Gold-catalysed process for manufacturing chromenes intended for the preparation of thermosetting resins

Patent metadata

Field	Value
Publication number	US-11820780-B2
Application number	US-202016936966-A
Country	US
Kind code	B2
Filing date	Jul 23, 2020
Priority date	Jul 23, 2019
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

Abstract

A process for manufacturing chromenes intended for the preparation of thermosetting resins, includes transforming an aromatic propargyl ether of general formula (I) into a chromene by homogeneous gold(I) catalysis with the catalyst (acetonitrile)[(2-biphenyl)di-tert-butylphosphine]gold(I) hexafluoroantimonate in an organic solvent under an inert or non-inert atmosphere. Moreover, a process for preparing a material made of thermoset resin, includes successively a) implementation of the above process; polymerization of the reaction product obtained in step a) so as to obtain the material made of thermoset resin; c) recovery of the material made of thermoset resin obtained in step b).

First claim

The invention claimed is:

1. A process for manufacturing chromenes which are intended for the preparation of thermosetting resins, comprising the step of transforming an aromatic propargyl ether of general formula (I) below

in which:
R 1 and R 5 represent, independently of each other, a hydrogen atom, a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne group, on condition that at least one from among R 1 and R 5 represents a hydrogen atom and that the groups R 1 and R 5 do not represent an O-propargyl group;
R 2 and R 1 represent, independently of each other, a hydrogen atom, a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne;
and R 3 represents a hydrogen atom or a C 2 -C 6 alkene group, the alkene group being optionally substituted with a group of general formula (II) below

in which:
R 6 and R 9 represent, independently of each other, a hydrogen atom, a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne group, on condition that at least one from among R 6 and R 9 represents a hydrogen atom;
and R 7 and R 8 represent, independently of each other, a hydrogen atom, a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne;
on condition that at least one from among R 1 , R 2 , R 3 , R 1 and R 5 does not represent a hydrogen atom or a O—(C 1 -C 6 )alkyl group;
and the cis/trans isomers thereof and the optical isomers thereof and the racemic mixtures thereof into a chromene by homogeneous gold(I) catalysis with the catalyst (acetonitrile)[(2-biphenyl)di-tert-butylphosphine]gold(I) hexafluoroantimonate in an organic solvent under an inert or non-inert atmosphere
wherein the aromatic propargyl ether of general formula (I) is chosen from the group consisting of propargylated resorcinol, propargylated eugenol, propargylated coupled eugenol, propargylated coupled isoeugenol, propargylated isoeugenol and mixtures thereof and the cis/trans isomers thereof and the optical isomers thereof and the racemic mixtures thereof.

2. The process according to claim 1 , wherein the molar percentage of residual propargyl functions in the chromene is less than 11% when the aromatic propargyl ether of general formula (I) is propargylated resorcinol, the molar percentage of residual propargyl functions in the chromene is less than 39% when the aromatic propargyl ether of general formula (I) is propargylated coupled eugenol and the molar percentage of residual propargyl functions in the chromene is less than 35% when the aromatic propargyl ether of general formula (I) is propargylated coupled isoeugenol.

3. The process according to claim 1 , wherein the organic solvent is chosen from tetrahydrofuran and 2-methyltetrahydrofuran.

4. The process according to claim 1 , wherein the content of catalyst in the reaction medium is between 0.1 mol % and 2 mol %.

5. The process according to claim 4 , wherein the content of catalyst in the reaction medium is between 0.1 mol % and 0.5 mol %.

6. The process according to claim 1 , wherein the aromatic propargyl ether of general formula (I) is propargylated resorcinol and wherein the chromene obtained has the formula C and/or D below

7. The process according to claim 1 , wherein the catalyst is removed from the reaction medium at the end of the process.

8. A process for preparing a material made of thermoset resin, comprising the following successive steps:
a) implementation of the process according to claim 1 ;
b) polymerization of the reaction product obtained in step a) so as to obtain the material made of thermoset resin;
c) recovery of the material made of thermoset resin obtained in step b).

9. The process according to claim 8 , wherein the enthalpy of polymerization of step b) is less than 500 J/g.

10. The process according to claim 8 , wherein the coke content of the thermoset resin obtained in step c) is greater than 50%.

11. The process according to claim 1 , wherein the aromatic propargyl ether of general formula (I) is propargylated resorcinol.

12. The process according to claim 6 , wherein the chromene obtained is a mixture of the formulae C and D.

Assignees

• Arianegroup Sas
• Centre Nat Rech Scient
• Univ Reims Champagne Ardenne

Inventors

• Pouyet Robin
• Coqueret Xavier
• Defoort Brigitte
• Rivieres Bastien

Classifications

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• C08G61/122

  derived from five- or six-membered heterocyclic compounds, other than imides · CPC title

• C08G2261/11

  Homopolymers · CPC title

• C08G2261/3242

  containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran · CPC title