120068-37-3

Basic information

• Product Name: Fipronil
• Synonyms: 4-((trifluoromethyl)sulfinyl)-;m&b46030;PRINCE;REGENT;FIPRONIL;5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile;(±)-5-amino-1-(2,6-dichloro)-4-(trifluoromethyl)phenyl-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile;(±)-5-amino-1-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile
• CAS NO: 120068-37-3
• Molecular Formula: C₁₂H₄Cl₂F₆N₄OS
• Molecular Weight: 437.15
• EINECS: 424-610-5
• Product Categories: PHARMACEUTICALS;Ectoparasiticide;API;INSECTICIDE;Baby Food Directives 13/2003 EC&14/2003 ECPesticides&Metabolites;AcaricidesMethod Specific;Alpha sort;E-GAlphabetic;European Community: ISO and DIN;F;FA - FLPesticides;Insecticides;Pesticides;Pesticides&Metabolites;Pyrazoles;Agro-Products;Heterocycles;Fipronil insecticidal spectrum is wide, and existing insecticide resistance without interaction;Pesticide intermediates;NULL;MYCODECYL;Pesticides intermediate
• Mol File: 120068-37-3.mol
• Article Data: 38

Chemical Properties

• Melting Point: 200-201°C
• Boiling Point: 510.1 ºC at 760 mmHg
• Flash Point: 262.3 ºC
• Appearance: clear colorless or slightly yellow liquid
• Density: 1.477-1.626
• Vapor Pressure: 1.61E-10mmHg at 25°C
• Refractive Index: 1.617
• Storage Temp.: 0-6°C
• PKA: -5.86±0.20(Predicted)
• Water Solubility: 1.9-2.4 mg 1l-1 (20 °C）
• Merck: 14,4085
• BRN: 8090115
• CAS DataBase Reference: Fipronil(CAS DataBase Reference)
• NIST Chemistry Reference: Fipronil(120068-37-3)
• EPA Substance Registry System: Fipronil(120068-37-3)

Safety Data

• Hazard Codes: T,N
• Statements: 23/24/25-48/25-50/53-55-57-36
• Safety Statements: 26-36/37/39-45-60-61-36/37-28
• RIDADR: 2588
• WGK Germany: 3
• RTECS: UQ4430250
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 120068-37-3(Hazardous Substances Data)

Usage

Uses

Used in Agricultural Industry:
Fipronil is used as an insecticide for the control of a wide range of insect species in rice, cereals, corn, cotton, top fruit, sugar beet, sugar cane, oilseed rape, and many vegetables and other high-value crops. It is effective against ants, beetles, cockroaches, fleas, ticks, termites, mole crickets, thrips, rootworms, and weevils.
Used in Veterinary Medicine:
Fipronil is used as an ectoparasiticide in the control of fleas, ticks, and chewing lice on domestic animals. It is also used as a topical insecticide, applied on the back side skin of dogs and cats. However,

Trade name

BES? 602; CEASEFIRE?; CHIPCO?; COMBAT?; FRONTLINE; MB-46030?; H&G?; ICON?; MAXFORCE? ANT STATION; MAXFORCE? ROACH STATION; REGENCY SOFION?; REGENT?; REGENT? 500-FS; TERMIDOR? L VI-NIL

Pharmacology

Fipronil is a phenylpyrazole, the mode of action of which is to inhibit nerve transmission in arthropods by blocking γ -aminobutyric acid-gated chloride channels. Fipronil is available as spray and spot-on formulations to control fleas and ticks on cats and dogs. The adulticidal activity of fipronil accounts for the majority of its activity, although additional activity against flea eggs and larvae results from the presence of fipronil on hairs and debris shed into the environment from treated pets.Autohistoradiography studies (11) into the cutaneous distribution of 14C-fipronil in the cat and dog following spot-on administration demonstrated that radioactivity was restricted principally to the stratum corneum, the viable epidermis, and the pilosebaceous units. Following its slow release from sebaceous glands, fipronil migrates in the sebum covering the skin and hairs by passive diffusion and was shown to persist on hair for up to 2 months after treatment.

Potential Exposure

Pyrazole/phenylpyrazole/organofluor ine insecticide; veterinary medicine. Fipronil was intro duced into the United States in 1996 for use in animal health and indoor pest control. It is the constituent of many products for controlling a wide spectrum of domestic ani mal and residential pests. Banned for use in EU.

