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

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

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

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

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.

Pyrazolyl benzyl ether derivatives containing a fluoromethoxyimino group and use thereof as pesticides

The invention relates to novel pyrazolyl benzyl ethers, to a plurality of processes for their preparation and to their use for controlling harmful organisms.

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.

2-(Pyrazolyloxy) -pyridin-3-ylacetic acid derivatives, agents containing the same and use thereof against noxious fungi and animal parasites

Compounds of the formula I and salts thereof, in which the substituents and the index n have the following meanings: Q is —C(═CHCH3)—COOCH3, —C(═CHOCH3)—COOCH3, —C(═NOCH3)—COOCH3or —C(═NOCH3)—CONH(CH3); R1is hydrogen, halogen, C1-C4-alkyl, C1-C2-haloalkyl, C1-C4-alkoxy or C1-C2-haloalkoxy; R2is halogen, C1-C4-alkyl, C1-C2-haloalkyl, C1-C4-alkoxy; n is 0, 1 or 2, where the substituents R2may be different if n=2; R3is phenyl, pyridyl or pyrimidyl, compositions comprising them and the use of the compounds I and the compositions for controlling harmful fungi and animal pests 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.

Method for combating harmful fungi

A method for control of harmful fungi is provided by treating the fungi, or the materials, plants, the soil or seeds to be protected against fungal infection, with an effective amount of a bisoxime of the formula I or a salt or adduct thereof, the index and the substituents having the following meanings: R1is halogen, alkyl or haloalkyl; R2is cyano, nitro, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylaminocarbonyl, substituted or unsubstituted phenyl, phenoxy or phenylthio; n is 0, 1, 2 or 3; R3is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or phenylalkyl.

Microbicidal benzotriazoles

Novel benzotriazoles of the formula STR1 in which R, X1, X2, X3, X4 and Y have the meanings given in the description, and their acid addition salts and metal salt complexes, a process for the preparation of these substances and their use as microbicides in crop protection and in material protection.

Halogen alkenyl azolyl microbicides

Novel halogenoalkenyl-azolyl derivatives of the formula STR1 in which R1 represents optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, optionally substituted aryl or represents optionally substituted heteroaryl, R2 represents alkyl, halogenoalkyl, 1-hydroxyalkyl, 2-hydroxyalkyl, 1-hydroxyhalogenalkyl, 1-alkenyl or 2-alkenyl, X1 represents fluorine, chlorine, bromine or iodine, X2 represents fluorine, chlorine, bromine or iodine, and Y represents nitrogen or a CH group, and addition products thereof with acids or metal salts are very active as microbicides in plant protection and in the protection of materials.

Acylated 5-aminopyrazoles and the use thereof to combat animal parasites

The present invention relates to new acylated 5-aminopyrazoles of the formula (I) STR1 in which R1, R2, R3, R4 and R5 have the meaning given in the description, to processes for their preparation and to their use as pesticides.

Substituted tetrahydro-5-nitro-pyrimidines

The present invention relates to novel substituted in that one tetrahydro-5-nitro-pyrimidine of the formula (I), according to claim 1, STR1 in which n, R1, R2 have the meaning given in the description, to a process for its preparation and to its use for combating animal pests, especially insects, arachnids and nematodes, which are encountered in agricultural, in forestry, in the protection of stored products and of materials and, in the hygiene sector.