NMR study, theoretical calculations for assignment of the<i>Z</i>‐ and<i>E</i>‐isomers, and kinetics investigation of stable phosphorus ylides involving a 2‐mercapto‐4,6‐dimethyl pyrimidine

Zakarianezhad, Mohammad; Habibi‐Khorassani, Sayyed Mostafa; Ebrahimi, Ali; Maghsoodlou, Malek Taher; Ghasempour, Hojjat

doi:10.1002/hc.20632

Cited by 13 publications

(4 citation statements)

References 39 publications

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“…Thus, the reaction between triphenyl phosphite 1, dimethyl acetylenedicarboxylate 2 and 3, 4-dicholoroaniline 3 follows second-order kinetics. The second-order rate constant (k 2 ) is then automatically calculated using a standard equation 35 within the program at 25°C. They are reported in Table 1.…”

Section: Methodsmentioning

confidence: 99%

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A Mechanistic Investigation of Stable Phosphonate Ester Derived from 3, 4 dichloro Aniline: A Kinetics Study and Theoretical Calculations

Habibi‐Khorassani¹,

Maghsoodluo²,

Ebrahimi³

et al. 2012

Orientjchem.

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For the first time, kinetic studies were made of the reactions between triphenyl phosphite 1, dialkyl acetylenedicarboxylates 2 in the presence of NH-acid, such as 3, 4-dicholoro aniline (as a protic/nucleophilic reagent) 3 for the generation of compound 4 with gauche arrangement and [(2S * , 3S * ) or (2R * , 3R * )] configuration. To determine the kinetic parameters of the reaction, monitoring was conducted using UV spectrophotometery. The second order fits were automatically drawn and the values of the second order rate constant (k 2 ) were automatically calculated using standard equations within the program. All reactions were repeated at different temperature ranges, the dependence of the second order rate constant (Ln k 2 ) and (Ln k 2 /T) on the reciprocal temperature were in good agreement with Arrhenius and Eyring equations, respectively. This provided the relevant plots to calculate the kinetic and activation parameters (Ea, ΔH # , ΔS # and ΔG # ) of all reactions. Furthermore, useful information was obtained from studying the of the effect of solvent, structure of reactants (dialkyl acetylenedicarboxylates) and also concentration of reactants on the reaction rates. The proposed mechanism was confirmed according to the obtained results and steady state approximation. The first and third steps (k 2 , k 3 ) of all reactions were recognized as rate determining and a fast steps, respectively on the basis of experimental data. Herein, theoretical calculations have been employed for the assignment of the most stable isomers ([(2S

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Section: Methodsmentioning

confidence: 99%

“…In fact, in recent works triphenyl phosphite has been used instead of triphenylphosphine in the previous work. [33][34][35][36][37][38][39][40][41] In addition, the product is phosphonate esters 4 not phosphorus ylides. Synthesis of compounds 4, shown in Figure 1, has been reported earlier.…”

Section: 3rmentioning

confidence: 99%

A Mechanistic Investigation of Stable Phosphonate Ester Derived from 3, 4 dichloro Aniline: A Kinetics Study and Theoretical Calculations

Habibi‐Khorassani¹,

Maghsoodluo²,

Ebrahimi³

et al. 2012

Orientjchem.

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“…24,25 These compounds also exhibit sedative, 26 antidepressants, 27 antitumor, and antimicrobial activities. 28,29 With wide kinetic studies been done in the synthesis of phosphorus ylides, [30][31][32][33][34] the structural effect of the reactant (different NH-acids and dialkyl acetylenedicarboxylates) on the reaction rate has been well investigated. Changes in the reactant structure that participates in the reaction, eventuates changes in the overall reaction rate.…”

Section: Introductionmentioning

confidence: 99%

Three-component reaction involving isoquinoline and dimethyl acethylenedicarboxylate in the presence of indole: Theoretical and experimental investigations of the reaction mechanism

