Monophenylantimony(III) Derivatives of Cyclic Dithiocarbamates; Synthesis,Spectroscopic Characterization,and Antimicrobial Study

Abstract

Some new monophenylantimony(III) compounds having the formulas have been synthesized by reaction of phenylantimony(III) dichloride with the sodium salt of cyclic dithiocarbamates in 1:1 and 1:2 molar ratios. These newly synthesized compounds have been characterized by elemental analyses, molecular weight measurements, and their plausible structures have been proposed on the basis of IR, NMR (¹H and ¹³C), and ESI-mass studies. Sodium salts of cyclic dithiocarbamates and their corresponding organoantimony(III) derivatives (1–8) have been screened for antimicrobial activity against E. coli, P. aeruginosa (Bacteria) and A. niger and A. flavus (Fungi).     

Tris(Trimethylsilyl)Phosphine in Reaction with Bis(Phenylenedioxa)Chlorophosphorane. The Way to Phosphoranylphosphines

Abstract

Tris(trimethy1silyl)phosphine (1) is the key reagent in the synthesis of one- and two-coordinated phosphorus compounds. Its characteristic features are extreme reactivity, high nucleophility of phosphorus atom and the P-Si bonds lability. The interaction of phosphine (1) with bis(catecho1)chlorophosphome (2) has been studied by dynamic ³¹P NMR method. On the reagents ratio 1:1 at first the nucleophilic substitution of chlorine occurs leading to formation of phosphome (3) with P^III-P^v bond (σ_P(III) -117.0, σ^P(V) 17.4 ppm, ¹J_pp 305.0 Hz) which converts then into more stable 2-(trimethylsiloxyphenyloxy)-4,5-bem- 1,3,2-dioxaphospholane (4).     

Microstructure of poly(alkylene phosphates) related to biopolymers (teichoic acids)

The microstructure of polyphosphites and polyphosphates obtained by the ring-opening polymerization of asymmetrically substituted 5-membered cyclic phosphites was studied. It has been established, using ³¹P NMR, that 4-substituted 2-hydro-2-oxo-1,3,2-dioxaphospholanes underwent polymerization giving polymers with head-to-tail dyads as well as head-to-head and tail-to-tail structures. Analyses of ³¹P NMR spectra of racemic and optically active poly(2-hydro-4-methyl-2-oxo-1,3,2-dioxaphospholane) and model compounds estimated the statistical mode of ring scission of cyclic phosphites. Similar results were obtained for the polymerization of 4-acetoxymethyl-2-hydro-2-oxo-1,3,2-dioxaphospholane, which provided the simplest model of teichoic acid, namely poly(1,2-glycerol phosphate).     

Thermochemistry of Heteroatomic Compounds XXI: Heat Capacities of Some Derivatives of Methylphosphonic and Dithiophosphorus Acids

The heat capacities of 2,4-dimethyl-2-oxo-(I)-, 2,5,5-trimethyl-2-oxo(II)-1,3,2-dioxaphosphorinanes, methylphosphonic acid (III), O,O-dimethyl(IV)-, O,O-diethyl(V)-, O,O-di-isopropyl(VI)esters of dithiophosphorus acid, 4,5-dimethyl-2-thiono-2-mercapto-1,3,2-dioxaphospholane(VII), and 4-methyl-2-thiono-2-mercapto-1,3,2-dioxaphosphorinane(VIII) were determined using the scanning calorimetry.     

Bismuth(III) dication trapped on a chlorobismuthate

Abstract

Metal cations observed with tetrachloroaluminate anion provide insights into the structure and stability of reactive cations. Addition of tris(3,5-dimethylpyrazolyl)borate anion (Tp^Me2) to [BiCl₂][AlCl₄] traps a bismuth(III) dication, [Tp^Me2Bi]²⁺, possessing a highly electrophilic bismuth center with short coordinate Bi―N bonds. [Tp^Me2Bi]²⁺ has weak interactions with the chlorides of [Bi₃Cl₁₃]_∞. Strong affinity of [Tp^Me2Bi]²⁺ with the triflate (OTf) observed in [Tp^Me2Bi(OTf)₃]^- demonstrates the high electrophilicity at bismuth.     

