The chemistry of N,N′-dimethylformamidine. I. Formation from potassium methylamide and its thermal stability

1978 ◽  
Vol 56 (11) ◽  
pp. 1455-1462 ◽  
Author(s):  
James D. Halliday ◽  
E. Allan Symons ◽  
J. Douglas Bonnett
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Potassium Salt ◽  
Rate Increase ◽  
Ion Pair ◽  
Concentrated Solutions ◽  
First Order ◽  
Pseudo First Order ◽  
Hydride Elimination ◽  
Rate Limiting

The thermal decomposition of methylamine solutions of potassium methylamide (PMA) to form the potassium salt (PDMFA) of N,N′-dimethylformamidine (DMFA) has been studied as a function of PMA concentration at 60 °C. Although concentrated solutions yield normal pseudo-first-order plots (analysis by ultraviolet–visible spectrophotometry), dilute solutions (< 0.05 mol L−1 PMA) show an increase to a new rate after about 20 h reaction.The mechanism for this novel amidine salt synthesis is discussed in terms of rate-limiting β-hydride elimination from the PMA ion pair. The relatively sharp rate increase with time for the low concentration runs may arise from a slow build up of one or more intermediates. The resulting inverse dependence of kobs on PMA concentration is probably related to ion pair–dimer association phenomena.Pure DMFA has been produced by this reaction, and its thermal stability examined. DMFA decomposes above 100 °C to form bis-N-(N′-methylmethylenimine)methylamine and methylamine; the series of equilibria involved have been shown to be reversible.

Kinetics of reconstitution of apotyrosinase by copper

1990 ◽  
Vol 68 (2) ◽  
pp. 476-479
Author(s):  
Donald C. Wigfield ◽  
Douglas M. Goltz
Keyword(s):  
Rate Constant ◽  
Copper Concentration ◽  
Copper Ions ◽  
Copper Ion ◽  
Order Rate Constant ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Rate Limiting ◽  
Kinetics Of

The kinetics of the reconstitution reaction of apotyrosinase with copper (II) ions are reported. The reaction is pseudo first order with respect to apoenzyme and the values of these pseudo first order rate constants are reported as a function of copper (II) concentration. Two copper ions bind to apoenzyme, and if the second one is rate limiting, the kinetically relevant copper concentration is the copper originally added minus the amount used in binding the first copper ion to enzyme. This modified copper concentration is linearly related to the magnitude of the pseudo first order rate constant, up to a copper concentration of 1.25 × 10−4 M (10-fold excess), giving a second order rate constant of 7.67 × 102 ± 0.93 × 102 M−1∙s−1.Key words: apotyrosinase, copper, tyrosinase.

Kinetic Study on the Esterification of Hexanoic Acid with N,N-Dialkylamino Alcohols: Evidence for an Activation by Hydrogen Bonding

2006 ◽  
Vol 61 (5) ◽  
pp. 583-588 ◽  
Author(s):  
Stefan Breitenlechner ◽  
Thorsten Bach
Keyword(s):  
Hydrogen Bonding ◽  
Rate Increase ◽  
Order Rate Constant ◽  
Hexanoic Acid ◽  
Hydroxyl Groups ◽  
First Order ◽  
Moderate Rate ◽  
Pseudo First Order ◽  
Related Compounds ◽  
Membered Transition State

The pseudo-first order rate constant for the esterification of hexanoic acid (1) and five different N,N-dialkylamino alcohols (2) was determined in comparison to 1-hexanol (k = 0.67 · 10−5 s−1). The values range from 0.60 · 10−5 s−1 to 9.3 · 10−5 s−1. The data suggest a differing reactivity for structurally related compounds, which is directly correlated to the ability of the corresponding amino alcohol to activate the carboxylic acid by hydrogen bonding. A seven-membered transition state C≠ is postulated for reactions of 2-amino alcohols. The fastest reaction was observed for trans-2-(N,N-dimethylamino) cyclohexanol (2e), in which the amino and the hydroxyl groups are in an almost perfect synperiplanar 1,2-position. Attempts to further enhance the rate of the esterification by the addition of potential catalysts failed. Only Cu(OTf)2 (2.5 mol-%) allowed for a moderate rate increase from 7.5 · 10−5 s−1 (uncatalyzed) to 14.8 · 10−5 s−1 (catalyzed) in the esterification of hexanoic acid (1) with 2-(N,N-dimethylamino)ethanol (2a).

