Processes for preparing calixarenes

Patent metadata

Field	Value
Publication number	US-11072572-B2
Application number	US-202016992747-A
Country	US
Kind code	B2
Filing date	Aug 13, 2020
Priority date	Feb 9, 2018
Publication date	Jul 27, 2021
Grant date	Jul 27, 2021

Abstract

This invention relates to a process for preparing a calixarene compound by reacting a phenolic compound and an aldehyde in the presence of at least one nitrogen-containing base as a catalyst to form the calixarene compound. The invention also relates to processes for high-yield, high solid-content production of a calixarene compound, with high selectivity toward a high-purity calix[8]arene compound, without carrying out a recrystallization step.

First claim

We claim:

1. A process for the selective synthesis of a calix[8]arene compound, comprising:
reacting a phenolic compound, an aldehyde, and a nitrogen-containing base as a catalyst, in the presence of an organic solvent; and
heating the reaction mixture at an elevated temperature to remove water from the reaction mixture and selectively produce a calixarene compound containing at least 70% calix[8]arene.

2. The process of claim 1 , wherein:
the reacting step is carried out under reflux conditions, for a time period of 10 hours or longer; and
the heating step is carried out at an elevated temperature of about 140° C. to about 180° C. for a time period of 4 hours or longer.

3. The process of claim 1 , wherein the heating step at the water removal stage is carried out over a time period of 6 hours or longer to selectively produce a calixarene compound containing at least 90% calix[8]arene.

4. The process of claim 1 , wherein the elevated temperature at the water removal stage ranges from about 140° C. to about 150° C.

5. The process of claim 1 , wherein the phenolic compound is phenol, an alkyl phenol, or an arylalkyl phenol.

6. The process of claim 5 , wherein the phenolic compound is a para-C 1 -C 24 alkyl phenol, benzyl phenol, or cumyl phenol.

7. The process of claim 1 , wherein the aldehyde is formaldehyde or paraformaldehyde.

8. A process for a one-step, selective synthesis of a high-purity calix[8]arene compound, comprising:
reacting, in a one-step process, a phenolic compound and an aldehyde in the presence of a base catalyst to form a high-purity calix[8]arene compound, without carrying out a recrystallization step; and
filtrating the reaction product and drying the filtrated reaction product, thereby producing a calix[8]arene compound with a purity of about 90% or higher.

9. The process of claim 8 ,
wherein the filtrating and drying produce a calix[8]arene compound with a purity of about 95% or higher.

10. The process of claim 8 ,
wherein the filtrating and drying produce a calix[8]arene compound with a purity of about 98% or higher.

11. The process of claim 8 , wherein the phenolic compound is an alkyl phenol, an alkyl phenol, or an arylalkyl phenol.

12. The process of claim 11 , wherein the phenolic compound is a para-C 1 -C 24 alkyl phenol, benzyl phenol, or cumyl phenol.

13. The process of claim 8 , wherein the aldehyde is formaldehyde or paraformaldehyde.

14. A process for the selective synthesis of a calix[8]arene compound with a low free phenolic monomer content, comprising:
reacting a phenolic compound and an aldehyde in the presence of a base catalyst, and
washing the reaction product to remove free phenolic compound monomers, to produce a calix[8]arene compound with a free phenolic monomer content of about 0.5% or lower,
wherein the process does not include a recrystallization step.

15. The process of claim 14 , wherein the free phenolic monomer content is about 0.1% or lower.

16. The process of claim 14 , further comprising:
filtrating the washed reaction product and drying the filtrated reaction product, thereby producing a high-purity calix[8]arene compound with a purity of about 95% or higher.

17. The process of claim 14 , wherein the phenolic compound is an alkyl phenol, an alkyl phenol, or an arylalkyl phenol.

18. The process of claim 17 , wherein the phenolic compound is a para-C 1 -C 24 alkyl phenol, benzyl phenol, or cumyl phenol.

19. The process of claim 14 , wherein the aldehyde is formaldehyde or paraformaldehyde.

20. A phenolic oligomer composition prepared by the process of claim 1 .

21. A phenolic oligomer composition prepared by the process of claim 8 .

22. A phenolic oligomer composition prepared by the process of claim 14 .

Assignees

• Si Group Inc

Inventors

• Haase Cornelius
• Biittig Ricky
• Staats Allyson
• Atwood Philip David
• Webb Jim
• Chichak Kelly

Classifications

• C08G8/12

  with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol · CPC title

• C07C39/15

  with all hydroxy groups on non-condensed rings {, e.g. phenylphenol} · CPC title

• C07C37/20 Primary

  using aldehydes or ketones · CPC title

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title

• B01J31/0239

  Quaternary ammonium compounds · CPC title