Process for the high-yield preparation of P-(R)calix[9-20]arenes

Patent metadata

Field	Value
Publication number	US-9809523-B2
Application number	US-201515122324-A
Country	US
Kind code	B2
Filing date	Feb 27, 2015
Priority date	Feb 28, 2014
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

A process for the high-yield preparation of p-(R)calix[9-20]arenes.

First claim

The invention claimed is:

1. A process for preparing:
a large p-(R)calixarene selected from the group consisting of a p-(R)calix[9]arene, a p-(R)calix[10]arene, a p-(R)calix[11]arene, a p-(R)calix[12]arene, a p-(R)calix[13]arene, a p-(R)calix[14]arene, a p-(R)calix[15]arene, a p-(R)calix[16]arene, a p-(R)calix[17]arene, a p-(R)calix[18]arene, a p-(R)calix[19]arene, and a p-(R)calix[20]arene, or
a mixture of at least two of said large p-(R)calixarenes in which said at least two large p-(R)calixarenes are present in said mixture each at a level of at least 5 mol. %,
said process comprising:
bringing at least one base selected from the group consisting of barium hydroxide, rubidium hydroxide, lithium hydroxide, caesium hydroxide, potassium hydroxide and sodium hydroxide, into contact with at least one phenol substituted in position 4 of the 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 OR b , 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, with the exclusion of the t-butyl group,
a benzyloxy 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 OR b , 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 alkyloxy group,
a linear or branched 1 to 10 O-PEG group, the —OH end group of which is alkylated with a linear or branched C 1 -C 20 alkyl,
a benzyl thioether group —S—CH 2 -Ph optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR′ and OR′, NR a R b , PR a R b , P(O)R a R b , P(O)OR a OR b , 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 thioether group, of formula —S—(C 1 -C 20 -alkyl),
an —NR a R b group, R a and R b representing, independently of one another, a linear or branched C 1 -C 20 alkyl, and
a dibenzylamine group of formula —N(benzyl) 2 , in which the two benzyl groups are, independently of one another, 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 OR b , R a and R b representing, independently of one another, a linear or branched C 1 -C 20 alkyl,

and a source of aqueous formaldehyde, in the absence of an organic solvent, thus constituting an initial reaction medium, said base being at a total concentration comprised from approximately 0.01 to 1 equivalent, with respect to said at least one phenol substituted in position 4 of formula (I), said initial reaction medium being heated to a temperature comprised from 100 to 165° C., in order to obtain a heated reaction medium;
optionally, after said heating, additional heat treating of said heated reaction medium, in the presence of heat transfer means, in order to obtain a mixture (b), comprising said large p-(R)calixarene or said mixture (a) of at least two of said large p-(R)calixarenes, said mixture (b) comprising in addition a mixture (c) of giant p-(R)calixarenes, the size of which is greater than 20; and
after said heating and optional additional heat treating, purifying said mixture (b), so as to remove said mixture (c) of giant p-(R)calixarenes, and to obtain said large p-(R)calixarene or said mixture (a) of at least two of said large p-(R)calixarenes, devoid of said mixture (c) of giant p-(R)calixarenes.

2. The process according to claim 1 , for the preparation of:
a large p-(R)calixarene selected from the group consisting of a p-(R)calix[9]arene, a p-(R)calix[10]arene, a p-(R)calix[11]arene, and a p-(R)calix[12]arene, or
a mixture of at least two of said large p-(R)calixarenes in which said at least two large p-(R)calixarenes are present in said mixture each at a level of at least 5 mol. %.

3. The process according to claim 1 , for the preparation of:
a large p-(R 1 -oxy)calixarene selected from the group consisting of a p-(R 1 -oxy)calix[9]arene, a p-(R 1 -oxy)calix[10]arene, a p-(R 1 -oxy)calix[11]arene, a p-(R 1 -oxy)calix[12]arene, a p-(R 1 -oxy)calix[13]arene, a p-(R 1 -oxy)calix[14]arene, a p-(R 1 -oxy)calix[15]arene, a p-(R 1 -oxy)calix[16]arene, a p-(R 1 -oxy)calix[17]arene, a p-(R 1 -oxy)calix[18]arene, a p-(R 1 -oxy)calix[19]arene, and a p-(R 1 -oxy)calix[20]arene, or
a mixture of at least two of said large p-(R 1 -oxy)calixarenes in which said at least two large p-(R 1 -oxy)calixarenes are present in said mixture each at a level of at least 5 mol. %,

said process comprising:
bringing at least one base selected from the group consisting of barium hydroxide, rubidium hydroxide, lithium hydroxide, caesium hydroxide, potassium hydroxide and sodium hydroxide, into contact with at least one phenol substituted in position 4 of the following formula (Ia):

in which R 1 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 OR b , 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, and
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,
and a source of aqueous formaldehyde, in the absence of an organic solvent, thus constituting an initial reaction medium, said base being at a total concentration comprised from approximately 0.01 to 1 equivalent, with respect to said at least one phenol substituted in position 4 of formula (I), said initial reaction medium being heated to a temperature comprised from 100 to 165° C., in order to obtain a heated reaction medium;
optionally, after said heating, additional heat treating of said heated reaction medium, in the presence of heat transfer means, in order to obtain a mixture (b), comprising said large p-(R 1 -oxy)calixarene or said mixture (a) of at least two of said large p-(R 1 -oxy)calixarenes, said mixture (b) comprising in addition a mixture (c) of giant p-(R 1 -oxy)calixarenes, the size of which is greater than 20; and
after said heating and optional additional heat treating, purifying said mixture (b), so as to remove said mixture (c) of giant p-(R 1 -oxy)calixarenes, and to obtain said large p-(R 1 -oxy)calixarene or said mixture (a) of at least two of said large p-(R 1 -oxy)calixarenes, devoid of said mixture (c) of giant p-(R 1 -oxy)calixarenes.

4. The process according to claim 1 , for preparing:
a large p-(R 1 -oxy)calixarene selected from the group consisting of a p-(R 1 -oxy)calix[9]arene, a p-(R 1 -oxy)calix[10]arene, a p-(R 1 -oxy)calix[11]arene, and a p-(R 1 -oxy)calix[12]arene, or
a mixture of at least two of said

Assignees

• Univ Paris-Sud Xi
• Centre Nat Rech Scient

Inventors

• Huc Vincent Germain
• Martini Cyril

Classifications

• C07C41/40

  by change of physical state, e.g. by crystallisation · CPC title

• C07C41/30 Primary

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C08G8/20

  with polyhydric phenols · CPC title

• C08G83/005

  Hyperbranched macromolecules · CPC title

• C07C67/14

  from carboxylic acid halides · CPC title