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Fipronil, ethiprole and synthesizing method for derivative thereof

A synthetic method and technology of trifluoromethylphenyl, applied in the field of synthesizing 1-phenyl-3-cyano-5-aminopyrazole derivatives, can solve the problem of low yield, complex operation and treatment, and inability to realize industrial production And other issues

Inactive Publication Date: 2008-04-30
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The problems encountered in the synthesis of ethiprole by the above method are that the conditions are too harsh, the operation is too complicated, the yield is low, and industrial production cannot be realized.

Method used

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  • Fipronil, ethiprole and synthesizing method for derivative thereof
  • Fipronil, ethiprole and synthesizing method for derivative thereof
  • Fipronil, ethiprole and synthesizing method for derivative thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Preparation of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethanesulfinyl-5-amino-pyrazole

[0027] In ionic liquid [Bmim]PF 6(20mL) and acetonitrile (20mL), add 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthio Pyrazole (2.15g, 5mmol), ruthenium trichloride (9.6mg, 0.05mmol), pyridine (1mL), add acetonitrile solution (10mL) containing trichloroisocyanuric acid (1.16g, 5mmol) dropwise, 20 minutes Finish. React at 40~50℃ for 1 hour, after the reaction is over, use NaHSO at 20℃ 3 The excess trichloroisocyanuric acid was quenched, ice water (200 mL) was added and stirred, the product was filtered, the ionic liquid was recovered and reused, and the colorless target product was obtained by column chromatography with a yield of 71% and no oxidation by-products.

[0028] The following are the physical data and detection data of 1-(2,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethanesulfinyl-5-amino-pyrazole.

[0029] Colorl...

Embodiment 2

[0035] The preparation reaction substrate of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-ethylsulfinyl-5-amino-pyrazole was changed to 1-(2 ,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-4-ethylmercapto-5-amino-pyrazole, the synthesis method is similar to that in Example 1, and the yield is 75%

[0036] The following are the physical and detection data of 1-(2,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-4-ethylsulfinyl-5-amino-pyrazole.

[0037] Colorless crystal, melting point: 179-181℃

[0038] IR (KBr): 3423, 3336, 3240, 2251, 1634, 1568, 1400, 1319, 1135, 875, 818cm -1 .

[0039] 1 H NMR(300MHz, C 3 D 6 O): δ = 8.12 (s, 2H), 6.36 (s, 2H), 3.21 (q, J = 7.4 Hz, 2H), 1.29 (t, J = 7.4 Hz, 3H).

[0040] 13 C NMR(75MHz, C 3 D 6 O): δ=7.0(1C), 51.5(1C), 100.0(1C), 111.2(1C), 122.4(q, J=271.5Hz, 1C), 126.3(1C), 126.6(2C), 126.7(2C) ), 134.4(q, J=34.1Hz, 1C), 134.8(1C), 136.6(1C).

[0041] 19 F NMR(220MHz, C 3 D 6 O): δ=-63.6(s, 3F).

[0042] In the same way, replace the substrate...

Embodiment 3

[0053] K 2 CO 3 (0.69g, 5mmol) was added to containing 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-5-amino-4-pyrazolyl disulfide (2g, 2.5 In a solution of DMF (30ml) in mmol), ethyl iodide (6mmol) was injected into the reaction mixture, water (0.5ml) was injected, and then HOCH was added. 2 SO 2 Na(1.18g, 10mmol), react at room temperature for 1 hour, pour into ice water and stir for 20 minutes, filter to obtain 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4 -Ethylmercapto-5-aminopyrazole, the yield is 95%.

[0054] Melting point: 150~151℃.

[0055] IR (KBr): 3456, 3320, 3220, 2925, 2252, 1625, 1554, 1392, 1314, 1146, 876, 811cm -1 .

[0056] 1 H NMR(300MHz, C 3 D 6 O): δ = 8.08 (s, 2H), 6.03 (s, 2H), 2.30 (s, 3H).

[0057] 13 C NMR(75MHz, C 3 D 6 O): δ=18.9(1C), 95.1(1C), 122.5(q, J=271.1Hz, 1C), 126.38(2C), 126.42(2C), 131.4(1C), 133.7(q, J=34.0Hz , 1C), 136.5(1C), 151.2(1C).

[0058] 19 F NMR(220MHz, C 3 D 6 O): δ=-63.6(s, 3F).

[0059] Replacing sodium hydroxymethanes...

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Abstract

The invention belongs to a synthetic method for insecticide fipronil and ethiprole, as well as the derivant thereof. The invention has the method that trichloroisocyanuric acid is taken as oxidant, room temperature ion solution and methyl cyanide mixture are taken as solvent, under the existence of catalyst, chemical compound 2 is oxidized selectively to prepare chemical compound 1. Chemical compound 3 and halogenated hydrocarbon are taken as starting material, and under the existence of the catalyst, the chemical compound 2 is prepared. The method has the advantages that the operation is simple, the yield rate is good, the invention is environmentally friendly, the cost is low, etc.

Description

Technical field [0001] The present invention relates to a new method for synthesizing 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-5-aminopyrazole derivatives. Such as 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-trifluoromethylsulfinyl-5-aminopyrazole (fipronil, English name: Fipronil ); 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylsulfinyl-5-aminopyrazole (Ethiprole, English name: Ethiprole) ; 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylmercapto-5-aminopyrazole; and other 1-(2,6-dichloro- Synthesis of 4-trifluoromethyl)phenyl-3-cyano-4-alkylmercapto-5-aminopyrazole. Background technique [0002] 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-5-aminopyrazole derivatives are compounds with insecticidal activity. For example, fipronil 1-(2,6-dichloro-4trifluoromethylphenyl)-4-trifluoromethylsulfinyl-5-aminopyrazole is a highly effective insecticide that can be used to control rice , Vegetables, fruit trees, cotton and corn and other crop pests. I...

Claims

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Application Information

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IPC IPC(8): C07D231/44
Inventor 钟平汤日元张小红
Owner WENZHOU UNIVERSITY
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