Reactions of (E)-(3-Aryl-3-oxoprop-1-en-1-yl)triphenylphosphonium Bromides with Arylhydrazines

(E)-(3-Aryl-3-oxoprop-1en-1-yl)triphenylphosphonium bromides reacted with arylhydrazines in an acidic medium to form hydrazones, the intramolecular heterocyclization of which led to the formation of (2,5- diaryl-2,3-dihydro-1H-pyrazol-3-yl)triphenylphosphonium bromides. Under the action of hydrobromic acid, the resulting quaternary phosphonium salts produced saturated (3-aryl-3-oxopropyl)triphenylphosphonium salts.

     

CYCLISCHE PHOSPHONIUM- UND ARSONIUM-SALZE ALS PHASENTRANSFER-KATALYSATOREN BEI DER FINKELSTEIN- UND KOLBE-REAKTION

Abstract

Die 1,4-Heterophosphorinanium- und arsenanium-Salze 1–23 werden auf ihre Eignung als Phasentransfer-Katalysatoren bei der Finkelstein- und Kolbe-Reaktion untersucht. Es wurde gefunden:

1) Die cyclischen Phosphonium- und Arsonium-Salze sind geeignete Phasentransfer-Katalysatoren von vergleichbarer katalytischer Reaktivität.

2) Bei gegebenen Reaktionsmedien hängt die Geschwindigkeit der Umsetzungen hauptsächlich von der Art des eingesetzten Nucleophils ab.

3) Methylgruppen am Phosphor bzw. Arsen verringern die katalytische Wirkung der Oniumsalze.

The phase-transfer-catalytic behaviour of the 1,4-heterophosphorinanium and -arsenanium salts 1–23 in the Finkelstein- and Kolbe-reaction has been investigated. The results indicate that:

1) The cyclic phosphonium and arsonium salts are suitable catalysts and have similar catalytic reactivity.

2) For a given reaction medium the reaction rate depends mainly on the nature of the nucleophile used.

3) Methyl groups bonded to phosphorus or arsenic reduce markedly the catalytic reactivity of the onium salts.     

Synthesis and Reactivity of Unsaturated Bisphosphonium Salts

Abstract

The synthesis of 1, 2 vinylene bisphosphonium salts 1 has now been enlarged to the vinylogous 1, 4-butadienylene bisphosphonium salts 2. The salts 2, a new class of unsaturated disalts, have also been prepared through a two-step isomerisation of acetylenic salts. New aspects of the reactivity of salts 1 and the comparative study of salts 2 (selective cleavage reactions of P-C bonds and reactions with nucleophiles having a mobile hydrogen) are described. This reactivity allows the preparation of new series of phosphonium salts substituted by heteroatomic groups.     

1-Acylamino-2-Chlorovinylphosphonium Salts as Versatile Reagents for Preparation of 1,3-Azole Derivatives

Abstract

The substituted vinylphoephonium salts (I) were obtained by the reaction of readily available N-(1,2,2-trichloro-ethyl)carboxamides with triphenylphosphine. These salts are active electrophilic reagents suitable for syntheeie of novel typee of phosphorylated aldehydes (11), mesome-ric ylides-betainee (111) and enamides (IV,V) All those compound8 undergo intramolecular cyclizations leading to different azolylphoephonium salte (VI-IX).     

PHOSPHORORGANISCHE VERBINDUNGEN 901

Abstract

Aus Allylamido-phosphoniumsalzen wird durch trockenes Tetrabutylammoniumcyanid in Methylenchlorid die Allylgruppe unter Erhaltung der Konfiguration und Bildung von Phosphinigsäureamiden abgespalten (P-C-Cyanolyse). Allyl-O-alkyl-phosphoniumsalze reagieren unter den oben genannten Bedingungen nach Arbusov, Allyl-S-alkyl-phosphoniumsalze aber unter Spaltung der P-S-Bindung ab. (P-S-Cyanolyse).

Das System: Tetrabutyl-ammoniumcyanid in Methylenchlorid kann ohne Nachteil für die Ausbeute durch KCN und katalytische Mengen 18-Krone-6 in Methylenchlorid ersetzt werden. Optisch aktives Benzyl-methyl-phenyl-phosphinsulfid kann auf diese Weise unter Erhaltung der Konfiguration desulfuriert werden.

Auch Dithiophosphinsäureester und Thiophosphinsäureamide werden nach vorausgehender S-Alkylierung (Überführung in die entsprechenden Quasiphosphoniumsalze) mit Tetrabutylammoniumcyanid unter Bildung von Thiophosphinigsäureestern bzw. Phosphinigsäureamiden desulfuriert. Thiophosphinsäure-O-alkylester R₂P(S)OR' liefern über diese Reaktionsfolge nach Arbusov Thiophosphinsäure-S-alkylester R₂P(O)SR′.

