Benzoxazolinones. II. Synthesis of 3-vinylbenzoxazolinones and 3-vinylbenzoxazolinethione

A method has been developed for obtaining 3-vinylbenzoxazolinones and 3-vinylbenzoxazolinethione. It has been shown that it is also possible to obtain 3-methylbenzoxazolinethione by this method in good yield (76%).     

Benzoxazolinones. II. Synthesis of 3-vinylbenzoxazolinones and 3-vinylbenzoxazolinethione

A method has been developed for obtaining 3-vinylbenzoxazolinones and 3-vinylbenzoxazolinethione. It has been shown that it is also possible to obtain 3-methylbenzoxazolinethione by this method in good yield (76%).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 553–556, July–August, 1980.     

226. Aminonucleosides. 3. Derivatives of 3-amino-3,5-dideoxy-D-lyxo- and D-ribo-pentoses

The 3-amino-3,5-didesoxy-1,2-O-isopropylidene-α-D -ribofuranose and -β-D -lyxo-furanose and several derivatives thereof have been prepared by hydride reduction of the corresponding oximes.     

Non-steroidal antiinflammatory agents. 3. Synthesis of 3-hydroxy-3-hydroxyphenyl-2,4-dioxo-1,2,3,4-tetrahydroquinolines

The acid-catalyzed condensation of quinisatines 5a-c or their aminals 4a-c with phenols 6a-i led to a number of 3-hydroxy-3-hydroxyphenyl-2,4-dioxo-1,2,3,4-tetrahydroquinolines 7a-s which were considered as potential antiinflammatory agents.     

Halogenbenzaldehyde, 3. Mitt.

Zusammenfassung Mittels der Konversion aromatischer Amine in die entsprechenden Benzaldehyde, einer Methode, die vonBeech entwickelt und von uns auf Haloaniline erweitert wurde, werden in einfacher, eleganter Weise zwei Halogenbenzaldehyde dargestellt.2. Mitt.:S. D. Jolad undS. Rajagopal, Naturwiss.48, 645 (1961).     

Thalidomid-Analoga, 3. Mitt.

Zusammenfassung Zur Untersuchung möglicher Struktur-Wirkungs-Beziehungen in der Reihe der verbrückten Thalidomid-Analoga wurden 36 offenkettige und verkürzte Abkömmlinge der Testsubstanz K 2004 (2) synthetisiert. Die pharmakologische Untersuchung der hergestellten Verbindungen ergab in keinem Falle eine signifikante sedative Aktivität. Dies legt den Schluß nahe, daß die intakte Glutarimid-Struktur bei1 und2 für das Zustandekommen der schlafinduzierenden Wirkung unentbehrlich ist.

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Thalidomide analogues

For the evaluation of possible structure-activity relationships in the series of bridged thalidomide analogues 36 openchain and shortended congeners of the test substance K 2004 (2) have been synthesized. The pharmacological evaluation of these compounds revealed in no case any significant sedative activity. This leads to the conclusion that the intact glutarimide structure must be essential for the sleep-inducing activity of1 and2.

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Herrn Prof. Dr.M. Pailer zum 60. Geburtstag gewidmet.     

Water-Soluble Copolymers. XLI. Copolymers of Acrylamide and Sodium 3-Acrylamido-3-methylbutanoate

Copolymers of acrylamide (AM, M ₁) with sodium 3-acrylamido-3-methylbutanoate (NaAMB, M ₂) synthesized in 1 M NaCl (the ABAM2 series) are compared to those synthesized in deionized water (the ABAM1 series). At fixed feed ratios, higher incorporation rates were found for NaAMB with increasing ionic strength of the polymerization solvent. Reactivity ratios calculated by the methods of Kelen-Tüdös changed from r ₁ = 1.23 and r ₂ = 0.50 in deionized water to r ₁ = 1.00 and r ₂ = 0.64 in 1 M NaCl. This change is in accord with a decrease in electrostatic repulsion between the macroradical and unreacted NaAMB. Dilute solution properties, examined as a function of composition and added electrolytes, indicate differences in microstructure for the ABAM1 and ABAM2 copolymers.     

Chemistry of the diazeniumdiolates. 3. Photoreactivity

We have found O(2)-substituted diazeniumdiolates, compounds of structure R(2)N-N(O)=NOR' that are under development for various possible pharmaceutical uses, to be rather photosensitive. With R = ethyl and R' = methyl, benzyl, or 2-nitrobenzyl, the observed product distributions suggest that two primary pathways are operative. A minor pathway involves the extrusion of nitrous oxide (N(2)O) with simultaneous generation of R(2)N(*) and R'O(*), which may then form amines, aldehydes, and alcohols. The major reaction pathway is an interesting photochemical cleavage of the N=N bond to form a nitrosamine (R(2)NN=O) and an oxygen-substituted nitrene (R'ON). The intermediacy of the O-nitrene was inferred from the production of abundant oxime, via rearrangement of the O-nitrene to a C-nitroso compound (R'ON --> O=NR'), and subsequent tautomerization to the more stable oxime. Involvement of the O-nitrene was confirmed by trapping with 2,3-dimethyl-2-butene to form the aziridine and with oxygen to generate the nitrate ester. 2-Nitro substitution on the benzyl derivative had surprisingly little effect on the reaction course. For each compound examined, minor amounts of nitric oxide (NO), presumably produced by secondary photolysis of the nitrosamine, were observed. Time-resolved infrared experiments provided additional support for the above reaction pathways and confirmed that the nitrosamine is a primary photoproduct. We have also found that the relative contributions of the reaction pathways can be altered in certain derivatives. For example, when R' = 2,4-dinitrophenyl, the contribution of the nitrosamine/O-nitrene-forming pathway was diminished. Pharmacological implications of these results are discussed.     

γ-Radiation-produced supported metal complex catalysts. 3. Phosphinated polypropylene supports

p-Styryldiphenylphosphine was grafted onto polypropylene by γ-radiation. However, olefinic phosphines in general do not readily undergo such grafting. Among the many other olefinic phosphines examined only 1-(4-diphenylphosphinophenyl)-prop-1-ene and vinyldiphenylphosphine were grafted successfully and both had low grafting yields. The optimum conditions for grafting involve low dose rates and high total doses of γ-radiation in dimethylsulfoxide as solvent. This grafting is sensitive to impurities and inhomogeneity in the product readily results, especially at high grafting yields. Oxygen must be rigorously excluded if oxidation of grafted phosphorus(III) to phosphorus (V) is to be avoided. Phosphine oxides can be reduced to phosphines when grafted to the polymer with trichlorosilane. Mass spectrometry has shown that more than one olefinic phosphine binds to a single site in the polymer. Solid-state, high-resolution ³¹P-NMR is a valuable technique for characterizing the grafted polymer. The preparation and characterization of the following hitherto unreported phosphines is described: In addition, the precursor halides none of which has been reported, were prepared and characterized.