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The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.

This paper focuses on the thermal behavior of mixtures of ammonium dinitramide (ADN) and amine nitrates. Because some mixtures of ADN and amine nitrate exhibit low melting points and high-energy content, they represent potential liquid propellants for spacecraft. This study focused on the melting behavior and thermal-decomposition mechanisms in the condensed phase of ADN/amine nitrate mixtures during heating. We measured the melting point and exothermal behavior during constant-rate heating using differential scanning calorimetry and performed thermogravimetry–differential thermal analysis–mass spectrometry (TG–DTA–MS) to analyze the thermal behavior and evolved gases of ADN/amine nitrate mixtures during simultaneous heating to investigate their reaction mechanisms. Results showed that the melting point of ADN was significantly lowered upon the addition of amine nitrate with relatively low molecular volume and low melting point. TG–DTA–MS results showed that the onset temperature of the thermal decomposition of ADN/amine nitrates was similar to that of pure ADN. Furthermore, during thermal decomposition in the condensed phase, ADN produced highly acidic products that promoted exothermic reactions, and we observed the nitration and nitrosation of amines from the dissociation of amine nitrates.

A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.

Described are our preliminary studies on the reactivity of thiophosphate in a setting which correlates with the cyanosulfidic systems chemistry we have previously reported. Thiophosphate adds to various nitrile groups giving the corresponding thioamides in a highly efficient manner and the mechanistic implications are briefly discussed. Thiophosphate can also act as a phosphorylating agent, which was demonstrated with adenosine. The prebiotic availability of thiophosphate must be questioned, but if a plausible synthesis can be found, the advantages it would bring to the field of prebiotic chemistry appear to be highly beneficial.

A process is proposed for production of formamides by reaction of carbon dioxide with hydrogen in a hydrogenation reactor I in the presence of a catalyst comprising an element from group 8, 9 or 10 of the periodic table,a tertiary amine comprising at least 6 carbon atoms per molecule, and alsoa polar solvent, to form formic acid-amine adducts as intermediates, which are subsequently reacted with ammonia or amines in a reactor to obtain a two-phase liquid reaction effluent from which the liquid phase enriched with the formamides is distillatively separated to recover the formamide.

α-Amino nitrones have been used successfully as an oxidizing reagent for the synthesis of aldehydes from various alkyl halides with an excellent yield. In addition, hydrolysis of the side product (imines) furnishes starting material amides which are recyclable along with corresponding amines.

Rates of thermal decomposition of glycine, alanine, and serine are described by the equation of first order reaction in the temperature range 200-300°C. Apparent rate constants and apparent activation energies of decomposition of α-amino acids were evaluated. It was found that the main gaseos reaction product is carbon dioxide.

The present invention relates to a composition of a phenylalkyl carbamate compound that results in improved stability, wherein the composition comprises a phenylalkyl carbamate compound in a mixture with an effective amount of one or more excipients and, wherein at least one excipient is dibasic calcium phosphate dihydrate.

Comblike, surfactant polymers for changing the surface properties of biomaterials are provided. Such surfactant polymers comprise a polymeric backbone of repeating monomeric units having functional groups for coupling with side chains, a plurality of hydrophobic side chains linked to said backbone via the functional groups, and a plurality of hydrophilic side chains linked to said backbone via the functional groups. The hydrophobic side chains comprise an alkyl group comprising from 2 to 18 methylene groups. The alkyl groups are linked to the polymeric backbone through ester linkages, secondary amine linkages, or, preferably, amide linkages. The hydrophilic side chain is selected from the group consisting of: a neutral oligosaccharide, which, preferably, has weight average molecular weight of less than 7000; a charged oligosaccharide, preferably a negatively charged oligosaccharide having a weight average molecular weight of less than 10,000; an oligopeptide of from about 3 to about 30 amino acid residues, said oligopeptide having an amino acid sequence which interacts with protein receptors on the surface of cells; and combinations thereof. Methods of making the surfactant polymers and using the surfactant polymers to alter the surface properties of a biomaterial are also provided.

Several amides were obtained in high yields by an efficient method from the corresponding imines which are readily prepared from aldehydes. This procedure involves the oxidation of aldimines with m-CPBA and BF3·OEt2. In this reaction, the product is strongly influenced by the electron releasing capacity of the aromatic substituent.

The catalytic activity of a series of metal oxides in oxidation of ethylene glycol was studied.

Reactivity at oxidation in basic water-ethanol solutions of the fallowing phenols: 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, and (3,5-di-tert-butyl-4-hydroxybenzyl)methyl ether was studied as affected by α-located oxygen-containing functional groups and the base nature. It is shown that the substrate reactivity drops in the order: alcohol ≥ ether > aldehyde. In the presence of NaOH, Na2CO3, and NaHCO3 the alcohol and the ether are similar in efficiency, while in aqueous ammonia the alcohol reactivity is much higher than that of ether. Aldehyde oxidizes in ammoniak with the tenfold faster than in solutions of NaOH, Na2CO3, and NaHCO3.

