Pyrolysis of anilino nitriles and anilino acids

Bain, William C (1955) Pyrolysis of anilino nitriles and anilino acids. PhD thesis, University of Glasgow.

Abstract

The pyrolyses of anilino nitriles and anilino acids, derived from C4 - C7 alicyclic ketones have been carried out. The C5, C6, and C7 anilino nitriles, as well as both geometric isomers of the C6 anilino nitrile with a 2-methyl substituent (Calpha and Cbeta ) have been found to undergo primary reversible dissociation into hydrogen cyanide and the corresponding anil. The yields of hydrogen cyanide and anil are almost theoretical, except from the C5 compound, which undergoes partial secondary decomposition into aniline and (2-cyclopentylidenecyclopentylidene)aniline. The rates of decomposition have been measured under constant though arbitrary conditions, alpha-Anilino-alpha-cyanodiphenyl-methane has also been pyrolysed and it too has been found to give hydrogen cyanide and anil. It has been concluded from this, and also from consideration of the pyrolysis of the geometric isomers of 1-anilino-1-cyano-2-methylcyclohexane, that the hydrogen atom that combines with the cyano group to eliminate hydrogen cyanide is likely to come from the anilino group (i.e., C/N elimination), rather than from the ring (i.e., C/C elimination). The C5, C6, and C7 anilino acids obtained by hydrolysis of the anilino nitriles all decompose thermally to give aniline and the corresponding unsaturated acid. The yield is by no means theoretical, however, and increases with ring size. Other products of decomposition have been isolated and identified and their probable origin discussed. These products are of the same functional group structure for the three ring sizes, the effect of ring size being to vary the yields of products rather than the main reaction route. Thus, although from the literature it would appear that the C5 and C6 compounds give completely different types of pyrolysis products, it has been found in the present work that products are of the same functional group structure. Here and throughout this thesis the subscripts of the letter C refer to the number of atoms in the ring.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Additional Information: Adviser: P D Ritchie
• Keywords: Organic chemistry
• Date of Award: 1955
• Depositing User: Enlighten Team
• Unique ID: glathesis:1955-73501
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 14 Jun 2019 08:56
• Last Modified: 14 Jun 2019 08:56
• URI: https://theses.gla.ac.uk/id/eprint/73501