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Kinetics and mechanism of the reaction between substituted benzoyl chlorides (1) and ammonium thiocyanate (2) were investigated theoretically and experimentally using the DFT method at M062x/6‐311G++(2d,2p) level of theory and UV-vis spectrophotometry technique, respectively. The reaction followed second‐order kinetics according to the effect of concentration on the reaction rate. The solvent effect demonstrates that media with the lower dielectric constant is in favour of the reaction rate. On the basis of the Eyring plot, activation parameters were determined in a lower dielectric constant solvent such as 1,4 dioxane, the low value of ∆G‡ (58.7 kJ mol-1) in this solvent relation to polar solvent, help to increase the reaction rate. In fact, unfavourable ∆S‡ value (-188.18 J mol-1 K-1) can be compensated by the favourable ∆H‡ value (lower, 4.01 kJ mol-1). In this case, the reaction is entropy controlled, while in the polar solvent (acetonitrile), the unfavourable ∆H‡ value (higher, 45.6 kJ mol-1) can be compensated by the favourable ∆S‡ value (-80.9 J mol-1 K-1), so the reaction is enthalpy-controlled. Different substituents examined on the reaction rate in both methods. The rate constant was in favour of strong para electron-withdrawing substituent (EWS) groups (i.e. NO2) on benzoyl chloride. A comparison of theoretical and experimental rate constant values in both methods indicated differences between data. This is expected, because of the real liquid phase (for experimental results) has a great difference from the unlike liquid phase (for theoretical data). Hammet study, exhibited that the large value of ρ=1.94 imply that TS structure is constructed with negative charges; hence, EWS plays a significant role in stabilizing TS character for increasing the reaction rate. The result of this study confirmed that the reactions in the presence of various para-substituted benzoyl chlorides have the same kinetics role. Also, the effect of leaving group was studied on the reaction between (1) and (2), theoretically. The result showed that the reaction rate in the presence of benzoyl bromide has been increased approximately 25 times more in the gas phase and also 170 times more in a liquid phase, compared to benzoyl chloride. A linear dependence of ΔH‡ versus ΔS‡ approved based on the isokinetic and Exner equations, so the reaction exhibited the same kinetics role in the different solvents.
Cho HJ, Lim DY, Kwon GT, Kim JH, Huang Z, Song H, Oh YS, Kang Y-H, Lee KW, Dong Z. Benzyl isothiocyanate inhibits prostate cancer development in the transgenic adenocarcinoma mouse prostate (TRAMP) model, which is associated with the induction of cell cycle G1 arrest. Int J Mol Sci. 2016;17: 264-273.
Kim M, Lee H. Growth‐Inhibiting Activities of Phenethyl Isothiocyanate and Its Derivatives against Intestinal Bacteria. J Food Sci. 2009; 74:467-471.
Bedane KG, Singh GS. Reactivity and diverse synthetic applications of acyl isothiocyanates. Arkivoc. 2015;206-245.
Ian Derek K, Nigel Simon S. ABC Transporters and Isothiocyanates. Lett Drug Des Discov. 2006;3:607-621.
Curt W, Justin JF, Rainer K. Amino-, Alkoxy-, and Alkylthio-Isocyanates and – Isothiocyanates, RX-NCY, their Isomers RX-YCN and RX-CNY, and their Rearrangements. Curr Org Chem. 2011;15:1745-1759.
Andrea M, Carmela F, Nicole T, Paolo N, Anna M, Vincenzo T. Isothiocyanate synthetic analogs: Biological activities, structure-activity relationships and synthetic strategies. Mini-Rev Med Chem. 2014;14:963-977.
Conaway CC, Yang-ming Y, Fung-lung C. Isothiocyanates as cancer chemopreventive agents: Their biological activities and metabolism in rodents and humans. Curr Drug Metab. 2002;3:233-255.
Keum YS, Jeong WS, Kong ANT. Chemopreventive functions of isothiocyanates. Drug News Perspect. 2005;18:445-451.
Fimognari C, Lenzi M, Hrelia P. Chemoprevention of Cancer by Isothiocyanates and Anthocyanins: Mechanisms of Action and Structure-Activity Relationship. Curr med chem.. 2008;15:440-447.
Seyyedeh Zahra SA, Zinatossadat H, Faramarz R-C, Hadi SG. Solvent-Free Synthesis of Functionalized Thiazoles Using Multicomponent Reaction of Isothiocyanates. Comb Chem High Throughput Screen. 2013; 16:758-761.
El-Sharkawy KA, El-Sehrawi HM, Ibrahim RA. The Reaction of 2-Amino-4, 5, 6, 7-tetrahydrobenzo [b] thiophenes with Benzoyl-Isothiocyanate: Synthesis of Annulated Thiophene Derivatives and Their Antitumor Evaluations. Int J Org Chem. 2012;2:126.
