Document Type

Thesis - Open Access

Award Date


Degree Name

Master of Science (MS)




At the outset of this research, the objective was to combine synthetic methods to give a cyclophane structure containing two heteroatoms that may be used as ligands for metal complexes. The cyclophane synthesis that was intended to be used to produce the final cyclic structure is that of sulfur extrusion. The heteroatoms that were chosen for this research were phosphorous atoms because of the possibility that combined with metal atoms, the complex may be used as a catalyst. The general cyclophane structure contains aromatic rings joined by two or more aliphatic bridges, an example being di-m-xylylene. This compound was first synthesized in 1899 by Pellegrin who prepared it by the use of the Wurtz coupling reaction. This procedure of first making the bromomethyl substituted aromatic rings and subsequently subjecting them to the Wurtz reaction was the method of choice for preparing these compounds up until 1969. The low yields of the cyclophanes and the inability to produce them with multiple bridges prompted a new synthetic technique. This procedure, first introduced by Vogtle in 1969, involved preparation of the dithiacyclophanes. These were then subjected to oxidation, followed by pyrolysis with removal of sulfur dioxide to give the desired cyclophane structure. To produce the dithiacyclophane structure, two procedures have been commonly used. The first of these is the synthesis of a bisbromomethylbenzene compound and the simultaneous addition of this compound with Na2s in a dilute medium. The drawbacks to this procedure are low yields and greater percentage of side products. The second procedure first converts the bisbromomethylbenzene to bismercaptomethyl by a substitution reaction using thiourea and basic decomposition of the bisisthiuronium salt.

Library of Congress Subject Headings

Organic compounds -- Synthesis



Number of Pages



South Dakota State University