MCPA

MCPA (2-methyl-4-chlorophenoxyacetic acid) is a powerful, selective, widely used phenoxy herbicide. The pure compound is a brown-colored powder. MCPA has been extensively used in agriculture to control broad-leaf weeds as a growth regulator primarily in pasture and cereal crops field since 1945. The mode of action of MCPA appears to be similar to auxins, which are growth hormone that naturally exist in plants. Overdose application of MCPA acts as an herbicide and results abnormal growth.[2][3]

MCPA
Names
Preferred IUPAC name
(4-Chloro-2-methylphenoxy)acetic acid
Other names
2-(4-Chloro-2-methylphenoxy)acetic acid
4-Chloro-o-tolyloxyacetic acid
MCPA
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.002.146
KEGG
UNII
Properties
C9H9ClO3
Molar mass 200.62 g·mol−1
Appearance White to light brown solid
Density 1.18-1.21 g/cm3
Melting point 114 to 118 °C (237 to 244 °F; 387 to 391 K)
825 mg/L (23 °C),[1]
amine salt: 866 g/L
ester: 5 mg/L
Hazards
Safety data sheet External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

History

In 1936 investigations began at ICIs Jealott's Hill research center into the effects of auxins on plant growth looking specifically for a way to kill weeds without harming crops such as wheat and oats. William Tempelman found that when indole-3-acetic acid (IAA), the naturally occurring auxin, was used at high concentrations, it could stop plant growth. In 1940, he published his finding that IAA killed broadleaf plants within a cereal field.[4][5] Templeman and the ICI group were searching for compounds with similar or greater selective activity than IAA or 1-naphthaleneacetic acid in inhibiting the growth of weeds while not adversely affecting the growth of cereal crops. They synthesized MCPA from the corresponding phenol by exposing it to chloroacetic acid and dilute base in a straightforward substitution reaction:[6]

2-methyl-4-chlorophenol + ClCH2CO2H + base → MCPA + base·HCl (hydrochloric acid)

By the end of 1941 it was clear to the Templeman group that MCPA was one of the most active compounds tested but other auxin herbicides including 2,4-D were also effective. This work took place during World War II and was a case of multiple discovery. Four groups worked independently in the United Kingdom and the United States: the ICI team; Philip S. Nutman and associates at Rothamsted Research in the UK; Franklin D. Jones and associates at the American Chemical Paint Company; and Ezra Kraus, John W. Mitchell, and associates at the University of Chicago and the United States Department of Agriculture. All four groups were subject to wartime secrecy laws and did not follow the usual procedures of publication and patent disclosure, although ICI did file an application relating to both MCPA and 2,4-D on 7 April 1941 in the UK. In December 1942, following a meeting at the Ministry of Agriculture the Rothamsted and ICI workers pooled resources and Nutman moved to Jealott's Hill to join the ICI effort.[5] The first publications about this group of herbicides were by other workers who were not the original inventors: the precise sequence of discovery events has been discussed.[7] MCPA was first reported in the open scientific literature by Slade, Templeman and Sexton in 1945.[8] ICI's decision to commercialise MCPA (rather than 2,4-D, for example) was influenced by the fact that ICI had access to 2-methyl-4-chlorophenol and following extensive field trials the material was first made available to UK farmers in 1946, as a 1% dust.[5]

Commercial use

MCPA is used as an herbicide, generally as its salt or esterified forms. Used thus, it controls broadleaf weeds, including thistle and dock, in cereal crops and pasture. It is selective for plants with broad leaves, and this includes most deciduous trees. Clovers are tolerant at moderate application levels. It is currently classified as a restricted use pesticide in the United States: its use is mapped by the US Geological Service, whose data show it is principally applied to wheat.[9] Its toxicity and biodegradation are topics of current research. One formulation is described by its manufacturer as "designed for specific markets that require the safest possible phenoxy product, primarily for use in the Pacific Northwest".[10] Though not extremely toxic,[11] it has recently been determined that MCPA can form complexes with metal ions and thereby increase their bioavailability,[12] though there is also work being done to utilize this ability.[13]

Chemical use

Because it is inexpensive, MCPA is used in various chemical applications. Its carboxylic acid group allows the formation of conjugated complexes with metals (see above). The acid functionality makes MCPA a versatile synthetic intermediate for more complex derivatives.[14]

Brand names

The following commercial products contain MCPA:[11]

  • Agritox, Agroxone, Chiptox, Chwastox, Cornox, Methoxone, Rhonox, Spurge Power, Tigrex, Verdone Extra (UK), Weed-Rhap, Weed'n'Feed, Weed-B-Gone, Zero Bindii & Clover Weeder (Aus), Jolt (Aus), BIN-DIE (Aus), Maatilan MCPA, K-MCPA, Hedonal, Basagran (Finland), and others.

