Title of Invention	"N-PHENYLPYRAZOLE DERIVATIVE INSECTICIDOL COMPOUNDS"
Abstract	The present invention provides a series of N-phenylpyrazole derivative insecticide compounds, in particularly provides six insecticide compounds represented by formula (I)-(VI). As an insecticide, N-phenylpyrazole derivative has good effect on a wide spectrum of insects, and is highly sensitive to resistant insects. Being compared with the effects of commercial insecticide Regent, the testing results of compound (1) and (IV) demonstrated that the effects of the compounds of the present invention are equal to or higher than that of commercial insecticide

Title of Invention

"N-PHENYLPYRAZOLE DERIVATIVE INSECTICIDOL COMPOUNDS"

Abstract

The present invention provides a series of N-phenylpyrazole derivative insecticide compounds, in particularly provides six insecticide compounds represented by formula (I)-(VI). As an insecticide, N-phenylpyrazole derivative has good effect on a wide spectrum of insects, and is highly sensitive to resistant insects. Being compared with the effects of commercial insecticide Regent, the testing results of compound (1) and (IV) demonstrated that the effects of the compounds of the present invention are equal to or higher than that of commercial insecticide

Full Text	Field of Research: This invention refers to kind of pylazole farm insecticide Background of the invention: In 1989, a kind of pyrazole broad-spectrum insecticide that has the trade name "Regent" had been developed in Rhone-Poulenc in France Such compound is a kind of broad-spectrum insecticide having excellent effect on many injurious insects, e g it displayed extremely high susceptihbily to the injurious insects which belong to Hemiptera, Lepidoptera, Thysanoptera and Coleoptera, etc. and to the injurious insects which are resistant to cyclopentadiene, chrysanthemate, aminoformate Molecule structure formula of the "Regent" is (Formula Removed) In 1999, a series of synthesis of "Regent" derivatives were introduced in US Patent 5916618 applied by Rhone-Poulenc Agncultuie Ltd Trifluoro methyl sulfonyl, tnfluoro methyl mercapto etc compounds are derived chiefly by replacing the ammo on heterocycle with acetylamino, chloracetylamino Trifluoro methyl subsulfonyl The structure of the compound in US Patent 6015910 applied by Rhone-Poulenc Agncultuie Ltd in France in 2000 shows as following (Formula Removed) Some charactensties of such compound have exceeded "Regent" The absorbing activity to cotton aphid is LC5o=0 21ppm, while that of "Regent" is 11 3ppm, and the absorbing activity to sorghum aphid is LC5o=0 6ppm, while that of "Regent" is > 20ppm At present, with the stricter and stricter requirement from environment, the old farm insecticides, especially some insecticides that can't be adapted to circumstance and are poisonous to human and animal's security (e g highly toxic organic phosphorus insecticide) should be replaced, so new breeds of insecticide having high activity, good environment harmomousness and new mode of action must be developed to promote development of home insecticide industry and chemical prevention of farm crop, solve renewing/changing of insecticide breeds, and reduce pressure to environment Invention Content: The highly active insecticide in this invention is the derivatives of N-phenylpyrazole They have the following general structure formula (Formula Removed) Wherein NH■ (Formula Removed) The structures of new compounds are shown in details as following The combination methods of the previous new compounds are shown as following (1) The combination of 5-amino-3-cyan-l- (2, 6-dichloro-4-tnfluoromethylphenyl) pyrazole (Formula Removed) The reactions include firstly, obtaining diazol by reacting 2,6-dichloro-4-trifluoromethylanihne with sodium nitrite, then reacting the outcome with 2,3-dicyan ethyl to form the end product through ammonia water close cycle, then (Formula Removed) (2)Combination of compound (I) (Formula Removed) The above reaction was carried through in tetrahydrofuran solvent and the compound (I) can be gotten through reflux reaction with sodium hydride as acid-binding (3) Combination of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) -4-ethyl phrazolone (Formula Removed) The thiocyanate hpo compound was obtained by reaction of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) phrazolone with sodium thiocyanate (Formula Removed) (4) Combination of compound (II) (Formula Removed) The above reaction was carried through in tetrahydrofuran solvent and the compound (II) can be obtained through reflux reaction with sodium hydride as acid-binding (5) Combination of compound (III) (Formula Removed) (6) Combination of compound (IV) (Formula Removed) This reaction was carried out in two stages Firstly, the amino substitute is obtained by the reaction with chloral, under effect of catalyst on toluenesulfomc acid and reflux in toluene solution, secondly the compound (IV) is gotten by the