US 9,809,523 B2
Process for the high-yield preparation of P-(R)calix[9-20]arenes
Vincent Germain Huc, Orsay (FR); and Cyril Martini, Bures sur Yvette (FR)
Assigned to UNIVERSITE PARIS-SUD XI, Orsay (FR); and CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR)
Appl. No. 15/122,324
Filed by UNIVERSITE PARIS-SUD XI, Orsay (FR); and CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR)
PCT Filed Feb. 27, 2015, PCT No. PCT/FR2015/050479
§ 371(c)(1), (2) Date Aug. 29, 2016,
PCT Pub. No. WO2015/128593, PCT Pub. Date Sep. 3, 2015.
Claims priority of application No. 14 51660 (FR), filed on Feb. 28, 2014.
Prior Publication US 2016/0368849 A1, Dec. 22, 2016
Int. Cl. C07C 41/30 (2006.01); C07C 41/34 (2006.01); C08G 8/00 (2006.01); C07C 67/14 (2006.01); C07C 41/40 (2006.01); C08G 8/20 (2006.01); C08G 8/28 (2006.01); C08G 83/00 (2006.01)
CPC C07C 41/30 (2013.01) [C07C 41/34 (2013.01); C07C 41/40 (2013.01); C07C 67/14 (2013.01); C08G 8/20 (2013.01); C08G 8/28 (2013.01); C08G 83/005 (2013.01); C07C 2603/92 (2017.05); C08G 2105/00 (2013.01)] 17 Claims
 
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):

OG Complex Work Unit Drawing
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 C1-C20 alkyl chain, a C3 to C20 cycloalkyl group, NRaRb, PRaRb, P(O)RaRb, P(O)ORaORb, Ra and Rb representing, independently of one another, a linear or branched C1-C20 alkyl,
a linear or branched C1-C20 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 C1-C20 alkyl chain, a C3 to C20 cycloalkyl group, NRaRb, PRaRb, P(O)RaRb, P(O)ORaORb, Ra and Rb representing, independently of one another, a linear or branched C1-C20 alkyl,
a linear or branched C1-C20 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 C1-C20 alkyl,
a benzyl thioether group —S—CH2-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′, NRaRb, PRaRb, P(O)RaRb, P(O)ORaORb, Ra and Rb representing, independently of one another, a linear or branched C1-C20 alkyl,
a linear or branched C1-C20 alkyl thioether group, of formula —S—(C1-C20-alkyl),
an —NRaRb group, Ra and Rb representing, independently of one another, a linear or branched C1-C20 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 C1-C20 alkyl chain, a C3 to C20 cycloalkyl group, NRaRb, PRaRb, P(O)RaRb, P(O)ORaORb, Ra and Rb representing, independently of one another, a linear or branched C1-C20 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.