Enolates de l'acetylacetate d'ethyle. Structure et reactivite du sel de potassium en presence d'ether couronne et de cryptand

It is shown that, through the addition of 18-crown-6 or cryptand (2.2.2) to potassium ethyl acetoacetate enolate solutions in tetrahydrofuran, 1:1 complexes are formed. A single crystal of the 1:1 potassium énolate-18-crown-6 complex has been obtained. Its structure has been determined by X-ray diffraction. The crystal includes entities formed from an enolate anion chelating a potassium cation externally complexed by the crown-ether. The vibrational spectrometry shows that the structure of the entity is kept in solution. In the species formed through the addition of cryptand (2.2.2), the enolate anion has a structure (IR spectroscopy) and a reactivity very close to that of the free anion, observed in a dissociating solvent (DMSO, HMPA). When crown ether is added, a contact ion pair is formed, in which the cation is externally solvated by the crown. On the other hand, the cation encapsulation by the cryptand leads to a released anion with an “ S-trans” or “W” structure. The reactivity and the orientation of the alkylation reactions of these entities have been measured in THF solutions. They are discussed in relation to the structure of the species present in the reaction medium.     

Alcoylation par l'iodure de butyle,de l'enolate de tetrabutylammonium de l'acetylacetone; nature de l'entite reagissante

The alkylation of tetrabutylammonium acetylacetonate with butyl iodide was studied in order to specify the nature of the reactive anionic species during the nucleophilic reaction of an ambident anion, under similar conditions to those of phase transfer catalysis. The C/O alkylation ratio changes with neither the solvents nor the enolate concentration; however k_obs, varies with the solvent but does not depend on the énolate concentration. The results and spectrophotometric UV data show that only one reactive species, the ion-pair, is involved.     

Reactivite des carbanions benzyliques : VIII. Etude de la structure d'alkyl-9 lithio-10 dihydro-9,10 anthracenes par rmn du proton et spectrometrie d'absorption electronique; influence du substituant,du solvant et de la temperature

The structure of the 9,10-dihydroanthracenyl anion and of a series of 9-alkyl-10-lithio-9-10-dihydroanthracenes (9-R-10-LiDHA, I–V where R = H, Me, Et, i-Pr, t-Bu) was studied in solution by electronic absortion spectrometry and proton magnetic resonance. Our electronic absorption results, in addition to those of other authors, show that the contact ion pairs (c.i.p.) have an absorption at λ_max}- 400 nm (I–III) and 415 nm (V) whereas the loose ion pairs (l.i.p.) absorb at λmax}- 450 nm (I–V). In the NMR the chemical shift of the proton para with respect to the carbanionic center was examined as a function of solvent (THF, THF/HMPA, and in some cases ether or pure HMPA) and temperature (+20 to ?40°C). The para proton is shielded significantly with regard to the aromatic protons of the hydrocarbon (Δδ(H_para) ca. 1–1.7 ppm). The weakest shielding was observed in ether, in agreement with the existence of c.i.p. The largest shielding (THF/HMPA or pure HMPA) is in connection with the presence of l.i.p. where the negative charge is less localised at position 10. Moreover, in the same solvent, and at the same temperature, Δδ(H_para) was observed to increase with the substituent bulk, up to the point that there are only l.i.p. present. As found previously (namely for the fluorenyl anion) the l.i.p./c.i.p. ratio increases when temperature decreases. The results of this structural study allow to rationalize the protonation stereochemistry of 9-alkyl-10-lithio-9,10-dihydroanthracenes in the above-mentioned solvents.     

Effet de solvant sur support solide:régiosélectivité de l'alkylation des énolates de l'acétylacétate d'éthyle par le sulfate d'éthyle en présence de “hmpt solide”

The reaction of Li, Na, K enolates of ethylaceto acetate with diethylsulfate in THF at room temperature gives 60–70% O-alkylation when performed in the presence of one molar equivalent of solid HMPA. Without HMPA, in the same conditions, Li enolate docs not react, Na enolate only gives C-alkylation while K enolate leads to 90% C-alkylation, the reactions being quite slower in the two latter cases. The effects of one molar equivalent of solid and liquid HMPA are compared: for the K enolate the reaction is faster and the degree of O-alkylation higher with solid HMPA; practically no difference is seen for Na enolate, while the reverse is observed with the Li enolate. The cooperative effect of the polymer should thus only work for a sufficiently large cation, as the Li enolate is fixed on the solid HMPA in a larger amount than the K enolate. The study of this reaction is proposed to test the efficiency of other “solid solvents” interacting strongly with cations.     