reducing of sodium borohydnde Compaied with foreign product "Regent", the insecticide compounds in this invention have the same effect to kill insects or better than Taking compound (I), (IV) as examples, the testing lesults show as following Table Contrast test results of 72 hours drug action to three kinds of army worm larva (Table Removed) Specific Preparation Way Example 1 To a solution of Regent (95 g) in tetrahydrofuran (100 ml), methylallylchonne (2 5 g) and sodium hydride (1 g) were added Under reflux for 22 hours, banana liquid (200ml) was added to extract The oil layer is washed and precipitated by 2> Example 2 To a solution of 5-amino-3-cyan-l- (2,6 dichloride-4-tnfluoromethylphenyl) -4-ethyl phrazolone (2 g) in tetrahydrofuran (60 ml), sodium hydride (0 5 g) and methylallyl chlorine (1 g) were added The solution was heated under reflux for 8 hours, cooled to room temperature and a further addition of ethyl acetate (100 ml) made to extract The Oil layer is washed twice by watei and precipitated at reduced pressure, then compound (II) (0 5 g) was gotten by column partition chromatography (Positive ethane banana hqmd=2 1) of the still residue Melting point 123 C-125 C The structure is confirmed by H-NMR Example 3 To a solution of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) -4-ethyl oxygen thiosulfonic pyrazole (2 5 g) in tetrahydrofuran (100 ml), sodium hydride (0 5 g) and chlorine methylallyl (1 g) were added The solution was heated under reflux for 4 hours, cooled to room temperature and a further addition of banana liquid (100 ml) made to extract The Oil layer is washed twice by water and precipitated at reduced pressure, then product (0 5 g) was gotten by column partition chromatography (Positive ethane banana hquid=2 1) of the still residue Finally, the compound (III) (0 1 g) was obtained after recrystalhzation Melting point 140 C - 144 C The structure is confirmed by H-NMR Example 4 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) -4- ethyl oxygen thiosulfonic pyrazole (5 g), methylbenzene (150 ml), para-toluenesulfonic (1 g) and chloral (3 5 g) were put into reaction bottle The mixture was heated under reflux for 5 hours, cooled, and washed twice by water (200 ml) The still residues (6 5 g) were precipitated at reduced pressure Then, the precipitation and sodium borohydnde (1 2 g), and carbinol (100 ml) were put into reaction bottle to react for 2 hours at room temperature and hydrochloric acid was added to balance Finally 200ml water was added to dilate and banana liquid (100 ml) was added to extract The Oil layer will be washed by 2> After the nitrosyl-Spint acid made from sodium nitrite (7 g) and dense sulfuric acid (27 5 ml) diluted by acetic acid, 2,6-dichlonde-4- trifluoromethylamline (21 2 g) and acetic solution (50 ml) were added After this mixture was heated to 55 C and reacted for 20 minutes, poured into the stiring solution (14 0 g) of 2,6-dicyan ethyl propionate in the acetic and water After 15 minutes, 200 ml water was added to laminate delaminate and dichloromethane was used to extract water layer After the reaction of oil layer with ammonia water (20 ml) for 2 hours, 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethomethylphenyl) pyrazole (22 g) was obtained by routine handling Melting point 140°C-142°C The structure is confirmed by H-NMR Example 6 Methyl benzyl (50 ml), 5-amino-3-cyan-l-(2,6 dichloride-4-tnfluoromethylphenyl) pyrazole (16 6 g) and catalyst were put into reaction bottle The mixture was stirred and cooled to 5°C Then chlorine tnfluoro methyl subsulfonyl (10 9 g) was added to react with at 5 C for 1 hour and at 50 C for 8 hours, cooled to room temperature and 100ml water was added After filtered and washed, the product "Regent" (19 7 g) was gotten Melting point 196°C-198°C Example 7 Dissolved sodium rhodanate (4 05 g) into carbinol (75 ml), cooled to -78 D and carbinol solution (10 ml) of bromine (5 g) was dropped into it After dropping, again carbinol solution (50 ml) of 5-amino-3-cyan-l- (2,6 dichloride-4-tnfluorometho methyl phenyl) pyrazole (5 g) was dropped at same temperature 250 ml water was added when the reaction was finished After filtered and dried, intermediate substitution rhodanicester was gotten Then ethyl-iodide and water solution (10 ml) of caustic potash (0 92 g) were added into industrial alcohol solution (50 ml) of the intermediate (3 1 g) Finally, 180 ml water was added when the reaction was finished After filtered, the product 5- amino-3-cyan-l- (2,6 dichloride-4-tnfluorometho methyl phenyl)-4- tnfluorometho ethyl thiosulfonic pyrazole was obtained Melting point 159°C-163°C. I claim: 1. An N-phenylpyrazole derivative insecticide compound of formula: (Formula Removed) wherein Rl is selected from a list comprising of (Formula Removed) and R.2 is selected from a list comprising of (Formula Removed) 2. An N-phenylpyrazole derivative insecticide compound as claimed in claim 1 selected from (Formula Removed)

