Patent GB-1285367-A (GB)
Title: Macrocyclic polyether compounds and ionic complexes thereof
IPC: C07D323/00
Filed: 1969-12-15
Abstract: 1285367 Macrocyclic polyether compounds; halopolyether alcohols E I DU PONT DE NEMOURS & CO 15 Dec 1969 [18 Dec 1968] 61094/69 Heading C2C The invention comprises macrocyclic polyether compounds consisting of 5-10 -O-X- units in which X is each of R 1  and R 2  independently being a hydrogen atom or a C 1 -C 4  alkyl group or consisting of 5-10-O-Y-units in which Y is each of R 1 , R 2 , R 3  and R 4  independently being hydrogen or a C 1 -C 4  alkyl group, or consisting of a single -O-Y unit and 4-9 -O-X- units and also complexes formed between one of these macrocyclic polyethers and an ionic compound having a compatible cation. Preferred ionic compounds are, for example, compounds of rubidium, caesium, calcium, strontium, barium or potassium. The polyether compounds may be obtained by ring closure of a linear polyether having halide and alkali metal alkoxide substituents at opposite ends thereof. Alternatively two polyether chains having the terminal groups referred to above may be condensed together to give the required compounds. The reaction is generally carried out in a solvent for both reactants and products. Suitable solvents include lower alkyl diether derivatives of ethylene glycol or polyethylene glycols having around boiling point below 150 C., dioxane and mixtures of ethers, the preferred solvent being 1,2-dimethoxyethane. The complexes of the macrocyclic polyethers with compounds of alkali metals or alkaline earth metals may be prepared by one of the following methods: (a) dissolving the polyether and metal compound in a solvent and later evaporating the solvent; (b) dissolving the polyether and metal compound in a minimum quantity of hot solvent and precipitating the complex by cooling; (c) heating the polyether with the metal compound in a solvent which only dissolves the latter compound and separating the crystalline complex formed; (d) heating the polyether with the metal compound and (e) reacting a benzene solution of a cyclic ether-potassium hydroxide complex with a protonated anion. Examples are given of the preparation of 1,4,7,10,13,16-hexaoxacyclooctadecane; 1,4,7,10,13 - pentaoxacyclopentadecane; 1,4,7,10,13,16,19 - heptaoxacycloheneicosane; 1,4,7,10,13,16,19,22 - octaoxacyclotetracosane; and 1,4,7,10,13,16,19,22,25,28- decaoxacyclotrinacontane. The compounds can be used to solubilize metal compounds which are normally insoluble and may be used for the separation of dissolved salts. An example is given of the extraction of the picrates of lithium, sodium, potassium, rubidium, caesium and barium from aqueous solutions into methylene chloride by means of the cylic polyethers. It is stated that complexes of the polyethers with potassium hydroxide or a potassium salt may be used as catalysts for the polymerization of formaldehyde and isocyanates and a complex with potassium hydroxide can bring about the alkaline hydrolysis of esters of 2,4,6-trimethyl benzoic acid. The halopolyether-alcohols used as starting materials may be prepared (a) by reacting 1 mole of an α- #-dihalopolyether with at least one mole of an α- #-dihydroxypolyether in the presence of 1 mole of an alkali metal hydroxide, e.g. (b) in the case of linear polyether reactants in which the oxygen atoms are separated by 2 carbon atoms by polymerizing an oxirane compound (e.g. ethylene oxide) by treatment with potassium hydroxide and then monochlorinating the product by treatment with thionyl chloride.