Sorption of Pb2+ on Mg-Al-Fe Hydrotalcite-Like Compounds

2012 ◽  
Vol 573-574 ◽  
pp. 86-91
Author(s):  
Xue Feng Liang ◽  
Wan Guo Hou ◽  
Ying Ming Xu ◽  
Lin Wang ◽  
Yue Bing Sun
Keyword(s):  
Kinetic Model ◽  
Rate Increase ◽  
Freundlich Isotherm ◽  
Order Kinetic ◽  
Sorption Mechanism ◽  
Chemical Binding ◽  
First Order ◽  
Maximum Sorption ◽  
Order Kinetic Model ◽  
Pseudo First Order

Hydrotalcite-like compounds containing Mg2+, Al3+ and Fe3+ with a constant M2+/M3+ ratio but varying Al3+/Fe3+ ratios have been prepared. The effects of iron contents on the structural and sorption of Pb2+ by Mg-Al-Fe HTlc samples were investigated. The maximum sorption amounts were about 88-201 mg/g for Mg-Al-Fe HTlc samples. The sorption isotherm and kinetic processes can be described with Freundlich isotherm and pseudo first order kinetic model, respectively. The sorption amounts and rate increase with the increase of iron contents in HTlc samples. The sorption mechanism of Pb2+ on Mg-Al-Fe HTlcs may be the surface-induced precipitation and chemical binding adsorption.

scholarly journals The carboxybiotin complex of pyruvate carboxylase. A kinetic analysis of the effects of Mg2+ ions on its stability and on its reaction with pyruvate

1984 ◽  
Vol 219 (1) ◽  
pp. 243-251 ◽  
Author(s):  
P V Attwood ◽  
J C Wallace ◽  
D B Keech
Keyword(s):  
Pyruvate Carboxylase ◽  
General Scheme ◽  
Order Rate Constant ◽  
Enzymic Activity ◽  
Slow Phase ◽  
First Order ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Pseudo First Order ◽  
Rate Limiting

The enzyme-[14C] carboxybiotin complex of sheep liver pyruvate carboxylase was isolated and the reaction between this and pyruvate was studied by using the quenched-flow rapid-reaction technique. At 0.5 degrees C the reaction was 80% complete within 180 ms. The reaction was monophasic and obeyed pseudo-first-order kinetics. Increasing concentrations of Mg2+ caused a decrease in the magnitude of the observed pseudo-first-order rate constant. Throughout the carboxylation of pyruvate, the rate-limiting step of the reaction occurred after the dissociation of carboxybiotin from the first sub-site, whereas in the slow phase of the reaction with 2-oxobutyrate this dissociation is the rate-limiting step. It is possible, from the reaction scheme proposed, that the inhibition of overall enzymic activity by high concentrations of Mg2+ could be caused by the transfer of the carboxy group from biotin to pyruvate becoming rate-limiting. The efficacy of a substrate as a signal for the movement of carboxybiotin from the first sub-site is reflected by the amount that the effective affinity of the enzyme- carboxybiotin complex for Mg2+ is lowered. In the presence of the substrates tested, the affinities of the carboxybiotin complex can be arranged in order of increasing magnitude, i.e.: (formula; see text). The kinetics of the decay of the enzyme-[14C] carboxybiotin complex at 0 degree C in the absence of substrates are similar to the reaction with pyruvate except that the carboxybiotin is also unstable in the first sub-site, to some degree. This similarity allows for the proposal of a general scheme for the decarboxylation of the enzyme- carboxybiotin complex in the presence or in the absence of substrates.

Thermal Decomposition of Aromatic Thioureas [1]

1986 ◽  
Vol 41 (1) ◽  
pp. 101-104 ◽  
Author(s):  
Cyril Párkányi ◽  
Mohammed A. Al-Salamah
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Transfer ◽  
Chemical Reactivity ◽  
Order Reaction ◽  
First Order ◽  
Reactivity Indices ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Intramolecular Hydrogen ◽  
Rate Limiting

Thermal decomposition of aromatic and heteroaromatic thioureas in boiling chlorobenzene is a first-order reaction. The reaction involves intramolecular hydrogen transfer followed by a cleavage of the C - N bond which is the rate-limiting step. The rate constants of decom position have been determined and correlated with quantum-chemical reactivity indices.