Full Text

Field of Research:
This invention refers to kind of pylazole farm insecticide
Background of the invention:
In 1989, a kind of pyrazole broad-spectrum insecticide that has the trade name "Regent" had been developed in Rhone-Poulenc in France Such compound is a kind of broad-spectrum insecticide having excellent effect on many injurious insects, e g it displayed extremely high susceptihbily to the injurious insects which belong to Hemiptera, Lepidoptera, Thysanoptera and Coleoptera, etc. and to the injurious insects which are resistant to cyclopentadiene, chrysanthemate, aminoformate Molecule structure formula of the "Regent" is
(Formula Removed)
In 1999, a series of synthesis of "Regent" derivatives were introduced in US Patent 5916618 applied by Rhone-Poulenc Agncultuie Ltd Trifluoro methyl sulfonyl, tnfluoro methyl mercapto etc compounds are derived chiefly by replacing the ammo on heterocycle with acetylamino, chloracetylamino Trifluoro methyl subsulfonyl
The structure of the compound in US Patent 6015910 applied by Rhone-Poulenc Agncultuie Ltd in France in 2000 shows as following
(Formula Removed)
Some charactensties of such compound have exceeded "Regent" The absorbing activity to cotton aphid is LC5o=0 21ppm, while that of "Regent" is 11 3ppm, and the absorbing activity to sorghum aphid is LC5o=0 6ppm, while that of "Regent" is >
20ppm
At present, with the stricter and stricter requirement from environment, the old farm insecticides, especially some insecticides that can't be adapted to circumstance and are poisonous to human and animal's security (e g highly toxic organic phosphorus insecticide) should be replaced, so new breeds of insecticide having high activity, good environment harmomousness and new mode of action must be developed to promote development of home insecticide industry and chemical prevention of farm crop, solve renewing/changing of insecticide breeds, and reduce pressure to environment
Invention Content: The highly active insecticide in this invention is the derivatives of N-phenylpyrazole They have the following general structure formula
(Formula Removed)
Wherein NH■
(Formula Removed)