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Through the use of simultaneous thermogravimetry modulated beam mass spectrometry (STMBMS) measurements, time-of-flight (TOF) velocity-spectra analysis, and (2)H, (13)C, (15)N and (18)O labeled analogues of 1,3,5-trinitrohexahydro-s-triazine (RDX), the thermal decomposition products of RDX have been identified as H2O, HCN, CO, CH2O, NO, N2O, NH2CHO, NO2, HONO, (CH3)NHCHO, oxy-s-triazine (OST), and 1-nitroso-3,5-dinitrohexahydro-s-triazine (ONDNTA) and all of their gas formation rates have been measured as a function of time.From these results the primary reaction pathways that control the decomposition of RDX in both the solid and liquid phases have been discovered.Four primary reaction pathways control the decomposition of RDX in the liquid phase between 200 and 215 deg C.Two pathways are first-order reactions solely in RDX.One produces predominantly OST, NO, and H2O and accounts for approximately 30percent of the decomposed RDX, and the other produces predominantly N2O and CH2O with smaller amounts of NO2, CO, and NH2CHO and accounts for 10percent of the decomposed RDX.The third pathway consists of formation of ONDNTA by reaction between NO and RDX, followed by the decomposition of ONDNTA to predominantly CH2O and N2O.The fourth reaction pathway consists of decomposition of RDX through reaction with a catalyst that is formed from the decomposition products of previously decomposed RDX.The third and fourth reaction channels each account for approximately 30percent of the decomposed RDX.Experiments with solid-phase RDX have shown that its decomposition rate is very much slower than that of liquid-phase RDX.ONDNTA is the only product that appears to be formed during the early stages of decomposition of RDX in the solid phase.As the solid-phase decomposition progresses, N2O and lesser amounts of CH2O start to evolve and their rates of evolution increase until products associated with the liquid-phase RDX decomposition appear and the rates of gas formation of all products rapidly increase.This behavior strongly suggests the decomposition of solid RDX occurs through formation of ONDNTA within the lattice, the subsequent decomposition of it within the lattice to N2O and CH2O, followed by the dispersion of CH2O in the RDX, leading to its eventual liquefaction and the onset of the liquid-phase decomposition reactions.

In the reaction of aromatic di- and tetracarboxylic anhydrides containing carboxyl groups at the ortho and peri position with amides the corresponding mono- and diimides were obtained.The reaction of phthalic anhydride with formamide, leading to phthalimide, takes place with the intermediate formation of N-formylphthalamic acid.

The reaction of benzoyl ion with ammonia in multiple-collision conditions in the second quadrupole assembly of a triple quadrupole mass spectrometer at (laboratory) ion kinetic energies from 0 to 20 eV produced the even-electron ions +, m>+ (m=0,1) and + (n=0,1,2,3) and the odd-electron ions p>+. (p=0,1).Thermochemical information could not be obtained under multiple-collision conditions: both exotermic and endotermic reactions were observed, with no translational-energy onset measurable for the endothermic pr/cesses, nor decrease in the yield of the exothermic processes at high energies.The behaviour of cluster-ions intensities as pressure varied was qualitatively as expected.There are pressure and energy regions where spectra change little; if this feature were to be general, it would point to some utility for these conditions in qualitative analysis.

The electrochemical reduction of some N-acylamino-, N-amino-, N-benzyl- and N-phenacyl-substituted pyridinium and triazolium ions is investigated in acetonitrile by voltammetric methods and potentiostatic electrolyses.The acylaminopyridinium ions 1 and the arylaminopyridinium ions 3 are cathodically cleaved into the pyridine derivative and the carboxylic amide or the aromatic amine.In the case of the 1-benzyl-4-acylaminotriazolium ions 5 the reductive formation of hydrogen from the acidic N-acylamino group is preferred and the corresponding ylide is formed, which reacts at more negative potential by splitting off the benzyl group.The reduction of the N-phenacylpyridinium ion 7d occurs with splitting off the phenacyl radical, which dimerizes to 1,2-dibenzoylethane in a good yield.In the case of N-benzyl- and N-p-cyanobenzylpyridinium ions the cathodic dimerization to the corresponding bisdihydropyridines was found, whereas the electrolysis of the N-nitrobenzylpyridinium ions occurs with cleavage of the N-substituent-bond, which is initiated by the primary formation of the nitrophenyl anion radical.It follows from electrogenerated chemiluminescence experiments that the cleavage of the cations 1 and 5 occurs with the uptake of one electron.

N,N-Dimethylformamide and N-methylformamide have been prepared from synthesis gas plus ammonia via ruthenium 'melt' catalysis.

In the photodecomposition of N-haloamides (ZCONRX) in the presence of olefins, the 1,2-addition chain competes with the hydrogen abstraction chain(s) leading to the parent amide (the quantum yields for these processes are greater than unity).The following factors were shown to have an influence on this competition as measured by the yield of 1,2-addition and the yield of parent amide in methylene chloride solutions: (i) the N-halogen (higher yields of addition with X=Cl than with X=Br); (ii) the electronegativity of Z (increase of the yield of addition as the electronegativity of Z increases); (iii) the temperature (higher yields of addition at lower temperatures, and at -70 degC, better yields of addition (>90percent, R=H) for X=Br than for X=Cl); and (iv) the size of R (dramatic decrease of the yield of 1,2-addition in going from R=H to R=CH3).Surprisingly, the presence of a scavenger for HX had no influence on the yield of 1,2-addition.Both the size and electronegativity of Z had an effect on the stereochemistry of 1,2-addition to cyclohexene.High yields of addition to a variety of olefins were obtained with N-chloroamides such as ClCH2CONHCl, C2H5OCONHCl, CF3CONHCl.Their addition to enol ethers at -70 degC led to the synthesis of α-amido acetals or ketals (aldehydes or ketones) and to an α-amido glycoside in good yields.