23564-05-8

Basic information

• Product Name: Thiophanate-methyl
• Synonyms: (1,2-phenylenebis(iminocarbonothioyl))bis-carbamicacidimethylester;[1,2-phenylenebis(iminocarbonothioyl)]bis-carbamicacidimethylester;1,2-bis(methoxycarbonylthioureido)benzene;1,2-di-(3-Methoxy-carbonyl-2-thioureido)benzene;4,4’-o-phenylenebis(3-thio-allophanicacidimethylester;bas32500f;caligran;Carbamicacid,[1,2-phenylenebis(iminocarbonothioyl)]bis-,dimethylester
• CAS NO: 23564-05-8
• Molecular Formula: C₁₂H₁₄N₄O₄S₂
• Molecular Weight: 342.39
• EINECS: 245-740-7
• Product Categories: FUNGICIDE;Alpha sort;MetabolitesPesticides&Metabolites;Q-ZAlphabetic;BenzimidazolesPesticides;CarbamatesEnvironmental Standards;Fungicides;MetabolitesAlphabetic;Pesticides;Pesticides&Metabolites;TF - TO;NULL
• Mol File: 23564-05-8.mol
• Article Data: 16

Chemical Properties

• Melting Point: 172°C
• Boiling Point: 478.4oC at 760 mmHg
• Flash Point: 243.1°C
• Appearance: colourless crystals, or white or light brown powder
• Density: 1.4542 (rough estimate)
• Vapor Pressure: 2.58E-09mmHg at 25°C
• Refractive Index: 1.6000 (estimate)
• Storage Temp.: 0-6°C
• PKA: 7.28
• Water Solubility: <0.1 g/100 mL at 20℃
• Stability: Stable. Incompatible with strong oxidizing agents, alkalies, copper salts.
• Merck: 13,9427
• BRN: 937942
• CAS DataBase Reference: Thiophanate-methyl(CAS DataBase Reference)
• NIST Chemistry Reference: Thiophanate-methyl(23564-05-8)
• EPA Substance Registry System: Thiophanate-methyl(23564-05-8)

Safety Data

• Hazard Codes: Xn;N,N,Xn
• Statements: 20-43-50/53-68
• Safety Statements: 36/37-46-60-61
• RIDADR: UN 3077
• WGK Germany: 2
• RTECS: BA3675000
• Hazardous Substances Data: 23564-05-8(Hazardous Substances Data)

Usage

Description

Thiophanate methyl is a member of benzimidazole and a systemic fungicide with protective and curative activity against a broad spectrum of fungal diseases including leaf spots, blotches, blights, fruit spots, rots, sooty mould, scabs, bulb/corn/tuber decays, blossom blights, powdery mildews, certain rusts, and common soil borne crown and root rots. It is used on a variety of tree, vine, root crops, canola, and wheat, as well as on lawns and ornamentals. Thiophanate methyl is absorbed by the roots and leaves. Thiophanate-methyl has a low mammalian toxicity. But, it is an irritant and a skin sensitizer. It may also be mutagen. Moderate toxicity of thiophanate methyl is observed for aquatic organisms and earthworms. In EU, thiophanate methyl is approved to control fungal diseases on crops, while in Australia it is not registered for use on food-producing species, while it is only for the control of soil-borne diseases of ornamentals plants. For application, Thiophanate-methyl is formulated into wettable powders containing 50 and 70% active ingredient.

References

https://apvma.gov.au https://www.epa.gov https://sitem.herts.ac.uk http://www.inchem.org Terry R Roberts, David H Hutson, Philip W Lee, Peter H Nicholls, and Jack R Plimmer, Metabolic Pathways of Agrochemicals: Part 2: Insecticides and Fungicides, 1999, ISBN 978-0-85404-499-3

Chemical Properties

Different sources of media describe the Chemical Properties of 23564-05-8 differently. You can refer to the following data:
1. colourless crystals, or white or light brown powder
2. Methyl thiophanate is a colorless crystals, prisms or light brown powder.

Uses

Different sources of media describe the Uses of 23564-05-8 differently. You can refer to the following data:
1. Thiophanate methyl is a fungicide/wound protectant used to control plant diseases in stone fruit, pome fruit, tropical and subtropical fruit crops, grapes and fruiting vegetables. Thiophanate methyl is effective against a wide variety of fungal diseases such as leaf spots, blotches and blights; fruit spots and rots; sooty mould; scabs; bulb, corn and tuber decays; blossom blights; powdery mildews; certain rusts; and common soil borne crown and root rots.
2. Thiophanate-Methyl is a systematic fungicide of the thiophanate class. Thiophanate-Methyl is commonly used in agriculture to protect against powdery mildew, rot and other fungal diseases in fruits, ve getables and other crops.
3. Systemic fungicide.

