Method for the high-yield production of P-(R-oxy)calix[9-20] arenes

1. A process for the preparation of a p-(R-oxy)calixarene or a mixture of at least two of said p-(R-oxy)calixarenes, comprising:

mixing (i) at least one base, (ii) at least one phenol substituted in position 4 of following formula (I):

in which R is selected from:

a benzyl group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR′ and OR′, R′ representing a linear or branched C 1 -C 20 alkyl chain, a C 3 to C 20 cycloalkyl group, NR a R b , PR a R b , P(O)R a R b , P(O)OR a ORb, R a and R b representing independently of one another a linear or branched C 1 -C 20 alkyl,

a linear or branched C 1 -C 20 alkyl group,

a linear or branched PEG-1 to 10, the —OH end group of which is alkylated with a linear or branched C 1 -C 20 alkyl,

(ii) a source of formaldehyde and (iii) an organic solvent, the mixture of said base, said phenol, said source of formaldehyde and said organic solvent constituting a reaction medium,

heating said reaction medium to carry out a reaction,

wherein said base being at a total concentration from more than 0.5 equivalent to 1.5 equivalent, with respect to said at least one phenol substituted in position 4 of formula (I), and

wherein said reaction forms a p-(R-oxy)calixarene selected from the group consisting of a p-(R-oxy)calix[9]arene, a p-(R-oxy)calix[10]arene, a p-(R-oxy)calix[11]arene, a p-(R-oxy)calix[12]arene, a p-(R-oxy)calix[13]arene, a p-(R-oxy)calix[14]arene, a p-(R-oxy)calix[15]arene, a p-(R-oxy)calix[16]arene, a p-(R-oxy)calix[17]arene, a p-(R-oxy)calix[18]arene, a p-(R-oxy)calix[19]arene, a p-(R-oxy)calix[20]arene, and a mixture of at least two of said p-(R-oxy)calixarenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %.

2. A process for preparing

a p-(R-oxy)calixarene selected from the group consisting of a p-(R-oxy)calix[9]arene, a p-(R-oxy)calix[10]arene, a p-(R-oxy)calix[11]arene, a p-(R-oxy)calix[12]arene, a p-(R-oxy)calix[13]arene, a p-(R-oxy)calix[14]arene, a p-(R-oxy)calix[15]arene, a p-(R-oxy)calix[16]arene, a p-(R-oxy)calix[17]arene, a p-(R-oxy)calix[18]arene, a p-(R-oxy)calix[19]arene, and a p-(R-oxy)calix[20]arene, or

a mixture of at least two of said p-(R-oxy)calixarenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %,

comprising a step of bringing a base, into contact with at least one phenol substituted in position 4 of following formula (I):

in which R is selected from:

a benzyl group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR′ and OR′, R′ representing a linear or branched C 1 -C 20 alkyl chain, a C 3 to C 20 cycloalkyl group, NR a R b , PR a R b , P(O)R a R b , P(O)OR a ORb, R a and R b representing independently of one another a linear or branched C 1 -C 20 alkyl,

a linear or branched C 1 -C 20 alkyl group,

a linear or branched PEG-1 to 10, the —OH end group of which is alkylated with a linear or branched C 1 -C 20 alkyl,

a source of formaldehyde and an organic solvent, the mixture of said base, said phenol, said source of formaldehyde and said organic solvent constituting a reaction medium,

said reaction medium being heated and said base being at a total concentration comprised from more than 0.5 equivalent to 1.5 equivalent with respect to said at least one phenol substituted in position 4 of formula (I).

3. The process according to claim 2 , wherein said phenol substituted in position of formula (I) is selected from 4-benzyloxyphenol or 4-octyloxyphenol.

4. The process according to claim 2 , wherein the source of formaldehyde is paraformaldehyde and the organic solvent is xylene.