Selectivite de la reduction d'α-enones polycycliques par les borohydrures: effet de l'addition de tetramethyl-ethylenediamine au borohydrure de tetrabutylammonium

3^1,9octalone, 3^1,9-10-methyl octalone and testosterone were reduced by NBu₄BH₄. alone or in the presence of tetramethylethylenediamine (TMEDA), in THF and in toluene. With TMEDA, the first step of the reduction is the regioselective 1,4 attack by BH^?₄ which leads either to the saturated ketones or to the corresponding saturated alcohols. The results observed under different conditions were interpreted by the intervention of various reductive species: diborane, enoxyborohydrides in the absence of TMEDA, amine-borane in its presence.     

Reactivite de lithiens derives d'ethers de la cyanhydrine du benzaldehyde vis-a-vis d'α-enones cycliques

Conjugate addition of reagent 1A to 2-cyclohexenone 3 can be realized in THF-HMPT, so that one-pot conjugate addition—CH₃I enolate trapping, leading to trans 2-methyl 3-benzoylcyclohexanone 17 can be easily performed. From isophorone 4 and Δ¹⁽⁹⁾-2-octalone 5, 1, 4-addition under kinetic control is observed in THF. In the presence of HMPA, the reaction is under thermodynamic control. At low temperatures enolate 19a is in equilibrium with 1A and 4; from 4 at 0° or 5 at ?65° or at 0°, the equilibrium lies on the side of starting materials. No reaction between 1A and 6 takes place in any solvent.The reaction of 1B and isophorone 4 in THF leads to 1, 2-addition under kinetic control and to 1, 4-addition under thermodynamic control. In THF-HMPT, retro-Michael addition is observed. However, 1, 2-addition takes place in THF to 6.The different results are interpreted in terms of interplay of ion-pairing, steric decompression and steric hindrance to 1, 4-addition as well as the possibility of participation of the Li cation for 1, 2-addition.     

Selectivite de la reduction de l'androsten-4 dione-3,17 et de la progesterone par divers borohydrures: role de l'assistance electrophile par le cation ou un solvant hydroxyle

The reduction of Δ⁴-androsten-3, 17 dione 1 and of progesterone 2 by nBu₄NBH₄ is highly chemioselective: in THF only the a-enone moiety is reduced, the saturated C₁₇ or C₂₀ keto group being kept unchanged. When TMEDA is added, saturated alcohols are obtained, without any allylic alcohol when the reaction goes to completion. However this reduction is poorly stereoselective as 70:30 mixtures of A/B cis and trans ring junction compounds are obtained. In MeOH, the saturated keto group is more than 90% selectively reduced. However, the reduction of 1 and 2 by LiBH₄ and Zn(BH₄)₂ is poorly chemioselective. These results are interpreted in terms of competition between electrophilic assistance and steric effects.     

Selectivite de la reduction de cyclohexen-2 ones par NBu4BH4 dans divers solvants et par NaBH4 dans des conditions de transfert de phase

The 2-cyclohexenone 1 and isophorone 2 reductions with NBu₄BH₄ in aprotic solvents lead to a highly preferential 1–4 attack; i.e. 85% with 1 and 96% with 2 in THF. These regioselectivities are nearly the same as those observed with LiBH₄ in the presence of[2.1.1) cryptand confirming thus the cation influence. This method which is inexpensive and easy to work up, seems to constitute a general way to reduction of α-enones to saturate alcohols while other reagents such as K(sec Bu)₃BH are not able to reduce the carbon-carbon double bond of isophoron.Phase transfer catalysis conditions are not useful for selective reduction: large amounts of allylic alcohols are formed in liquid-liquid phase transfer conditions (60% in toluene-water); a good regioselectivity is only obtained when a cryptand is used as a transfer agent in solid-liquid conditions.     

Influence des solvants sur la copolymérisation de l'acrylamide avec l'acrylonitrile

The copolymerization of acrylamide with acrylonitrile was investigated in various solvents, which can be put into three groups according to their influence on molecular associations; (1) solvents autoassociated by hydrogen- bonds (acetic acid, methanol, water, dimethylformamide); (2) polar solvents which can associate with the NH group of acrylamide (acetonitrile, dioxane, acetone); (3) inert solvents (toluene, benzene, hexane). The reaction kinetics and the compositions of the copolymers are different for each group of solvents. The composition of copolymers formed in solvents of group 1 vary widely, depend- ing on the solvent. Copolymers formed in all solvents of group 2 have the same composition which is that of copolymers formed in bulk. The amount of acrylamide is highest in copolymers formed in inert solvents of group 3. Such parameters as the degree of conversion, the reaction temperature, the mode of initiation and the extent of dilution only slightly affect the composition of copolymers. Homopolymerizations of acrylamide and acrylonitrile were investigated in all solvent used.The results suggest that the effects of solvents on the copolymerization of acrylamide with acrylonitrile are consequences of the various modes of molecular association of acrylamide. The solvents affect the equilibrium between auto- association of acrylamide and its association with solvent and thereby affect the reactivity of the monomer.     

