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23.3.2020 Quaternary cation - Wikipedia

Quaternary ammonium cation

Quaternary ammonium cations, also known as quats, are + positively charged polyatomic of the structure NR4, R being an [1] + group or an aryl group. Unlike the ammonium (NH4) and the primary, secondary, or tertiary ammonium cations, the quaternary ammonium cations are permanently charged, independent of the pH of their solution. Quaternary ammonium salts or quaternary ammonium compounds (called quaternary in oilfield parlance) are salts of quaternary ammonium cations. Polyquats are a variety of engineered polymer forms which provide multiple quat molecules within a larger molecule.

Quaternary ammonium cation. The Contents R groups may be the same or different alkyl or aryl groups. Also, Synthesis the R groups may be connected. Reactions Applications As antimicrobials Phase transfer catalysts Fabric softeners and hair conditioners Plant growth retardants Natural occurrence Health effects Possible reproductive effects in laboratory animals Quantification References + External links "Top" view of one view of Bu4N as determined by X-ray crystallography.[2] Synthesis

Quaternary ammonium compounds are prepared by the alkylation of tertiary amines with a halocarbon.[3] In older literature this is often called a Menshutkin reaction, however modern chemists usually refer to it simply as quaternization.[4] The reaction can be used to produce a compound with unequal alkyl chain lengths; for example when making cationic one of the alkyl groups on the [5] + is typically longer than the others. A typical synthesis is for "Side" view of Bu4N as determined from a long-chain alkyldimethylamine and by X-ray crystallography.[2] benzyl chloride:

+ − CH3(CH2)nN(CH3)2 + ClCH2C6H5 → [CH3(CH2)nN(CH3)2CH2C6H5] Cl

Reactions

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation 1/7 23.3.2020 Quaternary ammonium cation - Wikipedia Quaternary ammonium cations are unreactive toward even strong , oxidants, and . They also are stable toward most nucleophiles. The latter is indicated by the stability of the salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Because of their resilience, many unusual anions have been isolated as the quaternary ammonium salts. Examples include − tetramethylammonium pentafluoroxenate, containing the highly reactive pentafluoroxenate (XeF5) ion. + [6][7] Permanganate can be solubilized in organic solvents, when deployed as its NBu4 . With exceptionally strong bases, quat cations degrade. They undergo Sommelet–Hauser rearrangement[8] and Stevens rearrangement,[9] as well as dealkylation under harsh conditions. Quaternary ammonium cations containing N–C–C–H units can also undergo the Hofmann elimination and Emde degradation.

Applications

Quaternary ammonium salts are used as , surfactants, fabric softeners, and as antistatic agents (e.g. in ). In liquid fabric softeners, the chloride salts are often used. In dryer anticling strips, the sulfate salts are often used. Older aluminium electrolytic Benzalkonium chloride is a common capacitors and spermicidal jellies also contain quaternary ammonium type of quat salt used as a biocide, salts. a cationic , and as a phase transfer agent.[10] ADBACs are a mixture of As antimicrobials alkylbenzyldimethylammonium chlorides, in which the alkyl group Quaternary ammonium compounds have also been shown to have has various even-numbered alkyl [11] antimicrobial activity. Certain quaternary ammonium compounds, chain lengths. especially those containing long alkyl chains, are used as antimicrobials and disinfectants. Examples are benzalkonium chloride, , methylbenzethonium chloride, cetalkonium chloride, , , , dofanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride and domiphen bromide. Also good against fungi, amoebas, and enveloped viruses,[12] quaternary ammonium compounds are believed to act by disrupting the cell membrane or viral envelope.[13] Quaternary ammonium compounds are lethal to a wide variety of organisms except endospores, Mycobacterium tuberculosis and non-enveloped viruses.

Quaternary ammonium compounds are cationic detergents, as well as disinfectants, and as such can be used to remove organic material. They are very effective in combination with . Quaternary ammonium compounds are deactivated by anionic detergents (including common soaps). Also, they work best in soft waters. Effective levels are at 200 ppm. They are effective at temperatures up to 100 °C (212 °F).

Quaternary ammonium salts are commonly used in the foodservice industry as sanitizing agents.

