Synthesen kondensierter „Hydroxy-aza- und-oxa-chinolizinone”

The synthesis of some condensed 4-hydroxy-2-pyridone derivatives by the reaction of 2,4,6-trichlorophenyl malonates (2) with azomethines incorporating the C=N bond in a ring system is reported. The reaction of 3-aryl- or 3-haloquinoxalines (1 a, b) with2 yields monopyrido-condensed quinoxalines (3 a-d), while 3-alkyl-quinoxalines (1 c, 9) react to give dipyrido-derivatives (4 and5). Dehydrogenation of5 with Pd/C is used to confirm the structure of the known product of the reaction between2 and 5,10-dihydrophenazine (8). The reaction of2 with monosubstituted quinoxalones10 a-d yields the corresponding monopyridoquinoxalones11 a-e.

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10. Mitt.:Th. Kappe, M. Hariri undF. S. G. Soliman, Arch. Pharm.309, 684 (1976).

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Aus der DissertationY. Linnau, Universität Graz, 1969.

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Aus der DissertationW. Stadlbauer, Universität Graz, 1975.     

Zur Reaktion von 4-Hydroxy-2-chinolon mit reaktiven Malonsäurederivaten

The reaction of 4-hydroxy-2-quinolone (1) with malonyl chlorides2 in the presence of N,N-dimethylaniline yields the linear pyrono-quinolones4. These are thermically rearranged to angular derivatives5, which can also be obtained by direct condensation of1 with trichlorophenyl malonates3. The reaction of 4-benzyloxy-2-quinolone with2a gives the mesoionic 1,3-oxazine derivative8.

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4. Mitt.:G. Schindler, D. Furtunopulos undTh. Kappe, Z. Naturforsch.31 b, 500 (1976).

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Aus der DissertationG. Nöhammer, Graz 1971.     

Application of the Cleavable Isocyanide in Efficient Approach to Pyroglutamic Acid Analogues with Potential Biological Activity

Two efficient procedures have been developed for the synthesis of pyroglutamic acid analogues 28, 29, and 34. According to the first method the Ugi (4C3C) reaction is followed by a post-transformation reaction, and the second method involves the Michael addition reaction. The present methodologies demonstrate the applicability of 1-(2,2-dimethoxyethyl)-2-isocyanobenzene (15) as a cleavable isocyanide in the Ugi/ post-transformation reaction and a strong nucleophile in the Michael addition reaction. The framework of pyroglutamic acid analogues has been constructed by the selective cleavage of the C-terminal amide bond and nucleophilic addition to the activated α,β-unsaturated carbonyl group.

     

Mechanismus der Reaktion von polaren Olefinen mit Diazoalkanen zu stickstoffreien Verbindungen

Zusammenfassung Die eingehende kinetische Untersuchung der Reaktion von Isobutylidenmeldrumsäure (1) mit Diazoessigester (2) zu Cyclopropanen und ungesätt. Verbindungen beweist, daß diese Umsetzung nach einem zweistufigen Folgemechanismus abläuft. Im ersten und geschwindigkeitsbestimmenden Teilschritt entsteht nach einem Zeitgesetz zweiter Ordnung das thermisch labile1-Pyrazolin3, im schnelleren zweiten Teilschritt zerfällt das kurzlebige Zwischenprodukt nach einer Reaktion erster Ordnung in die stickstoffreien Endprodukte. Mit Hilfe der UV-Spektroskopie gelang es, den Konzentrationsverlauf des intermediären 1-Pyrazolins unmittelbar zu messen.

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Mechanism of the reaction of polar olefines with diazoalkanes to nitrogen-free products

Detailed kinetic investigation shows that the reaction of isobutylideneMeldrum's acid (1) and ethyl diazoacetate (2) consists of two steps. The first step, which produces the thermally unstable 1-pyrazoline3 in a second order reaction, is rate-determining and followed by a rapid first order thermolysis of the short-lived intermediate3 to nitrogen free products. The change in concentration of the intermediate 1-pyrazoline was observed by UV-spectroscopy directly.

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Mit 2 Abbildungen

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Herrn Prof. Dr.E. Broda zum 60. Geburtstag gewidmet.

