Action d'organozinciques α-ethyleniques sur le chloroformiate d'ethyle: preparation d'esters β-ethyleniques

The reaction of organozinc compounds RCHCHCH₂ZnBr with ethyl chloroformate gives β-ethylenic esters CH₂CHCH(R)COOC₂H₅ in good yields; these esters are readily converted to the corresponding α-ethylenic esters on treatment with piperidine.     

Influence des interactions attractives non liees sur les stabilites relatives d'ethers et d'acetates d'enol renfermant un groupe styryle

The measure of relative stabilities of β-alcoxystyrene isomers I: C₆H₅-CHCH-OR shows that the trans compound is the most stable when RCH₃ and C₂H₅ and the cis compound is the most stable when Ri-C₃H₇ and t-C₄H₉. The orientation of the OR group can be determined by RMN ¹³C. The stabilities of these molecules are discussed in terms of non bounded attractive interactions. This interpretation is confirmed by the measure of relative stabilities of α-methyl β-alcoxy (and acetoxy)-styrene isomers II: C₆H₅-C(CH3)CH-OR. (RCH₃, C₂H₅ et COCH₃).     

Effets de micelles cationiques sur l'hydrolyse alcaline d'acetanilides a groupe acyle active par des substituants electro-attracteurs

Micellar effects of CTAB upon the alkaline hydrolysis of CF₃-CO-N(CH₃)C₆H₅, CHCl₂-CO-N(CH₃)C₆H₄X and CH₂Cl-CO-N(CH₃)C₆H₄X, (X=p-OCH₃H,p-Cl) are reported. Variations of k_obs, and of kinetic order of the reaction with respect to HO^? ion, are interpreted as an acceleration of HO^?-catalyzed steps, and a decrease of catalysis by water for decomposition of tetrahedral intermediates; these two effects oppose each other in HO^? and H₂O catalyzed steps. Differences between micellar and DMSO effects suggest a very small local concentration of HO^? ions in micelles.     

Nucleophilic cosubstitution of poly(dichlorophosphazene) with alkyl ether and amino acid ester

The nucleophilic substitution reaction of poly(dichlorophosphazene) with sodium 2‐methoxyethoxide and glycine ethyl ester has been studied in detail. Polymers prepared with different methods have been characterized by ¹H NMR, and the results reveal that the addition sequence of the two nucleophilic reagents is an important factor in determining the structure of the resultant polymer. If alkyl ether is added first, the subsequently introduced amino acid ester not only reacts with residual P? Cl but also attacks the alkyl ether side units present by replacing either the whole group or just ? OCH₃. As a result, a new kind of side group (? OCH₂CH₂NHCH₂COOC₂H₅) can be detected in the macromolecule. To obtain polymers with desired compositions {poly[(methoxyethoxy)_x(ethylglycino)_yphosphazene]}, the amino acid ester should be introduced initially to react with poly(dichlorophosphazene), and it should be followed by the alkyl ether. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2417–2425, 2005     

35Cl Nqr spectroscopy of the [PO2Cl2]− and POCl3 groups in Me(PO2Cl2)2·2D (Me = Mg,Ca, Mn; D = POCl3,CH3COOC2H5,CH3COCH3)

³⁵Cl NQR spectra of dichlorophosphates Me(PO₂Cl₂)₂ · 2D (Me = Mg, Ca, Mn; D = CH₃COOC₂H₅, CH₃COCH₃, POCl₃) are studied in the temperature range 77 ? T (K) ? 305. It is shown that the three compounds with CH₃COOC₂H₅ as donor are isomorphic at 77 K, the crystal structure of Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. The structure of Mg(PO₂Cl₂)_2^?· 2CH₃COCH₃ and of Mg(PO₂Cl₂)₂ · 2POCl₃ probably consists of infinite chains as found for Mn(PO₂Cl₂)₂· 2CH₃COOC₂H₅. Mg(PO₂Cl₂)₂· 2CH₃COOC₂H₅ shows phase transformations and a complicated dynamical behaviour leading to strong deviations from a Bayertype NQR function v = f(T). The donor capacity of POCl₃ in Mg(PO₂Cl₂)₂· 2POCl₃ is comparable with the donor strength in AsCl₃ · POCl₃ · A d_π-p_π overlap of the P-O bond influences the P-Cl bond.     

