Mixtures Of Nitriles Research Articles

Effects of nitrile compounds on the structure and function of soil microbial communities as revealed by metagenomes

The proliferation of nitrile mixtures has significantly exacerbated environmental pollution. This study employed metagenomic analysis to investigate the short-term effects of nitrile mixtures on soil microbial communities and their metabolic functions. It also examined the responses of indigenous microorganisms and their functional metabolic genes across various land use types to different nitrile stressors. The nitrile compound treatments in this study resulted in an increase in the abundance of Proteobacteria, Actinobacteria, and Firmicutes, while simultaneously reducing overall microbial diversity. The key genes involved in the denitrification process, namely, nirK, nosZ, and hao, were down-regulated, and NO3−-N, NO2−-N, and NH4+-N concentrations decreased by 7.7%–12.3%, 11.1%–21.3%, and 11.3%–30.9%, respectively. Notably, pond sludge samples exhibited a significant increase in the abundance of nitrogen fixation-related genes nifH, vnfK, vnfH, and vnfG following exposure to nitrile compounds. Furthermore, the fumarase gene fumD, which is responsible for catalyzing fumaric acid into malic acid in the tricarboxylic acid cycle, showed a substantial increase of 7.2–10.6-fold upon nitrile addition. Enzyme genes associated with the catechol pathway, including benB-xylY, dmpB, dmpC, dmpH, and mhpD, displayed increased abundance, whereas genes related to the benzoyl-coenzyme A pathway, such as bcrA, dch, had, oah, and gcdA, were notably reduced. In summary, complex nitrile compounds were found to significantly reduce the species diversity of soil microorganisms. Nitrile-tolerant microorganisms demonstrated the ability to degrade and adapt to nitrile pollutants by enhancing functional enzymes involved in the catechol pathway and fenugreek conversion pathway. This study offers insights into the specific responses of microorganisms to compound nitrile contamination, as well as valuable information for screening nitrile-degrading microorganisms and identifying nitrile metabolic enzymes.

Cubic-two-state equation of state for modeling liquid-liquid and vapor-liquid equilibria of nitriles + hydrocarbons or water mixtures

The cubic-two-state (CTS) equation of state (EoS) was employed for modeling the liquid-liquid and vapor-liquid equilibria of nitriles + hydrocarbons (alkanes and aromatics) or water mixtures. For nitriles, the five pure compound parameters were determined by fitting the model simultaneously to experimental saturation pressure, density of saturated liquid, enthalpy of vaporization and liquid-liquid equilibrium data when mixed with n-dodecane. For alkanes, the pure parameters were those determined from conventional corresponding states correlations for Soave-Redlich-Kwong EoS. The van der Waals mixing and combining rules were applied for dispersive parameter and covolume, with a temperature-dependent binary parameter. In the case of nitrile mixtures with aromatics and water, cross-association were considered with the previously published CTS combining rules, and no association binary parameters were required. The correlations were very good in all cases. The model was also able to predict selective extraction of sulfur compounds (benzothyophene and benzothyophene 1,1-oxide) from alkanes. Because of its simplicity, therefore, the CTS EoS is a very attractive option for process simulation involving this class of mixtures.

Plastic-crystalline solid-state electrolytes: Ionic conductivity and orientational dynamics in nitrile mixtures.

Many plastic crystals, molecular solids with long-range, center-of-mass crystalline order but dynamic disorder of the molecular orientations, are known to exhibit exceptionally high ionic conductivity. This makes them promising candidates for applications as solid-state electrolytes, e.g., in batteries. Interestingly, it was found that the mixing of two different plastic-crystalline materials can considerably enhance the ionic dc conductivity, an important benchmark quantity for electrochemical applications. An example is the admixture of different nitriles to succinonitrile, the latter being one of the most prominent plastic-crystalline ionic conductors. However, until now, only few such mixtures were studied. In the present work, we investigate succinonitrile mixed with malononitrile, adiponitrile, and pimelonitrile to which 1 mol. % of Li ions was added. Using differential scanning calorimetry and dielectric spectroscopy, we examine the phase behavior and the dipolar and ionic dynamics of these systems. We especially address the mixing-induced enhancement of the ionic conductivity and the coupling of the translational ionic mobility to the molecular reorientational dynamics, probably arising via a "revolving-door" mechanism.

