Structural effects on kinetics and a mechanistic investigation of the reaction between DMAD and N–H heterocyclic compound in the presence of triphenylarsine: spectrophotometry approach
© The Author(s) 2017
Received: 16 August 2016
Accepted: 12 July 2017
Published: 1 August 2017
Kinetics and a mechanistic investigation of the reaction between dimethyl acetylenedicarboxcylate (DMAD) and saccharin (N–H heterocyclic compound) has been spectrally studied in methanol environment in the presence of triphenylarsine (TPA) as a catalyst. Previously, in a similar reaction, triphenylphosphine (TTP) (instead of triphenylarsine) has been employed as a third reactant (not catalyst) for the generation of an ylide (final product) while, in the present work the titled reaction in the presence of TPA leaded to the especial N-vinyl heterocyclic compound with different kinetics and mechanism. The reaction followed second order kinetics. In the kinetic study, activation energy and parameters (Ea, ΔH‡, ΔS‡ and ΔG‡) were determined. Also, the structural effect of the N–H heterocyclic compound was investigated on the reaction rate. The result showed that reaction rate increases in the presence of isatin (N–H compound) that participates in the second step (step2), compared to saccharin (another N–H compound). This was a good demonstration for the second step (step2) of the reaction that could be considered as the rate- determining step (RDS). As a significant result, not only a change in the structure of the reactant (TPA instead of TPP) creates a different product, but also kinetics and the reaction mechanism have been changed.
Experimental chemicals and apparatuses used
All acquired chemicals were used without further purification. Dimethyl acetylenedicarboxcylate (1), triphenylarsine (2) saccharin and isatin as the two N–H heterocyclic compounds were supplied by Merck (Darmstadt, Germany), Acros (Geel, Belgium) and Fluka (Buchs, Switzerland). Extra pure methanol and ethanol were also obtained from Merck (Darmstadt, Germany). A Cary UV–vis spectrophotometer model Bio-300 with a 10 mm light-path quartz spectrophotometer cell equipped with a thermostated housing cell was used to record the absorption spectra in order to the follow reaction kinetics.
Results and discussion
From the later experiment, c, is one.
So, order of reaction with respect to DMAD (1) is one (a = 1).
Effects of solvents and temperature
The two parameters, dielectric constant and polarity of solvent influence the relative stabilization of the reactants and the corresponding transition state in the solvent environment which in turn effects the rate of the reaction [24, 25]. For examining the effect of the solvent on the rate of reaction, the same kinetic procedure is followed in the presence of ethanol at 18 °C.
The reaction rate is increased in methanol (k ovr = 3.0 min1 M−2) compared to ethanol (k ovr = 0.74 min1 M−2) as the dielectric constant decreased from 32.7 to 24.5 , respectively.
Effect of temperature
Reaction rate constants (k ovr min1 M−2) at different temperatures (± 0.1) under the same conditions for the reaction between (1) (10−2 M), (2) (5 × 10−3 M) and N–H compound (10−2 M)
18 °C ± 0.1
The Gibbs activation energy is essentially the energy requirement for a molecule (or a mole of them) to undergo the reaction. It is of interest to note that the Gibbs activation energy is positive. The Gibbs activation energy changed with enthalpy and entropy. Sometimes ∆H‡ is the main provider, and sometimes T∆S‡ consider the main provider in Eq. 5 that refer to enthalpy or entropy-controlled reaction, respectively.
As can be seen from the Table 2, T∆S‡ (51.17 kJ mol−1K−1) is much greater than ∆H‡ (17.5 kJ mol−1) which implies that the reaction is entropy-controlled.
Effect of N–H compounds
The rate of reaction speeds up in comparison with saccharin. This experiment indicated that N–H compounds (saccharin or isatin) participated in the rate-determining step (RDS) of the reaction mechanism (step2).
To investigate which step of the reaction mechanism is a rate determining step (RDS), further experiments were performed as follows:
Equation 9 is a rate law for the first-order kinetic reaction that is not agreement with the experiment results (Eq. 1). The acceptable rate law, Eq. 8, involving N–H compound and compound (1) is a rate determining step which depends on the concentration of N–H compound. In previous section, can be seen that the different structures of N–H compound (containing saccharin or isatin) with their different ability of acidity and geometries had a great effect on step2 (k2).
Kinetics for the formation of the N-vinyl heterocyclic compounds was examined in the presence of triphenylarsine (TPA) as a catalyst, (DMAD) and N–H heterocyclic compound in methanol using UV–vis spectrophotometer technique. The results demonstrated that the overall order of the reaction is two and the partial orders with regard to each reactant (1) or N–H heterocyclic compound is one.
Previously, in a similar reaction, with triphenylphosphine (TPP) (instead of triphenylarsine (TPA) in the current work), the generated product was an ylide, while in this work is a N-vinyl heterocyclic compound.
Different behavior of both reactants (TPP or TPA) provides a different mechanism and kinetics for both the previous or present works.
In the previous work, the reaction followed second-order kinetics and step1 of reaction was recognized as a rate determining step. The rate law depended on concentration of (DMAD) and (TPP) and was independent of concentration of N–H heterocyclic compound, while in present work, step2 of the reaction is a rate determining step (RDS) and the rate law depends on concentrations of both (DMAD) and N–H heterocyclic compound. Herein (TPA) has a catalyst role in the reaction medium.
In the present work, the structural effect of N–H heterocyclic compound on the reaction rate was investigated in the presences of isatin as another N–H compound that participates in the second step (step2), compared to saccharin. This is a good demonstration for the second step of the reaction (step2) that could be considered the RDS.
Reaction rate is accelerated by increasing the temperature and the dielectric constant of solvent.
Also, enhancement of the steric effect on the structure of solvent from methanol to ethanol can be considered as an effective factor for a proton transfer process between N–H heterocyclic compound and intermediate I 1 . Less hindrance in methanol has a great effect on enhancement of the reaction rate, compared to ethanol.
The reaction is entropy-controlled (T∆S‡ is much greater than ∆H‡).
SMH-K and MSH conceived and designed the experiments. SMH-K contributed reagents/materials/analysis tools. MD performed the experiments. SMH-K and MS analyzed the data. MD wrote the paper. All authors read and approved the final manuscript.
We gratefully acknowledge the financial support provided by the Research Council of the University of Sistan and Baluchestan.
The authors declare that they have any no competing interests.
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