Phase transfer catalysts

In organic chemistry, quaternary ammonium salts are employed as phase transfer catalysts (PTCs). Such catalysts accelerate reactions between reagents dissolved in immiscible solvents. The highly reactive reagent dichlorocarbene is generated via PTC by reaction of and aqueous hydroxide.

Fabric softeners and hair conditioners

In the 1950s, distearyldimethylammonium chloride (DHTDMAC), was introduced as a fabric softener. This compound was discontinued because the cation biodegrades too slowly. Contemporary fabric softeners are based on salts of quaternary ammonium cations where the fatty is linked to the quaternary center via linkages; these are commonly referred to as betaine- or ester-quats and

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation 2/7 23.3.2020 Quaternary ammonium cation - Wikipedia are susceptible to degradation, e.g., by hydrolysis.[14] Characteristically, the cations contain one or two long alkyl chains derived from fatty acids linked to an ethoxylated ammonium salt.[15] Other cationic compounds can be derived from imidazolium, guanidinium, substituted amine salts, or quaternary alkoxy ammonium salts.[16]

Cationic surfactants used as fabric softeners Anion exchange resins, in the form of beads, contain quaternary ammonium ions bound to a polymer.

Distearyldimethylammonium chloride, an early generation fabric softener with low biodegradability that was phased out.

Another diesterquat, a Diethyl ester dimethyl ammonium contemporary fabric softener. chloride used as a fabric softener.

Another diesterquat used as a fabric softener.

The antistatic qualities that make quaternary ammonium salts useful as fabric softeners also make them useful in hair conditioners and shampoos.[17] The idea was pioneered by Henkel with a 1984 patent.[18] Examples include and .[19]

Plant growth retardants

Cycocel (chlormequat chloride) reduces plant height by inhibiting the production of gibberellins, the primary plant hormones responsible for cell elongation. Therefore, their effects are primarily on stem, petiole and flower stalk tissues. Lesser effects are seen in reductions of leaf expansion, resulting in thicker leaves with darker green color.[20]

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Glycine betaine, found in osmolytes, stabilizes osmotic pressure in cells.[21]

Choline is a precursor for the neurotransmitter acetylcholine. Choline is also a constituent of lecithin, which is present in many plants and animal organs.[22] It is found in phospholipids. For Glycine betaine is a example, phosphatidylcholines, a major naturally occurring component of biological membranes, are a Choline is a quat compound. quaternary ammonium member of the lecithin group of fatty cation. Its degradation substances in animal and plant tissues.[23] product, trimethylamine, is responsible for the Carnitine participates in the beta-oxidation of fatty acids. odor of spoiled fish. Health effects

Quaternary ammonium compounds can display a range of health effects, amongst which are mild skin and respiratory irritation [24] up to severe caustic burns on skin and the gastrointestinal wall (depending on concentration), gastrointestinal symptoms (e.g., nausea and vomiting), coma, convulsions, hypotension and death.[25]

They are thought to be the chemical group responsible for 1-Oleoyl-2-palmitoyl- anaphylactic reactions that occur with use of neuromuscular blocking phosphatidylcholine drugs during general anaesthesia in surgery.[26] Quaternium-15 is the single most often found cause of allergic contact dermatitis of the hands (16.5% in 959 cases)[27]

Possible reproductive effects in laboratory animals

Quaternary ammonium-based disinfectants (Virex and Quatricide) were tentatively identified as the most probable cause of jumps in birth defects and fertility problems in caged lab mice. The quat ingredients in the disinfectants include alkyl dimethyl benzyl ammonium chloride (ADBAC) and didecyl dimethyl ammonium chloride (DDAC).[28][29] A similar link was tentatively identified in nurses.[30] The studies contradict earlier toxicology data reviewed by the U.S. Environmental Protection Agency (U.S. EPA) and the EU Commission.[31]

Quantification

The quantification of quaternary ammonium compounds in environmental and biological samples is problematic using conventional chromatography techniques because the compounds are highly soluble in water. While analyzing them by liquid chromatography coupled tandem mass spectrometry it has been found that they follow an exception rule. Under standard electrospray ionization (ESI) conditions, mono- q m m + z and di-quaternary ammonium compounds form molecular ions with the formula of zq rather than z . mq Formation of 2 is observed for di-quaternary ammonium compounds (like diquat) as precursor ion and mq 1 as product ion due to the loss of one of the quaternary charge during CID. In di-quaternary ammonium compounds, this process can also result in the formation of fragment ions with higher mass as compared to their precursor ion. Hydrophilic interaction liquid chromatographic separation has been reported to demonstrate a successful separation of quaternary ammonium compounds for their quantification in ESI-MS/MS with higher precision.[32]

