Sels de N-alcoxypyridinium porteurs d'une fonction acide on ester au niveau d'un carbone α tertiaire. Synthèse et réactivite vis-à-vis des ions hydroxydes

Pyridine N-oxide does not react directly with α-bromoiso-butyric acid or with its ethyl ester, but the resulting adducts can be obtained easily as crystallized nitrates 1 and 2 if the reaction is performed in the presence of silver nitrate in acetonitrile solution. Although salt 2 bearing an ester group, does not undergo solvolysis of its O-C_α bond, and cannot be decomposed according to the classical mode A, the kinetic study of its ring opening by hydroxide ions cannot be performed free of any side reaction; hydrolysis of the ester group, followed by opening of the resulting betaine accounts for an observed order of reaction greater than 2 with respect to hydroxide ion. This ring opening competes with a decomposition to carbon dioxide, acetone and pyridine, which is carboxylog of the mode A and which occurs when salt 1 is treated by hydroxide ions.     

Mechanisms of elimination reactions—XXVI: The α'-β mechanism in elimination reactions of sulforium salts

Tracer studies with β-deuterated sulfonium salts have shown that the α'-β, or ylid mechanism can be the major path of elimination in the reaction of sulfonium salts with t-butoxide in t-butyl alcohol, while the E2 reaction is dominant with hydroxide in water or n-butoxide in n-butyl alcohol. The structure of the sulfonium salt also affects the propensity toward α'-β elimination, with 3-pentyl > 3-propyl and eyclopentyl > 3-pentyl > cyclohexyl. The S-methyl protons of the sulfonium salt exchange at a rate much faster than that of the elimination reaction. A strongly basic medium and a syn-periplanar arrangement of the α-C-S and β-C-H bonds seem to be the two most important factors favoring the α'-β mechanism.     

Three component reaction of aryl diazonium salt with sulfonamide & actonitrile to synthesize N-sulfonyl amidine

A new method was developed to prepare N-sulfonyl amidine compounds through three-component reaction of aryl diazonium salts with sulfonamides and acetonitrile, in which, nitrilium ion intermediate, generated from the reaction of aryldiazonium salt with nitrile, was subsequently trapped by sulfonamides. A series of N-sulfonyl amidine derivatives were synthesized by using various types of aryl diazonium salts, sulfonamides and nitriles. In addition, indolyl imine products could also be prepared by using indole as the nucleophile to trap nitrilium ion intermediate.     

A polarographic study of the complexes formed in alkaline solution by the cadmium(II) ion with ethylenediamine,N-(2-hydroxyethyl)ethylenediamine,and N,N′-bis(2-hydroxyethyl)ethylenediamine

A multiple regression analysis of polarographic data has been used to determine the formulas and formation constants of complexes formed in alkaline solution by reaction of cadmium(II) ion and hydroxide ion with ethylenediamine (en), N-(2-hydroxyethyl)-ethylenediamine (hn) and N,N′-bis(2-hydroxyethyl)ethylenediamine (2hn). The complexes formed are designated by the general formula Cd(A)_p(OH)_p^2?q and the formation constants are given as log β_pq. The complexes found and their formation constants are: for en, 1 : 2 (10.3), 1 : 3 (12.3), and 1 : 2 : 1 (12.2); for hn, 1 : 2 (9.5), 1 : 2 : 1 (12.2), and 1 : 2 : 2 (12.6); and for 2hn, 1 : 2 (8.9), 1 : 1 : 2 (11.1), 1 : 2 : 1 (11.2), and 1 : 2 : 2 (12.6). It is concluded that in each case for which the hydroxide ion is reacted, a proton is removed from an alcoholic hydroxyl group which is coordinated to form a five-membered chelate ring linking a nitrogen atom and oxygen atom to the cadmium(II) ion.     

Mechanistic investigation and DFT calculation of the new reaction between S-methylisothiosemicarbazide and methyl acetoacetate

A study on the synthesis and mechanistical aspects of formation of 3-methyl-5-oxo-3-pyrazolin-1-carboxamide (MOPC) starting from S-methylisothiosemicarbazide hydrogen iodide and methyl acetoacetate was performed. In the alkaline aqueous solution, the intermediate methyl acetoacetate S-methylisothiosemicarbazone undergoes substitution of CH₃S^? anion by hydroxide anion, cyclization, carbanion formation, and elimination of methanol, thus yielding corresponding Na-enolate salt of pyrazol-5-one derivative. The structure of the compound obtained after protonation of the formed enolate salt was determined by means of spectroscopic techniques and single-crystal X-ray diffraction analysis. The mechanism of conversion of methyl acetoacetate S-methylisothiosemicarbazone into MOPC was investigated by means of the B3LYP functional, and it was found that the reaction is thermodynamically controlled.     

