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Quinone methide

From Wikipedia, the free encyclopedia
(Redirected from Quinomethide)
Quinone methide
Identifiers
3D model (JSmol)
o- 1922177
ChEBI
ChemSpider
UNII
  • o-: InChI=1S/C7H6O/c1-6-4-2-3-5-7(6)8/h2-5H,1H2
    Key: NSDWWGAIPUNJAX-UHFFFAOYSA-N
  • p-: InChI=1S/C7H6O/c1-6-2-4-7(8)5-3-6/h2-5H,1H2
    Key: OJPNKYLDSDFUPG-UHFFFAOYSA-N
  • o-: C=C1C=CC=CC1=O
  • p-: C=C1C=CC(=O)C=C1
Properties
C7H6O
Molar mass 106.124 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

A quinone methide is a type of conjugated organic compound that contain a cyclohexadiene with a carbonyl and an exocyclic methylidene or extended alkene unit. It is analogous to a quinone, but having one of the double bonded oxygens replaced with a carbon. The carbonyl and methylidene are usually oriented either ortho or para to each other. There are some examples of transient synthetic meta quinone methides.

Properties

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Quinone methides are cross-conjugated rather than aromatic. Nucleophilic addition at the exo-cyclic double bond will result in rearomatisation, making such reactions highly favourable. As a result, quinone methides are excellent, electrophilic Michael acceptors, react quickly with nucleophiles and can be easily reduced. They are able to act as radical scavengers via a similar process, a behaviour exploited by certain polymerisation inhibitors. Quinone methides are more polar than quinones, and therefore more chemically reactive. Simple unhindered quinone methides are short lived reactive intermediates that are not stable enough to be isolated under normal circumstances, they will trimerise in the absence of nucleophiles.[1] Sterically hindered quinone methides can be sufficiently stable to be isolated, with some examples being commercially available.

Preparation

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Quinone methides are often prepared by oxidation of the corresponding ortho or para cresol.

Quinone methides can be produced in aqueous solution by photochemical dehydration of o-hydroxybenzyl alcohols (i.e. salicyl alcohol).

Occurrence and applications

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Lignification and delignification

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Quinone methides are intermediates in both the biosynthesis and in chemical delignification of lignin. Lignin arises by the coupling of monolignols, via the intermediacy of their quinone methides. The process is promoted by oxidative enzymes.

Delignification is central to the pulp and paper industry. The goal of this industry is the production of cellulose from lignocellulose. Typically, wood is subjected to the Kraft process to cleave the lignin (and hemicellulose) away from the cellulose, which is the main component of paper. The Kraft process uses a combination of sodium hydroxide and sodium hydrosulfide to degrade the lignin, allowing it to be liberated from the cellulose. This breakdown occurs via deprotonation of alkylphenoxides, precursors to quinone methides.[2][3]

Biochemistry

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In the biosynthesis of hydrogenase active site, quinone methide (per se) arises by the degradation of tyrosine.[4]

Medicine

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Quinone methides have been implicated as the "ultimate" cytotoxins responsible for the effects of such agents as antitumor drugs, antibiotics, and DNA alkylators.[5] Oxidation to a reactive quinone methide is the mechanistic basis of many phenolic anti-cancer drugs.

Proposed sequence of reactions with N-acetyldopamine as substrate resulting in sclerotization (formation of exoskeletons of arthropods). The middle step, involving conversion of the ortho quinone to quinone methide, is catalyzed by the enzyme quinone isomerase.[6]

Natural products

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Maytenoquinone
Kendomycin

Although quinone methides are rarely observed in the laboratory, several have been identified from natural sources. Some are bioactive with promise as medicines.

