Quaternary ammonium cation - Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Quaternary_ammonium_cation

Quaternary ammonium cation

From Wikipedia, the free encyclopedia

Quaternary ammonium cations, also known as quats, are

positively charged polyatomic ions of the structure NR4+, R
being an alkyl group or an aryl group.[1] Unlike the ammonium
ion (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 amines in oilfield parlance) are salts of
quaternary ammonium cations.

Contents
1 Synthesis
2 Reactions
3 Applications
3.1 As antimicrobials
3.2 As phase transfer catalysts
3.3 Fabric softeners
3.4 Osmolytes
3.5 Plant growth retardants
4 Health effects
4.1 Possible reproductive effects in laboratory
animals
4.2 Quantification
5 See also
6 References
7 External links

Quaternary ammonium cation.

The R groups may be the same or
different alkyl or aryl groups. Also,
the R groups may be connected.

Synthesis
Quaternary ammonium compounds are prepared by the alkylation of tertiary amines with a
halocarbon. In older literature this is often called a Menshutkin reaction, however modern chemists
usually refer to it simply as quaternization.[2] The reaction can be used to produce a compound
with unequal alkyl chain lengths; for example when making cationic surfactants one of the alkyl
groups on the amine is typically longer than the others.[3] A typical synthesis is for benzalkonium
chloride from a long-chain alkyldimethylamine and benzyl chloride:
CH3(CH2)nN(CH3)2 + ClCH2C6H5 [CH3(CH2)nN(CH3)2CH2C6H5]+Cl

Reactions
While not very reactive, quaternary ammonium salts undergo SommeletHauser rearrangement[4]
and Stevens rearrangement,[5] as well as dealkylation under harsh conditions. Quaternary
ammonium cations can also undergo the Hofmann Elimination and Emde degradation if there are
hydrogens beta to the nitrogen.

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Applications
Quaternary ammonium salts are used as disinfectants, surfactants, fabric softeners, and as
antistatic agents (e.g. in shampoos). In liquid fabric softeners, the chloride salts are often used. In
dryer anticling strips, the sulfate salts are often used. Spermicidal jellies also contain quaternary
ammonium salts.

As antimicrobials
Quaternary ammonium compounds have also been shown to have antimicrobial activity.[6] Certain
quaternary ammonium compounds, especially those containing long alkyl chains, are used as
antimicrobials and disinfectants. Examples are benzalkonium chloride, benzethonium chloride,
methylbenzethonium chloride, cetalkonium chloride, cetylpyridinium chloride, cetrimonium,
cetrimide, dofanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride
and domiphen bromide. Also good against fungi, amoebas, and enveloped viruses,[7] quats are
believed to act by disrupting the cell membrane. Quaternary ammonium compounds are lethal to a
wide variety of organisms except endospores,
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 phenols.
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 212 F (100 C).
Quaternary ammonium salts are commonly used in the foodservice industry as sanitizing agents.

As phase transfer catalysts

In organic synthesis, 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 chloroform and
sodium hydroxide.

Fabric softeners
In the 1950's, 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
acid is linked to the quaternary center via ester linkages; these are commonly referred to as
betaine-esters or ester-quats and are susceptible to degradation, e.g., by hydrolysis.[8]
Characteristically, the cations contain one or two long alkyl chains derived from fatty acids linked to
an ethoxylated ammonium salt.[9] Other cationic compounds can be derived from imidazolium,
guanidinium, substituted amine salts, or quaternary alkoxy ammonium salts.[10]
Cationic surfactants used as fabric softeners

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Distearyldimethylammonium
chloride, an early generation fabric
softener with low biodegradability.

"Monoesterquat", a contemporary
fabric softener.

Diethylester dimethyl ammonium

chloride used as a fabric softener.

Another diesterquat used as a fabric

softener.