Zheng H, Mei YJ, Du K, Cao XT, Zhang PF. One-Pot Chemoenzymatic Multicomponent Synthesis of Thiazole Derivatives. Molecules. 2013;18:13425-13433.
Almstead NG, Bradley RS, Pikul S, De B, Natchus MG, Taiwo YO, Gu F, Williams LE, Hynd BA, Janusz MJ. Design, synthesis, and biological evaluation of potent thiazine-and thiazepine-based matrix metalloproteinase inhibitors. J Med Chem. 1999;42:4547-4562.
Heydari R, Shahrekipour F, Graiff C. Synthesis and crystal structures of Some pyridyl aminothiazole and Thiazolidin-2-ylidene Benzamide Derivatives. Lett Org Chem. 2016; 13:263-271.
Sharma S. Isothiocyanates in Heterocyclic Synthesis. J Sulfur. 1989;8:327-454.
Joanna S, Karolina S, Anna B, Daniel S, Barbara M, Anna EK, Giuseppina S, Filippo I, Silvia M, Michal J, Marta S. Antimicrobial and Anti-biofilm Activity of Thiourea Derivatives Bearing 3-amino-1H-1,2,4-triazole Scaffold. Medicinal Chemistry. 2016;12:478-488.
Lucia CdSA, Gil MV, Marcus VdSR, Marcio VC, Bruno SB. A simple and green procedure for the synthesis of N-Benzylthioureas. Lett. Org. Chem. 2011;8:540-544.
Faramarz RC, Asadollah H, Zinatossadat H. Microwave-assisted multicomponent reactions of alkyl bromides: Synthesis of thiophene derivatives. Comb. Chem. High Throughput Screen. 2012;15:822-825.
Hamid AMA. Addition–cyclization reactions of furan-2-carbonyl isothiocyanate with nitrogen nucleophiles as a synthetic route to novel azines and azoles of potential biological activity. J Iran Chem Soc. 2019;16:1853–1861.
Umape PG, Patil VS, Padalkar VS, Phatangare KR, Gupta VD, Thate AB, Sekar N. Synthesis and characterization of novel yellow azo dyes from 2-morpholin-4-yl-1, 3-thiazol-4 (5H)-one and study of their azo–hydrazone tautomerism. Dyes Pigm. 2013;99:291-298.
Hossaini M, Heydari R, Maghsoodlou MT, Kolahdoozan M, Graiff C. Synthesis and crystal structures of novel (4‐phenylthiazol‐2 (3H)‐ylidene) benzamide and ((benzoylimino)‐3‐(9, 10‐dioxo‐9, 10‐dihydroanthracen‐1‐yl)‐4‐oxothiazolidin‐5‐ylidene) acetate derivatives. Heteroat Chem. 2017;28:e21409.
Hossaini M, Heydari R, Maghsoodlou MT, Graiff C. Novel (4-oxothiazolidine-2-ylidene) benzamide derivatives: Synthesis, characterization and crystal structures. Res. Chem. Intermed. 2017;43:4189-4199.
Kodomari M, Suzuki M, Tanigawa K, Aoyama T. A convenient and efficient method for the synthesis of mono-and N, N-disubstituted thioureas. Tetrahedron letters. 2005;46:5841-5843.
Entezari N, Akhlaghinia B, Rouhi-Saadabad H. Direct and facile synthesis of acyl isothiocyanates from carboxylic acids using trichloroisocyanuric acid/triphenylphosphine system. Croat Chem Acta. 2014;87:201-206.
Deng M-Z, Caubere P, Senet J, Lecolier S. Condensation of acyl chloride on sodium cyanate: Preparation of acyl isocyanates. Tetrahedron. 1988;44:6079-6086.
Wen-Bing Y, Mei-Jung L, Chung-Ming S. Combinatorial synthesis of biheterocyclic benzimidazoles by microwave irradiation. Comb Chem High Throughput Screen. 2004;7: 251-255.
Douglass IB, Dains F. Some derivatives of benzoyl and furoyl isothiocyanates and their use in synthesizing heterocyclic compounds. J Am Chem Soc. 1934;56:719-721.
Reeves WP, Simmons Jr A, Keller K. Phase Transfer Catalysis Preparation of Arvl, Thiocyanates. Synth Commun. 19820;10:633-636.
Fieser LF, Fieser M, Ho TL, Smith JG. Fieser and Fieser's Reagents for Organic Synthesis. Wiley; 1967.
