Higher tertiary amines were prepared by transalkylation of triethylamine with commercially available alcohols such as Tergitol
15-S-3 and tridecyl alcohol. This reaction carried out at 250–300 C and 20 kg/cm2 initial hydrogen pressure, using Cu−Cr−Mn−O catalyst, gave about 80% yield of higher alkyl tertiary amines. Tertiary amine
hydrochlorides, quaternary ammonium bromides and amine oxides were prepared from these tertiary amines. Specific surface tension,
wetting power, foaming power and foam stability were measured. The characteristic properties with respect to tertiary amine
derivatives containing ether linkages were observed. These products have excellent wetting power, reduced surface tension,
low foaming power and unstable foam. 相似文献
Lignin, which is the second most abundant polymeric aromatic organic substance in wood biomass after cellulose, and contains many oxygen‐based functional groups, has been proposed as an alternative source of chemical compounds. Guaiacol, a model compound for lignin, was reacted in supercritical water using a batch‐type reactor at temperatures of 653–673 K and various pressures under an argon atmosphere. The effects of temperature and reaction time at the same pressure were combined into a single severity parameter that was used to monitor the decomposition of guaiacol to its derived compounds. The main products in aqueous solution were catechol, phenol, and o‐cresol. The amounts present approached 40.73 wt %, 14.18 wt %, and 4.45 wt %, respectively. With an increase in the reaction time at the same conditions, the amount of guaiacol decreased and the quantity of derived compounds of guaiacol increased. Based on the experimental results, a reaction mechanism for the decomposition of guaiacol was proposed. The process investigated in this study may form the basis for an efficient method of wood biomass decomposition. 相似文献
The chemical reactions between nitrogen dioxide vapour and diphenylamine (DPA), some of its nitro/nitroso derivatives and between their consecutive products have been studied at temperatures of about 23 °C, whereby cellulose was used as substrate material. The following stabilizer compounds were used as starting components: DPA, N‐NO‐DPA, 2‐NO2‐DPA and 4‐NO2‐DPA. Concentration profiles as function of added nitrogen dioxide have been measured by HPLC. These profiles are similar to the ones obtained by accelerated aging, and the typical consecutive stabilizer products have been formed. The profiles are interpreted in terms of possible reactions. Furthermore, the influences of time and light on the decomposition of the mono‐nitro‐N‐nitroso compounds have been investigated. The consequences of these reactions are discussed to explain differences between the storage aging at ambient temperatures and the higher temperature induced accelerated aging. The reactivity towards nitrogen dioxide for each stabilizer compound was obtained by a kinetic model for the decrease of the starting component. 相似文献
The formation of Mannich bases from secondary aliphatic amines and primary alkoxymethyl compounds of urea and melamine in basic media have been studied. The rate of formation of the Mannich base is equal to the rate of decomposition of the alkoxymethyl compound. This is explained by a reaction of the amine with the Schiff base, the intermediate formed during the alkoxymethyl decomposition. In a mixture of primary alkoxymethyl and hydroxymethyl compounds of urea and melamine, the amine reacts almost selectively with the alkoxymethyl compound. An analytical method for the determination of primary dimethylene ether groups of primary alkoxymethyl groups in mixture with hydroxymethyl groups is developed. 相似文献
The reactivity of homogeneous copper catalysts towards the selective C C bond cleavage of both phenolic and non‐phenolic arylglycerol β‐aryl ether lignin model compounds has been explored. Several copper precursors, nitrogen ligands, and solvents were evaluated in order to optimize the catalyst system. Using the optimized catalyst system, copper(I) trifluoromethanesulfonate [Cu(OTf)]/L/TEMPO (L=2,6‐lutidine, TEMPO=2,2,6,6‐tetramethyl‐piperidin‐1‐yl‐oxyl), aerobic oxidation of the non‐phenolic β‐O‐4 lignin model compound proceeded with good selectivity for Cα Cβ bond cleavage, affording 3,5‐dimethoxybenzaldehyde as the major product. Aerobic oxidation of the corresponding phenolic β‐O‐4 lignin model proceeded with different selectivity, affording 2,6‐dimethoxybenzoquinone and α,β‐unsaturated aldehyde products resulting from cleavage of the Cα Caryl bond. At low catalyst concentrations, however, a change in selectivity was observed as oxidation of the benzylic secondary alcohol predominated with both substrates.
