PHOSPHORORGANISCHE VERBINDUNGEN 118.1 UMPOLUNG UND SELEKTIVITÄT BEI 2,4-DINITROPHENYLESTERN VON PHOSPHIN-UND SULFONSÄUREN

Abstract

Phosphinsäure-4-nitrophenylester (z.B.A) sind OH-selektiv. Sie reagieren mit Alkoholen zu Phosphin-säureestern (z.B.B). (P-O-Angriff). Phosphinsäure-2,4-dinitrophenylester 1 reagieren dagegen unter Umpolung (O-C-Angriff) analog dem Sangers Reagenz praktisch chemoselektiv mit NH-Verbindungen nach (1).

Der nicht fluoreszierende 1-(5-Dimethylaminonaphthalin)-sulfonsäure-2′,4′-dinitrophenylester 4 ist ebenfalls NH-selektiv. Aus 4 entstehen mit NH-Verbindungen nach (3) unter O-C-Spaltung wie mit 2,4-Dinitrofluorbenzol 2,4-Dinitroanilinderivate.     

A NOVEL ROUTE TO SPIRO PHOSPHORUS-HETEROCYCLE VIA LAWESSON'S REAGENT

ABSTRACT

2-Aryl-spiro-[5,5]-1,3,2-dioxaphosphorinane-2-sufides were prepared by the cyclization reaction of Lawesson's reagent with pentaerythritol and monobenzalpentaerythritol, respectively.     

Synthesis of Chiral Bis-Thiazolines and Asymmetric Diels–Alder Reactions

Abstract

New chiral ligands, bis-thiazoline derivatives (sulfur analogues of known oxazolines) were prepared from chiral bis-(N-acylamino alcohols) with Lawesson's reagent. Bis-thiazolines thus obtained proved to be useful chiral ligands for metal in asymmetric Diels–Alder reaction.     

REACTIONS OF TETRAPHOSPHORUS DECASULFIDE AND LAWESSON'S REAGENT WITH SILANES CONTAINING A FEW Si-O BONDS

Abstract

The reactions of tetraphosphorus decasulfide and Lawesson's reagent with tetra-, tri- and dialkoxysilanes were studied. On the basis of these reactions, new S-silyl esters of phosphorus(V) thioacids have been prepared. The prepared compounds were identified by IR, ¹H, and ³¹P NMR and mass spectra as well as elemental analyses.     

Synthesis,Spectroscopic Analysis,and In-Vitro Antimicrobial Evaluation of some Tetrahydrobenzo[a]Xanthene-11-Thiones

Abstract

A series of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-thiones were synthesized by the reaction of substituted 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-ones with Lawesson's Reagent in toluene under standard reaction conditions. All synthesized compounds were characterized by IR, NMR (¹H and ¹³C), and mass spectra. Moreover, 2D-NMR (HOMOCOSY, HSQC, and HMBC) studies were also performed for compound 10b. The synthesized compounds were also screened for their antibacterial activities.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]     

Thionation of Chalcone and Aurone Derivatives by Lawesson's Reagent

Abstract

The reaction of Lawesson's reagent (LR 5) with chalcones (4a–h) and aurones (12a–h) proceeds in refluxing toluene to give the respective benzofuranylprop-2-en-1-thiones (8a–h) and benzodifuran-3-thiones (13a–h). Correct elemental analyses and spectroscopic data were obtained for the new compounds.     

The Behavior of Certain Coumarins and Furocoumarins Toward Sulfur Reagents

The behavior of 4-hydroxycoumarin (1), 7-hydroxycoumarin (2), 4-hydroxy-bergapten (3), and 4-hydroxyisopimpinellin (4) toward sulfur reagents, namely, thionyl chloride, phosphorus pentasulfide, thiolacetic acid, and Lawesson's reagent (5), was studied. The nature of products in each case depended upon the type of reactants and reaction conditions. Possible reaction mechanisms were considered, and structural elucidations of the new products were based upon compatible elementary and spectroscopic evidences.     