Degradation in soil

Since MCPA is extensively used in the USA, the extensively dispensed MCPA and its biological and photochemical metabolites might be deemable as environmentally hazardous. However, current studies showed that there is no resistance of MCPA to degrade in soil.

Behaviors in soil

MCPA herbicide is usually sprayed to soil surface and plant leaves surface in its water solution,sometimes with additional surfactant. MCPA in soil can be absorbed by plant roots, and translocated in phloem to leaves and stems. The MCPA residue left in soil typically have a half life of 24 days.[15] However, the degradation rate is depending on environmental conditions, such as temperature and soil moisture.[16] MCPA is rather mobile in soil, and not very adsorpted to soil particles, with Kf = 0.94 and 1/n = 0.68 of Freundlich adsorption.[15][16]

Environmental risks

Widely usage of MCPA as an herbicide raises concern of environmental risks so considerable research has been done in recent decades to evaluate the environmental risk of MCPA. MCPA can be moderately toxic to mammal and aquatic organisms, and relatively less toxic to birds.[17] MCP (4-chloro-2-methylphenol) is the intermediate in the synthesis of phenoxy herbicide, and is also the metabolite of MCPA's degradation. It has been estimated as a total of 15000 tons of MCP were produced in 1989 in EU.[18] The MCP chemical is considered very toxic to aquatic organisms. However, the concentration of MCPA and MCP detected in water and soil are lower than the predicted no effect levels of all environmental compartments, and considered under low potential of risk.[18][19]

The carboxyl group of MCPA can form conjugated complex with metals as a ligand.[20] In general pH range of aqueous environment,the MCPA-metal complex has higher solubility than metal ion. MCPA may be environmentally hazardous by affecting the mobility and bio-availability of heavy metal, such as cadmium and lead.The acid functionality makes MCPA a versatile synthetic intermediate for more complex derivatives[21]

-COOH + M+ → -COOM + H+

Bio-degradation
Bio-degradation of MCPA in soils

The MCPA can be degraded biologically in soils by plants and microorganisms. The major metabolite of MCPA degradation are MCP (4-chloro-2-methylphenol). The pathway could be the cleavage of the ether linkage, yielding MCP and acetate acid. Another pathway could be the hydroxylation of methyl group, yielding cloxyfonac (4-Chloro-2-hydroxymethylphenoxyacetic acid). Recent studies demonstrated that biologically degradation of MCPA is enzymatically catalyzed by an α-ketoglutarate-dependent dioxygenase encoded by the tfdA gene of soil microorganisms. Soil indigenous bacteria that carry tfdA gene could use MCPA as the sole source of carbon.[22][23]

Photo-degradation
Oxidation of MCPA by hydroxyl radicals
Oxidation of MCPA by positive holes h+

MCPA also could be photochemical degraded. Two scheme pathways can be proposed for the formation of the main intermediate MCP. One scheme is MCPA oxidation by hydroxyl radical, •OH. Hydroxyl radical adds on the ring, then the radical transfer to ether carbon. With oxygen present, the addition of hydroxyl radical leads the cleavage of ether link, yielding MCP. The other scheme is MCPA oxidation by positive electron holes h+. The positive holes h+ polarize carboxyl group, CH2-COOH bond is split to produce 4-chloro-2-methylphenylformate. With the presence of oxygen, the positive holes h+ oxidation finally yields MCP as well.[21]

