Sels d'aziridinium stables C-fonctionnalisés III: Synthèse et caractérisation d'aziridines protonées épimères à l'azote

Aziridinium ions were prepared from aziridines bearing a functionality on a ring carbon and as isolated crystalline fluorosulfate salts either by protonation in fluorosulfuric acid solution or by alkylation with methyl fluorosulfate. The structural assignement of these ions is based on nmr spectra and on quenching experiments with sodium carbonate. The configurations of the epimeric ions have been assigned by the nuclear Qverhauser effect and the stereoselectivity in protonation is disucussed.     

Additions radicalaires du tétrahydrothiophène à des dérivés éthyléniques: Préparation de tétrahydrothiophènes substitués en 2

Di-t-butyl peroxide induces a free radical addition of tetrahydrothiophene to ethylenic compounds. The main products arise from an α-attack of the substrate. This reaction seems to be an interesting synthesis of these heterocycles.     

A mass spectrometry/mass spectrometry investigation of the nature of [C10H10]+˙, [C9H7]+ and [C10H8]+˙ gas phase ions

Additional evidence for the rearrangement of the 1- and 3-phenylcyclobutene radical cations, their corresponding ring-opened 1,3-butadiene ions and 1,2-dihydronaphthalene radical cations to methylindenetype ions has been obtained for the decomposing ions by mass analysed ion kinetic energy spectroscopy (MIKES). The nature of the [C₉H₇]⁺ and [C₁₀H₈]^+˙ daughter ions arising from the electron ionization induced fragmentation of these [C₁₀H₁₀]^+˙ precursors has been investigated by collisionally activated dissociation (CAD), collisional ionization and ion kinetic energy spectroscopy. The [C₉H₇]⁺ produced from the various C₁₀H₁₀ hydrocarbons are of identical structure or an identical mixture of interconverting structures. These ions are similar in nature to the [C₉H₇]⁺ generated from indene by low energy electron ionization. The [C₁₀H₈]^+˙ ions also possess a common structure, which is presumably that of the maphthalene radical cation.     

Etude par RPE des radicaux libres daus le tétraoxane irradié

The free radicals induced in tetraoxane at liquid nitrogen temperatures by ⁶⁰Co γ-rays have been studied by ESR. The powder spectrum as well as he spectra of the single crystal rotated around the b axis have been studied through their modifications from ?196°C up to + 80°C. These spectra show that at low temperatures two radicals exist conserving the cyclic nature of the parent molecule. During the course of annealing, starting at ?140°C and towards ?85°C they are gradually replaced by radicals with a linear structure, this being the first step in the post-polymerization process of tetraoxane. Further increase in temperature leads to radical sites situated on the polymer chains. At low temperatures evidence has also been found for the formyl radical, radical pairs, and a photo-sensitive radical.     

The potential energy surface for the [C2H2O]+˙ system: The ketene radical cation [CH2CO]+˙ and its isomers

Ab initio molecular orbital calculations with large, polarization basis sets and incorporating valence electron correlation have been employed to examine the [C₂H₂O]^+˙ potential energy surface. Four [C₂H₂O]^+˙ isomers have been identified as potentially stable, observable ions. These are the experimentally well-known ketene radical cation, [CH₂?C?O]^+˙ (a), and the presently unknown ethynol radical cation, [CH₂?C? OH]^+˙ (b), the oxirene radical cation (c) and an ion resembling a complex of CO with [CH₂]^+˙, (d). The calculated energies of b, c and d relative to a are 189, 257 and 259 kJ mol^?1, respectively. Dissociation of ions a and d is found to occur without reverse activation energy.     

