Cyclobenzoins

Patent metadata

Field	Value
Publication number	US-10138192-B2
Application number	US-201615559817-A
Country	US
Kind code	B2
Filing date	Mar 17, 2016
Priority date	Mar 20, 2015
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

One-step cyanide-catalyzed benzoin condensations for synthesizing shape persistent cyclobenzoin macrocycles. Selected dialdehydes, and cyanide salts are reacted in aqueous solvents to form such cyclobenzoin macrocycles.

First claim

What is claimed is:

1. A one-step method of synthesizing a cyclobenzoin macrocycle, comprising:

reacting a dialdehyde (A) in a concentration of between 0.1M to 1M, and a cyanide salt catalyst in an aqueous solvent wherein said solvent is in a 1:1 molar ratio with H 2 O to form a cyclobenzoin (B) macrocycle, wherein n is selected from group comprising 1, 2, or 3; and M is 3, or 4, and wherein said reacting the dialdehyde and the cyanide salt catalyst comprises refluxing at a temperature of about 100° C.

2. The method of claim 1 , wherein said solvent is an alcohol.

3. The method of claim 2 , wherein said alcohol is selected from the group consisting of 2-methoxyethanol; ethanol; methanol; propanol, butanol, pentanol isomers, and glycols.

4. The method of claim 1 , wherein said dialdehyde is selected from the group consisting of isophthaldehyde; tetraphthaldehyde; phthaldehyde, and aromatic analogs thereof, wherein one or more substituted or unsubstituted aromatic or hetoroaromatic rings, and/or triple bonds are inserted between two formyl groups.

5. The method of claim 4 , wherein said dialdehyde is isophthaldehyde in a concentration of about 0.5M.

6. The method of claim 4 , wherein said dialdehyde is tetraphthaldehyde in a concentration of about 0.17M.

7. The method of claim 1 , wherein said reacting a dialdehyde and a cyanide salt comprises refluxing under nitrogen gas at a temperature of about 100° C. for about 48 hrs.

8. The method of claim 1 , wherein said cyanide salt is selected from the group consisting of NaCN, cyanide salts of metals; and thiazolium salts.

9. The method of claim 5 , wherein said cyclobenzoin macrocycle is cyclotribenzoin or a cyclotetrabenzoin.

10. The method of claim 1 , wherein said cyclobenzoin macrocycle forms a microporous three-dimensional organic framework, or a one dimensional nanotube channel.

11. The method of claim 1 , wherein said cyclobenzoin macrocycle is porous.

12. The method of claim 1 , wherein said cyclotetrabenzoin comprises a Langmuir surface area of about 52 m 2 g −1 .

13. The method of claim 1 , wherein said cyclobenzoin macrocycles further comprise porous materials, assemblies at liquid-solid interfaces, or organic nanowires and nanofibrils.

14. The method of claim 1 , wherein said cyclobenzoin comprises a synthetic receptor macromolecule.

15. A cyclotetrabenzoin macrocycle; comprising:
a square shape-persistent 3-dimensional structure, wherein said square shape-persistent 3-dimensional structure comprises four outer polar α-hydroxyketone moieties; and
a central nonpolar cavity, or a cone shape-persistent 3-dimensional structure, wherein said cone shape-persistent 3-dimensional structure comprises convergent anionic and cationic binding groups .

16. The cyclotetrabenzoin macrocycle of claim 15 , wherein said macrocycle is intrinsically porous, and comprises a 10% void volume.

17. The cyclotetrabenzoin macrocycle of claim 15 , wherein said central non-polar cavity comprises an area of about 6.9×6.9Å.

18. The cyclotetrabenzoin macrocycle of claim 15 , wherein said α-hydroxyketone moieties comprise hydrogen bonds to further units of cyclotetrabenzoin to form hydrogen-bonded nanotubular subunits.

19. The cyclotetrabenzoin macrocycle of claim 15 , wherein said α-hydroxyketone moieties comprise hydrogen bonds to molecular guest molecules.

20. The cyclotetrabenzoin macrocycle of claim 15 , wherein said α-hydroxyketone moieties, cationic binding groups, or anioic binding groups are selectively derivatized.

21. The cyclotribenzoin macrocycle of claim 20 , wherein said anionic and cationic binding groups bond with guest molecules.

Assignees

• Univ Houston System

Inventors

• Miljanic Ognjen
• Ji Qing

Classifications

• C07C15/50

  polycyclic non-condensed · CPC title

• C07C47/544

  Diformyl benzenes; Alkylated derivatives thereof · CPC title

• C07C49/215

  polycyclic · CPC title

• C07C2601/06

  with a five-membered ring · CPC title

• C07C49/727

  a keto group being part of a condensed ring system · CPC title