Startseite Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
Artikel
Lizenziert
Nicht lizenziert Erfordert eine Authentifizierung

Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions

  • Takashi Hosoya , Ute Henniges , Antje Potthast und Thomas Rosenau EMAIL logo
Veröffentlicht/Copyright: 30. Januar 2015
Veröffentlichen auch Sie bei De Gruyter Brill

Abstract

2,5-Dihydroxy-[1,4]-benzoquinone (DHBQ) is one of the key chromophores in cellulosics. Due to its special resonance stabilization, it is a prime survivor of bleaching treatments and its degradation is essential in pulp bleaching. The clarification of the degradation mechanism of this compound is indispensable for targeting improvements of pulp bleaching processes. Previous studies revealed that DHBQ degradation by hydrogen peroxide (H2O2) is influenced by salts. This study addresses the effects of alkaline metal salts, alkaline earth metal salts, and Al2(SO4)3 on the degradation of DHBQ under simulated conditions of pulp bleaching in a peroxide stage. The degradation by excess H2O2 followed first-order kinetics in the presence of alkaline metal salts and alkaline earth metal salts, which enhanced and retarded the reaction, respectively. Kinetic studies and theoretical computations provided detailed mechanistic insights: Li+, Na+, and K+ stabilize several reaction intermediates by complex formation, causing the enhancement of the degradation, whereas Mg2+ and Ca2+ coordinate and stabilize the reactant, resulting in the observed retardation. Al2(SO4)3 exhibited a strong enhancing effect, but the degradation followed second-order kinetics with regard to DHBQ, suggesting a fundamentally different degradation mechanism.


Corresponding author: Thomas Rosenau, Division of Chemistry of Renewables, Department of Chemistry, University of Natural Resources and Life Sciences, Muthgasse 18, A-1190 Vienna, Austria, e-mail:

Acknowledgments

We performed quantum chemical calculations with the workstation in the Sakaki Group, Fukui Institute for Fundamental Chemistry at Kyoto University, Japan, and we thank them for the access. The financial support from the Austrian Christian Doppler Research Society (CDG) through the CD-lab “Advanced Cellulose Chemistry and Analytics” and from the Austrian Research Promotion Agency (FFG; project 829443) is gratefully acknowledged.

References

Abrahams, B.F., Bond, A.M., Le, T.H., McCormick, L.J., Nafady, A., Robson, R., Vo, N. (2012) Voltammetric reduction and re-oxidation of solid coordination polymers of dihydroxybenzoquinone. Chem. Commun. (Cambridge) 48:11422–11424.10.1039/c2cc34687gSuche in Google Scholar

Barry, N.P.E., Edafe, F., Dyson, P.J., Therrien, B. (2010) Anticancer activity of osmium metalla-rectangles. Dalton Trans. 39:2816–2820.10.1039/b925015hSuche in Google Scholar

Brassard, P., L’Ecuyer, P. (1958) L’arylation des quinones par les sels de diazonium: IV sur la réaction de ces sels avec la 2,5-dihydroxy-p-benzoqunone at la synthése du la 3-hydoxy-2,5-bisphenyl-p-benzoquinone. Can. J. Chem. 36:1346–1349.10.1139/v58-199Suche in Google Scholar

Di, C., Li, J., Yu, G., Xiao, Y., Guo, Y., Liu, Y., Qian, X., Zhu, D. (2008) Trifluoromethyltriphenodioxazine: air-stable and high-performance n-type semiconductor. Org. Lett. 10:3025–3028.10.1021/ol8008667Suche in Google Scholar

Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A. Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, N.J., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, Ö., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J. Gaussian 09. Revision D.01. Gaussian, Inc., Wallingford, CT, 2009.Suche in Google Scholar

Gellerman, G., Rudi, A., Kashman Y. (1994) The biomimetic synthesis of marine alkaloid related pyrido- and pyrrolo[2,3,4-k]acridines. Tetrahedron 50:12959–12972.10.1016/S0040-4020(01)81215-1Suche in Google Scholar

Hosoya, T., Rosenau, T. (2013a) Degradation of 2,5-dihydroxy-1,4-benzoquinone by hydrogen peroxide: a combined kinetic and theoretical study. J. Org. Chem. 78:3176–3182.10.1021/jo4001178Suche in Google Scholar PubMed

