Several experiments were undertaken to investigate the mechanism of
photodechlorination of pentachlorobenzene. The thermal methoxydechlorination
reaction of pentachlorobenzene was studied. In DMSO at 50 °C sodium
methoxide reacts smoothly with pentachlorobenzene to give three
tetrachloroanisole isomers. A second-order kinetic plot for this reaction is linear to
high precision, indicating that...
The effect of the conjugation with cyclopropyl rings
on the activation parameters for the formation of
carbenes from the corresponding diazo compounds was
investigated using diisopropylcarbene (46), cyclopropyl-isopropylcarbene
(47), and dicyclopropylcarbene (48).
Each of these three carbenes was generated by the
thermolysis of the parent benzenesulfonylhydrazone
potassium salts using DMSO...
The photochemistry of some analogs of insect growth regulators
(IGR's) was studied. Methyl geranate, TY, was synthesized and the
mechanisms of its photochemical reaction pathways were studied by a
variety of techniques. Direct irradiation of 71 in ether leads to the
formation of five new products: 98, the product of...
Feeding of [3-¹³C, 2-¹⁵N]arginine, 38a, unequivocally established that the β-
arginine moiety of blasticidin S, 1, was formed from α-arginine by an intramolecular
migration of the α-amino group to the β- position. Further feedings using chirally
deuteriated arginines 38e and 38f revealed that the aminomutase process occurred with
inversion of...
The photochemistry of aldicarb and two related compounds,
0-(methylcarbamoyl) isobutyraldehyde oxime and 0-(methylcarbamoyl)
trimethylacetaldehyde oxime was explored under laboratory
conditions. Upon irradiation aldicarb decomposed rapidly to
methylamine, dimethylamine, tetramethylsuccinonitrile, and
1-methylthio-2, 3-dicyano-2, 3-dimethylbutane. The other two
compounds decomposed only after a long period of irradiation. The
difference in reactivity was...
The photohydrodebromination of brominated paracyclophanes was studied to
help elucidate the possible mechanistic pathways leading to product for
bromoarenes in general. Several brominated [2.2]paracyclophanes were studied to
determine the effect of substitution patterns on this reaction. [2.2]Paracyclophanes
were chosen for this study in order to investigate possible intramolecular excimer
formation...