Electrochemistry of methanofullerenes embedded in hydrophobic ammonium cation films

The electrochemical behavior of several methanofullerenes, including methyl-C₆₁-propionic acid esters (Ph-C₆₁-(CH₂)₂COOC _n H_{2n + 1}, n = 1–4, 8), in tetraoctyl- and didodecyldimethylammonium bromide films on conducting glass was studied. A cyclic voltammetry study showed that the introduction of methanofullerene derivatives in a cation matrix led to redox transformations of these compounds at potentials accessible for aqueous solutions. The shift of their formal potentials toward positive values is mainly caused by the electrostatic interactions of the reduction products (methanofullerene anions) with the matrix cations. The chemical stability of the reduction products is provided by their hydrophobic microenvironment in the matrix in all cases. This makes it possible to perform quasireversible redox transformations in neutral aqueous media. The duration of the adjustment of the structure of the coating depends on the solvent used for its preparation, the length of the alkyl radical in the ester group of methanofullerene, and the length of the alkyl chain between the cyclopropane fragment and the COOC _n H_{2n + 1} group. The redox potentials of methanofullerene Ph-C₆₁-(CH₂)₂COOC₂H₅ incorporated in the didodecyldimethylammonium bromide film lie in the range of higher negative values relative to the potentials of the compound in the tetraoctylammonium bromide film.     

Saponification of ethyl acetate in 2,6-lutidine + water near its critical point

We have measured the rate of saponification of ethyl acetate (CH₃COOC₂H₅) in 2,6-lutidine (2,6-DMP)?+?water (H₂O) near and far away from its critical point by electrical conductivity experiment. We found that the rate of saponification slowed in the one-phase region at temperatures near the critical point. This behaviour is evidence in support of critical slowing down. Moreover, the experimental results were compared with those of the same reaction in a different critical mixture of 2-butoxyethanol?+?H₂O [Y.W. Kim, Int. J. Thermophys. 25, 1025 (2004)].     

Über Chalkogenolate. 81. Untersuchungen über N-Hydroxydithiocarbamidsäure 3. Ester der N-Hydroxydithiocarbimidsäure und -carbamidsäure

On Chalcogenolates. 81. Studies on N-Hydroxy Dithiocarbamic Acid. 3- Esters of N-Hydroxy Dithiocarbimic Acid and Dithiocarbamic Acid The reaction between hydroxylamine, carbon disulfide, and alkyl halide leads to the corresponding ester of N-hydroxy dithiocarbimic acid HO? N?C(SR)₂ with R = CH₃, C₂H₅; R₂ = ? CH₂? CH₂? . The phenyl ester of N-hydroxy dithiocarbamic acid HO? NH? CS(SC₆H₅) has been prepared by reaction of hydroxylammonium chloride with the phenyl ester of chlorodithioformic acid. N-Methyl hydroxylammonium chloride reacts with carbon disulfide and alkyl iodide to form the corresponding ester of the dithiocarbamic acid HO? N(CH₃)? CS(SR) with R = CH₃, C₂H₅. The unstable compounds have been characterized by different methods.     

Preparation of polymers with substituted allyl end group using dimer of α-methylvinyl monomer as addition fragmentation chain transfer agent at high temperatures

The dimerization of methyl methacrylate, ethyl methacrylate, methacrylonitrile, and α-methylstyrene to 2-substituted-1-allylic compounds [CH₂?C(X)CH₂C(CH₃)₂X] (X = COOR, C₆H₅, or CN), and methyl α-ethylacrylate to a 3-substituted-2-allylic compound [CH₃CH?C(COOCH₃)CH₂C(CH₃)(C₂H₅) COOCH₃] was carried out by catalytic chain transfer using benzylbis (dimethylglyoximato) (pyridine) cobalt (III). These dimers were then used as addition-fragmentation chain transfer agents in the polymerizations of methyl methacrylate and styrene at 80⁰C or above. Cross-dimers from methacrylic ester-α-methylstyrene and methacrylonitrile-α-methylstyrene mixtures were similarly prepared. Except for those from methyl α-ethylacrylate and methacrylonitrile, all the dimers participated in the addition-fragmentation and the copolymerization to different extents. The dimer of methyl α-ethylacrylate was actually inactive during the styrene and methyl methacrylate polymerizations. The methacrylonitrile dimer was primarily incorporated in the polymer chain through copolymerization. Among the dimer and the cross-dimers from α-methylstyrene with the other monomers, those bearing the α-methylstyrene moiety in the α-substituent [CH₂?C(X)CH₂C(CH₃)₂C₆H₅, X?COOCH₃, COOC₂H₅, and CN] are noted as highly reactive chain transfer agents. © 1994 John Wiley & Sons, Inc.     

