HYDROLYSE DE SPIROPHOSPHORANES I. Dérivés du Tétraoxa-1,4,6,9 Phospha V-5 Spiro (4–4) et de l'Heptaméthyl-2,2,4,7,7,8,8 Trioxa-1,6,9 aza 4 Phospha V-5 Spiro (4,4) Nonane

Abstract

L'hydrolyse de tétraoxaspirophosphoranes (1) et de trioxazaspirophosphoranes (2) conduit essentiellement soit [sgrave] des mono et des diesters phosphoniques (cas de 1) soit [sgrave] des monoesters phosphoniques (cas de 2). Le rôle de differents facteurs sur la réaction d'hydrolyse (solvant, température, groupements R extracycliques, nature du cycle) a été précisé. Un cas particulier de labilité de liaison P^v–C a été mis en évidence.

Tetraoxaspirophosphoranes (1) and trioxazaspirophosphoranes (2) hydrolysis lead mainly and respectively to phosphonic mono or diesters and to phosphonic monoesters. The effect of differents factors (solvent, temperature, extracyclic R groups, nature of the ring) has been examined. In one case the P^v–C bond has been found to be particularly labile.     

SYNTHESE ET PROPRIETES DE 2-HYDRAZONOPHENYL-SELENOACETAMIDES

Abstract

The two steps synthesis of 2-hydrazonophenylselenoacetamides is described starting from sulfur analogs. Depending on the substitution of hydrazono and selenamide groups they allow the preparation of a 1,2,3-selenadiazolium salt, a 5-imino-Δ³-1,2,3-selenadiazoline, 3,6-dihydro-2H-1,3,4-selenadiazines and a 5-selenoxo-2,3,4,5-tetrahydro-1,2,4-triazin- 3-one.

Les 2-hydrazonophénylsélénoacétamides sont obtenus en deux étapes à partir de leurs analogues soufrés. Selon le degré de substitution de l'atome d'azote du groupement hydrazono et de celui du sélénamide, ils permettent d'accéder à un sel de 1,2,3-sékénadiazolium, à une 5-imino-Δ³-1,2,3-sélénadiazoline, aux 3,6-dihydro-2H- 1,3,4-sélénadiazines ou à une 5-sélénoxo-2,3,4,5-térahydro-1,2,4-triazin-3-one.     

OXAZOLIDONES ET DIOXOLONNES DU GERMANIUM (IV) ET (II) DU PHOSPHORE (III), DE L'ARSENIC (III) ET DU SOUFRE

Abstract

Diffèrents modes de synthèse d'oxazolidones 1.2.4-7 et de dioxolonnes 8-11 germaniées sont décrites.

La stabilité thermique de germadioxolonnes a été étudiée. La décomposition procède d'un méchanisme du type (2 + 2 + 1), avec ouverture du cycle et formation de germylène.

La réactivité chimique des oxazolidones et dioxolonnes germaniées a été étudité. Des réactions d'échange avec des dérives organominéraux dichlorés conduit facilement et avec de bons rendements aux derives isologues, phosphorés(III). arseniés(III), soufrés. ou germaniés(IV). La réaction d'échange entre une dioxolonne germaniée et le dichlorogermylène nous a permis d'obtenir un nouveau germylène fonctionnel cyclique stable 20 qui a été caractérisé par spectrographie (RMN ¹H. masse).

Different synthetic ways for germaoxazolidones 1.2.4-7 or dioxolonnes 8-11 have been described.

The thermal stability of germadioxolonnes has been studied. Decomposition occurs by a [2 + 2 + 1] ring opening with formation of germylene.

The chemical reactivity of germaoxazolidones or dioxolonnes has been studied. Exchange reactions with dihalogenated covalent compounds occur readily lcading to phosphorus(III). arsenic(III). sulphur or germanium(IV) analogs.

From dichlorogermylene, new stable fonctionnal cyclic germylene 20 is obtained and characterized.     

The Determination of Impurities in 233UO2 by Spark Source Mass Spectrometry

Abstract

A method for the determination of impurities in ²³³UO₂ has been developed and applied to the analysis of a product stream of ceramic grade ²³³UO₂ powder. The analytical method has combined isotope dilution and internal standard methods to permit the determination of impurities at concentrations between 0.1 and 500 ppm in a single sample.     

