Compositions containing ionic liquids and their uses, in particular in organic synthesis

Patent metadata

Field	Value
Publication number	US-9452425-B2
Application number	US-46302709-A
Country	US
Kind code	B2
Filing date	May 8, 2009
Priority date	Sep 26, 2002
Publication date	Sep 27, 2016
Grant date	Sep 27, 2016

Abstract

An ionic liquid is used as liquid matrix for organic synthesis in homogeneous phase on soluble support, the ionic liquid being presented in liquid or solid form at ambient temperature, of formula A 1 + X 1 − , A 1 + representing a cation, functional or non-functional, or a mixture of cations in which either none of the cations is functional or at least one of the cations is functional, and X 1 − an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional.

First claim

The invention claimed is:

1. A method of performing a Heck coupling reaction in a homogeneous phase on a soluble reaction support, without volatile organic solvents, comprising:
(i) dissolving a soluble reaction support in the form of a functionalized onium salt in a liquid matrix in the form of a ionic liquid of formula A 1 + X 1 − to form a composition, wherein said ionic liquid of formula A 1 + X 1 − is not functionalized;
(ii) adding at least one reagent to the composition obtained in step (i); and
(iii) converting the chemical function(s) of said functionalized onium salt to provide a Heck coupling on the soluble reaction support, without volatile organic solvents, wherein,
said non-functionalized ionic liquid of formula A 1 + X 1 − is in liquid or solid form at ambient temperature,
A 1 + is a non organic-functional cation or a mixture of non organic-functional cations, and
X 1 − a non organic-functional anion or a mixture of non organic-functional anions.

2. A method of performing a Heck coupling reaction in a homogeneous phase on a soluble reaction support, without volatile organic solvents, comprising:
(i) dissolving a soluble reaction support in the form of a functionalized onium salt in a liquid matrix in the form of a ionic liquid of formula A 1 + X 1 − to form a composition, wherein said ionic liquid of formula A 1 + X 1 − is not functionalized,
(ii) adding at least one reagent to the composition obtained in step (i); and
(iii) converting the chemical function(s) of said functionalized onium salt to provide a Heck coupling on the soluble reaction support, without volatile organic solvents, wherein,
said non-functionalized ionic liquid of formula A 1 + X 1 − is in liquid or solid form at ambient temperature,
A 1 + is a non organic-functional cation or a mixture of cations in which none of the cations is organic functional,
X 1 − is a non organic-functional anion or a mixture of anions in which none of the anions is organic functional,
said soluble reaction support is at least one organic functionalized salt of formula A 2 + X 2 − ,
A 2 + is selected from the group consisting of an organic functional cation, a non organic-functional cation, a mixture of cations in which none of the cations is organic functional, and a mixture of cations in which at least one of the cations is organic functional,
X 2 − is selected from the group consisting of an organic functional anion, non organic-functional anion, a mixture of anions in which none of the anions is organic functional, and a mixture of anions in which at least one of the anions is organic functional, and
at least one of A 2 + and X 2 − is a organic functional ion,
said organic functional cation is of a formula Y + -L-F i , and said organic functional anion is of a formula Y − -(L) k -F i ,
Y + — and Y − — are ionic entities, the charge of which corresponding to the charge of the cation of formula Y − -L-F i and the charge of the anion of formula Y − -(L) k -F i , respectively, linked via a linker L to at least one organic function F i ,
L is an alkyl group of 1 to 20 carbon atoms,
F i varies from F 0 to F n , n being an integer varying from 1 to 10, with F 0 being an organic function initially linked to said cationic entities and anionic entities and F 1 to F 10 being organic functions converted from said Fo after sequential and subsequent reactions with said cationic or anionic entities,
said organic function F i is selected from the group consisting of hydroxyl, carboxylic, amide, sulphone, primary amine, secondary amine, aldehyde, ketone, ethenyl, ethynyl, dienyl, ether, epoxide, primary phosphine, secondary phosphine, tertiary phosphine, azide, imine, ketene, cumulene, heterocumulene, thiol, thioether, sulphoxide, phosphorus-containing moieties, heterocycles, sulphonic acid, silane, stannane and functional aryl functions,
k is equal to 0 or 1 so that when k is equal to 0,
Y − —F i is selected from the group consisting of OH − , F − , CN − , RO − or RS − , and
R is an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 30 carbon atoms.

