WO2012034403A1 - Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof - Google Patents

Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof Download PDF

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WO2012034403A1
WO2012034403A1 PCT/CN2011/073810 CN2011073810W WO2012034403A1 WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1 CN 2011073810 W CN2011073810 W CN 2011073810W WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1
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alkyl
ih
dc
cyano
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PCT/CN2011/073810
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窦花妮
陈杰
郑昀红
许天明
邢家华
郑志文
彭伟立
许勇华
董德臻
魏优昌
孔小林
袁静
刘刚
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中化蓝天集团有限公司
浙江省化工研究院有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in positions 3 or 5
    • C07D231/22One oxygen atom attached in positions 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Abstract

Fluoromethoxypyrazole anthranilamide compounds of formula (I) or agrochemical salts thereof, as well as synthesization methods and uses thereof. The compounds of formula (I) have broad-spectrum insecticidal activities and are effective to pests of lepidopteron (such as Plutella xylostella), hemipteran (such as Aphis medicaginis), homopteran (such as Nilaoarvata lugens) and the like. Agricultural preparations including compounds of formula (I) and methods of preventing and controlling pests are involved.

Description

Instructions

Containing a difluoromethoxy-pyrazol o carboxamido benzamides, their synthesis and application Field

The present invention provides a method of o-carboxamido benzamides. Background technique

O carboxamido benzamides (Ryanodine receptor inhibitors) are developed in recent years in the control of animal pests tapered ridge insecticidally effective.

PCT Patent Application WO2003 / 015519 discloses the following compounds having pesticidal activity:

Figure imgf000003_0001

R = CF 3, Cl, Br or OCH 2 CF 3

PCT patent application WO2004 / 033468 discloses the following compounds having pesticidal activity:

Figure imgf000003_0002

PCT patent application WO2004 / 067528 discloses the following compounds having pesticidal activity:

Figure imgf000003_0003

PCT Patent Application WO2006 / 080311 discloses the following compounds having pesticidal activity:

Figure imgf000004_0001
Figure imgf000004_0002

PCT Patent Application WO2008 / 134969 discloses the following compounds having pesticidal activity:

Figure imgf000004_0003

The above PCT patent application, although all of the compounds disclosed have some similarities with the compound of the present invention, but did not contain a description with o-difluoromethoxy-pyrazole corresponds to the present invention represented by the formula (I) carboxamido benzamides. Although for controlling an invertebrate pest of many products can be purchased, but still need to be more effective, low toxicity, low cost, environmentally safe new compounds. SUMMARY

Object of the present invention to provide a novel pest control agent, can control a problem in the field of various agricultural and horticultural pests or pests parasitic on animals, with high pest at low doses control effect.

To achieve the above object, the present invention provides the following technical means:

Suitable amine compound or agriculturally the o-aminobenzoyl carboxamido containing a difluoromethoxy-pyrazole salt of a configuration represented by the formula (I),

Figure imgf000005_0001

Its towel:

A is N or CH;

R 1 is hydrogen, halo, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block groups, block groups halo, alkoxy, cyano, alkoxy group, ^ alkoxy group, an alkylthio group, on behalf of ^ alkylthio, alkylsulfonyl, alkylcarbonyl, substituting ^ alkylcarbonyl, alkoxycarbonyl, substituting ^ alkoxycarbonyl or an amino group;

R 2 is hydrogen, halo, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;

R 3 is hydrogen, alkyl or alkoxy;

R 4 is hydrogen, cyano, alkyl, alkoxy, alkylamino, ^ alkyl group, alkoxy group ^, ^ alkane amino, cyano, cycloalkyl, substituting ^ cycloalkyl, hydroxyalkyl alkyl group, an alkoxycarbonyl group, an alkoxy group, an amide group, an alkyl amide group, an amide group ^ substituted alkyl, cyano-substituted aromatic heterocyclic alkyl group or an amide group;

Or R 3 and R 4 form a ternary starting with N- attached, quaternary, five- or six-membered ring;

m is an integer of 0~4;

n is an integer of 0~4. A fluorine-containing o-methoxy-pyrazol-carboxamido benzamides as a preferred embodiment, the structure represented by formula (I) in which:

R 1 is hydrogen, halo, cyano, nitro, d-Ce-wan group, d-Ce-haloalkyl, cyano-d-Ce-alkyl, C 2 _C 6 alkenyl group,