Metabolic pathway

Through the abiotic degradation of fipronil in aqueous solution and on the soil surface, 5-amino-3- carbamoyl-1-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4- [(trifluoromethyl)sulfinyl]pyrazole is the only hydrolysis product detected. Fipronil in acidic aqueous solution exposed under a xenon lamp degrades with the concomitant appearance of 5-amino-3-cyano-1-[2,6- dichloro-4-(trifluoromethyl)-phenyl]-4- (trifluoromethyl)pyrazole and 5-amino-3-cyano-1-[2,6- dichloro-4-(trifluoromethyl)phenyl]pyrazole-4-sulfonic acid. Under field conditions, when fipronil is applied in formulation, four metabolites which include one product resulting from reduction on the sulfur atom of fipronil are detected.

Shipping

UN2588 Pesticides, solid, toxic, Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required. UN2902 Pesticide, liquid, toxic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required.

Degradation

Fipronil is stable in water at pH 5 and 7 but is slowly hydrolysed at pH 9 (DT50 28 days) to the amide (2). It undergoes rapid aqueous photolysis with a DT50 of ﹤0.5 day. The major photodecomposition product in water and on soil surfaces is desulfinyl-fipronil(3) which is formed by extrusion of the SO group. A minor photoproduct in water, on soil and on plant surfaces is the sulfonic acid (4). The mechanisms of these reactions are discussed in a recent paper by Bobe et al. (1998).

Toxicity evaluation

Acute oral LD50 for rats: 100 mg/kg

Waste Disposal

It is the responsibility of chemical waste generators to determine the toxicity and physical properties and of a discarded chemical and to properly identify its classification and certification as a haz ardous waste and to determine the disposal method. United States Environmental Protection Agency guidelines for the classification determination are listed in 40 CFR Parts 261.3. Additionally, waste generators must consult and fol low all regional, national, state and local hazardous waste laws to ensure complete and accurate classification and dis posal methods.

InChI:InChI=1/C12H4Cl2F6N4OS/c13-5-1-4(11(15,16)17)2-6(14)8(5)24-10(22)9(7(3-21)23-24)26(25)12(18,19)20/h1-2H,22H2

Synthetic route

trifluoromethylsulfinyl chloride (20621-29-8) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → fipronil (120068-37-3)

Conditions	Yield
With dimethylamine p-toluenesulfonate for 10h; Heating;	99%
With dimethylamine p-toluenesulfonate at 50℃; for 8h;	92%
With benzyltrimethylammonium chloride In 1,2-dichloro-ethane at 35℃; for 2h; Temperature; Industrial scale;	90.3%

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;

trifluoromethylsulfinyl chloride (20621-29-8) + dimethylamine p-toluenesulfonate (2840-22-4) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → fipronil (120068-37-3)

Conditions	Yield
In water; toluene	88%

Langlois reagent (2926-29-6) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → fipronil (120068-37-3)

Conditions	Yield
With trichlorophosphate; dimethylamine p-toluenesulfonate at 40℃; for 14h; Product distribution / selectivity;	80.2%
With thionyl chloride; dimethylamine p-toluenesulfonate at 40℃; for 10h; Product distribution / selectivity;	74.8%
Stage #1: Langlois reagent With thionyl chloride; dimethylamine p-toluenesulfonate In toluene at 0 - 5℃; for 0.5h; Stage #2: 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole In toluene at 5 - 50℃; for 6.08333h; Product distribution / selectivity;	73%

potassium triflinate (41804-89-1) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → fipronil (120068-37-3)

Conditions	Yield
Stage #1: potassium triflinate With thionyl chloride; triethylamine hydrochloride In toluene at 0 - 5℃; for 0.5 - 0.833333h; Stage #2: 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole In toluene at 5 - 35℃; for 11.75h; Product distribution / selectivity;	66%
Stage #1: potassium triflinate With thionyl chloride; pyridine hydrochloride In toluene at 0 - 5℃; for 0.833333h; Stage #2: 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole In toluene at 5 - 35℃; for 11.75h; Product distribution / selectivity;
Stage #1: potassium triflinate With thionyl chloride; trimethylamine hydrochloride In toluene at 0 - 5℃; for 0.833333h; Stage #2: 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole In toluene at 5 - 35℃; for 11.75h; Product distribution / selectivity;