Cryolite precipitation by the Reaction of aluminium salt with sodium fluoride in aqueous solution

When aqueous solution of aluminium salt involving nitrate, chloride or sulfate was added into sodium fluoride solution, an immediate reaction occured to form cryolite-like precipitate. Examination into the resultant solution and analysis for the precipitate were carried out, leading to the fact that fluorine ion can substitute for bound water molecules around central Al⁺⁺⁺ ion, but hardly for bound hydroxide and sulfate ion which should go or be “frozen”, as it is, into cryolite-like precipitate. These ligand substitution reaction seems to contribute to identification of ion species of aluminium in aqueous solution.     

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]−, Stabilized by a Weakly Coordinating Cation

The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH₂)₃]^? salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water‐stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene‐base‐catalyzed preparation of the Ruppert–Prakash reagent Me₃SiCF₃ using fluoroform (HCF₃) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.     

Reaktionsmechanismen des Oxoniumions von neuen Gesichtspunkten der Säure—Basen-Katalyse

Hydroxide ion is shown to react with α-glucose in two ways. Firstly, it catalyses mutarotation of α-glucose in conjunction with the hydrate sheath, and secondly, it reacts extremely rapidly as partially dehydrated hydroxide ion with formation of α-glucosate ion without mutarotation of α-glucose. This knowledge, combined with the author's determination of the hydrogen bond entropy of the hydrated oxonium ion leads to new views on the mechanism of very rapid oxonium ion reactions. The hydrogen bond entropy of the hydrated oxonium ion ΔS was determined by the author from the coefficients of the water catalysisk _W and oxonium ion catalysiskH₃O⁺ of the mutarotation of α-glucose $$\Delta S = R ln {{k_w } \mathord{\left/ {\vphantom {{k_w } {k_{H_3 O^ + } }}} \right. \kern-\nulldelimiterspace} {k_{H_3 O^ + } }},$$ As the proton of the hydrated oxonium ion is attracted by both oxygen atoms with the same intensity, (ΔS)/2 is the hydrogen bond entropy of the single hydrated proton, which is to be considered as the activated oxonium ion of the reactions between the oxonium ion and the anions. While only the activation of the oxonium ion is necessary for the reaction of the oxonium ion with hydroxide ion, the reaction of the oxonium ion with acetate ion needs furthermore the activation of this anion, which consists of rupture of the internal hydrogen bond of this anion. The enthalpy of activation of the acetate ion is determined by the author from the acetate ion catalysis and the water catalysis of the α-glucose mutarotation. The activation enthalpy of the reaction of the oxonium ion with acetate is therefore the sum of the activation enthalpies of the oxonium ion and of the anion. Furthermore it is shown that the high migration velocity of the hydrogen ion in aqueous solution is due to the proton exchange between the water molecules, initiated by the single hydrated proton.     

Structure and thermal decomposition of sulfated β-cyclodextrin intercalated in a layered double hydroxide

The sodium salt of hexasulfated β-cyclodextrin has been synthesized and intercalated into a magnesium-aluminum layered double hydroxide by ion exchange. The structure, composition and thermal decomposition behavior of the intercalated material have been studied by variable temperature X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma emission spectroscopy (ICP), and thermal analysis (TG-DTA) and a model for the structure has been proposed. The thermal stability of the intercalated sulfated β-cyclodextrin is significantly enhanced compared with the pure form before intercalation.     

Characteristics of the voltammetric behavior of the hydroxide ion oxidation at disordered mesoporous titanium dioxide electrocatalyst

The alkaline water electrochemical splitting reactions need economical, very energetic, and durable catalysts. Here, a disordered mesoporous and highly defected titanium dioxide (dom-TiO₂) electrocatalyst for the oxidation of hydroxide ion was prepared via ligand-assisted evaporation-induced self-assembly. The (dom-TiO₂) electrocatalyst showed significant electrocatalytic performance for the oxidation of hydroxide ion compared to that of non-porous TiO₂ (bare-TiO₂) and highly-ordered hexagonal mesoporous (hm-TiO₂) electrodes. The chemical and electrochemical parameters of the diffusion (D), concentration in the bulk (C_b), the number of transferred electrons (n), rate constant of heterogeneous electron transfer (k_s), redox potential (E°), and homogeneous chemical rate constant (k_c) for the oxidation of hydroxide ion reaction at the porous TiO₂ electrodes were determined via the convolution–deconvolution voltammetry and competed against that of non-porous (bare-TiO₂) and hm-TiO₂ and catalysts. In addition to the effect of dom-TiO₂ film thickness and the type of supporting electrolytes on the electrochemical parameters of the electrocatalytic oxidation of OH^– ions have been estimated. The convolutive–deconvoluted results show that the dom-TiO₂ electrode catalyst exhibits a superior reaction rate constant among the studied electrodes that depend on the film thickness and type of supporting electrolyte.     