Hosoya, T., Rosenau, T. (2013b) Degradation of 2,5-dihydroxy-[1,4]-benzoquinone by hydrogen peroxide under moderately alkaline conditions resembling pulp bleaching: a combined kinetic and computational study. J. Org. Chem. 78:11194–11203.10.1021/jo401486dSuche in Google Scholar PubMed

Ikeda, M., Kitahara, K., Nishi, H. (1992) Carbazoledioxazines having long alkyl groups. 3. Syntheses and properties of halogen free carbazoledioxazines. J. Heterocycl. Chem. 29:289–294.10.1002/jhet.5570290203Suche in Google Scholar

Jimenez-Alonso, S., Estevez-Braun, A., Ravelo, A.G., Zarate, R., Lopez, M. (2007) Double domino Knoevenagel hetero Diels-Alder strategy towards bis-pyrano-1,4-benzoquinones. Tetrahedron 63:3066–3074.10.1016/j.tet.2007.01.033Suche in Google Scholar

Jimenez-Alonso, S., Perez-Lomas, A.L., Estevez-Braun, A., Martinez, F.M., Orellana, H.C., Ravelo, A.G., Gamarro, F., Castanys, S., Lopez, M. (2008) Bis-pyranobenzoquinones as a new family of reversal agents of the multidrug resistance phenotype mediated by P-glycoprotein in mammalian cells and the protozoan parasite Leishmania. J. Med. Chem. 51:7132–7143.10.1021/jm800403bSuche in Google Scholar

Krainz, K., Potthast, A., Suess, U., Dietz, T., Nimmerfroh, N., Rosenau, T. (2009) Effects of selected key chromophores on cellulose integrity upon bleaching. Holzforschung 63: 647–655.10.1515/HF.2009.118Suche in Google Scholar

Lang, M., Muhlbauer, A., Jagers, E., Steglich, W. (2008) Studies on the biosynthesis of bovilactone-4,4 and related fungal meroterpenoids. Eur. J. Org. Chem. 20:3544–3551.10.1002/ejoc.200800232Suche in Google Scholar

Lee, D.-C., Cao, B., Jang, K., Forster, P.M. (2010) Self-assembly of halogen substituted phenazines. J. Mater. Chem. 20: 867–873.10.1039/B917601BSuche in Google Scholar

Lehaire, M.L., Scopelliti, R., Herdeis, L., Polborn, K., Mayer, P., Severin, K. (2004) Diastereoselective formation of metallamacrocyclic (arene)ruII and CpRhIII complexes. Inorg. Chem. 43:1609–1617.10.1021/ic035328iSuche in Google Scholar

Koulouri, S., Malamidou-Xenikaki, E., Spyroudis, S. (2005) Acid-catalyzed addition of indoles to hydroxyquinones. Tetrahedron 61:10894–10902.10.1016/j.tet.2005.09.003Suche in Google Scholar

Manthey, M.K., Pyne, S.G., Truscott, R.J.W. (1989) Addition of aliphatic and aromatic amines to catechol under oxidising condition. Aust. J. Chem. 42:365–373.10.1071/CH9890365Suche in Google Scholar

Misiolek, A., Ichimura, A.S., Gentner, R.A., Huang, R.H., McCaffrey, V.P., Jackson, J.E. (2009) Building blocks for molecule-based magnets: radical anions and dianions of substituted 3,6-dimethylene-cyclohexane-1,2,4,5-tetrones as paramagnetic bridging ligands. Inorg. Chem. 48:9005–9017.10.1021/ic901390nSuche in Google Scholar

Nicolaides, D.N., Gautam, D.R., Litinas, K.E., Papamehael, T. (2002) Synthesis of some 3,4-dihydro-2H-benzo[f]pyrano[2,3-h]chromen-6-one derivatives. J. Chem. Soc. Perkin Trans. 1:1455–1460.10.1039/b202640fSuche in Google Scholar

Placin, F., Clavier, G., Najera, F., Desvergne, J.P., Pozzo, J.L. (2000) New organogelators based on linear azapolycyclic arenes. Polycycl. Arom. Comp. 19:107–117.10.1080/10406630008034726Suche in Google Scholar

Reuben, G., Shonle, H.A. (1946) Preparation of some 9-diethylaminoalkylphenazines. J. Am. Chem. Soc. 68:2246–2247.10.1021/ja01215a037Suche in Google Scholar