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation 4/7 23.3.2020 Quaternary ammonium cation - Wikipedia References 1. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "quaternary ammonium compounds (https://goldbook.iupac.org/Q05003.html)". doi:10.1351/goldbook.Q05003 (https://doi.org/10.1351%2Fgoldbook.Q05003) 2. Kern, Axel; Näther, Christian; Studt, Felix; Tuczek, Felix (2004). "Application of a Universal Force Field to Mixed Fe/Mo−S/Se Cubane and Heterocubane Clusters. 1. Substitution of Sulfur by Selenium in the Series [Fe4X4(YCH3)4]2-; X = S/Se and y = S/Se†". . 43 (16): 5003–5010. doi:10.1021/ic030347d (https://doi.org/10.1021%2Fic030347d). PMID 15285677 (https://pubmed.ncbi. nlm.nih.gov/15285677). 3. Brasen, W. R.; Hauser, C. R. (1954). "o-Methylbenzyl ". Organic Syntheses. 34: 58. doi:10.15227/orgsyn.034.0058 (https://doi.org/10.15227%2Forgsyn.034.0058). 4. Smith, Michael B.; March, Jerry (2001), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (5th ed.), New York, NY: Wiley-Interscience, ISBN 0-471-58589-0 5. Kosswig, K. "Surfactants". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a25_747 (https://doi.org/10.1002%2F14356007.a25_747). 6. Herriott, Arthur W. (1977). "Purple : Solubilization of anions in organic solvents". Journal of Chemical Education. 54 (4): 229. Bibcode:1977JChEd..54Q.229H (https://ui.adsabs.harvard.edu/abs/ 1977JChEd..54Q.229H). doi:10.1021/ed054p229.1 (https://doi.org/10.1021%2Fed054p229.1). 7. Doheny, Anthony J., Jr.; Ganem, Bruce (1980). "Purple benzene revisited". Journal of Chemical Education. 57 (4): 308. Bibcode:1980JChEd..57..308D (https://ui.adsabs.harvard.edu/abs/1980JChE d..57..308D). doi:10.1021/ed057p308.1 (https://doi.org/10.1021%2Fed057p308.1). 8. Brasen, W. R.; Hauser, C. R. (1963). "2-Methylbenzyldimethylamine" (http://www.orgsyn.org/demo.as px?prep=cv4p0585). Organic Syntheses.; Collective Volume, 4, p. 585 9. Pine, Stanley H. (2011). "The -Promoted Rearrangements of Quaternary Ammonium Salts". Organic Reactions. pp. 403–464. doi:10.1002/0471264180.or018.04 (https://doi.org/10.1002%2F0471 264180.or018.04). ISBN 978-0471264187. 10. Lackner, Maximilian; Guggenbichler, Josef Peter (2013). "Antimicrobial Surfaces". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–13. doi:10.1002/14356007.q03_q01 (https://doi.org/10.10 02%2F14356007.q03_q01). ISBN 9783527306732. 11. Jia, Zhishen; Shen, Dongfeng; Xu, Weiliang (2001). "Synthesis and antibacterial activities of quaternary ammonium salt of chitosan". Carbohydrate Research. 333 (1): 1–6. doi:10.1016/S0008- 6215(01)00112-4 (https://doi.org/10.1016%2FS0008-6215%2801%2900112-4). PMID 11423105 (http s://pubmed.ncbi.nlm.nih.gov/11423105). 12. Abedon, Stephen T. "Specific Antimicrobials" (https://web.archive.org/web/20081015002934/http://ww w.mansfield.ohio-state.edu/~sabedon/biol2032.htm). Ohio State University. Archived from the original (http://www.mansfield.ohio-state.edu/~sabedon/biol2032.htm) on 2008-10-15. Retrieved 2020-02-14. 13. Cocco, Alexandra; Wellington Luiz de Oliveira da Rosa; Adriana Fernandes da Silva; Rafael Guerra Lund; Evandro Piva (2015). "A systematic review about antibacterial monomers used in dental adhesive systems, current status and further prospects". Journal of Dental Material. 31: 1345–1362. doi:10.1016/j.dental.2015.08.155 (https://doi.org/10.1016%2Fj.dental.2015.08.155). 14. Hellberg, Per-Erik; Bergström, Karin; Holmberg, Krister (January 2000). "Cleavable surfactants". Journal of Surfactants and Detergents. 3 (1): 81–91. doi:10.1007/s11743-000-0118-z (https://doi.org/1 0.1007%2Fs11743-000-0118-z). 15. "Henkel Consumer Info" (http://www.henkelconsumerinfo.com). Henkelconsumerinfo.com. Retrieved 2009-06-04. 16. Smulders, E.; Sung, E. "Laundry Detergents, 2. Ingredients and Products". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.o15_013 (https://doi.org/10.100 2%2F14356007.o15_013). 17. Record (https://householdproducts.nlm.nih.gov/cgi-bin/household/brands?tbl=chem&id=1000) in the Household Products Database of NLM 18. "Quaternary ammonium compound hair conditioners US4744977" (https://patents.google.com/patent/ US4744977). Google Patents. 14 November 1985.