Tin(IV) Complexes of 1,5-Diphenylthiocarbazone and Thiosemicarbazide: Synthesis,X-Ray Characterization,and Biological Activity

Abstract

The reaction of Me₂SnCl₂ with dithizone or thiosemicarbazide produced two novel di-organotin derivatives in good yields, which were characterized by X-ray diffraction. The crystal structures show that the compounds present a distorted pentacoordinated tin(IV) metal center. The antimicrobial activity of the new compounds was studied against Gram-negative (Escherichia coli, Klebsiella pneumonia, Salmonella enteritidis) and Gram-positive (Staphylococcus aureus) bacteria, and the yeast Saccharomyces cerevisiae. It was observed that the coordination of tin metal has a pronounced effect on the microbial activities of the ligands. All the tin complexes have shown higher antimicrobial effect than the free ligands.

GRAPHICAL ABSTRACT     

Caged phosphorane with P-C bond based on chloral and 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane

The key methods of caged phosphoranes synthesis are analyzed. Reaction of 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane (prepared from the meso-form of 2,3-butanediol) with chloral has yielded the caged phosphorane containing a phosphorus-carbon bond: 1,1-(1,2-dimethylethylenedioxy)-3,4-diphenyl-6-trichloromethyl-2,5,7,1-trioxaphosphabicyclo[2.2.1^1,4]heptane; spatial structure of the product has been elucidated with X-ray diffraction analysis.

     

New Dithiocarbamate Compounds from Organotin(IV)

Abstract

A series of new organotin(IV) dithiocarbamate compounds of type R_nSn (S₂CNR′R″)_4-n (n = 2, 3; R = dimethyl, dibutyl, diphenyl, triphenyl and tert-butyl; R′ = methyl, ethyl, benzyl; R″ = isopropyl, ethyl, ethanol) have been successfully synthesized. Elemental analysis showed that the percentage of the elements conformed to the general formula of these compounds. The important peaks of the infrared spectra for the stretching mode ν(C?N), ν(C?S), and v(Sn-S) for the compounds were observed in the area of 1440–1480 cm^?1, 940–1000 cm^?1, and 340–90 cm^?1, respectively. The ¹³C NMR spectra showed the most important peak for N¹³CS₂ chemical shifts were observed in the range 190–210 ppm. X-ray single crystal studies for several structures of these compounds showed that the chelating mode of the dithiocarbamate groups to the central tin atoms were either bidentate or anisobidentate.

GRAPHICAL ABSTRACT     

One-Pot Green Synthesis of 3'-(2-Aminobenzimidazolyl)-2-Phenyl Spiro[4H-Benzopyran-4,2'-Thiazolidin]-4-Ones and Acylation Using Trifluoroacetic Anhydride

Abstract

An expeditious one-pot synthesis of a novel heterocyclic system, 3′-(2-aminobenzimidazolyl)-2-phenyl spiro[4H-benzopyran-4,2′-thiazolidin]-4-ones, has been accomplished by condensing substituted hydrazinobenzimidazole, flavanone, and mercaptoacetic acid by conventional heating in ethanol or toluene, and in an ionic liquid, viz., 1-butyl-3-methyl-imidazolium hexafluorophosphate. Excellent yields (85%–90%) and higher purity are obtained in the ionic-liquid-mediated synthesis as compared with the conventional procedure (55%–60%). Further, these compounds were acylated with trifluoroacetic anhydride. The structures of the compounds were confirmed by IR, ¹H NMR, ¹³C NMR, mass spectral data, and elemental analysis. The compounds, upon evaluation for their antibacterial, antifungal, and insecticidal activities, exhibited excellent results.

[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, S2, and S3]

GRAPHICAL ABSTRACT      

One-Pot Synthesis and Asymmetric Oxidation of 2-Nitro-4-(Trifluoromethyl)Benzene Containing Sulfides

Abstract

An efficient one-pot method for the preparation of 2-nitro-4-(trifluoromethyl)benzene containing sulfides from 1,1′-disulfanediylbis[2-nitro-4-(trifluoromethyl)benzene] is proposed. The corresponding enantiomerically enriched sulfoxides with up to 78% enantiomeric excess are prepared by the asymmetric oxidation of sulfides using a modified Sharpless method. The yield of sulfoxides is shown to decrease with an increase in the bulk of the aliphatic group and with a decrease of the inductive effect of the hydrocarbonic moiety on the sulfur atom.

