The tosylhydrazones of 2-heptanone, 4,4-dimethy1-2-
heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2-
one were synthesized and decomposed under a variety of
reaction conditions: dry lithium and sodium salt pyrolyses,
sodium methoxide thermolyses in diglyme and photolyses of
the lithium salt in tetrahydrofuran. The saturated analogues
2-heptanone tosylhydrazone and its 4,4-dimethyl
isomer afforded the...
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...
Photolysis of pentachlorobenzene was carried out in the absence
of an electron donor species at 254 nm in cetyltrimethylammonium
bromide surfactant solution. The results are consistent with the
excited triplet undergoing homolytic cleavage of a C-Cl bond in
competition with formation of the excimer, in which the radical anion
undergoes...
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 tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript...
The photodebromination of selected bromoarenes has been studied at 300 nm
to determine the the possible mechanistic pathways leading to product.
Irradiation of 4-bromobiphenyl (BpBr) at this wavelength leads to the product
biphenyl. The quantum yield of intersystem crossing (0.98) and quenching
studies with cis-1 ,3-pentadiene suggest that the reaction...
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...