Reactivity in Friedel–Crafts aromatic benzylation: the role of the electrophilic reactant

Cheshmedzhieva, Diana; Atanasov, Ivan; Ilieva, Sonia; Galabov, Boris; Schaefer III, Henry F.

doi:10.1039/D4CP03181D

Reactivity in Friedel–Crafts aromatic benzylation: the role of the electrophilic reactant

Journal Article · Wed Dec 18 00:00:00 EST 2024 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D4CP03181D· OSTI ID:2475532

^[1]; Atanasov, Ivan ^[1]; Ilieva, Sonia ^[1]; Galabov, Boris ^[1]; ^[2]

Department of Chemistry and Pharmacy, University of Sofia, Sofia 1164, Bulgaria
Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA

Density functional theory is employed in understanding the reactivity in the TiCl ₄ catalyzed Friedel–Crafts benzylation of benzene with substituted benzyl chlorides in nitromethane solvent.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018412

OSTI ID:: 2475532

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 1 Vol. 27; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (53)

Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model Bickelhaupt, F. Matthias; Houk, Kendall N. Angewandte Chemie International Edition, Vol. 56, Issue 34 https://doi.org/10.1002/anie.201701486	journal	July 2017
Structural Distortion of Cycloalkynes Influences Cycloaddition Rates both by Strain and Interaction Energies Hamlin, Trevor A.; Levandowski, Brian J.; Narsaria, Ayush K. Chemistry – A European Journal, Vol. 25, Issue 25 https://doi.org/10.1002/chem.201900295	journal	March 2019
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni Journal of Computational Chemistry, Vol. 24, Issue 6 https://doi.org/10.1002/jcc.10189	journal	April 2003
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Noncatalytic bromination of benzene: A combined computational and experimental study Shernyukov, Andrey V.; Genaev, Alexander M.; Salnikov, George E. Journal of Computational Chemistry, Vol. 37, Issue 2 https://doi.org/10.1002/jcc.23985	journal	July 2015
Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W. Journal of Computational Chemistry, Vol. 4, Issue 3 https://doi.org/10.1002/jcc.540040303	journal	October 1983
Some methods and applications of electron density distribution analysis Ritchie, James P.; Bachrach, Steven M. Journal of Computational Chemistry, Vol. 8, Issue 4 https://doi.org/10.1002/jcc.540080430	journal	June 1987
The mechanism of alkaline hydrolysis of amides: a comparative computational and experimental study of the hydrolysis of N -methylacetamide, N -methylbenzamide, and acetanilide: MECHANISM OF ALKALINE HYDROLYSIS OF AMIDES Cheshmedzhieva, Diana; Ilieva, Sonia; Hadjieva, Boriana Journal of Physical Organic Chemistry, Vol. 22, Issue 6 https://doi.org/10.1002/poc.1492	journal	December 2008
A remarkable difference in the deprotonation steps of the Friedel–Crafts acylation and alkylation reactions Yamabe, Shinichi; Yamazaki, Shoko Journal of Physical Organic Chemistry, Vol. 22, Issue 11 https://doi.org/10.1002/poc.1564	journal	June 2009
Bonded-atom fragments for describing molecular charge densities Hirshfeld, F. L. Theoretica Chimica Acta, Vol. 44, Issue 2 https://doi.org/10.1007/BF00549096	journal	January 1977
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 Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Mechanism and regioselectivity of electrophilic aromatic nitration in solution: the validity of the transition state approach Liljenberg, Magnus; Stenlid, Joakim Halldin; Brinck, Tore Journal of Molecular Modeling, Vol. 24, Issue 1 https://doi.org/10.1007/s00894-017-3561-z	journal	December 2017