5. The process according to claim 2 , wherein said base is selected from caesium hydroxide and rubidium hydroxide.

6. The process according to claim 2 , according to claim 5 , comprising the following steps:

a. bringing caesium and/or rubidium hydroxide, into contact with at least one phenol substituted in position 4 of formula (I), said base being at a total concentration comprised from more than 0.5 equivalent to 1.5 equivalent, with respect to said at least one phenol substituted in position 4 of formula (I), a source of formaldehyde, in an organic solvent then heating while optionally removing said water formed from the reaction medium,

in order to obtain:

a p-(R-oxy)calixarene selected from the group consisting of a p-(R-oxy)calix[9]arene, a p-(R-oxy)calix[10]arene, a p-(R-oxy)calix[11]arene, a p-(R-oxy)calix[12]arene, a p-(R-oxy)calix[13]arene, a p-(R-oxy)calix[14]arene, a p-(R-oxy)calix[15]arene, a p-(R-oxy)calix[16]arene, a p-(R-oxy)calix[17]arene, a p-(R-oxy)calix[18]arene, a p-(R-oxy)calix[19]arene, and a p-(R-oxy)calix[20]arene, or,

a mixture of at least two of said p-(R-oxy)calix[9-20]arenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %,

in the salified form in the final reaction medium,

b. neutralizing said salified form of said p-(R-oxy)calixarene or of said mixture in order to obtain said p-(R-oxy)calixarene or said mixture in the neutralized form.

7. The process according to claim 2 , in which said base is selected from sodium hydroxide or potassium hydroxide in an aqueous solution.

8. The process according to claim 7 , comprising the following steps:

a. bringing sodium hydroxide or potassium hydroxide in an aqueous solution, into contact with at least one phenol substituted in position 4 of formula (I), said base being at a total concentration comprised from more than 0.5 equivalent to 1.5 equivalent with respect to said at least one phenol substituted in position 4 of formula (I), of the paraformaldehyde in an organic solvent then heating,

in order to obtain:

a p-(R-oxy)calixarene selected from the group consisting of a p-(R-oxy)calix[9]arene, a p-(R-oxy)calix[10]arene, a p-(R-oxy)calix[11]arene, a p-(R-oxy)calix[12]arene, a p-(R-oxy)calix[13]arene, a p-(R-oxy)calix[14]arene, a p-(R-oxy)calix[15]arene, a p-(R-oxy)calix[16]arene, a p-(R-oxy)calix[17]arene, a p-(R-oxy)calix[18]arene, a p-(R-oxy)calix[19]arene, and a p-(R-oxy)calix[20]arene, or,

a mixture of at least two of said p-(R-oxy)calixarenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %,

and a p-(R-oxy)calix[7]arene,

in the salified form in the final reaction medium,

b. optionally filtering the reaction medium in order to obtain said p-(R-oxy)calix[7]arene in the form of the sodium or potassium monosalt, followed by an additional stage of neutralization of the p-(R-oxy)calix[7]arene in the form of the sodium or potassium monosalt in order to obtain the p-(R-oxy)calix[7]arene in the neutralized form and a filtered final reaction medium,

c. neutralizing said final reaction medium or of said filtered final reaction medium in order to obtain:

said p-(R-oxy)calixarene or said mixture, substantially devoid of p-(R-oxy)calix[7]arene, in the neutralized form, or

said p-(R-oxy)calixarene or said mixture, in combination with p-(R-oxy)calix[7]arene, in the neutralized form,

d. optionally purifying:

of said p-(R-oxy)calixarene or of said mixture, substantially devoid of p-(R-oxy)calix[7]arene, in the neutralized form, or

said p-(R-oxy)calixarene or said mixture, in combination with p-(R-oxy)calix[7]arene, in the neutralized form.

9. A phenolic dimer substituted in position 4 of following formula (II):

in which R is as defined in claim 1 .

10. A p-(R-oxy)calix[n]arene or mixture of at least two p-(R-oxy)calix[n]arenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %, of following formula (III):

in which n is an integer comprised from 9 to 20, R being as defined in claim 1 .