Synthesis and Properties of Thiophene and Dithiin Functionalized Tetrathiafulvalenes

Abstract

Syntheses of two analogues of tetrathiafulvalene (TTF), fused to 1,4-dithiin and thiophene rings, substituted with thiophene moieties, have been illustrated. The syntheses were accomplished through the reaction of a 1,8-diketone with phosphorus pentasulfide or Lawesson's reagent in boiling dry toluene. Conversion of the thioketones to their the oxo forms with mercury (II) acetate, was followed by self-coupling in freshly distilled boiling triethyl phosphite. Attempts for their electro-polymerizations through the thiophene groups at the peripherals were unsuccessful. Computational chemistry studies revealed that the thiophene groups did not exhibit enough spin densities to perform polymerization.

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.     

Reaction of 2-Thioxo-4-Thiazolidinones Toward Lawesson's Reagent,Phosphorus Pentasulfide,Dialkylaminophosphines, and Phosphorus Ylides

Abstract

2-Thioxo—3-allyl-4-thiazolidinone 1a reacts with Lawesson's reagent (LR, 2) to give the ethylenic product 5 through a coupling reaction along with the dithioxo compound 6. Coupling reaction products of types 8 and 9 are also produced upon reacting thiazolidinones 1 and with the appropriate tris(diallkylamino) phosphine reagent (3 a,b). Reaction of the thiazolidinone 1a with the ylidenetriphenylphosphorane reagents 4 a–c proceeds according to the Wittig mechanism yielding ethylenes 10a–c, respectively. Structural elucidations for the new products were based upon compatible analytical and spectroscopic measurements as well a confirmatory single crystal X-ray structure for 5.

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.     

Application of Lawesson'S Reagent in Syntheses of Biologically Active Phosphorus Heterocycles

Abstract

The reactions of Lawesson's reagent-2.4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide, with long-chain 1 - glycerin rnonoethers, 3-mercapto-4-amino-1,2,4-triazoles, 1,3-disubstituents glycinamides, and 2-methyl-1,3-butadiene have been investigated and found to form cyclic analogues 1, fused heterocycles 2, 5-membered phosphorus rings 3, and 6-membered heterocycle 4, respectively, in moderate yield. The preliminary biological screening tests for these rings showed that they possess significant selective herbicidal activity against rape.     

Synthesis and Spectroscopic Characterization of Novel Aryl-Dithiofluorophosphonate Derivatives and X-Ray Studies of [(4-CH3OC6H4)(F)P(S)S−][PH4P+]

Abstract

Potassium and tetraphenylphosphonium salts of novel aryldithiofluorophosphonic acids were synthesized. Lawesson's Reagent was allowed to react with KF in acetonitrile to yield the potassium salt of p-methoxyphenyldithiofluorophosphonic acid. Treatment of the latter with tetraphenylphosphonium chloride resulted in the formation of the tetraphenylphosphonium salt. The structures of the compounds were elucidated by FTIR, ¹H, ¹³C, ¹⁹F, and ³¹P NMR spectroscopy as well as by ESI-mass spectrometry. The molecular and crystal structure of the tetraphenylphosphonium salt, determined by single crystal X-ray diffraction, is also presented.

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.     

NEW PRODUCTS OF REACTION OF LAWESSON'S REAGENT WITH DIOLS

Reaction of the Lawesson's reagent (LR) with aliphatic 1,2- and 1,3-diols as well as with aromatic 2,2′-dihydroxybiphenyl led to new products. Stable di-tert-butylammonium salts of bis-anisyldithiophosphonic acids 6 were isolated and were then converted into unique 9-, 9-, and 10-membered cyclic disulfides 7 and into S,S-dimethyl esters 8. The salts of bis-anisyldithiophosphonic acids 6 were shown to be capable of splitting the disulfide bond of Ellman's reagent.     

