PREPARATION OF POLY(CROWN ETHER)S
The present disclosure relates to methods for preparing a poly(crown ether). The present disclosure also relates to poly(crown ether)s prepared according to such methods.
1 . A method of preparing a poly(crown ether), the method comprising:
contacting a compound of Formula (I):
with a compound of Formula (II):
in the presence of a base;
wherein:
A is C 6 -C 40 aryl or C 4 -C 38 heteroaryl, each optionally substituted with 1-8 R a ;
each R a is independently selected from oxo, cyano, C 6 -C 14 aryl, C 1 -C 4 alkyl, and C 1 -C 4 alkoxy;
R 1 and R 2 are each independently halo;
p and q are each independently 1-4; and
n is 0-8.
2 . The method of claim 1 , wherein each —OH is attached to a carbon ring member of an all-carbon aromatic ring.
3 . The method of claim 2 , wherein each carbon ring member attached to an —OH is further attached to one other carbon ring member attached to an —OH.
4 . The method of claim 1 , wherein A is C 6 -C 20 aryl.
5 . The method of claim 4 , wherein A is C 6 -C 14 aryl optionally substituted with 1-6 R a , and wherein each R a is independently C 6 -C 14 aryl.
6 . The method of claim 1 , wherein A is C 10 -C 40 aryl.
7 . The method of claim 1 , wherein A comprises a multiple-condensed ring system.
8 . The method of claim 7 , wherein A comprises an all-carbon multiple-condensed ring system.
9 . The method of claim 7 , wherein the multiple-condensed ring system comprises two or more spiro-linked rings.
10 . The method of claim 7 , wherein the multiple-condensed ring system comprises two or more bridged rings.
11 . The method of claim 7 , wherein the multiple-condensed ring system is substituted with 1-4 R a , and wherein each R a is independently selected from oxo, C 6 -C 14 aryl, and C 1 -C 4 alkyl.
12 . The method of claim 7 , wherein the multiple-condensed ring system comprises one or more rings derived from fluorene, indane, indene, chromane, naphthalene, or any combination thereof.
13 . The method of claim 12 , wherein the multiple-condensed ring system comprises two or more spiro-linked rings derived from fluorene, indane, indene, or any combination thereof.
14 . The method of claim 1 , wherein the compound of Formula (I) is
15 . The method of claim 1 , wherein p and q are each 1.
16 . The method of claim 1 , wherein p and q are each 2.
17 . The method of claim 16 , wherein n is 0.
18 . The method of claim 16 , wherein n is 1-4.
19 . The method of claim 1 , wherein R 1 and R 2 are the same.
20 . The method of claim 1 , wherein R 1 and R 2 are each independently —F or —Cl.
21 . The method of claim 1 , wherein the base comprises an inorganic base, an organic base, or any combination thereof.
22 . The method of claim 21 , wherein the inorganic base comprises potassium carbonate, sodium carbonate, lithium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, or any combination thereof.
23 . The method of claim 21 , wherein the organic base comprises N,N-diisopropylethylamine, trimethylamine, or any combination thereof.
24 . The method of claim 1 , wherein the compound of Formula (I) and the compound of Formula (II) are contacted in a reaction mixture comprising the base and a solvent.
25 . The method of claim 24 , wherein the solvent comprises dimethylformamide, dimethyl sulfoxide, n-methyl pyrrolidone, diethylformamide, or any combination thereof
26 . The method of claim 24 , wherein the compound of Formula (I) and the compound of Formula (II) are each independently present in the reaction mixture in an amount of about 1 wt % to about 25 wt % of the reaction mixture.
27 . The method of claim 24 , wherein a molar ratio of the compound of Formula (I) and the compound of Formula (II) present in the reaction mixture is about 1:1.5 to about 1:2.5.
28 . The method of claim 24 , wherein a molar ratio of the compound of Formula (I) and the base present in the reaction mixture is about 1:1 to about 1:10.
29 . The method of claim 24 , wherein a temperature of the reaction mixture is about 20° C. to about 140° C.
30 . The method of claim 24 , comprising contacting the compound of Formula (I) and the compound of Formula (II) for about 1 hour to about 14 days.
31 . A poly(crown ether), prepared according to the method of claim 1 .
32 . A poly(crown ether) comprising a structural repeat unit of Formula (III):
wherein:
A is C 6 -C 40 aryl or C 4 -C 38 heteroaryl, each optionally substituted with 1-8 R a ;
each R a is independently selected from oxo, cyano, C 6 -C 14 aryl, C 1 -C 4 alkyl, and C 1 -C 4 alkoxy;
p and q are each independently 1-4; and
n is 0-8.