Mechanism of SNi reactions. The effect of the base strength of the anionic fragments

1978 ◽  
Vol 56 (19) ◽  
pp. 2582-2589 ◽  
Author(s):  
D. J. Verrinder ◽  
M. J. Hourigan ◽  
J. M. Prokipcak
Keyword(s):  
Thermal Decomposition ◽  
Optical Activity ◽  
Ion Pair ◽  
Decomposition Rates ◽  
First Order ◽  
First Order Kinetics ◽  
Cyclic Mechanism ◽  
Base Strength ◽  
Oxygen Bond ◽  
Anionic Fragment

The kinetics and stereochemical aspects of the thermal decomposition of aralkyl carbonates, thiocarbonates, and carbamates were examined. The rates for the decompositions as well as the rates of loss of optical activity followed first-order kinetics. The decompositions appear to involve the heterolysis of the aralkyl–oxygen bond followed by the breakdown of the subsequent ion pair via a cyclic mechanism. However, it was found that this ion pair could return to covalency without completely decomposing to products leading to the racemization of the starting materials. This type of racemization occurred more readily in the case of the carbamates than in the thiocarbonates and carbonates. The dependence of the decomposition rates and the loss of optical activity on the nature of the hetero atom of the anionic fragment of the starting material is discussed.

Polychloroalicyclic Ketones as Promoters for Crosslinking Polymers

1970 ◽  
Vol 43 (2) ◽  
pp. 171-187 ◽  
Author(s):  
E. Morita
Keyword(s):  
Thermal Stability ◽  
High Reactivity ◽  
Specific Rate ◽  
Curing Process ◽  
First Order ◽  
Pseudo First Order ◽  
Accelerator System ◽  
Curing Systems

Abstract Polychloroalicyclic ketones are chlorine liberating compounds which in combination with activators and coagents promote crosslinking of saturated and unsaturated polymers. One of the most active ketone is octachloro-3-cyclohexen-l-one (OCTA). During the curing process the alicyclic ketones transform into phenols and probably some phenates. The most effective activators are magnesium and calcium hydroxides and oxides. These curing systems are also activated by acidic and basic fillers. Active coagents are sulfur, p-benzoquinones and maleimides. EPM of superior thermal stability is obtained with the chlorinated p-benzoquinones as the coagent. The apparent order of crosslink formation in EPM using these curing systems is pseudo first order. In case of OCTA/MgO/coagent system, the specific rate of crosslink formation is directly proportional to (MgO)1/2/(OCTA) and the maximum crosslinks formed vary linearly with (MgO)1/2/(OCTA). The OCTA system is most suitable for curing saturated polymers or their blends, and not for black stocks of high unsaturation polymers because of its high reactivity. Saturated polymers may be heated with OCTA and MgO and modified to unsaturated polymers which are curable by the conventional sulfur-accelerator system.

In-vitro Kinetic Hydrolysis Study of Metronidazole Derivatives with Carvacrol and Eugenol Using Validated RP-HPLC Method

2020 ◽  
Vol 16 ◽  
Author(s):  
M. Alarjah
Keyword(s):  
Half Life ◽  
Hplc Method ◽  
Hydrolysis Rate ◽  
First Order ◽  
First Order Kinetics ◽  
Rp Hplc ◽  
Pharmacokinetic Properties ◽  
Pseudo First Order ◽  
Kinetic Hydrolysis