5-amino-4-trifluoromethylsulfinyl-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-thiocarbamoylpyrazole (208652-17-9) → fipronil (120068-37-3)

Conditions	Yield
With hydrogenchloride In water; acetonitrile Product distribution / selectivity;
In water; acetonitrile Product distribution / selectivity; fluorescent light;
In water; acetonitrile at 65℃; Product distribution / selectivity;

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-3-bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole (120067-94-9) → 5-amino-3-bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole (120068-43-1) + fipronil (120068-37-3)

trifluoromethanesulfinic acid (34642-42-7) + 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (120068-79-3) → fipronil (120068-37-3)

Conditions	Yield
Stage #1: trifluoromethanesulfinic acid With thionyl chloride; triethylamine In toluene at 0 - 5℃; for 0.5h; Stage #2: 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole; triethylamine hydrochloride In toluene at 50℃; for 6h; Product distribution / selectivity;
With thionyl chloride; N,N-dimethylisopropyl amine; potassium chloride; isopropyl-dimethyl-amine; hydrochloride In ethylbenzene at 0 - 35℃; for 11.75h; Inert atmosphere;

2,6-dichloro-4-(trifluoromethyl)aniline (24279-39-8) → fipronil (120068-37-3)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: nitrosylsulfuric acid; acetic acid / 30 - 55 °C 1.2: 0 - 15 °C 2.1: dichloromethane 3.1: boric acid; trichloroacetic acid; dihydrogen peroxide / chlorobenzene; water / 20 h / 15 - 20 °C View Scheme

1,2-dichloro-4-(trifluoromethyl)benzene (328-84-7) → fipronil (120068-37-3)

Conditions	Yield
Multi-step reaction with 5 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 5.1: boric acid; trichloroacetic acid; dihydrogen peroxide / chlorobenzene; water / 20 h / 15 - 20 °C View Scheme
Multi-step reaction with 5 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 5.1: boric acid; trichloroacetic acid; dihydrogen peroxide / chlorobenzene; water / 20 h / 15 - 20 °C View Scheme

2-chloro-4-(trifluoromethyl)aniline (39885-50-2) → fipronil (120068-37-3)

Conditions	Yield
Multi-step reaction with 4 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 4.1: boric acid; trichloroacetic acid; dihydrogen peroxide / chlorobenzene; water / 20 h / 15 - 20 °C View Scheme

dihydrogen peroxide (7722-84-1) + 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 hydrogenchloride; sodium tungstate In water; 1,2-dichloro-ethane at 2 - 8℃; Large scale;

orthoformic acid triethyl ester (122-51-0) + fipronil (120068-37-3) → 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-ethoxymethylideneamino-4-trifluoromethylsulfinylpyrazole

Conditions	Yield
	99%
	99%

4-nitrobenzaldehdye (555-16-8) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-((4-nitro-benzylidene)amino)-4-(trifluoromethanesulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	98.9%

n-Butyl chloride (109-69-3) + fipronil (120068-37-3) → N-5-butylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazole

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 80℃; for 8h; Sonication;	96.7%

4-fluorobenzaldehyde (459-57-4) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-(4-fluorobenzylideneamino)-4-(trifluoromethylsulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	96.5%
With toluene-4-sulfonic acid In chlorobenzene for 1h; Molecular sieve; Microwave irradiation; Sealed tube;	73%

2-Nitrobenzenesulfonyl chloride (1694-92-4) + fipronil (120068-37-3) → C18H7Cl2F6N5O5S2 (1225373-70-5)

Conditions	Yield
With sodium hydride In ethyl acetate at 0 - 20℃;	96%
With sodium hydride In ethyl acetate at 2 - 20℃; for 4h;	79.3%

1,4-dibromo-butane (110-52-1) + fipronil (120068-37-3) → N-bis(1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazol-5ylamino)butyl

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 3h; Sonication; Microwave irradiation; Heating;	95.2%

1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-(4-bromophenylsulfonylamino)-1H-pyrazole-3-carbonitrile (1014394-95-6) + fipronil (120068-37-3) → C18H7BrCl2F6N4O3S2 (1225373-68-1)

