120067-83-6

Basic information

• Product Name: FIPRONIL-SULFIDE
• Synonyms: 1h-pyrazole-3-carbonitrile,5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-((trifluoromethyl)s;1H-Pyrazole-3-carbonitrile, 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-((trifluoromethyl)thio)-;5-Amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-((trifluoromethyl)thio)pyrazole-3-carbonitrile;1-(2,6-Dichloro-4-trifluoroMethylphenyl)-3-cyano-5-aMino-4-(trifluoroMethylthio)pyrazole;5-AMino-1-(2,6-dichloro-4-trifluoroMethylphenyl)-4-trifluoroMethylthio-1H-pyrazole- 3-carbonitrile;5-AMino-3-cyano-1-(2,6-dichloro-4-trifluoroMethylphenyl)-4-(trifluoroMethylthio)pyrazole;MB 45950;Fipronil-sulde
• CAS NO: 120067-83-6
• Molecular Formula: C₁₂H₄Cl₂F₆N₄S
• Molecular Weight: 421.152
• Product Categories: Agro-Products;Aromatics;Heterocycles;Intermediates & Fine Chemicals;Metabolites & Impurities;Pharmaceuticals
• Mol File: 120067-83-6.mol
• Article Data: 23

Chemical Properties

• Melting Point: 161-163 °C(Solv: toluene (108-88-3))
• Boiling Point: 393.242oC at 760 mmHg
• Flash Point: 191.626oC
• Appearance: /
• Density: 1.761g/cm3
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.592
• PKA: -4.16±0.20(Predicted)
• CAS DataBase Reference: FIPRONIL-SULFIDE(CAS DataBase Reference)
• NIST Chemistry Reference: FIPRONIL-SULFIDE(120067-83-6)
• EPA Substance Registry System: FIPRONIL-SULFIDE(120067-83-6)

Safety Data

• Hazardous Substances Data: 120067-83-6(Hazardous Substances Data)

Usage

Uses

Fipronil Sulfide is a degradation product of the insecticide Fipronil (F342200).

Definition

ChEBI: A member of the class of pyrazoles that is 1H-pyrazole that is substituted at positions 1, 3, 4, and 5 by 2,6-dichloro-4-(trifluoromethyl)phenyl, cyano, (trifluoromethyl)sulfanyl, and amino groups, respectively. It is a metabolite of the agrochemical fipronil.

InChI:InChI=1/C12H4Cl2F6N4S/c13-5-1-4(11(15,16)17)2-6(14)8(5)24-10(22)9(7(3-21)23-24)25-12(18,19)20/h1-2H,22H2

Synthetic route

Langlois reagent (2926-29-6) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
Stage #1: Langlois reagent; 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole With C7H16O3P(1-)*C6H11N2O(1+) In toluene at -2℃; for 0.0833333h; Stage #2: With phosphorus trichloride In toluene at 50℃; for 5h; Temperature;	96%
Stage #1: Langlois reagent; 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole; dimethylamine p-toluenesulfonate In N,N-dimethyl-formamide; toluene at 20 - 25℃; for 0.75h; Stage #2: With phosphorus trichloride In N,N-dimethyl-formamide; toluene at 0 - 70℃; for 8h; Product distribution / selectivity;	66.7%
Stage #1: Langlois reagent; 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole; dimethylamine p-toluenesulfonate In N,N-dimethyl-formamide; toluene at 25℃; for 0.75h; Industry scale; Stage #2: With phosphorus trichloride In N,N-dimethyl-formamide; toluene at 0 - 70℃; for 10h; Product distribution / selectivity;

