Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Ion exchange resins in steel analysis

The metals vanadium, chromium and molybdenum may be separated from the other constituents of steel by passing an acetate buffered solution of the steel through a strongly basic onion exchanger and selectively eluting the above metals from the resin column with aqueous solutions of 0.6 N sodium hydroxide, 8 N hydrochloric acid and 1 N hydrochloric acid, respectively.     

Determination of silicon in fats and oils by electrothermal atomic absorption spectrometry with in-furnace air oxidation

A graphite-furnace atomic absorption spectrometric emthod is reported for determination of dimethylpolysiloxane (silicone) in edible fats and oils. It incorporates an air-oxidation step in the furnace program to reduce matrix interferences. The detection limit is 0.3 mg kg^?1 in soils, and short-term precision is about 6% at silicon concentrations of 1.7–2.0 mg kg^?1. The procedure was successfully applied to a variety of commercial frying fats and oils, to quantify silicone loss during polish filtration during oil manufacture, to quantify sorption of antifoam onto fried food, and to detect fugitive sources of silicone encountered in deep-fat frying operations.     

A New Synthesis and the 13C-NMR OF β-Cyperone 1,3-Dibromo-2-Pentene,A New Ethyl Vinyl Ketone Equivalent

In connection with another study underway i n this lab we have been investigating the use of vinylogous thioester 1 as a synthon f o r sesquiterpene synthesis. We have found that 1 is useful for ring annelations and introduction of multiple substituents when pursuing carbocyclic synthesis. In recent studies with thioesters we have found that the lithium enolate of 1 (LDA/THF) will undergo 1,4-addition to Michael acceptors such as ethyl vinyl ketone (2, - EVK) in moderate yields (～60).     

1,4-Diazabicyclo[2.2.2]octane as an Efficient Catalyst for a Clean,One-Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives via Multicomponent Reaction in Aqueous Media

1,4-Diazabicyclo[2.2.2]octane (DABCO) has been used as a mild and efficient catalyst for the synthesis of various tetrahydrobenzo[b]pyran derivatives via a one-pot, three component condensation of aromatic aldehydes, dimedone, and active methylene compounds. This method provides several advantages: a simple workup procedure, environmental friendliness, neutral conditions, and good yields. In addition, water or 50% aqueous ethanol was chosen as a green solvent.