135158-54-2

Basic information

• Product Name: ACIBENZOLAR-S-METHYL
• Synonyms: ACIBENZOLAR-S-METHYL STANDARD;acibenzolar-S-methyl benzo[1,2,3]thiadiazole-7-carbothioic acid S-methyl ester;Unix Bion;S-Methyl-1,2,3-benzothiadiazole-7-carbothioate;1,2,3-Benzothiadiazole-7-carbothiolic acid, S-methyl ester;Acibenzolar-S-methyl [iso];Actigard;Bendicar
• CAS NO: 135158-54-2
• Molecular Formula: C₈H₆N₂OS₂
• Molecular Weight: 226.34
• EINECS: 420-050-0
• Mol File: 135158-54-2.mol
• Article Data: 10

Chemical Properties

• Melting Point: 134-135℃
• Boiling Point: 267°C (rough estimate)
• Flash Point: 154.5 °C
• Appearance: /
• Density: 1.450
• Vapor Pressure: 4.4 x 10-4 Pa (25 °C)
• Refractive Index: 1.5690 (estimate)
• Storage Temp.: 0-6°C
• Solubility: Chloroform (Slightly), Methanol (Very Slightly)
• PKA: -3.90±0.50(Predicted)
• Water Solubility: 7.7 mg l-1 (25 °C)
• CAS DataBase Reference: ACIBENZOLAR-S-METHYL(CAS DataBase Reference)
• NIST Chemistry Reference: ACIBENZOLAR-S-METHYL(135158-54-2)
• EPA Substance Registry System: ACIBENZOLAR-S-METHYL(135158-54-2)

Safety Data

• Hazard Codes: Xi,N
• Statements: 36/37/38-43-50/53
• Safety Statements: 24/25-37-46-59-60-61
• RIDADR: UN 3077 9 / PGIII
• WGK Germany: 3
• Hazardous Substances Data: 135158-54-2(Hazardous Substances Data)

Usage

Description

Acibenzolar-S-methyl (Novartis) has attracted special attention because it acts against a very wide range of plant diseases but does not directly affect the growth or metabolism of the causal organisms. It is known to act by stimulating systemic activated resistance (SAR) in the treated plant. The well-established compound probenazole, which for some years has been the leading treatment for rice blast in Japan, is thought to act in a similar way. Pathogen resistance to probenazole has not developed, and such stability of performance may well be a general feature of SAR-inducing compounds.

Uses

Different sources of media describe the Uses of 135158-54-2 differently. You can refer to the following data:
1. Acibenzolar-S-methyl is a S-methyl thioester derivative of acibenzolar. Acibenzolar-S-Methyl acts as a fungicide in pesticidal formulations.
2. Plant disease resistance activator.
3. CGA245704 is used to control a range of diseases in wheat and it is being developed for use on rice, bananas, vegetables and tobacco.

Definition

ChEBI: A benzothiadiazole that is the S-methyl thioester derivative of acibenzolar. It is used as a fungicide and plant activator on a variety of crops, including cotton, chili peppers, lettuce, onions, spinach, tobacco, and tomatoes.

Metabolic pathway

Very little information on the fate of CGA245704 has been published. It is readily degraded in soil and plants and it is rapidly eliminated from animals. A partial metabolic pathway is shown in Scheme 1.

Degradation

CGA245704 is a stable substance and it is very stable in solution other than at high pH values. Its DT50 values (20 °C) at pH 5, 7 and 9 were 3.8 years, 23 weeks and 19 hours, respectively (PM). Hydrolysis of the thioester link and ring opening would be anticipated.

InChI:InChI=1/C8H6N2OS2/c1-12-8(11)5-3-2-4-6-7(5)13-10-9-6/h2-4H,1H3

Synthetic route

methylthiol (74-93-1) + benzothiadiazole-7-carboxylic acid chloride (124371-49-9) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Esterification;
With triethylamine In toluene
With sodium hydroxide

benzothiadiazole-7-carboxylic acid chloride (124371-49-9) + sodium thiomethoxide (5188-07-8) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
In dichloromethane at 20℃; for 5h;	0.12 g

benzo[d][1,2,3 ]thiadiazol-7-carboxylic acid (35272-27-6) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: SOCl2 / 8 h / 90 °C 2: 0.12 g / CH2Cl2 / 5 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: SOCl2 View Scheme
Multi-step reaction with 2 steps 1: thionyl chloride 2: sodium hydroxide View Scheme

Benzo[1,2,3]thiadiazole-7-nitrile (23615-90-9) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 3 steps 1: 88 percent / KOH / butan-1-ol 2: SOCl2 View Scheme

2-chloro-3-nitrobenzoic acid methyl ester (53553-14-3) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 6 steps 1: 99 percent 2: H2 / Raney nickel / tetrahydrofuran 3: 86 percent / NaNO2; H(+) 4: 98 percent / NaOH; H2O 5: SOCl2 View Scheme