5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato-1H-pyrazole-3-carbonitrile (120069-10-5) + Bromotrifluoromethane (75-63-8) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
Stage #1: 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato-1H-pyrazole-3-carbonitrile With sulfur dioxide; sodium formate In DMF (N,N-dimethyl-formamide) at 20℃; for 0.0833333h; Stage #2: Bromotrifluoromethane In DMF (N,N-dimethyl-formamide) at 20 - 45℃; under 8625.86 Torr; for 1.5h; Product distribution / selectivity;	90.8%
Stage #1: 5-amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato-1H-pyrazole-3-carbonitrile With sulfur dioxide In DMF (N,N-dimethyl-formamide) at 20℃; for 0.0333333h; Stage #2: Bromotrifluoromethane With sodium formate In DMF (N,N-dimethyl-formamide) at 20 - 54℃; for 2.33333h; Product distribution / selectivity;	84.7%
With sulfur dioxide; potassium formate In DMF (N,N-dimethyl-formamide); water at -60 - 55℃; for 3h; Product distribution / selectivity;	81%

Bromotrifluoromethane (75-63-8) + 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] (130755-46-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With sulfur dioxide; sodium formate In N,N-dimethyl-formamide at 60℃; under 9000.7 - 9750.8 Torr; for 4h; Mechanism; Product distribution; other reagent, other perhalogenoalkanes, other disulfide;	85%
With sulfur dioxide; sodium formate In N,N-dimethyl-formamide at 60℃; under 9000.7 - 9750.8 Torr; for 4h;	85%
With disodium hydrogenphosphate; sodium dithionite In water; N,N-dimethyl-formamide at 20℃; for 4h;	51%

Trifluoromethylsulfenyl chloride (421-17-0) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
In dichloromethane at 18 - 20℃; for 12h; Large scale;	68%
With sodium hydroxide In dichloromethane at 10 - 20℃; for 12h; Large scale;	68%
In dichloromethane for 2h; Heating;

Reaxys ID: 12045767 → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With copper dichloride In chlorobenzene at 100℃; for 4h;	65%

fipronil (120068-37-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With trifluoroacetic anhydride; sodium iodide In acetone at 0℃; for 10h;	60%

5-amino-3-cyano-4-(trifluoromethylsulfenyl)-1-(2,6-dinitro-4-trifluoromethylphenyl)pyrazole (183288-98-4) + aminosulfonic acid (5329-14-6) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With lithium chloride In 1-methyl-pyrrolidin-2-one; water	48%

Bromotrifluoromethane (75-63-8) + sulfur dioxide (7446-09-5) + 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] (130755-46-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With sodium formate; sodium hydrogencarbonate In water; N,N-dimethyl-formamide

CF3 Br + sodium hydrogen phosphate 12H2 O + 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] (130755-46-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
In N-methyl-acetamide; water

2,6-dichloro-4-(trifluoromethyl)aniline (24279-39-8) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: nitrosylsulfuric acid; acetic acid / 30 - 55 °C 1.2: 0 - 15 °C 2.1: dichloromethane View Scheme

1,2-dichloro-4-(trifluoromethyl)benzene (328-84-7) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: dimethylsulfone; potassium fluoride; ammonia / 6 h / 30 - 235 °C / 18751.9 - 19502 Torr / Autoclave 2.1: sulfuryl dichloride; 1-methyl-pyrrolidin-2-one / 1-methyl-pyrrolidin-2-one; chlorobenzene / 8 h / 55 - 60 °C 3.1: nitrosylsulfuric acid; acetic acid / 30 - 55 °C 3.2: 0 - 15 °C 4.1: dichloromethane View Scheme
Multi-step reaction with 4 steps 1.1: 1-methyl-pyrrolidin-2-one; potassium fluoride; ammonia / 10 h / 245 - 250 °C / 22502.3 - 30003 Torr / Autoclave 2.1: sulfuryl dichloride; 1-methyl-pyrrolidin-2-one / 1-methyl-pyrrolidin-2-one; chlorobenzene / 8 h / 55 - 60 °C 3.1: nitrosylsulfuric acid; acetic acid / 30 - 55 °C 3.2: 0 - 15 °C 4.1: dichloromethane View Scheme

chlorothio-trichloro-methane (594-42-3) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
In dichloromethane	225 g