One-step multicomponent synthesis of chiral oxazolinyl-zinc complexes

BackgroundTypically, oxazolinyl metal complexes are synthesized in two steps, where the free ligand is prepared by the condensation reaction between a functionalized nitrile and an amino alcohol in the presence of a Lewis or Brønsted acid catalyst, followed by a further reaction with metal salts to obtain the corresponding metal complexes. Very often, the yield afforded by the two-step procedure is not high, and very few oxazolinyl zinc complexes have been prepared by this route. Given that metal-oxazoline complexes often contain Lewis acidic metals, it is conceivable that the two steps may be telescoped.ResultsA series of novel chiral organozinc complexes 1–15 were assembled in a single step, All crystalline compounds were fully characterized, including the report of 15 X-ray crystal structures, including a wide structural diversity.ConclusionsA series of novel chiral organozinc complexes were assembled in a single step, from nitriles, chiral D/L amino alcohols, and a stoichiometric amount of ZnCl2, with moderate to high yields (20–90%).Graphical abstractA series of novel chiral organozinc complexes can be assembled in moderate to high yields (20–90%), from a mixture of nitriles, chiral amino alcohols and ZnCl2. All crystalline compounds were fully characterized, including the report of 15 X-ray crystal structures, including a wide structural diversity.

Redox-Neutral α-Arylation of Alkyl Nitriles with Aryl Sulfoxides: ARapid Electrophilic Rearrangement.

A facile α-arylation of nitriles has been developed by simply introducing Tf2O and DABCO to the mixture of nitriles and aryl sulfoxides. The transformation consists of two sequential steps: (i) Tf2O-initiated electrophilic assembly and and (ii) DABCO-triggered rearrangement. Each step can be tuned independently by changing the temperature and/or base. This adjustability allows the method to accommodate a wide range of substrates. Notable features of this new protocol include remarkable efficiency (20 min, -30 °C), exclusive regioselectivity, and high functional group compatibility, which can be challenging issues in traditional approaches. NMR studies not only identified a unique, highly unstable sulfonium imine complex but also demonstrated the importance of temperature in the formation and manipulation of this key intermediate. Further DFT calculations suggested that an electrophilic assembly, followed by removal of HOTf (by base), and finally [3,3]-sigmatropic rearrangement are three key stages in the reaction. The versatile transformability of the products and easy scalability of this reaction are also exhibited here.

Orientational Effects and Random Mixing in 1-Alkanol + Nitrile Mixtures

1-Alkanol + alkanenitrile or + benzonitrile systems have been investigated by means of the molar excess functions—enthalpies (HmE), isobaric heat capacities (Cp,mE), volumes (VmE), and entropies—and using the Flory model and the concentration–concentration structure factor (SCC(0)) formalism. From the analysis of the experimental data available in the literature, it is concluded that interactions are mainly of dipolar type. In addition, large HmE values contrast with rather low VmE values, indicating the existence of strong structural effects. HmE measurements have been used to evaluate the enthalpy of the hydroxyl–nitrile interactions (ΔHOH–CN). They are stronger in methanol systems and become weaker when the alcohol size increases. In solutions with a given short chain 1-alkanol (up to 1-butanol), the replacement of ethanenitrile by butanenitrile weakens the mentioned interactions. Application of the Flory model shows that orientational effects exist in methanol or 1-nonanol, or 1-decanol + ethanenitrile mixtures. In the former solution, this is due to the existence of interactions between unlike molecules. For mixtures including 1-nonanol or 1-decanol, the systems at 298.15 K are close to their UCST (upper critical solution temperature), and interactions between like molecules are dominant. Orientational effects also are encountered in methanol or ethanol + butanenitrile mixtures because self-association of the alcohol plays a more important role. Aromaticity effect seems to enhance orientational effects. For the remainder of the systems under consideration, the random mixing hypothesis is attained to a rather large extent. Results from the application of the SCC(0) formalism show that homocoordination is the dominant trend in the investigated solutions, and are consistent with those obtained from the Flory model.

Non-Cryogenic CeCl3-Promoted Double Additions of Methyllithium and n-Butyllithium to Unsaturated Nitriles

Subjection of methyl or n-butyllithium to a mixture of nitriles and activated cerium chloride in THF at -10 to 0 °C afforded the corresponding carbinamines, which were isolated as either the hydrochloride salts or acetamide or benzamide derivatives in 30-91% vields.