Umsetzung von 1,5-Dimethyl-2,3,3,4-tetrachlor-1,5,2,4-diazadiphosphorinan-6-on mit Anilinderivaten,Heptamethyldisilazan und tert.-Butylamin: Oxidative Addition von Tetrachlor-o-benzochinon an einige P(III)-haltige Produkte

The reaction of the title compound 1 with the p-R-aniline derivatives (R═H, F, OCH₃, NO₂, and NH₂) led to the formation of the aza-2σ³,4σ³-diphosphetidines 2a– 2e, whereas 2-trimethylsiloxyaniline furnished the azadiphosphetidine 2f. The reaction of the sterically crowded 2,6-dimethylaniline with 1 furnished the disubstituted derivative 3. The tricyclic compound 5 was formed during the reaction of 1,2-phenylenediamine with 1. Heptamethyldisilazane formed the aza-2σ ³ ,4σ ³ -diphosphetidine 6 on reaction with 1. The bulkier tert.-butylamine formed with 1 a mixture of the aza-2,4-diphosphetidine 7a and the disubstituted derivative 7b, which could not be separated. The reaction of 2b and 6 with tetrachloro-o-benzoquinone resulted in the formation of the bis-spirophosphoranes 8 and 9b, respectively. The formation of the monospirophosphorane 9a was observed in the ³¹P NMR spectrum. The characterization of compounds is based in particular on NMR investigations (¹H, ¹³C, ³¹P). 2a was characterized by a single-crystal X-ray structure analysis. The dimethylurea fragment is planar; the four-membered ring is folded about the P···P vector by 38.7°.     

Reactions of (E)-4-Stilbenethiole with Dibromoalkanes

New substituted stilbenes have been prepared by reactions of (E)-4-stilbenethiole with dibromoalkanes. ¹H and ¹³C NMR spectra of new compounds have been assigned unambiguously on the basis of a combination of homo- (¹H?¹H COSY) and heteronuclear (¹ H?¹³C COSY-HETCOR) two-dimensional methods, chemical shifts, and spin-coupling constants.     

Spectres 13C-nmr de Quelques Glutarimides Substitues en α et en β

Abstract

¹³C-nmr spectra of α and β glutarimides have been determined and analyzed. Assignments related to the imidocarbonyls are discussed.     

Étude des Interactions du Zinc et de l'Or dans l'Étain Liquide

Abstract

Les auteurs ont étudié par voie électroehimique l'influence de faibles additions d'or sur les propriétés thermodynamiques du zinc en solution diluée dans l'étain fondu. Le paramètre d'interaction de Wagner ?_Zn ^Au et sa variation avec la température ont été déterminés dans l'intervalle de température 420–650°C: ?_Zn ^Au = 2.71 – 5.92. 10³/T.     

The fully deprotonated anion of 1,3,5-benzene-triphosphonic acid: 1H, 31P,and 13C{1H} NMR and some comments on corresponding [AX]3 and AXX′2 spin systems and spectra

Abstract

The fully deprotonated anion of 1,3,5-benzene-triphosphonic acid 1,3,5-C₆H₃[PO₃^2?]₃ gives rise to deceptively simple ¹H and ³¹P NMR spectra due to a corresponding [AX]₃ spin system. The ¹³C{¹H} NMR spectrum reveals two ¹³C isotopomers which are identified via AXX′₂ systems. Results from analysis and iteration are described.     

Aluminum 2-Methoxyethoxide: An Internally Coordinated Aluminum Alkoxede

Abstract

Aluminum 2-methoxyethoxide was isolated and characterized by ¹H, ¹³C and ²⁷Al NMR. The ²⁷Al NMR and mass spectra show that the compound is an internally coordinated dimer. This aluminum alkoxide is less susceptible to hydrolysis in comparison to other aluminum alkoxides.     

Structure de Modeles de Polyesters 2.-Determination de la Purete optique par RMN 13C et H de Dibenzoyloxy 1,2 Propane,l,3 Butane et 3-Methyl 1,4 Butane a l'Aide de Reactifs chiraux

Abstract

The enantiomeric purity of a series of polyester model compounds has been assayed by NMR spectroscopy, using chiral lantha-nide shift reagents. The dependencc of proton and ¹³ C NMR spectra on concentration and temperature has been investigated.     

Polymerization of Bis(Pyridine)bis-(2,4,6-tribromophenoxo)copper(II) Complex (Py2Cu(TBrP)2) by Electrooxidation and Structural Characterization by 1H-NMR, 13C-NMR,and FTIR Spectroscopies

Abstract

Electroinitiated polymerization of bis(2,4,6-tribromophenoxo)- bis(pyridine)copper(II) complex was achieved in dimethylformamide-tetrabutylammonium tetrafluoroborate solvent-electrolyte couple under air or nitrogen at room temperature by constant potential electrolysis. Polymerization conditions were based on the peak potentials measured by cyclic voltammetry. The structural analyses of the polymers were done by ¹H-NMR, ¹³C-NMR, and FTIR spectral analyses along with molecular weight measurements by cryoscopy. The poly(dibromo phenylene oxide)s obtained only at oxidation potentials in either atmosphere were found to be highly linear, indicating mainly 1,4-catenation was taking place.     