Definition

ChEBI: A member of the class of thioureas that is the dimethyl ester of (1,2-phenylenedicarbamothioyl)biscarbamic acid. A fungicide effective against a broad spectrum of diseases in fruit, vegetables, turf and other crops including eyespot, scab, powdery mildew a d grey mould.

General Description

Colorless crystals or light brown powder.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Thiophanate-methyl is incompatible with strong acids and bases, and with strong reducing agents such as hydrides. Produces flammable gaseous hydrogen with active metals or nitrides. Incompatible with strong oxidizing acids, peroxides. Incompatible with alkaline material. Forms complexes with copper salts .

Fire Hazard

Flash point data for Thiophanate-methyl are not available. Thiophanate-methyl is probably combustible.

Flammability and Explosibility

Notclassified

Agricultural Uses

Fungicide: Thiophanate-methyl is a systemic fungicide used to control a broad spectrum of fungal diseases on fruits, vegetables, turf and ornamentals, including shade trees, and diseases in the field, nurseries, and in greenhouses. Note: Do not confuse with thiophanate-ethyl (CAS: 23564-06-9), which is not currently registered for use in the U.S. Registered for use in EU countries. Registered for use in the U.S.

Trade name

BASF? 32500 F; BASF? 32500 Fungicide; CERCOBIN?; CLEARY? 3336; CONSYST?; DITEK?[C]; DOMAIN?; DOUSAN?[C]; ENOVIT?; EVOLVE?; FANATE?; FUNGITOX?; FUNGO?; MILDOTHANE? Turf Liquid; NEOTOPSIN?; NF- 35?; NF-44?; NSC 170810?; PELT?; PRO-TURF?; SIPCAVIT?; SNARE?; SPECTRO?; SYSTEC?; SYSTEMIC? FUNGICIDE; TD 1771?; TOPSIN?; TOPSIN-WP METHYL?; 3336 TURF FUNGICIDE?; ZYBAN?

Potential Exposure

Methyl thiophanate is thiocarbamate ester, used in the synthesis of polymers and in agriculture as pesticides, soil fumigants, and seed disinfectants.

Carcinogenicity

Those long-term studies evaluated a variety of toxicity end points including carcinogenicity. Both benomyl and carbendazim were weak carcinogens in some in vivo studies. Rats of the SpDxAug strain were fed 80, 400, and 2000 ppm for 2 years and no evidence for an increase in tumors was seen. In carcinogenicity studies in mice with carbendazim, similar liver tumor finding were found in CD-1 or Swiss strains. On the other hand, no evidence of tumors was seen in a similar study conducted using the NMRKf mouse strain, a strain that has a low incidence of spontaneous tumors.

Metabolic pathway

Thiophanate methyl degradation in water (hydrolytic/ photolysis), soils, plants and animals follows a common pathway that involves the initial conversion into methyl benzimidazol-2-ylcarbamate (carbendazim). Prior to benzimidazole ring formation, at least one side chain undergoes an oxidative desulfuration reaction and partial hydrolysis (even to the substituted aniline). Once formed, carbendazim is degraded primarily via an oxidative mechanism (in animals) or through hydrolysis to 2-aminobenzimidazole (in soils). Possible metabolism pathways of thiophanate methyl are depicted in Scheme 1.

Shipping

UN2771 Thiocarbamate pesticides, solid, toxic, Hazard Class: 6.1; Labels: 6.1-Poisonous materials. UN3077 Environmentally hazardous substances, solid, n.o.s., Hazard class: 9; Labels: 9-Miscellaneous hazardous material, Technical Name Required.

Degradation

Thiophanate methyl (1) is susceptible to alkaline hydrolysis. The principal degradation product is carbendazim (2). Thiophanate methyl degraded slowly in water (pH 7-7.4, Noguchi et al., 1971), and in fruit juice (grape homogenate, Shiga et al., 1985) to primarily carbendazim, but also to 1-(3- methoxycarbony1thioureido)-2-(3-methoxycarbony1ureido)benzene (3) and dimethyl 4,4'-(o-phenylene)bis(allophanate) (4). Thiophanate methyl underwent photolysis in aqueous solution to carbendazim (DT50 <1 day) when illuminated with UV light (254 nm) or natural sunlight. A similar photolytic transformation occurred on moist cotton foliage, although no photolysis occurred when thiophanate methyl was exposed as a dry film to light (Buchenauer et al., 1973). Thiophanate methyl on wet filter paper decomposed in sunlight to yield carbendazim and small amounts of compounds 3 and 4 (Ono and Tohyama, 1982).

