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Current Organic Chemistry

Editor-in-Chief

ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

Research Article

Chemically Modified Chitosan Supports for Phosphine-free Pd-catalyzed Crosscoupling Reaction of Arylboronic Acids with Acid Chlorides

Author(s): Hyoung-Jun Kong, Do-Won Bang, Minji Kim, Soo-Youl Park and Seung-Hoi Kim*

Volume 26, Issue 4, 2022

Published on: 05 April, 2022

Page: [418 - 425] Pages: 8

DOI: 10.2174/1385272826666220209115416

Price: $65

Abstract

Background: Phosphine-free Pd-catalytic platforms, i) combination with chitosan- Schiff base (CS-Py/Pd), ii) immobilized on chitosan-Schiff base (CS-Py@Pd), and iii) anchored to modified carbon nanotube support (CNT@CS-Py@Pd),

Methods: They were evaluated regarding a novel pathway for the cross-coupling reaction of arylboronic acids with acid chlorides.

Results: The CS-Py@Pd platform had the highest catalytic efficiency of the three platforms, yielding moderate to excellent yields of diaryl ketones.

Conclusion: The catalytic activity of the Pd-catalyst was highly dependent upon the manufacturing process and type of support.

Keywords: Phosphine-free Pd-catalyst, Chitosan-Schiff base@Pd, CNT@chitosan-Schiff base@Pd, arylboronic acids, diaryl ketones, coupling reaction.