Bis(Diethyldithiocarbamato)Antimony(III) Derivatives with Oxygen- and Sulfur-Donor Ligands: Synthesis,Esi-Mass,and Spectral Characterization

Abstract

Replacement reactions of bis(diethyldithiocarbamato)antimony(III) chloride have been carried out with oxygen and sulfur donor ligands such as disodium oxalate, sodium acetate, sodium salicylate, benzoic acid, thioglycolic acid, acetylacetone, thiphenol, ethane-1,2-dithiol, and 2,2-dimethylpropane-1,3-diol to give mixed bis(diethyldithiocarbamato)antimony(III) derivatives of the corresponding ligands. These derivatives have been characterized by the physicochemical [melting point and molecular weight determination, elemental analysis (C, H, N, S, and Sb)], spectral [FT-IR, far-IR, NMR (¹H and ¹³C)], ESI-mass, powder XRD, and SEM studies.

[Supplementary 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 files: Additional figures and tables]     

13C, 15N and 113Cd NMR and Molecular Orbital Studies of Novel Bile Acid N-(2-aminoethyl)amides and Their Cd2+-complexes

Lithocholic acid N-(2-aminoethyl)amide (1) and deoxycholic acid N-(2-aminoethyl)amide(2) have been prepared and characterized by¹H, ¹³C and ¹⁵N NMR. The accurate molecular masses of 1 and 2 have been determined by ESI MS. The formation of the Cd²⁺-complexes (1+Cd and 2+Cd) in CD₃OD solution have been detected by ¹H,¹³C, ¹⁵N and ¹¹³Cd NMR. The ¹³C NMR chemical shift assignments of 1 and 2 and their Cd²⁺-complexes are based on DEPT-135 and z-GS ¹H,¹³C HMQC experiments as well as comparison with the assignments of the related structures. The ¹⁵N NMR chemical shiftassignments of the ligands and theirCd²⁺-complexes are based on z-GS¹H,¹⁵N HMBC experiments. ¹³C NMR chemical shift differences between 1and its 1:1 Cd²⁺-complex based on ab initiocalculations at Hartree-Fock SCI-PCM level using3-21G(d) basis set are in agreement with theexperimental shift changes observed onCd²⁺-complexation.     

Identification Des Produits De La Reduction Electrochimique d'Un Nouvel Antiinflammatoire: Le Piroxicam

Abstract

The electrochemical reduction of piroxicam has been investigated on a mercury pool in acidic and alcaline media.

After exhaustive electrolysis, the extraction followed by chromatographic separation of the reaction products gives the reduced compounds which have been identified by spectroscopic techniques. From the analysis of the NMR ¹H, ¹³C and IR spectra and the results of our preceding electrochemical investigation, the polarographic behaviour of piroxicam has been elucidated. The process occurs by the irreversible reduction of the double bond of the enol function over the total pH range investigated. However, in alkaline and highly acidic solutions, a preceding two-electron step occurs, giving rise to the opening of the thiazine ring.     

Synthesis and evaluation of multitopic bisbenzothiazolyl calix[4]arenes for ionic toxicants

Abstract

Two new benzothiazolyl calix[4]arene-based multitopic molecular receptors L-1 and L-2 have been synthesised and evaluated for recognition of ionic toxicants. The receptors selectively interact with copper, silver and fluoride ion toxicants as assessed through UV-visible, NMR and colorimetric techniques. The stability of L-1:Cu⁺² and L-2:Cu⁺² complexes was found to be higher than that of complexes formed with Ag⁺ and F^– complexes in the presence of trifluoroacetic acid. Superiority of L-1 over L-2 for analysis of identified toxicants has been determined by measurement of binding constants.     

Determination of [13C-15N] Labeled Methylxanthines by Gas Chromatography-Atomic Emission Detection (GC-AED) and Compound-Independent Calibration

ABSTRACT

Compound independent calibration (CIC) can be used to measure stable isotopically labeled molecules and their metabolites. This study was designed to demonstrate that gas chromatography coupled to atomic emission detection and CIC are useful analytical tools for the specific and quantitative determination of ¹³C and ¹⁵N labeled caffeine and its metabolites. These labeled compounds can be measured by monitoring either ¹³C or ¹⁵N atomic emission lines and using only one calibration function from one of the analytes. This method can be helpful when it is difficult or impossible to obtain an authentic reference material, which is often the case in metabolic studies.     

Identification of Initiator Fragments in Polyisobutylene by Nmr Spectroscopy

Abstract

Deuterated polyisobutylenes carrying protonated initiator fragments were prepared by the living polymerization technique employing perdeuterated isobutylene [CD₂=C(CD₃)₂] and select protonated initiators (see Scheme 1). The polymers were analyzed by ¹H- and ¹³C-NMR spectroscopy, and the resonances due to the protic initiator fragments were unequivocally assigned. The assignments of ¹³C-NMR signals were affected by the distortionless enhancement by polarization transfer mode of spectra accumulation.