Holla BS, Malini K, Rao BS, Sarojini B, Kumari NS. Synthesis of some new 2, 4-disubstituted thiazoles as possible antibacterial and anti-inflammatory agents. Eur J Med Chem. 2003;38:313-318.
Darijani M, Habibi-Khorassani SM, Shahraki M. Effect of reactivity on kinetics and a mechanistic investigation of the reaction between dimethyl acetylenedicarboxylate and 1, 3-dicarbonyl compounds in the presence of a catalyst: A spectrophotometric approach. Prog react kinet mech. 2018;43:79-90.
Mostafa B, Habibi‐Khorassani SM, Shahraki M. An experimental investigation of substituent effects on the formation of 2, 3‐dihydroquinazolin‐4 (1H)‐ones: A kinetic study. J Phys Org Chem. 2017;30:e3616.
Habibi-Khorassani SM, Shahraki M, Darijani M. 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, Chemistry. Chem Cent J. 2017;11:71-80.
Shahraki M, Habibi-Khorassani SM, Dehdab M. Effect of different substituents on the one-pot formation of 3, 4, 5-substituted furan-2 (5 H)-ones: a kinetics and mechanism study. RSC Adv. 2015;5:52508-52515.
Shahraki M, Habibi‐Khorassani SM. Kinetic spectrophotometric approach to the reaction mechanism of pyrrole phosphorus ylide formation based on monitoring the zwitterionic intermediate by using the stopped‐flow technique. J Phys Org Chem. 2015;28:396-402.
Dehdab M, Habibi-Khorassani S, Shahraki M. Kinetics and mechanism investigation of the synthesized highly diasteroselective substituted tetrahydropyridines in the presence of La (NO3)3. 6H2O as a Catalyst. Catal Lett. 2014; 144:1790-1796.
Pourpanah SS, Habibi-Khorassani SM, Shahraki M. Fructose-catalyzed synthesis of tetrahydrobenzo [b] pyran derivatives: Investigation of kinetics and mechanism. Chin J Catal. 2015;36:757-763.
Ghodsi F, Habibi-Khorassani SM, Shahraki M. Kinetic spectrophotometric method for the 1, 4-diionic organophosphorus formation in the Presence of Meldrum′ s Acid: Stopped-Flow Approach. Molecules. 2016;21:1514.
Yaghoubian H, Habibi-Khorassani SM, Ebrahimi A. Mechanistic and full kinetic study of the reaction between 4-chlorobenzaldehyde, malononitrile and dimedone using caffeine as a green catalyst. Orient J Chem. 2015;31:2107-2113.
Habibi‐Khorassani SM, Shahraki M, Ebrahimi A, Darijani M. Experimental and theoretical insight into the kinetics and mechanism of the synthesis reaction of 2, 3‐Dihydro‐2‐ phenylquinazolin‐4 (1H)‐one Catalyzed in Formic Acid. Int J Chem Kinet. 2017;49:157-172.
Osman A, Habibi‐Khorassani SM, Shahraki M. Mechanistic studies on the three component synthesis of Tetrahydrobenzo[b]pyran Catalyzed by Agar Curr Organocatal. 2016;3: 52-59.
Habibi-Khorassani SM, Maghsoodlou MT, Talaiefar S, Kazemian MA, Aboonajmi J. Full kinetics and a mechanistic investigation of the synthesis of Tetrahydrobenzo[b]pyrans in the Presence of Sodium Acetate as a Catalyst by a One-pot Three-component Reaction. J Lett Org Chem. 2014;11:413-421.
Habibi-Khorassani SM, Shahraki M, Ebrahim A, Pourpanah SS, Keshavarz Majdabadi S. Caffeine Catalyzed Synthesis of Tetrahydrobenzo[b]pyran Derivatives: Synthesis and Insight into Kinetics and Mechanism. Comb Chem High Throughput Screen. 2016;19:865-874.
Habibi-Khorassani, SM, Ebrahim A, Maghsoodlou MT, Zakarianezhad M, Ghasempour H, Ghahghaie Z. Theoretical, NMR study, kinetics and a mechanistic investigation of the reaction between Triphenylphosphine, Dialkyl Acetylenedicarboxylates and 2-Aminothiophenol. Curr Org Chem. 2011;15: 942-952.
Maskill H. The investigation of organic reactions and their mechanisms. Wiley; 2007.
Rashad AE, Hegab MI, Abdel-Megeid RE, Micky JA, Abdel-Megeid FM. Synthesis and antiviral evaluation of some new pyrazole and fused pyrazolopyrimidine derivatives. Biorg Med Chem. 2008;16:7102-7106.
Qamar R, Saeed A, Saeed M, Shah BH, Ashraf Z, Abbas Q, Seo SY. Synthesis and enzyme inhibitory kinetics of some novel 3-(substituted benzoyl)-2-thioxoimidazolidin-4-one derivatives as α-glucosidase/α-amylase inhibitors. Med Chem Res. 2018;27:1528-1537.