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[1]
Romines, K.R.; Freeman, G.A.; Schaller, L.T.; Cowan, J.R.; Gonzales, S.S.; Tidwell, J.H.; Andrews, C.W., III; Stammers, D.K.; Hazen, R.J.; Ferris, R.G.; Short, S.A.; Chan, J.H.; Boone, L.R. Structure-activity relationship studies of novel benzophenones leading to the discovery of a potent, next generation HIV nonnucleoside reverse tran-scriptase inhibitor. J. Med. Chem., 2006, 49(2), 727-739.
[http://dx.doi.org/10.1021/jm050670l] [PMID: 16420058]
[2]
Compere, D.; Marazano, C.; Das, B.C. Enantioselective Access to Lobelia Alkaloids. J. Org. Chem., 1999, 64, 4528-4532.
[http://dx.doi.org/10.1021/jo981912a]
[3]
Deng, Y.; Chin, Y.W.; Chai, H.; Keller, W.J.; Kinghorn, A.D. Anthraquinones with quinone reductase-inducing activity and benzophenones from Morinda citrifolia (noni) roots. J. Nat. Prod., 2007, 70(12), 2049-2052.
[http://dx.doi.org/10.1021/np070501z] [PMID: 18076142]
[4]
Storm, J.P.; Andersson, C.M. Iron-mediated synthetic routes to unsymmetrically substituted, sterically congested benzophenones. J. Org. Chem., 2000, 65(17), 5264-5274.
[http://dx.doi.org/10.1021/jo000421z] [PMID: 10993355]
[5]
Olah, G.A. Freidel-Crafts Chemistry, (Interscience monographs on organic chemistry); Wiley & Sons: New York, 1973.
[6]
Khedkar, M.V.; Sasaki, T.; Bhanage, B.M. Efficient, recyclable and phosphine-free carbonylative Suzuki coupling reaction using immobilized palladium ion-containing ionic liquid: Synthesis of aryl ketones and heteroaryl ketones. RSC Advances, 2013, 3, 7791-7797.
[http://dx.doi.org/10.1039/c3ra40730f]
[7]
Khedkar, M.V.; Tambade, P.J.; Qureshi, Z.S.; Bhanage, B.M. Pd/C: An efficient, heterogeneous and reusable catalyst for phosphane-free carbonylative suzuki coupling reactions of aryl and heteroaryl Iodides. Eur. J. Org. Chem., 2010, 6981-6986.
[http://dx.doi.org/10.1002/ejoc.201001134]
[8]
Cai, M.; Zheng, G.; Zha, L.; Peng, J. Carbonylative Suzuki–Miyaura Coupling of Arylboronic Acids with Aryl Iodides Catalyzed by the MCM-41- Supported Bidentate Phosphane Palladium(II) Complex. Eur. J. Org. Chem., 2009, 1585-1591.
[http://dx.doi.org/10.1002/ejoc.200801253]
[9]
Neumann, H.; Brennfhrer, A.; Beller, M. An efficient and practical sequential one-pot synthesis of Suprofen, Ketoprofen and other 2-Arylpropionic Acids. Adv. Synth. Catal., 2008, 350, 2437-2442.
[http://dx.doi.org/10.1002/adsc.200800415]
[10]
Li, J.J.; Gribble, G.N. Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist, 2nd ed; Elsevier, 2016.
[11]
Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of Organoboron compounds. Chem. Rev., 1995, 95, 2457-2483.
[http://dx.doi.org/10.1021/cr00039a007]
[12]
Amaike, K.; Muto, K.; Yamaguchi, J.; Itami, K. Decarbonylative C-H coupling of azoles and aryl esters: Unprecedented nickel catalysis and application to the synthesis of muscoride A. J. Am. Chem. Soc., 2012, 134(33), 13573-13576.
[http://dx.doi.org/10.1021/ja306062c] [PMID: 22870867]
[13]
Huihui, K.M.M.; Caputo, J.A.; Melchor, Z.; Olivares, A.M.; Spiewak, A.M.; Johnson, K.A.; DiBenedetto, T.A.; Kim, S.; Ackerman, L.K.G.; Weix, D.J. Decarboxylative cross-electrophile coupling of N-Hydroxyphthalimide Esters with Aryl Iodides. J. Am. Chem. Soc., 2016, 138(15), 5016-5019.
[http://dx.doi.org/10.1021/jacs.6b01533] [PMID: 27029833]
[14]
Muto, K.; Yamaguchi, J.; Itami, K. Nickel-catalyzed C-H/C-O coupling of azoles with phenol derivatives. J. Am. Chem. Soc., 2012, 134(1), 169-172.
[http://dx.doi.org/10.1021/ja210249h] [PMID: 22148419]
[15]
Hie, L.; Fine Nathel, N.F.; Hong, X.; Yang, Y.F.; Houk, K.N.; Garg, N.K. Nickel-catalyzed activation of Acyl C-O bonds of methyl esters. Angew. Chem. Int. Ed. Engl., 2016, 55(8), 2810-2814.
[http://dx.doi.org/10.1002/anie.201511486] [PMID: 26804615]
[16]
Cornella, J.; Edwards, J.T.; Qin, T.; Kawamura, S.; Wang, J.; Pan, C.M.; Gianatassio, R.; Schmidt, M.; Eastgate, M.D.; Baran, P.S. Practical Ni-catalyzed Aryl-Alkyl cross-coupling of secondary redox-active esters. J. Am. Chem. Soc., 2016, 138(7), 2174-2177.
[http://dx.doi.org/10.1021/jacs.6b00250] [PMID: 26835704]
[17]
Yu, B.; Sun, H.; Xie, Z.; Zhang, G.; Xu, L.W.; Zhang, W.; Gao, Z. Privilege ynone synthesis via palladium-catalyzed alkynylation of “super-active esters”. Org. Lett., 2015, 17(13), 3298-3301.
[http://dx.doi.org/10.1021/acs.orglett.5b01466] [PMID: 26065590]
[18]
LaBerge, N.A.; Love, J.A. Nickel-catalyzed decarbonylative coupling of aryl esters and arylboronic acids. Eur. J. Org. Chem., 2015, 5538-5546.
[19]
Muto, K.; Hatakeyama, T.; Itami, K.; Yamaguchi, J. Palladium-catalyzed decarbonylative cross-coupling of azinecarboxylates with arylboronic acids. Org. Lett., 2016, 18(19), 5106-5109.
[http://dx.doi.org/10.1021/acs.orglett.6b02556] [PMID: 27673382]
[20]
Guo, L.; Chatupheeraphat, A.; Rueping, M. Decarbonylative Silylation of esters by combined nickel and copper catalysis for the synthesis of Arylsilanes and Het-eroarylsilanes. Angew. Chem. Int. Ed. Engl., 2016, 55(39), 11810-11813.
[http://dx.doi.org/10.1002/anie.201604696] [PMID: 27560460]
[21]
Pu, X.; Hu, J.; Zhao, Y.; Shi, Z. Nickel-catalyzed decarbonylative borylation and silylation of esters. ACS Catal., 2016, 6, 6692-6698.
[http://dx.doi.org/10.1021/acscatal.6b01956]
[22]
Guo, L.; Rueping, M. Functional group interconversion: Decarbonylative borylation of esters for the synthesis of organoboronates. Chemistry, 2016, 22(47), 16787-16790.
[http://dx.doi.org/10.1002/chem.201604504] [PMID: 27717095]
[23]
Desnoyer, A.N.; Friese, F.W.; Chiu, W.; Drover, M.W.; Patrick, B.O.; Love, J.A. Exploring regioselective bond cleavage and cross-coupling reactions using a low-valent Nickel Complex. Chemistry, 2016, 22(12), 4070-4077.
[http://dx.doi.org/10.1002/chem.201504959] [PMID: 26879766]
[24]
Ben Halima, T.; Zhang, W.; Yalaoui, I.; Hong, X.; Yang, Y.F.; Houk, K.N.; Newman, S.G. Palladium-catalyzed Suzuki-Miyaura coupling of Aryl Esters. J. Am. Chem. Soc., 2017, 139(3), 1311-1318.