Zakarianezhad

Habibi‐Khorassani

Makiabadi

et al. 2021

Progress in Reaction Kinetics and Mechanism

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The reaction kinetics among isoquinoline, dimethyl acetylenedicarboxylate, and indole (as NH-acid) were investigated using ultraviolet (UV) spectrophotometry. The reaction rate equation was obtained, the dependence of the reaction rate on different reactants was determined, and the overall rate constant ( kov) was calculated. By studying the effects of solvent, temperature, and concentration on the reaction rate, some useful information was obtained. A logical mechanism consistent with the experimental observations was proposed. Also, comprehensive theoretical studies were performed to evaluate the potential energy surfaces of all structures that participated in the reaction mechanism. Finally, the proposed mechanism was confirmed by the obtained results and the probable and logical reaction paths and also a correct product configuration were suggested based on the theoretical results.

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“…Phosphorus ylides are reactive intermediates, which have been used in many reactions and are involved a lot in the synthesis of organic compounds . In continuation of our investigation on the organophosphorous synthesis by trivalent phosphorus nucleophiles and following the first report for the synthesis of C ‐amino phosphorous ylides by hexamethyl phosphorous triamide , we have recently described the synthesis of new phosphorous ylides from a reaction between hexamethyl phosphorous triamide and dimethyl acetylenedicarboxylate (DMAD) in the presence of N—H acids . Herein, we wish to report a convenient and facial one‐pot, three‐component reaction between hexamethyl phosphorous triamide and DMAD in the presence of C—H acids 3a–d and 5 for the preparation of new and stable phosphorous ylides 4a–d and 1,4‐diionic organophosphorus 7 , respectively, in excellent yields at ambient temperature (Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of New Stable Phosphorus Ylides and 1,4‐Diionic Organophosphorus Compound from a Reaction between Hexamethyl Phosphorous Triamide and Dimethyl Acetylenedicarboxylate in the Presence of CH‐Acids

Ziyaadini

Maghsoodlou

Hazeri

et al. 2012

Heteroatom Chemistry

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A simple and efficient one‐pot three‐component reaction between hexamethyl phosphorous triamide and dimethyl acetylenedicarboxylate (DMAD) in the presence of CH‐acids, such as acetylacetone, 1,3‐indandione, dibenzoylmethane, anthrone, and N,N‐dimethylbarbituric acid, has been studied. In all cases, new and stable phosphorus ylides are obtained in excellent yields. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon–carbon partial double bond, resulting from conjugation of the ylide moiety with the adjacent carbonyl group. From the reaction of N,N‐dimethylbarbituric acid with DMAD in the presence of hexamethyl phosphorous triamide, a 1,4‐diionic organophosphorus compound is obtained. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 24:84–89, 2013; View this article online at http://wileyonlinelibrary.com. DOI 10.1002/hc.21067

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NMR study, theoretical calculations for assignment of theZ‐ andE‐isomers, and kinetics investigation of stable phosphorus ylides involving a 2‐mercapto‐4,6‐dimethyl pyrimidine

Abstract: ABSTRACT:In the present work, NMR, theoretical, kinetics, and mechanism investigations were undertaken for a one-pot condensation reaction between 2-mercapto-4,6-dimethyl pyrimidine and dialkyl

Cited by 13 publications

References 39 publications

A Mechanistic Investigation of Stable Phosphonate Ester Derived from 3, 4 dichloro Aniline: A Kinetics Study and Theoretical Calculations

A Mechanistic Investigation of Stable Phosphonate Ester Derived from 3, 4 dichloro Aniline: A Kinetics Study and Theoretical Calculations

Three-component reaction involving isoquinoline and dimethyl acethylenedicarboxylate in the presence of indole: Theoretical and experimental investigations of the reaction mechanism

Synthesis of New Stable Phosphorus Ylides and 1,4‐Diionic Organophosphorus Compound from a Reaction between Hexamethyl Phosphorous Triamide and Dimethyl Acetylenedicarboxylate in the Presence of CH‐Acids

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