Über halogen- und stickstoffhaltige Derivate aliphatischer Carbonsäuren, 10. Mitt. (Über Reaktionen mit Aluminiumalkylen, 13. Mitt.): Über die Reduktion von tertiären α-Nitrocarbonsäureestern mit LiAlH4, Diisobutylaluminiumhydrid und Diäthylaluminiumhydrid

Zusammenfassung Die Reduktion tertiärer -Nitroester mit LiAlH₄ verläuft anomal. Infolge Abspaltung der Carboxylgruppe sind Aminoalkane Hauptprodukte dieser Reduktion. Daneben entstehen in geringer Menge unter Erhaltung des Kohlenstoffgerüstes -Hydroxylaminoalkohole. Diese Reaktion wird mit der Reduktion von sekundären -Nitroestern und von -Oximinoestern verglichen.Mit Dialkylaluminiumhydriden erleiden die tertiären Nitroester ebenfalls in der Hauptsache Reduktion unter C-C-Spaltung zu Aminoalkanen. Eine Nebenreaktion führt jedoch über die Stufe der Hydroxylaminoalkohole hinaus zu Aminoalkoholen. Außerdem tritt alkylierung am Stickstoffatom zu Alkylaminoalkanen bzw.-alkoholen auf.

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Halogen and nitrogen containing derivatives of aliphatic carboxylic acids, X (reactions with aluminium alkyls, XIII): Reduction of tertiary -nitro carboxylic acid esters with LiAlH₄, diisobutyl aluminium hydride, and diethyl aluminium hydride

The reduction of tertiary -nitro esters with LiAlH₄ proceeds anomalously. As a result of a decarboxylation amino alkanes are the main products of this reductions. Besides -hydroxylamino alcohols are obtained in small amounts by conservation of the carbon skeleton. This reaction is compared with the reduction of secondary -nitro esters and of -oximino esters.Tertiary -nitro esters are reduced by dialkyl aluminium hydrides to amino alkanes under cleavage of the C-C-bond. In a side-reaction one obtains amino alcohols via the stage of hydroxylamino alcohols. Besides the nitrogen atom is alkylated leading to alkylamino alkanes respectively alkohols.

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9. Mitt.:H. Reinheckel, Mh. Chem.99, 2215 (1968).

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12. Mitt.:H. Reinheckel undR. Gensike, J. Organometal. Chem.13, 45 (1968).     

A Sensitive HPTLC Method for Estimation of Amentoflavone,a Bioactive Principle from Biophytum sensitivum (Linn.) DC. and Putranjiva roxburghii Wall.

JPC – Journal of Planar Chromatography – Modern TLC - A sensitive high-performance thin-layer chromatographic (HPTLC) method has been developed for estimation of amentoflavone, an...     

Reaction of 5-haloanthra[1,9-cd]-6-isoxazolones with aziridine

The reaction of 5-haloanthra[1,9-cd]-6-isoxazolones with aziridine gave 5-aziri-dinoanthra[1,9-cd]-6-isoxazolones. The latter, upon reaction with acids, undergo cleavage of the aziridine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 885–888, July, 1984.     

Synthesis and chiral-optical properties of some benzolactams

Five- and seven-membered benzolactarns — (–)-S-2, 3-dimethyl-2, 3-dihydroisoindolone and (+)-S-5-methyl-2, 3, 4, 5-tetrahydrobenz[c]azepin-1-one — were synthesized. A study of their chiral-optical properties and comparison with the previously studied six-membered lactam (–)-S-4-methyl-3, 4-dihydroisoquinol-1-one showed that their circular dichroism spectra are similar: The spectra contain dichroic absorption bands due to ^* transitions in the aromatic chromophore (270 and 220 nm) and a band of charge transfer in the benzamide chromophore at 240–250 nm. The magnitude of the Cotton effect due to the charge-transfer band increases as the lactam ring becomes larger (five-membered < six-membered < sevenmembered benzolactam). The change in the magnitude of the Cotton effect is explained by the development of a strictly dissymetric chromophore.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 656–662, May, 1978.     