C 2 _C 6 haloalkenyl, C 2 -C 6 block basis, C 3 -C 6 halo-block basis, (- (: 6 alkoxy, cyano dC 6 alkoxy, haloalkoxy dC 6 , d-Ce-alkylthio, d-Ce-haloalkylthio, d-Ce-alkyl sulfonyl group, a carbonyl group CFCE alkyl, haloalkyl CFCE alkylcarbonyl, (of Ce alkoxycarbonyl, substituting ^ dC 6 alkoxycarbonyl dC 6 alkyl or amino;

R 2 is hydrogen, halogen, d-Ce-alkyl, halo-d-Ce-alkyl, d-Ce alkoxy, haloalkoxy CfCe alkoxy or cyano;

R 3 is hydrogen or alkyl;

R 4 is hydrogen, cyano, d-Ce-alkyl, d-Ce-alkoxy, d-Ce-alkylamino, haloalkyl CfCe alkyl, halo CfCe alkoxy, halo (- (: 6 alkylamino group, cyano dC 6 alkyl, (: 3 _ (: 6 cycloalkyl, halo (: 3 _ (: 6 cycloalkyl, hydroxyalkyl (- (: 6 alkyl, DC 6 alkoxycarbonyl group, (^ - (: 6 alkoxy amido, alkylamido 6 DC, DC substituting ^ 6 alkyl amide group, cyano group or alkyl amide 6 DC aromatic heterocyclic group;

m is 2;

n is 1. A fluorine-containing o-methoxy-pyrazol-carboxamido benzamides as a further preferred embodiment, represented by the structural formula (I) in which:

A is N;

R 1 is hydrogen, halo, cyano, alkyl CFCE, d- d- haloalkyl or alkylcarbonyl;

R 2 is halogen, cyano, d-Ce alkyl or haloalkyl group dC 3.

A fluorine-containing o-methoxy-pyrazol-carboxamido benzamides as a still further preferred embodiment, represented by the structural formula (I) in which:

R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;

R 2 is halogen or cyano.

O carboxamido containing a benzamide compound difluoromethoxy-pyrazole as a most preferred embodiment, the structure represented by formula (I)

Figure imgf000006_0001

In the above A, RR 2, R 3, R 4 and R 5 groups:

As RR 2 or R 4 is halogen or halogen as the substituent include fluorine, chlorine, bromine or iodine atoms each. Examples of the halogen substituents may be 1 or 2 or more, in the case of 2 or more, respective halogens may be the same or different. Further, the halogen substitution position may be any position.

RR 2, R 3 or alkyl or alkyl moiety R 4 may be linear or may be branched. Specific examples thereof include, d- such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and the like 6 alkyl group.

Alkenyl or alkenyl moiety in R 1, may be either straight chain or branched eleven kinds. Specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3-butadienyl, 1-hexenyl such C 2 - block or block group moieties of R 6 1, may be either straight chain or branched eleven kinds. Specific examples thereof include acetylene group, 2-block group, 2-block basis, a block group such as 3-hexyl C 2 - 6 group of blocks.

Containing a difluoromethoxy-pyrazol o carboxamido benzamides represented by the above formula (I) in such isomers may exist optical isomers, geometric isomers, the present invention comprises different isomer and the isomer mixture of the two cases. Further, within the technical knowledge in the art, the present invention also includes various isomers other than the above. Further, although depending on the type isomer may result in different chemical structure of the case is formed with the above-described structural formula (the I), but as long as it can be sufficiently skilled in the art recognize that this is a relationship between isomers, and therefore was a clear within the scope of the invention.

The present invention further provides a fluorine-containing o-methoxy-pyrazol-carboxamido benzamides represented by the preparation of the above structural formula (I) is used, having the following structural formula (Π):

Figure imgf000007_0001

Wherein A, R 1 and R 2 groups, and! ! ! with! ! O carboxamido benzamides the groups containing a difluoromethoxy-pyrazoles represented by the formula (I) corresponds, namely:

A is N or CH;

R 1 is hydrogen, halo, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block groups, block groups halo, alkoxy, cyano, alkoxy group, ^ alkoxy group, an alkylthio group, on behalf of ^ alkylthio, alkylsulfonyl, alkylcarbonyl, substituting ^ alkylcarbonyl, alkoxycarbonyl, substituting ^ alkoxycarbonyl or an amino group;

R 2 is hydrogen, halo, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;

m is an integer of 0~4;

n is an integer of 0~4.