[http://dx.doi.org/10.1021/jacs.6b12329] [PMID: 28001393]
[25]
Goossen, L.J.; Ghosh, K. Palladium-Catalyzed Synthesis of Aryl Ketones from Boronic Acids and Carboxylic Acids or Anhydrides We thank M. Rössig and L. Winkel for technical assistance, Prof. Dr. M. T. Reetz for generous support and constant encouragement, and the DFG for financial support. Angew. Chem. Int. Ed. Engl., 2001, 40(18), 3458-3460.
[http://dx.doi.org/10.1002/1521-3773(20010917)40:18<3458::AIDANIE3458>3.0.CO;2-0] [PMID: 11592170]
[26]
Goossen, L.J.; Koley, D.; Hermann, H.L.; Thiel, W. The palladium-catalyzed cross-coupling reaction of carboxylic anhydrides with arylboronic acids: A DFT study. J. Am. Chem. Soc., 2005, 127(31), 11102-11114.
[http://dx.doi.org/10.1021/ja052435y] [PMID: 16076218]
[27]
Xin, B.; Zhang, Y.; Cheng, K. Phosphine-free cross-coupling reaction of arylboronic acids with carboxylic anhydrides or acyl chlorides in aqueous media. J. Org. Chem., 2006, 71(15), 5725-5731.
[http://dx.doi.org/10.1021/jo060749d] [PMID: 16839154]
[28]
Chen, Q.; Fan, X.H.; Zhang, L.P.; Yang, L.M. Nickel-catalyzed cross-coupling of carboxylic anhydrides with arylboronic acids. RSC Advances, 2014, 4, 53885-53890.
[http://dx.doi.org/10.1039/C4RA11520A]
[29]
Liebeskind, L.S.; Srogl, J. Thiol Ester-Boronic Acid Coupling. A mechanistically unprecedented and general ketone synthesis. J. Am. Chem. Soc., 2000, 122, 11260-11261.
[http://dx.doi.org/10.1021/ja005613q]
[30]
Wittenberg, R.; Srogl, J.; Egi, M.; Liebeskind, L.S. Ketone synthesis under neutral conditions. Cu(I) diphenylphosphinate-mediated, palladium-catalyzed coupling of thiol esters and organostannanes. Org. Lett., 2003, 5(17), 3033-3035.
[http://dx.doi.org/10.1021/ol034962x] [PMID: 12916974]
[31]
Tokuyama, H.; Yokoshima, S.; Yamashita, T.; Fukuyama, T. A novel ketone synthesis by a palladium-catalyzed reaction of thiol esters and organozinc reagents. Tetrahedron Lett., 1998, 39, 3189-3192.
[http://dx.doi.org/10.1016/S0040-4039(98)00456-0]
[32]
Prokopcová, H.; Kappe, C.O. The Liebeskind-Srogl C-C cross-coupling reaction. Angew. Chem. Int. Ed. Engl., 2009, 48(13), 2276-2286.
[http://dx.doi.org/10.1002/anie.200802842] [PMID: 19067446]
[33]
Weires, N.A.; Baker, E.L.; Garg, N.K. Nickel-catalysed Suzuki-Miyaura coupling of amides. Nat. Chem., 2016, 8(1), 75-79.
[http://dx.doi.org/10.1038/nchem.2388] [PMID: 26673267]
[34]
Li, X.; Zou, G. Acylative Suzuki coupling of amides: Acyl-nitrogen activation via synergy of independently modifiable activating groups. Chem. Commun. (Camb.), 2015, 51(24), 5089-5092.
[http://dx.doi.org/10.1039/C5CC00430F] [PMID: 25712409]
[35]
Meng, G.; Szostak, M. Sterically Controlled Pd-catalyzed chemoselective ketone synthesis via N-C cleavage in twisted amides. Org. Lett., 2015, 17(17), 4364-4367.
[http://dx.doi.org/10.1021/acs.orglett.5b02209] [PMID: 26284604]
[36]
Shi, S.; Szostak, M. Efficient synthesis of Diaryl Ketones by Nickel-Catalyzed Negishi Cross-Coupling of amides by carbon-nitrogen bond cleavage at room temperature accelerated by a solvent effect. Chemistry, 2016, 22(30), 10420-10424.
[http://dx.doi.org/10.1002/chem.201602202] [PMID: 27304392]
[37]
Shi, S.; Meng, G.; Szostak, M. Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage. Angew. Chem. Int. Ed. Engl., 2016, 55(24), 6959-6963.
[http://dx.doi.org/10.1002/anie.201601914] [PMID: 27101428]
[38]
Meng, G.; Szostak, M. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: General strategy for amide N-C bond activation. Org. Biomol. Chem., 2016, 14(24), 5690-5707.
[http://dx.doi.org/10.1039/C6OB00084C] [PMID: 26864384]
[39]
Meng, G.; Szostak, M. General Olefin Synthesis by the Palladium-Catalyzed Heck Reaction of Amides: Sterically Controlled Chemoselective N-C Activation. Angew. Chem. Int. Ed. Engl., 2015, 54(48), 14518-14522.
[http://dx.doi.org/10.1002/anie.201507776] [PMID: 26458248]
[40]
Baker, E.L.; Yamano, M.M.; Zhou, Y.; Anthony, S.M.; Garg, N.K. A two-step approach to achieve secondary amide transamidation enabled by nickel catalysis. Nat. Commun., 2016, 7, 11554.
[http://dx.doi.org/10.1038/ncomms11554] [PMID: 27199089]
[41]
Simmons, B.J.; Weires, N.A.; Dander, J.E.; Garg, N.K. Nickel-Catalyzed Alkylation of Amide Derivatives. ACS Catal., 2016, 6(5), 3176-3179.
[http://dx.doi.org/10.1021/acscatal.6b00793] [PMID: 32257581]
[42]
Hie, L.; Fine Nathel, N.F.; Shah, T.K.; Baker, E.L.; Hong, X.; Yang, Y.F.; Liu, P.; Houk, K.N.; Garg, N.K. Conversion of amides to esters by the nickel-catalysed activa-tion of amide C-N bonds. Nature, 2015, 524(7563), 79-83.
[http://dx.doi.org/10.1038/nature14615] [PMID: 26200342]
[43]
Hu, J.; Zhao, Y.; Liu, J.; Zhang, Y.; Shi, Z. Nickel-Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C-N Bond Activation. Angew. Chem. Int. Ed. Engl., 2016, 55(30), 8718-8722.
[http://dx.doi.org/10.1002/anie.201603068] [PMID: 27258597]
[44]
Meng, G.; Shi, S.; Szostak, M. Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling of Amides via Site-Selective N–C Bond Cleavage by Cooperative Catalysis. ACS Catal., 2016, 6, 7335-7339.
[http://dx.doi.org/10.1021/acscatal.6b02323]
[45]
Prabhu, R.N.; Ramesh, R. Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids. Tetrahedron Lett., 2017, 58, 405-409.
[http://dx.doi.org/10.1016/j.tetlet.2016.12.032]
[46]
Weng, F.; Wang, C.; Xu, B. Direct C–H bond arylation of 2-hydroxybenzaldehydes with arylboronic acids via ligand-free palladium catalysis. Tetrahedron Lett., 2010, 51, 2593-2595.
[http://dx.doi.org/10.1016/j.tetlet.2010.02.166]
[47]
Kuriyama, M.; Hamaguchi, N.; Sakata, K.; Onomura, O. One-Pot Synthesis of Heteroaryl and Diheteroaryl Ketones through Palladium-Catalyzed 1,2-Addition and Oxidation. Eur. J. Org. Chem., 2013, 3378-3385.
[http://dx.doi.org/10.1002/ejoc.201300269]
[48]