Production of Polyether Polyols Using Phosphate Calcium Salt

The synthesis of bifunctional polyols using glycerol phosphate calcium salt hydrate as initiator and caesium hydroxide and potassium tert-butoxide as catalyst by means of anionic polymerization was achieved. If a phosphate salt is used as initiator, this reaction allows us to obtain polyols with phosphate groups in its structure not previously described. The relationship to catalyst type was also studied. The kinetic studies revealed that there was a linear relationship between the propylene oxide consumption and time. Both the polydispersity indexes of the polyol and the reaction time decreased using caesium hydroxide instead of potassium tert-butoxide under the same synthesis conditions. The incorporation of phosphorus in the polyol chain was confirmed by MALDI-TOF spectra and ³¹P-NMR spectra. GPC analyses showed an additional small peak in the product, attributed to the allyl adduct. The purification procedure of polyether polyols was also studied by means of liquid-liquid extraction, desorption and ion exchange.     

Cage octaphenylsilsesquioxane from cyclic tetrasiloxanetetraol and its sodium salt

Cage octasilsesquioxane with various substituents were obtained by the condensation reaction of various all-cis cyclic tetrasiloxanetetraol (R-T₄-tetraol, R = phenyl, p-tolyl, i-butyl, naphthyl) with benzyltrimethylammonium hydroxide or tetrabutylammonium fluoride as a catalyst. Co-condensation of phenyl-T₄-tetraol with phenyl-d₅-T₄-tetraol or with p-tolyl-T₄-tetraol were found to proceed through reshuffling process evidenced by scrambling of the substituents. Pure octa(4-bromo-substituted phenyl)octasilsesquioxane was synthesized for the first time from tetra(4-bromo-substituted phenyl)tetrasiloxanetetraol sodium salt.     

Highly enantioselective organocatalysis of the Michael addition of benzyloxyacetaldehyde to nitroolefins

A novel category of di(N,N-dimethylbenzylamine)prolinol silyl ether catalyst, which when used in conjunction with an acidic co-catalyst, generates an ammonium salt supported organocatalyst. This catalytic system is shown to be very effective for the Michael reaction of benzyloxyacetaldehyde and various nitroolefins in isopropanol. Excellent enantioselectivities (up to 99%) and diastereoselectivities (syn/anti of 75:25) and short reaction times were obtained. The presence of the bulky OTMS group combined with the presence of two large N,N-dimethylbenzyl ammonium ion groups accounts for the effectiveness of this catalytic system.     

Cathodic stripping voltammetry: Part II. Study of the release of inorganic sulfide from proteins during denaturation in alkaline media

The concentration of inorganic sulfide ion liberated from a wide range of proteins denatured in 0.2 M NaOH at 25°C was measured using direct cathodic stripping voltammetry (c.s.v.), as well as by ion selective electrode potentiometry and c.s.v. after separation of the H₂S by an isothermal microdiffusion technique. The sulfide produced in 0.2 M NaOH was equivalent to the number of protein disulfide bridges broken, and using several model proteins it was shown that only surface, or solvent-accessible disulfide bonds are attacked. The reaction obeyed first-order kinetics, and the rate was proportional to hydroxide ion concentration. Some simple disulfide compounds were also studied, and possible reaction mechanisms for the formation of sulfide ion are discussed. Some iron proteins were denatured in 0.2 M NaOH and the dissociation of the heme-protein bond was monitored by measuring the iron redox wave at the mercury electrode. Normal and cancerous blood serum samples were analysed by c.s.v. measurement of the sulfide released in alkali, both before and after separation of the albumin and globulin by precipitation and gel permeation chromatography.     