Quantum Chemical‐QSPR Estimation of the Acidities and Basicities of Organic Compounds Seybold, Paul G. Advances in Quantum Chemistry, Vol. 64, p. 83-104 https://doi.org/10.1016/B978-0-12-396498-4.00015-6	book	July 2012
Theory and Modeling of Asymmetric Catalytic Reactions Lam, Yu-hong; Grayson, Matthew N.; Holland, Mareike C. Accounts of Chemical Research, Vol. 49, Issue 4 https://doi.org/10.1021/acs.accounts.6b00006	journal	March 2016
A Predictive Tool for Electrophilic Aromatic Substitutions Using Machine Learning Tomberg, Anna; Johansson, Magnus J.; Norrby, Per-Ola The Journal of Organic Chemistry, Vol. 84, Issue 8 https://doi.org/10.1021/acs.joc.8b02270	journal	October 2018
Atomic Charges Wiberg, Kenneth B.; Rablen, Paul R. The Journal of Organic Chemistry, Vol. 83, Issue 24 https://doi.org/10.1021/acs.joc.8b02740	journal	November 2018
Atomic Charges in Describing Properties of Aromatic Molecules Nikolova, Valia; Cheshmedzhieva, Diana; Ilieva, Sonia The Journal of Organic Chemistry, Vol. 84, Issue 4 https://doi.org/10.1021/acs.joc.8b02908	journal	January 2019
Some Recent Advances in Density-Based Reactivity Theory He, Xin; Li, Meng; Rong, Chunying The Journal of Physical Chemistry A, Vol. 128, Issue 7 https://doi.org/10.1021/acs.jpca.3c07997	journal	February 2024
Quantifying Reactivity for Electrophilic Aromatic Substitution Reactions with Hirshfeld Charge Liu, Shubin The Journal of Physical Chemistry A, Vol. 119, Issue 12 https://doi.org/10.1021/acs.jpca.5b00443	journal	March 2015
Theoretical Investigation into Rate-Determining Factors in Electrophilic Aromatic Halogenation Liljenberg, Magnus; Stenlid, Joakim Halldin; Brinck, Tore The Journal of Physical Chemistry A, Vol. 122, Issue 12 https://doi.org/10.1021/acs.jpca.7b10781	journal	March 2018
Superelectrophilic Gallium(III) Homodimers in Gallium Chloride-Mediated Methylation of Benzene: A Theoretical Study Yang, Shengwen; Bour, Christophe; Gandon, Vincent ACS Catalysis, Vol. 10, Issue 5 https://doi.org/10.1021/acscatal.9b05509	journal	February 2020
Mini-Review on Structure–Reactivity Relationship for Aromatic Molecules: Recent Advances Galabov, Boris; Ilieva, Sonia; Cheshmedzhieva, Diana ACS Omega, Vol. 7, Issue 10 https://doi.org/10.1021/acsomega.1c07176	journal	March 2022
The path of chemical reactions - the IRC approach Fukui, Kenichi Accounts of Chemical Research, Vol. 14, Issue 12 https://doi.org/10.1021/ar00072a001	journal	December 1981
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Sigma- and Pi-Electron Delocalization: Focus on Substituent Effects Krygowski, Tadeusz Marek; Stȩpień, Beata Tamara Chemical Reviews, Vol. 105, Issue 10 https://doi.org/10.1021/cr030081s	journal	August 2005
Some Relations between Reaction Rates and Equilibrium Constants. Hammett, Louis P. Chemical Reviews, Vol. 17, Issue 1 https://doi.org/10.1021/cr60056a010	journal	August 1935
A Reëxamination of the Hammett Equation. Jaffé, H. H. Chemical Reviews, Vol. 53, Issue 2 https://doi.org/10.1021/cr60165a003	journal	October 1953
Mechanism of formation of bicyclic phosphazenes. Isolation of a versatile tetrakis(amino) intermediate, N4P4Cl4(NMe2)2(NHEt)2 Narayanaswamy, P. Y.; Dhathathreyan, K. S.; Krishnamurthy, S. S. Inorganic Chemistry, Vol. 24, Issue 5 https://doi.org/10.1021/ic00199a002	journal	February 1985