Influence de certains ions inorganiques, de l'éthanol et du peroxyde d'hydrogène sur la photominéralisation du β-naphtol en présence de TiO2

TiO₂ photocatalytic mineralization of β-naphthol: influence of some inorganic ions, ethanol, and hydrogen peroxide. In this work, the photocatalytic oxidation of β-naphthol in aqueous suspensions of TiO₂ was investigated at room temperature, by following the formation of CO₂. The disappearance of β-naphthol fits a Langmuir-Hinshelwood kinetic model. The activation energy for the degradation reaction of β-naphthol is estimated at 10.2 kJ/mol. The effects of some additives such as ethanol, H₂O₂, and inorganic ions (Cl⁻, SO₄²⁻, HCO₃⁻, NO₃⁻, Fe³⁺, Cu^2+, and Cr³⁺) on the photomineralization of β-naphthol were examined. The inhibition of the anions for this reaction was in the order : NO₃⁻ < HCO₃⁻ < SO₄²⁻ < Cl⁻. This can be due to a partial blockage of catalyst active sites by these ions or their reaction with an oxidizing radical such as OH. The most photoactive systems for β-naphthol degradation were found in the presence of ferric ions, while the addition of Cr³⁺ strongly inhibited the photocatalytic decomposition of β-naphthol.     

Synthèse de 3,5-divinylidènepipéridines N-substituées à partir du 1,7-bis(triméthylsilyl)hepta-2,5-diyne et applications

The 1,7-bis(trimethylsilyl)hepta-2,5-diyne reacts with iminium ions generated in situ from primary alkyl- or primary functional amines by a double aminomethylation–desilylation process leading to N-substituted 3,5-divinylidenepiperidines.

Résumé

Le 1,7-bis(triméthylsilyl)hepta-2,5-diyne réagit avec les ions iminium générés in situ à partir d'alkylamines primaires ou d'amines primaires fonctionnelles pour conduire à des 3,5-divinylidènepipéridines N-substituées via un double processus d'aminométhylation–désilylation.     

Synthèse de copolymères greffés à base de polyéthylène—1

Polyethylene macromolecular free radical initiators, obtained by ozonization, are used to prepare graft copolymers with methyl methacrylate, styrene and vinyl chloride. The reactions parameters are the number of initiator groups (found by DPPH), peroxide and hydroperoxide proportions (respectively 36 and 64%), decomposition rate (K_d at 90° 10⁻¹sec⁻¹) and monomer concentration. The molecular structure of these copolymers is defined.     

Selenoketene (H2CCSe)+• and selenoketyl cumulene (HCCSe)+ ions and their neutral counterparts: a tandem mass spectrometric and computational study

Dissociative electron ionization (70eV) of selenophene (C₄H₄Se) generates m/z 106 ions of composition [H₂, C₂, ⁸⁰Se]^+? and m/z 105 ions of [H, C₂, ⁸⁰Se]⁺. From tandem mass spectrometric experiments, Density Functional Theory (DFT) and ab initio calculations, it is concluded that these ions have the structure of selenoketene H₂C?C?Se^+? (1a^+? )and selenoketyl HC?C?Se⁺ (2a⁺) ions respectively. The calculations predict that selenoketene ion 1a^+? is separated by high energy barriers from its isomers selenirene (H e)^+? 1b^+?, ethyne selenol (HCCSeH)^+? 1c^+?, (CCHSeH)^+? 1d^+? and (CCSeH₂)^+? 1e^+?. The selenoketyl ion 2a⁺ is separated by high barriers from its isomers (CCHSe)⁺ 2b⁺, and (CCSeH)⁺ 2c⁺. Neutralization‐reionization mass spectra (NRMS) of these structurally characterized ions confirmed that the corresponding neutral analogues, selenoketene H₂CCSe 1a and selenoketyl radical HCCSe 2a^? are stable in the rarefied gas phase. The relative, dissociation, and isomerization energies for selenoketene and selenoketyl ions and neutrals studied at B3LYP/6–31G(d,p) and G2/G2(MP2) levels are used to support and interpret the experimental results. Copyright © 2005 John Wiley & Sons, Ltd.     

Additions radicalaires. 16 Additions d'hétérocycles oxygénés aux allènes

Free radical addition of tetrahydrofuran and tetrahydropyran to various allenes gives mainly 1:1 adducts. Increasing substitution on the allenic triad involves a change in ratio of adduct formed by way of central attack (1% with propadiene, 99% with 2,4-dimethyl-2,3-pentadiene).     

Sels d'aziridinium stables c-fonctionnalisés II: Stéréochimie de la quaternisation,synthèses stérèodirigées de composés n-trideutériométhylés et attribution de leurs configurations relatives par el'fet overhauser nucléaire

Aziridines bearing a functionality on a ring carbon and an alkyl or deuteriomethyal group on nitrogen have been quaternized at different temperatures. The configurations of the resulting, stable, diastereomeric aziridinium ions have been assigned by Nuclear Overhauser effect. The stereoselectivity in quaternization is discussed.     

