Visual detection of fluoride ions
View Patent ↗Dendrimer-hydrazides are coupled to polycyclic aromatic hydrocarbons for use in the visual detection of the presence of low levels of fluoride in a sample. The dendrimers can have a phenyl core, a first generation of aralkyl ethers, and an optional second generation of aralkyl ethers. The compounds form gels with solvents. In the presence of fluoride ion, the gels undergo color changes and/or gel to liquid phase change.
1. A compound according to the formula (XX)
a tautomer thereof, or a salt thereof, wherein:
Ar 1 is a —C 10 -C 36 polycyclic aromatic hydrocarbon; and
R D is a dendrimer comprising a phenyl core and at least a first generation layer of —O—(C 1 -C 12 )alkyl-aryl bonded to the core.
2. The compound of claim 1 , wherein the dendrimer further comprises a second generation layer of —O—(C 1 -C 12 )alkyl-aryl bonded to the aryl of the first generation layer.
3. The compound of claim 1 , wherein Ar 1 is unsubstituted.
4. The compound of claim 1 , wherein Ar 1 is substituted with one or two R 0 groups independently selected from trifluoromethyl, trifluoroethyl, nitro, cyano, —OH, or —C 1 -C 20 alkyl.
5. The compound of claim 1 , wherein Ar 1 is naphthalene, anthracene, phenanthrene, chrysene, pyrene, tetracene, perylene, decacyclene, or triphelene.
6. The compound of claim 1 , wherein the —O—(C 1 -C 12 )alkyl-aryl of the first generation layer comprise —O—(C 1 -C 12 )alkyl-phenyl.
7. The compound of claim 6 , wherein the dendrimer further comprises a second generation layer comprising two or three individual —O—(C 1 -C 12 )alkyl-phenyl groups bonded to the phenyl of each of at least two of the —O—(C 1 -C 12 )alkyl-phenyl groups of the first generation layer.
8. The compound of claim 1 , wherein:
the —O—(C 1 -C 12 )alkyl-aryl of the first generation layer comprise —O—(C 1 -C 2 )alkyl-phenyl, and the first generation layer comprises one of:
an individual —O—(C 1 -C 2 )alkyl-phenyl group bonded to the phenyl core at each of positions 3 and 5; and
an individual —O—(C 1 -C 2 )alkyl-phenyl group bonded to the phenyl core at each of positions 3, 4 and 5; and
the dendrimer further comprises a second generation layer comprising at least one of:
individual —O—(C 1 -C 2 )alkyl-phenyl groups bonded to the phenyl of the —O—(C 1 -C 2 )alkyl-phenyl groups of the first generation layer at each of positions 3 and 5; and
individual —O—(C 1 -C 2 )alkyl-phenyl groups bonded to the phenyl of the —O—(C 1 -C 2 )alkyl-aryl groups of the first generation layer at each of positions 3, 4 and 5.
9. The compound of claim 1 , according to the formula (XXI)
a tautomer thereof, or a salt thereof, wherein:
Ar 1 is naphthalene, anthracene, phenanthrene, chrysene, pyrene, tetracene, perylene, decacyclene or triphelene;
R 1 is —O—(C 1 -C 12 )alkyl-aryl; and
n is 2 or 3.
10. The compound of claim 9 , wherein the aryl of each —O—(C 1 -C 12 )alkyl-aryl is substituted with up to three additional —O—(C 1 -C 12 )alkyl-aryl.
11. The compound of claim 1 , according to the formula (XXII)
a tautomer thereof, or a salt thereof, wherein:
R 1 is —O—(C 1 -C 12 )alkyl-aryl; and
n is 2 or 3.
12. The compound of claim 11 , wherein the aryl of each —O—(C 1 -C 12 )alkyl-aryl is substituted with up to three additional —O—(C 1 -C 12 )alkyl-aryl.
13. The compound of claim 1 , according to the formula (XXIII)
a tautomer thereof, or a salt thereof, wherein:
R 3 , R 4 , and R 5 are independently hydrogen or —O—(C 1 -C 2 )alkyl-aryl, and, if present, no more than one of R 3 , R 4 , and R 5 is hydrogen; and
each R 3 , R 4 , or R 5 aryl, if present, is substituted with 0, 1, 2, or 3-O—(C 1 -C 2 )alkyl-aryl.
14. The compound of claim 13 , wherein:
R 3 , R 4 , and R 5 are independently hydrogen, or —O—CH 2 -aryl, and, if present, no more than one of R 3 , R 4 , R 5 is hydrogen; and
each R 3 , R 4 , or R 5 aryl, if present, is substituted with 0, 1, 2, or 3-O—CH 2 -aryl.
15. The compound of claim 1 , according to the formula (XXIV):
a tautomer thereof, or a salt thereof, wherein R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently hydrogen or —O—(C 1 -C 2 )alkyl-aryl.
16. The compound of claim 15 , wherein each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are hydrogen.
17. The compound of claim 15 , wherein R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently hydrogen or —O—CH 2 -aryl, and, if present:
no more than one of R 6 , R 7 , or R 8 is hydrogen;
no more than one of R 9 , R 10 , and R 11 is hydrogen; and
no more than one of R 12 , R 13 , and R 14 is hydrogen.
18. The compound of claim 1 , according to the formula (XXV):
a tautomer thereof, or a salt thereof, wherein R 6 , R 7 , R 8 , R 12 , R 13 , and R 14 are independently hydrogen or —O—(C 1 -C 2 )alkyl-aryl.
19. The compound of claim 18 , wherein each of R 6 , R 7 , R 8 , R 12 , R 13 , and R 14 are hydrogen.
20. The compound of claim 18 , wherein R 6 , R 7 , R 8 , R 12 , R 13 , and R 14 are independently hydrogen or —O—CH 2 -aryl, and, if present:
no more than one of R 6 , R 7 , or R 8 is hydrogen; and
no more than one of R 12 , R 13 , and R 14 is hydrogen.
21. The compound of claim 1 , wherein the compound is:
N′-(anthracen-9-ylmethylene)-3,4,5-tris(benzyloxy)benzohydrazide;
a fluoride salt of N′-(anthracen-9-ylmethylene)-3,4,5-tris(benzyloxy)benzohydrazide;
N′-(anthracen-9-ylmethylene)-3,5-bis(benzyloxy)benzohydrazide;
a fluoride salt of N′-(anthracen-9-ylmethylene)-3,5-bis(benzyloxy)benzohydrazide;
N′-(anthracen-9-ylmethylene)-3,4,5-tris(3,4,5-tris(benzyloxy)benzyloxy)benzohydrazide;
a fluoride salt of N′-(anthracen-9-ylmethylene)-3,4,5-tris(3,4,5-tris(benzyloxy)-benzyloxy)benzohydrazide;
N′-(anthracen-9-ylmethylene)-3,5-bis(3,5-bis(benzyloxy)benzyloxy)benzohydrazide; or
a fluoride salt of N′-(anthracen-9-ylmethylene)-3,5-bis(3,5-bis(benzyloxy)benzyloxy)benzohydrazide.
22. The compound of claim 1 , wherein the compound is characterized by at least one of:
its ability to selectively sequester fluoride ions;
its ability to undergo a phase change from gel to liquid upon fluoride sequestration; and
its ability to undergo a color change upon fluoride sequestration.