Electrophilic aromatic substitution. 12. Kinetic studies of the titanium tetrachloride-catalyzed reactions of benzyl chloride, p-xylyl chloride, and p-nitrobenzyl chloride with benzene and anisole in nitromethane and dichloromethane DeHaan, Franklin P.; Chan, Wai H.; Chang, Jeffrey Journal of the American Chemical Society, Vol. 112, Issue 1 https://doi.org/10.1021/ja00157a054	journal	January 1990
Electron density distribution analysis for nitromethane, nitromethide, and nitramide Ritchie, James P. Journal of the American Chemical Society, Vol. 107, Issue 7 https://doi.org/10.1021/ja00293a005	journal	April 1985
Electrophilic aromatic substitution. 8. A kinetic study of the Friedel-Crafts benzylation reaction in nitromethane, nitrobenzene, and sulfolane. Substituent effects in Friedel-Crafts benzylation DeHaan, Franklin P.; Delker, Gerald L.; Covey, William D. Journal of the American Chemical Society, Vol. 106, Issue 23 https://doi.org/10.1021/ja00335a029	journal	November 1984
Aromatic substitution. XXX. Friedel-Crafts benzylation of benzene and toluene with benzyl and substituted benzyl halides Olah, George A.; Kobayashi, Shiro; Tashiro, Masashi Journal of the American Chemical Society, Vol. 94, Issue 21 https://doi.org/10.1021/ja00776a030	journal	October 1972
Kinetics and Relative Rates of the Gallium Bromide-Catalyzed Reactions of Alkyl Bromides with Aromatic Hydrocarbons in 1,2,4-Trichlorobenzene Solution Choi, Sang Up.; Brown, Herbert C. Journal of the American Chemical Society, Vol. 85, Issue 17 https://doi.org/10.1021/ja00900a016	journal	September 1963
Kinetics of the Reaction of Representative Benzyl Halides with Aromatic Compounds; Evidence for a Displacement Mechanism in the Friedel—Crafts Reactions of Primary Halides ^1,2 Brown, Herbert C.; Grayson, Martin Journal of the American Chemical Society, Vol. 75, Issue 24 https://doi.org/10.1021/ja01120a052	journal	December 1953
Kinetics of Methylation and Ethylation of Benzene and Toluene in 1,2,4-Trichlorobenzene under the Influence of Aluminum Bromide; Mechanism of the Alkylation Reaction^1,2 Jungk, Hans; Smoot, Charles R.; Brown, Herbert C. Journal of the American Chemical Society, Vol. 78, Issue 10 https://doi.org/10.1021/ja01591a045	journal	May 1956
A Case Study of the Mechanism of Alcohol-Mediated Morita Baylis–Hillman Reactions. The Importance of Experimental Observations Plata, R. Erik; Singleton, Daniel A. Journal of the American Chemical Society, Vol. 137, Issue 11 https://doi.org/10.1021/ja5111392	journal	March 2015
Mechanism of an Organocatalytic Cope Rearrangement Involving Iminium Intermediates: Elucidating the Role of Catalyst Ring Size Sanders, Jacob N.; Jun, HyunJune; Yu, Roland A. Journal of the American Chemical Society, Vol. 142, Issue 39 https://doi.org/10.1021/jacs.0c08427	journal	August 2020
Electrophile Affinity: Quantifying Reactivity for the Bromination of Arenes Galabov, Boris; Koleva, Gergana; Schaefer, Henry F. The Journal of Organic Chemistry, Vol. 75, Issue 9 https://doi.org/10.1021/jo902730g	journal	April 2010
Electronic Perturbations of the Aromatic Nucleus: Hammett Constants and Electrostatic Potential Topography ^† Gadre, Shridhar R.; Suresh, C. H. The Journal of Organic Chemistry, Vol. 62, Issue 8 https://doi.org/10.1021/jo961679l	journal	April 1997
Performance of M06, M06-2X, and M06-HF Density Functionals for Conformationally Flexible Anionic Clusters: M06 Functionals Perform Better than B3LYP for a Model System with Dispersion and Ionic Hydrogen-Bonding Interactions Walker, Martin; Harvey, Andrew J. A.; Sen, Ananya The Journal of Physical Chemistry A, Vol. 117, Issue 47 https://doi.org/10.1021/jp408166m	journal	November 2013