Conversion of taxodone into taxodione
  • Maytenoquinone, an isomer of taxodione, is found in Maytenus dispermus.[26]
  • Kendomycin is a quinone methide macrolide first isolated from the bacterium Streptomyces violaceoruber.[27]
  • Elansolid A3 is a quinone methide from the bacterium Chitinophaga sancti.[28]
  • Quinone methides 20-epi-isoiguesterinol, 6-oxoisoiguesterin, isoiguesterin, and isoiguesterinol were found in Salacia madagascariensis.[29]
  • Quinone methides tingenone and netzahualcoyonol were isolated from Salacia petenensis.[30]
  • Nortriterpenoid quinone methides amazoquinone and (7S, 8S)-7-hydroxy-7,8-dihydro-tingenone were isolated from Maytenus amazonica.[31] An antimicrobial quinone methide, 15 alpha-hydroxypristimerin, was isolated from a South American medicinal plant, Maytenus scutioides.[32]

Quinone dimethides

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A quinone dimethide (or "xylylene") is a compound with the formula C6H4(=CH2)2. Thus they are related to quinone monomethides (the topic of this article) by replacing the keto group with methylidene. A well studied example is tetracyanoquinodimethane.

References

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  1. ↑ Cavitt, S. B.; R., H. Sarrafizadeh; Gardner, P. D. (April 1962). "The Structure of o-Quinone Methide Trimer". The Journal of Organic Chemistry. 27 (4): 1211–1216. doi:10.1021/jo01051a021.
  2. ↑ Lachenal, Dominique (2016). "Kraft Pulping". Lignocellulosic Fibers and Wood Handbook. pp. 207–223. doi:10.1002/9781118773727.ch7. ISBN 978-1-118-77352-9.
  3. ↑ Quinone Methides in Lignification
  4. ↑ Stich, T. A.; Myers, W. K.; Britt, R. D., "Paramagnetic intermediates generated by radical S-adenosylmethionine (SAM) enzymes", Acc. Chem. Res. 2014, 47, 2235-2243.
  5. ↑ Wang P, Song Y, Zhang L, He H, Zhou X (2005). "Quinone methide derivatives: important intermediates to DNA alkylating and DNA cross-linking actions". Curr Med Chem. 12 (24): 2893–2913. doi:10.2174/092986705774454724. PMID 16305478.
  6. ↑ Andersen, Svend Olav (2010). "Insect Cuticular Sclerotization: A Review". Insect Biochemistry and Molecular Biology. 40 (3): 166–178. Bibcode:2010IBMB...40..166A. doi:10.1016/j.ibmb.2009.10.007. PMID 19932179.
  7. ↑ Allison AC, Cacabelos R, Lombardi VR, Alvarez XA, Vigo C (2001). "Celastrol, a potent antioxidant and anti-inflammatory drug, as a possible treatment for Alzheimer's disease". Prog Neuropsychopharmacol Biol Psychiatry. 25 (7): 1341–1357. doi:10.1016/S0278-5846(01)00192-0. PMID 11513350. S2CID 21569585.
  8. ↑ Kim DH, Shin EK, Kim YH, Lee BW, Jun JG, Park JH, Kim JK (2009). "Suppression of inflammatory responses by celastrol, a quinone methide triterpenoid isolated from Celastrus regelii". Eur J Clin Invest. 39 (9): 819–827. doi:10.1111/j.1365-2362.2009.02186.x. PMID 19549173. S2CID 205291261.
  9. ↑ Lee JH, Choi KJ, Seo WD, Jang SY, Kim M, Lee BW, Kim JY, Kang S, Park KH, Lee YS, Bae S (2011). "Enhancement of radiation sensitivity in lung cancer cells by celastrol is mediated by inhibition of Hsp90". Int J Mol Med. 27 (3): 441–446. doi:10.3892/ijmm.2011.601. PMID 21249311.
