Custom ionic liquid electrolytes for electrolytic decarboxylation

1. A method of making a compound of formula R 1 -R 2 , comprising:

providing an electrolytic cell, comprising:

an anode compartment comprising an ionic liquid electrolyte;

a cathode compartment comprising aqueous sodium hydroxide;

an alkali ion selective membrane separating the anode compartment and the cathode compartment;

an anode in communication with the ionic liquid electrolyte;

a cathode in communication with the aqueous sodium hydroxide;

a power supply; and

applying an electric current to the ionic liquid electrolyte;

wherein the ionic liquid comprises compounds having formulas R 1 COOM and R 2 COOM and wherein each of R 1 and R 2 is independently selected from unsubstituted and substituted alkyl, unsubstituted and substituted cycloalkyl, unsubstituted and substituted heterocyclyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, and substituted and unsubstituted heteroaryl;

wherein each M is independently an alkali metal;

wherein the power supply provides an electric potential between the anode and the cathode; and

wherein the electric potential provided by the power supply oxidizes the anode and decarboxylates the compounds of formulas R 1 COOM and R 2 COOM to form a decarboxylated radical of R 1 and R 2 , which further undergo radical-radical coupling to provide a compound of formula R 1 -R 2 ;

wherein the ionic liquid has the formula [(R′)(R″)(R′″)(R″″)X];

wherein X is selected from substituted or unsubstituted pyridinium, substituted or unsubstituted pyridazinium, substituted or unsubstituted pyrimidinium, substituted or unsubstituted pyrazinum, substituted or unsubstituted pyrrolidinium, substituted or unsubstituted imidazolium, substituted or unsubstituted pyrazolium, substituted or unsubstituted thiazolium, substituted or unsubstituted oxazolium, substituted or unsubstituted triazolium, phosphonium, and ammonium; and

wherein each of R′, R″, R″, and R″″ is the same and is selected from fluoro, phosphinates, alkylphosphinates, alkylthiophosphinates, sulfates, sulphonates, amides, tosylates, aluminates, borates, arenates, cuprates, nitrates, carboxylates, hydrogen, unsubstituted and substituted alkyl, unsubstituted and substituted cycloalkyl, unsubstituted and substituted heterocyclyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, and substituted and unsubstituted heteroaryl,

provided that when X is ammonium or phosphonium, then each of R′, R″, R′″, and R″″ may also independently be hydrogen.

2. The method of claim 1 , wherein substitutions on substituted alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, and heteroaryl are selected from halogen, unsubstituted C 1-8 alkyl, —CN, —NO 2 , ═O, —C(O)R A , —CO 2 R A , —C(O)NR A R B , —OR A , —OC(O)R A , —OC(O)NR A R B , —NR C C(O)R A , —NR C (O)NR A R B , —NR A R B , —NR C CO 2 R A , —NR C S(O) 2 R A , —SR A , —S(O)R A , —S(O) 2 R A , —S(O) 2 NR A R B ;

wherein each of R A , R B , and R C , when present, is independently selected from the group consisting of: —H, unsubstituted C 1-8 alkyl, unsubstituted C 2-8 alkenyl, and unsubstituted C 2-8 alkynyl.

3. The method of claim 1 , wherein substitutions on substituted alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, and heteroaryl are located geminal to —COOM.

4. The method of claim 1 , further comprising contacting a compound of formula R 1 COOH with an alkaline hydroxide of formula MOH to provide a compound of formula R 1 COOM.

5. The method of claim 1 , further comprising contacting a compound of formula R 2 COOH with an alkaline hydroxide of formula MOH to provide a compound of formula R 2 COOM.

6. The method of claim 1 , further comprising heating the ionic liquid.

7. The method of claim 1 , wherein each M is sodium.

8. The method of claim 1 , wherein R 1 and R 2 are the same or different.

9. The method of claim 1 , further comprising contacting the ionic liquid with an organic solvent.

10. The method of claim 1 , further comprising contacting the ionic liquid with a supporting electrolyte.

11. The method of claim 10 , wherein the supporting electrolyte is selected from alkali metal hydroxide, alkali metal salts, tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, tetramethylammonium perchlorate, and tetraethylammonium perchlorate.