2-chloro-4-(trifluoromethyl)aniline (39885-50-2) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sulfuryl dichloride; 1-methyl-pyrrolidin-2-one / 1-methyl-pyrrolidin-2-one; chlorobenzene / 8 h / 55 - 60 °C 2.1: nitrosylsulfuric acid; acetic acid / 30 - 55 °C 2.2: 0 - 15 °C 3.1: dichloromethane View Scheme

5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With dimethylamine p-toluenesulfonate; Langlois reagent; trichlorophosphate In N,N-dimethyl-formamide; toluene at 0 - 45℃; for 20h; Reagent/catalyst; Temperature; Solvent;	4.95 g

2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene (118754-53-3) + 5-amino-4-((trifluoromethyl)thio)-1H-pyrazole-3-carbonitrile (183288-97-3) → 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6)

Conditions	Yield
With 1,10-Phenanthroline; copper In tetrahydrofuran; dimethyl sulfoxide at 60℃; for 8h; Temperature;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → fipronil (120068-37-3)

Conditions	Yield
Stage #1: 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile With dichloro-acetic acid; sulfuric acid at 15℃; for 0.5h; Stage #2: With dihydrogen peroxide In water at 15℃; Product distribution / selectivity;	98%
With caro's acid In dichloromethane at 0 - 5℃; Reagent/catalyst; Industrial scale;	97.9%
With dihydrogen peroxide In dichloro-acetic acid; water; trichloroacetic acid at 20℃; for 2h; Product distribution / selectivity;	95%

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → fipronil (120068-37-3) + fipronil sulfone (120068-36-2)

Conditions	Yield
With dihydrogen peroxide; trifluoroacetic acid In dichloromethane at 10 - 12℃; for 3h;	A 96% B n/a
Stage #1: 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile With trifluoroacetic acid for 0.25h; Stage #2: With Oxone at -15℃; Product distribution / selectivity;	A 55.4% B n/a
Stage #1: 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile With trifluoroacetic acid for 0.25h; Industry scale; Stage #2: With Oxone at -15℃; Product distribution / selectivity; Industry scale;

sulfure de methyle et de 2-chloroethyle (542-81-4) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(N-methyl-N-(2-methylthioethyl)amino)-4-trifluoromethylthiopyrazole (847779-93-5)

Conditions	Yield
With potassium phosphate In acetonitrile at 20 - 30℃; for 8h; Conversion of starting material; Heating / reflux;	89%
With potassium phosphate In 1-methyl-pyrrolidin-2-one at 20 - 30℃; for 8h; Conversion of starting material; Heating / reflux;	7 %Spectr.
With sodium hydride In dimethyl sulfoxide; N,N-dimethyl-formamide at 20 - 30℃; for 8h; Conversion of starting material; Heating / reflux;	10 %Spectr.
With sodium hydride In N,N-dimethyl-formamide at 20 - 30℃; for 8h; Conversion of starting material; Heating / reflux;	10 %Spectr.

dimethyl cis-but-2-ene-1,4-dioate (624-48-6) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → C18H11ClF6N4O4S

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃; for 3h;	84%

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthio-1H-pyrazole-3-carboxylic acid

Conditions	Yield
With sulfuric acid In water at 135℃; for 7h;	82%

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + acrylic acid methyl ester (292638-85-8) → 5-(2'-bromo-2'-carbomethoxy)ethyl-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthio-1H-pyrazole-3-carbonitrile (192988-64-0)

Conditions	Yield
With tert.-butylnitrite; copper(I) bromide In acetonitrile	78%
With tert.-butylnitrite; copper(ll) bromide In acetonitrile at 0 - 20℃; for 12h;

Methoxyacetyl chloride (38870-89-2) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfenyl-5-(methoxyacetamido)pyrazole

Conditions	Yield
With dmap; triethylamine In chloroform	52%

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → fipronil sulfone (120068-36-2)

