The syntheses of various macrocyclic sulfides are reviewed. Tables containing information on hundreds of compounds are included. The types of cyclic compounds reviewed include: macrocyclic aliphatic dithioethers, macrocyclic mercaptals and mercaptoles, macrocyclic polysulfides, dithiacyclophanes, tris‐bridged polythiacyclophanes, dithia[2,6]pyridinophanes, thiophene macrocycles, and macrocyclic polyether sulfides.

Macroeyclic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dimercaptan or sodium sulfide as reported in a previous paper (6). The following new compounds were prepared: 1,4,7‐trithia(15‐crown‐5) (1); 1,4,10‐trithia(15‐crown‐5) (II): 1,4,7,10‐tetrathia(15‐crown‐5) (III); I‐thia(18‐crown‐6) (IV); 1,4‐dithia(18‐crown‐6) (V); 1,7‐dithia(18‐crown‐6) (VI); 1,4,7‐trithia(18‐crown‐6) (VII); 1,7‐dithia(21‐crown‐7) (VIII); and 1,4,7‐trithia(21‐crown‐7) (IX). The melting points of these and previously reported thia‐crown compounds correlate with their structures. X‐ray analyses of two thia‐crown compounds indicate that the large sulfur atoms are directed away from the center of the ring.

Macrocyelic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dithiol or sodium sulfide in ethanol. The trivial naming system for these compounds is an extension of the trivial crown nomenclature (5). A thia prefix is used to show that sulfur atoms have replaced ether oxygen atoms in the polyether ring. The following new compounds were prepared: 1‐thia‐(15‐crown‐5) (II) 1,4‐dithia‐(15‐crown‐5) (III) 1,7‐dithia‐(15‐crown‐5) (IV) 1,4‐dithia‐(12‐crown‐4) (VII) 1,4,7‐trithia‐(12‐crown‐4) (VIII) 1‐thia‐(9‐crown‐3) (IX) and 1,4‐dithia‐(9‐crown‐3) (X). Four other previously reported maerocyelic polyether sulfides were also prepared. The symmetry of the nmr spectra of these compounds gives added evidence for the proposed ring structures.

17K 1,11‐Dichlor‐3,6,9‐trioxa‐undecan (I) liefert mit 1,2‐Äthandithiol (II) das Polyäthersulfid (III) und mit Natriumsulfid‐nonahydrat das Polyäthersulfid (IV) in Ausbeuten zwischen l0 und 30%.

Die Herstellung der makrocyclischen Polyäther (I)‐(IX) nach den üblichen Verfahren wird beschrieben.