Osmolytes
Quaternary ammonium compounds are present in osmolytes, specifically glycine betaine, which
stabilize osmotic pressure in cells.[11]

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.[12]

Health effects
Quaternary ammonium compounds can display a range of health effects, amongst which are mild
skin and respiratory irritation [13] up to severe caustic burns on skin and gastro-intestinal lining
(depending on concentration), gastro-intestinal symptoms (e.g., nausea and vomiting), coma,
convulsions, hypotension and death.[14]
They are thought to be the chemical group responsible for anaphylactic reactions that occur with
use of neuromuscular blocking drugs during general anaesthesia in surgery.[15] Quaternium-15 is
the single most often found cause of allergic contact dermatitis of the hands (16.5% in 959
cases)[16]

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.[17] See also
Hunt and Hrubek (Reproductive Toxicology, 50:163-70, 2014).

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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- and di-quaternary ammonium compounds form molecular ions
with the formula of
rather than
. Formation of
is observed for
di-quaternary ammonium compounds (like diquat) as precursor ion and
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.[18]

See also
Benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium
chloride, cetylpyridinium chloride, cetrimonium, cetrimide, dofanium chloride,
tetraethylammonium bromide, and domiphen bromide antimicrobial ingredients found in
various over-the-counter products
Diquat -diquaternary ammonium compound recognized as a contact herbicide
Carnitine
Cetyl trimethylammonium bromide (CTAB), stearalkonium chloride cationic surfactants
commonly used in toiletries
Choline
Cocamidopropyl betaine (CAPB), a common Zwitterionic surfactant used ubiquitously in
toiletries
Denatonium, the most bitter compound known
Dimethyldioctadecylammonium chloride
Paraquat, an herbicide
Polyquaternium, designations for quaternary ammonium-containing polymers used for
personal care products
Quaternary ammonium muscle relaxants
Silicone quaternary amine
Tetra-n-butylammonium bromide and Aliquat 336, common phase transfer catalysts
Tetramethylammonium chloride
Tetramethylammonium hydroxide
Tetramethylammonium pentafluoroxenate, containing the unusual pentagonal
pentafluoroxenate (XeF5) ion
Triazene cleavage

References
1. IUPAC,
, 2nd ed. (the "Gold Book") (1997). Online corrected
version: (2006) "quaternary ammonium compounds (http://goldbook.iupac.org/Q05003.html)".
2. Smith, Michael B.; March, Jerry (2001),
(5th ed.), New York: Wiley-Interscience, ISBN 0-471-58589-0
3. Kosswig, K. "Surfactants" in Ullmanns Encyclopedia of Industrial Chemistry 2002, Wiley-VCH,
Weinheim. doi:10.1002/14356007.a25_747 (https://dx.doi.org/10.1002%2F14356007.a25_747).
4. W. R. Brasen; C. R. Hauser (1963). "2-Methylbenzyldimethylamine".
;
4, p. 585
5. Pine, Stanley H. (2011). "Organic Reactions". doi:10.1002/0471264180.or018.04 (https://dx.doi.org
/10.1002%2F0471264180.or018.04). ISBN 0471264180. |chapter= ignored (help)