As a preferred embodiment of the compounds represented by the formula ([pi) in which:

A is N;

R 1 is hydrogen, halo, cyano, nitro, C r C 6 alkyl, C r C 6 haloalkyl, cyano C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 block basis, C 3 -C 6 halo-block basis, -C 6 alkoxy, dC 6 alkoxy, cyano, -C 6 haloalkoxy, ^ - ^ alkoxy thio, CC 6 ^ substituting alkylthio, C r C 6 alkylsulfonyl group, a C r C 6 alkylcarbonyl, C r C 6 substituting ^ alkylcarbonyl, -C 6 alkoxycarbonyl group, -C ^ substituting 6 alkoxycarbonyl group or an amino -C 6 alkyl;

R 2 is hydrogen, halo, C r C 6 alkyl, halo C r C 6 alkyl, C r C 6 alkoxy, halo C r C 6 alkoxy or cyano; m is 2; n is 1.

As a further preferred compound represented by the formula ([pi) in which:

R 1 is hydrogen, halo, cyano, dC 6 alkyl, haloalkyl or dC 6 dC 6 alkylcarbonyl;

R 2 is halogen, cyano, alkyl or haloalkyl CFCE dC 3 alkyl.

As a more preferred compound represented by the formula ([pi) in which:

R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;

R 2 is halogen or cyano.

The present invention also provides a method for synthesizing ortho-carboxamido benzamides containing a difluoromethoxy-pyrazoles represented by the above formula (I).

O carboxamido-containing synthetic benzamides a difluoromethoxy-pyrazoles represented by a structural formula (I), comprising the steps of:

Compound (1) in an aprotic solvent, represented by the structural formula (VI) with a fluorine bromide in a acid binding agent to act, reaction of formula (W) a compound represented by;

(2) in a protic solvent of formula (W) a compound represented by the action of an alkali hydrolysis to give a fluorine-containing carboxylic acid methoxy pyrazole represented by the formula (III);

CHPF

Yesterday

Figure imgf000008_0001

(VI) (VD) (III)

(3) in an aprotic solvent, adding a base, and an alkylsulfonyl chloride, a fluorine-containing carboxylic acid, and methoxy pyrazole of formula (V) represents a substituted anthranilic acid represented by the structural formula (III) reacted formula ( [pi) containing a fluorine-methoxy-4H- benzo pyrazole represented by [1, 3] oxazin-4-ones;

Figure imgf000008_0002

A fluorine-containing pyrazole 4Η- methoxy-benzo (4) in an aprotic solvent, represented by the structural formula (Π) [1, 3] oxazin-4 compound represented by the structural formula and the ketone compound (IV) a fluorine-containing o-methoxy-pyrazol-carboxamido benzamide compound represented by formula reacted (the I);

Figure imgf000009_0001

(II) (IV) (I)

Containing a difluoromethoxy compound A of formula (II) to (YD) represented, RR 2, R 3, R 4 and R 5 groups, and m and n are as defined and preferred above structural formula (I) represented by o pyrazole compound carboxamido benzamides, wherein the structure represented by the formula (VI),! ^ To ^ - 6 alkyl.

Compound represented by the formula (VI) is a known compound which can be prepared with reference to PCT Patent Application WO03015519 and WO2006023783.

As a preferred embodiment, the synthetic method of step (1), a compound represented by the structural formula (VI) with a ratio of a methyl bromide and fluorine feed acid scavenger substance is 1: 1.1~2: 1.1~2, more preferably 1: 1.1~1.5: 1.1~ 1.5; the aprotic solvent is selected from tetrahydrofuran, acetonitrile, 1, 4-dioxane, acetone or one or two or more thereof; reaction temperature is 10~90 ° C , more preferably 20~80 ° (:.

Step (1) treatment after the compound represented by formula (W) are: filter cake was rinsed with a small amount of an organic solvent, the filtrate was combined and concentrated. You need not be directly isolated and purified in step (2) hydrolysis reaction.

As a preferred embodiment, the synthetic method of step (2), the structural formula (W) represents a ratio of the feed material with an alkali compound is 1: ~ 1.5, more preferably 1: 1~1.2; said protic solvent is methanol and / or ethanol; reaction temperature is 10~90 ° C, more preferably 20~80 ° (:.