  10. ↑ Tiedemann; et al. (2009). "Identification of a potent natural triterpenoid inhibitor of proteosome chymotrypsin-like activity and NF-kappaB with antimyeloma activity in vitro and in vivo". Blood. 113 (17): 4027–37. doi:10.1182/blood-2008-09-179796. PMC 3952546. PMID 19096011.
  11. ↑ Zhu H, Liu XW, Cai TY, Cao J, Tu CX, Lu W, He QJ, Yang B (2010). "Celastrol acts as a potent antimetastatic agent targeting beta1 integrin and inhibiting cell-extracellular matrix adhesion, in part via the p38 mitogen-activated protein kinase pathway". J Pharmacol Exp Ther. 334 (2): 489–499. doi:10.1124/jpet.110.165654. PMID 20472666. S2CID 25854329.
  12. ↑ Byun; et al. (2009). "Reactive oxygen species-dependent activation of Bax and Poly(ADP)-ribose) polymerase-1 is required for mitochondrial cell death induced by triterpenoid Pristimerin in human cervical cancer cells". Mol. Pharmacol. 76 (4): 734–44. doi:10.1124/mol.109.056259. PMID 19574249. S2CID 6541041.
  13. ↑ Avilla J, Teixidò A, Velázquez C, Alvarenga N, Ferro E, Canela R (2000). "Insecticidal activity of Maytenus species (Celastraceae) nortriterpene quinone methides against codling moth, Cydia pomonella (L.) (Lepidoptera: tortricidae)". Journal of Agricultural and Food Chemistry. 48 (1): 88–92. Bibcode:2000JAFC...48...88A. doi:10.1021/jf990008w. PMID 10637057.
  14. ↑ Murayama T, Eizuru Y, Yamada R, Sadanari H, Matsubara K, Rukung G, Tolo FM, Mungai GM, Kofi-Tsekpo M (2007). "Anticytomegalovirus activity of pristimerin, a triterpenoid quinone methide isolated from Maytenus heterophylla (Eckl. & Zeyh.)". Antivir Chem Chemother. 18 (3): 133–139. doi:10.1177/095632020701800303. PMID 17626597. S2CID 22381089.
  15. ↑ Nadja Mannowetz; Melissa R. Miller; Polina V. Lishko (2017). "Regulation of the sperm calcium channel CatSper by endogenous steroids and plant triterpenoids". Proceedings of the National Academy of Sciences of the United States of America. 114 (22): 5743–5748. Bibcode:2017PNAS..114.5743M. doi:10.1073/pnas.1700367114. PMC 5465908. PMID 28507119.
  16. ↑ Kupchan, S. M.; Karim, A; Marcks, C. (1968). "Tumor inhibitors. XXXIV. Taxodione and taxodone, two novel diterpenoid quinone methide tumor inhibitors from Taxodium distichum". J Am Chem Soc. 90 (21): 5923–4. Bibcode:1968JAChS..90.5923K. doi:10.1021/ja01023a061. PMID 5679178.
  17. ↑ Zaghloul AM, Gohar AA, Naiem ZA, Abdel Bar FM (2008). "Taxodione, a DNA-binding compound from Taxodium distichum L. (Rich.)". Z Naturforsch C. 63 (5–6): 355–360. doi:10.1515/znc-2008-5-608. PMID 18669020. S2CID 23956301.
  18. ↑ Ayhan Ulubelen, Gülaçtı Topçu, Hee-Byung Chai and John M. Pezzuto (1999). "Cytotoxic Activity of Diterpenoids Isolated from Salvia hypargeia". Pharmaceutical Biology. 37 (2): 148–151. doi:10.1076/phbi.37.2.148.6082.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  19. ↑ Vivek K. Bajpai & Sun Chul Kang (2010). "Antibacterial abietane-type diterpenoid, taxodone from Metasequoia glyptostroboides Miki ex Hu". Journal of Biosciences. 35 (4): 533–538. doi:10.1007/s12038-010-0061-z. PMID 21289435. S2CID 25656295.
  20. ↑ Vivek K. Bajpai; Minkyun Na; Sun Chul Kang (2010). "The role of bioactive substances in controlling foodborne pathogens derived from Metasequoia glyptostroboides Miki ex Hu". Food and Chemical Toxicology. 48 (7): 1945–1949. doi:10.1016/j.fct.2010.04.041. PMID 20435080.