Incompatibilities

Thiocarbamate esters are combustible; dust may form explosive mixture with air. Decomposes163℃Thiocarbamate esters are combustible. They react violently with powerful oxidizers such as calcium hypochlorite. Poisonous gases are generated by the thermal decomposition of thiocarbamate compounds, including carbon disulfide, oxides of sulfur, oxides of nitrogen, hydrogen sulfide, ammonia, and methylamine. Thio and dithio carbamates slowly decompose in aqueous solution to form carbon disulfide and methylamine or other amines. Such decompositions are accelerated by acids. Flammable gases are generated by the combination of thiocarbamates with aldehydes, nitrides, and hydrides. Thiocarbamates are incompatible with acids, peroxides, and acid halides.

Waste Disposal

In accordance with 40CFR 165 recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency, or by contacting your regional EPA office. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal.

InChI:InChI=1/C12H14N4O4S2/c1-19-11(17)15(9(13)21)7-5-3-4-6-8(7)16(10(14)22)12(18)20-2/h3-6H,1-2H3,(H2,13,21)(H2,14,22)

Upstream product

• 35266-49-0 methoxycarbonylisothiocyanate 
• 95-54-5 1,2-diamino-benzene 

Relevant articles and documents

Synthesis method of thiophanate-methyl

The invention belongs to the technical field of pesticide synthesis, and particularly relates to a synthesis method of thiophanate-methyl. The synthetic method of thiophanate-methyl comprises the following steps: dropwise adding an acetone solution of methyl isothiocyanate into an acetone-acetonitrile solution of o-phenylenediamine; carrying out insulation reaction, cooling crystallization to obtain thiophanate-methyl crystals, wherein a small amount of methyl isothiocyanate is contacted with a large amount of o-phenylenediamine, the contact area of methyl isothiocyanate and o-phenylenediamineis increased, the problem that molecular contact is uneven when o-phenylenediamine is dropwise added into methyl isothiocyanate conventionally is solved, the reaction process is more controllable, and the material rushing phenomenon does not exist. According to the method, acetone and acetonitrile are strong polar solvents, o-phenylenediamine is dissloved in an acetone-acetonitrile mixed solvent,and the volume ratio of acetone to acetonitrile is controlled to be 100: (11-15), so that the solubility of o-phenylenediamine is improved, the contact time of methyl isothiocyanate and o-phenylenediamine is prolonged, the reaction is more complete, and the productivity is improved.

Iminooxy-substituted benzyl phenyl ethers, processes and intermediates for their preparation, compositions comprising them, and their use for controlling harmful fungi

Iminooxy-substituted benzyl phenyl ethers of the formula I in which the substituents and the index are as defined below: Y is H, CH3, F or Cl; Q is C(═CHOCH3)—COOCH3, C(═CHCH3)—COOCH3, C(═NOCH3)—COOCH3, C(═NOCH3)—CONHCH3 or N(—OCH3)—COOCH3; X is hydrogen, halogen, alkyl, alkoxy or CF3; m is 1 or 2, where the radicals X may be different if m=2; R1 is alkyl and R2 is hydrogen or alkyl; or R1 and R2 together are cyclopropyl, cyclopentyl or cyclohexyl; R3 is alkyl or CF3; and R4 is alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl or haloalkynyl; processes and intermediates for their preparation, compositions comprising them, and their use, are described.

Bisimino-substituted phenyl compounds and their use as pesticides

Imino-substituted phenyl compounds of the formula I where the substituents have the following meanings:z is a group A or B ?where? denotes the bond with the phenyl ring and?Ra is halogen, alkyl or alkoxy;y is halogen, alkyl, haloalkyl or alkoxy;n is 0, 1 or 2, it being possible for the radicals Y to be different if n=2;R1 is halogen, haloalkyl or alkoxy;R2 is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl;R3 is cyano, alkyl, haloalkyl, alkoxy, cycloalkoxy, alkoxyalkyl;?unsubstituted or substituted cycloalkyl, aryl, aryloxy or arylmethylene, heteroaryl, heterocyclyl,?C(R3a)=N—OR3b or C(R3a)=CR3cR3d, whereR3a, R3b, R3c, R3d independently of one another are hydrogen, alkyl or unsubstituted or substituted phenyl,processes for their preparation, and their use.