The structures of new compounds are shown in details as following
The combination methods of the previous new compounds are shown as following (1) The combination of 5-amino-3-cyan-l- (2, 6-dichloro-4-tnfluoromethylphenyl) pyrazole
(Formula Removed)
The reactions include firstly, obtaining diazol by reacting 2,6-dichloro-4-trifluoromethylanihne with sodium nitrite, then reacting the outcome with 2,3-dicyan ethyl to form the end product through ammonia water close cycle, then
(Formula Removed)
(2)Combination of compound (I)
(Formula Removed)
The above reaction was carried through in tetrahydrofuran solvent and the compound (I) can be gotten through reflux reaction with sodium hydride as acid-binding
(3) Combination of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl)
-4-ethyl phrazolone
(Formula Removed)
The thiocyanate hpo compound was obtained by reaction of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) phrazolone with sodium thiocyanate
(Formula Removed)
(4) Combination of compound (II)
(Formula Removed)
The above reaction was carried through in tetrahydrofuran solvent and the compound (II) can be obtained through reflux reaction with sodium hydride as acid-binding
(5) Combination of compound (III)
(Formula Removed)
(6) Combination of compound (IV)
(Formula Removed)
This reaction was carried out in two stages Firstly, the amino substitute is obtained by the reaction with chloral, under effect of catalyst on toluenesulfomc acid and reflux in toluene solution, secondly the compound (IV) is gotten by the reducing of sodium borohydnde
Compaied with foreign product "Regent", the insecticide compounds in this invention have the same effect to kill insects or better than Taking compound (I), (IV)
as examples, the testing lesults show as following
Table Contrast test results of 72 hours drug action
to three kinds of army worm larva
(Table Removed)
Specific Preparation Way Example 1
To a solution of Regent (95 g) in tetrahydrofuran (100 ml), methylallylchonne (2 5 g) and sodium hydride (1 g) were added Under reflux for 22 hours, banana liquid (200ml) was added to extract The oil layer is washed and precipitated by 2> Example 2
To a solution of 5-amino-3-cyan-l- (2,6 dichloride-4-tnfluoromethylphenyl) -4-ethyl phrazolone (2 g) in tetrahydrofuran (60 ml), sodium hydride (0 5 g) and methylallyl chlorine (1 g) were added The solution was heated under reflux for 8 hours, cooled to room temperature and a further addition of ethyl acetate (100 ml) made to extract The Oil layer is washed twice by watei and precipitated at reduced pressure, then compound (II) (0 5 g) was gotten by column partition chromatography (Positive ethane
banana hqmd=2 1) of the still residue Melting point 123 C-125 C The structure is confirmed by H-NMR
Example 3
To a solution of 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) -4-ethyl oxygen thiosulfonic pyrazole (2 5 g) in tetrahydrofuran (100 ml), sodium hydride (0 5 g) and chlorine methylallyl (1 g) were added The solution was heated under reflux for 4 hours, cooled to room temperature and a further addition of banana liquid (100 ml) made to extract The Oil layer is washed twice by water and precipitated at reduced pressure, then product (0 5 g) was gotten by column partition chromatography (Positive ethane banana hquid=2 1) of the still residue Finally, the compound (III) (0 1 g) was obtained after recrystalhzation Melting point 140 C - 144 C The structure is confirmed by H-NMR
Example 4
5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethylphenyl) -4- ethyl oxygen thiosulfonic pyrazole (5 g), methylbenzene (150 ml), para-toluenesulfonic (1 g) and chloral (3 5 g) were put into reaction bottle The mixture was heated under reflux for 5 hours, cooled, and washed twice by water (200 ml) The still residues (6 5 g) were precipitated at reduced pressure Then, the precipitation and sodium borohydnde (1 2 g), and carbinol (100 ml) were put into reaction bottle to react for 2 hours at room temperature and hydrochloric acid was added to balance Finally 200ml water was added to dilate and banana liquid (100 ml) was added to extract The Oil layer will be washed by 2> After the nitrosyl-Spint acid made from sodium nitrite (7 g) and dense sulfuric acid (27 5 ml) diluted by acetic acid, 2,6-dichlonde-4- trifluoromethylamline (21 2 g) and