3. The method of claim 2 , wherein,
at least one of the A 2 + cation and the X 2 − anion of the at least one organic functionalized salt corresponding to a Y— ionic entity linked to at least one organic function F i , is immobilized in the liquid matrix and cannot be extracted from the liquid matrix by solvent extraction, and
the organic function or functions F i of the at least one organic functionalized salt can be converted after at least one reaction resulting from the addition of at least one reagent to said composition.

4. The method of claim 3 , wherein more than one organic functionalized salt is immobilized.

5. The method of claim 2 , wherein A 2 + cation is organic functional.

6. The method of claim 2 , wherein the X 2 − anion is organic functional.

7. The method of claim 2 , wherein A 2 + and X 2 − are organic functional.

8. The method of claim 2 , wherein,
said A 1 + X 1 − is an ionic liquid that is solid at ambient temperature and liquefiable with a temperature range from approximately 25° C. to approximately 250° C., and
said organic functionalized salt A 2 + X 2 − is selected from the group consisting of: an ionic liquid that is solid at ambient temperature and that is soluble in a liquefied solid form of A 1 + X 1 − , and
an ionic liquid that is a liquid at ambient temperature and that is miscible with the liquefied solid form of A 1 + X 1 − .

9. The method of claim 2 , wherein,
said A 1 + X 1 − is an ionic liquid that is liquid at ambient temperature, and
said organic functionalized salt A 2 + X 2 − is selected from the group consisting of: an ionic liquid that is solid at ambient temperature and that is soluble or partially soluble in the liquid form of A 1 + X 1 − within a temperature range from approximately 25° C. to approximately 250° C., and an ionic liquid that is liquid at ambient temperature and that is miscible with the liquid form of A 1 + X 1 − .

10. The method of claim 1 , wherein said non-functionalized ionic liquid of formula A 1 + X 1 − has a viscosity less than or equal to approximately 1500 cp (15 N·s/m 2 ).

11. A method of performing a Heck coupling reaction,
in a stable composition comprising, in solution:
an non-functionalized ionic liquid of formula A 1 + X 1 − providing a liquid matrix; and
one organic functionalized salt of formula A 2 + X 2 − providing a soluble reaction support and being dissolved in the liquid matrix so that the composition forms a homogeneous phase, wherein,
A 1 + is a non organic-functional cation or a mixture of cations in which none of the cations is organic functional,
X 1 − is a non organic-functional anion or a mixture of anions in which none of the anions is organic functional,
A 2 + is selected from the group consisting of an organic functional cation, non organic-functional cation, a mixture of cations in which none of the cations is organic functional, and a mixture of cations in which at least one cation is organic functional, X 2 − is selected from the group consisting of an organic functional anion, a non organic-functional anion, a mixture of anions in which none of the anions is organic functional, and a mixture of anions in which at least one anion is organic functional, at least one of A 2 + and X 2 − is an organic functional ion, said organic functional cation is of a formula Y + -L-F i , and said organic functional anion is of a formula Y − -(L) k -F i ,
Y + — and Y − are ionic entities, the charge of which corresp

Assignees

• Vaultier Michel
• Gmouh Said
• Centre Nat Rech Scient
• Univ Rennes

Inventors

• Vaultier Michel
• Gmouh Said

Classifications

• B01J31/0224

  being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds · CPC title

• C07B37/12

  Diels-Alder reactions · CPC title

• B01J31/0281 Primary

  the nitrogen being a ring member · CPC title

• C07C69/65

  of unsaturated acids · CPC title

• B01J2231/326

  Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues · CPC title