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Methoprotryne

HCID 13290
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Basic information

CAS
841-06-5
Standard SMILES
COCCCNc1nc(NC(C)C)nc(SC)n1
InChIKey
DDUIUBPJPOKOMV-UHFFFAOYSA-N
Molecular formula
C11H21N5OS
Average molar mass
271.39 g/mol
Monoisotopic mass
271.14668148

Overview

Methoprotryne is a member of 1,3,5-triazines.

Names & identifiers

Preferred name
Methoprotryne
IUPAC
4-N-(3-methoxypropyl)-6-methylsulfanyl-2-N-propan-2-yl-1,3,5-triazine-2,4-diamine
English name
Methoprotryne
Molecular formula
C11H21N5OS
Molecular weight
271.38

Names & synonyms

METHOPROTRYNEMethoproptryne841-06-5MethoprotrynMetoprotryneMethotryneMetoprotrynCaswell No. 509AMethoprotryne [BSI:ISO]Metoprotryne [ISO-French]HSDB 1728G-36393
Show more names
g36393Gesaran 25MethoprotyneMetoprotrine
EINECS 212-664-0EPA Pesticide Chemical Code 509200BRN 0616626G 363932-Isopropylamino-4-(3-methoxypropylamino)-6-methylthio-s-triazine31X54QGQ171,3,5-Triazine-2,4-diamine, N-(3-methoxypropyl)-N'-(1-methylethyl)-6-(methylthio)-GESARAN-25

Database identifiers

CAS
841-06-5
PubChem CID
13290
DTXSID
DTXSID2040286
ChEBI
CHEBI:82226
UNII
31X54QGQ17
EC Number
212-664-0
Nikkaji
J9.467F

Properties

Computed structural properties

XLogP
2.8
Topological polar surface area
97.3 Ų
Hydrogen bond donors
2
Hydrogen bond acceptors
7
Rotatable bonds
8
Heavy atoms
18
Formal charge
0
Complexity
220

Experimental & physicochemical properties

Pesticides · 5 items

Herbicides

Active substance -> EU Pesticides database: Not approved

Pesticides -> Herbicides, Triazine

Pesticide

Pesticide (Methoprotryne) -> USDA PDB

LogP2.96
Density1.186 g/cu cm @ 20 °C
Color/Form · 2 items

CRYSTALLINE SOLID

Colorless powder

Solubility · 5 items

320 mg/l water @ 20 °C

450 g/l acetone @ 20 °C

650 g/l dichloromethane @ 20 °C

5 g/l hexane @ 20 °C

For more Solubility (Complete) data for METHOPROTRYNE (7 total), please visit the HSDB record page.

Human DrugsPharmaceuticals
DecompositionWhen heated to decomp it emits very toxic fumes of /nitrogen oxides and sulfur oxides/.
Melting Point68-70 °C
Vapor Pressure

Safety & regulation

Safety information is for reference only and does not replace the supplier’s Safety Data Sheet (SDS), applicable regulations, or professional assessment.

GHS classification

GHS Classification · 5 items

This chemical does not meet GHS hazard criteria for 7.3% (3 of 41) of reports.

Danger

H310 (92.7%): Fatal in contact with skin [Danger Acute toxicity, dermal]

P262, P264, P270, P280, P302+P352, P316, P321, P361+P364, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 41 reports by companies from 2 notifications to the ECHA C&L Inventory.

