Thiophanate-methyl (Ref: NF 44)

Thiophanate-methyl (Ref: NF 44)	Last updated: 13/01/2021
(Also known as: thiophanate; thiofanate; banrot)

SUMMARY

Thiophanate methyl is an approved EU fungicide used widely to control fungal diseases on crops. It has a low aqueous solubility, low volatility and tends not to be persistent in soil or water systems. It has a low mammalian toxicity, however it is an irritant, a skin sensitiser and may also be mutagen. It is moderately toxic to most aquatic organisms and earthworms but less so to birds and honeybees.

GENERAL INFORMATION

Description

A systemic fungicide effective with protective and curative activity against a broad spectrum of diseases in fruit, vegetables and other crops

Example pests controlled

Eyespot; Scab; Powdery mildew; Grey mould; Leaf spot; Rusts; Brown spot; Brown Rot; Root rots

Example applications

Apples & pears; Small grains; Curcubits; Soybeans; Peanuts, Pecans; Garlic & onions; Almonds; Strawberries; Grapes; Tomatoes; Aubergines

Efficacy & activity

Wheat/Ear blight=Low; Soybean/Leaf blight=Moderate; Soybean/Rust=Moderate; Soybean/White mould=Moderate

Availability status

Current

Introduction & key dates

1971, first registered Japan

UK regulatory status

UK COPR regulatory status

Phasing out

Date COPR inclusion expires

UK LERAP status

None (may vary with mixtures)

EC Regulation 1107/2009 (repealing 91/414)

EC Regulation 1107/2009 status

Not approved

Dossier rapporteur/co-rapporteur

Sweden/Finland

Date EC 1107/2009 inclusion expires

31/10/2021

EU Candidate for substitution (CfS)

Listed in EU database

Yes

Approved for use (✓) under EC 1107/2009 in the following EU Member States

ATAustria	BEBelgium	BGBulgaria	CYCyprus	CZCzech Republic	DEGermany	DKDenmark	EEEstonia	ELGreece
✓	✓	✓	✓	✓	✓	✓	✓	✓
ESSpain	FIFinland	FRFrance	HRCroatia	HUHungary	IEIreland	ITItaly	LTLithuania	LULuxembourg
✓	✓	✓	✓	✓		✓	✓
LVLatvia	MTMalta	NLNetherlands	PLPoland	PTPortugal	RORomania	SESweden	SISlovenia	SKSlovakia
✓	✓	✓	✓	✓	✓	✓	✓	✓

Also used in

Australia, USA

Chemical structure

Isomerism

Chemical formula

C₁₂H₁₄N₄O₄S₂

Canonical SMILES

COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC

Isomeric SMILES

No data

International Chemical Identifier key (InChIKey)

QGHREAKMXXNCOA-UHFFFAOYSA-N

International Chemical Identifier (InChI)

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

2D structure diagram/image available?

Yes

Cambridge Crystallographic Data Centre diagrams

Common Name	Relationship	Link
thiophanate-methyl	-

General status

Pesticide type

Fungicide

Substance group

Benzimidazole

Minimum active substance purity

950 g kg⁻¹

Known relevant impurities

EU dossier - DAp, HAp, carbendazim

Substance origin

Synthetic

Mode of action

Inhibition of mitosis and cell division (Beta-tubulin assembly in mitosis).

CAS RN

23564-05-8

EC number

245-740-7

CIPAC number

262

US EPA chemical code

102001

PubChem CID

3032791

Molecular mass

342.39

PIN (Preferred Identification Name)

dimethyl N,N'-[1,2-phenylenebis(azanediylcarbonothioyl)]dicarbamate

IUPAC name

dimethyl 4,4'-(o-phenylene)bis(3-thioallophanate)

CAS name

dimethyl (1,2-phenylenebis(iminocarbonothioyl))bis(carbamate)

Other status information

Relevant Environmental Water Quality Standards

Herbicide Resistance Classification (HRAC)

Not applicable

Herbicide Resistance Classification (WSSA)

Not applicable

Insecticide Resistance Classification (IRAC)

Not applicable

Fungicide Resistance Classification (FRAC)

Examples of recorded resistance

Physical state

Colourless to light brown crystalline powder

Related substances & organisms

iprodione

solvent naphtha

Formulations

Property

Value

Example manufacturers & suppliers of products using this active now or historically

Snare
Mildothane Turf Liquid
3336Plus
Topsin M
Senator
Frumidor

Example products using this active

Bayer Environ
Headland
Makhteshim-Agan
Scotts
Nufarm

Formulation and application details

Usually formulated as a suspension concentrate, flowable, ULV or wettable powder

ENVIRONMENTAL FATE

Property

Value

Source; quality score; and other information

Interpretation

Solubility - In water at 20 °C (mg l⁻¹)

