Quinolines, polyquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and methods of their synthesis

Patent metadata

Field	Value
Publication number	US-11945780-B2
Application number	US-202117156403-A
Country	US
Kind code	B2
Filing date	Jan 22, 2021
Priority date	Dec 31, 2014
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

Quinolines, polyquinolines, polybenzoquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and processes for producing such materials are provided. The processes utilize a form of an aza-Diels-Alder (Povarov) reaction to first form quinolines and/or polyquinolines. In some such embodiments polyquinolines thus produced are used to form graphene nanoribbon precursors, and molecular segments and graphene nanoribbons. In many such embodiments the graphene nanoribbone precursors are formed from polybenzoquinolines.

First claim

What is claimed is:

1. A method of producing biquinolines or polyquinolines comprising:
reacting a bifunctional aromatic aldimine with an aromatic mono- or bi-alkynyl in the presence of a Lewis acid mediator and an oxidant to produce the corresponding biquinoline or polyquinoline, wherein:
the bifunctional aromatic aldimine is of formula:

comprising:
a first aromatic core comprising aromatic or heteroaromatic rings, wherein
n is a number of distinct rings and is an integer of at least 1, and
the first aromatic core is substituted with at least one halogen;

a first aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R1 is an aromatic or heteroaromatic functionality optionally substituted with one or more substituents, each independently selected from the group consisting of: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof; and

a second aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R2 is one of the functionalities selected from the group consisting of: R1, a substituted aromatic ring, an unsubstituted aromatic ring, a substituted heteroaromatic ring, and an unsubstituted heteroaromatic ring; and wherein
the at least one halogen is at meta position of the first aromatic core relative to the first aldimine functionality; and

the aromatic mono- or bi-alkynyl comprises a second aromatic core and one or two aromatic terminal alkyne functionalities respectively; and wherein
the first and the second aldimine functionalities of the bifunctional aromatic aldimine react with the one or two aromatic terminal alkyne functionalities of the aromatic mono- or bi-alkynyl to yield the corresponding biquinoline or polyquinoline comprising quinoline moieties incorporating the nitrogens of the first and the second aldimine functionalities.

2. The method of claim 1 , wherein the at least one halogen is chlorine.

3. The method of claim 1 , wherein n is 2, such that the first aromatic core is a naphthyl and the quinoline moieties are benzoquinoline.

4. The method of claim 1 , wherein n is 2, and the ring that does not bear the first aldimine functionality is heteroaromatic.

5. The method of claim 4 , wherein the heteroaromatic ring is a pyridine-type and the quinoline moieties are of the phenanthroline variant.

6. The method of claim 1 , wherein n is at least 2, and some or all of the aromatic rings of the first aromatic core are linked at the 4 and 6 positions rather than fused, such that the aromaticity of the first aromatic core is maintained.

7. The method of claim 1 , wherein the second aromatic core is a naphthyl moiety.

8. The method of claim 7 , wherein the naphthyl moiety is optionally substituted with one or more halogens.

9. The method of claim 8 , wherein the at least one halogen is chlorine.

10. A method of forming nitrogen-doped aromatic molecular segments or graphene nanoribbons comprising:
reacting a bifunctional aromatic aldimine with an aromatic mono- or bi-alkynyl in the presence of a Lewis acid mediator and an oxidant to produce the corresponding biquinoline or polyquinoline, and
forming intramolecular C—C bonds between aromatic and heteroaromatic moieties of the corresponding biquinoline or polyquinoline to form the corresponding nitrogen-doped molecular segment or graphene nanoribbon, wherein:
the bifunctional aromatic aldimine is of formula:

comprising:
a first aromatic core comprising aromatic or heteroaromatic rings, wherein
n is a number of distinct rings and is an integer of at least 1, and
the first aromatic core is substituted with at least one halogen;

a first aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R1 is an aromatic or heteroaromatic functionality optionally substituted with one or more substituents, each independently selected from the group consisting of: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof; and

a second aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R2 is one of the functionalities selected from the group consisting of: R1, a substituted aromatic ring, an unsubstituted aromatic ring, a substituted heteroaromatic ring, and an unsubstituted heteroaromatic ring, wherein
the at least one halogen is at meta position of the first aromatic core relative to the first aldimine functionality; and

the aromatic mono- or bi-alkynyl comprises a second aromatic core, and one or two aromatic terminal alkyne functionalities, respectively; and wherein
the first and the second aldimine functionalities of the bifunctional aromatic aldimine react with the one or two aromatic terminal alkyne functionalities of the aromatic mono- or bi-alkynyl to yield the corresponding biquinoline or polyquinoline comprising quinoline moieties incorporating the nitrogens of the first and the second aldimine functionalities.

11. The method of claim 10 , wherein the at least one halogen is chlorine.

12. A bifunctional aromatic aldimine for producing quinolines, polyquinolines, nitrogen-doped aromatic molecular segments, and graphene nanoribbons according to:

and comprising:
an aromatic core comprising aromatic or heteroaromatic rings, wherein
n is a number of distinct rings and is an integer of at least 1, and
the aromatic core is substituted with at least one halogen;

an aldimine functionality immediately and covalently attached to the aromatic core, wherein R is a substituted or unsubstituted aromatic or heteroaromatic ring; and
an aromatic terminal alkyne functionality immediately and covalently attached at any position of the aromatic core and capable of reacting with an aromatic aldimine in an aza-Diels Alder Povarov reaction, wherein
the at least one halogen is at meta position of the aromatic core relative to the aldimine functionality.

13. The bifunctional aromatic aldimine of claim 12 , wherein the at least one halogen is chlorine.

14. The bifunctional aromatic aldimine of claim 12 , wherein R is substituted with at least one functionality, each independently selected from the group consisting of: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof.

15. The bifunctional aromatic aldimine of claim 14 , wherein R has at least two substitutions.

16. The bifunctional aromatic aldimine of claim 12 , wherein n is at least 2.

17. The bifunctional aromatic aldimine of claim 12 , wherein n is 2, and the ring that does not bear the aldimine functionality is heteroaromatic.

18. The bifunctional aromatic aldimine of claim 12 , wherein n is 2, and the ring that does not bear the aldimine functionality is further functionalized with at least one of:
aliphatic group, electron withdrawing group, electron donating g

Assignees

• Univ California

Inventors

• Gorodetsky Alon
• Dibble David Joshua
• Umerani Mehran
• Mazaheripour Amir
• Park Young Suk
• Burke Anthony

Classifications

• C07D215/06 Primary

  having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom · CPC title

• C07C5/02

  by hydrogenation (simultaneous hydrogenation and dehydrogenation C07C5/52) · CPC title

• C07D215/04

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms · CPC title

• C07D215/12

  with substituted hydrocarbon radicals attached to ring carbon atoms · CPC title

• C07D215/18

  Halogen atoms or nitro radicals · CPC title