The thermolysis of trans-1 -trimethylsiloxy- 1-vinylcyclotridec-
3-ene (VI-OTMS) led to the formation of two major products: 4-vinylcyclotridecanone
(VII) and cyclopentadec-5-en-l-one (VIII) after
hydrolysis. Ketone VII is produced by a concerted [3, 3] sigmatropic
shift, while ketone VIII is formed by a [1, 3] sigmatropic shift with
a concerted or diradical...
Major and minor minerals have been separated from
three L-6 chondritic meteorites (Alfianello, Colby (Wisconsin),
and Leedey). Olivine, hypersthene, diopside, feldspar,
troilite, chromite, phosphate minerals, and metallic
minerals were analyzed for major, minor and trace elements
using instrumental neutron activation analysis and radiochemical
neutron activation analysis techniques. Concentrations
df the...
In order to examine some possible tyrosyl interactions, poly-tyrosyl lysozyme and poly-O-methyltyrosyl lysozyme were prepared and their solubilities were compared. Both derivatives exhibited
similar pH dependent solubilities, showing a minimum solubility at
about pH 8. Their solubilities varied with temperature, having a
positive enthalpy of solution. The effect of a...
Polypeptidyl derivatives of bovine pancreatic ribonuclease
(RNase) containing two or three tyrosine chains
with an average of two to three residues per chain have
been prepared. The effects of various perturbants such as
neutral salts, ethanol, urea and guanidine hydrochloride
on the thermal transition of the derivatives have been
studied....
Synthesis and discovery lies at the core of every field in chemistry. The investigation of the structure-property relationships in compounds known or new is the fundamental purpose of solid state chemistry. Mixing related solid state compounds to form solid solutions can lead to exciting new and/or unexpected properties. Layered compounds...
Part I
The pyrolysis of cis- and trans- 1, 2-divinyl-1- trimethylsiloxy -
cyclohexane, II- and III-TMS, under the same conditions as the
pyrolysis of cis-l-vinyl -1-trimethylsiloxycyclooct-3-ene, I-TMS,
confirms that a sequence of concerted reactions for the rearrangement
of II- and III-TMS to trans-l-trimethylsiloxycyclodec-3-ene,
IV-TMS, is a viable pathway in the...
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...