Xia, Y.; Wang, J.; Dong, G. Suzuki-miyaura coupling of simple ketones via activation of unstrained carbon-carbon bonds. J. Am. Chem. Soc., 2018, 140(16), 5347-5351.
[http://dx.doi.org/10.1021/jacs.8b02462] [PMID: 29652498]
[49]
Bykov, V.V.; Korolev, D.N.; Bumagin, N.A. Palladium-catalyzed reactions of organoboron compounds with acyl chlorides. Russ. Chem. Bull. Int. Ed, 1997, 46, 1631-1638.
[50]
Haddach, M.; McCarthy, J.R. A new method for the synthesis of ketones: The palladium-catalyzed cross-coupling of acid chlorides with arylboronic acids. Tetrahedron Lett., 1999, 40, 3109-3112.
[http://dx.doi.org/10.1016/S0040-4039(99)00476-1]
[51]
Bumagin, N.A.; Korolev, D.N. Synthesis of unsymmetric ketones via ligandless Pd-catalyzed reaction of acyl chlorides with organoboranes. Tetrahedron Lett., 1999, 40, 3057-3060.
[http://dx.doi.org/10.1016/S0040-4039(99)00364-0]
[52]
Urawa, Y.; Ogura, K. A convenient method for preparing aromatic ketones from acyl chlorides and arylboronic acids via Suzuki–Miyaura type coupling reaction. Tetrahedron Lett., 2003, 44, 271-277.
[http://dx.doi.org/10.1016/S0040-4039(02)02501-7]
[53]
Chen, H.; Deng, M.Z. A novel stereocontrolled synthesis of 1,2-trans cyclopropyl ketones via suzuki-type coupling of acid chlorides with cyclopropylboronic acids. Org. Lett., 2000, 2(12), 1649-1651.
[http://dx.doi.org/10.1021/ol000013h] [PMID: 10880192]
[54]
Nishihara, Y.; Inoue, Y.; Fujisawa, M.; Takai, K. Room-temperature palladium-catalyzed and Copper(I)-mediated coupling reactions of acid Chlorides with Boronic Acids under neutral conditions. Synlett, 2005, 2309-2312.
[http://dx.doi.org/10.1055/s-2005-872661]
[55]
Bandgar, B.P.; Patil, A.V. A rapid solvent-free ligandless and mild method for preparing aromatic ketones from acyl chlorides and arylboronic acids via a Suzuki–Miyaura type of coupling reaction. Tetrahedron Lett., 2005, 46, 7627-7630.
[http://dx.doi.org/10.1016/j.tetlet.2005.08.111]
[56]
Xin, B.; Zhang, Y.; Cheng, K. The surfactant-promoted cross-coupling reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides in water. Synthesis, 2007, 1970-1978.
[57]
Ekoue-Kovi, K.; Xu, H.; Wolf, C. Palladium-phosphinous acid-catalyzed cross-coupling of aliphatic and aromatic acyl chlorides with boronic acids. Tetrahedron Lett., 2008, 49, 5773-5776.
[http://dx.doi.org/10.1016/j.tetlet.2008.07.115]
[58]
Rafiee, F.; Hajipour, A.R. A versatile method for the synthesis of diaryl and alkyl aryl ketones via palladium-catalysed cross-coupling reaction of arylboronic acids with acyl chlorides. Appl. Organomet. Chem., 2015, 29, 181-184.
[http://dx.doi.org/10.1002/aoc.3269]
[59]
Mondala, M.; Bora, U. Eco-friendly Suzuki–Miyaura coupling of arylboronic acids to aromatic ketones catalyzed by the oxime-palladacycle in biosolvent 2-MeTHF. New J. Chem., 2016, 40, 3119-3123.
[http://dx.doi.org/10.1039/C5NJ02734A]
[60]
Zang, L.; Wu, J.; Shi, L.; Xia, C.; Li, F. Ionically tagged benzimidazole palladium(II) complex: Preparation and catalytic application in cross-coupling reactions. Tetrahedron Lett., 2011, 52, 3897-3901.
[http://dx.doi.org/10.1016/j.tetlet.2011.05.079]
[61]
Semler, M. Štěpnička, P. Synthesis of aromatic ketones by Suzuki-Miyaura cross-coupling of acyl chlorides with boronic acids mediated by palladium catalysts depos-ited over donor-functionalized silica gel. Catal. Today, 2015, 243, 128-133.
[http://dx.doi.org/10.1016/j.cattod.2014.06.017]
[62]
Movassagh, B.; Hajizadeh, F.; Mohammadi, E. Polystyrene-supported Pd (II)–N-heterocyclic carbene complex as a heterogeneous and recyclable precatalyst for cross-coupling of acyl chlorides with arylboronic acids. Appl. Organomet. Chem., 2018, 32, e3982.
[http://dx.doi.org/10.1002/aoc.3982]
[63]
Mohammadi, E.; Hajilou, Z.; Movassagh, B. Multiwalled carbon nanotubes supported Pd (II)-Salen complex: An effective, phosphorous-free, and reusable heterogene-ous precatalyst for the synthesis of Diaryl Ketones. Helv. Chim. Acta, 2016, 99, 747-752.
[http://dx.doi.org/10.1002/hlca.201600161]
[64]
Mondal, M.; Bora, U. Ligandless heterogeneous palladium: An efficient and recyclable catalyst for Suzuki-type cross-coupling reaction. Appl. Organomet. Chem., 2014, 28, 354-358.
[http://dx.doi.org/10.1002/aoc.3135]
[65]
Muniyappan, N.; Sabiah, S. Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions. Appl. Organometal. Chem., 2020, 2020, e5421.
[66]
There are several examples using chitosan@Pd catalytic systems for the performance of traditional coupling of boronic acid with halo(pseudo) compounds; see, Baran, T.; Baran, N.Y.; Menteş A. Sustainable chitosan/starch composite material for stabilization of palladium nanoparticles: Synthesis, characterization and investigation of catalytic behaviour of Pd@chitosan/starch nanocomposite in Suzuki–Miyaura reaction. Appl. Organomet. Chem., 2018, 32, e4075.
[67]
Hardy, J.J.E.; Hubert, S.; Macquarrie, D.J.; Wilson, A.J. Chitosan-based heterogeneous catalysts for Suzuki and Heck reactions. Green Chem., 2004, 6, 53-56.
[http://dx.doi.org/10.1039/b312145n]
[68]
Joo, S.R.; Kwon, G.T.; Park, S.Y.; Kim, S.H. Chemically modified chitosan as a biopolymer support in Copper-catalyzed ipso-Hydroxylation of Arylboronic acids in water. Bull. Korean Chem. Soc., 2019, 40, 465-468.
[http://dx.doi.org/10.1002/bkcs.11708]
[69]
Zhang, G.; Li, Y.; Liu, J. Acid-promoted metal-free protodeboronation of arylboronic acids. RSC Advances, 2017, 7, 34959-34962.
[http://dx.doi.org/10.1039/C7RA05979E]
[70]
de Meijere, A.; Diederich, F. Metal-Catalyzed Cross-Coupling Reactions, 2nd ed; Wiley-VCH Verlag GmbH & Co.: Weinheim, 2004.
[http://dx.doi.org/10.1002/9783527619535]
[71]
Joo, S.R.; Kim, S.H.; Shin, U.S.; Kim, H.S. Pd-catalyst anchored on Schiff base-modified chitosan-CNT nanohybrid for the Suzuki–Miyaura coupling reaction. Curr. Org. Chem., 2020, 24, 2383-2390.
[http://dx.doi.org/10.2174/138527282499920091712294]