Nouvelle méthode de détermination des taux de réativité des copolymères par résonance magnétique nucléaire: Application aux poly(méthacrylate de méthyle–chlorure de vinylidène)

Constant-composition copolymers of methyl methacrylate and vinylidene chloride produced by radical copolymerization are studied by ¹H-NMR at 60 and 250 MHz. The different methods of the literature for the derivation of reactivity ratios from either the copolymer composition or the sequence average lengths, or even the diad distribution, are applied but lead to rather dispersed results. A new graphical method is proposed, based on the use of peculiar values of the triad distribution functions. It allows us to detect a penultimate effect for the vinylidene chloride-rich region. In the same range, a change in tacticity of the diads and triads on the methylmethacrylate sequences, as compared with homopolymers, is observed; it suggests that the anomaly is caused by the competition of the depropagation reaction.     

Étude par rayons X de copolymères téléchéliques butadiène acide méthacrylique

The telechelic polybutadiene–methacrylic acid copolymer (Hycar CTB) containing 2 mole percent acid and neutralized (5–100%) by alkali ions, Na⁺, K⁺, and Cs⁺, has been studied by small-angle x-ray scattering. Salt groups form clusters, and the average value of the radii of gyration is approximately 8 Å; this value seems to be independent of the nature of the cation and the degree of neutralization. The existence of a low-angle maximum in the scattering intensity gives evidence of a mean distance of 80 Å between clusters in the fully neutralized sample. This distance increases slightly with a decreasing degree of neutralization. A more precise analysis of the small-angle scattering curve gives further information on the cluster structure: the ionic groups may form small bilayer disks while the polymer chains maintain a regular distance of 80 Å between the disks.     

13-乙酰基-9-甲基-11-羰基-8-氧代-10,12-二氮杂三环[7.3.1.02,7]十三碳-2,4,6-三烯的一锅煮合成和结构表征

An efficient and environmentally friendly procedure for the one-pot synthesis of 13-acetyl-9-methyl-11-oxo-8-oxa-10,12-diazatricyclo7.3.1.02,7trideca-2,4,6-triene from salicylaldehyde, acetylacetone and urea via Biginelli condensation and intramolecular Michael-addition by using magnesium bromide as an inexpensive and easily available catalyst in a solvent-free condition is described. The structural elucidation of the product is reported by 1H- and 13C-NMR spectra. The product can also be identified by its EI TOF mass spectrometry based on the molecular ion at m/s 246(10%) and on the fragment ions in which two nitrogen atoms are remained. Three kinds of characteristic fragmentation pathways from the molecular ion were observed. One is the loss of the OH radical to form the dihydropyrimidinone cation at m/z 229(48%), followed by elimination of a molecular methane forming the pyrimidinone cation at m/z 213(27%). The second is the cleavage of the C6H4OH radical, and the formation of the dihydropyrimidinone cation at m/z 153(24%). The third one is the loss of MeC=O radical to afford the oxygen-bridged fragment ion at m/z 203(33%).     

The distonic ions HO+CHCH2C˙H2 and CH3C(O+H)CH2C˙H2

The distonic ions HO⁺?CHCH₂C^˙H₂ (1) and CH₃C(?O⁺H)CH₂C^˙H₂ (2) were directly generated, their decompositions characterized and their appearance energies determined by photoionization. Heats of formation derived from the appearance energies were 757 kJ mol^?1 for 1 and 692 kJ mol^?1 for 2. Deuterium labeling demonstrates that both ions decompose at low energies in the same ways as their isomers with the same skeletal structures, consistent with proposals that 1 and 2 are intermediates in the decompositions of those systems. Surprisingly, the values of the translational energy releases accompanying the formation of CH₃CO⁺ and C₂H₅CO⁺ from 2 appear to be inversely proportional to the available excess energy. The 1,2-H-shift RC(?O⁺H)CH₂C˙H₂ → RC(?O₊H)C˙HCH₃ is compared to the corresponding, non-occurring 1,2-H-shift in alkyl free radicals.     

