In previous work done in our laboratories, a method was discovered to produce phenolic mono-ethers from 4-hydroxyacetophenone and other 4-hydroxyketones by treating with ammonium peroxy-disulfate in an alcohol as a reaction solvent and in the presence of concentrated sulphuric acid or other strong protonic acids. Since this method of producing 4-alkoxyphenol ethers provides a very convenient way to modify hydroquinone and substituted hydroquinones to produce a variety of phenol mono-ethers, it was of interest to study the general scope of this reaction, including a more detailed investigation of the reaction mechanism. In previous studies, it was suggested that interaction between the aromatic pi-system of hydroquinone and the cyclohexa-2,5-diene structure of benzoquinone plays a significant role during the reaction. It was therefore of interest to investigate whether other compounds that are also capable of forming the cyclohexa-2,5-diene structure, will interact in a manner analogous to the hydroquinone/benzoquinone couple. Two specific compounds were selected for this purpose, namely 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one . The scope of etherification reactions of hydroquinone-benzoquinone or hydroquinone/benzoquinone like substrates such as 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one in the presence of acid catalyst and alcohols was investigated. These studies showed that hydroquinone, 4- nitrosophenol and 4-(diphenylmethylene)cyclohexa-2,5-dien-1-one successfully affords the phenolic ethers in good to excellent yield. For example, quantitative yield of 4-methoxyphenol could be obtained from a 1:1 mixture of hydroquinone and benzoquinone at the reflux temperature of methanol. In order to study the reaction mechanism, the cross-over reaction between tertbutylhydroquinone and benzoquinone (or hydroquinone and tertbutylbenzoquinone) was studied in detail. The results of these cross-over reactions were used to propose a mechanistic pathway that could explain the requirement for pi-interaction between the hydroquinone and benzoquinone molecules, the role of the acid catalyst, as well as the relative rates of hydroquinone and benzoquinone consumption during these reactions. The mechanism was also capable of explaining all the reaction products observed during these reactions. The work was then extended to reactions of 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one with methanol in the presence of either hydroquinone or benzoquinone. The results of these investigations strongly suggest the presence of similar interactions between these molecules that also influence the outcome of the reactions. The exploitation of pi-interactions between two molecules of these types investigated during this work opens an interesting field of chemistry. Clearly, the level of understanding developed during this work is only beginning to address this interesting field of chemistry and much work will need to be done to gain a fuller understanding of the chemistry involved as well as the potential synthetic value of these interactions.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:nmmu/vital:10402 |
| Date | January 2008 |
| Creators | Indurkar, Jayant R |
| Publisher | Nelson Mandela Metropolitan University, Faculty of Science |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Doctoral, DTech |
| Format | xxiv, 171 leaves, pdf |
| Rights | Nelson Mandela Metropolitan University |
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