Lists
Lists
Collins, R. F. (1956) Observations on the constitution of Reissert's compound. Doctoral thesis, Sir John Cass College.
In 1906, Reissert prepared a crystalline complex by the interaction of quinoline with benzoyl chloride in the presence of aqueous potassium cyanide, and assigned to it the structure of l-benzoyl-2-cyano-1:2-dihydroquinoline (I) to account in part for the production of quinaldinic acid and benzaldehyde on hydrolysis with acid. An investigation has been undertaken in an attempt to obtain further evidence for the structure of the Reissert complex, to determine which structural features of the molecule are necessary to produce this type of hydrolytic fission, and hence to provide a reasonable mechanism for the hydrolysis reaction. The Reissert complex has been partially hydrogenated to 1-benzoyl-2-cyano-1:2:3:4-tetrahydroquinoline (XXX) which has been synthesised also by an alternative route; this observation supports structure (I) for the complex. However (XXX), unlike (I), does not give benzaldehyde on acid hydrolysis. A number of model compounds incorporating the structure features of (I) and of an alternative formulation as 2-henzoyl-2-cyano-1:2-dihydroquinoline (XIII), have been investigated and subjected to treatment with acid. Reactions have also been carried out on the nature and reactivity of the 2-cyano group in (I). An attempt to prepare the ethyl imideate derivative by Finner's method, resulted in fission of the molecule to benzaldehyde and ethyl quinoline-2-carboxyimidoate (XLIX) which was confirmed by the conversion of the latter product into the corresponding amidine. However, a modified Hoesch reaction of (l) with resorcinol appeared to give the expected product. Some substituted Reissert complexes having different aroyl groups have been prepared to assess the effect, if any, on the ease of hydrolysis, of para substituents of different electronic character. A qualitative discussion is included of a possible reaction sequence to account for the products and the mode of hydrolysis of (I)
 |
View Item |