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24. Mitt.:F. Nierlich, P. Schuster undO. E. Polansky, Mh. Chem.102, 438 (1971).

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Teil der DissertationH. Kisch, Universität Wien 1969.     

Molecular Iodine as a Versatile Reagent for the Synthesis of Thiazoloquinoline—A Potential Antibacterial Agent

Abstract

A series of 3-(2-aminothiazol-4-yl)quinolin-2[1H]-ones 3 was prepared by neat reaction of quinolin-2[1H]-ones 1 with thioureas 2 in the presence of molecular iodine. The synthesized compounds were evaluated for their in vitro antimicrobial activities against Escherichia coli, Paedococcus sp., Lactobacillus, Yersinia enterocolitica, and Staphylococcus aureus. The green chemical approach for the synthesis of thiazoloquinolinone 3 was performed under neat conditions using molecular iodine as catalyst as well as reaction medium.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Synthesis and Application of 3,3-Spirocyclopropane Derivatives Obtained from 1,2:5,6-Di-O-Isopropylidene-α-D-Glucofuranose

Abstract

3,3-Spirocyclopropane derivatives (5 and 7) were prepared by three different methods of cyclopropanation starting from 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (2). Subsequent radical induced cyclopropane ring opening reaction stereo-specifically provided the 3-C-allyl derivative (9). However, activation of the cyclopropyl ring through the aldehyde (10) followed by hydrogenation gave a quaternary chiral derivative (11) which was elaborated to the versatile intermediate (1) by using Bamford-Stevens reaction.

     

Concise Synthesis of Photocleavable Molecular Tag for Laser Desorption Ionization Mass Spectrometry via Fries Reaction

Abstract

A new synthetic route for the photocleavable molecular tag for laser desorption ionization mass spectrometry (LDI-MS) was achieved using the Fries reaction of 2,6-dimethylphenyl ester as its key reaction. Zirconium chloride was used as uniquely efficient adjuvant to promote the reaction. The molecular tag was obtained in five steps without chromatographic purification.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

An Efficient and Simple Method for Diazotization-Thiocyanation of Aryl Amine using Cross-Linked Poly (4-Vinylpyridine) Supported Thiocyanate Ion

Abstract

An efficient and simple method for the facile synthesis of arylthiocyanates via diazotization-thiocyanation of aryl amines using cross-linked poly (4-vinylpyridine) supported thiocyanate ion is described. Various primary aromatic amines, with electron-withdrawing and electron-donating groups, were transformed into aryl thiocyanates in high to excellent yields in a short reaction time. The present procedure offers advantages such as short reaction time, simple reaction work-up, and the polymeric reagents can also be regenerated and reused for several times without significant loss of their activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Iodine and Its Interhalogen Compounds: Versatile Reagents in Carbohydrate Chemistry V. Synthesis of 1,2-trans-Linked 1-Thioglycosides from the Per-O-acetylated Glycoses 1 2

Abstract

Treatment of per-O-acetylated mono- and di-saccharides with (alkyl/arylthio)tri-methylsilane and iodine at ambient temperature results in the formation of the corresponding 1,2-trans-1-thioglycosides in very high yield. In the case of higher boiling thiols such as ethanethiol, the reaction can be effectively carried out in the presence of the thiol itself instead of the silylated derivative, but the reaction is not stereospecific. Moreover, in the latter reactions a portion of the starting material remains unchanged even on prolonged reaction. With β-D-glucose pentaacetate (11) as the starting material, its epimerisation occurred during the reaction and therefore the recovered starting material was of α-D-configuration. In addition, the methyl disulphide-hexamethyldisilane system has been found to serve as an effective and cheaper alternative to the expensive (methylthio)-trimethylsilane.

