946578-00-3

Basic information

• Product Name: Sulfoxaflor
• Synonyms: Sulfoxaflor;Sulfoxaflor solution;Sulfoxaflor solution,1000ppm;Cyanamide,N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-l4-sulfanylidene]-;[methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda~4~-sulfanylidene]cyanamide
• CAS NO: 946578-00-3
• Molecular Formula: C₁₀H₁₀F₃N₃OS
• Molecular Weight: 277.2661096
• Mol File: 946578-00-3.mol
• Article Data: 13

Chemical Properties

• Boiling Point: 363.8°C at 760 mmHg
• Flash Point: 173.8°C
• Appearance: /
• Density: 1.34g/cm³
• Vapor Pressure: 1.76E-05mmHg at 25°C
• Refractive Index: 1.519
• CAS DataBase Reference: Sulfoxaflor(CAS DataBase Reference)
• NIST Chemistry Reference: Sulfoxaflor(946578-00-3)
• EPA Substance Registry System: Sulfoxaflor(946578-00-3)

Safety Data

• Hazardous Substances Data: 946578-00-3(Hazardous Substances Data)

Usage

Description

Sulfoxaflor is an insecticide that is used to control aphids in field crops and favourably compares with imidacloprid in efficiacy. It is relatively volatile, whilst potentially mobile in soils it has a low potential for leaching due to its rapid degradation rate. It has a high potential to bioaccumulate, generally moderately toxic to birds and mammals and has a low toxicity to most aquatic species. It is toxic to honeybees and earthworms

History

lt was first registered by EPA for emergency use on cotton to controltarnished plant bug, Lygus lineolaris in the state of Mississippi,Arkansas,Louisiana, and Tennessee in June 2012. lts use was extended to other cropsin 2013.Sulfoxaflor is registered for use in Minnesota in June 2013.

benefits

Sulfoxaflor may be registered for use on the following major crops inMinnesota: soybeans, potatoes, wheat. According to UMN extension,sulfoxaflor worked well against aphids in soybean and potatoes. It will beof use against piercing/sucking insects such as aphids, leafhoppers, plantbugs, etc. lt is not labeled for residential uses.

Toxicology

EPA's screening models generote high-end, conservative exposure estimates for active ingredients and toxicologically significant degrodates. Model inputs include annual usage ot moximum use rates, maximum treated acres, maximum food residues, peak runoffand drift scenarios, etc. Ssome proposed products, application rates and use scenarios are not relevant to Minnesota.EPA's estimates,therefore, may not reflect future use and impacts in Minnesota.

Environmental Fate

The fate of sulfoxoflor in the environment is highly dependent on whether it is in a soil ystem, groundwater system, or surface watersystem. Environmental fate characteristics are listed for parent and all relevant degradates where appropriate.

InChI:InChI=1/C10H10F3N3OS/c1-7(18(2,17)16-6-14)8-3-4-9(15-5-8)10(11,12)13/h3-5,7H,1-2H3

Synthetic route

C10H10F3N3S → sulfoxaflor (946578-00-3)

Conditions	Yield
With sodium permanganate In dichloromethane; water at 3 - 20℃; for 0.5 - 3h; Product distribution / selectivity;	93%
With sodium permanganate In water; acetonitrile at 5 - 24℃; for 0.833333h; Product distribution / selectivity;	83%

(1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)-(methyl)-λ4-sulfanylidenecyanamide (1049684-75-4, 1049684-74-3, 1046119-63-4) → sulfoxaflor (946578-00-3)

Conditions	Yield
With sodium disulfite; sodium permanganate In dichloromethane; water at 3 - 30℃; for 3.55 - 6.5h; Product distribution / selectivity; Cooling with ice;	93%
With sodium disulfite; sodium permanganate In water; acetonitrile at 5 - 24℃; for 1.16667h; Product distribution / selectivity;	52%
With sodium permanganate In dichloromethane; water at 13 - 20℃; for 1.91667h; Solvent; Reagent/catalyst;	259 g

5-[1-(methylsulfonimidoyl)ethyl]-2-(trifluoromethyl)pyridine (946578-43-4) + bromocyane (506-68-3) → sulfoxaflor (946578-00-3)

Conditions	Yield
With dmap In dichloromethane at 20℃; for 16h;	70%

(1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)(methyl)-λ4-sulfanylidenecyanamide (1046119-63-4, 1049684-75-4, 1049684-74-3) → sulfoxaflor (946578-00-3)