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      • 11. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • INSERT INTO visitor_ip_address (ip_address,visitor_agent,visitor_count, created_on,updated_on) VALUES ('58766425','',1,1740776165,1740776165) ON DUPLICATE KEY UPDATE visitor_count=visitor_count + 1, updated_on=1740776165
      1.02msalphaeurekaselec_live_10_06_2022UserAccessCheck.php#24
      Backtrace
      • 11. middleware::check_user_access:24
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 14. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 15. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • INSERT INTO visitor_ip_address_detail (ip_address,visitor_url,visitor_count, created_on,updated_on) VALUES ('58766425','/article/120770',1,1740776165,1740776165)
      170μsalphaeurekaselec_live_10_06_2022UserAccessCheck.php#27
      Backtrace
      • 11. middleware::check_user_access:27
      • 12. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 14. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 15. vendor/laravel/framework/src/Illuminate/Foundation/Http/Middleware/VerifyCsrfToken.php:88
    • (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_trail WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_journal_volume_token WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_trail WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_ebook_volume_token WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_trail WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_issue_token WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_trail WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_article_token WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_trail WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_chapter_token WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) union (select `user_id`, `to_ip`, `from_ip` from (select user_id, to_ip, from_ip FROM user_access_disease_corporate WHERE to_ip >= 58766425 ORDER BY to_ip ASC LIMIT 1) as `tjv` where `from_ip` <= 58766425) limit 1
      20.34msalphaeurekaselec_live_10_06_2022UserAccess.php#784
      Bindings
      • 0: 58766425
      • 1: 58766425
      • 2: 58766425
      • 3: 58766425
      • 4: 58766425
      • 5: 58766425
      • 6: 58766425
      • 7: 58766425
      • 8: 58766425
      • 9: 58766425
      • 10: 58766425
      • 11: 58766425
      • 12: 58766425
      • 13: 58766425
      • 14: 58766425
      • 15: 58766425
      Backtrace
      • 14. app/Models/UserAccess/UserAccess.php:784
      • 15. middleware::check_user_access:114
      • 16. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Middleware/SubstituteBindings.php:50
      • 18. vendor/laravel/framework/src/Illuminate/Pipeline/Pipeline.php:183
    • SELECT at.type_name, p.copyright, p.publisher_location,m.month,y.year, a.publish_on, a.nid article_nid,a.article_id, a.pmid, a.issue_id, a.title, a.abstract,a.podcast,a.altmetric_score,a.altmetric_url,a.kudos_url, a.page_count, a.first_page, a.elocator, a.last_page, i.publication_date, a.file_name, a.file_path, a.doi, a.is_epub,a.epub_type, a.volume_id, a.is_uploaded, a.editor_choice, a.is_epub, j.image_file_name, a.article_no, a.art_type AS article_type, a.supplementary_filename,a.html_filename,a.prc_filename,a.epub_filename, a.graph_abs_lg_filename, a.graph_abs_sm_filename, a.oa_image_lg_filename, a.oa_image_sm_filename, j.journal_banner,a.animated_abstract,a.erratum_in,a.erratum_for, (CASE WHEN a.issue_id =0 THEN j.epub_price ELSE j.price END) AS sell_price, j.epub_price, j.nid AS jour_nid, j.title AS journal_title, j.issn, j.eissn,j.journal_id, j.subtitle AS jour_subtitle, v.volume_id,v.volume_name AS volume, v.year_id, i.title AS issue, i.month_id ,i.type issue_type, j.subtitle,j.formerly_title, ac.subtitle AS epub_title,a.crossmark_enabled,a.text_mining_urls,a.license_urls,a.created, a.receivedate, a.revisedate, a.acceptdate,js.js_title FROM article a LEFT JOIN article_section ac ON a.is_epub = ac.art_sec_id LEFT JOIN journal_section js ON a.js_id = js.js_id LEFT JOIN article_type at ON a.art_type = at.art_type_id LEFT JOIN issue i ON a.issue_id = i.issue_id LEFT JOIN month m ON m.id = i.month_id LEFT JOIN volume v ON v.volume_id = a.volume_id INNER JOIN year y ON y.id = v.year_id INNER JOIN journal j ON j.journal_id = a.journal_id INNER JOIN publisher p ON p.publisher_id = j.publisher_id WHERE a.article_id=120770
      1.1msalphaeurekaselec_live_10_06_2022Article.php#408
      Backtrace
      • 11. app/Models/Article.php:408
      • 12. app/Http/Controllers/ArticleController.php:2515
      • 13. app/Http/Controllers/ArticleController.php:2035
      • 14. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 15. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `journal` where `journal_id` = 19 limit 1
      1msalphaeurekaselec_live_10_06_2022Journal.php#64
      Bindings
      • 0: 19
      Backtrace
      • 14. app/Models/Journal.php:64
      • 15. app/Http/Controllers/ArticleController.php:2516
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select count(*) as aggregate from (select j.nid as journal_nid,j.flyer_link,j.title ,j.issn,j.eissn,j.keyword, j.journal_id as journal_id, j.subtitle, j.image_file_name,j.description,j.journal_insight_url,j.doi from `subject_journal` as `sj` inner join `journal` as `j` on `j`.`journal_id` = `sj`.`journal_id` where j.journal_status=1 and subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and sj.journal_id!=19 group by `j`.`nid`) as `aggregate_table`
      740μsalphaeurekaselec_live_10_06_2022Subject.php#200
      Backtrace
      • 16. app/Models/Subject.php:200
      • 17. app/Http/Controllers/ArticleController.php:2517
      • 18. app/Http/Controllers/ArticleController.php:2035