DFT study of the effect of sigma-ligands on the structure of ester enolates in THF, as models of the active center in the anionic polymerization of methyl methacrylate.

A Density Functional Theory (DFT) study was carried out on structures of the lithium ester enolate of methyl isobutyrate (MIB-Li) in THF solution, in the presence of TMEDA, dimethoxyethane (DME), crown ether 12-crown-4, and cryptand-2,1,1, as electron donor ligands (sigma-ligands). Both specific solvation with THF and/or ligand molecules and nonspecific solvation by the solvent continuum were taken into account. The possibility of ligand-separated ion pair formation was analyzed for each of the ligands, including THF alone. In most cases peripherally solvated dimers are the most stable species. Only in the presence of cryptand-2,1,1 was a ligand-separated triple ion pair, (MIB-Li-MIB)(-)(THF)(2),Li(2,1,1)(1)(+), shown to be comparable in stability to the THF-solvated dimer, (MIB-Li)(2)(THF)(4). These results are in agreement with experimental NMR data on the structure of MIB-Li in the presence of DME, 12-crown-4, and cryptand-2,1,1. An upfield shift of the (13)C NMR signal of the alpha-carbon of MIB-Li observed in the presence of cryptand-2,1,1, originally attributed to a ligand-separated monomer, MIB(-),Li(2,1,1)(+), was well reproduced by Hartree--Fock calculated NMR shifts for the predicted ligand-separated triple ion pair.     

Polymerisation de l'isoprene par les tetraethyles zincates de metaux alcalino-terreux

Polymerization of isoprene in polar and non-polar media with alkaline-earth tetraethylzincates (Ca, Sr, Ba) has been investigated. The kinetic results, as well as the molecular weights of the polymers, confirm the presence of living species (tight and/or loose ion pairs).     

Homoleptic 2,2′‐bipyridine metalates(–I) of iron and cobalt,one cocrystallized with an anthracene radical anion and the other with neutral anthracene

Homoleptic 2,2′‐bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2′‐bipyridine)ferrate(–I) anthracene(–I), [K(C₁₈H₃₆N₂O₆)]₂[Fe(C₁₀H₈N₂)₃](C₁₄H₁₀), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2′‐bipyridine)cobaltate(–I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C₁₈H₃₆N₂O₆)][Co(C₁₀H₈N₂)₂]·0.5C₁₄H₁₀·2C₄H₈O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry‐related bipy ligands such that aromatic donor–acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).     

Étude thermodynamique de la complexation de l'argent par la pyridazine,la pyrimidine et la pyrazine

The stability constants of the complexes of Ag⁺ ion with pyridazine, pyrimidine and pyrazine as ligands are determined, at 25°C in KNO₃ 0.1 M, using the corresponding metal-complex electrodes.Enthalpies for the two steps of complexation observed are obtained from direct calorimetric measurements, under the same conditions of temperature and medium.A comparison of these values and of the entropies derived from them forms the basis for a discussion of the effects of the relative position of the nitrogen atoms in each heterocycle on their ability to form coordination compounds.     

Étude thermodynamique de la complexation de l'argent par la pipérazine et quelques-uns de ses derives en milieu eau—ethanol

The stability constants of the complexes of Ag⁺ ion with piperazine and its 2-methyl-, 2-methyl-1-m-tolyl-, 2-methyl-1-p-tolyl- and 1-(p-methoxyphenyl)-2-methyl-derivatives are obtained at 25°C in water—ethanol (52%, w/w) solvent and KNO₃ 0.1 M ionic strength, by means of corresponding metal-complex electrodes.The enthalpies of formation are determined by direct calorimetry, in the same conditions of temperature and medium.The comparison of the thermodynamic functions ΔG_n°, ΔH_n°, ΔS_n° allows a discussion about the ability of each amine to coordinate, in terms of nature and position of the entering group.     