Conditions	Yield
With sodium permanganate; acetic acid In water; acetonitrile at 15 - 20℃; for 1.58333 - 1.75h; Product distribution / selectivity;	65%

[(6-trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ4-sulfanylidenecyanamide (946577-99-7) + methyl iodide (74-88-4) → sulfoxaflor (946578-00-3)

Conditions	Yield
Stage #1: [(6-trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ4-sulfanylidenecyanamide With N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane In tetrahydrofuran at -78℃; for 0.333333h; Stage #2: methyl iodide In tetrahydrofuran for 1h;	59%
Stage #1: [(6-trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ4-sulfanylidenecyanamide With N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; Stage #2: methyl iodide In tetrahydrofuran; toluene at -78 - 20℃; for 1h;	59%
Stage #1: [(6-trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ4-sulfanylidenecyanamide With N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; for 0.333333h; Stage #2: methyl iodide In tetrahydrofuran; toluene at -78 - 20℃; for 1h;	59%

5-[(methylthio)methyl]-2-(trifluoromethyl)pyridine (946577-96-4) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: [bis(acetoxy)iodo]benzene / dichloromethane / 0 - 20 °C 2: 3-chloro-benzenecarboperoxoic acid; potassium carbonate / ethanol; water / 1.5 h / 0 - 20 °C 3: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 - 20 °C View Scheme
Multi-step reaction with 3 steps 1.1: [bis(acetoxy)iodo]benzene / dichloromethane / 0 - 20 °C 2.1: potassium carbonate; 3-chloro-benzenecarboperoxoic acid / ethanol; water / 1.5 h / 0 - 20 °C 3.1: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 °C 3.2: 1.33 h / -78 - 20 °C View Scheme

C9H8F3N3S (946577-97-5) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid; potassium carbonate / ethanol; water / 1.5 h / 0 - 20 °C 2: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 - 20 °C View Scheme
Multi-step reaction with 2 steps 1.1: potassium carbonate; 3-chloro-benzenecarboperoxoic acid / ethanol; water / 1.5 h / 0 - 20 °C 2.1: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 °C 2.2: 1.33 h / -78 - 20 °C View Scheme

3-chloromethyl-6-(trifluoromethyl)pyridine (386715-33-9) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: dimethyl sulfoxide 2: [bis(acetoxy)iodo]benzene / dichloromethane / 0 - 20 °C 3: 3-chloro-benzenecarboperoxoic acid; potassium carbonate / ethanol; water / 1.5 h / 0 - 20 °C 4: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 - 20 °C View Scheme
Multi-step reaction with 4 steps 1.1: dimethyl sulfoxide 2.1: [bis(acetoxy)iodo]benzene / dichloromethane / 0 - 20 °C 3.1: potassium carbonate; 3-chloro-benzenecarboperoxoic acid / ethanol; water / 1.5 h / 0 - 20 °C 4.1: N,N,N,N,N,N-hexamethylphosphoric triamide; potassium hexamethylsilazane / tetrahydrofuran; toluene / -78 °C 4.2: 1.33 h / -78 - 20 °C View Scheme

1,1,1-trifluoro-6-(methylthio)-5-(pyrrolidine-1-ylmethylene)hept-3-en-2-one (1380070-36-9) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere 2: [bis(acetoxy)iodo]benzene / acetonitrile / 2.17 h / 10 - 30 °C 3: sodium permanganate / water; dichloromethane / 1.92 h / 13 - 20 °C View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 5 steps 1: potassium carbonate / toluene / 5 h / 10 - 20 °C / Inert atmosphere 2: acetonitrile / 15 - 20 °C / Inert atmosphere 3: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere 4: [bis(acetoxy)iodo]benzene / acetonitrile / 2.17 h / 10 - 30 °C 5: sodium permanganate / water; dichloromethane / 1.92 h / 13 - 20 °C View Scheme

3-(methylthio)-1-(pyrrolidin-1-yl)-1-butene (1045854-57-6) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: acetonitrile / 15 - 20 °C / Inert atmosphere 2: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere 3: [bis(acetoxy)iodo]benzene / acetonitrile / 2.17 h / 10 - 30 °C 4: sodium permanganate / water; dichloromethane / 1.92 h / 13 - 20 °C View Scheme

sulfoxaflor (946578-00-3) → N-(methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ4-sulfanylidene)urea (1186104-89-1)