18.5

Low

Solubility - In organic solvents at 20 °C (mg l⁻¹)

8400

Ethyl acetate

0.47

n-Hexane

7800

Methanol

110

Xylene

Melting point (°C)

Decomposes before melting

Boiling point (°C)

Decomposes before boiling

Degradation point (°C)

165

Flashpoint (°C)

Not expected to self ignite; Not highly flammable

Octanol-water partition coefficient at pH 7, 20 °C

2.51 X 10⁰¹

Calculated

Log P

1.40

at 25 °C

Low

Bulk density (g ml⁻¹)

1.45

Dissociation constant pKa) at 25 °C

7.28

Weak acid

Vapour pressure at 20 °C (mPa)

9.0 X 10^-03

Low volatility

Henry's law constant at 25 °C (Pa m³ mol⁻¹)

1.67 X 10^-04

Non-volatile

Maximum UV-vis absorption L mol⁻¹ cm⁻¹

268nm = 19046, 305nm = shoulder

Surface tension (mN m⁻¹)

72.2

Degradation

Property

Value

Source; quality score; and other information

Interpretation

General biodegradability

Not readily biodegradable

Soil degradation (days) (aerobic)

DT₅₀ (typical)

0.5

Non-persistent

DT₅₀ (lab at 20 °C)

0.5

Non-persistent

DT₅₀ (field)

2.0

Non-persistent

DT₉₀ (lab at 20 °C)

1.66

Non-persistent

DT₉₀ (field)

13.3

DT₅₀ modelling endpoint

Note

EU 2016 dossier Lab studies DT₅₀ range 0.29-0.70 days, DT₉₀ range 0.96-2.3 days, Soils=4; Field studies DT₅₀ range 1.0-3.3 days, DT₉₀ range 6.0-17.0, Soils=4

Dissipation rate RL₅₀ on plant matrix

Value

29.6

Note

Undercover ornamentals, leaves, n=1

Dissipation rate RL₅₀ on and in plant matrix

Value

4.2

Note

Published literature RL₅₀ range 1.0-15.4 days, 11 field grown crops, various matrices, n=17

Aqueous photolysis DT₅₀ (days) at pH 7

Value

2.2

Moderately fast

Note

Data for natural sunlight at pH 5

Aqueous hydrolysis DT₅₀ (days) at 20 °C and pH 7

Value

46.8

Moderately persistent

Note

pH sensitive: DT₅₀ Stable - 867 days at pH 5; 1.0 days at pH 9, all at 22 °C

Water-sediment DT₅₀ (days)

Fast

Water phase only DT₅₀ (days)

Moderately fast

Soil adsorption and mobility

Property

Value

Source; quality score; and other information

Interpretation

Linear

K_d

K_oc

Notes and range

Freundlich

K_f

2.41

Moderately mobile

K_foc

220

¹/_n

0.86

Notes and range

EU 2016 dossier K_f range 0.27-14.1 mL g⁻¹, K_foc range 54-859 mL g⁻¹, ¹/_n range 0.75-0.99, Soils=10

pH sensitivity

Some studies suggest that adsorption is stronger in acid soils

Fate indices

Property

Value

Source; quality score; and other information

Interpretation

GUS leaching potential index

0.50

Calculated

Low leachability

SCI-GROW groundwater index (μg l⁻¹) for a 1 kg ha⁻¹ or 1 l ha⁻¹ application rate

Value

1.06 X 10^-03

Calculated

Note

Potential for particle bound transport index

Low

Calculated

Potential for loss via drain flow

Moderately mobile

Calculated

Key metabolites

Metabolite

Formation medium

Estimated maximum occurrence fraction

1107/2009 relevancy

carbendazim (Ref: BAS 346F)

Soil

0.758

Major fraction, Relevant

methyl 4-(2-(methoxycarbonylamino)benzothiazoyl)allophanate (Ref: CM-0237)

Soil

0.098

Minor fraction, Relevant

Other known metabolites

Metabolite name and reference

Aliases

Formation medium / Rate

Estimated maximum occurrence fraction

Metabolising enzymes

dimethyl 4,4-(4-hydroxy-ortho-phenylene)bis(3-thioallophanate) sulphate

5-OH-thiophanate-menthyl sulfate

Rodent

dimethyl 4,4-(3-hydroxy-ortho-phenylene)bis(3-thioallophanate)

