl comprising 1-6 heteroatoms selected O, S, and N, wherein the heterocyclyl is optionally substituted with 1-6 R b ;
each occurrence of R b is independently selected from the group consisting of:
(i) halo;
(ii) cyano;
(iii) C 1-6 alkyl;
(iv) C 2-6 alkenyl;
(v) C 2-6 alkynyl;
(vi) C 1-4 haloalkyl;
(vii) C 1-4 alkoxy;
(viii) C 1-4 haloalkoxy;
(ix) —(C 0-3 alkylene)-C 3-6 cycloalkyl optionally substituted with 1-4 independently selected C 1-4 alkyl;
(x) —(C 0-3 alkylene)-heterocyclyl including 3-10 ring atoms, wherein 1-3 ring atoms are each independently selected from the group consisting of NH, O, and S, wherein the heterocyclyl is optionally substituted with 1-4 independently selected C 1-4 alkyl;
(xi) —(C 0-3 alkylene)-phenyl;
(xii) —(C 0-3 alkylene)-heteroaryl including 5-10 ring atoms, wherein 1-4 ring atoms are each independently selected from the group consisting of N, NH, O, and S;
(xiii) —S(O) 1-2 (C 1-4 alkyl); and
(xiv) —NR′R″;
(xv) —OH;
(xvi) —S(O) 1-2 (NR′R″);
(xvii) —C 1-4 thioalkoxy;
(xviii) —NO 2 ;
(xix) —N(R′)(C(═O)C 1-3 alkyl);
(xx) —C(═O)(C 1-4 alkyl);
(xxi) —C(═O)O(C 1-4 alkyl);
(xxii) —C(═O)OH, and
(xxiii) —C(═O)N(R′)(R″); and

alternatively, any two R b , taken together with the atoms they are bonded to and any atoms that intervene the atoms they are bonded to, form a ring selected from:
(i) a C 3-10 cycloalkyl, wherein the a C 3-10 cycloalkyl is optionally substituted with 1-6 R d ;
(ii) a 5-10-membered heterocyclyl comprising 1-6 heteroatoms selected O, S, and N, wherein the heterocyclyl is optionally substituted with 1-6 R d ;
(iii) a C 6-10 aryl, wherein the aryl is optionally substituted with 1-6 R d ; and
(iv) a 5-10 membered heteroaryl comprising 1-6 heteroatoms selected O, S, and N, wherein the heteroaryl is optionally substituted with 1-6 R d ; and
5-10-membered heterocyclyl comprising 1-6 heteroatoms selected O, S, and N, wherein the heterocyclyl is optionally substituted with 1-6 R d ;
each occurrence of R c is independently selected from the group consisting of:
(i) hydrogen;
(ii) C 1-10 alkyl optionally substituted with 1-4 R d ;
(iii) C 3-10 alkenyl optionally substituted with 1-4 R d ;
(iv) C 3-10 alkynyl optionally substituted with 1-4 R d ;
(v) C 6-10 aryl optionally substituted with 1-4 R d ;
(vi) 5-10 membered heteroaryl including 5-10 ring atoms, wherein 1-4 ring atoms are each independently selected from the group consisting of N, NH, O, and S, wherein the heteroaryl is optionally substituted with 1-4 R d ;
(vii) C 3-10 cycloalkyl that is optionally substituted with 1-4 R d ;
(vii) 5-10 membered heterocyclyl including 3-10 ring atoms, wherein 1-3 ring atoms are each independently selected from the group consisting of N, NH and O, wherein the heterocyclyl is optionally substituted with 1-4 R d ;
(viii) —C(O)R b ;
(ix) —CO 2 R b ; and
(x) —Si(R′) 3 ;

each occurrence of R d is independently selected from the group consisting of:
(i) C 1-8 alkyl substituted with 1-3 R b ;
(ii) (C 0-6 alkylene)-C 3-10 cycloalkyl, wherein the cycloalkyl is optionally substituted with from 1-4 R b ;
(iii) (C 0-6 alkylene)-heterocyclyl including 3-10 ring atoms, wherein 1-3 ring atoms are each independently selected from the group consisting of NH, O, and S, wherein the heterocyclyl is optionally substituted with 1-4 R b ;
(iv) (C 0-6 alkylene)-(C 6-10 aryl), wherein the aryl is optionally substituted with 1-5 R b ; or
(v) (C 0-6 alkylene)-heteroaryl including 5-10 ring atoms, wherein 1-4 ring atoms are each independently selected from the group consisting of N, NH, O, and S, wherein the heteroaryl is optionally substituted with 1-3 R b ;
(vi) C 1-4 alkoxy optionally substituted with 1-3 R b ;
(vii) C 1-4 haloalkoxy;
(viii) —COH;
(ix) —CO 2 R b ;
(x) —CONR b R b ;
(xi) cyano;
(xii) —NR b R b ;
(xiii) —NR b C(O)NR b R b ;
(xiv) —NR b C(O)OR b ;
(xv) —NR b C(O)R b ;
(xvi) C 1-4 thioalkoxy;
(xvii) —N 3 ;
(xviii) —CO 2 H;
(xix) —C(O)R b ;
(xx) —SO 1-2 (R b ); and
(xxi) —O n P(O) n Y 2 , wherein n is independently 0 or 1, and wherein each Y is independently selected from —OR b and C 1-6 alkyl; and

each occurrence of R′, R″, and R′″ is independently selected from the group consisting of: H, C 1-4 alkyl, and phenyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including 3-8 ring atoms, wherein the ring includes: (a) 1-7 ring carbon atoms; and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S;
alternatively, R 1 and R 2 , taken together with the oxygen atoms they are bonded to, form a 5-10-membered heterocyclyl comprising 1-6 heter

Assignees

• Nutech Ventures

Inventors

• Dussault Patrick H
• Olson Andrew

Classifications

• C07B41/02 Primary

  of hydroxy or O-metal groups · CPC title