11. A method for the constitution of a material, comprising adding to said material a p-(R-oxy)calixarene selected from the group consisting of a p-(R-oxy)calix[9]arene, a p-(R-oxy)calix[10]arene, a p-(R-oxy)calix[11]arene, a p-(R-oxy)calix[12]arene, a p-(R-oxy)calix[13]arene, a p-(R-oxy)calix[14]arene, a p-(R-oxy)calix[15]arene, a p-(R-oxy)calix[16]arene, a p-(R-oxy)calix[17]arene, a p-(R-oxy)calix[18]arene, a p-(R-oxy)calix[19]arene, and a p-(R-oxy)calix[20]arene, or of a mixture of at least two of said p-(R-oxy)calix[9-20]arenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %, said material being able to be used in the implementation of a process for obtaining gels or foams, for the constitution of a material in the context of the mechanical reinforcement of materials, for the synthesis of metallic particles with controlled dimensions and a low dispersion, for nanofiltration, for gas filtration, for the complexing of ions, and for the vectorization or encapsulation of molecules.

12. A method for the constitution of a material, comprising adding to said material a p-(R-oxy)calix[n]arene or mixture of at least two p-(R-oxy)calix[n]arenes in which said at least two p-(R-oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %, of following formula (III):

in which n is an integer comprised from 9 to 20, R being as defined in claim 1 ,

and:

said material being able to be used in the implementation of a process for obtaining gels or foams, for the constitution of a material in the context of the mechanical reinforcement of materials, for the synthesis of metallic particles with controlled dimensions and a low dispersion, for nanofiltration, for gas filtration, for the complexing of ions, and for the vectorization or encapsulation of molecules.

13. The process according to claim 1 , wherein said at least one base is selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide and caesium hydroxide.

14. The process according to claim 2 , wherein said at least one base is selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide and caesium hydroxide.

15. The process according to claim 6 , wherein bringing the caesium and/or rubidium hydroxide into contact with at least one phenol substituted in position 4 of formula (I) is in an aqueous solution.

16. The process according to claim 6 , further comprising an additional step of purifying said p-(R-oxy)calixarene or said mixture in the neutralized form.

17. The process according to claim 16 , wherein said additional step of purifying is by crystallization from a mixture of solvents based on DMSO in order to obtain said p-(R-oxy)calixarene or said mixture in the purified neutralized form.

18. The process according to claim 8 , wherein purifying is carried out by crystallization from a mixture of solvents based on DMSO to obtain

said p-(R-oxy)calixarene or said mixture, substantially devoid of p-(R-oxy)calix[7]arene, in the neutralized form, or

said p-(R-oxy)calixarene or said mixture, in combination with p-(R-oxy)calix[7]arene, in the neutralized form.

19. The phenolic dimer according to claim 9 , wherein R is a benzyl group or an octyl group.

20. The p-(R-oxy)calix[n]arene or mixture of at least two p-(R-oxy)calix[n]arenes according to claim 10 , wherein R is a benzyl group or an octyl group.

21. The p-(R-oxy)calix[n]arene or mixture of at least two p-(R-oxy)calix[n]arenes according to claim 10 , wherein said p-(R-oxy)calixarene or said mixture of p-(R-oxy)calixarenes is in combination with p-(R-oxy)calix[7]arene.

22. The p-(R-oxy)calix[n]arene or mixture of at least two p-(R-oxy)calix[n]arenes according to claim 21 , wherein said p-(R-oxy)calix[7]arene is in the form of the sodium or potassium monosalt.

23. The method according to claim 11 , wherein said p-(R-oxy)calixarene or said mixture is in combination with p-(R-oxy)calix[7]arene.

24. The method according to claim 12 , wherein R is a benzyl group or an octyl group.

25. The method according to claim 12 , wherein said p-(R-oxy)calixarene or said mixture of p-(R-oxy)calixarenes is in combination with p-(R-oxy)calix[7]arene.

26. The method according to claim 25 , wherein said p-(R-oxy)calix[7]arene is in the form of the sodium or potassium monosalt.