Macrocyclic sulfides

Реферат: 1287339 Macrocyclic sulphides EI DU PONT DE NEMOURS & CO 7 April 1970 [7 April 1969] 16505/70 Heading C2C The invention comprises a macrocyclic sulphide having a macrocyclic ring of carbon and hetero-atoms totalling 12 to 30 ring atoms, at least one hetero-atom being sulphur and the remainder being oxygen, each hetero-atom in the ring being separated from its adjoining heteroatoms in the ring by 2 or 3 carbon atoms and the macrocyclic ring being fused through pairs of vicinal carbon atoms which themselves are attached to hetero-atoms to 1 to 4 carbocyclic rings selected from: (a) phenylene, naphthylene, phenanthrylene, anthrylene, (b) saturated analogues of (a), and (c) substitution derivatives of (a) or (b); provided that a single pair of adjoining ring-sulphur atoms can be methyleneseparated; and metal complexes thereof. They may be obtained by reacting (a) a compound having a substituted or unsubstituted aromatic or alicyclic nucleus as defined above and also having vicinal substituents which are hydroxy groups on said aromatic nucleus or mercapto 'groups on said aromatic or alicyclic nucleus; and (b) an alkylene, alkylene ether, alkylene thioether or alkylene ether thioether compound which is halogen-diterminated and in which the halogen, oxygen and sulphur atoms are separated from one another by chains of 2 or 3 carbon atoms; in the presence of at least one equivalent of strong base for each equivalent of hydroxy or mercapto groups. In a modification of this process one of said vicinal substituents is protected by a blocking group, said blocking group is removed from the product of the reaction of reactants (a) and (b) and the product is then reacted with a second reactant (b) which may be the same or different as the first reactant (b). The metal complexes may be obtained by dissolving the macrocyclic sulphide and metal compound in a solvent for both compounds and subsequently removing the solvent by evaporation. Examples are given for the preparation of the compounds. They are useful for extraction of metal salts that form crowned complexes from mixtures thereof with salts that do not. Cyclohexane-trans-1,2-dithiol is obtained by reduction of cyclohexene trithiocarbonate with LiAlH 4 . [m-CH 3 -C 6 H 3 S(CH 2 OCH 3 )-S-CH 2 -CH 2 -l 2 -O is obtained by reacting the monomethoxy-methylthio derivative of toluene-3,4- dithiol with bis-(#-chloroethyl) ether in the presence of NaOH in n-butanol.