  21. ↑ Tada M, Kurabe J, Yoshida T, Ohkanda T, Matsumoto Y (2010). "Syntheses and antibacterial activities of diterpene catechol derivatives with abietane, totarane and podocarpane skeletons against methicillin-resistant Staphylococcus aureus and Propionibacterium acnes". Chem Pharm Bull. 58 (6): 818–824. doi:10.1248/cpb.58.818. PMID 20522992.
  22. ↑ Ufuk Kolak; Ahmed Kabouche; Mehmet Öztürk; Zahia Kabouche; Gülaçtı Topçu; Ayhan Ulubelen (2009). "Antioxidant diterpenoids from the roots of Salvia barrelieri". Phytochemical Analysis. 20 (4): 320–327. Bibcode:2009PChAn..20..320K. doi:10.1002/pca.1130. PMID 19402189.
  23. ↑ Norihisa Kusumoto; Tatsuya Ashitani; Tetsuya Murayama; Koichi Ogiyama; Koetsu Takahashi (2010). "Antifungal Abietane-Type Diterpenes from the Cones of Taxodium distichum Rich". Journal of Chemical Ecology. 36 (12): 1381–1386. Bibcode:2010JCEco..36.1381K. doi:10.1007/s10886-010-9875-2. PMID 21072573. S2CID 11861719.
  24. ↑ Norihisa Kusumoto; Tatsuya Ashitani; Yuichi Hayasaka; Tetsuya Murayama; Koichi Ogiyama; Koetsu Takahashi (2009). "Antitermitic Activities of Abietane-type Diterpenes from Taxodium distichum Cones". Journal of Chemical Ecology. 35 (6): 635–642. Bibcode:2009JCEco..35..635K. doi:10.1007/s10886-009-9646-0. PMID 19475449. S2CID 42622420.
  25. ↑ M. C. Ballesta-Acosta, M. J. Pascual-Villalobos and B. Rodríguez (2008). "Short communication. The antifeedant activity of natural plant products towards the larvae of Spodoptera littoralis". Spanish Journal of Agricultural Research. 6 (1): 85–91. doi:10.5424/sjar/2008061-304.
  26. ↑ J. D. Martín (1973). "New diterpenoids extractives of Maytenus dispermus". Tetrahedron. 29 (17): 2553–2559. doi:10.1016/0040-4020(73)80172-3.
  27. ↑ H B Bode & A Zeeck (2000). "Structure and biosynthesis of kendomycin, a carbocyclic ansa-compound from Streptomyces". J Chem Soc Perkin Trans 1. 323 (3): 323–328. doi:10.1039/a908387a.
  28. ↑ Jansen R, Gerth K, Steinmetz H, Reinecke S, Kessler W, Kirschning A, Müller R (2011). "Elansolid A3, a Unique p-Quinone Methide Antibiotic from Chitinophaga sancti". Chem. Eur. J. 17 (28): 7739–44. doi:10.1002/chem.201100457. PMID 21626585.
  29. ↑ Thiem DA, Sneden AT, Khan SI, Tekwani BL (2005). "Bisnortriterpenes from Salacia madagascariensis". J Nat Prod. 68 (2): 251–254. Bibcode:2005JNAtP..68..251T. doi:10.1021/np0497088. PMID 15730255.
  30. ↑ Setzer WN, Holland MT, Bozeman CA, Rozmus GF, Setzer MC, Moriarity DM, Reeb S, Vogler B, Bates RB, Haber WA (2001). "Isolation and frontier molecular orbital investigation of bioactive quinone-methide triterpenoids from the bark of Salacia petenensis". Planta Med. 67 (1): 65–69. Bibcode:2001PlMed..67...65S. doi:10.1055/s-2001-10879. PMID 11270725.
  31. ↑ Chávez H, Estévez-Braun A, Ravelo AG, González AG (1999). "New phenolic and quinone-methide triterpenes from Maytenus amazonica". J Nat Prod. 62 (3): 434–436. doi:10.1021/np980412+. PMID 10096852.
  32. ↑ González AG, Alvarenga NL, Bazzocchi IL, Ravelo AG, Moujir L (1998). "A new bioactive norquinone-methide triterpene from Maytenus scutioides". Planta Med. 64 (8): 767–771. Bibcode:1998PlMed..64..769G. doi:10.1055/s-2006-957581. PMID 10075545. S2CID 11522064.
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