Scope and Limitation of the Reactions of 3-Imino Derivatives of Pentane-2,4-Diones with Organophosphorus Reagents

Abstract

3-(Hydroxyimino)pentane-2,4-dione reacts with phosphonium ylides, Wittig–Horner reagents, trialkyl phosphites, and Lawesson's reagents to give the olefinic and cyclic products, the phosphonate adducts, the dialkyl phosphate products, the phosphinodithioic acid, and 2,4-dithione products, respectively. Furthermore, the reaction of 3-(phenylimino)pentane-2,4-dione with Wittig, Wittig–Horner reagents and trialkyl phosphite resulted in the formation of 2,5-diendioate, diethoxy phosphoryl hexanoate and the phosphate products. Possible reaction mechanisms are considered and the structural assignments are based on analytical and spectroscopic results. The antibacterial and antifungal activities for some of the new compounds are also reported.     

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS VI1–5: Utility of Lawesson's Reagent for Synthesis of Thiaphosphorine,Thioxanthene, and Thiaphosphole Derivatives

Arylidene malonate derivatives 2a–c reacted with Lawesson's reagent (1) LR in equimolar ratio to yield the oxathiaphosphorine derivatives 3a–c. The behaviour of LR towards cyclic ketones was also examined and yielded the thioxanthene derivatives 5a,b. On the other hand, arylidene pyrazolone 8 reacted with LR to give the phosphole 10. Aminobenzenethiophene 11 reacted with LR under reflux to produce the corresponding thiazaphosphorine 12.     

Isocoumarin Thioanalogues as Potential Antibacterial Agents

A series of 3-substituted-1H-isochromene-1-thiones (3) were prepared by the reaction of 3-substituted isocoumarins (2) with Lawesson's reagent in the presence of toluene under a nitrogen atmosphere. The antimicrobial activities of the newly synthesized products were measured using Gram-negative (Escherichia coli, Salmonella typhi, and Proteus mirabilis) and Gram-positive bacteria (Staphylococcus aureus and Bacillus cereus). Synthesized thioanalogue of isocoumarins showed good antibacterial activity against Proteus mirabilis.     

ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN,XVII1 Dithiophosphinsäuren RR'P(S)SH,Ihre Synthese,Derivate und Metallkomplexe

Abstract

A wide range of dithiophosphinic acids RR'P(S)SH with different organogroups was obtained in good yields by nucleophilic fission of perthiophosphonic anhydrids (RPS₂)₂ with Grignard reagents R'MgX. Some reactions, derivatives and metal complexes [RR'P(S)S] M/n of these acids, which are useful intermediates for the synthesis of chiral organophosphorus compounds, are reported.

Eine Vielzahl von Dithiophosphinsäuren RR'P(S)SH mit unterschiedlichen Organoresten konnte in guter Ausbeute durch nukleophile Spalung von Perthiophosphonsäureanhydriden (RPS₂)₂ mit Grignardverbindungen R'MgX dargestellt werden. Einige Reaktionen, Derivate und Metallkomplexe [RR'P(S)S] M/n dieser Säuren, die für die Synthese chiraler Organophosphorverbindungen von Interesse sind, werden beschrieben.     

Synthesis and Antibacterial Activity of Some New S-Triazole Derivatives

Abstract

Alkylation of 4-anilino-5-phenyl-4H-1,2,4-triazole-3-thiol (1) with some halo compounds yielded the corresponding sulfides 2a–f. Some sulfides 2e,f were cyclized to give triazolothiadiazines 3 and 4. Triazolothiadiazoles 5 and 6 were prepared through the reaction of compound 1 with carbon disulfide or ethyl orthoformate, respectively. Treatment of compound 1 with ethyl chloroformate or phenyl isothiocyanate yielded triazolo-thiadiazole and triazole 9 and 10, respectively. Reaction of compound 1 with Lawesson's reagent gave triazolothiadiazaphosphole derivative 11. Also, compound 1 underwent cyclocondensation reactions with some bidentate reagents to give triazolothiazines 4, 12, and 13. Triazolo-thiazepines and triaziepine 14–16 were synthesized via the reaction of compound 1 with β-ketoesters or ethyl cyanoacetate. Tricyclic systems 19 and 20 were prepared through the reaction of compound 4 with the appropriate reagent. Some synthesized compounds were tested for antibacterial 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.     

