Cyril A. Grob

Twin γ-silicon effects in 1-bromoadamantane solvolysis.

Abstract A γ-trimethylsilyl substituent enhances the solvolysis rate of1-bromoadamantane in 80% ethanol by a factor of 8.6, a second suchsubstituent by a factor of 3.8.

Bridging strain in the solvolysis of epimeric bicyclic toluenesulfonates

Abstract The large variations in the rate ratios for the epimeric bicyclic p-toluenesulfonates 1 to 5 are ascribed to differential bridging strain accompanying the formation of intermediate cations.

Bridging strain in bicyclic carbocations

Abstract The solvolysis rates and products of 6-exo- and 6-endo-bicyclo[3.2.1.]-octyl toluenesulfonate confirm that differential bridging strain is a major factor in determining the reactivity of epimeric bicyclic sulfonates.

Epimeric 2-norbornyl cations in the solvolysis of 6-exo- and 6-endo-substituted 2-exo-norbornyl p-toluenesulfonates

Abstract Solvolysis of 6-exo- and 6-endo-substituted 2-exo-norbornyl tosylates 1 and 3 , respectively, yields identical or different product mixtures depending on the inductive effect of the substituent, indicating that induction involves graded σ-participation.

Mechanism of the beckmann rearrangement of α,β-unsaturated ketoximes

Aus den Ketoximderivaten (I) erhalt man uber die Zwischenstufen (II) die ungesattigten Amide (III).

Inductive charge dispersal in the solvolysis of 3-substituted bicyclo[1.1.1] pentyl bromides

Abstract Solvolysis rates and products of 3-substituted bicyclo[1.1.1]pentyl bromides indicate extremely strong inductive charge dispersal in the ionization to bicyclo[1.1.1]pentyl-1-cations, the precursors of 3-methylenecyclobutanols.

Polar effects in the solvolysis of 6-exo-substituted endo-2-norbornyl p-toluenesulfonates

The solvolysis rates of endo-2-norbornyl p-toluenesulfonates 1 are affected far less by 6-exo-substituents than are the rates of the corresponding exo-2-norbornyl p-toluenesulfonates 21.

Inductive charge dispersal in the solvolysis of 2-exo- and 2-endo-norbornyl toluenesulfonates.

Abstract The effect of substituents at C4, 5, 6 and 7 on solvolysis rates and products of 2-exo- and 2-endo-norbornyl tosylates confirms that differential carbon participation is responsible for varying exo/endo rate and product ratios.

Inductivity and bridging in the formation of 2-norbornyl cations

Abstract The effects of substituents at C5, C6 and C7 on the solvolysis rates of 2-norbornyl p-toluene sulfonates confirm that through space induction is directional and depends on distance and bridging strain.

Stereoelectronic control of exo/endo rate ratios in the solvolysis of 2-norbornyl p-toluenesulfonates

Abstract The variable exo/endo rate ratios observed in the solvolysis of 6-exo-substituted exo- and endo-2-norbornyl p-toluenesulfonates are due to differential transmission of polar effects in the transition state for ionization.