Conditions	Yield
Stage #1: sulfoxaflor With sulfuric acid In acetonitrile at 40℃; Stage #2: With sodium hydroxide In acetonitrile at 5℃;	93%

sulfoxaflor (946578-00-3) → 5-[1-(methylsulfonimidoyl)ethyl]-2-(trifluoromethyl)pyridine (946578-43-4)

Conditions	Yield
Stage #1: sulfoxaflor With trifluoroacetic anhydride In dichloromethane at 0 - 20℃; for 2h; Stage #2: With potassium carbonate In methanol at 20℃; for 2h; Product distribution / selectivity;	77%
Stage #1: sulfoxaflor With trifluoroacetic anhydride In dichloromethane at 0 - 25℃; Stage #2: With potassium carbonate In methanol at 25℃;	77%

sulfoxaflor (946578-00-3) → [methyl(oxido){1-[1-oxido-6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ6-sulfanylidene]cyanamide (1523297-83-7)

Conditions	Yield
With urea hydrogen peroxide adduct; trifluoroacetic anhydride In acetonitrile at 20℃; for 3h; Inert atmosphere;	34%
With urea hydrogen peroxide adduct; trifluoroacetic anhydride In acetonitrile at 20℃; for 3h; Inert atmosphere;	34%

sulfoxaflor (946578-00-3) → N-hydroxy-N-(methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ4-sulfanylidene)guanidine (1186104-58-4)

Conditions	Yield
With hydroxylamine hydrochloride; sodium carbonate In ethanol; water for 8h; Reflux;	31%

sulfoxaflor (946578-00-3) + 1-Hydroxy-2-butanone (5077-67-8) → 5-{1-[methyl(4-ethyl-1,3-oxazol-2-yl)sulfonimidoyl]ethyl}-2-(trifluoromethyl)pyridine (1106809-81-7)

Conditions	Yield
With hydrogenchloride at 25℃;	30%

sulfoxaflor (946578-00-3) → 1-[methyl(oxido){1-[1-oxido-6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ6-sulfanylidene]urea (1523297-89-3)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: urea hydrogen peroxide adduct; trifluoroacetic anhydride / acetonitrile / 3 h / 20 °C / Inert atmosphere 2.1: sulfuric acid / acetonitrile / 3 h / 20 °C 2.2: 25 h / 20 - 70 °C View Scheme

Upstream product

• 946578-43-4 5-[1-(methylsulfonimidoyl)ethyl]-2-(trifluoromethyl)pyridine 
• 506-68-3 bromocyane 
• 1045854-57-6 3-(methylthio)-1-(pyrrolidin-1-yl)-1-butene 
• 16630-52-7 3-(methylthio)butyraldehyde 
• 1380070-36-9 1,1,1-trifluoro-6-(methylthio)-5-(pyrrolidine-1-ylmethylene)hept-3-en-2-one 
• 386715-33-9 3-chloromethyl-6-(trifluoromethyl)pyridine 
• 946577-97-5 C₉H₈F₃N₃S 
• 946577-96-4 5-[(methylthio)methyl]-2-(trifluoromethyl)pyridine 
• 946577-99-7 [(6-trifluoromethylpyridin-3-yl)methyl](methyl)-oxido-λ⁴-sulfanylidenecyanamide 
• 74-88-4 methyl iodide 
• 1046119-63-4 (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)(methyl)-λ4-sulfanylidenecyanamide 
• 1049684-75-4 (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)-(methyl)-λ⁴-sulfanylidenecyanamide 

Relevant articles and documents

Anodic Dehydrogenative Cyanamidation of Thioethers: Simple and Sustainable Synthesis of N-Cyanosulfilimines

A novel and very simple to perform electrochemical approach for the synthesis of several N-cyanosulfilimines in good to excellent yields was established. This method provides access to biologically relevant sulfoximines by consecutive oxidation using electro-generated periodate. This route can be easily scaled-up to gram quantities. The S,N coupling is carried out at an inexpensive carbon anode by direct oxidation of sulfide. Therefore, the designed process is atom economic and represents a new “green route” for the synthesis of sulfilimines and sulfoximines.

Development of a scalable process for the crop protection agent isoclast

A scalable process to the insecticide Isoclast manufactured by Dow AgroSciences LLC is described. The process involves the de novo construction of a fully elaborated pyridine sulfide using enamine-mediated cyclization followed by two efficient and inexpensive oxidations to introduce the sulfoximine.

Stable insecticide compositions

Insect controlling compositions including an N-substituted (6-haloalkylpyridin-3-yl)alkyl sulfoximine compound and an organic acid or a salt thereof exhibit increased stability.