Electrocatalytic oxidation of reduced nicotinamide coenzymes by graphite electrodes modified with an adsorbed phenoxazinium salt,meldola blue

Meldola Blue (7-dimethylamino-1,2-benzophenoxazine) can be adsorbed on graphite to give chemically modified electrodes. The electrochemical redox reactions of the phenoxazine are fairly reversible at low coverages with an E′^o of ?175 mV vs. SCE at pH 7.0. The electrode was most stable in acid solutions, at pH 6.0 its electrochemical activity decreased by 15% during 2h. The adsorbed compound mediated electron transfer in the electrocatalytic oxidation of the nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between Meldola Blue and the coenzyme is demonstrated by experiments with a rotating disk electrode. The complex decomposes in a rate limiting step (k₊₂=30 s^?1) to the oxidized coenzyme and the reduced Meldola Blue. The latter can be reoxidized in a fast electrochemical step. The overall result is an electrocatalytic oxidation at a voltage which is about 500 mV lower than at an unmodified electrode.     

Abbau von Palustrin zu (−)-Dihydropalustraminsäure ((2R, 6S, 1′S)-[6-(1′-Hydroxypropyl)-2-piperidyl]essigsäure) und Struktur von Palustrin und Palustridin. Mitteilung über Schachtelhalmalkaloide

Degradation of palustrin to (?)-dihydropalustramic acid ((2R,6S,1′S)-[6-(1′-hydroxypropyl)-2-piperidyl]acetic acid), and the structure of palustrin and palustridin The structure of the macrocyclic alkaloid palustrin is shown to be 1a . Its piperidine unit can be obtained as (?)-dihydropalustramic acid ( 6a ) by the following sequence of degradation reactions (Scheme 1): catalytic hydrogenation of 1a followed by methylation and Hofmann degradation provides the allyl base 4 . the regioselectivity of the Hofmann elimination is explained by intramolecular proton abstraction at C(3) by C(18)-O^?. Catalytic reduction of 4 and subsequent acidic hydrolysis yielded 6a and N, N-dimethylputrescine (?N,N-dimethyl-1,4-butanediamine; 7 ). Loss of the N-alkyl group in the formation of 6a occurs during the catalytic hydrogenation step. This interpretation is supported by the results of model experiments. The position of the double bond in 1a is deduced from the IR. spectrum of the bromo-δ-lactone 19 prepared by treatment of 1a with N-bromosuccinimide at pH 4 (Scheme 3). Some of our previously published results on the degradation of dihydropalustrin ( 2a ) are obviously at variance with the newly proposed structure for palustrin ( 1a ). They can easily be explained by assuming a partial hydrogenolysis of the C(17)-N(1) bond during the preparation of dihydropalustrin from palustrin. Periodate cleavage of dihydropalustramic acid methyl ester ( 6b ) liberates propionaldehyde, which can be trapped by working at pH 7.5 (Scheme 2); at lower pH values it condenses rapidly with the simultaneously generated 3,4,5,6-tetrahydropyridine derivative 15 . The structure of the condensation product is proposed to be 16 on the basis of the isolation of its hydrogenation product, an isomeric dihydropalustramic acid ( 17 ).     

Isolation and Absolute Configuration of β,β-Carotene Diepoxide

The 5,6:5′,6′-diepoxy-5,6:5′,6;-tetrahydro-β,β-carotene, isolated from tubers of a white-fleshed variety of sweet potato (Ipomoea batatas LAM .) has been assigned the (5R,6S,5′R,6′S)-chirality on the basis of its HPLC, UV/VIS, and CD data.     

über einige Kondensationsreaktionen von dimerem Malonitril, dimerem Cyanessigs?ure?thyl- bzw.-methylester mit aromatischen Aldehyden

Aromatic aldehydes (1 a-g) yield linear condensation products (3 a-1) with dimeric ethyl and methyl cyanoacetate, resp., and dimeric malonitrile. Reduction of the condensation product of o-nitrobenzaldehyde with dimeric methyl cyanoacetate leads to methyl (3-methoxycarbonyl-1,2-dihydro-2-chinolinylidene)-cyanoacetate (4), with o-aminobenzaldehyde a carbostyril derivative5 a is obtained. In the presence of ammonium acetate aromatic aldehydes react with dimeric methyl and ethyl cyanoacetate, resp. to hexahydro-pyrimidinylidene cyanoacetates (8).     

Zur Chemie derMeldrums?ure, 3. Mitt. Synthesen von Heterocyclen, 188. Mitt.