STUDIEN ZUM VORGANG DER WASSERSTOFFÜBERTRAGUNG 511 RANEY-NICKEL ALS REAGENS ZUR HYDRIERENDEN ABSPALTUNG DES CHALKOGENATOMS AUS SCHWEFEL-, SELEN- UND TELLUR-VERBINDUNGEN

Abstract

Thioäther, Sulfoxide, Sulfone, organische Selenide und Telluride (R – Y – R': R, R', = Alkyl, Aryl, Y=S, SO, SO₂, Se, Te) werden an der Grenzfläche von Raney-Nickel hydrogenolysiert. Als Spaltprodukte entstehen die Verbindungen RH und R'H sowie eine Grenzflächenverbindung (Raney-Nickel-Y) (Y=S, Se, Te; S auch aus Sulfoxiden und Sulfonen. Letztere entbinden ebenfalls mit Mineralsäuren YH₂).

Die Größe und ‘Struktur’ der Oberfläche des Raney-Nickels entscheidet über die Hydrogenolysekapazität. Bei einer technischen Raney-Nickel-Probe liegt bei Diphenylsulfid die Sättigungsausbeute an Benzol bei 1,1 mmol/g Raney-Nickel. Die Sättigungskapazität hängt ab von der Struktur von R bzw. R' und dem Heteroatom Y. (Auch Benzylether können–wenn auch langsamer als Thioether–zu Toluol aufgespalten werden). Auf Grund bekannter Daten werden Vorstellungen entwickelt, die ein Bild über den topochemischen Verlauf der Hydrogenolyse von R–Y–R' vermitteln sollen.

Vergiftetes Raney-Nickel ist im Gegensatz zum aktivierten Raney-Nickel nicht mehr oder nur stark vermindert zur Isomerisierung, Disproportionierung und zum H-D-Austausch befähigt. Bei diesen Prozessen spielt offenbar der im Nickel strukturgebundene Wasserstoff eine wichtige Rolle.

Some thioethers, sulphoxides, sulphones, organoselenium and tellurium compounds (R–Y–R' R, R'= Alkyl, Aryl, Y?S, SO, SO₂, Se, Te) have been reductively cleaved on the surface of Raney-nickel. The products comprise RH and R'H, and a surface bound material (Raney-nickel-Y) (Y?S, also from sulphoxides and sulphones, Se, Te. The latter may be released as YH₂ on treatment with mineral acids).

The area and ‘structure’ of the surface determines the hydrogenolysis capacity of the catalyst. For technical quality Raney-nickel, the limiting yield of benzene from diphenylsulphide is 1.1 mmol/g. The limiting yield is dependent on the structure of R and R' and also the nature of Y. (Benzyl ethers may also be reduced to toluene, if somewhat slower than the corresponding thioether).

Proposal for the processes possibly involved at the surface during hydrogenolysis of R–Y–R' are put forward in the basis of consideration of the available experimental data.

Poisoned Raney-nickel (in contrast to the activated catalyst) is practically inactive as agent for isomerization, disproportionation, or H–D exchange, and hence surface bound hydrogen clearly plays an important role in these processes.     

PHOSPHORORGANISCHE VERBINDUNGEN 921

Abstract

Optisch aktive Phosphinigsäureamide R¹R²PNR₂ 4 (R¹ [dbnd] Ph, R² [dbnd] Me bzw. Et, R [dbnd] Et) sind durch kathodische Spaltung bzw.Cyanolyse optisch aktiver Amidophosphoniumsalze [R¹R²R³PNR₂]X (R¹ [dbnd] Ph. R² [dbnd] Me bzw. Et. R³ [dbnd] Bz bzw. All, R [dbnd] Et) unter Erhaltung der Konfiguration in hohen Ausbeuten zugänglich.