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
Role of Lewis Acid(AlCl ₃ )−Aromatic Ring Interactions in Friedel−Craft's Reaction: An ab Initio Study Tarakeshwar, P.; Lee, Jin Yong; Kim, Kwang S. The Journal of Physical Chemistry A, Vol. 102, Issue 13 https://doi.org/10.1021/jp9807322	journal	March 1998
Towards physical interpretation of substituent effects: the case of meta- and para-substituted anilines Szatylowicz, Halina; Siodla, Tomasz; Stasyuk, Olga A. Physical Chemistry Chemical Physics, Vol. 18, Issue 17 https://doi.org/10.1039/C5CP06702B	journal	January 2016
Fast and accurate prediction of the regioselectivity of electrophilic aromatic substitution reactions Kromann, Jimmy C.; Jensen, Jan H.; Kruszyk, Monika Chemical Science, Vol. 9, Issue 3 https://doi.org/10.1039/C7SC04156J	journal	January 2018
Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies Jorner, Kjell; Brinck, Tore; Norrby, Per-Ola Chemical Science, Vol. 12, Issue 3 https://doi.org/10.1039/D0SC04896H	journal	January 2021
In situ spectroscopic studies related to the mechanism of the Friedel–Crafts acetylation of benzene in ionic liquids using AlCl3 and FeCl3Based on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany. Csihony, Szilárd; Mehdi, Hasan; Homonnay, Zoltán Journal of the Chemical Society, Dalton Transactions, Issue 5 https://doi.org/10.1039/b109303g	journal	January 2002
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Aromatic reactivity revealed: beyond resonance theory and frontier orbitals Brown, James J.; Cockroft, Scott L. Chemical Science, Vol. 4, Issue 4 https://doi.org/10.1039/c3sc50309g	journal	January 2013
A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons Fukui, Kenichi; Yonezawa, Teijiro; Shingu, Haruo The Journal of Chemical Physics, Vol. 20, Issue 4 https://doi.org/10.1063/1.1700523	journal	April 1952
Tests of the RPBE, revPBE, τ-HCTHhyb, ωB97X-D, and MOHLYP density functional approximations and 29 others against representative databases for diverse bond energies and barrier heights in catalysis Yang, Ke; Zheng, Jingjing; Zhao, Yan The Journal of Chemical Physics, Vol. 132, Issue 16 https://doi.org/10.1063/1.3382342	journal	April 2010
Electrostatic Potential Topology for Probing Molecular Structure, Bonding and Reactivity Gadre, Shridhar R.; Suresh, Cherumuttathu H.; Mohan, Neetha Molecules, Vol. 26, Issue 11 https://doi.org/10.3390/molecules26113289	journal	May 2021
A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis Rueping, Magnus; Nachtsheim, Boris J. Beilstein Journal of Organic Chemistry, Vol. 6 https://doi.org/10.3762/bjoc.6.6	journal	January 2010

Similar Records

Method of concurrent reactions to describe Friedel-Crafts benzylation

Journal Article · Mon Nov 30 23:00:00 EST 1987 · Kinet. Catal. (Engl. Transl.); (United States) · OSTI ID:5251723

Reaction of 1-chloro-1-methylcyclohexane with phenyl- and benzyl-trimethylsilanes in the presence of aluminum chloride

Journal Article · Thu Oct 20 00:00:00 EDT 1988 · J. Org. Chem. USSR (Engl. Transl.); (United States) · OSTI ID:5971608

Friedel-crafts isopropylation of a bituminous coal under remarkably mild conditions

Journal Article · Wed Jun 21 00:00:00 EDT 1978 · J. Am. Chem. Soc.; (United States) · OSTI ID:6675368

Reactivity in Friedel–Crafts aromatic benzylation: the role of the electrophilic reactant

Citation Formats

References (53)

Similar Records

Related Subjects