     

4-Methylisocamphenilansäure und 4-(3,3,4-Trimethyl-2-exo-norbornyl)-3-buten-2-on

The synthesis of 4-methylisocamphenilanic acid (7) and of the unsaturated ketone 4-(3,3,4-trimethyl-2-exo-norbornyl)-3-buten-2-one (2), an analogue of -irone (1), are described. The preparation of2 has been accomplished by: catalyzedDiels—Alder reaction of methylcyclopentadiene and mesityl oxide, hydrogenation and isomerization of the resulting ketone mixture to theexo-ketone6, oxidation of6 to the acid7, reduction of7 to the corresponding aldehyde8 and aldol reaction of8 with acetone. The structure of the key intermediate6 was established by mass, 100 MHz¹H-NMR and¹³C-NMR spectra. The odour of2 is discussed briefly.

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Teil der Diplomarbeit vonI. Schmidmayer.

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9. Mitt.,G. Buchbauer undM. Wiltschko. J. Soc. Cosmet. Chem., im Druck.

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8. Mitt.,G. Buchbauer undE. Klissenbauer, Mh. Chem.109, 499 (1978).     

Copper (I) Iodide-Catalyzed Solvent-Free Synthesis of α-Aminophosphonates

Abstract

A method for the synthesis of α-aminophosphonates through the three-component coupling reaction of aldehydes, amines, and diisopropyl phosphite using copper (I) iodide salt catalyst is demonstrated, The reaction is highly efficient, economic, and also environment friendly.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Table S1, Figures S1–S9.]

GRAPHICAL ABSTRACT      

HYDROCHLORINATION OF 2,3-ACETYLENIC ACIDS WITH THIONYL CHLORIDE IN DIMETHYLFORMAMIDE

ABSTRACT

The reaction of 2,3-acetylenic acids (1a–d) with thionyl chloride in DMF under mild conditions gave E,Z-3-chloro-2-alkenoic acids (2a–d) or esters (3a–d) depending on treating the reaction mixture with either water or alcohols.     

Zur Kenntnis cyclischer Acylale, 18. Mitt.: Über die Einwirkung von Diazomethan auf substituierte Benzylidenmeldrumsäuren und ähnliche Verbindungen

Zusammenfassung Es wird die Reaktion der Kondensationsprodukte (1–3) vonMeldrumsäuren mit Diazomethan in Methanol/Äther beschrieben, die zu den Cyclopropanverbindungen1 b-3 b führt. Diese Reaktionsweise ist bekannt und auch nach quantenchemischen Berechnungen des einen von uns (P. Schuster) zu erwarten.Eine neue, bisher nicht beobachtete Reaktion wurde bei der Verbindung4 gefunden. Bei verschiedenen Temperaturen führt die Reaktion mit CH₂N₂ in Methanol/Äther (außer zu den Verbindungen4 a und4 b) zu4 c. In CHCl₃ entsteht nur4 b neben viel allem Anschein nach hochmolekularen Produkten.

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The reaction is described of the condensation products ofMeldrum's acid with aldehydes1–3 ² with diazomethane in methanol/ether, which leads to the cyclopropane compounds1 b-3 b. This is a known mode of reaction and is predicted by quantum chemical calculations ofP. Schuster.A reaction hitherto unobserved was found in the case of the compound4. The reaction with CH₂N₂ in methanol/ether at various temperatures yields the compound4 c as well as4 a and4 b. In CHCl₃ the reactions yields only4 b in addition to many other high molecular weight products.

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Mit 1 Abbildung

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Herrn Prof. Dr.F. Asinger zum 60. Geburtstag gewidmet.     

Highly Regioselective Synthesis of Novel 4-O-Phosphorylated Paeonol Analogs

Abstract

4-O-phosphorylated paeonol derivatives were conveniently prepared by a facile method. Resacetophenone was prepared by the Friedel–Crafts acylation reaction of acetic acid with resorcinol. It was then phosphorylated regioselectively at the 4-O position using the Atherton–Todd reaction. An efficient, highly regioselective method to synthesize 4-O-phosphorylated paeonol derivatives is provided, and the approach has the merits of mild reaction conditions.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

CHOLESTERYL PHOSPHITE AND RELATED COMPOUNDS

Abstract

The preparation of cholesteryl phosphorodichloridite (2) is described; this compound with aniline (2 mol. equiv.) gave the N-phenylphosphoramidochloridite (5) and the latter by condensation with water afforded the N-phenyl-amidophosphite (6).