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 20. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select j.nid as journal_nid,j.flyer_link,j.title ,j.issn,j.eissn,j.keyword, j.journal_id as journal_id, j.subtitle, j.image_file_name,j.description,j.journal_insight_url,j.doi from `subject_journal` as `sj` inner join `journal` as `j` on `j`.`journal_id` = `sj`.`journal_id` where j.journal_status=1 and subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and sj.journal_id!=19 group by `j`.`nid` order by `j`.`journal_id` asc limit 10 offset 0
      670μsalphaeurekaselec_live_10_06_2022Subject.php#200
      Backtrace
      • 14. app/Models/Subject.php:200
      • 15. app/Http/Controllers/ArticleController.php:2517
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select count(*) as aggregate from (select v.nid as volume_id,e.nid,e.title,v.issn,v.eissn,v.isbn,v.eisbn,e.ebook_id, v.image_file_name,v.file_path,v.flyer_link,v.ebook_volume_id, v.volume_name,v.doi,v.year_id,v.introduction from `subject_ebook` as `se` inner join `ebook` as `e` on `e`.`ebook_id` = `se`.`ebook_id` inner join `ebook_volume` as `v` on `v`.`ebook_id` = `se`.`ebook_id` inner join `year` as `y` on `y`.`id` = `v`.`year_id` where subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and v.ebook_status='1' and y.year > 2020 group by `v`.`nid`) as `aggregate_table`
      1.92msalphaeurekaselec_live_10_06_2022Subject.php#220
      Backtrace
      • 16. app/Models/Subject.php:220
      • 17. app/Http/Controllers/ArticleController.php:2518
      • 18. app/Http/Controllers/ArticleController.php:2035
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 20. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select v.nid as volume_id,e.nid,e.title,v.issn,v.eissn,v.isbn,v.eisbn,e.ebook_id, v.image_file_name,v.file_path,v.flyer_link,v.ebook_volume_id, v.volume_name,v.doi,v.year_id,v.introduction from `subject_ebook` as `se` inner join `ebook` as `e` on `e`.`ebook_id` = `se`.`ebook_id` inner join `ebook_volume` as `v` on `v`.`ebook_id` = `se`.`ebook_id` inner join `year` as `y` on `y`.`id` = `v`.`year_id` where subject_id IN (SELECT subject_id FROM subject_journal WHERE journal_id=19) and v.ebook_status='1' and y.year > 2020 group by `v`.`nid` order by `v`.`ebook_volume_id` desc limit 10 offset 0
      2.7msalphaeurekaselec_live_10_06_2022Subject.php#220
      Backtrace
      • 14. app/Models/Subject.php:220
      • 15. app/Http/Controllers/ArticleController.php:2518
      • 16. app/Http/Controllers/ArticleController.php:2035
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `keywords` where `article_id` = '120770'
      1.52msalphaeurekaselec_live_10_06_2022Keywords.php#43
      Bindings
      • 0: 120770
      Backtrace
      • 13. app/Models/Keywords.php:43
      • 14. app/Http/Controllers/ArticleController.php:2519
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select * from `article_citation` where `article_id` = '120770'
      5.29msalphaeurekaselec_live_10_06_2022Article.php#1570
      Bindings
      • 0: 120770
      Backtrace
      • 13. app/Models/Article.php:1570
      • 14. app/Http/Controllers/ArticleController.php:2520
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select CONCAT_WS(' ',au.first_name, ' ', ifnull(au.initials,''), ' ', au.last_name) as authors, CONCAT(au.last_name, IFNULL(CONCAT(' ', au.initials), ''), ' ', au.first_name) AS authorsRIS, CONCAT_WS(' ',au.last_name, ' ', ifnull(au.initials,''), ' ', au.first_name) as authorsCiteAs, CONCAT_WS(' ',au.first_name, IFNULL(CONCAT(' ', au.initials), ''), IFNULL(CONCAT(' ', au.last_name), '')) as authorsmodal , `au`.*, `af`.`ror_id`, `af`.`institution`, `af`.`department`, `af`.`country`, `af`.`city`, `af`.`address`, (GROUP_CONCAT(TRIM(BOTH ', ' FROM CONCAT(ifnull(concat(af.institution,','),''), ifnull(concat(af.department,','),''), ifnull(concat(af.address,','),''), ifnull(concat(af.city,','),''), ifnull(concat(af.country,','),''), ifnull(concat(af.postal_code,','),''), ifnull(concat(af.phone,','),''), ifnull(concat(af.fax,','),''))) SEPARATOR '|')) as `author_affiliation`, (GROUP_CONCAT(TRIM(BOTH ', ' FROM CONCAT(ifnull(concat(af.web_view,','),''))) SEPARATOR '|')) as `web_view` from `author` as `au` left join `author_affiliation` as `af` on `au`.`author_id` = `af`.`author_id` where `au`.`article_id` = '120770' group by `au`.`author_id` order by `au`.`article_id` asc, `au`.`sequence` asc
      2.65msalphaeurekaselec_live_10_06_2022Author.php#86
      Bindings
      • 0: 120770
      Backtrace
      • 13. app/Models/Author.php:86
      • 14. app/Http/Controllers/ArticleController.php:2533
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select `bo`.* from `bundle_offer` as `bo` where `bo`.`bundle_status` = 'A' order by `bo`.`bundle_id` desc
      330μsalphaeurekaselec_live_10_06_2022BundleOffer.php#57
      Bindings
      • 0: A
      Backtrace
      • 13. app/Models/BundleOffer.php:57
      • 14. app/Http/Controllers/ArticleController.php:2535
      • 15. app/Http/Controllers/ArticleController.php:2035
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
    • select `subtitle` from `journal` where `continues_publication_journal` = 1
      730μsalphaeurekaselec_live_10_06_2022Article.php#1960
      Bindings
      • 0: 1
      Backtrace
      • 13. app/Models/Article.php:1960
      • 14. app/Http/Controllers/ArticleController.php:2062
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • Select j.subtitle, v.volume_id as volume_id,v.year_id,y.year as year,v.volume_name, v.total_no_of_issues, i.issue_id as issue_id,i.title as issue, i.publication_date as issue_pub_date from journal j join volume v on j.journal_id = v.journal_id join issue i on v.volume_id = i.volume_id join article a on a.issue_id = i.issue_id join year y on v.year_id = y.id where j.journal_id = 19 and i.is_uploaded = 1 order by v.volume_name+0 desc, i.title+0 desc limit 1
      47.47msalphaeurekaselec_live_10_06_2022Issue.php#298
      Backtrace
      • 11. app/Models/Issue.php:298
      • 12. app/Http/Controllers/ArticleController.php:2068