12. The method of claim 1 , wherein the alkali ion selective membrane comprises at least one of LISICON and NASICON.

13. A method of making a compound of formula R 1 -R 2 , comprising:

providing an electrolytic cell, comprising:

an anode compartment comprising an ionic liquid electrolyte;

a cathode compartment comprising aqueous sodium hydroxide;

an alkali ion selective membrane separating the anode compartment and the cathode compartment;

an anode in communication with the ionic liquid electrolyte;

a cathode in communication with the aqueous sodium hydroxide;

a power supply; and

applying an electric current to the ionic liquid electrolyte;

wherein the ionic liquid comprises compounds having formulas R 1 COOM and R 2 COOM and wherein each of R 1 and R 2 is independently selected from unsubstituted and substituted alkyl, unsubstituted and substituted cycloalkyl, unsubstituted and substituted heterocyclyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, and substituted and unsubstituted heteroaryl;

wherein each M is independently an alkali metal;

wherein the power supply provides an electric potential between the anode and the cathode; and

wherein the electric potential provided by the power supply oxidizes the anode and decarboxylates the compounds of formulas R 1 COOM and R 2 COOM to form a decarboxylated radical of R 1 and R 2 , which further undergo radical-radical coupling to provide a compound of formula R 1 -R 2 ;

wherein the ionic liquid has the formula [(R′)(R″)(R′″)(R″″)X];

wherein X is selected from substituted or unsubstituted pyridinium, substituted or unsubstituted pyridazinium, substituted or unsubstituted pyrimidinium, substituted or unsubstituted pyrazinum, substituted or unsubstituted pyrrolidinium, substituted or unsubstituted imidazolium, substituted or unsubstituted pyrazolium, substituted or unsubstituted thiazolium, substituted or unsubstituted oxazolium, substituted or unsubstituted triazolium, phosphonium, and ammonium; and

wherein at least one of R′, R″, R′″, and R″″ is different from the others and each of R′, R″, R′″, and R″″ is independently selected from fluoro, phosphinates, alkylphosphinates, alkylthiophosphinates, sulfates, sulphonates, amides, tosylates, aluminates, borates, arenates, cuprates, nitrates, carboxylates, hydrogen, unsubstituted and substituted alkyl, unsubstituted and substituted cycloalkyl, unsubstituted and substituted heterocyclyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, and substituted and unsubstituted heteroaryl,

provided that when X is ammonium or phosphonium, then each of R′, R″, R′″, and R″″ may also independently be hydrogen.

14. The method of claim 13 , wherein substitutions on substituted alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, and heteroaryl are selected from halogen, unsubstituted C 1-8 alkyl, —CN, —NO 2 , ═O, —C(O)R A , —CO 2 R A , —C(O)NR A R B , —OR A , —OC(O)R A , —OC(O)NR A R B , —NR C (O)R A , —NR C (O)NR A R B , —NR A R B , —NR C CO 2 R A , —NR C S(O) 2 R A , —SR A , —S(O)R A , —S(O) 2 R A , —S(O) 2 NR A R B ;

wherein each of R A , R B , and R C , when present, is independently selected from the group consisting of: —H, unsubstituted C 1-8 alkyl, unsubstituted C 2-8 alkenyl, and unsubstituted C 2-8 alkynyl.

15. The method of claim 13 , wherein substitutions on substituted alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, and heteroaryl are located geminal to —COOM.

16. The method of claim 13 , further comprising contacting a compound of formula R 1 COOH with an alkaline hydroxide of formula MOH to provide a compound of formula R 1 COOM.

17. The method of claim 13 , further comprising contacting a compound of formula R 2 COOH with an alkaline hydroxide of formula MOH to provide a compound of formula R 2 COOM.

18. The method of claim 13 , further comprising heating the ionic liquid.

19. The method of claim 13 , wherein each M is sodium.

20. The method of claim 13 , wherein R 1 and R 2 are the same or different.

21. The method of claim 13 , further comprising contacting the ionic liquid with an organic solvent.

22. The method of claim 13 , further comprising contacting the ionic liquid with a supporting electrolyte.

23. The method of claim 22 , wherein the supporting electrolyte is selected from alkali metal hydroxide, alkali metal salts, tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, tetramethylammonium perchlorate, and tetraethylammonium perchlorate.

24. The method of claim 13 , wherein the alkali ion selective membrane comprises at least one of LISICON and NASICON.