Reaction equilibrium for lipase-catalyzed condensation in organic solvent systems

Lipase-catalyzed condensation in an organic solvent is useful for the syntheses of esters. To reasonably design and optimize the reaction conditions, knowledge of the reaction equilibrium is required. The interaction of water with other reactants and the quantitative predictions for adsorption of water by a desiccant are discussed. The solvent effects on the reaction equilibrium are also elucidated in mixtures of nitrile and tert-alcohol.

Excess Enthalpies of {CH3(CH2)nCN,n= 5 to 12} + Methyl Methylthiomethyl Sulfoxide or + Dimethyl Sulfoxide at 298.15 K

Excess enthalpies of binary mixtures between each of {CH 3 (CH 2 ) n CN (n = 5-12)} and methyl methylthiomethyl sulfoxide or dimethyl sulfoxide have been determined at 298.15 K. All mixtures show positive enthalpy changes over the whole range of mole fractions. Excess enthalpies of the mixtures of nitriles increased with increasing size of the aliphatic groups. The increments of dipole interaction terms of μ 1 2μ 2 2(r 1 + r 2 ) -6 on excess partial molar enthalpies at infinite dilution showed different behavior on the border of pentanenitrile.

Copper quadrupole coupling constants in binary mixtures of acetonitrile with some other nitriles at 298 K

63Cu and 65Cu nuclear magnetic resonance (NMR) and viscosity studies of 0.064 M CuClO 4 have been made in binary mixtures of acetonitrile (AN) with succinonitrile (SN), adiponitrile (ADN), n-butyronitrile (n-BTN) and iso-butyronitrile (iso-BTN) as co-solvents at 298 K using 500 MHz NMR spectrometer and an Ubbelohde viscometer, respectively. Chemical shift ( δ) and linewidth (Δ) for both 63Cu and 65Cu signals have been recorded relative to 0.064 M CuClO 4 solution in pure anhydrous AN. Quadrupole relaxation rates (1/ T 2) Q , reorientational correlation times ( τ R) and copper quadrupole coupling constants ( e 2 Qq/h) have been calculated in all cases. The variation of these NMR parameters has been examined as a function of molecular percent co-solvent to compare the relative effects of these co-solvents on the solvation behaviour of Cu + and hence on the stabilization of copper (I) complexes formed. The ( e 2 Qq/h) values in all AN+nitrile mixtures are larger than the values in pure AN and increase with the increase of molecular percent co-solvent. The strong increase of ( e 2 Qq/h) values in all AN+nitrile mixtures with the increase of molecular percent co-solvent indicates the formation of mixed complexes of the form [Cu(CH 3CN) 4− x (S) x ] + ( x=1−4) due to the replacement of AN molecules from the original complex [Cu(CH 3CN) 4] + formed in pure AN by the co-solvent molecules (S). The results also show that mixed copper (I) complexes in all cases remain stable even at high co-solvent compositions. The ( e 2 Qq/h) values also indicate that the effect of dinitriles is relatively stronger than that of mononitriles, the effect of 63Cu isotope is relatively stronger than that of 65Cu and the effect of iso-BTN is relatively stronger than that of n-BTN in the formation of mixed copper (I) complexes.

Ketones to Amides via a Formal Beckmann Rearrangement in “One Pot”: A Solvent‐Free Reaction Promoted by Anhydrous Oxalic Acid. Possible Analogy with the Schmidt Reaction.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Ketones to amides via a formal Beckmann rearrangement in ‘one pot’: a solvent-free reaction promoted by anhydrous oxalic acid. Possible analogy with the Schmidt reaction

A variety of ketones can be directly converted into the secondary amides expected from a Beckmann rearrangement of the corresponding oximes in high yield, by heating them with hydroxylamine hydrochloride and anhydrous oxalic acid at similar to 100degreesC for 4-12 h. (Aromatic aldehydes afforded mixtures of nitrile and amide.) The transformation is apparently (kinetically) driven by the coupled decomposition of oxalic acid (to CO+CO2) via the fragmentation of an intermediate oxime mono-oxalate. However, an alternative pathway, mechanistically analogous to the Schmidt reaction, is not only equally likely but may well be general for the Beckmann rearrangement.

