181587-01-9

Basic information

• Product Name: ETHIPROLE
• Synonyms: 5-Amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(ethylsulfinyl)-1H-pyrazole-3-carbonitrile;5-Amino-1-[2,6-Dichloro-4-(trifluoromethyl)phenyl]-4-(ethylsulfinyl)pyrazole-3-carbonitrile;5-AMINO-1-(2,6-DICHLORO-ALPHA,ALPHA,ALPHA-TRIFLUORO-P-TOLYL)-4-(ETHYLSULFINYL)PYRAZOLE-3-CARBONITRILE;ETHIPROLE;5-amino-1-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-4-(ethylsulfinyl)pyrazole-3-carbonitrile;ethiprole (bsi, pa iso);rpa 107382;ETHIPROLE STANDARD
• CAS NO: 181587-01-9
• Molecular Formula: C₁₃H₉Cl₂F₃N₄OS
• Molecular Weight: 397.2
• EINECS: 446-630-3
• Mol File: 181587-01-9.mol
• Article Data: 5

Chemical Properties

• Melting Point: ~174°
• Boiling Point: 563.464 °C at 760 mmHg
• Flash Point: 294.572 °C
• Appearance: /
• Density: 1.691 g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.655
• Storage Temp.: 0-6°C
• PKA: -3.91±0.20(Predicted)
• Water Solubility: 9.2mg/L at 20℃
• CAS DataBase Reference: ETHIPROLE(CAS DataBase Reference)
• NIST Chemistry Reference: ETHIPROLE(181587-01-9)
• EPA Substance Registry System: ETHIPROLE(181587-01-9)

Safety Data

• Hazard Codes: T,N,Xn
• Statements: 23/24/25-48/25-50/53-48/22
• Safety Statements: 36/37-45-60-61
• RIDADR: UN2811 6.1/PG 3
• WGK Germany: 3
• Hazardous Substances Data: 181587-01-9(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 181587-01-9 differently. You can refer to the following data:
1. Ethiprole is a phenylpyrazole based insecticide used in rice ecosystem on Trichogramma japonicum, and egg parasitoid of rice lepidopterans.
2. Insecticide for chewing and sucking insects.

General Description

Ethiprole, is a pyrazole insecticide, which can be used to control a broad spectrum of insects(1), like those with chewing and sucking mouthparts that tend to damage the plants. It can be mainly used for rice and cotton cultivation.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C13H9Cl2F3N4OS/c1-2-24(23)11-9(5-19)21-22(12(11)20)10-7(14)3-6(4-8(10)15)13(16,17)18/h3-4H,2,20H2,1H3

Synthetic route

5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylthio-1H-pyrazole-3-carbonitrile (120068-56-6) → ethiprole (181587-01-9)

Conditions	Yield
With dihydrogen peroxide; trifluoroacetic acid In dichloromethane at 10 - 12℃; for 4h;	95%
With dihydrogen peroxide; acetic acid at 30℃; for 10h; Time; Temperature; Reagent/catalyst;

4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] (130755-46-3) → ethiprole (181587-01-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 89 percent / Na2S2O4; Na2HPO4 / dimethylformamide; H2O / 1 h / 20 °C 2: 95 percent / CF3COOH; aq. H2O2 / CH2Cl2 / 4 h / 10 - 12 °C View Scheme

ethiprole (181587-01-9) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]4(ethylsulfonyl)-1H-pyrazole-3-carbonitrile (120068-68-0)

Conditions	Yield
With potassium permanganate; magnesium sulfate In acetone at 20℃;	93%

2,6-Pyridinedicarbonyl dichloride (3739-94-4) + ethiprole (181587-01-9) → N,N'-bis[3-cyano-4-ethylsulfinyl-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazolyl]-2,6-pyridinedicarboxamide

Conditions	Yield
With triethylamine at 130℃; for 6h;	82.4%

methanesulfonyl chloride (124-63-0) + ethiprole (181587-01-9) → C14H11Cl2F3N4O3S2

Conditions	Yield
With pyridine at 20℃;	80.1%

ethiprole (181587-01-9) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]4(ethylsulfinyl)-1H-pyrazole-3-carboxamide (623151-90-6)