Optisch aktive Amidophosphoniumverbindungen, z.B. Ethyl-methyl-phenyl-diethylamido-phosphoniumiodid 10 oder Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 12 werden erhalten:

a) aus den optisch aktiven tertiären Phosphinen, z.B. R-(+)Benzyl-methyl-phenyl-phosphin 6 bzw. S-(-)Ethyl-methyl-phenyl-phosphin 13 durch Umsetzung mit Alkyl- oder Arylaziden über die Phosphinimine 7 mit anschließender Alkylierung.

b) durch Alkylierung der optisch aktiven Phosphinigsäureamide 4. Die unter a) und b) genannten Umsetzungen verlaufen unter Erhaltung der Konfiguration.

c) Bei der Umsetzung optisch aktiver tertiärer Phosphine mit N-Halogenaminen entstehen nur racemische Amidophosphoniumsalze.

Optisch aktive Amidophosphoniumsalze, z.B. S(+)-Benzyl-methyl-phenyl-diethylamido-phosphoniumbromid 8 oder R-(-)-Ethyl-methyl-phenyl-diethylamido-phosphoniumiodid 10 werden bei der Einwirkung wäßriger Alkalien unter Inversion zu den entsprechenden Phosphinoxiden 9 bzw. 11 abgebaut. Optisch aktive Amidophosphoniumsalze, z.B. S(+)-Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 12, werden mit LiAlH₄ retentiv unter Abspaltung des Aminliganden in die zugrundeliegenden optisch aktiven tertiären Phosphine übergeführt. Die Olefinierung von Benzaldehyd mit S(+)-Benzyl-ethyl-phenyl-diethylamido-phosphoniumbromid 5 ergibt unter Retention Stilben und optisch aktives Ethyl-phenyl-phosphinsäure-diethylamid 17, das auch durch Oxidation von R(-)-4 mit H₂O₂ erhalten wird. Schwefelung von R(-)-4 liefert das optisch aktive Ethyl-phenyl-thiophosphinsäure-diethylamid 18.

Das optisch aktive Phosphinigsäure-diethylamid 4 racemisiert allein und in Kohlenwasserstoffen gelöst bei 130°C nach einer Reaktion nullter Ordnung. Die Racemisierung wird durch Austausch der sekundären Aminogruppe über cyclische Assoziate verursacht. Beweis: Verbindungen mit unterschiedlichen. Substituenten am Phosphor- und Stickstoff tauschen beim dreistündigen Erhitzen auf 200°C die sekundären Aminogruppen aus. Es entstehen neue Phosphinigsäureamide in annähernd äquivalenten Mengen.

In Nitrobenzol bildet sich mit Phosphinigsäureamiden ein Charge-Transfer-Komplex, der im Falle des optisch aktiven Ethyl-phenyl-phosphinigsäure-diethylamids 4 bereits bei Zimmertemperatur eine schnelle Racemisierung bewirkt.

Optisch aktives Ethyl-phenyl-phosphinigsäure-diethylamid 4 liefert als Co-Katalysator bei der Homogenhydrierung von α-Ethylstyrol mit (RhCl-Hexadien-1,5)₂ 2-Phenylbutan mit einer optischen Ausbeute von 34%.     

Synthesis and Antiproliferative Activity of Some 1H-Isochromen-1-ones and Their Thio Analogues

A series of 1H-isochromen-1-one derivatives and their thio analogues were synthesized by thionation using Lawesson's reagent for evaluation of their cytotoxic effect on cancer cells. The effect of these derivatives was tested on the growth of human epidermoid carcinoma A431 cell line by MTT [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide] colorimetric assay. MTT assay revealed that these new compounds are potent inhibitors of cell growth.

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.