Hazard information

Regulatory Information2002/2076
Hazards Summary · 2 items

For the triazine herbicides, systemic toxicity unlikely unless large amounts are ingested; May cause irritation; [EPA Pesticides, p. 121] May cause irritation; [MSDSonline]

The major hazards encountered in the use and handling of methoprotryne stem from its toxicologic properties. Toxic by inhalation and ingestion, exposure to this white, crystalline substance may occur from its manufacture, formulation, and use as a herbicide. Effects from exposure may include nausea, vomiting, and diarrhea. In activities and situations where over exposure may occur, wear a self-contained breathing apparatus and personal protective clothing. If contact should occur, immediately flush affected skin or eyes with running water for at least 15 minutes. Remove contaminated clothing and shoes at the site. While methoprotryne does not ignite easily, it may burn with the production of irritating and poisonous gases. For fires involving this substance, extinguish with dry chemical, CO2, Halon, water spray, fog, or standard foam. Methoprotryne may be shipped via air, rail, road, and water, in containers bearing the label "Poison". Small dry spills of methoprotryne may be placed into a clean, dry, covered container for later disposal (liquid solutions are first absorbed in sand or other noncombustible absorbent). Large liquid spills should be diked far ahead to prevent methoprotryne from entering water sources and sewers. Before implementing land disposal of methoprotryne, consult with regulatory agencies for guidance.

Chemistry & industry

Pharmacology

Mechanism of Action · 3 items

Inhibits photosynthesis.

... Their chief mode of action appears to involve carbohydrate metabolism. The chlorinated s-triazines inhibit starch accumulation by blocking the prodn of sugars. Similar behavior has been shown for the methoxy & methylthio-s-triazines. It has been reported that the s-triazines affect the tricarboxylic acid cycle with activation of phospho-phenyl pyruvate-carboxylase causing the disappearance of sucrose & glyceric acid with the formation of aspartic & malic acids. /s-Triazines/

SINCE CHLOROSIS IS THE FIRST SIGN OF THE EFFECT OF TRIAZINES ON PLANTS, INTERFERENCE WITH CARBON DIOXIDE ASSIMILATION & SUGAR FORMATION CAN BE EXPECTED. STUDIES SHOWING THAT HILL REACTION IS INHIBITED CONFIRMED THIS. /TRIAZINES/

Metabolism/Metabolites · 2 items

All of ... /methoxy & methylthio-substituted triazine/ herbicides were rapidly absorbed and metabolized when ingested; amine dealkylation and side chain oxidation are the predominant detoxification reactions. The mercapto derivatives of triazine may also undergo sulfoxidation followed by reaction with hepatic glutathione to yield mercapturic acid derivatives. /Prometon/

In ... plants, cleavage of the thiomethyl group and replacement with hydroxyl /occurs presumably/ after oxidation of the sulfur to sulfoxide and sulfone. Demethylation of the amino groups at C4 and C6, cleavage of the amine moieties and their replacement by hydroxyl, presumably followed by ring opening.

Absorption, Distribution and ExcretionAfter oral administration, 85-95% elimination occurs within 24 hr, in the metabolized form and mainly in the urine. /In plants it is/ absorbed via the leaves and roots.

Uses & manufacturing

Uses · 4 items

Used as post-emergence herbicide for control of weeds in winter-sown cereals; [HSDB]

Farming (Pesticides) [Category: Industry]

Methoprotryne is herbicide used post emergence for the control of weed grasses in winter-sown cereals at 1.5-2.0 kg active ingredient/hectare

Suppliers

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Related reactions

1 records
New reaction record
HRID 317351 reaction equation
HRID 317351As productTraining data from https://doi.org/10.1039/C8SC04228D (8/10)

Compound notes

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On this pageBasic informationOverviewNames & identifiersPropertiesSafety & regulationChemistry & industryRelated reactionsCompound notes
· 2 items

0.00000028 [mmHg]

2.85X10-7 mm Hg @ 20 °C

Physical DescriptionColorless solid; [HSDB]
Stability/Shelf LifeSTABLE UNDER NORMAL CONDITIONS
Dissociation ConstantsPK: 4.0 @ 21 °C