Fragmentation de la Méthyl-2 Indolizine sous Impact Electronique: perte de H˙ à partir de l'Ion Moléculaire; perte de HCN à partir de l'Ion [M?H˙]+

The origin of the hydrogen radical lost in the ionization chamber from the molecular ion of 2-methylindolizine has been studdied by examination of the spectra of four specifically deuterated species. Hydrogen loss involves preferentially a hydrogen from the methyl substituent but also one of the hydrogens of either ring, especially those of the 5-membered ring. The HCN elimination from the metastable [M? H^˙]⁺ ions was studied using a linked scan method; the results are consistent with loss of identity of all the hydrogen atoms of the precursor ion, which implies an extensive reorganization prior to fragmentation.     

Spectrométrie de Masse d'Hétérocycles Azotés. VII—Phenyl-1 Triazole-1,2,3

Comparison of the ‘normal’ and mass analysed ion kinetic energy spectra of 1-phenyl-1,2,3-triazole and a few D and ¹³C labelled derivatives indicates that the ions may follow two competing decomposition pathways: a simple rupture without rearrangement is preferred by the ions of high internal energy content (normal spectrum). On the other hand, for low internal energy metastable ions, loss of HCN is more important and occurs after a complete randomization of the H atoms.     

The question of cyclic versus acyclic ions: The structure of [C10H12]+˙ gas phase ions

The extent of isomerization of acyclic and cyclic gas phase radical cations of composition [C₁₀H₁₂]⁺˙ has been investigated by using collisionally activated dissociation spectroscopy. Both electron and charge exchange ionizaiton were employed to form the ions with various internal energies. The [C₁₀H₁₂]⁺˙ ions investigated consisted of ionized phenylbutenes, ring-substituted methyl derivatives of allylbenzene and phenylpropene, 1-methyl-2-isopropenylbenzene, benzylcyclopropane, phenylcyclobutane, tetralin and 1-methylindan. The 1-methylindan and tetralin radical cations are the most stable of the C₁₀H₁₂ isomeric radical ions. The [C₁₀H₁₂]⁺˙ formed from acyclic olefins having the double bond in conjugation with the aromatic ring retain the initial structure to a significant extent. However, ions derived from olefins with the double bond out of conjugation with the benzene ring preferentially cyclize to stable five- and six-membered cyclic ions. Ring opening of small-ring cyclic ions, such as ionized benzylcyclopropane and phenylcyclobutane, occurs, followed by ring closure to the tetralin radical cation.     

Synthèse de sucres aminés ramifiés. IV Synthèse de quelques dérivés nouveaux par l'intermédiaire d'une hexose-spiro-aziridine

Treatment of 3-C-cyano-1,2:5,6-di-O-isopropylidene-3-O-(toluene-p-sulfonyl)-α-D -allofurannose with AlLiH₄ yields a sugar-spiro-aziridine and a branched chain sulfonamide. Reaction mechanisms are briefly discussed and the configurations of the products obtained are proved by chemical reactions. With hydrogenation, the spiro compound is opened to a branched chain amino sugar with the same tertiary carbon as in vancosamine. Several derivatives of this new compound are described: the 6-deoxy sugars in series L and D and the pentose resulting from its oxidation by periodic acid. The conformation around C(4)–C(5) bond is deduced for three compounds from NMR. data.     

Polymérisation anionique de l'isoprène: Nature de la paire d'ions et stéréospécificité. II. Influence de la nature du solvant

The present work reports some new results on the dependence between the stereospecificity of the anionic propagation of isoprene and the nature of the active centers. The stereospecificity of the propagation of macroheterobicylce separated ion pairs does not depend on the nature of the alkali counterions, and the microstructure of the polyisoprenes obtained does not differ from that of those produced by free ions. Variations in the microstructure were observed in the propagation of contact ion pairs, depending on the nature of the cation and the solvent used. These variations are likely to be related to the degree of intimacy of the contact ion pairs. There are two main factors which affect the stereospecificity of the propagations in different ways: the size of the cation and the donating power of the solvent. Finally, the external solvation of the propagation ions pairs was confirmed by the microstructure of polyisoprenes synthesized in mixed (inert + donor) solvents.