Kouhkan M, Zardashti M, Souldozi A, Hussein Jazani N, Darabi N. Green synthesis and preliminary pharmacological evaluation of three-substituted thiazide derivatives as antibacterial agents. J Chem Pharm Res. 2016; 8:149-154.
Habibi-Khorassani SM, Maghsoodlou MT, Aghdaei E, Shahraki M. 1H NMR technique for kinetic investigation of equilibrium between the Z-and E-isomers in a stable phosphorus ylide involving a 2-indolinone. Prog React Kinet Mech. 2012;37:301-310.
Shahraki M, Habibi-Khorassani SM, Pourpanah SS. Kinetic aspects of tetrahydrobenzo [b] pyran formation in the presence of agar as a green catalyst: A mechanistic investigation. Biosci Biotech Res Asia. 2016;13:715-723.
Kazemian MA, Karimi P, Habibi-Khorassani SM, Ebrahimi A, Maghsoodlou MT, Milani FJ. Synthesis of stable phosphorus ylides from 6-chloro-2-benzoxazolinone and kinetic investigation of the reactions by UV spectrophotometry. Prog React Kinet Mech. 2009;34:77-96.
Habibi‐Khorassani SM, Ebrahimi A, Maghsoodlou M, Asheri O, Shahraki M, Akbarzadeh N, Ghalandarzehi Y. Synthesis of stable phosphorus ylides from 6-chloro-2-benzoxazolinone and kinetic investigation of the reactions by UV spectrophotometry. Int J Chem Kinet. 2013;45:596-612.
Schwartz LM, Gelb RI (1978) Alternative method of analyzing first-order kinetic data. Anal Chem 50: 1592-1594.
Dimroth K, Reichardt C, Seipmann T, Bohlmann F. Über Pyridinium-Nphenolbetaine undihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln. Justus Liebigs Annalen der Chemie. 1963;661:1-37.
Kamlet MJ, Abboud JLM, Abraham MH, Taft R. Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters,. pi.*,. alpha., and. beta., and some methods for simplifying the generalized solvatochromic equation. J Org Chem. 1983;48:2877-2887.
Abraham MH, Grellier PL, Abboud JLM, Doherty RM, Taft RW. Solvent effects in organic chemistry — recent developments. Can J Chem. 1988;66:2673-2686.
Hansch C, Leo A, Taft R. A survey of Hammett substituent constants and resonance and field parameters. Chem Rev. 1991;91:165-195.
Xinhao L, Jiaxi Xu. Identification of microwave selective heating effort in an intermolecular reaction with hammett linear relationship as a molecular level probe. Curr Microw Chem. 2017;4:339-346.
Martinez-Aguirre MA, Villamil-Ramos R, Guerrero-Alvarez JA, Yatsimirsky AK. Substituent effects and pH profiles for stability constants of arylboronic acid diol esters. J Org Chem. 2013;78:4674-4684.
Glasstone S, Laidler KJ, Eyring H. The theory of rate processes: The kinetics of chemical reactions, viscosity, diffusion and electrochemical phenomena. McGraw-Hill Book Company, Incorporated; 1941.
Glasstone S, Eyring H, Laidler KJ. The theory of rate processes. McGraw-Hill; 1941.
Vladislav MV. Activation Parameter Changes as a Mechanistic Tool in Acyl-Transfer Reactions in Solution. Curr Org Chem. 2014; 18:1097-1107.
Lente G, Fábián I, Poë AJ. A common misconception about the Eyring equation, New J Chem. 2005;29:759-760.
Liu L, Guo QX. Isokinetic relationship, isoequilibrium relationship, and enthalpy− entropy compensation. Chem Rev. 2001;101: 673-696.
Exner O. Entropy–enthalpy compensation and anticompensation: solvation and ligand binding Chem Commun. 2000;17:1655-1656.
Zhao Y, Truhlar DG. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc. 2008;120: 215-241.
Zhao Y, Truhlar DG. Applications and validations of the Minnesota density functionals. Chem Phys Lett. 2011;502:1-13.
Zhezheng D, Yayi Y, Fei X, Qingzhu Z, Xiaoli X, Wenxing W. Mechanistic and kinetic study of atmospheric oxidation of chlordane initiated by OH Radicals. Lett Org Chem. 2019;16:647-655.
Vincenzo B, Cossi M. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model. J Phys Chem A. 1998;102:1995-2001.
Gonzalez C, Schlegel HB. An improved algorithm for reaction path following. J. Chem. Phys. 1989;90:2154-2161.