Similarly the N-phenylphosphoramidochloridite (5) with morpholine gave the morpholidite (7); phenylhydrazine gave the hydrazinophosphite (8) and ethanol the amidoethyl phosphite (9). Cholesteryl phosphorodichloridite (2) by reaction with aniline (4 mol. equiv.) gave the N,N ¹?diphenylphosphorodiamidite (10).

The reaction of cholesteryl phosphorodichloridite (2) with methanol and ethanol are discussed in relation to the analogous reactions with cholesteryl phosphorodichloridate. Boiling ethanol gave cholesterol as the only isolatable product but at room temperature a low yield of the diethylphosphite (11; R=Et) was obtained. The yield of the phosphite was greatly increased in the presence of base. Similarly the dichloridite 2 with boiling water gave cholesterol (1), but at room temperature cholesteryl phosphite 3 was isolated: the mechanistic basis for these different results is briefly discussed.

trans-4-t-Butylcyclohexanol with phosphorus trichloride gave the phosphorodichloridite, which was characterised by conversion to the corresponding N,N ¹?diphenylphosphorodiamidite.     

Molybdic Acid-Catalysed Isomerization of D-Ribulose and D-Xylulose to the Corresponding 2-C-(Hydroxymethyl)-D-Tetroses

ABSTRACT

2-C-(Hydroxymethyl)-D-erythrose (2) and 2-C-(hydroxymethyl)-D-threose (4) have been stereospecifically synthesized in one-step by a molybdic acid-catalysed isomerization reaction from respective D-xylulose (1) and D-ribulose (3). In the case of interconversion of 1 to 2, the content of the 2-C-branched chain tetrose in the equilibrium mixture can be doubled if boric acid is present in the reaction mixture in addition to the catalyst.     

REACTION OF ORGANOCADMIUM REAGENTS WITH SULFONYL HALIDES III. ACTION OF ALKANESULFONYL CHLORIDES ON SELECTED DIARYLCADMIUM COMPOUNDS

Abstract

The reaction of methane- and ethanesulfonyl chloride with selected diarylcadmium compounds was investigated. In contrast with arenesulfonyl chlorides which react with diarylcadmium to give sulfones in appreciable yields, ethanesulfonyl chloride did not yield sulfones. Methane-sulfonyl chloride gave sulfones in very poor yields. The major products were haloarenes, alkane-sulfinic acids and biaryls.

Cross-over experiments revealed that the formation of biaryls involve an inter-not intra-molecular reaction (cf. eq. 4).     

REACTIONS OF TELLURIUM TETRAHALIDES WITH GLYCOLS

Abstract

Tellurium tetrahalides undergo reaction with glycols to yield three different products: O,O'-dioxotrihalotellurates; bis(alkoxy)dihalotellurium (IV) compounds and hexahalotellurates. The course of the reaction appears to be determined primarily by the nature of the glycol. The structure of dichlorobis(cis- 2-hydroxycyclohexyloxy)tellurium(IV) has been determined crystallographically     

One Pot Synthesis of Aryldiazepinothiophenones

Abstract

Aryldiazepinothiophenones 2 were prepared from the reaction of o-phenylenediamines with acetone in the presence of 2-mercaptopropionic acid. Fused thiazolobenzodiazepines 3 along with fused thiazolobenzimidazoles 4 and 1,5-benzodiazepines 5 were obtained as by-products. The benzodiazepinothiophenone 2a and the benzodiazepine 5a were also isolated from the reaction of o-phenylenediamine with phorone.     

Sila-Analogon des Cicloniumbromids

Sila-AnaloguesB 2 andA 2 of the spasmolytic ciclonium bromide (B 1) respectively the corresponding free baseA 1 were synthesized for the first time according to the reaction steps shown in scheme 1, and they and their precursors I and II were characterized by physical (Table 1) and chemical properties and their structures confirmed by NMR, and mass spectroscopy (Tables 2 and 3). The pharmacological effects ofA 2 andB 2 were investigated and compared with those of the parent carbon compoundB 1 (chapter 5).

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3. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.107, 439 (1976).

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Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974.