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select a.nid,a.publish_on, a.pmid,a.article_id,a.doi,j.journal_id,j.subtitle,v.volume_name,a.volume_id as volume_id, a.issue_id,a.title,first_page, last_page, page_count,abstract,ifnull(is_abstract,"y"),asec.title as article_section,at.type_name as article_type_name, a.article_id as ArticleID ,is_epub,epub_price,epub_type,a.created, y.year from `article` as `a` left join `article_section` as `asec` on `asec`.`art_sec_id` = `a`.`is_epub` left join `article_type` as `at` on `at`.`art_type_id` = `a`.`art_type` left join `journal` as `j` on `j`.`journal_id` = `a`.`journal_id` inner join `volume` as `v` on `a`.`volume_id` = `v`.`volume_id` inner join `year` as `y` on `v`.`year_id` = `y`.`id` where a.article_status != "W" and a.is_epub = 1 and a.journal_id = 19 and a.is_uploaded = 1 group by `a`.`article_id` order by `a`.`publish_on` desc
      23.69msalphaeurekaselec_live_10_06_2022Article.php#528
      Backtrace
      • 13. app/Models/Article.php:528
      • 14. app/Http/Controllers/ArticleController.php:2070
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select a.nid,a.publish_on, a.pmid,a.article_id,a.doi,j.journal_id,j.subtitle,v.volume_name,a.volume_id as volume_id, a.issue_id,a.title,first_page, last_page, page_count,abstract,ifnull(is_abstract,"y"),asec.title as article_section,at.type_name as article_type_name, a.article_id as ArticleID ,is_epub,epub_price,epub_type,a.created, y.year from `article` as `a` left join `article_section` as `asec` on `asec`.`art_sec_id` = `a`.`is_epub` left join `article_type` as `at` on `at`.`art_type_id` = `a`.`art_type` left join `journal` as `j` on `j`.`journal_id` = `a`.`journal_id` inner join `volume` as `v` on `a`.`volume_id` = `v`.`volume_id` inner join `year` as `y` on `v`.`year_id` = `y`.`id` where a.article_status != "W" and a.is_epub = 4 and a.journal_id = 19 and a.is_uploaded = 1 group by `a`.`article_id` order by `a`.`publish_on` desc
      21.2msalphaeurekaselec_live_10_06_2022Article.php#528
      Backtrace
      • 13. app/Models/Article.php:528
      • 14. app/Http/Controllers/ArticleController.php:2071
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select pdf, html, epub, prc from `article_metrics` where `article_id` = 120770 limit 1
      13.47msalphaeurekaselec_live_10_06_2022Article.php#744
      Bindings
      • 0: 120770
      Backtrace
      • 14. app/Models/Article.php:744
      • 15. app/Http/Controllers/ArticleController.php:2091
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from content_by_diseases where content_id = 120770 and content_type = 'article' order by status desc limit 1
      10.54msalphaeurekaselec_live_10_06_2022Article.php#751
      Backtrace
      • 11. app/Models/Article.php:751
      • 12. app/Http/Controllers/ArticleController.php:2094
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `node_meta` where `nid` = 200966 limit 1
      1.28msalphaeurekaselec_live_10_06_2022Meta.php#30
      Bindings
      • 0: 200966
      Backtrace
      • 14. app/Models/Meta.php:30
      • 15. app/Http/Controllers/ArticleController.php:2101
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `bo`.* from `bundle_offer` as `bo` where `bo`.`bundle_status` = 'A' order by `bo`.`bundle_id` desc
      380μsalphaeurekaselec_live_10_06_2022BundleOffer.php#57
      Bindings
      • 0: A
      Backtrace
      • 13. app/Models/BundleOffer.php:57
      • 14. app/Http/Controllers/ArticleController.php:2108
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `tbl_ht_submission` as `h` where `h`.`subtitle` = 'COC' and (h.proposal_closing_date = 0 OR TO_DAYS(FROM_UNIXTIME(h.proposal_closing_date)) >= TO_DAYS(NOW())) order by `h`.`manuscript` asc
      610μsalphaeurekaselec_live_10_06_2022Article.php#2025
      Bindings
      • 0: COC
      Backtrace
      • 13. app/Models/Article.php:2025
      • 14. app/Http/Controllers/ArticleController.php:2112
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '120770' and content_type = 'a' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      590μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2186
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '11555' and content_type = 'i' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      570μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2207
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select count(*) as total_count, content_type_access_id as access_type from journal_access where content_type_id = '3226' and content_type = 'v' and ( (from_date <= CURDATE() and to_date >= CURDATE() and perpetual= 0) or (from_date is null and to_date is null and perpetual= 1) )
      530μsalphaeurekaselec_live_10_06_2022ContentAccess.php#647
      Backtrace
      • 11. app/Models/ContentAccess.php:647
      • 12. app/Http/Controllers/ArticleController.php:2231
      • 13. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 14. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"volume" as access_level,"" as issue_id,"" as article_id from `user_access_journal_volume_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.volume_id = 3226)
      21.87msalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2272
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11555) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11555) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"issue" as access_level,j.issue_id,"" as article_id from `user_access_issue_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.issue_id = 11555)
      1.1msalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2297
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 120770) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 120770) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"article" as access_level, j.issue_id, j.article_id from `user_access_article_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 58766425 and j.to_ip >=58766425 )) and ((j.from_date <= 1740776165 and j.to_date >= 1740776165 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.article_id = 120770)