Conditions	Yield
With sodium hydride In ethyl acetate at 0 - 20℃;	95%

benzaldehyde (100-52-7) + fipronil (120068-37-3) → 5-(benzylideneamino)-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylsulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	94.8%
With toluene-4-sulfonic acid In toluene for 1h; Reagent/catalyst; Molecular sieve; Microwave irradiation; Sealed tube;	84%

5-bromo-2-thiophenesulfonyl chloride (55854-46-1) + fipronil (120068-37-3) → C16H5BrCl2F6N4O3S3

Conditions	Yield
With sodium hydride In ethyl acetate at 0 - 20℃;	93%

1-bromo-butane (109-65-9) + fipronil (120068-37-3) → N-5-butylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazole

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 3h; Time; Sonication; Microwave irradiation; Heating;	92.6%
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h;	92.6%

4-methyl-benzaldehyde (104-87-0) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-((4-methylbenzylidene)amino)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	92.6%

3-methoxy-benzaldehyde (591-31-1) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-((3-methoxybenzylidene)amino)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	91.8%

ethyl bromoacetate (105-36-2) + fipronil (120068-37-3) → ethyl N-[3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4-[(trifluoromethyl)-sulfinyl]-1H-pyrazol-5-yl]-aminoacetate (1430089-22-7)

Conditions	Yield
With sodium hydride In tetrahydrofuran at 20℃; for 3h; Cooling with ice;	91%

1,4-diphenyl-but-2-ene-1,4-dione (4070-75-1) + fipronil (120068-37-3) → C28H15ClF6N4O3S

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃;	91%

ethoxyacetyl chloride (14077-58-8) + triethylamine (121-44-8) + fipronil (120068-37-3) → triethylamine salt of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-5-(ethoxyacetamido)pyrazole (379215-14-2)

Conditions	Yield
In tetrahydrofuran at 60℃; for 1.5h;	90%

benzenesulfonyl chloride (98-09-9) + fipronil (120068-37-3) → C18H8Cl2F6N4O3S2 (1225373-74-9)

Conditions	Yield
With sodium hydride In ethyl acetate at 0 - 20℃;	90%

fipronil (120068-37-3) + 1,4-dimethyl but-2-enedioate (23055-10-9) → C18H11ClF6N4O5S

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃;	90%

1,4-bibromocyclohexane (35076-92-7) + fipronil (120068-37-3) → N-bis(1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazol-5-ylamino)cyclohexyl

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 3h; Sonication; Microwave irradiation; Heating;	89.5%

1,4-bis(bromomethyl)benzene (623-24-5) + fipronil (120068-37-3) → N-bis(1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazol-5ylamino)benzyl

Conditions	Yield
With potassium hydroxide In toluene at 20℃; for 3h; Sonication; Microwave irradiation; Heating;	89.3%

ortho-anisaldehyde (135-02-4) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-((2-methoxybenzylidene)amino)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	88.7%

p-toluenesulfonyl chloride (98-59-9) + fipronil (120068-37-3) → C19H10Cl2F6N4O3S2 (1225373-72-7)

Conditions	Yield
With sodium hydride In ethyl acetate at 0 - 20℃;	88%

C7H12O7S + fipronil (120068-37-3) → C18H11ClF6N4O5S

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃;	88%

4-methoxy-benzaldehyde (123-11-5) + fipronil (120068-37-3) → 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-((4-methoxybenzylidene)amino)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 200℃; for 3h; Temperature; Time; Molecular sieve; High pressure; Sonication; Autoclave; Sealed tube;	87.4%
With toluene-4-sulfonic acid In 1,3,5-trimethyl-benzene for 1h; Molecular sieve; Microwave irradiation; Sealed tube;	78%

α,α',α''-trichloromesitylene (17299-97-7) + fipronil (120068-37-3) → N-1,3,5-tri(1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-1H-pyrazol-5ylamino)benzyl

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 3h; Sonication; Microwave irradiation; Heating;	87.2%

ethoxyacetyl chloride (14077-58-8) + fipronil (120068-37-3) → potassium salt of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-5-(ethoxyacetamido)pyrazole

Conditions	Yield
With potassium hydroxide In acetonitrile at -5℃; for 4h;	87%
Stage #1: ethoxyacetyl chloride; fipronil With triethylamine In tetrahydrofuran at 30℃; for 5h; Stage #2: With hydrogenchloride In tetrahydrofuran; dichloromethane; water pH=2; Stage #3: With potassium carbonate In tetrahydrofuran; dichloromethane; water	65%