Synthesis and X-Ray Crystal Structure of the TiMgCl6(CH3COOC2H5)4 Adduct

The molecular and crystal structure of TiMgCl₆(CH₃COOC₂H₅)₄, obtained by reacting TiCl₄ with a solution of MgCl₂ in dry CH₃COOC₂H₅, have been determined by x-ray diffraction. The structure was solved by direct and Fourier methods and refined by least-squares techniques to R = 0.052 for 2722 independent observed reflections. Unit-cell dimensions are a = 17.122(7), b = 9.833(3), c = 9.646(3) Å, α = 111.10(7)°, β = 107.22(6)°, γ = 103.11(6)° with Z = 2 for P1 . The titanium(IV) atom is octahedrally coordinated by six chlorine atoms (Ti? Cl_t = 2.293(2) Å, Ti? Cl_b = 2.480(2) Å) and magnesium by two chlorine atoms (Mg? Cl_b = 2.528(2) Å) and the carbonyl oxygen atoms of the four CH₃COOC₂H₅ residues (Mg? O = 2.038(5) Å). The octahedra share an edge by a double chlorine bridge between the magnesium and titanium atoms. Changes in the configurations and dimensions of the free acceptor and donor molecules on adduct formation are discussed. One of the ethylacetate residues shows positional disorder, eventually with Bonding through its ethereal oxygen.     

The relationship between properties of fluorinated graphite intercalates and matrix composition 7

Inclusion compounds (intercalates) of fluorinated graphite matrix with ethyl acetate (C₂F_xBr_z·yCH₃COOC₂H₅, x = 0.49, 0.69, 0.87, 0.92, z = 0.01) were prepared by guest substitution from acetonitrile to ethyl acetate. The kinetics of the thermal decomposition (the first stage of filling → the second stage of filling) was studied under isothermal conditions at 291–307 K. The relationship of the host matrices’ structure with inclusion compounds’ thermal properties and kinetic parameters is discussed.     

Kinetic Studies on the Thermal Dissociation of β-Cyclodextrin·Ethyl Benzoate Inclusion Complexes

The stability of β-cyclodextrin·ethyl benzoate·6H₂O(β-CD·C₆H₅COOC₂H₅·6H₂O) was investigated by TG and DSC. The mass loss takes place in three stages: the dehydration occurs at 50-120°C; the dissociation of β-CD·C₆H₅COOC₂H₅occurs at 200-260°C; the decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C₆H₅COOC₂H₅in a dry nitrogen flow was studied by means of thermogravimetry both at constant temperature and linearly increasing temperature. The results show that the dissociation of β-CD·C₆H₅COOC₂H₅is dominated by a three-dimensional diffusion process (D₃). The activation energy E is 116.19 kJ mol^-1and the pre-exponential factor A 6.5358·10⁹min^-1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the studies focus on the energy of binding between cyclodextrin and the guest molecule. In this paper, the β-cyclodextrin·ethyl benzoate inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show that the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of van der Waals interaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Emulsion polymerization of butyl acrylate: Spin trapping and EPR study

The propagating radical in the emulsion polymerization reaction of butyl acrylate was detected by Electron Paramagnetic Resonance (EPR) spectroscopy using two spin-trapping agents, 2-methyl-2-nitrosopropane (MNP) and α-(4-pyridyl 1-oxide)-N-tert-butylnitrone (PyOBN). Through analysis of hyperfine structure of the spectra obtainedfrom the trapped radicals, the propagating radical is inferred to be the well known acrylate radical, ? [CH₂? CH(COOC₄H₉)]_n? CH₂? CH(COOC₄H₉)? . © 1994 John Wiley & Sons, Inc.     

Telomeres photoreticulables—3. Synthèse de telomeres photoreticulables a partir du cinnamate d'allyle et de l'acetate d'allyle

Photocrosslinkable telomers cannot be prepared by the direct telomerisation of allyl cinnamate. However, such materials can be prepared by reaction of cinnamoyl chloride with hydrolysed telomers of allyl acetate. Transfer constants of the three telogens, (H-P(0)(OEt)₂, CCl₂HCO₂CH₃ and CCl₃CO₂CH₃) towards allyl acetate were determined also.     