The water soluble phthalocyanine complex trisodium tetra-4-sulfonatophthalocyanineiron(III) (Fe(TSPc)) was found to be an effective catalyst for the cleavage of the β-ether bonds in the phenolic lignin model compounds guaiacylglycol β-guaiacyl ether (1) and guaiacylglycerol β-guaiacyl ether (11). The products of these reactions were very different from those formed in the corresponding reactions catalyzed by anthraquinone (AQ) or Co(SPP).1–4 In particular, they gave large quantities of oxidized products, even though the reactions were performed in the absence of oxygen or other added oxidant. Mechanisms have been proposed for the oxidation reactions involving 1 and 11. In both cases the first step involves one electron oxidation of the lignin model compound by the catalyst. The radical derived from 1 then undergoes further one electron oxidation and deprotonation to give 4′-hydroxy-3′-methoxy-l-(2″-methoxyphenoxy)acetophenone (8) whereas that derived from 11 undergoes Cα-Cβ bond cleavage to give vanillin (4). Reactions of the reduced form of the catalyst with 8 and the quinone methides produced from the phenolic models are important routes for guaiacol formation and regeneration of the oxidized form of the catalyst. The feasibility of these proposed reaction pathways was investigated by studying the reactions of the intermediate compounds with the catalyst. 相似文献
Energetic azoles have shown great potential as powerful energetic molecules, which find various applications in both military and civilian fields. This work describes the synthesis, characterization and performance evaluation of two energetic triazole derivatives, viz. N‐(2,4‐dinitrophenyl)‐3‐nitro‐1H‐1,2,4‐triazole ( 1a ) and N‐(2,4‐dinitrophenyl)‐3‐azido‐1H‐1,2,4‐triazole ( 1b ). The compounds were synthesized from 3‐nitro‐1,2,4‐triazole and 3‐azido‐1,2,4‐triazole, by a simple synthetic route and structurally characterized using FT‐IR and NMR (1H, 13C) spectroscopy as well as elemental analysis. Thermal analyses on the molecules were performed using simultaneous TG‐DTA. Both compounds ( 1a , 1b ) showed good thermal stability with exothermic decomposition peaks at 348 °C and 217 °C, respectively, on DTA. The energetic and sensitivity properties of both compounds like friction sensitivities and heats of formation are reported. The heats of combustion at constant volume were determined using oxygen bomb calorimetry and the results were used to calculate the standard molar heats of formation (ΔfHm). The azido derivative ( 1b ) showed a higher positive heat of formation. The thermo‐chemical properties of the compounds as well as the thermal decomposition products were predicted using the REAL thermodynamic code. 相似文献
Burning rate characteristics of the low‐sensitivity explosive 5‐nitro‐1,2,4‐triazol‐3‐one (NTO) have been investigated in the pressure interval of 0.1–40 MPa. The temperature distribution in the combustion wave of NTO has been measured at pressures of 0.4–2.1 MPa. Based on burning rate and thermocouple measurements, rate constants of NTO decomposition in the molten layer at 370–425 °C have been derived from a condensed‐phase combustion model (k=8.08⋅1013⋅exp(−19420/T) s−1. NTO vapor pressure above the liquid (ln P=−9914.4/T+14.82) and solid phases (ln P=−12984.4/T+20.48) has been calculated. Decomposition rates of NTO at low temperatures have been defined more exactly and it has been shown that in the interval of 180–230 °C the decomposition of solid NTO is described by the following expression: k=2.9⋅1012⋅exp(−20680/T). Taking into account the vapor pressure data obtained, the decomposition of NTO in the gas phase at 240–250 °C has been studied. Decomposition rate constants in the gaseous phase have been found to be comparable with rate constants in the solid state. Therefore, a partial decomposition in the gas cannot substantially increase the total rate. High values of the activation energy for solid‐state decomposition of NTO are not likely to be connected with a sub‐melting effect, because decomposition occurs at temperatures well below the melting point. It has been suggested that the abnormally high activation energy in the interval of 230–270 °C is a consequence of peculiarities of the NTO transitional process rather than strong bonds in the molecule. In this area, the NTO molecule undergoes isomerization into the aci‐form, followed by C3‐N2 heterocyclic bond rupture. Both processes depend on temperature, resulting in an abnormally high value of the observed activation energy. 相似文献
The temperature histories of aminoguanidinium 5,5′‐azobis‐1H‐tetrazolate (C4H14N18, AGAT) were measured in order to construct a thermal decomposition model of the compound. The effects of chamber pressure and AGAT particle size were also examined. The results of the study suggest that the thermal decomposition of AGAT occurs in three phases: solid phase, condensed phase, and residue. It was found that the condensed phase consists of decomposition zone I where dramatic temperature rise occurs, decomposition zone II where gradual temperature rise occurs, and the cooling zone where decomposition and temperature stop rising. It was also suggested that the temperature of the decomposition surface which is the interface of the solid phase and the condensed phase was ∼500 K, and that N2 and NH3 were suggested to occur in the vicinity of the decomposition surface of decomposition zone I. In addition, it was suggested that the thickness of the decomposition zones I and II decreases and that the maximum‐temperature‐reached increases with an increase in atmospheric pressure. The rate of decomposition of AGAT was found to follow Vieille's equation and the rate of decomposition increases with an increase in pressure. The rate of decomposition increased slightly with an increase in particle size. 相似文献