Dimethyl oxalate (553-90-2) + fipronil (120068-37-3) → N,N'-bis[3-cyano-4-trifluoromethylsulfinyl-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazolyl]ethanediamide

Conditions	Yield
With sodium ethanolate In toluene at 120℃; for 12h; Temperature; Time;	86.5%

Upstream product

• 120067-83-6 5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile 
• 7722-84-1 dihydrogen peroxide 
• 39885-50-2 2-chloro-4-(trifluoromethyl)aniline 
• 328-84-7 1,2-dichloro-4-(trifluoromethyl)benzene 
• 24279-39-8 2,6-dichloro-4-(trifluoromethyl)aniline 
• 34642-42-7 trifluoromethanesulfinic acid 
• 120068-79-3 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole 
• 2926-29-6 Langlois reagent 
• 41804-89-1 potassium triflinate 
• 20621-29-8 trifluoromethylsulfinyl chloride 
• 2840-22-4 dimethylamine p-toluenesulfonate 
• 120067-94-9 5-amino-3-bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole 
• 7446-09-5 sulfur dioxide 
• 208652-17-9 5-amino-4-trifluoromethylsulfinyl-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-thiocarbamoylpyrazole 

Downstream Products

• 205650-65-3 MB 46513 
• 209248-72-6 5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazole-4-sulfonic acid 
• 205650-69-7 fipronil amide 
• 379215-14-2 triethylamine salt of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-5-(ethoxyacetamido)pyrazole 
• 209966-79-0 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfinyl-1H-pyrazole-3-carboximidic acid methyl ester 
• 1192822-71-1 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-(prop-2-yn-1-ylamino)-4-((trifluoromethyl)sulfinyl)-1H-pyrazole-3-carbonitrile 

Relevant articles and documents

Preparation method of trifluoromethyl sulfinyl chloride

The invention relates to a preparation method of trifluoromethyl sulfinyl chloride. The preparation method does not need to use a toxic reagent, namely thiophosgene, does not need to be further oxidized, and has the advantages of simple production process and low cost. The trifluoromethyl sulfinyl chloride is prepared from bis(trifluoromethyl) disulfide, a chlorination reagent and an oxidizing agent in a solvent by a one-pot method, the weight ratio of the solvent to the bis(trifluoromethyl) disulfide is (1: 1)-(500: 1), the temperature of the chlorination reaction is -30 DEG C to 80 DEG C, and the temperature of the oxidation reaction is -30 DEG C to 30 DEG C. The preparation method has the advantages that the preparation of the trifluoromethyl sulfinyl chloride does not need to use a toxic reagent, namely thiophosgene, further oxidation is not needed, meanwhile, the production process is simple, the conversion rate is high, and the production cost is low.

Method for preparing fipronil (by machine translation)

The invention relates to a simple and feasible, economical and reasonable,pair equipment has no corrosivity, selectivity and fewer byproducts, and a preparation method, of fipronil has a structural formula of : The compound (is prepared by oxidizing MP) with a persulphated compound under the conditions of chlorohydrocarbon solvent for short, and a target product fipronil, (:) is obtained by oxidation of the persulphated compound. . (by machine translation)

Preparation method of trifluoromethylsulfinyl halide (by machine translation)

The invention relates to a trifluoromethylsulfinyl halide (chemical formula of F. 3 Process CSOX) of, This compound is used as a pesticide, for the preparation of pesticides and fine chemicals, in particular for preparing insecticide fipronil, and its preparation process :1) trichloromethyl thionyl chloride, i.e. Cl3 Reaction of CSCl with oxidant gives trichloromethyl sulfinyl chloride, (Cl)3 CSOCl;2) Trichloromethyl sulfinyl chloride Cl3 Reaction of CSOCl) with fluoride to give trifluoromethanesulphonyl halide, i.e. F3 CSOX. Has the advantage: that the preparation of trifluoromethylsulfinyl halide avoids the low boiling, highly toxic starting materials and intermediates, namely trifluoromethyl sulfachloride and di (trifluoromethyl) bisulfide, has the advantages, of simple, efficient, safe; convenience and the like, and uses cheap and readily available raw material trichloromethyl sulfur chloride or a mixture, thereof to reduce manufacturing cost. (by machine translation)

