Exploratory synthesis is the discovery of new compounds with interesting structures and properties. The subject of this thesis is exploratory synthesis of bismuth containing oxides. Bismuth containing oxides have many interesting properties, which are ionic conductivity, ferromagnetism, superconductivity, ferroelectricity, ferroelasticity and catalytic. These properties are closely related to their specific...
Pyrolysis of 4-cycloheptene-l-methyl acetate under flow conditions at 285° gives only rearranged bicyclic acetates and hydrocarbons rather than the anticipated simple elimination product methylenecyclohept- 4-ene. These rearranged acetates have the same structures and are formed in virtually the same relative percentages as those observed in the "π- route" solvolysis of...
The potassium salts of a series of 1-vinylcycloalk-3-en-l-ols were found to undergo ring expanding [1, 3]-sigmatropic shifts at 25° when dissolved in hexamethylphosphoramide (HMPA) or 1, 2-dimethoxyethane (DME) with 18-crown-6. The yields and reaction rates were compared with those of the corresponding Siloxy-Cope ring expansions. These anionic cases showed about...
The reaction of cyclodeca-1,215triene with mercuric salts
gave only rearranged hydrocarbon, tricyclo[4.4.0.0²'⁴]deca-5ene
in acetic acid. Other catalysts [Rh(CO)₂C1]₂ and AgC10₄ gave
the same rearranged hydrocarbon. The isomerization is proposed
to proceed through a "metalcomplexed" carbenoid intermediate.
The reaction of bicyclo[7.1.0 ]deca-213diene gave
oxymercurated products.
This paper describes the synthesis of t-butyl bicyclo[7.1.0]
decane-2-percarboxylate and its photolytic decomposition. The title
compound was found to undergo simple homolytic cleavage when exposed
to light of 2537 A; producing the cyclodecyl radical, carbon dioxide,
and t-butoxy radical. The largest percentage of products arose from
an intimate radical pair...
Both oxy-Cope and siloxy-Cope rearrangements involve
(1, 3) and (3, 3) sigrnatropic shifts. Both the concerted mechanism,
and the stepwise mechanism via a diradical intermediate are possible.
In a cyclic system such as cis-l-vinylcyclooct-3-en-l-ol, the thermal
rearrangement takes place preferably through a diradical intermediate.
At high temperature, the reaction also...