Hexazinone

Last updated
Hexazinone
Hexazinone.png
Names
Preferred IUPAC name
3-Cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4(1H,3H)-dione
Other names
Velpar
Hexazinone
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.051.869 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 257-074-4
KEGG
PubChem CID
UNII
  • InChI=1S/C12H20N4O2/c1-14(2)10-13-11(17)16(12(18)15(10)3)9-7-5-4-6-8-9/h9H,4-8H2,1-3H3 X mark.svgN
    Key: CAWXEEYDBZRFPE-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C12H20N4O2/c1-14(2)10-13-11(17)16(12(18)15(10)3)9-7-5-4-6-8-9/h9H,4-8H2,1-3H3
    Key: CAWXEEYDBZRFPE-UHFFFAOYAU
  • O=C(N1C2CCCCC2)N=C(N(C)C)N(C)C1=O
  • O=C1/N=C(\N(C(=O)N1C2CCCCC2)C)N(C)C
Properties
C12H20N4O2
Molar mass 252.31
AppearanceWhite crystalline solid
Density 1.25 g/cm3
Melting point 116 °C (241 °F; 389 K)
Soluble
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H302, H319, H332, H410
P261, P264, P264+P265, P270, P271, P273, P280, P301+P317, P304+P340, P305+P351+P338, P317, P330, P337+P317, P391, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Hexazinone is an organic compound that is used as a broad spectrum herbicide. It is a colorless solid. It exhibits some solubility in water but is highly soluble in most organic solvents except alkanes. A member of the triazine class herbicides, it is manufactured by DuPont and sold under the trade name Velpar. [1]

Contents

It functions by inhibiting photosynthesis and thus is a nonselective herbicide. It is used to control grasses, broadleaf, and woody plants. In the United States approximately 33% is used on alfalfa, 31% in forestry, 29% in industrial areas, 4% on rangeland and pastures, and < 2% on sugarcane. [2]

Hexazinone is a pervasive groundwater contaminant. Use of hexazinone causes groundwater to be at high risk of contamination due to the high leaching potential it exhibits. [3]

History

Hexazinone is widely used as a herbicide. It is a non-selective herbicide from the triazine family. It is used among a broad range of places. It is used to control weeds within all sort of applications. From sugarcane plantations, forestry field nurseries, pineapple plantations to high- and railway grasses and industrial plant sites. [4]

Hexazinone was first registered in 1975 for the overall control of weeds and later for uses in crops. [5]

Structure and reactivity

Triazines like hexazinone can bind to the D-1 quinone protein of the electron transport chain in photosystem II to inhibit the photosynthesis. These diverted electrons can thereby damage membranes and destroy cells. [6]

Synthesis

Hexazinone can be synthesized in two different reaction processes. One process starts with a reaction of methyl chloroformate with cyanamide, forming hexazinone after a five-step pathway: [7]

Hexazinon1.svg

A second synthesis starts with methylthiourea.: [7]

Hexazinon2.svg

Degradation

The degradation of hexazinone has long been studied. [8] It degrades approximately 10% in five weeks, when exposed to artificial sunlight in distilled water. However, degradation in natural waters can be three to seven times greater. Surprisingly, the pH and the temperature of the water do not affect the photodegradation significantly. [9] It is mainly degraded by aerobic microorganisms in soils. [10]

Mechanism of action

Hexazinone is a broad-spectrum residual and contact herbicide, rapidly absorbed by the leaves and roots. It is tolerated by many conifers, and therefore it is a very effective herbicide for the control for annual and perennial broadleaf weeds, some grasses, and some woody species. Hexazinone works as rain or snowmelt makes it possible for the herbicide to move downward into the soil. There the hexazinone is absorbed from the soil by the roots. [11] It moves through the conductive tissues to the leaves, where it blocks the photosynthesis of the plant within the chloroplasts. Hexazinone binds to a protein of the photosystem II complex, which blocks the electron transport. The result are multiple following reactions. First triplet-state chlorophyll reacts with oxygen to form singlet oxygen. Both chlorophyll and singlet oxygen then remove hydrogen ions from the unsaturated lipids present in de cells and the organelle membranes, forming lipid radicals. These radicals will oxidize other lipids and proteins, eventually resulting in loss of the membrane integrity of the cells and organelles. This will result in a loss of chlorophyll, leakage of cellular contents, cell death, and eventually death of the plant. [12] Woody plants first show yellowing of the leaves before they start to defoliate, eventually they will die. [13] Sometimes plants are able to refoliate and defoliate again during the growing season.