1,2-Dichloro-3-nitrobenzene (3209-22-1) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 7 steps 1: K2CO3 / N,N-dimethyl-acetamide 2: Na2S / propan-2-ol; H2O 3: 76 percent / Ni(PPh3)4 4: 97 percent / isoamyl nitrite; HCl / butan-1-ol 5: 88 percent / KOH / butan-1-ol 6: SOCl2 View Scheme

2-chloro-3,5-dinitrobenzoic acid (2497-91-8) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 7 steps 1.1: K2CO3 / dimethylformamide 2.1: K2CO3 3.1: H2 / Raney nickel / tetrahydrofuran 4.1: NaNO2; H(+) 4.2: 65 percent / H3PO2 5.1: 98 percent / NaOH; H2O 6.1: SOCl2 View Scheme

benzo[1,2,3]thiadiazole-7-carboxylic acid methtyl ester (23621-08-1) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 3 steps 1: 98 percent / NaOH; H2O 2: SOCl2 View Scheme

2-chloro-3-nitrobezoic acid (3970-35-2) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 7 steps 1: 99 percent / H2SO4 2: 99 percent 3: H2 / Raney nickel / tetrahydrofuran 4: 86 percent / NaNO2; H(+) 5: 98 percent / NaOH; H2O 6: SOCl2 View Scheme

2-amino-6-chlorophenyl-isopropylsulfane (179104-32-6) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 5 steps 1: 76 percent / Ni(PPh3)4 2: 97 percent / isoamyl nitrite; HCl / butan-1-ol 3: 88 percent / KOH / butan-1-ol 4: SOCl2 View Scheme

2-chloro-6-nitrophenyl isopropyl sulfide (178551-27-4) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 6 steps 1: Na2S / propan-2-ol; H2O 2: 76 percent / Ni(PPh3)4 3: 97 percent / isoamyl nitrite; HCl / butan-1-ol 4: 88 percent / KOH / butan-1-ol 5: SOCl2 View Scheme

3-amino-2-isopropylthiobenzonitrile (179104-33-7) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 4 steps 1: 97 percent / isoamyl nitrite; HCl / butan-1-ol 2: 88 percent / KOH / butan-1-ol 3: SOCl2 View Scheme

Methyl 3-amino-2-benzylthiobenzoate (124371-58-0) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 4 steps 1: 86 percent / NaNO2; H(+) 2: 98 percent / NaOH; H2O 3: SOCl2 View Scheme

2-benzylthio-3-nitrobenzoic acid methyl ester (124371-57-9) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 5 steps 1: H2 / Raney nickel / tetrahydrofuran 2: 86 percent / NaNO2; H(+) 3: 98 percent / NaOH; H2O 4: SOCl2 View Scheme

2-benzylthio-3,5-diamino-benzoic acid methyl ester (124371-52-4) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: NaNO2; H(+) 1.2: 65 percent / H3PO2 2.1: 98 percent / NaOH; H2O 3.1: SOCl2 View Scheme

2-(phenylmethylsulfanyl)-3,5-dinitrobenzenecarboxylic acid (475096-00-5) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 6 steps 1.1: K2CO3 2.1: H2 / Raney nickel / tetrahydrofuran 3.1: NaNO2; H(+) 3.2: 65 percent / H3PO2 4.1: 98 percent / NaOH; H2O 5.1: SOCl2 View Scheme

methyl 2-(phenylmethylsulfanyl)-3,5-dinitrobenzenecarboxylate (124371-61-5) → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: H2 / Raney nickel / tetrahydrofuran 2.1: NaNO2; H(+) 2.2: 65 percent / H3PO2 3.1: 98 percent / NaOH; H2O 4.1: SOCl2 View Scheme

Lawessons reagent (19172-47-5) + benzo-1,2,3-thiadiazole-7-thiomethyl ester → S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene

S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2) → potassium benzo[1,2,3]thiadiazole-7-carboxylate (124370-60-1)

Conditions	Yield
With potassium hydroxide In water; toluene at 110℃; for 12h;	90%

dimethyl sulfate (77-78-1) + S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2) → C9H9N2OS2(1+)*CH3O4S(1-) (1613377-49-3)

Conditions	Yield
at 80 - 110℃;	82%

methyl trifluoromethanesulfonate (333-27-7) + S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2) → C9H9N2OS2(1+)*CF3O3S(1-) (1613377-52-8)

Conditions	Yield
In N,N-dimethyl-formamide at 120 - 155℃; for 0.333333h; Inert atmosphere;	65%

S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2) → choline benzothiadiazole-7-carboxylate (1585196-00-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium hydroxide / water; toluene / 12 h / 110 °C 2: methanol / 12 h View Scheme

S-methyl-benzo[1,2,3]thiadiazole-7-carbothioate (135158-54-2) → C9H9N2OS2(1+)*C20H37O7S(1-) (1613377-51-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 - 110 °C 2: water; dichloromethane View Scheme

