Fluordiazadiphosphetidine, 5. Mitt.

Reaction of (CH₃NPF₃)₂ with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH₃N)₄P₃F₇, the new spiro-isomer F₃P(CH₃N)₂PF(CH₃N)₂PF₃ and the spiro-compound F₃P(CH₃N)₂PF(CH₃N)₂PF(CH₃N)₂PF₃, an isomer of the known compound (CH₃N)₆P₄F₈.     

Functional polymers. II. Preparation and polymerization of methyl 5-vinylsalicylate,methyl 5-vinylacetylsalicylate, 5-vinylsalicylic acid,and 5-vinylacetylsalicylic acid

Four new derivatives of 5-vinylsalicylic acid were prepared and their homopolymerization and copolymerization with acrylic acid and methacrylic acid investigated. Methyl 5-vinylsalicylate was prepared in a six-step synthesis from methyl salicylate in an overall yield of 35%. Acetylation in the last step yielded methyl 5-vinylacetylsalicylate. Hydrolysis of methyl 5-vinylsalicylate gave 5-vinylsalicylic acid which was acetylated to 5-vinylacetylsalicylic acid (5-vinyl aspirin). The 5-vinyl-substituted salicylic acid derivatives could be readily homopolymerized and copolymerized with acrylic acid and methacrylic acid to give various compositions of copolymers. It is worth noting that even the monomers with free phenol groups could be readily polymerized with azobisisobutyronitrile as radical initiator to high molecular weight polymers without interference of the phenolic OH group.     

4-Hydroxy-1-thiacumarine, 5. Mitt.

Zusammenfassung Eine große Zahl von 3-acylierten 4-Hydroxy-1-thiacumarinen mit verschiedenen Halogen- oder Alkylsubstituenten am Benzolkern wurde durch Kondensation von 4-Hydroxy-1-thiacumarinen mit verschiedenen aliphatischen Säuren in Gegenwart von POCl₃ synthetisiert.

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The synthesis of a large number of 3-acylated 4-hydroxy-1-thiacoumarins carrying various substituents in the benzenoid nucleus (halogen, alkyl) has been carried out by the condensation of 4-hydroxy-1-thiacoumarins with various aliphatic acids in the presence of phosphorus oxychloride.

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Diese Veröffentlichung wird ein Teil der Dissertation vonP. S. Jamkhandi zur Erlangung des Ph.D. der Karnatak University sein.     

Reactions of 1, 5-diketones. XX. Semicyclic 1, 5-diketones in the fischer reaction

Monophenylhydrazones involving both the phenacyl carbonyl group and the ring carbonyl group are formed as intermediates in the reaction of semicyclic 1, 5-diketones of the 2-(phenacylobenzyl) cyclohexanone type with phenylhydrazine in acid media. The former undergo subsequent conversion to the corresponding substituted indoles, whereas the latter are converted to substituted 1H-2, 3, 3a, 4-tetrahydropyrido [3, 2, l-j, k] carbazoles; in addition, the corresponding 5, 6, 7, 8-tetrahydroquinoline derivatives are also partially formed.See [1] for communication XIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 645–650, May, 1976.     

Halogenaldehyd-Polymere. 5. Mitt. Polymerblends, die Chloralpolymere enthalten

Ohne Zusammenfassung     

Isomerization of 5, 5-dimethylpyrazolines. preparation and properties of 5, 5-dimethyl-Δ1-pyrazoline and 3, 4-dimethyl-Δ2-pyrazoline

Slow distillation of 5, 5, -dimethyl-²-pyrazoline isomerizes it to 5, 5-dimethyl-¹-pyrazoline, and heating the latter with hydrazine hydrochloride reconverts it to the ² isomer. This is the first experimental evidence that the ² double bond in a pyrazoline can move to the ¹ position, i. e., in a direction the reverse of that previously known. The 5, 5-dimethyl-¹ -pyrazoline described is the simplest ¹ pyrazoline hitherto isolated.The authors heartily thank A. A. Petrov for making it possible to chart the PMR spectra, and V. B. Lebedev and V. S. Stopskom for obtaining and treating the spectrograms.     

Synthesis of some 3',5'-dideoxy-5'-C-phosphonomethyl nucleosides.

Ammonium [1-(3',5',6'-trideoxy-beta-D-erythro-hexofuranosyl)thymine]-6'- phosphonate (1), ammonium 3',5'-dideoxycytidine-5'-C-methylphosphonate (2) and 3',5'-dideoxyadenosine-5'-C-methyl phosphonic acid (3) have been synthesized and tested for anti-HIV activity. The key steps involved an Arbuzov reaction between triethyl phosphite and 3,5,6-trideoxy-6-iodo-1,2-O-isopropylidene-alpha-D-erythro- hexofuranose (7), followed by condensation with the appropriate nucleoside bases. The substances 1, 2 and 3 have been tested in vitro against HIV.     