Related Research Articles

<span class="mw-page-title-main">Chlorophyll</span> Green pigments found in plants, algae and bacteria

Chlorophyll is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words χλωρός and φύλλον. Chlorophyll allows plants to absorb energy from light.

<span class="mw-page-title-main">Photosynthesis</span> Biological process to convert light into chemical energy

Photosynthesis is a system of biological processes by which photosynthetic organisms, such as most plants, algae, and cyanobacteria, convert light energy, typically from sunlight, into the chemical energy necessary to fuel their metabolism. Photosynthesis usually refers to oxygenic photosynthesis, a process that produces oxygen. Photosynthetic organisms store the chemical energy so produced within intracellular organic compounds like sugars, glycogen, cellulose and starches. To use this stored chemical energy, an organism's cells metabolize the organic compounds through cellular respiration. Photosynthesis plays a critical role in producing and maintaining the oxygen content of the Earth's atmosphere, and it supplies most of the biological energy necessary for complex life on Earth.

<span class="mw-page-title-main">Herbicide</span> Type of chemical used to kill unwanted plants

Herbicides, also commonly known as weed killers, are substances used to control undesired plants, also known as weeds. Selective herbicides control specific weed species while leaving the desired crop relatively unharmed, while non-selective herbicides kill plants indiscriminately. The combined effects of herbicides, nitrogen fertilizer, and improved cultivars has increased yields of major crops by three to six times from 1900 to 2000.

<span class="mw-page-title-main">Thylakoid</span> Membrane enclosed compartments in chloroplasts and cyanobacteria

Thylakoids are membrane-bound compartments inside chloroplasts and cyanobacteria. They are the site of the light-dependent reactions of photosynthesis. Thylakoids consist of a thylakoid membrane surrounding a thylakoid lumen. Chloroplast thylakoids frequently form stacks of disks referred to as grana. Grana are connected by intergranal or stromal thylakoids, which join granum stacks together as a single functional compartment.

<span class="mw-page-title-main">Paraquat</span> Chemical compound used as an herbicide

Paraquat (trivial name; ), or N,N′-dimethyl-4,4′-bipyridinium dichloride (systematic name), also known as methyl viologen, is a toxic organic compound with the chemical formula [(C6H7N)2]Cl2. It is classified as a viologen, a family of redox-active heterocycles of similar structure. This salt is one of the most widely used herbicides worldwide. It is quick-acting and non-selective, killing green plant tissue on contact.

<span class="mw-page-title-main">Photosystem</span> Structural units of protein involved in photosynthesis

Photosystems are functional and structural units of protein complexes involved in photosynthesis. Together they carry out the primary photochemistry of photosynthesis: the absorption of light and the transfer of energy and electrons. Photosystems are found in the thylakoid membranes of plants, algae, and cyanobacteria. These membranes are located inside the chloroplasts of plants and algae, and in the cytoplasmic membrane of photosynthetic bacteria. There are two kinds of photosystems: PSI and PSII.

<span class="mw-page-title-main">Photosystem II</span> First protein complex in light-dependent reactions of oxygenic photosynthesis

Photosystem II is the first protein complex in the light-dependent reactions of oxygenic photosynthesis. It is located in the thylakoid membrane of plants, algae, and cyanobacteria. Within the photosystem, enzymes capture photons of light to energize electrons that are then transferred through a variety of coenzymes and cofactors to reduce plastoquinone to plastoquinol. The energized electrons are replaced by oxidizing water to form hydrogen ions and molecular oxygen.

Chlorophyll <i>a</i> Chemical compound

Chlorophyll a is a specific form of chlorophyll used in oxygenic photosynthesis. It absorbs most energy from wavelengths of violet-blue and orange-red light, and it is a poor absorber of green and near-green portions of the spectrum. Chlorophyll does not reflect light but chlorophyll-containing tissues appear green because green light is diffusively reflected by structures like cell walls. This photosynthetic pigment is essential for photosynthesis in eukaryotes, cyanobacteria and prochlorophytes because of its role as primary electron donor in the electron transport chain. Chlorophyll a also transfers resonance energy in the antenna complex, ending in the reaction center where specific chlorophylls P680 and P700 are located.

<span class="mw-page-title-main">Diquat</span> Chemical compound

Diquat is the ISO common name for an organic dication that, as a salt with counterions such as bromide or chloride is used as a contact herbicide that produces desiccation and defoliation. Diquat is no longer approved for use in the European Union, although its registration in many other countries including the USA is still valid.

<span class="mw-page-title-main">Glufosinate</span> Broad-spectrum herbicide

Glufosinate is a naturally occurring broad-spectrum herbicide produced by several species of Streptomyces soil bacteria. Glufosinate is a non-selective, contact herbicide, with some systemic action. Plants may also metabolize bialaphos and phosalacine, other naturally occurring herbicides, directly into glufosinate. The compound irreversibly inhibits glutamine synthetase, an enzyme necessary for the production of glutamine and for ammonia detoxification, giving it antibacterial, antifungal and herbicidal properties. Application of glufosinate to plants leads to reduced glutamine and elevated ammonia levels in tissues, halting photosynthesis and resulting in plant death.

<span class="mw-page-title-main">Photosynthetic reaction centre</span> Molecular unit responsible for absorbing light in photosynthesis

A photosynthetic reaction center is a complex of several proteins, biological pigments, and other co-factors that together execute the primary energy conversion reactions of photosynthesis. Molecular excitations, either originating directly from sunlight or transferred as excitation energy via light-harvesting antenna systems, give rise to electron transfer reactions along the path of a series of protein-bound co-factors. These co-factors are light-absorbing molecules (also named chromophores or pigments) such as chlorophyll and pheophytin, as well as quinones. The energy of the photon is used to excite an electron of a pigment. The free energy created is then used, via a chain of nearby electron acceptors, for a transfer of hydrogen atoms (as protons and electrons) from H2O or hydrogen sulfide towards carbon dioxide, eventually producing glucose. These electron transfer steps ultimately result in the conversion of the energy of photons to chemical energy.

<span class="mw-page-title-main">Clomazone</span> Chemical compound

Clomazone is an agricultural herbicide, and has been the active ingredient of products named "Command" and "Commence". The molecule consists of a 2-chlorobenzyl group bound to a N-O heterocycle called isoxazolidinone. It is a white solid.

<span class="mw-page-title-main">Photoinhibition</span>

Photoinhibition is light-induced reduction in the photosynthetic capacity of a plant, alga, or cyanobacterium. Photosystem II (PSII) is more sensitive to light than the rest of the photosynthetic machinery, and most researchers define the term as light-induced damage to PSII. In living organisms, photoinhibited PSII centres are continuously repaired via degradation and synthesis of the D1 protein of the photosynthetic reaction center of PSII. Photoinhibition is also used in a wider sense, as dynamic photoinhibition, to describe all reactions that decrease the efficiency of photosynthesis when plants are exposed to light.

Non-photochemical quenching (NPQ) is a mechanism employed by plants and algae to protect themselves from the adverse effects of high light intensity. It involves the quenching of singlet excited state chlorophylls (Chl) via enhanced internal conversion to the ground state, thus harmlessly dissipating excess excitation energy as heat through molecular vibrations. NPQ occurs in almost all photosynthetic eukaryotes, and helps to regulate and protect photosynthesis in environments where light energy absorption exceeds the capacity for light utilization in photosynthesis.

<span class="mw-page-title-main">Dinoseb</span> Chemical compound used as a herbicide

Dinoseb is a common industry name for 6-sec-butyl-2,4-dinitrophenol, a herbicide in the dinitrophenol family. It is a crystalline orange solid which does not readily dissolve in water. Dinoseb is banned as an herbicide in the European Union (EU) and the United States because of its toxicity.

<span class="mw-page-title-main">Propanil</span> Chemical compound

Propanil is a widely used contact herbicide. With an estimated use of about 8 million pounds in 2001, it is one of the more widely used herbicides in the United States. Propanil is said to be in use in approximately 400,000 acres of rice production each year.

<span class="mw-page-title-main">Monolinuron</span> Chemical compound

Monolinuron is a pesticide, more specifically a selective systemic herbicide and an algaecide. As an herbicide, it is used to control broad-leaved weeds and annual grasses in vegetable crops such as leeks, potatoes, and dwarf French beans. Monolinuron affects the photosynthesis in weeds. Following uptake of monolinuron through roots and leaves of weeds, monolinuron causes early symptoms of yellowing and die-back of the leaves, eventually resulting in weed death. In fishkeeping, it is used to control blanket weed and hair algae.

<span class="mw-page-title-main">Light-dependent reactions</span> Photosynthetic reactions

Light-dependent reactions are certain photochemical reactions involved in photosynthesis, the main process by which plants acquire energy. There are two light dependent reactions: the first occurs at photosystem II (PSII) and the second occurs at photosystem I (PSI).

<span class="mw-page-title-main">Crop desiccation</span>

Pre-harvest crop desiccation is the application of an agent to a crop just before harvest to kill the leaves and/or plants so that the crop dries out from environmental conditions, or "dry-down", more quickly and evenly. Crop desiccants include herbicides and defoliants, used to accelerate the natural drying of plant tissues. Desiccation of crops through the use of herbicides is practiced worldwide on a variety of food and non-food crops.

<span class="mw-page-title-main">Cyanazine</span> Chemical compound

Cyanazine is a herbicide that belongs to the group of triazines. Cyanazine inhibits photosynthesis and is therefore used as a herbicide.

References

  1. Arnold P. Appleby, Franz Müller, Serge Carpy "Weed Control" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a28_165
  2. Hexazinone, Herbicide Profile, Pesticide Management Education Program, Cornell University
  3. da Silva, Cydianne Cavalcante; Souza, Matheus de Freitas; Passos, Ana Beatriz Rocha de Jesus; Silva, Tatiane Severo; Borges, Maiara Pinheiro da Silva; dos Santos, Matheus Silva; Silva, Daniel Valadão (March 2022). "Risk of environmental contamination due to the hexazinone application in agricultural soils in northeastern Brazil". Geoderma Regional. 28: e00481. Bibcode:2022GeodR..2800481D. doi:10.1016/j.geodrs.2022.e00481. S2CID   246338359.
  4. Wang, Huili; Xu, Shuxia; Tan, Chengxia; Wang, Xuedong (2009-05-30). "Anaerobic biodegradation of hexazinone in four sediments". Journal of Hazardous Materials. 164 (2–3): 806–811. Bibcode:2009JHzM..164..806W. doi:10.1016/j.jhazmat.2008.08.073. PMID   18824297.
  5. "Hexazinone: Reregistration Eligibility Decision (RED) Fact Sheet" (PDF).
  6. "Agronomy 317 - Iowa State University". agron-www.agron.iastate.edu. Archived from the original on 2016-11-23. Retrieved 2017-03-15.
  7. 1 2 Ullmann's agrochemicals. Wiley-VCH. 2007-01-01. ISBN   9783527316045. OCLC   470787466.
  8. Helling, C. S.; Kearney, P. C.; Alexander, M. (1971). "Behavior of pesticides in soil". Adv. Agron. Advances in Agronomy. 23: 147–240. doi:10.1016/S0065-2113(08)60153-4. ISBN   9780120007233.
  9. Rhodes, R. C. (1980b). "Studies with 14C-labeled hexazinone in water and bluegill sunfish". J. Agric. Food Chem. 28 (2): 306–310. doi:10.1021/jf60228a002. PMID   7391368.
  10. Rhodes, R. C. (1980a). "Soil Studies with 14C-labeled hexazinone". J. Agric. Food Chem. 28 (2): 311–315. doi:10.1021/jf60228a012.
  11. Ghassemi, M.; et al. (1981). Environmental fates and impacts of major forest use pesticides. Washington D.C. pp. 169–194.{{cite book}}: CS1 maint: location missing publisher (link)
  12. "Weed Science Society of America". wssa.net. Retrieved 2017-03-15.
  13. Sidhu, S. S.; Feng., J. C. (1993). "Hexazinone and its metabolites in boreal forest vegetation". Weed Sci. 41 (2): 281–287. doi:10.1017/S0043174500076177. S2CID   83421922.