Cyclization of acylium ions with nitriles: gas-phase synthesis and characterization of 1,3,5-oxadiazinium ions

Gas phase reactions of mass-selected acylium ions [CH3-C+O (1), CH2CH-C+O (2), C6H5-C+O (3), and (CH3)2N-C+O (4)] with nitriles (CH3CN, C2H5CN, CH2CHCN, and C6H5CN) were investigated using pentaquadrupole multiple-stage mass spectrometry. In analogy with the solution behavior, the ions were found to react readily with benzonitrile by cyclization via double nitrile addition to form aromatic 1,3,5-oxadiazinium ions. Cyclization with acetonitrile, propionitrile, and acrylonitrile is less general and occurs readily only for 4, by far the most reactive acylium ion tested. In “one-pot” reactions of 4 with two-component nitrile mixtures, cyclization via double nitrile addition occurs readily and forms both equally and differently 4,6-disubstituted isomeric 1,3,5-oxadiazinium ions. Using MS3 experiments, the 1,3,5-oxadiazinium ions were mass-selected and then either reacted with nitrogen nucleophiles or dissociated by low-energy collisions with argon. The nucleophiles add readily to the ions, whereas the symmetry of the 1,3,5-oxadiazinium ring allows two competitive dissociation pathways: double retro-addition that re-forms the reactant acylium ion, or an analogous dissociation that, formally and combined with cyclization, promotes group exchange between one nitrile and the acylium ion: RCO+ + 2 R1CN → cyclic 1,3,5-oxadiazinium ion → R1CO+ + R1CN + RCN. Isomeric 4,6-disubstituted 1,3,5-oxadiazinium ions are easily distinguished because the nitrile added second is lost first via the double retro-addition dissociation.

Ultrasonic investigation of molecular interaction in binary mixtures of nitriles with methanol/toluene

Ultrasonic velocity, density, and viscosity have been measured in the binary mixtures of nitriles with (CH3OH / C6H5CH3) at different temperatures. Excess thermodynamic functions that have extensive applications in the characterizing aspects of the physico-chemical behaviour of liquid mixtures are evaluated. Other useful thermo-acoustical parameters, which can compliment the study of molecular interactions in binary mixtures, are also evaluated. An analysis of the thermo-acoustical parameters and excess thermodynamic functions suggests the presence of a strong intermolecular interaction in all four binary mixtures and a stronger, specific interaction in (C6H5CN + CH3OH) mixtures.

Ion pairs of indobenzimidazolo cyanines: a structural study based on conductivity, absorption, fluorescence and [formula omitted]-NMR

Asymmetric benzimidazolo carbo, di- and tricarbocyanines form ion pairs of the solvent-separated and contact types with different counterions in tetrahydrofuran, toluene and toluene–nitrile mixtures. The dissociation constants of the ion pairs in tetrahydrofuran, evaluated from conductivity data, do not depend on the length of the polymethine chain and show only a small decrease with decreasing counterion size. The absorption and fluorescence excitation spectra of the contact ion pairs exhibit a pronounced hypsochromic shift with respect to the solvated ions and the solvent-separated ion pairs. 1 H−NMR experiments have provided information about the electronic structures of the ions of both the asymmetric dyes and the corresponding symmetric carbocyanines. They have also revealed different preferred anion locations in the contact ion pairs of the symmetric indocarbocyanine on one hand, and of the benzimidazolo carbocyanine and the asymmetric dyes on the other. This structural difference is suggested to be a cause of the observed opposite effects of ion pairing on the isomerization kinetics of the two groups of dyes.

Natural product analogs: Stable mimics of aldehyde pheromones

AbstractUnder field conditions, the aldehyde components of the pheromones of important lepidopteran and coleopteran pests undergo chemical transformations (oxidation, polymerization, etc.) resulting in behaviorally inactive compounds. In our search for pheromone analogs with favorable chemical and biological properties, a series of nitriles, oximes and isothiocyanates, as novel functional group mimics of some cyclic and long chain pheromones, were prepared and tested. The biological activities of these nitrogen‐containing analogs were studied by electrophysiological and field experiments with three different insect species showing the nitrile analogs to be the most potent mimics, but their activities were lower than those of the natural pheromones. Thus, a 1:1 mixture of pheromone analogs in place of the corresponding natural aldehyde components III and IV elicited dose‐dependent electroantennogram (EAG) responses of antennal preparations of the female boll weevil, Anthonomus grandis. In field trials, the nitrile analogs were poor substituents for the corresponding aldehydes. In EAG experiments with antennal preparations of males of the southwestern corn borer, Diatraea grandiosella, Z11‐16:Nitrile ((Z)‐11‐hexadecenonirile) elicited dose‐dependent responses while single neuron recording from antennal preparations of this species revealed that a neuron responsive to the pheromone component was also stimulated by the mimic Z11‐16:Nitrile. In field experiments, a 97:3 mixture of nitriles Z11‐16:Nitrile and Z9‐16:Nitrile ((Z)‐9‐hexadecenonitrile) effectively attracted males of the cranberry girdler moth, Chrysoteuchia topiaria. © 1993 Wiley‐Liss, Inc.

