Process for the preparation of N-iodoamides

Patent metadata

Field	Value
Publication number	US-9637462-B2
Application number	US-201415034751-A
Country	US
Kind code	B2
Filing date	Nov 5, 2014
Priority date	Nov 7, 2013
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

The present invention provides new stable crystalline N-iodoamides-1-iodo-3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.

First claim

What is claimed is:

1. A process for the preparation of organic iodide comprising the steps of:
(a) reacting an amide with iodine and [bis(acyloxy)iodo]arene in aprotic solvent to yield N-iodoamide and iodoarene as co-product;
(b) reacting an organic compound with said N-iodoamide of step (a) to yield desired organic iodide and amide as co-product; and
(c) recovering said amide co-product from the reaction mixture of step (b);
wherein said amide is 4,4-dimethyloxazolidin-2-one, saccharin or 3,5,5-trimethylhydantoin and said N-iodoamide is 3-iodo-4,4-dimethyloxazolidin-2-one (IDMO), N-iodosaccharin (NISac) or 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), respectively.

2. The process of claim 1 , wherein said organic compound is a carboxylic acid, an alkene, an alkyne, an alkane, a cycloalkane, methylarene, ketone, aromatic compound or combination thereof.

3. The process of claim 2 , wherein said carboxylic acid is a compound of formula R—CO 2 H and said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH) or 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO); wherein R is saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted aryl; substituted or unsubstituted Ph(CH 2 ) p — wherein p is an integer between 1 and 6, saturated substituted or unsubstituted cycloalkyl, heterocycloalkyl or combination thereof and wherein said organic iodide is R—I;
wherein said reaction of step (b) is radical iododecarboxylation represented by scheme (1):
R—CO 2 H+N-iodoamide→R—I+amide  (1)

wherein said reaction is provided under visual light irradiation of the reaction mixture.

4. The process of claim 2 , wherein said carboxylic acid is acrylic acid derivative of formula R—CH═CH—CO 2 H; said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), or N-iodosaccharin (NISac); wherein R is saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted aryl; substituted or unsubstituted Ph(CH 2 ) p — wherein p is an integer between 1 and 6; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl or combination thereof; and wherein said organic iodide is R—CH═CH—I;
wherein said reaction of step (b) is electrophylic iododecarboxylation of acrylic acid derivative represented by scheme (2):
R—CH═CH—CO 2 H+N-iodoamide→R—CH═CH—I+amide  (2)

wherein said reaction is provided under heterolytic reaction conditions; wherein said reaction further comprises a catalyst, wherein said catalyst is an organic base, LiOAc, Bu 4 N + , or CF 3 CO 2 − .

5. The process of claim 2 , wherein said carboxylic acid is propiolic acid derivative of formula R—C≡C—CO 2 H; wherein said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), or N-iodosaccharin (NISac); wherein R is saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted Ph(CH 2 ) p — wherein p is an integer between 1 and 6; substituted or unsubstituted aryl; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl ring or combination thereof; and wherein said organic iodide is R—C≡C—I;
wherein said reaction of step (b) is electrophylic iododecarboxylation of propiolic acid derivative represented by scheme (3):
R—C≡C—CO 2 H+N-iodoamide→R—C≡C—I+amide  (3)

wherein said reaction is provided under heterolytic reaction conditions; said reaction further comprises a catalyst, wherein said catalyst is an organic base, LiOAc, Bu 4 N + , or CF 3 CO 2 − .

6. The process of claim 2 , wherein said aromatic compound is a compound of formula Ar—H, said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), or N-iodosaccharin (NISac); wherein said Ar is substituted or unsubstituted aryl group; and wherein said organic iodide is Ar—I;
wherein said reaction of step (b) is electrophilic aromatic iodination represented by scheme (4):
Ar—H+N-iodoamide→Ar—I+amide  (4)

wherein said reaction is provided under heterolytic reaction conditions.

7. The process of claim 2 , wherein said methylarene is compound of formula ArCH 3 ; said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH) or 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO); wherein said Ar is substituted or unsubstituted aryl group; and wherein said organic iodide is ArCH 2 I;
wherein said reaction of step (b) is a radical iodination of methyl group of methylarene represented by scheme (5):
ArCH 3 +N-iodoamide→ArCH 2 I+amide  (5)

wherein said reaction is provided under visual light irradiation of the reaction mixture.

8. The process of claim 2 wherein said alkane or cycloalkane is compound of formula R 3 —H; said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH) or 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), wherein R 3 is linear or branched, substituted or unsubstituted alkyl or cycloalkyl; and wherein said organic iodide is R 3 —I;
wherein said reaction of step (b) is a radical iodination of alkane or cycloalkane represented by scheme (6):
R 3 —H+N-iodoamide→R 3 —I+amide  (6)

wherein said reaction is provided under visual light irradiation of the reaction mixture.

9. The process of claim 2 , wherein said alkene is compound of formula RCH═CHR 1 , wherein said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), or N-iodosaccharin (NISac); wherein R is saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted Ph(CH 2 ) p — wherein said p is an integer between 1 and 6; substituted or unsubstituted aryl; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl; R 1 is hydrogen, saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted aryl; substituted or unsubstituted Ph(CH 2 ) t — wherein t is an integer between 1 and 6; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl; and R and R 1 optionally form a ring;
wherein said reaction of step (b) is electrophilic iodination of alkene represented by scheme (7):
RCH═CHR 1 +N-iodoamide+HX→RCHXCHIR 1 +amide  (7)

wherein said reaction is provided under heterolytic reaction conditions;
wherein X is OH, halogen, alkoxy or acyloxy group; and wherein said organic iodide is RCHXCHIR 1 .

10. The process of claim 2 , wherein said alkyne is a compound of formula RC≡CR 1 , said N-iodoamide is 1-iodo-3,5,5-trimethylhydantoin (1-ITMH), 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO), or N-iodosaccharin (NISac); wherein R is saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted Ph(CH 2 ) p — wherein said p is an integer between 1 to and 6; substituted or unsubstituted aryl; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl; R 1 is hydrogen, saturated, linear or branched, substituted or unsubstituted alkyl; substituted or unsubstituted aryl; substituted or unsubstituted Ph(CH 2 ) t — wherein said t is an integer between 1 and 6; saturated or unsaturated, substituted or unsubstituted cycloalkyl or heterocycloalkyl;
wherein said reaction of step (b) is electrophilic iodination of alkyne represented by scheme (8):
RC≡CR 1 +N-iodoamide+HX→RCX=CIR 1 +amide  (8)

wherein said reaction is provided under heterolytic reaction conditions;
wherein X is OH, halogen, alkoxy, or acyloxy group; and wherein said organic iodide is RCX═CIR 1 or its tautomer, if X is OH.

11. The process of claim 2 , wherein said ketone is a compound of formula RCOCH 2 R 1 , said N-iodoamide is 1-iodo-3,5,5-trimethylhydan

Assignees

• Technion Res & Dev Foundation

Inventors

• Nisnevich Gennady
• Kulbitski Kseniya
• Gandelman Mark
• Artaryan Alexander

Classifications

• C07D275/06

  with hetero atoms directly attached to the ring sulfur atom · CPC title

• C07D233/82

  Halogen atoms · CPC title

• C07C23/10

  with a six-membered ring · CPC title

• C07C25/13

  containing fluorine · CPC title

• C07D207/46

  with hetero atoms directly attached to the ring nitrogen atom · CPC title