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation 5/7 23.3.2020 Quaternary ammonium cation - Wikipedia 19. What is cetrimonium chloride? (http://www.naturallycurly.com/curlreading/curly-q-a/curlchemist-what-is -cetrimonium-chloride) Archived (https://web.archive.org/web/20120304041725/http://www.naturallycu rly.com/curlreading/curly-q-a/curlchemist-what-is-cetrimonium-chloride) 2012-03-04 at the Wayback Machine at naturallycurly.com 20. "Archived copy" (https://web.archive.org/web/20110925004831/http://users.in.gr/dimpet/thesis/growth _retardants.htm). Archived from the original (http://users.in.gr/dimpet/thesis/growth_retardants.htm) on September 25, 2011. Retrieved July 19, 2012. Wageningen Agricultural University, The Netherlands 21. Sleator, Roy D.; Wouters, Jeroen; Gahan, Cormac G. M.; Abee, Tjakko; Hill, Colin (2001). "Analysis of the Role of OpuC, an Osmolyte Transport System, in Salt Tolerance and Virulence Potential of Listeria monocytogenes" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC92926). Applied and Environmental Microbiology. 67 (6): 2692–2698. doi:10.1128/AEM.67.6.2692-2698.2001 (https://doi.org/10.1128%2F AEM.67.6.2692-2698.2001). PMC 92926 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC92926). PMID 11375182 (https://pubmed.ncbi.nlm.nih.gov/11375182). 22. Zeisel, S. H.; da Costa, K. A. (November 2009). "Choline: an essential nutrient for public health" (http s://www.ncbi.nlm.nih.gov/pmc/articles/PMC2782876). Nutrition Reviews. 67 (11): 615–23. doi:10.1111/j.1753-4887.2009.00246.x (https://doi.org/10.1111%2Fj.1753-4887.2009.00246.x). PMC 2782876 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2782876). PMID 19906248 (https://pub med.ncbi.nlm.nih.gov/19906248). 23. Jackowski, Suzanne; Cronan, jr., John E.; Rock, Charles O. (1991). "Chapter 2: Lipid metabolism in procaryotes" (https://archive.org/details/biochemistryofli0000unse). In Vance, Dennis E.; Vance, J. (eds.). Biochemistry of Lipids, Lipoproteins and Membranes (https://archive.org/details/biochemistryofl i0000unse/page/80). Elsevier. pp. 80–81 (https://archive.org/details/biochemistryofli0000unse/page/8 0). ISBN 0-444-89321-0. 24. Bello, Anila; Quinn, Margaret M.; Perry, Melissa J.; Milton, Donald K. (2009). "Characterization of occupational exposures to cleaning products used for common cleaning tasks-a pilot study of hospital cleaners" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2678109). Environmental Health. 8: 11. doi:10.1186/1476-069X-8-11 (https://doi.org/10.1186%2F1476-069X-8-11). PMC 2678109 (https://ww w.ncbi.nlm.nih.gov/pmc/articles/PMC2678109). PMID 19327131 (https://pubmed.ncbi.nlm.nih.gov/193 27131). 25. Quaternary ammonium (PIM G022) (http://www.inchem.org/documents/pims/chemical/pimg022.htm# SectionTitle:2.1%20%20Main%20risk%20and%20target%20organs) 26. Harper, N. J. N.; et al. (2009). "Suspected anaphylactic reactions associated with anaesthesia" (http s://www.ncbi.nlm.nih.gov/pmc/articles/PMC3082210). Anaesthesia. 64 (2): 199–211. doi:10.1111/j.1365-2044.2008.05733.x (https://doi.org/10.1111%2Fj.1365-2044.2008.05733.x). PMC 3082210 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3082210). PMID 19143700 (https://pub med.ncbi.nlm.nih.gov/19143700). 27. Warshaw, E. M.; et al. (2007). "Contact dermatitis of the hands: Cross-sectional analyses of North American Contact Dermatitis Group Data, 1994-2004". Journal of the American Academy of Dermatology. 57 (2): 301–314. doi:10.1016/j.jaad.2007.04.016 (https://doi.org/10.1016%2Fj.jaad.200 7.04.016). PMID 17553593 (https://pubmed.ncbi.nlm.nih.gov/17553593). 28. Hunt, P (June 2008). "Lab harms mouse fertility. Patricia Hunt interviewed by Brendan Maher". Nature. 453 (7198): 964. doi:10.1038/453964a (https://doi.org/10.1038%2F453964a). PMID 18563110 (https://pubmed.ncbi.nlm.nih.gov/18563110). 29. Melin VE, Potineni H, Hunt P, Griswold J, Siems B, Werre SR, Hrubec TC (2014). "Exposure to common quaternary ammonium disinfectants decreases fertility in mice" (https://www.ncbi.nlm.nih.go v/pmc/articles/PMC4260154). Reproductive Toxicology. 50: 163–70. doi:10.1016/j.reprotox.2014.07.071 (https://doi.org/10.1016%2Fj.reprotox.2014.07.071). PMC 4260154 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4260154). PMID 25483128 (https://pub med.ncbi.nlm.nih.gov/25483128). 30. Gaskins, Audrey (2017). "Occupational use of high-level disinfectants and fecundity among nurses" (h ttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC5840865). Scand J Work Environ Health. 43 (2): 171– 180. doi:10.5271/sjweh.3623 (https://doi.org/10.5271%2Fsjweh.3623). PMC 5840865 (https://www.nc bi.nlm.nih.gov/pmc/articles/PMC5840865). PMID 28125764 (https://pubmed.ncbi.nlm.nih.gov/281257 64). 31. Office of Prevention, Pesticides and Toxic Substances, US EPA (August 2006). "Reregistration Eligibility Decision for Aliphatic Alkyl Quaternaries (DDAC)". Epa739-R-06-008.