Thermal transformations of oxazole endoperoxides: Rearrangements, fragmentations and methanol additions

Oxazole endoperoxides 1 carrying a phenyl group at C-2 rearrange to triacylamines 3 ; those carrying a hydrogen atom at C-2 undergo a fragmentation into 1:1 mixtures of nitriles (or HCN) 4 and anhydrides 5 , whereas methyl substitution at C-2 gives rise to competition between these two modes of reaction. Methanol addition to 1 leads to4-methoxy-5-hydroperoxides 6 which easily transform into methyl esters 7 and diacylamines 8 .

Role of glucosinolates in the causation of liver haemorrhages in laying hens fed water-extracted or heat-treated rapeseed cakes

Glucosinolates were removed from whole rapeseed by a hot-water extraction procedure or depleted by heat treatment. When laying hens were maintained for three months on diets containing about 300 g kg-1 of these rapeseed cakes, the incidence of liver haemorrhages detected at post mortem examination was similar to that in birds maintained on 300 g kg-1 commercial rapeseed meal and significantly greater than in control birds fed soya-based diets. The effectiveness of glucosinolate extraction or depletion was determined by chemical analysis and by histological examination of the thyroid glands. Histologically the haemorrhages were similar after feeding extracted and commercial rapeseed meals. Diets containing mixtures of nitriles and glucosinolates severely depressed food intake and egg production but did not cause a greater incidence of haemorrhages than the other rapeseed products tested. Mortality from causes other than liver haemorrhage was higher with the diets containing rapeseed and this suggests that rapeseed has a more generalised effect on the body's defence mechanisms. These observations suggest that other factors in rapeseed meal, alone or acting with glucosinolates, may be responsible for inducing liver haemorrhages in laying hens.

The thermal decomposition of polyurethanes and polyisocyanurates

AbstractThe thermal decomposition of a number of TDI‐ and MDI‐based biscarbamates (model compounds for polyurethane foams) between 200°C and 1000°C showed that the urethane linkage undergoes an O‐acyl fission at about 300°C to generate the free isocyanate and alcohol. In the case of the flexible foam analogues, the newly generated TDI reacts further to generate volatile polyureas, termed ‘yellow smoke’. The MDI residues generated in the decomposition of a rigid foams react to yield non‐volatile polycarbodiimides. Both the yellow smokes and the polycarbodiimides decompose above 600°C to give a mixture of nitriles (including HCN) as well as a number of olefinic and aromatic compounds. The use of 13C labeling indicated that HCN and all the other nitriles generated during the high temperature decompositions originate in the thermal fission of the aromatic ring, the nitrile carbon being the 2‐, 4‐ or 6‐ carbon of MDI.

Etudes photochimiques en série hétérocyclique. V. Mise en évidence d'oxazoles par photooxydation de thiazoles

Formation of oxazoles as by‐products of photooxydation of thiazolesIn the presence of air, light (high pressure mercury lamp) and iodine as sensitizer, benzene solution of arylthiazoles 2, 3 and 13 (see scheme 1) were converted into a mixture of photoisomers and aryloxazoles (see scheme 2).Upon shorter times of irradiation under oxygen in chloroform containing methylene blue as a sensitizer 2,4,5‐triphenylthiazole (7) is converted in 2,4,5‐triphenyloxazole.Under usual photooxidation conditions, in methanol as solvent, most of arylthiazoles studied gave a mixture of nitriles, amides, acids esters and diketones. In the case of thiazole 7, the corresponding oxazole was also found.A possible mechanism for the photochemical oxidation of arylthiazoles to aryloxazoles, via 2,5‐ and 4,5‐endo‐peroxides, may be proposed (see schemes 5 and 6).