acetic solution (50 ml) were added After this mixture was heated to 55 C and reacted for 20 minutes, poured into the stiring solution (14 0 g) of 2,6-dicyan ethyl propionate in the acetic and water After 15 minutes, 200 ml water was added to laminate delaminate and dichloromethane was used to extract water layer After the reaction of oil layer with ammonia water (20 ml) for 2 hours, 5-amino-3-cyan-l- (2,6 dichlonde-4-tnfluoromethomethylphenyl) pyrazole (22 g) was obtained by routine handling Melting point 140°C-142°C The structure is confirmed by H-NMR
Example 6
Methyl benzyl (50 ml), 5-amino-3-cyan-l-(2,6 dichloride-4-tnfluoromethylphenyl) pyrazole (16 6 g) and catalyst were put into reaction bottle The mixture was stirred and cooled to 5°C Then chlorine tnfluoro methyl subsulfonyl (10 9 g) was added to react with at 5 C for 1 hour and at 50 C for 8 hours, cooled to room temperature and 100ml water was added After filtered and washed, the product "Regent" (19 7 g) was gotten Melting point 196°C-198°C
Example 7
Dissolved sodium rhodanate (4 05 g) into carbinol (75 ml), cooled to -78 D and carbinol solution (10 ml) of bromine (5 g) was dropped into it After dropping, again carbinol solution (50 ml) of 5-amino-3-cyan-l- (2,6 dichloride-4-tnfluorometho methyl phenyl) pyrazole (5 g) was dropped at same temperature 250 ml water was added when the reaction was finished After filtered and dried, intermediate substitution rhodanicester was gotten Then ethyl-iodide and water solution (10 ml) of caustic potash (0 92 g) were added into industrial alcohol solution (50 ml) of the intermediate (3 1 g) Finally, 180 ml water was added when the reaction was finished After filtered, the product 5- amino-3-cyan-l- (2,6 dichloride-4-tnfluorometho methyl phenyl)-4- tnfluorometho ethyl thiosulfonic pyrazole was obtained Melting point 159°C-163°C.

I claim:
1. An N-phenylpyrazole derivative insecticide compound of formula:
(Formula Removed)
wherein Rl is selected from a list comprising of
(Formula Removed)
and R.2 is selected from a list comprising of
(Formula Removed)
2. An N-phenylpyrazole derivative insecticide compound as claimed in claim 1 selected
from (Formula Removed)

Documents:

467-delnp-2005-abstract.pdf

467-delnp-2005-claims.pdf

467-delnp-2005-complete specification (as files).pdf

467-delnp-2005-complete specification (granted).pdf

467-delnp-2005-correspondence-po.pdf

467-delnp-2005-description (complete).pdf

467-delnp-2005-form-1.pdf

467-delnp-2005-form-18.pdf

467-delnp-2005-form-2.pdf

467-delnp-2005-form-3.pdf

467-delnp-2005-form-5.pdf

467-delnp-2005-gpa.pdf

467-delnp-2005-pct-210.pdf

467-delnp-2005-pct-409.pdf

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Patent Number

240659

Indian Patent Application Number

467/DELNP/2005

PG Journal Number

22/2010

Publication Date

28-May-2010

Grant Date

21-May-2010

Date of Filing

07-Feb-2005

Name of Patentee

WANG ZHENGQUAN

Applicant Address

NO. 101 XINANYAO, JINZHOU, DALIAN CITY, 116100 LIAONING PROVINCE, CHINA.

Inventors:

#	Inventor's Name	Inventor's Address
1	WANG ZHENGQUAN	NO. 101 XINANYAO, JINZHOU, DALIAN CITY, 116100 LIAONING PROVINCE, CHINA.
2	LI YANLONG	NO. 101 XINANYAO, JINZHOU, DALIAN CITY, 116100 LIAONING PROVINCE, CHINA.
3	GUO TONGJUAN	NO. 101 XINANYAO, JINZHOU, DALIAN CITY, 116100 LIAONING PROVINCE, CHINA.
4	SONG YINGXIA	NO. 101 XINANYAO, JINZHOU, DALIAN CITY, 116100 LIAONING PROVINCE. CHINA.

PCT International Classification Number

C07D 231/44

PCT International Application Number

PCT/CN2003/00343

PCT International Filing date

2003-05-12

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	02128312.5	2002-07-30	China