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation 6/7 23.3.2020 Quaternary ammonium cation - Wikipedia 32. Velpandiana, Thirumurthy; Nirmala, Jayabalan; Aroraa, Beauty; Ravia, Alok Kumar; Kotnalaa, Ankita (October 2012). "Understanding the Charge Issues in Mono and Di-Quaternary Ammonium Compounds for Their Determination by LC/ESI-MS/MS". Analytical Letters. 45 (16): 2367–2376. doi:10.1080/00032719.2012.693140 (https://doi.org/10.1080%2F00032719.2012.693140).

External links

Toxicities of quaternary ammonium (http://www.inchem.org/documents/pims/chemical/pimg022.htm) Zhang, Chang; Cui, Fang; Zeng, Guang-ming; Jiang, Min; Yang, Zhong-zhu; Yu, Zhi-gang; Zhu, Meng-ying; Shen, Liu-qing (15 June 2015). "Quaternary ammonium compounds (QACs): A review on occurrence, fate and toxicity in the environment". Science of the Total Environment. 518–519: 352– 362. Bibcode:2015ScTEn.518..352Z (https://ui.adsabs.harvard.edu/abs/2015ScTEn.518..352Z). doi:10.1016/j.scitotenv.2015.03.007 (https://doi.org/10.1016%2Fj.scitotenv.2015.03.007). PMID 25770948 (https://pubmed.ncbi.nlm.nih.gov/25770948).

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