The application of linear discriminant analysis in the diagnosis of thyroid diseases

The effectiveness of five in-vitro laboratory tests for differentiation between three thyroid functional states (EU, HYPO and HYPER thyroidism) has been determined by using statistical linear discriminant analysis. The optimal linear combination of laboratory tests obtained by means of linear discriminant analysis results in a better use of the information present in each test, so that the possible redundancy of tests can be assessed. In this context, some feature selection criteria were evaluated. It is shown that in this application only two laboratory tests are necessary to obtain a sufficiently high diagnostic effectiveness when linear discriminant analysis is applied.     

First-principles calculations of K-edge X-ray absorption near edge spectra of some transition metal dimers

Theoretical X-ray absorption near-edge spectra have been evaluated for different bond lengths of Mn₂, Co₂ and Ni₂ using a modified Xα scattered-wave procedure.     

Homolytic alkylation of quinaldine and quinoxaline with 18-crown-6

Homolytic alkylation of protonated quinoxaline with 18-crown-6, initiated by the system pivalic acid-iron(II) sulfate at 20–25C, gives (quinoxalin-2-yl)-18-crown-6 in 85% yield. Under analogous conditions, the reaction with quinoline affords two isomers: (quinolin-4-yl)-18-crown-6 and (quinolin-2-yl)-18-crown-6, in yields of 20 and 30% respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 75–76, January, 1988.     

On the extraction with long-chain amines

The extraction of tracer mercury(II) from aqueous HCl-solutions by TLA (trilaurylamine) dissolved in benzene can simply be described by the reaction (1) $$TLAHCl \cdot H_2 O(org) + HgCl_2 (aq) \rightleftharpoons TLAHCl \cdot HgCl_2 (org) + H_2 O(aq)$$ Using the chloride ion activity coefficient function recently introduced by HÖGFELDT (2) $$\lg y_{Cl^ - } = - 0.5115 \sqrt I /(1 + 1.176 \sqrt I ) - \lg C_{corr} $$ together with the model for excess acid extraction developed by AGUILAR and HÖGFELDT, the only unknown quantity is the equilibrium constant for the reaction above since the stability constants for the formation of the Hg(II)-CT-complexes are also well known. Using distribution data for HgCl₂ (tracer) between HCl-solutions and benzene Eq. (2) gets further support as being a useful expression for the activity coefficient of Cl^? in solutions more concentrated than ≈0.6M. Some scouting experiments about the extraction of HgCl₂ from NaCl brines containing 270 g NaCl/l showed that in the pH-range 1–13 the best extraction was obtained at about pH 1–2 irrespective if the diluent was benzene, o-xylene or a mixture of kerosene and benzene.     

Jahn-Teller effect in the cyclopentadienyl radical: an example of three mode coupling

The cyclopentadienyl radical C₅H₅· vibronic wavefunctions and energy levels are calculated and used to discuss the vibrational structure of the allowed ²A″₂ ←²E″₁ electronic transition in C₅H₅ and allowed A←E transitions in similar systems in which Jahn-Teller coupling occurs through two or three vibrational modes. As has been pointed out by Alpert and Silbey, the vibrational pattern predicted for single mode coupling is markedly distorted. With larger coupling parameters than those used by Alpert and Silbey, in an E ← A transition (e.g., the benzene Rydberg states) progressions in the individual coupling vibrations cannot be distinguished. In an A ← E transition (e.g., C₅H₅·), the higher progression members lose intensity and combination levels in the coupling vibrations appear. In both cases, a complex pattern of 1-1 hot band splittings results. Comparison is made with the experimental C₅H₅· spectrum, and assignments are suggested for three of the observed A″₂ state frequencies.     

Simultaneous solid-phase extraction and chromatographic analysis of morphine and hydromorphone in plasma by high-performance liquid chromatography with electrochemical detection.

High-performance liquid chromatography has become an important analytical tool for the quantitation of opioid drugs. Using solid-phase extraction and coulometric electrochemical detection, we have developed a chromatographic method for the simultaneous measurement of morphine and hydromorphone which is both sensitive and specific. Using 1 ml of plasma, intra-assay and inter-assay data show that the detection limit for accurate quantitation of these compounds is about 1.2 ng/ml (coefficient of variation 11.6%) for morphine and 2.5 ng/ml (coefficient of variation 10.5%) for hydromorphone. The method is simple and readily adaptable to most pharmacokinetic studies and toxic screens involving these drugs.