3-OH-thiophanate-methyl

Animal

dimethyl 4,4-(4-hydroxy-ortho-phenylene)bis(3-thioallophanate)

4-OH-thiophanate-methyl

Animal

methyl 4-(2-(3-methoxycarbonyl-2-thioureido)phenyl)allophanate

DX-105

Water (photoylsis), Rat, Plant

dimethyl 4,4-(ortho-phyenylene)bis(allophanate))

FH-432; Allophanate

Water, Animal, Plant

dimethyl 4,4-)4-hydroxy-ortho-phenylene)bis(allophanate)

4-OH-FH-432

Rat

dimethyl 4,4-)4-hydroxy-ortho-phenylene)bis(allophanate) sulphate

4-OH-FH-432-S

Rat

[2-N-methoxy carbonyl thioureido) phenylene] thiourea

AV-1951

Water

methyl-N-(2-aminophenylaminocarbonothioyl)carbamate

FH-73

methyl (4-hydroxy-1H-benzimidazol-2-yl)carbamate

4-OH-MBC

Animal

methyl (4-hydroxy-1H-benzimidazol-2-yl)carbamate sulphate

4-OH-MBC-S

Rodent

methyl (5-hydroxy-1H-benzoimidazol-2-yl)carbamate

5-OH-MBC

Animal

methyl (5-hydroxy-1H-benzoimidazol-2-yl)carbamate sulphate

5-OH-MBC-s

Animal

2-amino-1H-benzimidazole

2-AB

Water-sediment systems, Soil, Animal, Plant

2-amino(-4-hydroxy)benzimidazole

4-OH-2-AB

2-amino-1H-benzimidazol-5-ol

5-OH-2-AB

Hen

ECOTOXICOLOGY

Property

Value

Source; quality score; and other information

Interpretation

Bio-concentration factor

BCF (l kg⁻¹)

Estimated

Low potential

CT₅₀ (days)

Not available

Mammals - Acute oral LD₅₀ (mg kg⁻¹)

> 5000

Rat

Low

Mammals - Short term dietary NOEL

(mg kg⁻¹)

Rat

(ppm diet)

> 2.5

Mammals - Chronic 21d NOAEL (mg kg⁻¹ bw d⁻¹)

> 147

Rat Reproductive NOAEL

Moderate

Birds - Acute LD₅₀ (mg kg⁻¹)

> 4640

Anas platyrhynchos

Low

Birds - Short term dietary (LC₅₀/LD₅₀)

> 10000 mg kg feed⁻¹

Unknown species

Birds - Chronic 21d NOEL (mg kg⁻¹ bw d⁻¹)

9.1

Colinus virginianus NOAEL

High

Fish - Acute 96 hour LC₅₀ (mg l⁻¹)

11.0

Oncorhynchus mykiss

Moderate

Fish - Chronic 21 day NOEC (mg l⁻¹)

0.32

Salmo gairdneri

Moderate

Aquatic invertebrates - Acute 48 hour EC₅₀ (mg l⁻¹)

5.4

Daphnia magna

Moderate

Aquatic invertebrates - Chronic 21 day NOEC (mg l⁻¹)

0.18

Daphnia magna

Moderate

Aquatic crustaceans - Acute 96 hour LC₅₀ (mg l⁻¹)

1.0

Americamysis bahia

Moderate

Sediment dwelling organisms - Acute 96 hour LC₅₀ (mg l⁻¹)

Sediment dwelling organisms - Chronic 28 day NOEC, static, water (mg l⁻¹)

0.5

Chironomus riparius emergence

Moderate

Sediment dwelling organisms - Chronic 28 day NOEC, sediment (mg kg⁻¹)

Aquatic plants - Acute 7 day EC₅₀, biomass (mg l⁻¹)

4.7

Lemna gibba

Moderate

Non-target plants

> 1570

Cabbage Corn Cucumber Lettuce Oats Onions Ryegrass Tomatoes
Vegetative vigour, ER₅₀
as g ha⁻¹

> 1680

Cabbage Corn Cucumber Lettuce Oats Onions Ryegrass Tomatoes
Seedling emergence, ER₅₀
as g ha⁻¹

Algae - Acute 72 hour EC₅₀, growth (mg l⁻¹)

> 25.4

Pseudokirchneriella subcapitata

Low

Algae - Chronic 96 hour NOEC, growth (mg l⁻¹)

Honeybees (Apis spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

> 100

Apis mellifera

Low

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

> 114.7

Apis mellifera

Low

Unknown mode acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Bumblebees (Bombus spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Mason bees (Osmia spp.)