Die P-C-Cyanolyse von Allyltriphenyl-phosphoniumbromid mit KCN/18-Krone-6 oder Tetrabutyl-ammoniumcyanid bleibt im aprotischen Medium auf der rotgefärbten Ylidstufe stehen. Erst nach Zugabe eines Protonendonators läuft die Isomerisierung zum Propenyl-phosphoniumsalz ab.

Treatment of allylamido-phosphorlum salts with dry tetrabutylammonium cyanide in methylenechloride delivers after removal of the allyl group phosphinous acid amides with retention of configuration (P-C-cyanolysis).

Allyl-O-alkylphosphonium salts undergo the Arbusov reaction under the above conditions, while allyl-S-alkyl phosphonium salts undergo fission of the P[sbnd]S bond (P-S cyanolysis).

Equally good results were obtained using KCN in methylene chloride accompanied by catalytic amounts of 18-crown-6 ether; thus optically active benzyl-methyl-phenyl-phosphine-sulfid gave the corresponding phosphine with retention of configuration.

Dithiophosphinic acid esters and thiophosphinic acid amides, after conversion to the corresponding quasiphosphonium salts via S-alkylation and subsequent treatment with tetrabutylammonium cyanide in methylenechloride, also give the corresponding thiophosphinous acid ester and phosphinous acid amide respectively. Thiophosphinic acid O-alkyl esters (R₂P(S)OR′) give however the thiophosphinic S-alkyl ester (R₂P(O)SR′) via an Arbusov reaction.

The P-C cyanolysis of allyl-triphenylphosphoniumbromide using KCN/18-crown-6 or tetrabutylammonium cyanide in aprotic medium stops at the stage of the intermediary red-coloured ylide; addition of a proton-donor then results in the subsequent rearrangement to the corresponding propenyl-phosphonium salt.     

5-Arylideneaminouracils: II. Synthesis of sodium and ammonium salts

In continuation of studies on the design of new 5-arylideneaminouracil derivatives possessing antimicrobial and antiviral properties, the corresponding ammonium and sodium salts were synthesized. The antimicrobial activity of water-soluble salts of substituted aminouracils in vitro was shown to be several times higher than that of parent neutral compounds.

     

THE SYNTHESIS OF DISODIUM O-n-ALKYLTHIOPHOSPHATES

Abstract

The disodium O-alkylthiophosphates were synthesized by reaction of PSCl₃ with the corresponding alcohols to the O-alkylphosphorodichloridothioates (1), which were hydrolyzed in aqueous triethylamin–sodium acetate solution.¹ The O-alkylthiophosphates (2) were isolated as barium salts and converted to the disodium salts by Na₂SO₄.

Because the barium salts of O-ethyl- and O-n-propyl-thiophosphate were soluble in water, the corresponding dichlorido compounds were hydrolyzed directly to the disodium salts in aqueous sodium hydroxide plus dioxane according to Gray and Hamer.²

Further purification was achieved by column chromatography on Sephadex LH20 using water as an eluant. Pure products, which were not contaminated by either inorganic thiophosphate or O-alkylphosphates, were thus obtained.     

Phosphocyanine Dyes

Abstract

The conjugated organic polymethine salts (cyanine dyes) are widely used in industry. Numerous applications in chemistry (dyes, photochemical sensitizers for photographic emulsions...) and physics (in optical devices, non linear optics and erasable laser disks) have been developed.

We present here a synthetic pathway towards previously unknown phosphocyanine dyes by condensation of N-silylated phosphinimines on carboxonium salts. As the synthesis of these dyes results in the enhancement of the conjugation path, new physical properties are expected. Furthermore their aza-Wittig reactivity allows the obtention of new series, i.e. the reaction with isocyanides lead to original αaminopyridines.     

A Stereoselective Cathodic Coupling of Aryl Styryl Sulfones

Abstract

The cathodic coupling of unsaturated sulfones (title compounds) performed in aprotic media in the presence of lithium salts as electrolyte affords d,l dimers almost exclusively.     

Synthesis of (E)-4-(4-chlorobenzylidene)-3,4-dihydro-2H-pyrrole-based pyrrolinium salts

Pyrrolinium salts containing 3-arylidene fragment were obtained. Their synthesis is based on the reaction of (E)-4-(4-chlorobenzylidene)-3,4-dihydro-2H-pyrrole with various bromo-alkanes. Structures of the obtained compounds were confirmed by a set of physico-chemical analysis methods.

