Anions are oxidatively added to nitronate anions to yield a-substituted nitroalkanes when potassium hexacyanoferrate( 111) is used as oxidant. Oxidation of nitronate anions yields intermediate anitroalkyl radicals, which undergo addition by anions to give intermediate a-substituted nitroalkane radical anions, which are further oxidised to yield the a-substituted nitroalkanes. The nitronate anions used are derived from 5-nitrohex-1 -ene, 6-nitrohept-1 -ene, endo-5-nitro-exo-6-phenylbicyclo[2.2.1]hept-2-ene, and 1 -(bicyclo[2.2.1] hept-5-en-endo-2-yl) -2-nitropropane. The intermediate a-nitroalkyl radicals underwent addition of anions to form radical anions faster than intramolecular cyclisation onto the a-alkenes. The a-nitroalkyl radical derived from 1 -(bicyclo[2.2.1] hept-5-en-endo-2yl)-2-nitropropane underwent cyclisation when the oxidation was carried out in the absence of an added anion. The addition of anions (thiocyanate, benzenesulfinate, 4-~hlorobenzenethiolate, and nitrite) to the a-nitroalkyl radicals derived from endo-5-nitro-exo-6-phenylbicyclo[2.2.1] hept-2-ene occurred stereoselectively from the less hindered exo face. Oxidative addition of 4-chlorobenzenethiolate to the nitronate from endo-5-nitro-exo-6-phenylbicyclo[2.2.1] hept-2-ene gave an unusual cyclisation via addition of a thiyl radical to the alkene.Iowa State University, Ames, for helpful discussions, and The Boots Company, Nottingham, for running high-field NMR spectra.
The cafeteria diet (CD), an experimental diet that mimics the obesogenic Western diet, can impair memory in adult rats. However, the suckling period is also particularly susceptible to diet-induced behavioural modification. Here, following exposure to CD feeding during lactation, 24-to 26-day-old offspring were tested to determine maternal dietary effects on either open field habituation, object location (OL) learning or on recency learning. Whereas no impact on habituation learning could be demonstrated, both OL and recency memory were impaired. In controls (C), OL memory was shown both after a 5 min (p < .05) or 60 min (p < .001) inter-trial interval (ITI). After the 60 min ITI, the difference between C and CD was significant (p < .05). Learning did not occur in the CD group at any time point and was not observed after the 24hr ITI in in either group. Whereas control rats demonstrated intact recency memory (p < .00001), no learning occurred in the CD group. Both groups differed significantly in their exploration ratios (p < .01). This study suggests a detrimental effect of exposure to an unhealthy Western diet during lactation, on cognitive functions in adolescent rats. These results could have implications for human cognition in the context of obesity epidemic.
1993 cleavage reactions, decomposition reactions, pyrolysis cleavage reactions, decomposition reactions, pyrolysis O 0100
-081Radical Reactions of Bicyclo(2.2.1)heptan-3-spiro-2'-oxiranes.-Reduction of the endo oxiranes (I) as well as their exo isomers leads to ring opening products which results from C-C bond cleavage. Under the same conditions the oxirane (IV) is converted into the C-O bond cleavage product (V). However, reduction of the imidazolides (VI) does not yield the expected ring opening products but the unusual methoxides (VIII) and the thioacetals (IX). -(BOWMAN, W. R.; BROWN, D. S.; BURNS, C. A.; MARPLES, B. A.; ZAIDI, N. A.; Tetrahedron 48 (1992) 33, 6883-6896; Dep. Chem., Univ. Technol., Loughborough, Leics. LE11 3TU, UK; EN)
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