Contact acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Oral acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg bee⁻¹)

Other pollinators (1)

Acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg insect⁻¹)

Mode of exposure

Other pollinators (2)

Acute LD₅₀ (worst case from 24, 48 and 72 hour values - μg insect⁻¹)

Mode of exposure

Earthworms - Acute 14 day LC₅₀ (mg kg⁻¹)

> 13.2

Eisenia foetida

Moderate

Earthworms - Chronic NOEC, reproduction (mg kg⁻¹)

1.60

Eisenia foetida

Moderate

Other soil macro-organisms

Acute LC₅₀ (mg kg⁻¹)

Chronic NOEC (mg kg⁻¹)

> 100

Folsomia candida

Other arthropod (1)

LR₅₀ g ha⁻¹

Harmless

[Dose: 400 g ha⁻¹]
Aphidius rhopalosiphi

% Effect

Parasitastion [Dose: 1.58 kg ha⁻¹]
Aphidius rhopalosiphi

Other arthropod (2)

LR₅₀ g ha⁻¹

1575

>
Typhlodromus pyri

% Effect

Mortality [Dose: 0.07 kg ha⁻¹]
Typhlodromus pyri

Soil micro-organisms

Nitrogen mineralisation: No adverse effect
Carbon mineralisation: No adverse effect

Dose: 5 kg ha⁻¹

Mesocosm study data

NOEAEC mg l⁻¹

HUMAN HEALTH AND PROTECTION

General

Property

Value

Source; quality score; and other information

Interpretation

Threshold of Toxicological Concern (Cramer Class)

High (class III)

Mammals - Acute oral LD₅₀ (mg kg⁻¹)

> 5000

Rat

Low

Mammals - Dermal LD₅₀ (mg kg⁻¹ body weight)

2000

Rat

Mammals - Inhalation LC₅₀ (mg l⁻¹)

1.7

Rat 4 hr (whole body)

Other Mammal toxicity endpoints

ADI - Acceptable Daily Intake (mg kg⁻¹ bw day⁻¹)

0.08

Dog SF=100 under review

ARfD - Acute Reference Dose (mg kg⁻¹ bw day⁻¹)

0.2

Rabbit SF=100 under review

AAOEL - Acute Acceptable Operator Exposure Level (mg kg⁻¹ bw day⁻¹)

Not established

AOEL - Acceptable Operator Exposure Level - Systemic (mg kg⁻¹ bw day⁻¹)

0.08

Dog SF=100 under review

Dermal penetration studies (%)

Dangerous Substances Directive 76/464

Exposure Routes

Public

Low risk for bystanders and residents

Occupational

Use of PPE/PPC recommended to reduce exposure risks

European MRLs

EU MRL pesticide database

Drinking Water Standards

Drinking Water MAC (μg l⁻¹)

Health issues

Specific human health issues

Carcinogen

Genotoxic

Endocrine disruptor

; ; ; ;

Reproduction / development effects

Acetyl cholinesterase inhibitor

Neurotoxicant

No data found

Respiratory tract irritant

Skin irritant

Skin sensitiser

Eye irritant

Phototoxicant

General human health issues

Mutagenic potential
USEPA - possible human carcinogen
Possible liver, kidney & thyroid toxicant

Handling issues

Property

Value and interpretation

General

Prevent generation of dust
Some explosive potential but generally considered not to have explosive or oxidising properties
IMDG Transport Code is usually 9

CLP classification 2013

Health: H317, H332, H340
Environment: H400, H410

EC Risk Classification

Mutagenic category 3: R68
Xn - Harmful: R20, R43
N - Dangerous for the environment: R50, R53

EC Safety Classification

S2, S36/37, S46, S60, S61

WHO Classification

U (Unlikely to present an acute hazard)

UN Number

Usually 3077

Waste disposal & packaging

Packaging Group III (minor danger)

TRANSLATIONS

Language

Name

English

thiophanate-methyl

French

thiophanate-methyle

German

Thiophanat-methyl

Danish

thiophanate-methyl

Italian

tiofanato-metile

Spanish

tiofanato de metilo

Greek

Polish

tiofanat metylowy

Swedish

tiofanatmetyl

Hungarian

tiophanate-methyl

Dutch

thiofanaat-methyl

Record last updated:	13/01/2021
Contact:	aeru@herts.ac.uk
Please cite as:	Lewis, K.A., Tzilivakis, J., Warner, D. and Green, A. (2016) An international database for pesticide risk assessments and management. Human and Ecological Risk Assessment: An International Journal, 22(4), 1050-1064. DOI: 10.1080/10807039.2015.1133242