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      

Stability Constants for Dimercaptosuccinic Acid with Bismuth(III), Zinc(II), and Lead(II)

Abstract

Stability constants for the complexation of zinc(II), lead(II), and bismuth(III) by the vicinal dithiolate chelating agent meso-dimercaptosuccinic acid (DMSA) have been determined by a combination of potentiometric titration and spectrophotometric competition at 25°C and 0.1 M ionic strength. The spectrophotometric studies use the shifts in the ultraviolet bands of the thiol groups to quantitate metal binding to DMSA in the presence of competitive aminocarboxylic acids. Bismuth(III) forms a bis(DMSA) chelate with an exceptionally high stability constant of 10^43,87. This complex undergoes a series of protonations over the pH range 10 to 2, but there appears to be no measurable dissociation of ligand over this pH range. The zinc-DMSA system is dominated by a Zn₂(DMSA)₂ dimer, which has a protonation constant of 10⁶ and dissociates completely at lower pH. No more than 20% of total zinc exists as a monomeric complex at any pH. Lead forms a 1:1 complex with a stability constant of 10^17,4. Insoluble protonated lead complexes precipitate at pH < 6.5. Speciation calculations have been used to evaluate the potential competition from serum zinc to the binding of Pb²⁺ and Bi³⁺ by DMSA. The results indicate that DMSA should be relatively effective for the in vivo chelation of both Bi³⁺ and Pb^{2 +}.     

The Synthesis of Novel S-, S,S-, S,S,S-, and N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols

Abstract

The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobutadienes were obtained from the reaction of the mono-thiosubstituted butadienes with morpholine, thiomorpholine, homopiperazine, and piperazine derivatives. The structures of new compounds were determined by spectroscopic techniques.

GRAPHICAL ABSTRACT      

Synthesis and Herbicidal Activity of O,O-Dialkyl(phenyl)-N-{1-[(6-chloropyridin-3-yl)methyl]-4-cyano-1H-1,2,3-triazol-5-yl}-1-amino-1-substitutedbenzyl-phosphonates

Abstract

A series of novel α-amino phosphonate derivatives containing both pyridine and 1,2,3-triazole moieties 4 were synthesized via a multi-step reaction. First, the condensation of 5-amino-1-[(6-chloropyridin-3-yl) methyl]-4-cyano-1H-1,2,3-triazole with various aromatic aldehydes in the presence of magnesium perchlorate afforded imines 3 in moderate yields; second, imines 3 reacted with dialkyl phosphites or triphenyl phosphite to give the title compounds 4 in moderate to good yields. Their structures were elucidated by spectroscopic data (IR, ¹H NMR, ³¹P NMR, ESI-MS) and elemental analysis. The preliminary bioassay (in vitro) indicated that some of the title compounds 4 possessed moderate herbicidal activities against dicotyledonous plants (Brassica campestris L) at a concentration of 100 mg/L. However, compounds 4 did not exhibit herbicidal activities against Brassica campestris L at a concentration of 10 mg/L.

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      

Synthetic,spectral as well as in vitro antimicrobial studies on some bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphates

Mixed sulfur donor ligand complexes of the type bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphate, [R₂NCS₂]₂BiS₂POGO [where R = CH₃ and C₂H₅; G = ‐CH₂‐C(C₂H₅)₂‐CH₂‐, ‐CH₂‐C(CH₃)₂‐CH₂‐, ‐CH(CH₃)‐CH(CH₃)‐ and ‐C(CH₃)₂‐C(CH₃)₂‐] were synthesized in 1:1 molar ratio of bismuth(III) bis(N,N‐dialkyldithiocarbamate) chloride and ammonium alkylenedithiophosphate in refluxing benzene and characterized by melting point, molecular weight determinations, elemental analysis (C, H, N, Bi and S) and spectral [UV, IR,NMR (¹H,¹³C and ³¹P) and powder X ray diffraction] studies; all these studies were in good agreement with the synthesized complexes. These newly synthesized derivatives are yellow and brown colored solids and are soluble in common organic solvents like benzene, chloroform, dichloromethane and DMF. Based on the physicochemical and spectral studies, a tentative structure of these newly synthesized complexes was assigned and the average particle size of the synthesized complexes determined by powder XRD, showing that nano range polycrystalline particles were formed with a monoclinic crystal system. These complexes were also screened for their antimicrobial activities using the well diffusion method. The free ligands as well as their mixed metal complexes were tested in vitro against four bacterial strains: two Gram‐positive, Staphylococcus aureus (ATCC 9144) (G⁺) and Bacillus subtilis (ATCC 6051), (G⁺) and two Gram‐negative, Escherichia coli (ATCC 9637) (G^?) and Pseudomonas aeruginosa (ATCC 25619) (G^?) to assess their antimicrobial properties. The results were indeed positive and exhibited good antibacterial effects. Chloroamphenicol used as a standard for comparison and synthesized complexes showed good antibacterial effects over chloroamphenicol. On the basis of these studies, the synthesized complexes help to understand the different structural and biological properties of main group elements with sulfur donor ligands. Copyright © 2010 John Wiley & Sons, Ltd.     