A PROCESS FOR SYNTHESIS OF FIPRONIL

The present disclosure relates to a process for the synthesis of Fipronil which is a broad spectrum insecticide (I). The process of the present disclosure provides fipronil with a yield in the range of 75% to 90% and purity in the range of 95% to 97%. By the process of the present disclosure, the amount of sulfone impurity i.e., 5-amino- 1 -(2, 6-dichloro-4-trifluoromethylphenyl)-3-cyano- 4-trifluoro methylsulfonyl pyrazole in fipronil observed is in the range of 0 % to 0.5 %.

Synthetic method of fipronil and analogues thereof

The invention discloses a method for synthesizing fipronil and analogues thereof. The fipronil and analogues thereof are shown as a formula (I). The synthesis method comprises the following steps: (a) mixing a thioether compound shown as a formula (II) with trichloroacetic acid and an aprotic organic solvent; (b) adding hydrogen peroxide into the mixture obtained in the step (a), and carrying out oxidation reaction, so as to obtain fipronil as shown in a formula (I) and analogues thereof; the substituents in the formula (I) and the formula (II) are defined in the specification. The novel synthetic method is simple in condition and easy for industrial production.

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.

Method for preparing high-purity fipronil

The invention relates to a preparation method of high-purity pesticide fipronil with the content of 98-99%. The preparation method specifically comprises the following steps: firstly adopting low-content 93-95% 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl) pyrazol to prepare 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl) pyrazol with the content up to 99.8% by selecting an appropriate reducing agent, and then enabling reaction with 98% trifluoromethyl sulfinyl chloride to obtain the fipronil of which the content can reach 98%-99%. Therefore, the preparation method solves the preparation problem of high-purity fipronil, the process route that the high-content fipronil is unlikely to be obtained by using the raw material of low-content fipronil to purify is avoided, and the disadvantages existing in an existing preparation technology are overcome. The raw materials adopted in the whole synthesis and purification method are easily obtained, the process conditions are simple and convenient, and the product is excellent in quality.

High-purity fipronil preparation method

The invention provides a high-purity fipronil preparation method. The method includes: under a micro vacuum condition, sequentially adding trifluoromethyl sulfinyl chloride, 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole, catalyst trimethylbenzyl ammonium chloride and solvent dichloroethane into a reaction kettle, adding trifluoromethyl sulfinyl chloride again after reaction for1-2h at 35-45 DEG C, continuing thermal reaction for 9-12h, adding reaction liquid into water, standing for layering, centrifugally filtering, distilling filtrate to recover dichloroethane for recycling and reusing, adding a filter cake A into mixed solvent, heating to 85-90 DEG C, stirring to dissolve completely, cooling for crystallization, centrifugally separating, and drying a filter cake B to obtain fipronil. A fipronil preparation process is simple and easy in operation; by mixed solvent recrystallization for fipronil purification, high fipronil yield and purity and uniformity in product particle size are realized.

A synthetic fipronil method

The invention relates to a method for synthesis of high-purity fipronil; with 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole and trifluoromethylsulphinyl chloride as raw materials, an acid-binding agent and a solvent are added, a reaction is carried out, through azeotropic distillation for water removal, and adopting of a drying agent, a dehydration agent or a reagent which can be subjected to a reaction with water, the high-purity fipronil is prepared through re-crystallization purification. Compared with the prior art, the method strictly controls the water content in the reaction system so as to reduce the consumption amount of the raw materials, reduce generation of by-products, increase the reaction yield and reduce environmental pollution.

NOXIOUS ARTHROPOD CONTROL AGENT CONTAINING AMIDE COMPOUND

An object of the present invention is to provide a compound having the controlling activity on a noxious arthropod, and a noxious arthropod controlling agent containing an amide compound of formula (I): wherein X represents a nitrogen atom or a CH group, p represents 0 or 1, A represents a tetrahydrofuranyl group or the like, R1, R2, R3, R4, R5, R6 and R7 represent a hydrogen atom or the like, n represents 1 or 2, Y represents an oxygen atom or the like, m represents any integer of 0 to 7, and Q represents a C1-8 chain hydrocarbon group optionally having a phenyl group or the like, has the excellent noxious arthropod controlling effect.