Sulfonation of chlorobenzene and the selectivity relation ; Bromine addition to cyclohexene in dichloromethane ; Thorpe's synthesis of the caged acid, 4-methyltricyclo[126.96.36.199[superscript 2-4]] butane-1,2,3-tricarboxylic acid
Aromatic sulfonation and some substitution reactions of chlorobenzene show deviations in the selectivity relation. A determination of chlorobenzene sulfonation provided the following rate ratio relative to benzene and partial rate factors: 1.0, [---] of 0.064 , mf 1.7 and pf 4. 2. Our work, Olah's nitration, Ferguson's bromination and Stock's chlorination define a new relation that can be express by adding an entropy term (A) to the selectivity relation. We determined the rate of bromine-cyclohexene addition in dichloro-methane at 0° to provide a basis for a systematic variation of solvents at low temperature. An unusual zero-order reaction was encountered. The reaction was light catalyzed and related to hydrogen bromide concentration. The reaction was independent of bromine, cyclohexene, hydroperoxide and oxygen concentration. The reaction order depended on a steady-state concentration of bromonium ion (Br+). We also observed a novel photo effect with mixtures of oxygen, nitrogen and air. The synthesis of Thorpe's caged triacid, 4-methyltricyclo[1.1.0.02-4] butane-1,2,3-tricarboxylic acid has never been repeated or verified. A key intermediate, 1,1,1-ethanetriacetic,was readily converted to 1,1,1-ethanetriacetyl bromide. This last compound could only be a-brominated in the presence of a trace of ether. This successful a-bromination represents an important breakthrough toward getting Thorpe's caged acid.
College and Department
Chemistry and Biochemistry
BYU ScholarsArchive Citation
Gurney, John A., "Sulfonation of chlorobenzene and the selectivity relation ; Bromine addition to cyclohexene in dichloromethane ; Thorpe's synthesis of the caged acid, 4-methyltricyclo[188.8.131.52[superscript 2-4]] butane-1,2,3-tricarboxylic acid" (1962). Theses and Dissertations. 8218.
Sulphonation, Chemistry, Organic, Bromine, Methane, Butane