Conditions	Yield
With sodium hydroxide In ethanol at 25℃; for 4h;	72%

dimethyl cis-but-2-ene-1,4-dioate (624-48-6) + ethiprole (181587-01-9) → methyl-6-chloro-2-cyano-3-(ethylsulfinyl)-5-(2-methoxy-2-oxoethyl)-8-(trifluoromethyl)-4,5-dihydropyrazolo[1,5-a]quinazoline-5-carboxylate

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃; for 3h;	72%

3-oxo-2,3-dihydrobenzo[b]furan (7169-34-8) + ethiprole (181587-01-9) → 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-cyano-5-[(2,3-dihydro-1-benzofuran-3-ylidene)amino]-4-ethylsulfinylpyrazole

Conditions	Yield
With toluene-4-sulfonic acid In toluene for 1h; Molecular sieve; Microwave irradiation; Sealed tube;	71%

ethiprole (181587-01-9) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylthio-1H-pyrazole-3-carbonitrile (120068-56-6)

Conditions	Yield
With trifluoroacetic anhydride; sodium iodide In acetone at 0 - 20℃; for 8h;	64%

1-bromocyclohexane (108-85-0) + ethiprole (181587-01-9) → N-5-cyclohexylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-ethylsulfinyl-1H-pyrazole

Conditions	Yield
With potassium hydroxide In tetrahydrofuran at 20℃; for 3h; Sonication; Microwave irradiation; Heating;	9.3%

ethiprole (181587-01-9) → C13H10Cl2F3N3O2S (209966-60-9)

ethiprole (181587-01-9) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylsulfinyl-N-amino-1H-pyrazole-3-carboximidamide

ethiprole (181587-01-9) → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-ethylsulfinyl-1H-pyrazole-3-carboximidamide (209965-85-5)

2-chloroethyl ethyl sulfone (25027-40-1) + ethiprole (181587-01-9) → 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[2-(ethylthio)ethylamino]-4-ethylsulfinyl-1H-pyrazole-3-carbonitrile (209966-90-5)

2-chloroethyl methyl sulfone (50890-51-2) + ethiprole (181587-01-9) → 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[2-(methylthio)ethylamino]-4-ethylsulfinyl-1H-pyrazole-3-carbonitrile (209966-88-1)

Conditions	Yield
Stage #1: ethiprole With potassium hydride In DMF (N,N-dimethyl-formamide) at 4℃; for 0.666667h; Stage #2: 2-chloroethyl methyl sulfone In DMF (N,N-dimethyl-formamide) at 4 - 50℃; for 72h;

dimethyl 2-bromosuccinate (760-90-7) + ethiprole (181587-01-9) → methyl-6-chloro-2-cyano-3-(ethylsulfinyl)-5-(2-methoxy-2-oxoethyl)-8-(trifluoromethyl)-4,5-dihydropyrazolo[1,5-a]quinazoline-5-carboxylate

Conditions	Yield
With potassium carbonate In acetonitrile at 50℃;

Upstream product

• 130755-46-3 4,4'-dithiobis [5-amino-3-cyano-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-1H-pyrazole] 
• 120068-56-6 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylthio-1H-pyrazole-3-carbonitrile 

Downstream Products

• 209966-88-1 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[2-(methylthio)ethylamino]-4-ethylsulfinyl-1H-pyrazole-3-carbonitrile 
• 209966-90-5 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[2-(ethylthio)ethylamino]-4-ethylsulfinyl-1H-pyrazole-3-carbonitrile 
• 209965-85-5 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-N-hydroxy-4-ethylsulfinyl-1H-pyrazole-3-carboximidamide 
• 209966-60-9 C₁₃H₁₀Cl₂F₃N₃O₂S 
• 623151-90-6 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]4(ethylsulfinyl)-1H-pyrazole-3-carboxamide 
• 120068-68-0 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]4(ethylsulfonyl)-1H-pyrazole-3-carbonitrile 
• 120068-56-6 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-ethylthio-1H-pyrazole-3-carbonitrile 

Relevant articles and documents

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.

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.

Pesticidal 5-amino-4-ethylsulfinyl-1-arylpyrazoles

The invention relates to 1-arylpyrazoles of formula (I) STR1 wherein X, Y and R1 are as defined in the description, and to their use as pesticides.