Physicochemical properties

Melting point
68 · 68-70℃ (ligroine )
Boiling point
444.1 · 444.1±47.0 °C(Predicted)
Density
1.186 g/cm3 · 1.186 g/cm3 (20℃)
refractive index
1.543 · 1.5430 (estimate)
storage temp.
0 · 0-6°C
pka
3 · 3+-.0.41(Predicted)
Water Solubility
0.32 g/L · 0.32g/L(20 ºC)
BRN
616626 · 616626
Henry's Law Constant
3.1 · 3.1×104 mol/(m3Pa) at 25℃, HSDB (2015)
FDA UNII
31 X54QGQ17 · 31X54QGQ17
EPA Substance Registry System
Methoprotryne (841-06-5)
Symbol(GHS)
6 · GHS06
Signal word
Danger
Hazard statements
310 · H310
Precautionary statements
262 · P262-P264-P270-P280-P302+P350-P310-P322-P361-P363-P405-P501
Hazard Codes
Xn
Risk Statements
22 · 22-36/38
Safety Statements
26 · 26-28-24/25-22
RIDADR
2020 · UN 2020 6.1/PG 3
WGK Germany
3 · 3
RTECS
8800000 · SK8800000
Hazardous Substances Data
841 · 841-06-5(Hazardous Substances Data)
Hazard Classes and CategoriesAcute Tox. 2 (92.7%)
Shipment Methods and Regulations · 3 items

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./

The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.

The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

Shipping Name/ Number DOT/UN/NA/IMOUN 2763; Triazine pesticide, solid, not otherwise specified

Safety & protection

Fire Fighting Procedures · 2 items

Extinguish fire using agent suitable for type of surrounding fire. ... Use water in flooding quantities as fog. Use "alcohol foam" ... Wear positive pressure self-contained breathing apparatus when fighting fires involving this material. /Triazine pesticide (compounds and preparations), solid (insecticides, agricultural, not elsewhere classified, other than liquid)/

Avoid breathing dusts & fumes from burning material. Keep upwind. /Triazine pesticide, solid, not otherwise specified, (compounds and preparations), (agricultural insecticides, not elsewhere classified, other than liquid)/

Disposal Methods · 4 items

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

Noncombustible containers should be crushed & buried under more than 40 cm of soil. /Herbicides/

Group I Containers: Combustible containers from organic or metallo-organic pesticides (except organic mercury, lead, cadmium, or arsenic compounds) should be disposed of in pesticide incinerators or in specified landfill sites. /Organic or metallo-organic pesticides/

Group II Containers: Noncombustible containers from organic or metallo-organic pesticides (except organic mercury, lead, cadmium, or arsenic compounds) must first be triple rinsed. Containers that are in good condition may be returned to the manufacturer or formulator of the pesticide product, or to a drum reconditioner for reuse with the same type of pesticide product, if such reuse is legal under Department of Transportation regulations (eg 49 CFR 173.28). Containers that are not to be reused should be punctured ... and transported to a scrap metal facility for recycling, disposal or burial in a designated landfill. /Organic or metallo-organic pesticides/

Preventive Measures · 3 items

Avoid contact with eyes, contact with skin, inhalation of dust, & contamination of food & feed.

If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. /Triazine pesticide, solid, not otherwise specified (compounds and preparations), (agricultural insecticides, not elsewhere classified, other than liquid)/ Not elsewhere classified.

Avoid bodily contact with the material. ... Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. /Triazine pesticide, solid, not otherwise specified (compounds and preparations), (agricultural insecticides, not elsewhere classified, other than liquid)/

Personal Protective Equipment (PPE)The use of personal protective equipment such as glasses, synthetic gloves & /NIOSH approved breathing apparatus/ ... is important. /Herbicides/