Reaktionen von o-Chinolacetaten mit Diazoalkanen, 5. Mitt.

Zusammenfassung Die durch Addition von Diazomethan an o-Chinolacetate mit unsubstituierter 5-und 6-Stellung erhaltenen Verbindungen der allgemeinen Struktur II besitzen zwei asymmetrische Kohlenstoffatome, so daß bei der Anlagerungsreaktion zwei Racemate entstehen sollten. Die beiden Racemate wurden im Falle des Diazomethan-additionsproduktes an das 2-Methyl-o-chinolacetat in Form ihrer N-Acetylderivate isoliert. Von diesen konnte auf Grund der leichter eintretenden thermischen Essigsäureabspaltung für die tiefer schmelzende Verbindung die cis-Stellung von H und Acetoxygruppe an den beiden asymmetrischen C-Atomen wahrscheinlich gemacht werden.Mit 4 AbbildungenMitt.:G. Spitteller, G. Schmidt, H. Budzikiewicz undF. Wessely, Mh. Chem.91, O/129 (1960).     

Neue Sulfonamide, 12. Mitt. 5-Halogen-substituierte Sulfanilamido-methoxy-pyrimidine

Zusammenfassung Es wird die Darstellung von 2-Sulfanilamido-4-methoxy-5-chlorpyrimidin, 2-Sulfanilamido-4-methoxy-5-jodpyrimidin sowie 4-Sulfanilamido-2-methoxy-5-chlorpyrimidin beschrieben. Die erste Verbindung wurde auf zwei voneinander unabhängigen Synthesewegen erhalten. W. Klötzer undJ. Schantl, Mh. chem.94, 1178 (1963).     

Pseudoesters and Derivatives. XXXI1. Synthesis of 5-Ethylthio-, 5-Ethylsulfinyl- and 5-Ethylsulfonylfuran-2(5H)-ones

Convenient syntheses of 5-(ethylthio) furan-2(5H)-ones 2a-k from the appropriate 5-methoxyfuran-2(5H)-one 1a-g are described. The oxidation to the corresponding sulfoxides 5a-c and sulfones 6a-f is also reported.     

Polarographische Untersuchungen in wasserfreiem Dimethylsulfoxid, 5. Mitt.

Zusammenfassung Auf Grund der Untersuchung des polarographischen Verhaltens von Aluminium(III)-chlorid und Aluminiumacetylacetonat in Dimethylsulfoxid werden die Bedingungen aufgezeigt, unter denen die polarographisch-analytische Erfassung von Aluminium möglich ist.Mit 1 Abbildung4. Mitt.:G. Schöber undG. Rehak, Mh. Chem.93, 445 (1962).     

4-dialkyldithiocarbamoyl-5-nitropyrimidines. Synthesis,structure, properties

The reaction of 4-chloro-5-nitropyrimidines with sodium dialkyldithiocarbamates gives the corresponding 4-dialkyldithiocarbamoyl derivatives. On heating these derivatives the nitro group is displaced and disulfides are formed at position 5 of the pyrimidine ring. Transformation to 1,3-dithiolo[4,5-d]pyrimidines has been demonstrated.Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1420–1423, October 1994. Original article submitted September 6, 1994.     

Surface tension of polymer solutions, 5.

Summary Surface tensions of four theta-solutions have been measured over a wide temperature range: Polystyrene-cyclohexane and decalin, polymethyl-methacrylate-heptanone-4 and polyisobutylene-benzene. Continuous surface tension measurements can only be regarded as equivalent to equilibrium measurements if, using appropriate speeds of temperature change, points of heating and cooling cycles give an identical curve. No transition can be found at the theta-temperature in this case.

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Zusammenfassung Es wurden die Oberflächenspannungen von vier Theta-Lösungen über einen großen Temperaturbereich gemessen: Polystyrol-Cyclohexan und Dekalin, Polymethylmethacrylat-Heptanon-4 und Polyisobutylen-Benzol. Kontinuierliche Oberflächenspannungsmessungen können nur dann als gleichwertig mit Gleichgewichtsmessungen betrachtet werden, wenn bei geeigneten Geschwindigkeiten der Temperaturänderung Punkte der Erhitzungs- und Abkühlungszyklen auf einer identischen Kurve liegen. In diesem Fall kann kein Übergang bei der Theta-Temperatur gefunden werden.

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With 3 figures     

Low-energy,low-temperature mass spectra. 5-alkanals

The low-energy, low-temperature mass spectra of thirteen alkanals are reported and their predominant modes of fragmentation discussed in terms of energetics. Characteristic of this class of compounds is the very high proportion of odd-electron ions in the mass spectra, namely [M ? C_MH_2m]^+˙, [M ? H₂O]^+˙ and [M ? H₂O ? C_mH_2m]^+˙.