42 research outputs found
Ferrocene Compounds. I. Acetylferrocene and Diethyl Oxalate Condensation Products and Their Derivatives
By the reaction of acetylferrocene with diethyl oxalate l ,6-
diferrocenyl-1,3,4,6-hexanetetrone (I), a, y-dioxo-y-ferrocenylbutyric
acid (II) and its ethyl ester (III) were prepared in a yield of 78.3,
55.1 and 51.5Ā°/o resp. The polyoxo compounds I, II and III were
converted through the action of suitable reagents into 2,3-bis
(ferrocenoy lmethy l)quinoxaline (IV), 5,5\u27 (3\u27)-diferroceny 1-1, 1\u27 -dipheny
l-3,3\u27 (5\u27)-dipyrazoly l (V), 3(5)-ferrocenyl-1-phenyl-5(3)-pyrazolecarboxylic acid (VI) and its ethyl ester (VII) and 3-ferrocenoylmethylene- 2-piperazinone (VIII)
Ferrocene Compounds. V. Indirect Electrochemical Reduction of Acetylferrocene
2,3-Diferrocenyl-2,3-butanediol (II) has been obtained by the
indirect electrochemical reduction of acetylferrocerie (I) using an
electrochemically generated sodium amalgam. The approximative
value of the half-wave reduction potential of acetylferrocene (I) .
and the stereochemistry of (II) has been determined. Pinacol (II)
was rearranged to 2,3-diferrocenylbutane-3-on (III) , dehydrated
to 2,3-diferrocenyl-1,3-butadiene (IV) and anhydride of 4,5- diferrocenyl-
4-cyclohexene-1,2-dicarboxylic aC!id (V) was formed by the
Diels-Alder reaction of (IV)
Ferrocene Compounds. VII. The Stobbe Condensation of Formylferrocene with Diethyl Glutarate
The Stobbe condensation of formylferrocene with diethyl
glutarate in the presence of potassium tert-butoxide gave (E)-1-ethyl
hydrogen 2-ferrocenylmethyleneglutarate (I), which was converted
by the action of diazomethane to (E)-1-ethyl 5-methyl 2-ferrocenylmethyleneglutarate
(II). The configurations of compounds I and II
are assigned through study of their 1H-NMR and IR spectra. This
stereochemical assignment is supported by the conversion df compound
I to cyclopentadienyl(5,6-dihydro-4-oxo-7-ethoxycarbonylazulenyl)
iron (III), which was hydrolized to the corresponding
acid (VI). The same acid VI was obtained from half ester I via the
corresponding diacid IV and anhydride V.
The stereoselectivity of the Stobbe condensation is discussed
Ferrocene Compounds. III*. On the Tautomerism and Reactions of Some Derivatives. of B-Ferrocenoylacrylic acid
The tautomerism of Fc-CO-CH2-CO-C02R (Fe = ferrocenyl)
(I, R = H; II, R = C2H5) and Fc-CO-CH2-C(= NR)-:-
C02C2H5 (III, R = H; IV-VI, R =alkyl; VII-IX, R = aryl) has
beenĀ· investigated on the basis of their IR, UV and NMR spectra.
Reactions of ester II with ammonia and primary aliphatic and
aromatic amines, as well as of the compounds I-IX with hydroxylamine
hydrochloride and hydrazine hydrate have been studied
Synthesis of β-Phenyl-α,β-dioxo-propionanilide. Peptide-Like Polyoxo Compounds
In the first communication of this series it was shown that 2,3,4-triketotetrahydropyridine exercises a diaibetogenic activity on white rats, the same as alloxane. It, was, further, suggested, fill.at the grouping -COCOCONH- may be responsible for this activity of 2,3,4-triketo-tetrahydropyridine, as for that of alloxane
Electrochemical Reduction of Acetonylacetone in Hydrochloric Acid
The electrochemical reduction of acetonylacetone on a mercury
cathode in aqueous hydrochloric acid medium has been studied. It
has been shown that the electroactive species is the protonated
form of acetonylacetone. The experimental results indicate -that
the rate of electrochemical reduction is dependent upon the preceding
chemical protonation step and/or adsorption of the electroactive
species. The electrolysis at controlled potential (- 1.2 V
vs. S. C. E .) yielded the following products : acetaldehyde; acetone,
acetic acid, 2,5-hexanediol and 2,5-dimethyltetrahydrofuran. Possible
mechanistic routes leading to the formation of these products
are discussed