Toxicology

Ecotoxicity Values · 4 items

LC50 BLUEGILL 15.5 MG/L/96 HR @ 18 °C (95% CONFIDENCE LIMIT 13.9-17.2 MG/L), WT 0.9 G STATIC BIOASSAY

LC50 Bluegill 9.8 mg/l/96 hr /Conditions for assay not given/

LC50 Rainbow trout 8 mg/l/96 hr /Conditions for assay not given/

LC50 Crucian carp 31 mg/l/96 hr /Conditions for assay not given/

Environmental Fate · 5 items

TERRESTRIAL FATE: ... TRIAZINES ... ARE NOT READILY DEGRADED BY SOIL MICROORGANISMS. THUS, THEIR RATE OF DECAY IS RELATIVELY SLOW, & AS THESE MATERIALS ALSO DO NOT READILY LEACH FROM THE SOIL, THEY MAY PERSIST FOR QUITE EXTENDED PERIODS OF TIME. /TRIAZINES/

TERRESTRIAL FATE: If methoprotryne is released to soil, it will be expected to exhibit moderate mobility based upon(1) a Koc estimated(5,SRC) using water solubility(4) and, therefore, it may leach to groundwater. It may be susceptible to slow hydrolysis in soil(2,3). Volatilization from near-surface soil is not expected to be an important removal mechanism(SRC). It is unknown whether methoprotryne will biodegrade in soil(SRC).

AQUATIC FATE: If released to water, methoprotryne will not be expected to bioconcentrate in aquatic organisms, adsorb to sediment and suspended particulate matter, or to volatilize. Methoprotryne may be susceptible to slow hydrolysis in water(2) and photooxidation by photochemically produced hydroxyl radicals(1) in water, based upon data for s-triazine herbicides with similar structures to methoprotryne such as prometryn(1,2). It is unknown whether methoprotryne will biodegrade in natural waters(SRC).

ATMOSPHERIC FATE: If methoprotryne is released to the atmosphere, it may be subject to gas-phase reaction with hydroxyl radicals with a half-life of about 2.4 hr estimated for this process(1).

TERRESTRIAL FATE: THE LONG SOIL PERSISTENCE OF THESE CMPD DOES ... CREATE THE PROBLEM OF SOIL CARRY OVER, WHICH CAN DAMAGE SUCCEEDING CASH CROPS. THEREFORE EXTREME CAUTION MUST BE TAKEN IN THEIR APPLICATION ON CROPLAND TO AVOID SUCH INJURY TO FOLLOWING CROPS. /TRIAZINES/

Acute Toxicity LinkChemical: METHOPROTRYNE
Medical Surveillance · 1 item

Preliminary medical exam to detect chronic diseases of CNS, liver, heart, kidneys, lungs & skin, as well as endocrinological or immunological disturbances, should ... /protect/ susceptible individuals. ... Periodical medical exam of internal organs, skin & eyes is important to avoid chronic occupational intoxications. It should include lab tests & patch tests if necessary. /Herbicides/

Soil Adsorption/Mobility · 2 items

ADSORPTION OF TRIAZINES THROUGH EXCHANGE PROCESS TO ORGANIC MATTER & CLAY MINERALS IS DEPENDENT ON PH OF SOLN & ACIDITY OF ADSORBENT SURFACE. HYDROGEN BONDING & HYDROPHOBIC BONDING ARE OTHER MECHANISMS BY WHICH SOIL ORGANIC MATTER ADSORBS TRIAZINE HERBICIDES, ESP AT HIGHER PH LEVELS. ... TRANSPORT FROM SOIL TO WATER OCCURS IN SOLUTION & IN SEDIMENTS. /TRIAZINE HERBICIDES/

Based upon a water solubility of 320 ppm at 20 degC(3), a Koc of 180 has been estimated(4). Based upon this estimated Koc, methoprotryne will be expected to exhibit medium mobility in soil(5). Evidence has been reported which indicates that the basicity of s-triazine herbicides, such as methoprotryne, is not the main factor governing adsorption to soil humic acids(1). It has been shown that the ability of s-triazines herbicides to act as electron donors to electron acceptor quinone-like units of humic acids also plays an important role in the adsorption(2).