沉淀法回收生物油高温馏分中的酚类物质

为了研究金属离子沉淀法对生物油高温馏分中酚类物质的回收,提高生物油中化学物质的利用率,利用气相色谱-质谱联用仪(GC-MS)从NaOH试剂浓度、反应温度和反应时间三个方面研究了镁离子对生物油中酚类物质的回收效果。结果表明,镁离子与酚类物质形成了不溶物,而且不同浓度的氢氧化钠溶液(1.0-4.0 mol/L)、不同的反应温度(25-85℃)以及不同的反应时间(5-35 min)对实验结果有着不同程度的影响。结果表明,在反应温度为25℃、氢氧化钠浓度为2.5mol/L,反应时间在20 min时为最佳反应条件。在此条件下,对生物油高温馏分中对乙基苯酚的回收率可达34.97%。     

Stereochimie et mecanisme de l'ouverture par les amines d'ions N-alcoxypyridinium : Formation competitive d'un ylure endocyclique; application a une nouvelle conversion heterocyclique

The N-alkoxypyridinium salt 1, with pyrrolidine, piperidine and diethylamine, undergoes reversible ring opening in acetonitrile. This competes with irreversible cyclization of an ylide to the bicyclic intermediate 3 which suffers subsequent ring opening to 3-ω-aminobutadienylisoxazol-4 ones in methanol. The different courses of the reaction is tentantively explained by means of HSAB theory. Stereochemistry of the primary open products is consistent with a disrotatory ring opening of cis-dihydropyridine adducts resulting from amine addition to the salt 1 or to the bicyclic ion 3. These primary products are further isomerized and all-trans structures have been isolated in the case of isoxazoline derivatives. Conversion of an N-alkoxypyridinium salt to substituted butadienylisoxazolones exemplifies a new type of heterocyclic ring transformation that can be described by the PARC-ANRO sequence: Proton Abstraction, Ring Closure—Addition of a Nucleophile, and Ring Opening.     

Calculation of proton activity in aqueous protolyte solutions

A general and thermodynamically exact equation for the calculation of the proton (hydroxide ion) activity of aqueous solutions of monoprotic acidic (and basic) species is given. Under certain conditions, various approximate equations can be derived from the exact form; the applicability of these depends mainly on both the thermodynamic equilibrium constant, K_p , of the protolytic reaction, and the stoichiometric concentration, C_o , of the protolyte. Taking into account the mean ionic activity coefficients which are calculated by means of the Davies equation, diagrams are constructed exhibiting those combinations of K_p and C_o for which the respective approximations can be applied without exceeding specified permissible values of the relative error.     

Bromures et ethers ortho- et para-acetoxybenzyliques: Hydrolyse alcaline et étude cinétique de leur réaction avec l'imidazole

A kinetic study of the alkaline hydrolysis and the imidazole-catalysed hydrolysis of a series of o - or p-acetoxybenzyl bromides and p-nitrophenyl ethers has been determined as a function of pH and temperature. The reactions were followed by disappearance of ester and by release of bromide or p-nitrophenolate anions. In both cases, the rates obtained were equal, and proportional to the ester and nucleophile concentrations. The formation of N- acetyl-imidazole intermediate, followed at 245 nm, as well as the observed deuterium isotope effect, correspond to a nucleophilic attack on the carbonyl group. When the acetoxy group is hindered, the reaction with hydroxide ion is slower, no catalysis can occur, and imidazole may react directly at the benzylic site of the molecule.     

A novel stereoselective preparation of various vinyl sulfide derivatives using beta-alkylthioalkenylselenonium salts

The treatment of alkynylselenonium salt and various thiophenol derivatives with a catalytic amount of triethylamine gave beta-arylthioalkenylselenonium salts in good yields. The alkenylselenonium salts thus prepared reacted with nucleophiles such as acetylides, thiolates, and alkoxides to produce (Z)-beta-arylthio-alpha-functionalized ethenes in high yields. The vinylselenonium salts bearing a hydroxy group on a beta-side chain caused intramolecular cyclization upon treatment with sodium hydride to produce medium-membered heterocyclic compounds containing sulfur and oxygen atoms. The reactions giving (Z)-beta-arylthio-alpha-functionalized ethenes would proceed via the formation of selenurane intermediates followed by the ligand coupling reaction.     

An efficient asymmetric synthesis of (3S)-3-amino-1-(4-cyanophenyl)-2-oxopyrrolidine hydrochloride salt

Reaction of 4-aminobenzonitrile with 2-bromo-4-chlorobutyryl bromide in the presence of sodium phosphate followed by treatment of the coupled product with sodium hydroxide followed by ammonium hydroxide in acetonitrile yielded the title compound as the racemic (R)-(−)-mandelic acid salt in an overall yield of 64%. The title compound was then obtained with an ee >96% and in 78% yield after a dynamic resolution of the racemic salt in IPA using a catalytic amount of salicylaldehyde followed by salt exchange.