31P High Resolution Solid State NMR Spectroscopy as a Tool for Structural Studies of Organothiophosporyl Compounds

Abstract

Employing 1,6-anhydro-2-0-(tosyl)-4-S-(5,5-dimethyl-2-tioxa-1,3,2-dioxaphosphorinan-2-yl) β-D-glucopyranose 1, bis-imidazole 5,5-dimethyl-1,3,2-dioxaphosphorinan-2-tioxa-2-hydroxy complex II and bis (organothiophosphoryl) dichalcognides III as models this report presents power of ¹³C and ³¹P CP/MAS experiment in structural studies organothiophosphoryl compounds [1,2,3].     

Imides of 2-Trifluoroacetylphenol and other Trifluoracetic acid Esters: Novel Reactions with Phosphorus(III) Derivates

Abstract

The imido derivates of 2-trifluoroacetylphenol, 1 (R¹=H, Me, iPr) react with the isocyanatophosphites (R²O)₂PNCO, 2 (R²[dbnd]Et, R²-R²[dbnd]CMe₂-CMe₂) to yield the bicyclic compounds 3, wheras in case of 1 (R¹[dbnd](CH₂)₂NMe2) the λ³σ³P compounds 4 are found. The phosphorus(III) chlorides R3PC12 (R³[dbnd]Ph, OEt) and 1 (R¹[dbnd]H, Me) give rise to furnish the tricyclic phosphoranes 5. However with 1 (R¹[dbnd]iPr) phosphite 6 is obtained, which adds hexafluoracetone to give the 1,3,2λ⁵σ⁵-dioxaphospholane 7. 2-(Trifluoracetoxy)pyridine 8. reacts with Tris(trimethylsily1)phosphite to yield the bis(phosph0nate) 10. Some molecular structures are discussed on the basis of x-ray diffraction results.     

New chiral phosphine-phosphonites derived from (2R,3R)-dimethyl tartrate, (S)-binaphthol and (1R,2S)-ephedrine

The reaction of 2-lithiophenyldiphenylphosphine with phosphorus trichloride afforded the new unsymmetric phosphine, dichloro(2-diphenylphosphinophenyl)phosphine (4). Condensation of 4 with (a) (2R,3R)-dimethyl tartrate or (b) (S)-binaphthol in the presence of triethylamine gave new chiral phosphine-phosphonite ligands, (2R,3R)-[2-(2′-(diphenylphosphino)phenyl)-4,5-bis(carbomethoxy)-1,3,2-dioxaphospholane] ((2R,3R)-5) and (S)-[2-(diphenylphosphino)benzene][1,1′-binaphthalen-2,2′-diyl]phosphonite] ((S)-6). The analogous reaction of 4 with (1R,2S)-ephedrine using N-methylmorpholine as the base, gave [2-(2′-(diphenylphosphino)phenyl)-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine] (7) as a 95:5 mixture of diastereoisomers.     

Design,synthesis and herbicidal activity of novel cyclic phosphonates with diaryl ethers containing pyrimidine

Abstract

Thirteen novel cyclic phosphates were rationally designed and synthesized by introducing diary ethers containing pyrimidine. All the target compounds were characterized by ¹H, ¹³C, ³¹P NMR and HRMS. The test of herbicidal activity indicated that most of the compounds showed good herbicidal activities against Amaranthus retroflexus. The compounds IA-2 (1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)propyl-2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoate) and IA-3 ((5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)(phenyl)methyl-2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoate) exhibited remarkable post-emergency herbicidal activity against the tested monocotyledonous weed at the dosage of 112.5?g ai/ha.     

THE SYNTHESIS AND CHARACTERIZATION OF A NOVEL vic-DIOXIME AND ITS MONO AND TRINUCLEAR COMPLEXES CARRYING A TRIOXADITHIA MACROCYCLE

Abstract

A new vicinal dioxime, l,15-bis(hydroxyimino)-2,14-dithia-5,8,11-trioxacyclopentadecane (H₂L) was synthesized by the reaction of (E,E)-dichloroglyoxime (1) with 1,11-dithio-3.6.9-trioxaundecane (2). Mononuclear copper(II) complexes with a metal/ligand ratio of 1/2 were prepared. The two ligands coordinate to copper(II) through the deprotonated oximate oxygens which then afford the trinuclear structure bridged by the oximate groups with 1,10-phenan-throline or 2,2′-dipyridyl as the end-cap ligand.