Conditions	Yield
With potassium permanganate; magnesium sulfate In water; acetone at 20℃;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylthio-1H-pyrazole-3-carboxaldehyde (120068-75-9)

Conditions	Yield
aluminum nickel In formic acid
aluminum nickel In formic acid

Ethyl oxalyl chloride (4755-77-5) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(ethoxycarbonyl)carbonylamino-4-trifluoromethylthiopyrazole

Conditions	Yield
With dmap; triethylamine In tetrahydrofuran at 50 - 70℃; for 8h; Heating / reflux;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + 2-chloropropionyl chloride (625-36-5) → 3-chloropropionylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole

Conditions	Yield
With zinc(II) chloride In toluene for 4h; Heating / reflux;

2-chloropropionyl chloride (7623-09-8) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-(2-chloropropionylamino)-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole

Conditions	Yield
With zinc(II) chloride In toluene for 16h; Heating / reflux;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + isopropyl alcohol (67-63-0) → 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-isopropyloxymethylamino-4-trifluoromethylthiopyrazole

Conditions	Yield
Stage #1: 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile; isopropyl alcohol for 0.0833333h; Stage #2: With formaldehyd at 20℃; for 120h;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + dimethyl amine (124-40-3) → 5-amino-3-cyano-1-[2,6-bis(dimethylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole (865854-41-7)

Conditions	Yield
In 1,4-dioxane; water at 200℃; for 0.666667h; Microwave irradiation;

ethanol (64-17-5) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-amino-1-(2-chloro-6-ethoxy-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole (865854-38-2)

Conditions	Yield
With copper(I) bromide; sodium t-butanolate In DMF (N,N-dimethyl-formamide) at 90℃; for 7h;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + methylamine (74-89-5) → 5-amino-1-(2-chloro-6-methylamino-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole (865854-36-0)

Conditions	Yield
In 1,4-dioxane; water at 200℃; for 0.666667h; Microwave irradiation;

N-Ethylmethylamine (624-78-2) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-amino-3-cyano-1-[2-chloro-6-(ethyl-methylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole (865854-58-6) + 5-amino-3-cyano-1-[2,6-bis(ethyl-methylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole (865854-42-8)

Conditions	Yield
In 1,4-dioxane at 140 - 145℃; under 12751.3 - 13501.4 Torr; Microwave irradiatio;

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 5-(dichlorophosphorylamino)-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole

Conditions	Yield
With N-ethyl-N,N-diisopropylamine; trichlorophosphate In 1,2-dichloro-ethane for 7h; Heating / reflux;

sulfur dioxide (7446-09-5) + 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → fipronil (120068-37-3)

Conditions	Yield
With dihydrogen peroxide; boric acid; trifluoroacetic acid In chlorobenzene

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) → 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-ethoxymethylideneamino-4-trifluoromethylthiopyrazole

Conditions	Yield
With hydrogenchloride In orthoformic acid triethyl ester
With hydrogenchloride In orthoformic acid triethyl ester

5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile (120067-83-6) + acetyl chloride (75-36-5) → 5-acetamido-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole (120068-03-3)

Conditions	Yield
With pyridine In dichloromethane; acetonitrile
With pyridine In dichloromethane; acetonitrile

Upstream product

• 421-17-0 Trifluoromethylsulfenyl chloride 
• 120068-79-3 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole 
• 130755-46-3 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] 
• 120068-37-3 fipronil 
• 118754-53-3 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene 
• 183288-97-3 5-amino-4-((trifluoromethyl)thio)-1H-pyrazole-3-carbonitrile 
• 39885-50-2 2-chloro-4-(trifluoromethyl)aniline 
• 594-42-3 chlorothio-trichloro-methane 
• 328-84-7 1,2-dichloro-4-(trifluoromethyl)benzene 
• 24279-39-8 2,6-dichloro-4-(trifluoromethyl)aniline 
• 2926-29-6 Langlois reagent 
• 183288-98-4 5-amino-3-cyano-4-(trifluoromethylsulfenyl)-1-(2,6-dinitro-4-trifluoromethylphenyl)pyrazole 
• 5329-14-6 aminosulfonic acid 
• 75-63-8 Bromotrifluoromethane 