Synthesis and biological activities of quinolone analogues: Pyridazino[3,4‐b]quinoxalin‐4‐one

Quinolone analogues I‐VI with pyridazino[3,4‐b]quinoxaline ring system were synthesized form the (l‐alkylhydrzino)quinoxalina N‐oxides 1 via oxidation of pyridazino[3,4‐b]quinoxalines 2,3,5,7 , quinoxalino[2,3‐c]cinnolines 4 , and 1,2‐dizepino[3,4‐b]quinoxalines 6 . The biological activities of quinolone analogues IVa (N₁‐methyl‐C₃‐methyl), Va (N₁‐methyl‐C₃‐ethyl), and VI (N₁‐methyl‐C₃‐H) were superior to those of quinolone analogues I (N₁‐ethyl‐C₃‐carboxyl), 26b (N₁‐ethyl‐C₃‐carboxylate), and IIIc,d [N₁‐alkyl‐C₃‐(CH₂)₃COOC₂H₅].     

Preparation d'olefines trisubstituees bifonctionnelles par voie photochimique

∝-methyl ∝-functionalized (CO₂CH₃, CN, CH₂OH and CH₂Cl) cyclopentanones $\text{2}$ when irradiated by UV light give title compounds : 5-substituted 4-hexen 1-al $\text{4}$ as a mixture of E and Z isomers. A comparison of the photochemical behaviour of this cyclopentanones and a simple and efficient chemical transformation of the isomers Z in the more demanded isomers $\text{4}$ E are described.     

Differences in the crystal structures of two dialkyl diester triphenyl­phospho­nium ylids

Hydrogen bonding and crystal packing play major roles in determining the conformations of ethyl methyl 2‐(triphenyl­phospho­ranyl­idene)malonate, Ph₃P=C(CO₂CH₃)CO₂CH₂CH₃ or C₂₄H₂₃O₄P, (I), and dimethyl 2‐(triphenyl­phosphor­anyl­idene)malonate, Ph₃P=C(CO₂CH₃)₂ or C₂₃H₂₁O₄P, (II). In (I), the acyl O atom of the ethyl ester group is anti to the P atom, while the O atom of the methyl ester group is syn. In (II), the dimethyl diester is a 1:1 mixture of anti–anti and syn–anti conformers.     

Mass spectra and peculiarities of the fragmentation of some substituted piperidines

N-Substituted piperidines with R = CH₂OCH₃, (CH₂)₄COCH₂, CH₃COOC₂H₅, (CH₂)₂N(CH₃)₂, (CH₂)₂N(C₂H₅)₂, N=0, CH₃, H, COOC₂H₅, and OH were investigated by mass spectrometry. The ratios of the intensities of the peaks and the behavior of the amine fragments with exocyclic double bonds attached to the quaternary nitrogen atom that are formed from the molecular ion by detachment of a radical from the C₂ atom and from the substituent attached to the nitrogen atom were studied. It is shown that the ratios of the intensities of the peaks of the amine fragments are determined both by the type of substituent and the energy of the ionizing electrons.Communication 11 from the series Application of mass spectrometry in structural and stereochemical studies. See [1] for Communication 10.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 221–228, February, 1981.     

Synthese d'isoquinoleines F-alkyl substituees

In this paper we report preparation of isoquinolines F-alkyl substituted in $\text{1}$ position by R_F chains such as CF₃, C₃F₇, C₅F₁₁, C₇F₁₅. These compounds are obtained by catalytic deshydrogenation of the F-alkyl-1 dihydro-3,4 isoquinolines which are prepared by cyclodeshydratation of the N-(phenyl-2 ethyl) F-amides and N- (phenyl-2 propyl) F-amides. These last compounds are obtained the N-allyl F-amides by Friedel-Crafts type reaction.The preparations as a whole yield 26 new F-alkyl compounds.     

Utilisation en synthese du cation iminium genere in situ par oxydation electrochimique d'amines tertiaires

The electrochemical oxidation in acetonitrile of aliphatic amines (ACH₃) in presence of a non-nucleophilic base (2,4,6-collidine) and of compounds containing weakly-activated hydrogens (RH) such as diethyl phosphonate and diethyl malonate gives the substituted derivatives ACH₂R. These compounds result from the addition of the anion R^? to the iminium cation ACH₂⁺. Such a reaction is obtained with tribenzylamine and N,N-dimethyl-p-toluidine. Moreover (CH₃)₂NCH₂-CH(CO₂C₂H₅)₂ is deaminated and gives by successive Michael reactions other substituted malonates which also react with the iminium cation (CH₃)2N⁺CH₂.