Rosenau, T., Potthast, A., Milacher, W., Hofinger, A., Kosma, P. (2004) Isolation and identification of residual chromophores in cellulosic materials. Polymer 45:6437–6443.10.1016/j.polymer.2004.07.031Suche in Google Scholar

Rosenau, T., Potthast, A., Milacher, W., Adorjan, I., Hofinger, A., Kosma, P. (2005) Discoloration of cellulose solutions in N-methylmorpholine-N-oxide (Lyocell). Part 2: isolation and identification of chromophores. Cellulose 12:197–208.10.1007/s10570-004-0210-3Suche in Google Scholar

Rosenau, T., Potthast, A., Kosma, P., Suess, H.-U., Nimmerfroh, N. (2007) Isolation and identification of residual chromophores from aged bleached pulp samples. Holzforschung 61:656–661.10.1515/HF.2007.108Suche in Google Scholar

Rosenau, T., Potthast, A., Krainz, K., Yoneda, Y., Dietz, T., Shields, Z.P., French, A.D. (2011) Chromophores in cellulosics, VI. First isolation and identification of residual chromophores from aged cotton linters. Cellulose 18:1623–1633.10.1007/s10570-011-9585-0Suche in Google Scholar

Schweinfurth, D., Das, H.S., Weisser, F., Bubrin, D., Sarkar, B. (2011) One-pot synthesis of symmetric and asymmetric p-quinone ligands and unprecedented substituent induced reactivity in their dinuclear ruthenium complexes. Inorg. Chem. 50:1150–1159.10.1021/ic101972uSuche in Google Scholar

Shaabani, A., Ghadari, R., Sarvary, A., Rezayan, A.H. (2009a) Synthesis of highly functionalized bis(4H-chromene) and 4H-benzo[g]chromene derivatives via an isocyanide-based pseudo-five-component reaction. J. Org. Chem. 74:4372–4374.10.1021/jo9005427Suche in Google Scholar PubMed

Shaabani, A., Ghadari, R., Ghasemi, S., Pedarpour, M., Rezayan, A., Sarvary, A., Ng, S.W. (2009b) Novel one-pot three- and pseudo-five-component reactions: synthesis of functionalized benzo[g]- and dihydropyrano[2,3-g]chromene derivatives. J. Comb. Chem. 11:956–959.10.1021/cc900101wSuche in Google Scholar PubMed

Seillan, C., Brisset, H., Siri, O. (2008) Efficient synthesis of substituted dihydrotetraazapentacenes. Org. Lett. 10:4013–4016.10.1021/ol801509vSuche in Google Scholar

Tang, Q., Liu, J., Chan, H.S., Miao, Q. (2009) Benzenoid and quinonoid nitrogen-containing heteropentacenes. Chem. Eur. J. 15:3965–3969.10.1002/chem.200900160Suche in Google Scholar

Wang, G.-L., Lin, Y.-J., Jin, G.-X. (2010) Syntheses and molecular structures of half-sandwich iridium metallarectangles containing bridging 2,5-dihydroxy-1,4- benzoquinonato (DHBQ) ligands. J. Organometal. Chem. 695:1225–1230.10.1016/j.jorganchem.2010.01.034Suche in Google Scholar

Zhang, D., Jin, G.X. (2003) Novel, highly active binuclear 2,5-disubstituted amino-p-benzoquinone-nickel(II) ethylene polymerization catalysts. Organometallics 22:2851–2854.10.1021/om030068ySuche in Google Scholar

Zhao, Y., Truhlar, D.G. (2008) 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 functional. Theor. Chem. Acc. 120:215–241.10.1007/s00214-007-0310-xSuche in Google Scholar

Received: 2014-9-19
Accepted: 2014-12-17
Published Online: 2015-1-30
Published in Print: 2015-8-1

©2015 by De Gruyter

Artikel in diesem Heft

  1. Frontmatter
  2. Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
  3. Novel insight in carbohydrate degradation during alkaline treatment
  4. Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
  5. Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
  6. Analysis of degradation products in rayon spinning baths
  7. Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
  8. Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
  9. Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
  10. Depolymerization of cellulose during cold acidic chlorite treatment
  11. Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
  12. Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
  13. Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
  14. Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
  15. Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
  16. Wood-based activated carbons for supercapacitors with organic electrolyte
  17. Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
  18. Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
  19. Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
  20. Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
Heruntergeladen am 6.9.2025 von https://www.degruyterbrill.com/document/doi/10.1515/hf-2014-0256/html?lang=de
Button zum nach oben scrollen