Dosage de l'oxygene dans l'uranium et ses composes par la methode au monochlorure de soufre

A sulfur monochloride method is proposed for the determination of oxygen in uranium compounds. Sulfur monochloride reacts with oxygenated compounds at temperatures depending upon their nature; the sulfur dioxide produced is titrated by iodometry, after the excess reagent has been eliminated by a selective adsorption-desorption process using activated charcoal. This method has been successfully applied to uranium oxides (UO₂, U₃O₈), to mixtures of uranium dioxide with uranium, uranium nitride, and uranium carbide, and to substituted carbides (UC_1-xO_x). The results are generally satisfactory for oxygen contents higher than 500 p.p.m. However, in the presence of free or combined carbon, this limit is considerably higher. A loss of oxygen as carbon monoxide is also possible, and a simultaneous determination of carbon monoxide must be carried out. The relative error is of the order of a few per cent.     

Activation a l'aide de polyamines tertiaires de la polymerisation anionique du styrene amorcee par les composes organolithiens

A study of the influence of tertiary polyamines on the reactivity of polystyryllithium ion-pairs in hydrocarbon solvents has been performed. The stability of active centres has been studied and allows the processing of kinetic data as for living systems. Rate constants of propagation have been measured in terms of the structure of the polyamine, its relative concentration, the concentration in organometallic species, the temperature and the nature of solvent; in all cases, they are absolute rate constants. The values show the important effect of the number of nitrogen atoms in the additive and especially the strong influence of its geometry: the cyclic polyamine studied leads to an activation of the reaction much greater than that of the corresponding linear substance. These results may be interpreted in terms of different solvation states for the polystyryllithium ion-pairs.     

Mecanisme de la reaction de Horner-Emmons—II: Effet de solvant sur la stereoselectivite de la reaction d'aldehydes aromatiques et de phosphononitriles

The ratio of Z and E cinnamonitriles obtained from aromatic aldehydes and phosphonitriles 1a and 1b mainly depends upon solvent and upon the phosphonate nature. If it has two H α to CN (1b), the solvent affects the equilibrium of the intermediate oxyanions 5b and 6b. The aldolization step reversibility and stereoselectivity does not intervene unless the aldehyde is orthosubstituted. If the phosphonate has only one H α to CN, kinetically controlled stereoselectivity of the whole process depends upon the solvent effect upon reversibility factor and aldolization selectivity: in DME and THF the total stereoselectivity is low, while in HMPT, the E isomer predominates; under equilibrating conditions (HNa-HMPT) the Z isomer predominates.     

Assistance d'un groupe voisin pour des tosylates secondaires β substitues diequatoriaux dans l'hexafluoroisopropanol 97%

Solvolysis rates in methanol and 97% hexafluoroisopropanol (HFIP) for four β-methyl and β-phenyl bicyclic tosylates, show that solvent nucleophilic assistance is operating in the former solvent. However, in 97% HFIP, for three of the mentioned compounds, the mechanism involves π or σ neighboring group assistance. The factors influencing the occurrence of these processes are discussed. Owing to these possible neighbouring group assistances in non-nucleophilic solvents used to obtain k_c reference mechanisms, it is concluded that the k_a/k_c ratio which was proposed as a quantitative evaluation of solvent nucleophilic assistance must be used with caution.     

Polymerisation cationique de l'indene amorcee par le tetrachlorure de titane-I Influence des impuretes du solvant,le chlorure de methylene,et effets cocatalytiques de l'eau et de l'acide chlorhydrique

The polymerization of the system indene-titanium tetrachloride-methylene chloride gave irreproducible kinetics which have been attributed to variable concentrations of impurities in the solvent. Incomplete yields sometimes observed at ?70° are also caused by impurities, but introduction of water and hydrochloric acid then gives complete yields. A new method of solvent purification has been used giving reproducible yields and rates. In such cases, monomer consumption at ?70° follows the rate law log [M]_o/[M] = kt.     

La fluoration de l'hexachlorobenzene et de la pentachloropyridine en milieu de fluorure de potassium solide

The fluorinations of hexachlorobenzene and pentachloropyridine were carried out in sealed tubes with KF in presence of inert gas; the fluorinated derivatives C₆F_xCl_y x + y = 6 0?x?6 and C₅F_xCl_yN x + y = 5 0?x?5 are obtained. The influence of contact time, temperature and the concentration of the ion F^? are investigated and compared; the molar yield varied from 45% to 90%. It is possible to get directly and selectively some fluorinated derivatives as C₅Cl₂F₃N. The fluorinations in liquid KFKCl and solid KF are compared.