Compounds for the selective solid-liquid extraction and liquid-liquid extraction of lithium chloride

1. A compound of the formula:

wherein:

R 1 , R 1 ′, R 2 , R 2 ′, R 3 , R 3 ′, R 4 , and R 4 ′ are each independently hydrogen, hydroxy, amino, cyano, or halo; or

alkyl (C≤6) , alkenyl (C≤6) , alkynyl (C≤6) , acyloxy (C≤6) , alkoxy (C≤6) , alkylamino (C≤6) , dialkylamino (C≤12) , amido (C≤6) , or a substituted version of any of these groups; or

one of these groups is attached to a solid support or a fluorophore;

R 5 , R 5 ′, R 6 , R 6 ′, R 7 , and R 8 are each independently hydrogen or alkyl (C≤12) , cycloalkyl (C≤12) , cycloalkenyl(C=12), alkenyl (C≤12) , alkynyl (C≤12) , aryl (C≤12) , heteroalkyl (C≤12) , heterocycloalkyl (C≤12) , alkoxy (C≤12) , alkylamino (C≤12) , dialkylamino (C≤18) , amido (C≤12) , or a substituted version of any of these groups; or one of these groups is attached to a solid support or a fluorophore;

R 9 , R 10 , R 11 , and R 12 are hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ;

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , cycloalkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , arenediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —O—, —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ; or one or more of these groups is attached to a solid support or a fluorophore;

Z is a group of the formula:

wherein:

A 1 and A 1 ′ are each independently arenediyl (C≤8) , substituted arenediyl (C≤8) , heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; and

A 2 is heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; or

Z is arenediyl (C≤24) , substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings;

wherein when a chemical group is used with the “substituted” modifier, one or more hydrogen atom has been replaced, independently at each instance, by —OH, —F, —Cl, —Br, —I, —NH 2 , —NO 2 , —CO 2 H, —CO 2 CH 3 , —CN, —SH, —OCH 3 , —OCH 2 CH 3 , —C(O)CH 3 , —NHCH 3 , —NHCH 2 CH 3 , —N(CH 3 ) 2 , —C(O)NH 2 , —C(O)NHCH 3 , —C(O)N(CH 3 ) 2 , —OC(O)CH 3 , —NHC(O)CH 3 , —S(O) 2 OH, or —S(O) 2 NH 2 ;

or a salt thereof.

2. The compound of claim 1 , wherein the compound is further defined as:

wherein:

R 1 , R 1 ′, R 2 , R 2 ′, R 3 , R 3 ′, R 4 , and R 4 ′ are each independently hydrogen, hydroxy, amino, cyano, or halo; or

alkyl (C≤6) , alkenyl (C≤6) , alkynyl (C≤6) , acyloxy (C≤6) , alkoxy (C≤6) , alkylamino (C≤6) , dialkylamino (C≤12) , amido (C≤6) , or a substituted version of any of these groups;

R 5 , R 5 ′, R 6 , R 6 ′, R 7 , and R 8 are each independently hydrogen or alkyl (C≤6) , alkenyl (C≤6) , alkynyl (C≤6) , or a substituted version of any of these groups;

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ;

Z is a group of the formula:

wherein:

A 1 and A 1 ′ are each independently arenediyl (C≤8) , substituted arenediyl (C≤8) , heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; and

A 2 is heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; or

Z is arenediyl (C≤24) , substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings;

or a salt thereof.

3. The compound of claim 1 , wherein the compound is further defined:

wherein:

R 1 , R 1 ′, R 2 , R 2 ′, R 3 , R 3 ′, R 4 , and R 4 ′ are each independently hydrogen, hydroxy, amino, cyano, or halo; or

alkyl (C≤6) , alkenyl (C≤6) , alkynyl (C≤6) , acyloxy (C≤6) , alkoxy (C≤6) , alkylamino (C≤6) , dialkylamino (C≤12) , amido (C≤6) , or a substituted version of any of these groups;

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ;

Z is a group of the formula:

wherein:

A 1 and A 1 ′ are each independently arenediyl (C≤8) , substituted arenediyl (C≤8) , heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; and

A 2 is heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; or

Z is arenediyl (C≤24) , substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings;

or a salt thereof.

4. The compound of claim 1 , wherein the compound is further defined:

wherein:

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ;

Z is a group of the formula:

wherein:

A 1 and A 1 ′ are each independently arenediyl (C≤8) , substituted arenediyl (C≤8) , heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; and

A 2 is heteroarenediyl(c) or substituted heteroarenediyl (C≤8) ; or

Z is arenediyl (C≤24) , substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings;

or a salt thereof.

5. The compound of claim 1 , wherein the compound is further defined:

wherein:

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ;

Z is a group of the formula:

wherein:

A 1 and A 1 ′ are each independently arenediyl (C≤8) , substituted arenediyl (C≤8) , heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ; and

A 2 is heteroarenediyl (C≤8) or substituted heteroarenediyl (C≤8) ;

or a salt thereof.

6. The compound of claim 1 , wherein the compound is further defined:

wherein:

L and L′ are taken together and form a group of the formula:

wherein:

X and X′ are each independently alkanediyl (C≤8) , alkenediyl (C≤8) , alkynediyl (C≤8) , or a substituted version of any of these groups;

Y and Y′ are each independently —C(O)—, —C(O)O—, —S(O)—, —S(O) 2 O—, —C(O)NR a —, or —S(O) 2 NR b —, wherein:

R a and R b are each independently hydrogen, alkyl (C≤6) , or substituted alkyl (C≤6) ; and

Z is arenediyl (C≤24) , substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings;

or a salt thereof.

7. The compound of claim 1 , wherein X and X′ are both alkanediyl (C≤8) or substituted alkanediyl (C≤8) .

8. The compound of claim 7 , wherein X and X′ are both ethanediyl or propanediyl.

9. The compound of claim 1 , wherein Y and Y′ are both —C(O)O— or —C(O)NR a —.

10. The compound of claim 1 , wherein A 1 and A 1 ′ are both the same.

11. The compound of claim 10 , wherein A 1 and A 1 ′ are both arenediyl (C≤8) or substituted arenediyl (C≤8) .

12. The compound of claim 1 , wherein A 2 is heteroarenediyl (C≤8) .

13. The compound of claim 1 , wherein Z is substituted arenediyl (C≤24) , heteroarenediyl (C≤24) , or substituted heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings.

14. The compound of claim 13 , wherein Z is heteroarenediyl (C≤24) , wherein the group comprises at least 3 fused rings.

15. The compound of claim 14 , wherein Z is heteroarenediyl (C≤18) , wherein the group comprises 3 fused rings and contains at least two nitrogen atoms.

16. The compound of claim 1 , wherein the compound is further defined:

17. A composition comprising (A) a compound of claim 1 ; and (B) a salt.

18. The composition of claim 17 , wherein the salt comprises an alkali metal cation.

19. The composition of claim 17 , wherein the compound is defined as: