Zinc bis(dimethyldithiocarbamate)

Last updated
Ziram
Zn(Me2dtc)2dimer.svg
Names
IUPAC name
(μ-Dimethylcarbamodithioato-1κS,2κS′)(μ-dimethylcarbamodithioato-1κS′,2κS)bis[(dimethylcarbamodithioato-κ2S,S′)zinc]
Other names
zinc dimethyldithiocarbamate, Ziram
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.004.808 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/2C3H7NS2.Zn/c2*1-4(2)3(5)6;/h2*1-2H3,(H,5,6);/q;;+2/p-2
    Key: DUBNHZYBDBBJHD-UHFFFAOYSA-L
  • CN(C)C(=S)[S-].CN(C)C(=S)[S-].[Zn+2]
Properties
C6H12N2S4Zn
Molar mass 305.80 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Zinc dimethyldithiocarbamate is a coordination complex of zinc with dimethyldithiocarbamate. It is a pale yellow solid that is used as a fungicide, the sulfur vulcanization of rubber, and other industrial applications. [1]

Contents

Applications

Known as ziram in agriculture, it was introduced in the United States in 1960 as a broad-spectrum fungicide. It was used to address scab on apples and pears, leaf curl in peaches, and anthracnose and blight in tomatoes. In 1981, additional uses for ziram were approved, including the prevention of leaf blight and scab on almonds, shot-hole in apricots, brown rot and leaf spot in cherries, and scab and anthracnose in pecans. Ziram also began to be used on residential ornaments as a bird and mammal repellent. [2] As a protectant fungicide, it active on the plant’s surface where it forms a chemical barrier between the plant and a fungus. A protectant fungicide is not absorbed into the plant and must be applied prior to infection. Ziram can either be directly sprayed on to a plant’s leaf or it can be used as a soil and seed treatment. The top five crops ziram is used on are: almonds, peaches, nectarines, pears, and table and raisin grapes. [3]

Alternatively, ziram is used as an additive ingredient in industrial adhesives, caulking, and paint. It also serves as a bird and mammal repellent on outdoor ornamental items.

Chemistry

The compound is a prototypical zinc dithiocarbamate, a broad class of coordination complexes with the formulae Zn(R2NCS2)2, where R can be varied. Such compounds are produced by treating zinc and dithiocarbamate (R2NCS2−), as illustrated with dimethyldithiocarbamate: [4]

2 (CH3)2NCS2− + Zn2+ → Zn((CH3)2NCS2)2

Annually, approximately 1.9 million pounds of the active ziram ingredient are used. Ziram is often sold in powder or granule form. [2]

Zinc bis(diethyldithiocarbamate) complexes degrade thermally to give zinc sulfide. [5]

Structure

Compounds of the type Zn(S2CNR2)2 are dimeric, i.e. their proper formula is [Zn(S2CNR2)2]2. [6] Each Zn center is in a distorted pentacoordinate site, with four Zn-S bonds of 2.3 Å length and one Zn---S interaction >2.8 Å in length. Mono-zinc derivatives are obtained by adding strong ligands (L) such as amines, which give adducts Zn(S2CNR2)2L. [7]

Ecological effects

The U.S. Environmental Protection Agency has concluded that ziram poses a low toxicity risk to mammals, a moderate risk to birds, and a high risk to aquatic species. After reviewing studies that investigated the effect of ziram on aquatic organisms, the Pesticide Action Network Pesticide Database concluded that its LC50 dose (amount of pesticide that is lethal to 50% of the test organisms within the stated study time) for amphibians places it in the "highly toxic" category.

See also

Structure of the ethyl-methyl carbamate derivative [Zn(S2CNEtMe)2]2. NAFQUGEtMedtcskewview.png
Structure of the ethyl-methyl carbamate derivative [Zn(S2CNEtMe)2]2.

Related Research Articles

Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. A fungistatic inhibits their growth. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. Chemicals used to control oomycetes, which are not fungi, are also referred to as fungicides, as oomycetes use the same mechanisms as fungi to infect plants. Fungicides can either be contact, translaminar or systemic. Contact fungicides are not taken up into the plant tissue and protect only the plant where the spray is deposited. Translaminar fungicides redistribute the fungicide from the upper, sprayed leaf surface to the lower, unsprayed surface. Systemic fungicides are taken up and redistributed through the xylem vessels. Few fungicides move to all parts of a plant. Some are locally systemic, and some move upwardly.

<span class="mw-page-title-main">Apple scab</span> Plant disease caused by fungus

Apple scab is a common disease of plants in the rose family (Rosaceae) that is caused by the ascomycete fungus Venturia inaequalis. While this disease affects several plant genera, including Sorbus, Cotoneaster, and Pyrus, it is most commonly associated with the infection of Malus trees, including species of flowering crabapple, as well as cultivated apple. The first symptoms of this disease are found in the foliage, blossoms, and developing fruits of affected trees, which develop dark, irregularly-shaped lesions upon infection. Although apple scab rarely kills its host, infection typically leads to fruit deformation and premature leaf and fruit drop, which enhance the susceptibility of the host plant to abiotic stress and secondary infection. The reduction of fruit quality and yield may result in crop losses of up to 70%, posing a significant threat to the profitability of apple producers. To reduce scab-related yield losses, growers often combine preventive practices, including sanitation and resistance breeding, with reactive measures, such as targeted fungicide or biocontrol treatments, to prevent the incidence and spread of apple scab in their crops.

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

Sodium diethyldithiocarbamate is the organosulfur compound with the formula NaS2CN(C2H5)2. It is a pale yellow, water soluble salt.

<span class="mw-page-title-main">Dithiocarbamate</span> Chemical group (>N–C(=S)–S–)

In organic chemistry, a dithiocarbamate is a functional group with the general formula R2NC(S)SR and structure >N−C(=S)−S−. It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms.

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

Dimethyldithiocarbamate is the organosulfur anion with the formula (CH3)2NCS2−. It is one of the simplest organic dithiocarbamate.

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

Thiuram disulfides are a class of organosulfur compounds with the formula (R2NCSS)2. Many examples are known, but popular ones include R = Me and Et. They are disulfides obtained by oxidation of the dithiocarbamates. These compounds are used in sulfur vulcanization of rubber as well as pesticides and drugs. They are typically white or pale yellow solids that are soluble in organic solvents.

Zineb is the chemical compound with the formula {Zn[S2CN(H)CH2CH2N(H)CS2]}n. Structurally, it is classified as a coordination polymer and a dithiocarbamate complex. This pale yellow solid is used as fungicide.

This article summarizes different crops, what common fungal problems they have, and how fungicide should be used in order to mitigate damage and crop loss. This page also covers how specific fungal infections affect crops present in the United States.

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

Maneb is a fungicide and a polymeric complex of manganese with the ethylene bis(dithiocarbamate) anionic ligand.

James Gordon Horsfall was an American biologist, plant pathologist, and agriculturist. The New York Times described Horsfall as a "leading plant pathologist." Horsfall served as director of the Connecticut Agricultural Experiment Station in New Haven from 1948 to 1971. He was succeeded by Paul E. Waggoner.

Pecan anthracnose is a fungal disease of pecan trees caused by the ascomycete Glomerella cingulata (Stoneman) Spauld. & H. It is a widespread disease found wherever pecan trees are grown. Pecan anthracnose has been reported as far back in time as 1914, and as far away as Argentina. Glomerella cingulata has two anamorphs which cause disease on pecan trees, Colletotrichum gloeosporioides and Colletotrichum acutatum. The occurrence of Colletotrichum on pecans has contributed to a significant decline in pecan production in various years. An increase in the incidence of pecan anthracnose is highly correlated with heavy rainfall, especially heavy rainfall occurring in early spring. The severity of symptoms increases as the season progresses, often culminating in leaf drop in the late autumn. This defoliation is linked to lower yield and poorer quality of nuts.

<span class="mw-page-title-main">Iron tris(dimethyldithiocarbamate)</span> Chemical compound

Iron tris(dimethyldithiocarbamate) is the coordination complex of iron with dimethyldithiocarbamate with the formula Fe(S2CNMe2)3 (Me = methyl). It is marketed as a fungicide.

<span class="mw-page-title-main">Nickel bis(dimethyldithiocarbamate)</span> Chemical compound

Nickel bis(dimethyldithiocarbamate) is the coordination complex on nickel and dimethyldithiocarbamate, with the formula Ni(S2CNMe2)2 (Me = methyl). It is the prototype for a large number of bis(dialkhyldithiocarbamate)s of nickel(II), which feature diverse organic substituents, all of which have similar structures. Nickel bis(dimethyldithiocarbamate) has been marketed as a fungicide and related complexes are used as stabilizers in polymers.

