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.
KeywordsKinetics Mechanism Catalyst N-vinyl heterocyclic
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.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.
- Melo TM (2009) Synthesis of functionalized N-vinyl nitrogen-containing heterocycles. Synthesis 2009:2403View ArticleGoogle Scholar
- Dengre R, Bajpai M, Bajpai S (2000) Release of vitamin B12 from poly (N‐vinyl‐2‐pyrrolidone)‐crosslinked polyacrylamide hydrogels: A kinetic study. J Appl Polym Sci 76:1706View ArticleGoogle Scholar
- Kabir MS, Lorenz M, Namjoshi OA, Cook JM (2009) First application of an efficient and versatile ligand for copper-catalyzed cross-coupling reactions of vinyl halides with N-heterocycles and phenols. Org Lett 12:464View ArticleGoogle Scholar
- Maghsoodlou MT, Heydari R, Habibi-Khorassani SM, Hazeri N, Lashkari M, Rostamizadeh M, Sajadikhah SS (2011) Triphenylarsine as an efficient catalyst in diastereospecific synthesis of N-vinyl heterocyclic compounds. Synth Commun 41:569View ArticleGoogle Scholar
- Abdel-Malek HA, Ewies EF (2013) State of the art on chemistry and applications of organoarsenic compounds. Am J Res Commun 1(12):268–325Google Scholar
- D’Ascenzio M, Carradori S, De Monte C, Secci D, Ceruso M, Supuran CT (2014) Design, synthesis and evaluation of N-substituted saccharin derivatives as selective inhibitors of tumor-associated carbonic anhydrase XII. Bioorg Med Chem 22:1821View ArticleGoogle Scholar
- Da Silva JF, Garden SJ, Pinto AC (2001) The chemistry of isatins: a review from 1975 to 1999. J Braz Chem Soc 12:273View ArticleGoogle Scholar
- Gençer N, Demir D, Sonmez F, Kucukislamoglu M (2012) New saccharin derivatives as tyrosinase inhibitors. Bioorg Med Chem 20:2811View ArticleGoogle Scholar
- Singh VK, Sharma LK, Singh RKP (2016) Iron mediated one pot three component synthesis of 3-substituted indoles via aerobic iminium ion formation. Tetrahedron Lett 57:407View ArticleGoogle Scholar
- Ziyaadini M, Maghsoodlou MT, Hazeri N, Habibi-Khorassani SM (2012) Novel synthesis of stable 1,5-diionic organophosphorus compounds from the reaction between triphenylphosphine and acetylenedicarboxylic acid in the presence of N–H heterocyclic compounds. Monatshefte für Chemie-Chem Mon 143:1681View ArticleGoogle Scholar
- Ramazani A, Motejadded AA, Ahmadi E (2006) Microwave-induced stereoselective conversion of dialkyl 2-(1, 1, 3-trioxo-1, 3-dihydro-2 H-1, 2-benzisothiazol-2-yl)-3-(triphenylphosphoranylidene) succinates to dialkyl 2-(1, 1, 3-trioxo-1, 3-dihydro-2 h-1, 2-benzisothiazol-2-yl)-2-butendioates in the presence of silica-gel powder in solvent-free conditions. Phosphorus Sulfur Silicon 181:233View ArticleGoogle Scholar
- Yavari I, Bayat M (2002) Triphenylphosphine-catalyzed simple synthesis of vinyl-substituted saccharins. Phosphorus Sulfur Silicon Relat Elem 177:2537View ArticleGoogle Scholar
- Lloyd D, Gosney I, Ormiston RA (1987) Ormiston, Arsonium ylides (with some mention also of arsinimines, stibonium and bismuthonium ylides). Chem Soc Rev 16:45View ArticleGoogle Scholar
- Yaozeng H, Yanchang S (1982) Arsonium ylides (with some mention also of arsinimines, stibonium and bismuthonium ylides). Adv Organomet Chem 20:115View ArticleGoogle Scholar
- Khorassani SH, Maghsoodlou M, Ebrahimi A, Zakarianejad M, Fattahi M (2007) Kinetics and mechanism of the reactions between triphenylphosphine, dialkyl acetylenedicarboxilates and a NH-acid, pyrazole, by UV spectrophotometry. J Sol Chem 36:1117View ArticleGoogle Scholar