Human Toxicity ExcerptsNAUSEA, VOMITING, & DIARRHEA CAN BE EXPECTED TO RESULT FROM INGESTION OF LARGE QUANTITIES. /UREA,- URACIL- & TRIAZINE-BASED HERBICIDES/
Artificial Pollution SourcesMethoprotryne is a herbicide that is not used in the U.S., but is used in Europe on various crops(1).
Environmental BiodegradationMOST OF THE TRIAZINES ARE VERY STABLE IN SOIL & DISSIPATE SLOWLY THROUGH ... DEGRADATION OF MOLECULAR SIDE CHAINS BY SOIL MICROORGANISMS. /TRIAZINES/
Environmental BioconcentrationBased upon a water solubility of 320 ppm at 20 °C(1), a BCF of 24 has been estimated(2). Based upon this estimated BCF, methoprotryne will not be expected to bioconcentrate in aquatic organisms(SRC).
Volatilization from Water/Soil · 2 items

Vapor transport losses of triazines are dependent on vapor pressure & pH of evaporating surface, since ionized cmpd are less volatile. /Triazine herbicides/

Based upon a water solubility of 320 mg/l at 20 °C(1) and a vapor pressure of 2.85X10-7 mm Hg at 20 °C(1), the Henry's Law constant for methoprotryne of 3.18X10-10 atm-cu m/mole can be calculated(2,SRC). This value of Henry's Law constant indicates volatilization of methoprotryne will not be environmentally important(2).

Non-Human Toxicity Excerpts · 2 items

In 90 day feeding trials, no effect level was: for rats 3750 mg active ingredient/kg diet (about 250 mg active ingredient/kg daily); for dogs 11,250 mg/kg diet (about 375 mg/kg daily).

Maize seeds (Zea mays) were germinated in Linhardt dishes to which the following herbicides: 2,4-D, dicamba, Icedin, Igran and Gesaran were added. The concentration of herbicides was similar to those used against various weeds. The tips of primary roots of 4-, 5- ad 7-day-old seedlings were cut and nuclear DNA was Feulgen stained. The relative amount of nuclear DNA was measured. The research showed that the 5 herbicides can produce significant variations in the amount of nuclear DNA depending on the nature of herbicide used. These variations may be related to the changes in the cell cycle of root meristems under the influence of herbicides.

Environmental Abiotic Degradation · 2 items

In soil ... cleavage of the thiomethyl group and replacement with hydroxyl /occurs/, presumably after oxidation of the sulfur to sulfoxide and sulfone. Demethylation of the amino groups at C4 and C6, cleavage of the amine moieties and their replacement by hydroxyl, presumably followed by ring opening.

The rate constant for the vapor-phase reaction of prometryn with photochemically produced hydroxyl radicals has been estimated to be 161.9 cu cm/molecule-sec at 25 °C which corresponds to an atmospheric half-life of about 2.4 hr at an atmospheric concn of 5X10+5 hydroxyl radicals per cu cm(1). Methoprotryne may be susceptible to slow hydrolysis in water or soil(3), and photooxidation by photochemically produced hydroxyl radicals(4), based upon data for s-triazine herbicides with similar structures with methoprotryne such as prometryn(3,4). The rate of hydrolysis may be increased by various catalysts based upon the observed increase in rate of hydrolysis rates for the chemically similar herbicide atrazine in water solutions upon addition of sterilized soil(5) and humic(6) and fulvic acids(2).

Safety data

wgk
3
rtecs
SK8800000
ridadr
UN 2020 6.1/PG 3
risk_code
22-36/38
Signal word
Danger
Symbol(GHS)
GHS06
hazard_code
Xn
safety_code
26-28-24/25-22
Hazard statements
H310
Precautionary statements
P262-P264-P270-P280-P302+P350-P310-P322-P361-P363-P405-P501
Hazardous Substances Data
841-06-5(Hazardous Substances Data)

METHOPROTRYNE IS HERBICIDE USED IN COMBINATION WITH SIMAZINE POST EMERGENCE FOR THE CONTROL OF WEED GRASSES IN WINTER SOWN CEREALS AT 2.5-4.0 KG GESARAN 2079/HA.

