Mixed metal double salt ionic liquids with tunable acidity

Patent metadata

Field	Value
Publication number	US-10357762-B2
Application number	US-201715416575-A
Country	US
Kind code	B2
Filing date	Jan 26, 2017
Priority date	Jan 26, 2016
Publication date	Jul 23, 2019
Grant date	Jul 23, 2019

Abstract

Disclosed are double salt ionic liquids that include at least one organic cation and at least two metal halide anions. Methods of making the double salt ionic liquids can include combining two or more metal halide containing salts, wherein the metal halide containing salts include at least one organic cation and at least two metal halide anions. The reaction between the two or more salts at any ratio allows fine tuning, rate of dissolution, solubility, and bioavailability of the double salt ionic liquids. The ionic liquids disclosed herein can be used as a catalyst for catalyzing a chemical reaction. The chemical reaction can be an acid catalyzed chemical reaction such as a Lewis acid catalyzed reaction, a Beckmann rearrangement reaction, a Meyer-Schuster rearrangement reaction, a heterocyclic synthesis, a reaction for biodiesel production, a mercury-catalyzed type reaction, or a hydrogen-fluoride catalyzed type reaction.

First claim

What is claimed is:

1. An ionic liquid comprising a salt, wherein the salt comprises at least one organic cation and at least two metal halide anions with a melting point at or below about 150° C.,
wherein the at least two metal halide anions interact non-covalently, are present in a molar ratio from 1:1 to 1:9, and comprise a metal selected from aluminum, iron, chromium, zinc, copper, tin, titanium, palladium, zirconium, gallium, or combinations thereof, and
wherein when the at least one organic cation includes triethylammonium, the ionic liquid does not include chlorocuprate.

2. The ionic liquid of claim 1 , wherein the salt having the formula
[ n C i+m C 2 ][ x M 1 X a +(1− x )M 2 Y b ]

wherein
C 1 and C 2 are cations;
M 1 and M 2 are metals;
X a and Y b are halides;
n is a number from 0 to 5;
m is a number from 0 to 5;
x is a number from 0.1 to 0.9;
wherein the sum of n+m is greater than 0; and
wherein at least one of C 1 and C 2 comprises an organic cation.

3. The ionic liquid of claim 1 , wherein the at least one organic cation is selected from an alkylammonium, an arylammonium, an allylammonium, an imidazolium, a pyridinium, a phosphonium, a sulphonium, and a combination thereof.

4. The ionic liquid of claim 1 , wherein the at least one organic cation is an ammonium cation of the structure + NR 1 R 2 R 3 R 4 , wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted carbonyl, or wherein two or more of R 1 , R 2 , R 3 , and R 4 optionally combine to form a ring.

5. The ionic liquid of claim 4 , wherein one or more of R 1 , R 2 , R 3 , and R 4 are methyl, ethyl, propyl, or butyl.

6. The ionic liquid of claim 4 , wherein two or more of R 1 , R 2 , R 3 , and R 4 combine to form a ring, the ring including between 3 and 12 atoms.

7. The ionic liquid of claim 4 , wherein two or more of R 1 , R 2 , R 3 , and R 4 combine to form a ring, the ring including at least one double bond.

8. The ionic liquid of claim 1 , wherein the at least one organic cation is a substituted or unsubstituted heteroaryl cation.

9. The ionic liquid of claim 8 , wherein the heteroaryl cation is selected from a substituted or unsubstituted pyridinium cation, a substituted or unsubstituted imidazolium cation, a substituted or unsubstituted morpholinium, a substituted or unsubstituted pyrrolidinium cation, a substituted or unsubstituted quinolinium cation, a substituted or unsubstituted isoquinolinium cation, and a substituted or unsubstituted morpholinium cation.

10. The ionic liquid of claim 1 , wherein the at least one organic cation is a phosphonium cation of the structure + PR 1 R 2 R 3 R 4 , wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted carbonyl, or wherein two or more of R 1 , R 2 , R 3 , and R 4 optionally combine to form a ring.

11. The ionic liquid of claim 1 , wherein the at least one organic cation is selected from the group consisting of dimethylammonium, trimethylammonium, tetramethylammmonium, diethylammonium, triethylammonium, tetraethylammmonium, dipropylammonium, tripropylammonium, and tetrapropylammmonium.

12. The ionic liquid of claim 1 , wherein the at least two metal halide anions are each independently a halometallate.

13. The ionic liquid of claim 1 , wherein the at least two metal halide anions are each independently selected from the group consisting of chloroaluminate, chlorozincate, chloroferrate, chlorogallate, chlorostannate, chloroindate, chlorochromate, chlorocuprate, chlorotitannate, chlorozirconate, chloropalladate, and combinations thereof.

14. The ionic liquid of claim 1 , wherein the molar ratio of the at least two metal halide anions is selected from 1, 1.5, 2, 2.33, 3, 4, and 9.

15. The ionic liquid of claim 1 , further comprising a solvent or a mixture of solvents.

16. A method of making an ionic liquid of claim 1 , the method comprising: combining two or more metal halide containing salts, wherein the metal halide containing salts include at least one organic cation and at least two metal halide anions,
wherein the at least two metal halide anions are present in a molar ratio from 1:1 to 1:9, and comprise a metal selected from aluminum, iron, chromium, zinc, copper, tin, titanium, palladium, zirconium, gallium, or combinations thereof, and
wherein when the at least one organic cation includes triethylammonium, the ionic liquid does not include chlorocuprate.

17. The method of claim 16 , wherein the organic cation is selected from alkylammonium, arylammonium, allylammonium, imidazolium, pyridiunium, phosphonium, sulphonium, and combinations thereof.

18. A catalyst comprising the ionic liquid of claim 1 .

19. The ionic liquid of claim 1 , wherein the at least two metal halide anions do not include chlorocuprate.

20. The ionic liquid of claim 1 , wherein the at least two metal halide anions do not include copper.

Assignees

• Univ Alabama

Inventors

• Rogers Robin D
• Gurau Gabriela
• Kelley Steven P
• Kore Rajkumar
• Shamshina Julia L

Classifications

• C07C45/00

  Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds · CPC title

• C07D215/06

  having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom · CPC title

• C07C231/10

  from compounds not provided for in groups C07C231/02 - C07C231/08 · CPC title

• B01J31/0298 Primary

  the ionic liquids being characterised by the counter-anions · CPC title

• C07C211/63

  having quaternised nitrogen atoms bound to acyclic carbon atoms · CPC title