      950μsalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ArticleController.php:2329
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `article` where `first_page` < '418' and is_uploaded = 1 and issue_id = 11555 order by cast(first_page as SIGNED) desc limit 1
      750μsalphaeurekaselec_live_10_06_2022Article.php#1819
      Bindings
      • 0: 418
      Backtrace
      • 14. app/Models/Article.php:1819
      • 15. app/Http/Controllers/ArticleController.php:2470
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select * from `article` where `last_page` > '425' and is_uploaded = 1 and issue_id = 11555 order by cast(first_page as SIGNED) asc limit 1
      610μsalphaeurekaselec_live_10_06_2022Article.php#1831
      Bindings
      • 0: 425
      Backtrace
      • 14. app/Models/Article.php:1831
      • 15. app/Http/Controllers/ArticleController.php:2472
      • 16. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 17. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `language_id` from `multilanguage` where `short_code` = 'en'
      240μsalphaeurekaselec_live_10_06_2022ArticleController.php#2497
      Bindings
      • 0: en
      Backtrace
      • 14. app/Http/Controllers/ArticleController.php:2497
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
      • 18. vendor/laravel/framework/src/Illuminate/Routing/Route.php:206
    • select `source_lang_label`, `target_lang_label` from `multilanguage_labels` where `target_lang_id` = 1
      310μsalphaeurekaselec_live_10_06_2022MultiLanguage.php#23
      Bindings
      • 0: 1
      Backtrace
      • 13. app/Models/MultiLanguage.php:23
      • 14. app/Http/Controllers/ArticleController.php:2498
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select `id` from `multilanguage_article` where `article_id` = 120770 limit 1
      3.93msalphaeurekaselec_live_10_06_2022ArticleController.php#2506
      Bindings
      • 0: 120770
      Backtrace
      • 16. app/Http/Controllers/ArticleController.php:2506
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 18. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 19. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
      • 20. vendor/laravel/framework/src/Illuminate/Routing/Route.php:206
    • select b.banner_link, b.banner_name, b.banner_script, b.banner_remarks, b.banner_file_name, b.banner_placement, bd.content_type, bd.content_id from `tbl_banner` as `b` inner join `tbl_banner_detail` as `bd` on `bd`.`banner_id` = `b`.`banner_id` inner join `users` as `u` on `u`.`id` = `b`.`updated_by` inner join `journal` as `j` on `j`.`journal_id` = `bd`.`content_id` where `b`.`banner_journal` = 1 and `bd`.`content_type` = 'J' and `bd`.`content_id` = 19 and `b`.`banner_from_date` <= 1740776165 and `b`.`banner_to_date` >= 1740776165 and `b`.`banner_status` = 'A' order by `b`.`banner_id` desc
      1.64msalphaeurekaselec_live_10_06_2022Banner.php#95
      Bindings
      • 0: 1
      • 1: J
      • 2: 19
      • 3: 1740776165
      • 4: 1740776165
      • 5: A
      Backtrace
      • 13. app/Models/Banner.php:95
      • 14. app/Http/helpers.php:404
      • 17. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 18. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    • select b.banner_link, b.banner_name, b.banner_script, b.banner_remarks, b.banner_file_name, b.banner_placement, bd.content_type, bd.content_id from `tbl_banner` as `b` inner join `tbl_banner_detail` as `bd` on `bd`.`banner_id` = `b`.`banner_id` inner join `users` as `u` on `u`.`id` = `b`.`updated_by` inner join `journal` as `j` on `j`.`journal_id` = `bd`.`content_id` where `b`.`banner_journal` = 1 and `bd`.`content_type` = 'J' and `bd`.`content_id` = 19 and `b`.`banner_from_date` <= 1740776165 and `b`.`banner_to_date` >= 1740776165 and `b`.`banner_status` = 'A' order by `b`.`banner_id` desc
      1.57msalphaeurekaselec_live_10_06_2022Banner.php#95
      Bindings
      • 0: 1
      • 1: J
      • 2: 19
      • 3: 1740776165
      • 4: 1740776165
      • 5: A
      Backtrace
      • 13. app/Models/Banner.php:95
      • 14. app/Http/helpers.php:404
      • 17. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 18. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    • select count(*) as aggregate from `uc_cart_products` where cart_id='021f6868ab0c3d5c48856fabf2a3f8ed'
      230μsalphaeurekaselec_live_10_06_2022Cart.php#271
      Backtrace
      • 15. app/Models/Cart.php:271
      • 16. view::layouts._header:291
      • 18. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 20. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    App\Models\MultiLanguage
    1MultiLanguage.php#?
        _token
        rvM2mPrDgiWHXVuurNuDZVtwUMzJ24zwAEzsjuA5
        uc_cart_id
        021f6868ab0c3d5c48856fabf2a3f8ed
        _previous
        array:1 [ "url" => "http://alpha.eurekaselect.com/article/120770" ]
        _flash
        array:2 [ "old" => [] "new" => [] ]
        PHPDEBUGBAR_STACK_DATA
        []
        path_info
        /article/120770
        status_code
        200
        
        status_text
        OK
        format
        html
        content_type
        text/html; charset=UTF-8
        request_query
        []
        
        request_request
        []
        
        request_headers
        0 of 0
        array:8 [ "accept-encoding" => array:1 [ 0 => "gzip, deflate" ] "accept" => array:1 [ 0 => "text/html,application/xhtml+xml,application/xml;q=0.9,image/avif,image/webp,image/apng,*/*;q=0.8,application/signed-exchange;v=b3;q=0.7" ] "user-agent" => array:1 [ 0 => "Mozilla/5.0 AppleWebKit/537.36 (KHTML, like Gecko; compatible; ClaudeBot/1.0; +claudebot@anthropic.com)" ] "upgrade-insecure-requests" => array:1 [ 0 => "1" ] "cache-control" => array:1 [ 0 => "no-cache" ] "pragma" => array:1 [ 0 => "no-cache" ] "connection" => array:1 [ 0 => "keep-alive" ] "host" => array:1 [ 0 => "alpha.eurekaselect.com" ] ]
        request_cookies
        []
        
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