Compositions and processes of preparing and using the same

Patent metadata

Field	Value
Publication number	US-9359277-B2
Application number	US-201214006386-A
Country	US
Kind code	B2
Filing date	Mar 22, 2012
Priority date	Mar 22, 2011
Publication date	Jun 7, 2016
Grant date	Jun 7, 2016

Abstract

The present invention relates to compositions, for example, the DBU/Hexafluoroacetone hydrate salt, and processes of preparing and using the same for the modification of chemical compounds via the release of trifluoroacetate. The DBU/Hexafluoroacetone hydrate salt can perform trifluoromethylation reactions on chemical compounds, such as carbonyl group-containing compounds.

First claim

What is claimed is:

1. A composition comprising a base and a compound of Formula (I)

wherein
R 1 is H, halo, or C 1-8 alkyl;
R 2 is H, halo, or C 1-8 alkyl; and
R 3 is H, halo, C 2-8 alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, (CO)R 6 , (CO)OR 6 , (CO)SR 6 , (CO)NR 6 R 7 , (SO 2 )R 6 , (PO)R 6 R 7 , or C(NR 6 )R 7 , wherein R 6 and R 7 are independently selected from H, C 1-8 alkyl, O—C 1-5 alkyl, C 3-6 cycloalkyl, aryl-C 1-5 alkyl, and heteroaryl-C 1-5 alkyl, aryl, substituted aryl, heteroaryl, and substituted heteoaryl
or R 2 and R 3 , together with the carbon atom to which they are attached, form a 4-7 membered cycloalkyl group or cyclo(hetero)alkyl group.

2. The composition of claim 1 , wherein the base is an organic base.

3. The composition of claim 1 , wherein the base is an amine compound.

4. The composition of claim 1 , wherein the base is DBU.

5. The composition of claim 1 , wherein R 1 is halo and R 2 is halo.

6. The composition of claim 1 , wherein R 1 is fluoro, R 2 is fluoro, and R 3 is fluoro.

7. The composition of claim 1 , wherein said composition is anhydrous.

8. A hexafluoroacetone hydrate and DBU salt represented by the formula:

9. A process for the modification of a chemical compound via the release of trifluoroacetate, the process comprising the step of
(a) reacting the chemical compound with a composition comprising a base and a compound of Formula (I)

wherein:
R 1 is H, halo, or C 1-8 alkyl;
R 2 is H, halo, or C 1-8 alkyl; and
R 3 is H, halo, C 2-8 alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, (CO)R 6 , (CO)OR 6 , (CO)SR 6 , (CO)NR 6 R 7 , (SO 2 )R 6 , (PO)R 6 R 7 , or C(NR 6 )R 7 , wherein R 6 and R 7 are independently selected from H, C 1-8 alkyl, O—C 1-5 alkyl, C 3-6 cycloalkyl, aryl-C 1-5 alkyl, and heteroaryl-C 1-5 alkyl, aryl, substituted aryl, heteroaryl, and substituted heteoaryl;
or R 2 and R 3 , together with the carbon atom to which they are attached, form a 4-7 membered cycloalkyl group or cyclo(hetero)alkyl group.

10. A process for preparing a composition comprising a base and a compound of formula (I)

wherein:
R 1 is H, halo, or C 1-8 alkyl;
R 2 is H, halo, or C 1-8 alkyl; and
R 3 is H, halo, C 2-8 alkenyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, (CO)R 6 , (CO)OR 6 , (CO)SR 6 , (CO)NR 6 R 7 , (SO 2 )R 6 , (PO)R 6 R 7 , or C(NR 6 )R 7 , wherein R 6 and R 7 are independently selected from H, C 1-8 alkyl, O—C 1-5 alkyl, C 3-6 cycloalkyl, aryl-C 1-5 alkyl, and heteroaryl-C 1-5 alkyl, aryl, substituted aryl, heteroaryl, and substituted heteoaryl;
or R 2 and R 3 , together with the carbon atom to which they are attached, form a 4-7 membered cycloalkyl group or cyclo(hetero)alkyl group,

the process comprising the step of
(a) reacting the base with the compound of Formula (I) in a solvent to form the composition.

11. The process of claim 10 , wherein the base is an organic base.

12. The process of claim 10 , wherein the base is DBU.

13. The process of claim 10 , wherein the solvent is diethyl ether.

14. The process of claim 10 , wherein the composition is the DBU/Hexafluoroacetone hydrate salt.

15. The process of claim 9 , wherein the chemical compound is an aldehyde or a ketone.

16. The process of claim 9 , wherein the chemical compound undergoes a trifluoromethylation reaction.

17. The process of claim 9 , comprising the step of adding the base to a solution comprising the chemical compound and the compound of Formula (I).

18. The process of claim 17 , wherein the chemical compound is an aldehyde.

19. The process of claim 17 , wherein the base is triethylamine.

20. The process of claim 17 , wherein the compound of Formula (I) is a compound of Formula (III)

wherein
R 4 is R 6 , OR 6 , SR 6 , or NR 6 R 7 , wherein R 6 and R 7 are independently selected from H, C 1-8 alkyl, O—C 1-5 alkyl, C 3-6 cycloalkyl, aryl-C 1-5 alkyl, and heteroaryl-C 1-5 alkyl, aryl, substituted aryl, heteroaryl, and substituted heteoaryl.

Assignees

• Colby David A
• Riofski Mark V
• Han Changho
• Purdue Research Foundation

Inventors

• Colby David A
• Riofski Mark V
• Han Changho

Classifications

• C07C205/45

  the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group · CPC title

• C07C49/807

  all halogen atoms bound to the ring · CPC title

• C07C2102/42

  Chemistry & Metallurgy · mapped topic

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C49/573

  containing hydroxy groups · CPC title