     

Synthesis and Reactivity of New Silylated Sulfur-Containing Heterocyles Through Thionation of Bis(Acylsilanes)

Abstract

The optimization of the synthesis of 2,6-bis(trialkylsilyl)4H-thiopyranes and some aspects of the reactivity of the corresponding lithium salts with alkyl halides and benzaldehyde are presented.     

Synthesis of Aminophosphonium Salts and Their Transformation

Abstract

Aminophosponium salts were obtained by two different methods: (1) catalytic phosphorilation of halogen derivatives containing Csp2-Hlg bonds; (2) uncatalytic phosphorilation of bromoacetal. Reactions mechanisms are discussed.     

Hypervalent Iodine in Synthesis. 94. A Facile Synthesis of 2-Substituted-imidazo[1,2-a]pyridines by Cyclocondensation of Alkynyl(phenyl) iodonium Salts and 2-Aminopyridine

Abstract

A facile method for the synthesis of 2-substituted-imidazo[1,2-a]pyridines is achieved by cyclocondensation of alkynyl(phenyl)iodonium salts with 2-aminopyridine.     

Reaction of [3-(Dimethylamino)-2-Phenyl-Prop-2-en-1-Ylidene] Dimethylammonium Perchlorate with Grignard and Lithium Reagents

Abstract

The reaction of simple iminium salts, such as the Eschenmoser reagent (1) with Grignard and lithium reagents has been recently described¹.     

X-Ray Structural Study of the Novel Tautomeric Orgaijophosphorus Compounds

Abstract

A number of acylsubstituted (diphenylphosphoryl)meth-yl-triphenylphosphonium salts I-IV, which are keto-enolic organophosphorus compounds with the new type of the phos-phoryl-hydroxyylide tautomerism, were studied by X-ray diffraction method.     

Koordinationschemie von Dinitroresorcin mit Kupfer-, Kobalt-, Nickel-, Eisen- und Zinksalzen

The reactions of the bidentate dinitrosoresorcinol (DNR) with copper, cobalt, nickel, iron and zinc salts were investigated. This ligand was found to react with these metal salts in aqueous media where hydrogen ion was confirmed to be liberated except in case of iron. The solid complexes were prepared in alcoholic media. Chemical analyses, magnetic and spectral data were compatible to determine the structure of these complexes and their mode of chelation.

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Mit 2 Abbildungen     

Stereochemie von metallocenen, 29. Mitt

Zusammenfassung Die optische Rotationsdispersion und der Circulardichroismus mehrerer N-Ferrocensulfonyl-(S)--aminosäuren und ihrer Äthylester wurden gemessen. In allen Fällen (mit Ausnahme der Prolin- und Hydroxyprolinderivate) entspricht einer (S)-Konfiguration am Chiralitätszentrum ein negativerCottoneffekt im Bereich der Ferrocenbande (um 450 nm).

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Stereochemistry of the metallocenes, XXIX. (Ferrocene derivatives, L): N-Ferrocenesulfonyl amino acids: New chromophoric derivatives of optically active -amino acids

Optical rotatory dispersion and circular dichroism of severalN-ferrocenesulfonyl-(S)--amino acids, as well as of their ethyl esters were recorded. In all cases (with the exception of the proline and hydroxyproline derivatives) the (S)-configuration of the center of chirality was found to correspond with a negativeCotton effect in the region of the ferrocene band (around 450 nm).

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Mit 1 Abbildung

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28. Mitt. (zugleich 49. Mitt. über Ferrocenderivate):H. Falk undO. Hofer, Mh. Chem.100, 1540 (1969).     

Synthesis of 5-arylazo-2,4-dithiohydantoins

It was shown that during the interaction between 2-thiohydantoin and P₂S₅ in dioxane 2,4-dithiohydantoin (I) is formed, and without isolation from the reaction solution this compound forms 5-arylazo-2,4-dithiohydantoins (II–XI) with salts of diazone. The structure of two of these compounds has been determined by countersynthesis. When 5-arylazo-2,4-dithiohydantoins interact with amines the corresponding 4-substituted derivatives are formed.

     

MULTIPLE PATHWAYS IN THE BASE-CATALYZED REACTIONS OF S-ALLYL SULFONIUM COMPOUNDS

Abstract

Various S-allyl sulfonium salts were allowed to react with bases (EtONa/EtOH, NaH/THF). From product analyses, it was found that modes of reaction depend on both the structure of sulfonium salts and the bases employed. Among the observations, it is worthy to note the formation of cyclopropane derivatives from some allyl sulfonium salts.