Microchemical investigation of medicinal plants. XV

Summary A method is described for the determination of alkaloids in morning glory leaves by means of spectrophotofluorimetry. The total alkaloidal contents found in different batches of leaves ranged from 0.027 to 0.04%.

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Zusammenfassung Ein Verfahren zur Bestimmung der Gesamtalkaloide in den Blättern vonIpomoea violacea wurde angegeben. Spektralfluoreszenzmessungen ergaben für verschiedene Chargen solcher Blätter Gehalte von 0,027 bis 0,04%.

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For part XIV see Mikrochim. Acta [Wien]1976 I, 227.     

Fischer indolization and its related compounds—VII : Development of abnormal fischer indolization of ortho-methoxyphenylhydrazone to provide a synthetic method for useful indole derivatives possessing an active methine group at C6 and novel 3,6′-biindole derivatives

Fischer indolization of ethyl pyruvate 2-methoxyphenylhydrazone (1) with p-toluene-sulfonic acid in benzene in the presence of an enolizable dicarbonyl or an indolic compound gave either an indole product having an active methine group at C₆ or a novel type of 3,6′-biindole compound. Structures of the products were established by NMR spectra and chemical evidence.     

The synthesis of cypridina etioluciferamine and the proof of structure of cypridina luciferin

An unambiguous synthesis of Cypridina etioluciferamine was accomplished in order to prove the structure of this important bioluminescent natural product. Several 2-aminopyrazine 1-oxides were synthesized in order to establish a spectroscopic method for determining the placement of substituents on the pyrazine nucleus of Cypridina etioluciferamine. Titanium tetrachloride was used to improve the yields of these compounds; for example, the yield of 2-amino-3-methyl-5-phenylpyrazine 1-oxide (19) from reaction of phenylglyoxal 1-oxime and α-aminopropionitrile was raised from 3% to 51% by the use of titanium tetrachloride. The pyrazine ring proton is found at τ 1·37 (DMSO-d₆). The isomeric 2-amino-3-methyl-6-phenylpyrazine 1-oxide (22) was similarly prepared and its pyrazine ring proton is found at τ 2·18. This large difference (0·81 ppm) in chemical shift was used to determine whether a 2-aminopyrazine 1-oxide was 5- or 6- substituted. Prepared in an analogous fashion were 2-amino-5-(indol-3-yl)-3-methylpyrazine 1-oxide (23) and 2-amino-5-(indol-3-yl)-3-(3-phthalimidopropyl)pyrazine 1-oxide (16). The structures of these compounds were verified by NMR spectroscopy. By treatment with Raney nickel and hydrogen gas, then 100% hydrazine hydrate, 16 was converted to 2-amino-3-(3-aminopropyl)-5-indol-3-ylpyrazine (5), isolated as the dihydrochloride. This compound, with the indole moiety definitely placed at C-5, is identical with Cypridina etioluciferamine dihydrochloride (IR, UV, TLC). These results show that the structures of Cypridina etioluciferamine and luciferin are correct as published.     

Spectral investigations of the tautomeric equilibria of thioacyl derivatives of 2-aminothiazole and 2-aminobenzothiazole

The positions of the tautomeric equilibria for a number of thioacyl derivatives of 2-aminothiazole and 2-aminobenzothiazole were determined by UV and IR spectroscopy with the use of model compounds. Quantum-chemical calculations by the CNDO/2 method were made for some of the acyl and thioacyl derivatives of 2-aminothiazole and 2-iminothiazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 24, No. 3, pp. 410–417, March, 1988.     

Catalytic dehydrocyclization of 3-isopropyl(n-propyl)-2,6-diphenylpyridine and 3-n-propyl-2,4,6-triphenylpyridine

The catalytic dehydrocyclization of 3-isopropyl-2,6-diphenylpyridine proceeds in two directions: conversion to 10-methyl-3-phenyl-4-azaphenanthrene and conversion to 9,9-dimethyl-4-azafluorene. C₍₉₎-Unsubstituted 4-azafluorenes were obtained in the dehydrocyclization of pyridine bases that contain a phenyl group in the position and an n-propyl group in the position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 648–650, May, 1984.     

Nuclear activation techniques in the life sciences 1978

The proceeding of the IAEA symposium held in 1978 on nuclear activation techniques in the life sciences are reviewed. A total of 56 papers are reviewed on methodology, analytical quality control, comparisons between neutron activation analysis and other methods, and applications of activation analysis in biology and medicine (including in-vivo activation analysis) and in public and environmental health. The materials analysed in the papers are adjusted in connection with the elements determined and the purposes of the study. Those elements are tabulated together with the analytical methods used for the element determination. The standard reference materials analysed for the check of the reliability of analysis are also arranged. Proc. Symp. Nuclear Activation Techniques in the Life Sciences, IAEA, Vienna, 1978.     

Nitropyrazoles

A method for the synthesis of bi-, ter-, and quaterpyrazoles by cyclization ofC-(diformylmethyl)nitropyrazoles with hydrazine has been elaborated. Some of theirC- andN-derivatives have been obtained. The compounds prepared have been characterized by¹H,¹³C,¹⁴N, and¹⁵N NMR spectra.For communication 6, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1941–1945, November, 1993.     

Targeting of mitomycin C to the liver by the use of asialofetuin as a carrier.

Desialylated fetuin (asialofetuin) was adopted as a carrier for introducing drugs in parenchymal liver cells. Mitomycin C, as a model guest-compound, was covalently attached to asialofetuin through a spacer of the succinyl group. The asialofetuin-mitomycin C conjugate contained 4.4 w/w% of mitomycin C and liberated it gradually at physiological conditions (t1/2 = 37 h). The survival time of the conjugate in rat blood circulation was significantly smaller than that of the non-desialylated fetuin conjugate; the elimination half-life was 7.3 min after intravenous injection. At 30 min after injection of the conjugate in rats, 40% of the dose was present in the liver. Parenchymal cells in the liver selectively took up the conjugate, which was highly distributed to the lysosomal fraction in the cell. The greater uptake of the conjugate by hepatocytes reflected the increased excretion in the bile; totally 10.4% of the dose was recovered.     

Screening of psychotropic drugs in human hair based on high-performance thin-layer chromatography and microliquid extraction

The monitoring of the physiological and functional state of personnel from dangerous industries is very important for the ensuring of ecological security. Usually, this involves testing for the consumption of alcohol and drugs of abuse. During the last several years the use of legal psychotropic drugs has increased and the control over these drugs has became an actual problem. As is well known, the long-term history of drugs present in the body is accessible through hair analysis. This is why the aim of our research is to create a screening procedure based on coupling high-performance thin-layer chromatography with microliquid extraction as a psychotropic drug testing method for hair. Some widely distributed antidepressants, neuroleptics, and sedative drugs are chosen for research. The optimal experimental conditions for all of the consequent steps for the screening detection of the model samples are determined. The visual and densitometric detection limits allow for the employment of the proposed technique for a fast and cost-effective analysis of the drugs of abuse.