Methods of Manufacturing · 2 items

React 2-chlor-4-isopropylamino-6-(3-methoxypropylamino)-1,3,5-triazine with methyl mercaptan in the presence of an equivalent of alkali or react 2-isopropylamino-4-mercapto-6-(3-methoxypropylamino)-1,3,5-triazine with a methylating agent in the presence of alkali.

46 parts of cyanuric chloride are dissolved in 300 parts of chlorobenzene. Then, at -15 °C to -5 °C, first 14 parts of isopropylamine dissolved in 22 parts of water and then 10 parts of sodium hydroxide dissolved in 40 parts of water are added dropwise. The whole is stirred until the reaction mixture has a neutral reaction, any traces of precipitated 2-chloro-4,6-bis-isopropylamino-s-triazine are removed and then, at room temp, 23 parts of gamma-methyoxy-propylamine in 46 parts of water and afterwards 10 parts of sodium hydroxide in 40 parts of water are added. The whole is stirred at 40 °C to 50 °C until the reaction mixture has a neutral reaction. The chlorobenzene is eliminated by steam distillation whereupon the difficultly soluble 2-chloro-4-isopropylamino-6-(gamma-methosy-propylamino)-s-triazine can be filtered off under suction and recrystallized. 26 parts of 2-chloro-4-isopropylamino-6-(gamma-methoxy-propylamino)-s-triazine are mixed with 100 ml of concentrated aq potassium hydrosulfide soln and stirred until a practically clear soln is obtained. The mixture is then neutralized with acetic acid whereby precipitation of the resulting 2-mercapto-4-isopropylamino-6-(gamma-methoxy-propylamino)-s-triazine occurs. The crystalline product is separated by filtration and washed with cold water. 2.3 parts of sodium are dissolved in 200 parts of anhydrous methanol and then 25.7 parts of 2-mercapto-4-isopropylamino-6-(gamma-methoxy-propylamino)-s-triazine are added. 20 parts of methyl iodide are then added dropwise and the reaction mixture is stirred at 40 °C to 50 °C until it has a neutral reaction. The solvent is then distilled off, the residue is taken up in benzene, the soln is washed with 2N caustic soda lye and with water, the benzene is eliminated and the 2-methylmercapto-4-isopropylamino-6-(gamma-methoxy-propylamino)-s-triazine is recrystallized from petroleum ether.

Formulations/Preparations · 2 items

GESARAN 2079--WETTABLE POWDER (225 G AI + SIMAZINE (50 G/KG).

Gesaran 25, WP (250 g ai/kg).

Use Classification · 2 items

Pharmaceuticals

HERBICIDES

General Manufacturing Information · 5 items

The WHO Recommended Classification of Pesticides by Hazard identifies Methoprotryne (technical grade) as an active ingredient believed to be obsolete or discontinued for use as a pesticide.

INTRODUCED IN 1965 BY GEIGY. SWISS PATENT 394,704; BRITISH PATENT 927,348; US PATENT 3,326,914.

Good compatibility with other wettable-powder herbicides.

Discontinued 1984 by Ciba-Geigy Ltd.

CROP ROTATION RESTRICTIONS OR PRECAUTIONS USUALLY ARE NOT REQUIRED BECAUSE OF THE SHORTER RESIDUAL LIFE & ALSO BECAUSE OF THE MUCH GREATER SAFETY MARGIN WHICH MANY SENSITIVE PLANTS HAVE TO METHYLTHIOTRIAZINES COMPARED TO CHLORO OR METHOXYTRIAZINES.

Additional notes

DefinitionChEBI: Methoprotryne is a member of 1,3,5-triazines.