Upstream product

• 23615-90-9 Benzo[1,2,3]thiadiazole-7-nitrile 
• 19172-47-5 Lawessons reagent 
• 124371-61-5 methyl 2-(phenylmethylsulfanyl)-3,5-dinitrobenzenecarboxylate 
• 475096-00-5 2-(phenylmethylsulfanyl)-3,5-dinitrobenzenecarboxylic acid 
• 124371-52-4 2-benzylthio-3,5-diamino-benzoic acid methyl ester 
• 124371-57-9 2-benzylthio-3-nitrobenzoic acid methyl ester 
• 124371-58-0 Methyl 3-amino-2-benzylthiobenzoate 
• 179104-33-7 3-amino-2-isopropylthiobenzonitrile 
• 178551-27-4 2-chloro-6-nitrophenyl isopropyl sulfide 
• 179104-32-6 2-amino-6-chlorophenyl-isopropylsulfane 
• 3970-35-2 2-chloro-3-nitrobezoic acid 
• 23621-08-1 benzo[1,2,3]thiadiazole-7-carboxylic acid methtyl ester 
• 2497-91-8 2-chloro-3,5-dinitrobenzoic acid 
• 3209-22-1 1,2-Dichloro-3-nitrobenzene 

Related news

ACIBENZOLAR-S-METHYL (cas 135158-54-2) is associated with yield reduction when used for managing bacterial wilt (Erwinia tracheiphila) in cantaloupe07/15/2019

Bacterial wilt, caused by Erwinia tracheiphila (Smith), can result in serious yield loss of cantaloupe in the Midwest United States. Although neonicotinoid insecticides are an effective means of managing the cucumber beetles that vector E. tracheiphila, this management regime may cause toxicity ...detailed

Integration of ACIBENZOLAR-S-METHYL (cas 135158-54-2) with antibiotics for protection of pear and apple from fire blight caused by Erwinia amylovora07/13/2019

Orchard experiments on integration of acibenzolar-S-methyl (ASM) with antibiotics for protection of pear and apple from fire blight were conducted in the west coast region of the United States over a period of 5 years. In 11 pathogen-inoculated trials, a single treatment of streptomycin or oxyte...detailed

ACIBENZOLAR-S-METHYL (cas 135158-54-2) treatment enhances antioxidant ability and phenylpropanoid pathway of blueberries during low temperature storage07/11/2019

Blueberry fruits were immersed in 100 mg/L acibenzolar-S-methyl (ASM) for 10 min and then stored at 4 °C with 40–50% relative humidity (RH) to investigate the changes of anti-oxidative enzyme activity, antioxidants and secondary metabolites in reactive oxygen species metabolism and phenylpropa...detailed

Relevant articles and documents

Novel benzo-1,2,3-thiadiazole-7-carboxylate derivatives as plant activators and the development of their agricultural applications

Plant activators are a novel kind of agrochemicals that could induce resistance in many plants against a broad spectrum of diseases. To date, only few plant activators have been commercialized. In order to develop novel plant activators, a series of benzo-1,2,3-thiadiazole-7-carboxylate derivatives were synthesized, and the structures were characterized by 1H NMR, IR, elemental analyses, and HRMS or MS. Their potential systemic acquired resistance as plant activators was evaluated as well. Most of them showed good activity, especially, fluoro-containing compounds 3d and 3e, which displayed excellent SAR-inducing activity against cucumber Erysiphe cichoracearum and Colletotrichum lagenarium in assay screening. Field test results illustrated that compounds 3d and 3e were more potent than the commercial plant activator, S-methyl benzo[1,2,3]thiadiazole-7-carbothioate (BTH) toward these pathogens. Further, the preparation of compound 3d is more facile than BTH with lower cost, which will be helpful for further applications in agricultural plant protection.

Synergistic Active Compound Combinations Comprising Phenyltriazoles

The present invention relates to novel active compound combinations comprising, firstly, at least one known compound of the formula (I) in which R1 and R2 have the meanings given in the description. and at least one further known active compound from groups (2) to (27) listed in the description, which combinations are highly suitable for controlling animal pests such as insects and unwanted acarids and also phytopathogenic fungi.

Novel, unnatural benzo-1,2,3-thiadiazole-7-carboxylate elicitors of taxoid biosynthesis

In order to establish the chemical biological technology for production of valuable secondary metabolites, a novel family of unnatural elicitors derived from the plant activator benzo-1,2,3-thiadiazole-7-carboxylic acid were designed and synthesized. New synthetic elicitors that showed powerful eliciting activities upon taxoid biosynthesis by Taxus chinensis suspension cells were obtained. For example, benzo-1,2,3-thiadiazole-7-carboxylic acid 2-(2-hydroxybenzoxyl)ethyl ester was more effective and resulted in nearly 40% increase in taxuyunnanine C content and production in comparison with methyl jasmonate, which was previously reported as the most powerful chemical elicitor for taxoid biosynthesis. The novel class of elicitors was found to induce plant defense responses, including promotion of H2O2 levels originating from oxidative burst and activation of phenylalanine ammonia lyase. Interestingly the plant defense responses induced corresponded well to the superior stimulating activity in T. chinensis cell cultures. The work indicates that the newly synthesized benzothiadiazoles can act as a new family of elicitors for taxoid biosynthesis in plant cells.