References
  1. Gimeno, Olga; Plucinski, Pawel; Kolaczkowski, Stan T.; Rivas, Francisco J.; Alvarez, Pedro M. (2003). "Removal of the Herbicide MCPA by Commercial Activated Carbons: Equilibrium, Kinetics, and Reversibility". Industrial & Engineering Chemistry Research. 42 (5): 1076–1086. doi:10.1021/ie020424x.
  2. Reade, J., Cobb, A. H. (2002). Herbicides: Modes of action and metabolism. Weed management handbook. pp. 157–158.
  3. Grossmann, K. (2010). "Auxin herbicides: current status of mechanism and mode of action". Pest Management Science. 66 (2): 2033–2043. doi:10.1002/ps.1860. PMID 19823992.
  4. Templeman, W. G.; Marmoy, C. J. (November 1940). "The effect upon the growth of plants of watering with solutions of plant-growth substances and of seed dressings containing these materials". Annals of Applied Biology. 27 (4): 453–471. doi:10.1111/j.1744-7348.1940.tb07517.x.
  5. Allen, H.P.; et al. (1978). "Chapter 5: Selective herbicides". In Peacock, F.C. (ed.). Jealott's Hill: Fifty years of Agricultural Research 1928-1978. Imperial Chemical Industries Ltd. pp. 35–41. ISBN 0901747017.
  6. W.G. Templeman; W.A. Sexton (1946). "The Differential Effect of Synthetic Plant Growth Substances upon Plant Species. I. Seed Germination and Early Growth Responses to α-Naphthylacetic Acid and Compounds of General Formula arylOCHCOO". Proceedings of the Royal Society of London. 133 (872): 300–313. doi:10.1098/rspb.1946.0014.
  7. Troyer, James (2001). "In the beginning: the multiple discovery of the first hormone herbicides". Weed Science. 49 (2): 290–297. doi:10.1614/0043-1745(2001)049[0290:ITBTMD]2.0.CO;2.
  8. Slade, R.E.; Templeman, W.G.; Sexton, W.A. (1945). "Differential effects of plant growth substances on plant species". Nature. 155: 497–498. doi:10.1038/155497a0.
  9. US Geological Survey. "Estimated Agricultural Use for MCPA in the USA, 2016". Retrieved 2020-02-15.
  10. "Chiptox". Nufarm.
  11. "MCPA". Extrnsion Toxicology Network. Cornell.
  12. J. Kobylecka; B. Ptaszynski; R. Rogaczewski; A. Turek (2003). "Phenoxyalkanoic acid complexes. Part I. Complexes of lead(II), cadmium(II) and copper(II) with 4-chloro-2-methylphenoxyacetic acid (MCPA)". Thermochimica Acta. 407 (1–2): 25–31. doi:10.1016/S0040-6031(03)00287-9.
  13. R. Kruszynski; T.J. Bartczak; B. Ptaszynski; A. Turek (2002). "A Novel Lead- bis (4-Chloro-2-Methylphenoxy)- Acetate Polymeric Complex". Journal of Coordination Chemistry. 55 (9): 1079–1089. doi:10.1080/0095897021000010035.
  14. Prasad, Attaluri R.; Ramalingam, Thallapalli; Rao, Adari B.; Diwan, Prakash V.; Sattur, Pralhad B. (1989). "Synthesis and biological evaluation of 3-aryloxyalkyl-6-aryl-7H-s-triazolo[3,4-b][1,3,4]thiadiazines". European Journal of Medicinal Chemistry. 25 (2): 199–201. doi:10.1016/0223-5234(89)90116-5.
  15. University of Hertfordshire (2016-10-17). "MCPA". sitem.herts.ac.uk. Retrieved 2016-11-21.
  16. Helweg, A. (1987). "Degradation and adsorption of 14C-MCPA in soil—influence of concentration, temperature and moisture content on degradation". Weed Research. 27 (4): 287–296. doi:10.1111/j.1365-3180.1987.tb00765.x.
  17. "Ecotoxicology of MCPA". Pesticide Properties DataBase. University of Hertfordshire. Retrieved 2016-10-17.
  18. UNEP publications, OECD SIDS, 4-chloro-2-methylphenol. http://www.inchem.org/documents/sids/sids/1570645.pdf
  19. Guidelines for drinking-water quality, 2nd ed. Vol.2. Health criteria and other supporting information. World Health Organization, Geneva, 1996.
  20. Bala, Tanushree; Prasad, B. L. V.; Sastry, Murali; Kahaly, Mousumi Upadhyay; Waghmare, Umesh V. (2007-07-19). "Interaction of different metal ions with carboxylic acid group: a quantitative study". The Journal of Physical Chemistry A. 111 (28): 6183–6190. doi:10.1021/jp067906x. ISSN 1089-5639. PMID 17585841.
  21. Zertal, A.; Molnár-Gábor, D.; Malouki, M.A.; Sehili, T.; Boule, P. (2004-05-01). "Photocatalytic transformation of 4-chloro-2-methylphenoxyacetic acid (MCPA) on several kinds of TiO2". Applied Catalysis B: Environmental. 49 (2): 83–89. doi:10.1016/j.apcatb.2003.11.015. ISSN 0926-3373.
  22. Bælum, Jacob; Nicolaisen, Mette H.; Holben, William E.; Strobel, Bjarne W.; Sørensen, Jan; Jacobsen, Carsten S. (2008-03-20). "Direct analysis of tfdA gene expression by indigenous bacteria in phenoxy acid amended agricultural soil". The ISME Journal. 2 (6): 677–687. doi:10.1038/ismej.2008.21. ISSN 1751-7362. PMID 18356824.
  23. Nielsen, Morten S.; Bælum, Jacob; Jensen, Malene B.; Jacobsen, Carsten S. (2011-05-01). "Mineralization of the herbicide MCPA in urban soils is linked to presence and growth of class III tfdA genes". Soil Biology and Biochemistry. 43 (5): 984–990. doi:10.1016/j.soilbio.2011.01.014.
  • MCPA in the Pesticide Properties DataBase (PPDB)
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