Environmentally-friendly hydroazidation of olefins

Patent metadata

Field	Value
Publication number	US-2021284601-A1
Application number	US-201917253966-A
Country	US
Kind code	A1
Filing date	Jun 28, 2019
Priority date	Jun 29, 2018
Publication date	Sep 16, 2021
Grant date	—

Abstract

The present invention provides processes for the synthesis of organic azides, intermediates for the production thereof, and compositions related thereto.

First claim

1 . A process for preparing an organic azide of Formula III comprising mixing an olefin of Formula I, a silylazide of Formula II, a hydrogen bond donor, and an organic promoter:

wherein:
R 1 and R 2 are independently selected from hydrogen, alkyl, cycloalkyl, heteroalkyl, and heterocycloalkyl, wherein each of R 1 and R 2 that is not hydrogen is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ;
wherein at least one of R 1 and R 2 is not hydrogen;
R 3 is selected from hydrogen, alkyl, cycloalkyl, heteroalkyl, and heterocycloalkyl, wherein R 3 other than hydrogen is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ; or
R 1 and R 2 or R 2 and R 3 are taken together with the carbons to which they are attached to form a cycloalkyl ring or an heterocycloalkyl ring, wherein each cycloalkyl or heterocycloalkyl ring is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ;
R 4 is independently selected at each occurrence from alkyl and cycloalkyl;
the organic promoter is selected from:

R 5 is independently selected from hydrogen, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)R 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)R 7 ;
m is 1, 2, 3, or 4;
Z is I;
R 6 and R 6′ are independently selected from —O(C═O)R 7 , —O(SO 2 )(R 7 ), hydroxyl, and azido;
R 7 is independently selected at each occurrence from hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, cycloalkyl, heterocycloalkyl, and trialkylsilyl, each of which R 7 other than hydrogen is optionally substituted with one or more substituents selected from alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, amino, alkylamino, dialkylamino, hydroxyl, halo, acylamino, aminoacyl, cyano, nitro, azido, acyl, acyloxy, carboxyl, carboxyl ester, alkanoyl, carboxamide, haloalkyl, and haloalkoxy; or
two R 7 groups may be brought together with the atoms to which they are attached to form a cycloalkyl, heterocycloalkyl, aryl, or heteroaryl ring, each of which ring is optionally substituted with one or more substituents selected from alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, amino, alkylamino, dialkylamino, hydroxyl, halo, acylamino, aminoacyl, cyano, nitro, azido, acyl, acyloxy, carboxyl, carboxyl ester, alkanoyl, carboxamide, haloalkyl, and haloalkoxy;
R 8 and R 8′ are independently selected from hydrogen, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)R 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ; or
R 8 and R 8′ may be brought together with the carbon to which they are attached to form a cycloalkyl or heterocycloalkyl ring, each of which ring is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ; or
R 8 and R 8′ are brought together to form an oxo or imino group;
R 9 is aryl or heteroaryl, wherein R 9 is optionally substituted with one or more substituents selected from oxo, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ; and
the hydrogen bond donor is water and optionally a second hydrogen bond donor.

2 - 4 . (canceled)

5 . The process of claim 1 , wherein the olefin of Formula I is selected from

6 . The process of claim 1 , wherein the olefin of Formula I is selected from

7 - 15 . (canceled)

16 . The process of claim 1 , wherein the hydrogen bond donor is water.

17 . The process of claim 1 , wherein the hydrogen bond donor is water and a second hydrogen bond donor selected from formic acid, an alkylcarboxylic acid, a (cycloalkyl)carboxylic acid, a (heteroalkyl)carboxylic acid, a (heterocycloalkyl)carboxylic acid, an arylcarboxylic acid, an (heteroaryl)carboxylic acid, sulfuric acid, an alkylsulfonic acid, a (cycloalkyl)sulfonic acid, a (heteroalkyl)sulfonic acid, a (heterocycloalkyl)sulfonic acid, a arylsulfonic acid, and a (heteroaryl)sulfonic acid.

18 . The process of claim 17 , wherein the hydrogen bond donor is water and trifluoroacetic acid.

19 - 22 . (canceled)

23 . The process of claim 1 , wherein the organic promoter is

24 . The process of claim 23 , wherein the organic promoter is selected from

25 . (canceled)

26 . The process of claim 1 , wherein the organic promoter is

27 . The process of claim 26 , wherein the organic promoter is selected from

wherein o is 1, 2, 3, 4, or 5.

28 . The process of claim 24 , wherein R 7 is trifluoromethyl or trichloromethyl.

29 . The process of claim 1 , wherein R 4 is alkyl.

30 . The process of claim 1 , wherein the silylazide of Formula II is trimethylsilylazide or triethylsilylazide.

31 . (canceled)

32 . A compound of Formula VII or Formula VIII

wherein
R 4 is independently selected at each occurrence from alkyl and cycloalkyl;
R 5 is independently selected from hydrogen, halo, cyano, azido, nitro, R 7 , —OR 7 , —N(R 7 )(R 7 ), —(C═O)R 7 , —(C═O)OR 7 , —(C═O)N(R 7 )(R 7 ), —O(C═O)R 7 , —N(R 7 )(C═O)R 7 , —O(C═O)N(R 7 )(R 7 ), and —N(R 7 )(C═O)OR 7 ;
R 7 is independently selected at each occurrence from hydrogen, alkyl, aryl, heteroalkyl, heteroaryl, cycloalkyl, heterocycloalkyl, and trialkylsilyl, each of which R 7 other than hydrogen is optionally substituted with one or more substituents selected from alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, amino, alkylamino, dialkylamino, hydroxyl, halo, acylamino, aminoacyl, cyano, nitro, azido, acyl, acyloxy, carboxyl, carboxyl ester, alkanoyl, carboxamide, haloalkyl, and h

Assignees

• Univ Georgia State Res Found

Inventors

• Xu Hao

Classifications

• C07D347/00 Primary

  Heterocyclic compounds containing rings having halogen atoms as ring hetero atoms · CPC title

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• C07C247/14

  with azido groups bound to carbon atoms of rings other than six-membered aromatic rings · CPC title

• C07D209/48

  with oxygen atoms in positions 1 and 3, e.g. phthalimide · CPC title

• C07C247/12

  being further substituted by carboxyl groups · CPC title