Patent GB-1108921-A (GB)
Title: Improvements relating to polyethers
IPC: C09B39/00
Filed: 1965-04-09
Abstract: A formaldehyde resin is prepared by condensing paraformaldehyde with a cyclic ether of the formula <FORM:1108921/C3/1> in chloroform solution in the presence of sulphuric and acetic acid (Example 5).  A benzene soluble complex of potassium hydroxide and the cyclic ether of the formula <FORM:1108921/C3/2> can be used as a catalyst for the anionic polymerization of pivalolactone.ALSO:Azo dyes containing the residue of a macrocyclic ether containing 4-8 ether oxygen atoms in the ring, each oxygen atom separated from the next by 2-10 carbon atoms and at least two oxygen atoms being attached to vicinal carbon atoms of an aromatic nucleus, are prepared either (1) by reacting said ether containing an hydroxy or amino substituent in the aromatic nucleus with a diazo compound or (2) by diazotizing an amino derivative of said ether and reacting the diazo compound with an aromatic compound containing active hydrogen.  Specified azo dyes are those obtained by reacting a solution of 1-amino-8-naphthol-3,6-disulphonic in aqueous NaOH with the diazo compound derived from amino derivatives of cyclic ethers of the formulae <FORM:1108921/C4-C5/1> <FORM:1108921/C4-C5/2> <FORM:1108921/C4-C5/3>ALSO:An organic halide solution of a macrocyclic polyether of the Formula (X) <FORM:1108921/C1/1> can be used to remove potassium ions, with which ether (10) forms a "crown" complex, from an aqueous solution of magnesium and potassium salts.ALSO:The invention comprises macrocyclic polyethers having 4-8 ether oxygen atoms in the ring, at least 2 of said ether oxygen atoms being attached to vicinal carbon atoms of an aromatic nucleus and each oxygen atom being separated from the next by 2-10 carbon atoms. Preferred compounds are those containing 14-28 ring atoms in which the ether oxygen atoms are separated by 3 or 4 carbon atoms.  The aromatic nucleus is preferably benzene which may be substituted, e.g. by alkyl, halogen, sulphonic, nitro, amino, hydroxyl and carboxylic groups. The compounds can be made by reacting (a) a vicinal dihydric phenol with (b) an a ,o -alkylene primary dihalide or ether in which neither primary halogen atom is attached closer than at the b -carbon to the other halogen or the ether linkage, and (c) at least 1 equivalent of a base per phenolic hydroxy group.  The process may yield a mixture of cyclic ethers which can be separated by conventional techniques, e.g. when the phenol is catechol, the product may have the formulae <FORM:1108921/C2/1> <FORM:1108921/C2/2> where A and B are the residues of alkylene dihalides.  Compounds of the above formula in which the residues B are different are made by reacting a dihydric phenol in which one of the hydroxy groups is protected, e.g. by reaction with dihydropyran or a -chloromethyl ether, with one alkylene dihalide, removing the protecting group and reacting the resulting dihydroxy ether with a second alkylene dihalide. Some substituents in the aromatic residue may be introduced after the formation of the polyether ring.  The cyclic ethers form complexes with a number of cations, particularly those derived from primary amines and metals of Groups I-III.  The stoichiometry of the complexes does not depend on the valency of the cation, thus 1 mol. of cyclic ether complexes with 1 gm. atom of Li+ or Cu++.  The complexes form most readily from those ethers and cations in which the ring diameter of the ether exceeds the ionic diameter of the cation.  The complexes are prepared by mixing the cyclic ether and a compound yielding the cation in a solvent in which at least one of the reactants is soluble.  The formation of these complexes can be used to form non-aqueous or non-alcoholic solutions containing cations which are normally insoluble therein, e.g. a benzene soluble complex of potassium hydroxide is obtained from potassium hydroxide and certain cyclic ethers by reaction in methanol followed by evaporation of the solvent. The cyclic ethers serve as intermediates in the synthesis of azo-dyes and formaldehyde resins and as scavenging agents for inorganic ions (see Divisions C3, C4 and C1). The crown complexes can be used as polymerization catalysts.