- Khorassani S, Maghsoodlou M, Ebrahimi A, Roohi H, Zakarianezhad M, Moradian M (2005) Kinetic investigation of the reactions between triphenylphosphine, dialkyl acetylenedicarboxylates and SH-acid such as 2-thiazoline-2-thiol or 2-mercaptobenzoxazole by UV spectrophotometry. Prog React Kinet 30:127View ArticleGoogle Scholar
- Zakarianejad M, Ghasempour H, Habibi-Khorassani SM, Maghsoodlou MT, Makiabadi B, Nassiri M, Ghahghayi Z, Abedi A (2013) Theoretical study, synthesis, kinetics and mechanistic investigation of a stable phosphorus ylide in the presence of methyl carbamate as a NH-acid. ARKIVOC 4:171Google Scholar
- Khorassani SMH, Maghsoodlou MT, Ghasempour H, Zakarianezhad M, Nassiri M, Ghahghaie Z (2013) AIM analysis, synthetic, kinetic and mechanistic investigations of the reaction between triphenylphosphine and dialkyl acetylenedicarboxylate in the presence of 3-methoxythiophenol. J Chem Sci 125:387View ArticleGoogle Scholar
- Mostafa Habibi-Khorassani S, Ebrahimi A, Taher Maghsoodlou M, Zakarianezhad M, Ghasempour H, Ghahghayi Z (2011) Theoretical, NMR study, kinetics and a mechanistic investigation of the reaction between triphenylphosphine, dialkyl acetylenedicarboxylates and 2-aminothiophenol. Curr Org Chem. 15:942View ArticleGoogle Scholar
- Habibi-Khorassani SM, Ebrahimi A, Maghsoodlou MT, Kazemian MA, Moradian M (2010) Kinetics and mechanism investigation of the reaction between triphenylphosphine, di-tert-butyl acetylenedicarboxilate and OH-acid. Chin J Chem 28:719View ArticleGoogle Scholar
- Khorassani SH, Maghsoodlou M, Ebrahimi A, Roohi H, Zakarianezhad M (2007) Kinetic investigation of the reactions between triphenylphosphine, dialkyl acetylenedicarboxylates and NH-acid such as 7-azaindole by the UV spectrophotometry. Indian J Chem 46:783Google Scholar
- Khorassani SH, Maghsoodlou M, Ebrahimi A, Mohammadzadeh P, Zakarianezhad M, Fattahi M (2007) Kinetic investigation of the reactions between triphenylphosphine, dialkylacetylenedicarboxilates and nh-acid, such as 5,6-dimethylbenzimidazole by theUV spectrophotometry technique. Sci Iran 14:133Google Scholar
- Schwartz LM, Gelb RI (1978) Alternative method of analyzing first-order kinetic data. Anal Chem 50:1592View ArticleGoogle Scholar
- Cerveny L, Ruzicka V (1981) Solvent and structure effects in hydrogenation of unsaturated substances on solid catalysts. Adv Catal Relat Subj 30:335View ArticleGoogle Scholar
- Mortimer M (2002) Chemical kinetics and mechanism. Royal Society of Chemistry, LondonView ArticleGoogle Scholar
- Reichardt C, Welton T (2011) Solvents and solvent effects in organic chemistry. Wiley, New YorkGoogle Scholar
- Glasstone S, Laidler KJ, Eyring H (1941) The theory of rate processes: the kinetics of chemical reactions, viscosity, diffusion and electrochemical phenomena. McGraw-Hill Book Company, ChennaiGoogle Scholar
- Lente G, Fábián I, Poë AJ (2005) A common misconception about the eyring equation. New J Chem 29:759View ArticleGoogle Scholar
- Okubo T, Maeda Y, Kitano H (1989) A precision conductance apparatus for studying fast ionic reactions in solution. J Phys Chem 93:3721View ArticleGoogle Scholar
- Tregloan P, Laurence G (1965) A precision conductance apparatus for studying fast ionic reactions in solution. J Sci Instrum 42:869View ArticleGoogle Scholar
- Wolff MA (1974) The adaptation of the aminco morrow stopped-flow apparatus for conductivity measurements. Instrum Sci Technol 5(1):59–64View ArticleGoogle Scholar