Background: Prodrugs principle is widely used to improve the pharmacological and pharmacokinetic properties of some active drugs. Much effort was made to develop metronidazole prodrugs to enhance antibacterial activity and or to improve pharmacokinetic properties of the molecule or to lower the adverse effects of metronidazole. Objective: In this work, the pharmacokinetic properties of some of monoterpenes and eugenol pro metronidazole molecules that were developed earlier were evaluated in-vitro. The kinetic hydrolysis rate constants and half-life time estimation of the new metronidazole derivatives were calculated using the validated RP-HPLC method. Method: Chromatographic analysis was done using Zorbbax Eclipse eXtra Dense Bonding (XDB)-C18 column of dimensions (250 mm, 4.6 mm, 5 μm), at ambient column temperature. The mobile phase was a mixture of sodium dihydrogen phosphate buffer of pH 4.5 and methanol in gradient elution, at 1ml/min flow rate. The method was fully validated according to the International Council for Harmonization (ICH) guidelines. The hydrolysis process carried out in an acidic buffer pH 1.2 and in an alkaline buffer pH 7.4 in a thermostatic bath at 37ºC. Results: The results followed pseudo-first-order kinetics. All metronidazole prodrugs were stable in the acidic pH, while they were hydrolysed in the alkaline buffer within a few hours (6-8 hr). The rate constant and half-life values were calculated, and their values were found to be 0.082- 0.117 hr-1 and 5.9- 8.5 hr., respectively. Conclusion: The developed method was accurate, sensitive, and selective for the prodrugs. For most of the prodrugs, the hydrolysis followed pseudo-first-order kinetics; the method might be utilised to conduct an in-vivo study for the metronidazole derivatives with monoterpenes and eugenol.

Non-Isothermal Decomposition Kinetic of Polypropylene/Hydrotalcite Composite

2019 ◽  
Vol 19 (11) ◽  
pp. 7493-7501 ◽  
Author(s):  
Sheng Xu ◽  
Min Zhang ◽  
Siyu Li ◽  
Moyu Yi ◽  
Shigen Shen ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Nitrogen Atmosphere ◽  
Heating Rates ◽  
Decomposition Reactions ◽  
Kinetic And Thermodynamic Parameters ◽  
Málek Method ◽  
Boundary Reaction ◽  
Phase Boundary Reaction ◽  
Thermal Stability Of

P3O5-10 pillared Mg/Al hydrotalcite (HTs) as a functional fire-retarding filler was successfully prepared by impregnation-reconstruction, where the HTs was used to prepare polypropylene (PP) and HTs composite (PP/HTs). Thermal decomposition was crucial for correctly identifying the thermal behavior for the PP/HTs, and studied using thermogravimetry (TG) at different heating rates. Based on single TG curves and Málek method, as well as 41 mechanism functions, the thermal decompositions of the PP/HTs composite and PP in nitrogen atmosphere were studied under non-isothermal conditions. The mechanism functions of the thermal decomposition reactions for the PP/HTs composite and PP were separately “chemical reaction F3” and “phase boundary reaction R2,” which were also in good agreement with corresponding experimental data. It was found that the addition of the HTs increased the apparent activation energy Ea of the PP/HTs comparing to the PP, which improved the thermal stability of the polypropylene. A difference in the set of kinetic and thermodynamic parameters was also observed between the PP/HTs and PP, particularly with respect to lower ΔS≠ value assigned to higher thermal stability of the PP/HTs composite.

scholarly journals MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses

2020 ◽  
Vol 10 (1) ◽  
pp. 001-010 ◽  
Author(s):  
Nikoletta Harsági ◽  
Betti Szőllősi ◽  
Nóra Zsuzsa Kiss ◽  
György Keglevich
Keyword(s):  
Ionic Liquids ◽  
Alkaline Hydrolysis ◽  
Alkyl Group ◽  
Phosphinic Acid ◽  
Reaction Times ◽  
Alternative Possibility ◽  
First Order ◽  
Pseudo First Order ◽  
Mw Irradiation ◽  
Hydrolysis Of

Abstract The optimized HCl-catalyzed hydrolysis of alkyl diphenylphosphinates is described. The reaction times and pseudo-first-order rate constants suggested the iPr > Me > Et ∼ Pr ∼ Bu order of reactivity in respect of the alkyl group of the phosphinates. The MW-assisted p-toluenesulfonic acid (PTSA)-catalyzed variation means a better alternative possibility due to the shorter reaction times, and the alkaline hydrolysis is another option. The transesterification of alkyl diphenylphosphinates took place only in the presence of suitable ionic liquids, such as butyl-methylimidazolium hexafluorophosphorate ([bmim][PF6]) and butyl-methylimidazolium tetrafluoroborate ([bmim][BF4]). The application of ethyl-methylimidazolium hydrosulfate ([emim][HSO4]) and butyl-methylimidazolium chloride ([bmim][Cl]) was not too efficient, as the formation of the ester was accompanied by the fission of the O–C bond resulting in the formation of Ph2P(O)OH. This surprising transformation may be utilized in the phosphinate → phosphinic acid conversion.

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