Thermolysis ofMeldrum acid in the presence of cycloalkanones leads to dioxaspiro-alkanediones (3 a–c) by the elimination of acetone. With increasing temperature an additional dehydratation is observed and with two moles ofMeldrum acid pyrano-cycloalkano-pyranediones (6 a–b) are formed. The reaction of dialkylMeldrum acids with cyclic 1,3-diones is investigated.     

Trennung,Identifizierung und Bestimmung von Bactericiden auf der Basis von halogenierten Aromaten mittels Gas-Chromatographie

The separation of a mixture of 22 bactericides has been achieved by gas chromatography on columns with silicone rubber W-982 as stationary phase with temperatures between 100° and 300°C. The unchanged compounds as well as their silylation products have been used. The latter are more conveniently used especially for the quantitative determination. To be able to calculate the retention indices after Kovats gas chromatography has been performed isothermally at 180°C for the more volatile compounds and at 250°C for all other bactericides.The retention indices obtained under these conditions are tabulated together with the limits of detection.     

ansa-Metallocene derivatives: VIII. Syntheses and crystal structures of ethylene-bridged titanocene and zirconocene derivatives with permethylated ring ligands

Ethylene-bridged titanocene and zirconocene derivatives with permethylated ring ligands, C₂H₄(C₅(CH₃)₄)₂TiCl₂ and C₂H₄(C₅(CH₃)₄)₂ZrCl₂, have been synthesized and their crystal structures determined.     

Electrophoretic clean-up of organic acids from coffee for the GC/MS analysis

The clean-up presented here includes a free flow field step electrophoresis followed by ultrafiltration. Thus, organic acids can be separated from non-acidic and high-molecular compounds in roasted and instant coffee. The acids are identified by gas chromatography/mass spectrometry after freeze-drying and trimethylsilylation. With the method presented, 31 acids could be identified in commercial roasted coffee blends and in instant coffee, among them for the first time in coffee: 3-hydroxypropionic, 2-oxobutyric, glyceric, 2,4-dihydroxybutyric, 5-hydroxymethylfuran-2-carboxylic and 2-hydroxyglutaric acid.     

On a new Segal algebra

By means of a certain kind of atomic representation a new Segal algebraS ₀(G) of continuous functions on an arbitrary locally compact abelian groupG is defined. From various characterizations ofS ₀(G), e. g. as smallest element within the family of all strongly character invariant Segal algebras, functorial properties of the symbolS ₀ are derived, which are similar to those of the spacel (G) of Schwartz-Bruhat functions, e. g. invariance under the Fourier transform, or compatibility with restrictions to closed subgroups. The corresponding properties of its Banach dualS' ₀(G) as well as some of their applications are to be given in a subsequent paper.     

Triaziridine 7. Mitteilung. Stabile pyramidale Konfigurationen an den Stickstoff-Atomen von Dialkyl-und Trialkyl-triaziridinen

Stable Pyramidal configurations at the Nitrogen Atoms of Dialkyl-and Trialkyl-triaziridines Stereochemical features of the recently synthesized nine samples of di- and trialkyl-triaziridines, namely the 1,3-cyclopentylen-(series a ) and the two stereoisomers of the diisopropyl derivatives (series b and c ), containing as the third substituent an H-atom ( 2 ), a CH₃ group ( 3 )or a CH₂OH group ( 4 ), were elaborated on the basis of the ¹H-, ¹³C-, and ¹⁵N-NMR spectra. The three N-atoms of the saturated N₃-homocycle were found to be stable to pyramidal inversion in all cases. According to their NMR spectra, 2 – 4 of the series a and b possess twofold symmetry (C_s), while 2 – 4 of series c are asymmetric. Thus, series c has the trans-configuration at N(2)/N(3) and, consequently, the cis-configuration at N(1)/N(2), while series a and b have the cis-configuration at N(2)/N(3) and -since the all-cis-arrangement is excluded-the trans-configuration at N(1)/N(2). The asymmetry of the trans-configurated 2c turned into twofold symmetry (C₂), when a little CF₃COOH was added. The ¹H- and ¹³C-NMR data of series b and c of our alkyl-triaziridines exhibit a shielding effect, according to which there are two types of i-Pr groups, i-Pr(a) and i-Pr(b). They differ in the NMR signals of the H- and the C-atoms of their CH groups: the H-atoms of i-Pr(a) are more deshielded by 0.75–1.111 ppm and its C-atoms are more shielded by 10.0–160.0 ppm as compared to the corresponding atoms of i-Pr(b). i-Pr(a) is cis (on the N₃-homocycle) to a large substituent (such as i-Pr, Me, CH₂OH) and to a lone pair, while i-Pr(b)is cis only to a small (H) or to no substituent and to one or two lone pairs. An analogous effect appears in the NMR signals of the CH₃ and CH₂OH groups at N(1) of 3 and 4 in the series b and c .