Synthesis of calix[4]resorcinarenes, containing phosphoryl fragments at the lower rim of the molecule

Abstract

Reaction of resorcinol with phosphorylated acetals or ethoxyvinylphosphonic acid esters in acidic media leads to calix[4]resorcinarenes, containing dialkoxyphosphoryl fragments at the lower rim of the molecule. When the alkyl substituent in alkoxy groups at phosphorus atom is not very long, a partial hydrolysis of the initially formed products takes place to give calixarenes with alkoxyhydroxyphosphoryl fragments.Exploration of chemistry of calix[n]arenes, in particu lar calix[4]resorcinarenes, is one of the most promising and intensively developing trends in organic chemistry. 1-3 The simplicity of their synthesis and the ability to form complexes of the "guest-host" type with various in struc ture organic compounds and metal ions, as well as the tendency to self association, leading to supramolecular ensembles, are the conditions of it. All the properties described above make this class of compounds very pro spective from the point of view of creation of new types of complex forming agents and the metal ions extragents, as well as new catalytic systems. The most widely used ap proach to the formation of calixarene matrix includes the reaction of polyphenols with aldehydes and their deriva tives. However, it has certain limitations, since the ques tion about influence of the starting aldehyde and polyphe nol structures on the composition of the forming final products is not entirely clear. It is known 4-6 that un substituted aliphatic and aromatic aldehydes, as well as aliphatic aldehydes with functional substituents, separated from the reaction center by four-eight carbon atoms, afford calix[4]resorcinarenes by condensation with resor cinol in acidic media. At the same time, such structures are not formed in the reaction of α halogen substituted aliphatic aldehydes with resorcinol. 5 Within the frame work of approach under discussion, there is no informa tion about a possibility of the synthesis of calixarenes by the reaction of resorcinol with aldehydes, containing func tional substituents, separated from the carbonyl group by two-three carbon atoms.Calix[4]resorcinarenes, bearing phosphoryl substi tuted alkyl groups at the lower rim of the molecule, are of particular interest as complex forming agents and extragents. Methods for the preparation of compounds of this type are not described in the literature, which, appar ently, is mainly connected with the difficulties in the synthesis of phosphorylated aliphatic aldehydes. It should be also noted that so far the attempts to obtain calixarenes, bearing phosphorus containing alkyl fragments at the lower rim of the molecule, by phosphorylation of the already made calixarene matrix failed and it is doubtful whether such an approach will be implemented in the nearest future. We came to a conclusion that the synthesis of calix [4]resorcinarenes, phosphorylated at the lower rim of the molecule, most likely can be fulfilled during forma tion of calixarene matrix. Since, as it was already men tioned above, phosphorylated aldehydes are not easily available, we tried to ...

An unusual reaction of 2‐ethoxyethenylphosphonic dichloride with resorcinol and its derivatives: Synthesis of bicyclic phosphonates with endocyclic P–C bond

“…We developed a facile one‐step method of synthesis of new framework compounds 3a–c of phosphonate structure by the condensation of available 2‐ethoxyethenylphosphonic dichloride 1 14 with resorcinol and its derivatives 2a–c in dichloromethane in the presence of trifluoroacetic acid. It should be noted that compounds obtained contain several hydroxy groups and for this reason they are interesting as basic compounds for the synthesis of novel polymer and macrocyclic structures (Scheme ).…”

“…It should be noted that the condensation of 2‐ethoxyethenylphosphonic dichloride 1 with resorcinol and its derivatives in the water–alcohol medium in the presence of hydrochloric acid gives another synthetic result, the formation of phosphorus‐containing calix4resorcinols, bearing phosphoryl groups at the bottom rim 14.…”

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…The alternative process, viz., the cyclophosphorylation, proceeds by only 23% even if the phos- phorylating agent is used in a deficient amount (the ratio is 1 : 2). The corresponding reaction with tetramethyloctol 93a always affords a mixture of products containing both cyclic (187) and acyclic (186) derivatives regardless of the reactant ratio. By contrast, the reaction with tetra-n-butyloctol 93g involves its cyclophosphorylation as the major process, and the reaction with the use of the reactants in the stoichiometirc ratio (1 : 4) follows only the path b.…”

Phosphorylated Aminoacetal in the Synthesis of New Acyclic, Cyclic, and Heterocyclic Polyphenol Structures

“…We have shown earlier that condensation of functionally substituted acetals with resorcinol and its derivatives in acidic media is a convenient method to prepare unique linear and cyclic polyphenols, namely, P,N‐containing calix[4]resorcinols , derivatives of diarylmethane series including those on macrocyclic framework , and imidazolidine‐2‐ones containing polyphenol fragments . It was determined that synthesized calix[4]resorcinols can be utilized in micellar catalysis and are able to complexation with rare earth metal ions and extraction of carbon nanotubes .…”