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

Methyl dimethyldithiocarbamate is the organosulfur compound with the formula (CH3)2NC(S)SCH3. It is the one of simplest dithiocarbamic esters. It is a white volatile solid that is poorly soluble in water but soluble in many organic solvents. It was once used as a pesticide.

<span class="mw-page-title-main">Sulfur vulcanization</span> Process to transform the material properties of natural rubber

Sulfur vulcanization is a chemical process for converting natural rubber or related polymers into materials of varying hardness, elasticity, and mechanical durability by heating them with sulfur or sulfur-containing compounds. Sulfur forms cross-linking bridges between sections of polymer chains which affects the mechanical and electronic properties. Many products are made with vulcanized rubber, including tires, shoe soles, hoses, and conveyor belts. The term vulcanization is derived from Vulcan, the Roman god of fire.

<span class="mw-page-title-main">Iron tris(diethyldithiocarbamate)</span> Chemical compound

Iron tris(diethyldithiocarbamate) is the coordination complex of iron with diethyldithiocarbamate with the formula Fe(S2CNEt2)3 (Et = ethyl). It is a black solid that is soluble in organic solvents.

<span class="mw-page-title-main">Cobalt tris(diethyldithiocarbamate)</span> Chemical compound

Cobalt tris(diethyldithiocarbamate) is the coordination complex of cobalt with diethyldithiocarbamate with the formula Co(S2CNEt2)3 (Et = ethyl). It is a diamagnetic green solid that is soluble in organic solvents.

<span class="mw-page-title-main">Transition metal dithiocarbamate complexes</span>

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc−. Many complexes are known. Several homoleptic derivatives have the formula M(R2dtc)n where n = 2 and 3.

<span class="mw-page-title-main">Iron bis(diethyldithiocarbamate)</span> Chemical compound

Iron bis(diethyldithiocarbamate) is a coordination complex with the formula [Fe(S2CNEt2)2]2 where Et = C2H5. A red solid, it is representative of several ferrous dithiocarbamates with diverse substituents in place of ethyl. In terms of structure, the species is dimeric, consisting of two pentacoordinate iron(II) centers. It is isostructural with [Zn(S2CNEt2)2]2, which in turn is similar to zinc bis(dimethyldithiocarbamate).

References

  1. ↑ Van Gysel, August B.; Musin, Willy (2000). "Methylamines". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a16_535.
  2. 1 2 "Ziram" (PDF). EPA R.E.D Facts. United States Environmental Protection Agency. Retrieved April 26, 2015.
  3. ↑ "Ziram". Extension Toxicology Network Pesticide Information Profiles. Cornell University, Oregon State University, the University of Idaho, and the University of California at Davis and the Institute for Environmental Toxicology, Michigan State University. Retrieved April 26, 2015.
  4. ↑ Rüdiger Schubart (2000). "Dithiocarbamic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_001. ISBN   3527306730.
  5. ↑ Shen, Shuling; Zhang, Yejun; Peng, Long; Xu, Bing; Du, Yaping; Deng, Manjiao; Xu, Huarui; Wang, Qiangbin (2011). "Generalized Synthesis of Metal Sulfide Nanocrystals from Single-Source Precursors: Size, Shape and Chemical Composition Control and Their Properties". CrystEngComm. 13 (14): 4572. doi:10.1039/c0ce00982b. ISSN   1466-8033.
  6. ↑ Mahid Motevalli, PaulO'Brien, John R.Walsh, Ian M.Watson (1996). "Synthesis, characterization and x-ray crystal structures of asymmetric bis(dialkyldithiocarbamates) of zinc: Potential precursors for ZnS deposition". Polyhedron. 15 (16): 2801–2808. doi:10.1016/0277-5387(95)00559-5.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. ↑ N. Sreehari, Babu Varghese, P. T. Manoharan (1990). "Crystal and molecular structure of dimeric bis[N,N-di-n-propyldithiocarbamato]zinc(II) and the study of exchange-coupled copper(II)-copper(II) pairs in its lattice". Inorg. Chem. 29 (20): 4011–4015. doi:10.1021/ic00345a020.{{cite journal}}: CS1 maint: uses authors parameter (link)
  8. ↑ Mahid Motevalli, PaulO'Brien, John R.Walsh, Ian M.Watson (1996). "Synthesis, characterization and x-ray crystal structures of asymmetric bis(dialkyldithiocarbamates) of zinc: Potential precursors for ZnS deposition". Polyhedron. 15 (16): 2801–2808. doi:10.1016/0277-5387(95)00559-5.{{cite journal}}: CS1 maint: multiple names: authors list (link)
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