Downstream Products

• 120068-37-3 fipronil 
• 120068-20-4 5-bromo-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethanesulphonylpyrazole 
• 847779-93-5 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(N-methyl-N-(2-methylthioethyl)amino)-4-trifluoromethylthiopyrazole 
• 120068-36-2 fipronil sulfone 
• 120068-26-0 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole 
• 120068-03-3 5-acetamido-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole 
• 865854-58-6 5-amino-3-cyano-1-[2-chloro-6-(ethyl-methylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole 
• 865854-42-8 5-amino-3-cyano-1-[2,6-bis(ethyl-methylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole 
• 865854-36-0 5-amino-1-(2-chloro-6-methylamino-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole 
• 865854-38-2 5-amino-1-(2-chloro-6-ethoxy-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole 
• 865854-41-7 5-amino-3-cyano-1-[2,6-bis(dimethylamino)-4-trifluoromethylphenyl]-4-trifluoromethylthiopyrazole 

Relevant articles and documents

Synthesis of fipronil sulfide, an active metabolite, from the parent insecticide fipronil

A convenient procedure for the synthesis of fipronil sulfide, one of several active metabolites identified from the insecticide fipronil, has been developed. Reduction of fipronil with trifluoroacetic anhydride-sodium iodide in acetone, followed by flash chromatography afforded fipronil sulfide in 60% yield and >99.9 percent purity. This represents the first direct synthesis of this key metabolite from fipronil.

A convenient conversion of pyrazolyl disulfide to sulfides by sodium dithionite and synthesis of sulfoxides

Indirectly introduce trifluoromethylthio-, alkylthio-, and trifluoromethylsulfinyl to pyrazole ring by a convenient reaction of a pyrazolyl disulfide with F3CBr and alkyl halides in the presence of sodium dithionite at room temperature. Followed by selective oxidation with H2O2 or trichloroisocyanuric acid (TCCA) to give trifluoromethylsulfenyl phenylpyrazole, alkylsulfenyl phenylpyazole, trifluoromethylsulfinyl phenylpyrazole 4a (a highly efficient insecticide named fipronil) and ethylsulfinyl phenylpyrazole 4c derivatives, respectively.

Method for preparing fipronil

The invention relates to a method for preparing fipronil. The method comprises the following steps: taking 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene as an initial raw material, reacting the initial raw material with 5-amino-4-((trifluoromethyl)sulfenyl)-1H-pyrazol-3-formonitrile, wherein the product does not need to be treated; and further reacting to obtain the target product fipronil. Compared with the traditional synthetic method, the method disclosed by the invention takes Cu as a catalyst, and is more efficient and relatively high in yield. Moreover, the operating method is simple and convenient, and the reaction conditions are mild.

Preparation method of 5-amino-1-(2,6-dihydro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylmercapto)-1H-parazole-3-nitrile

The invention discloses a preparation method of 5-amino-1-(2,6-dihydro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylmercapto)-1H-parazole-3-nitrile, which comprises the following steps: (1) adding 5-amino-3-cyano-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-parazole, trifluoromethyl sulfinate, an organic solvent, and a phosphorus-containing iminazole liquid to a reactor, mixing under stirring, and cooling the mixture in an ice bath; and (2) dropwise adding phosphorus trihalide or an organic solution of phosphorus trihalide to the reactor under stirring, reacting at 30-60 DEG C for 1-5h under stirring, quenching the reaction with ice water, extracting with an extracting agent, washing, drying and concentrating to obtain 5-amino-1-(2,6-dihydro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylmercapto)-1H-parazole-3-nitrile. The method is simple and convenient to operate, and can obtain the effects of good yield and purity, etc.