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6. Jia, Zhishen; Shen, Dongfeng; Xu, Weiliang (2001). "Synthesis and antibacterial activities of quaternary
333 (1): 16.
ammonium salt of chitosan".
doi:10.1016/S0008-6215(01)00112-4 (https://dx.doi.org/10.1016%2FS0008-6215%2801%2900112-4).
PMID 11423105 (https://www.ncbi.nlm.nih.gov/pubmed/11423105).
7.
(http://www.mansfield.ohio-state.edu/~sabedon/biol2032.htm), outline of lecture
by Stephen T. Abedon, Ohio State U., URL accessed Dec 2008.
8. Hellberg, Per-Erik; Bergstrm, Karin; Holmberg, Krister (January 2000). "Cleavable surfactants".
3 (1): 8191. doi:10.1007/s11743-000-0118-z (https://dx.doi.org
/10.1007%2Fs11743-000-0118-z).
9. "Henkel Consumer Info" (http://www.henkelconsumerinfo.com). Henkelconsumerinfo.com. Retrieved
2009-06-04.
10. E. Smulders, E. Sung "Laundry Detergents, 2. Ingredients and Products" in Ullmann's Encyclopedia of
Industrial Chemistry, Wiley-VCH, Weinheim, 2012. doi:10.1002/14356007.o15_013 (https://dx.doi.org
/10.1002%2F14356007.o15_013)
11. 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".
67: 26922698. doi:10.1128/AEM.67.6.2692-2698.2001
(https://dx.doi.org/10.1128%2FAEM.67.6.2692-2698.2001).
12. http://users.in.gr/dimpet/thesis/growth_retardants.htm Wageningen Agricultural University, The
Netherlands
13. 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
8: 11.
cleaners" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2678109).
doi:10.1186/1476-069X-8-11 (https://dx.doi.org/10.1186%2F1476-069X-8-11). PMC 2678109
(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2678109). PMID 19327131
(https://www.ncbi.nlm.nih.gov/pubmed/19327131).
14. Quaternary ammonium (PIM G022) (http://www.inchem.org/documents/pims/chemical
/pimg022.htm#SectionTitle:2.1%20%20Main%20risk%20and%20target%20organs)
15. Harper, NJ; Dixon, T; Dugu, P; Edgar, DM; Fay, A; Gooi, HC; Herriot, R; Hopkins, P; Hunter, JM;
Mirakian, R; Pumphrey, RS; Seneviratne, SL; Walls, AF; Williams, P; Wildsmith, JA; Wood, P; Nasser,
AS; Powell, RK; Mirakhur, R; Soar, J; Working Party of the Association of Anaesthetists of Great Britain
Ireland (2009). "Suspected anaphylactic reactions associated with anaesthesia"
(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3082210).
64 (2): 199211.
doi:10.1111/j.1365-2044.2008.05733.x (https://dx.doi.org/10.1111%2Fj.1365-2044.2008.05733.x).
PMC 3082210 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3082210). PMID 19143700
(https://www.ncbi.nlm.nih.gov/pubmed/19143700).
16. Warshaw, EM; Ahmed, RL; Belsito, DV; Deleo, VA; Fowler Jr, JF; Maibach, HI; Marks Jr, JG; Toby
Mathias, CG; Pratt, MD; Rietschel, RL; Sasseville, D; Storrs, FJ; Taylor, JS; Zug, KA; North American
Contact Dermatitis Group (2007). "Contact dermatitis of the hands: Cross-sectional analyses of North
American Contact Dermatitis Group Data, 1994-2004".
57 (2): 30114. doi:10.1016/j.jaad.2007.04.016 (https://dx.doi.org
/10.1016%2Fj.jaad.2007.04.016). PMID 17553593 (https://www.ncbi.nlm.nih.gov/pubmed/17553593).
17. Hunt, P (June 2008). "Lab disinfectant harms mouse fertility. Patricia Hunt interviewed by Brendan
Maher".
453 (7198): 964. doi:10.1038/453964a (https://dx.doi.org/10.1038%2F453964a).
PMID 18563110 (https://www.ncbi.nlm.nih.gov/pubmed/18563110).
18. Thirumurthy Velpandiana; Jayabalan Nirmala; Beauty Aroraa; Alok Kumar Ravia; Ankita Kotnalaa
(October 2012). "Understanding the Charge Issues in Mono and di-Quaternary Ammonium Compounds
for Their Determination by LC/ESI-MS/MS".
45 (16): 23672376.
doi:10.1080/00032719.2012.693140 (https://dx.doi.org/10.1080%2F00032719.2012.693140).

External links
Toxicities of quaternary ammonium (http://www.inchem.org/documents/pims/chemical
/pimg022.htm)
Chang Zhang, Fang Cui, Guang-ming Zeng, Min Jiang, Zhong-zhu Yang, Zhi-gang Yu,
Meng-ying Zhu, Liu-qing Shen:
Science of The Total Environment, Volumes
518519, 15 June 2015, Pages 352362, doi:10.1016/j.scitotenv.2015.03.007

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