Step (2) containing a post-treatment difluoromethoxy-pyrazole carboxylic acid represented by the formula (III) are: an organic solvent distilled off, water was added, extracted with ether, the aqueous phase was then made acidic with dilute hydrochloric acid, large amount of solid precipitated was filtered, washed with water, dried infrared light, to obtain a structure represented by formula (III) containing a difluoromethoxy-pyrazole carboxylic acid solid.

Difluoromethoxy containing a pyrazole carboxylic acid and formula (V) represents a substituted anthranilic acid and the alkyl chloride feed as a preferred embodiment, the synthetic method of step (3) the structure of formula (III) represented by ratio was 1: ~ 1.5: 2 to 3, more preferably 1: 1~1.2: 2~2.5; said alkyl sulphonyl chloride methanesulfonyl chloride; the aprotic solvent is selected from tetrahydrofuran, acetonitrile, , 1, 4-dioxane, diethyl ether or toluene, one or two or more thereof; the base is an organic base, an organic base and more preferably a self triethylamine, pyridine or 3-methyl pyridine or two or more thereof; reaction temperature is -30~80 ° C, more preferably -15~30 ° C. Wherein the volume of the amount of the organic base containing a pyrazole carboxylic mass difluoromethoxy-1 to 4 times (ml / g) represented by the structural formula (III), preferably 1 to 2 times (ml / g).

Step (3) post-processing is: the reaction was filtered, the filter cake was washed with water, a mixed solvent of organic solvent and water and a small amount of an organic solvent to give a first batch of washed solid; the filtrate was distilled off the solvent, adding an organic solvent, no after drying over anhydrous sodium sulfate, filtered, concentrated, and recrystallized from ethanol to give a second batch of solid; two batches of solid were combined to give a compound represented by the structural formula (II).

Substituted anthranilic acid represented by the structural formula wherein (V) is a known compound, can be prepared by a number of methods, can refer to the following documents: Organic Synthesis, Coll.Vol.79, pl96 (2002); Vol.l0, p23 (2004); Adv.Heterocycl.Chem.1975, 18, 1 -58; Journal of the Brazilian Chemical Society 2001,12 (3), 273-324; Angew.Chem.Int.Ed.Engl.1980, 19,222-223 .

As a preferred embodiment, the synthetic method of step (4), containing a difluoromethoxy-4H- benzo pyrazole represented by the structural formula (Π) [1, 3] oxazin-4-ones and structural formula ( IV) the feed ratio of the compound represented substance is 1: 1 ~ 5, more preferably 1: 1 to 2; said aprotic solvent is selected from tetrahydrofuran, acetonitrile, 1,4-dioxane, diethyl ether, toluene , methylene chloride or chloroform, one or two or more thereof. Which contains a difluoromethoxy-pyrazol-4H- benzo volume amount of aprotic solvents are of the formula ([pi) represented by [1, 3] oxazin-4-5 to 60 times the mass of the ketone compound (ml / g), preferably from 5 to 20 times (ml / g).

Hereinafter, the present invention is concerned

Figure imgf000010_0001

The following abbreviations in Table 1 using an index as follows: t is tertiary, n being normal, i is iso, s is secondary, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl; corresponding i- Pr is isopropyl and the like. Index Table 1 R 2 = 3_C1, n = l, R: and R 4 may be independent substituents may be integrally connected.

Figure imgf000010_0002

Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001

The following Table 2 Index of physical and chemical properties and NMR data of the index table 1 portion of the compound. Note: the index table index number 2 in Table 1 correspond to compound numbers. Where s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, brs is broad singlet. Index Table 2

No. m.p. / ° c ¾NMR (unless otherwise indicated, reagents are CDC1 3)

0. 95-0. 98 (m, 3H), 1. 58-1. 62 (m, 2H), 2. 19 (s, 3H),

3. 32-3. 37 (m, 2H), 5. 83- 5. 96 (d, 2H), 6. 12 (s, 1H),

1

6. 66 (s, 1H), 7. 22 (s, 1H), 7. 33-7. 37 (m, 1H),

7. 82-7. 84 (d, 1H), 8 · 45- 8 · 46 (d, 1H), 10. 00 (s, 1H)

1. 20-1. 22 (d, 6H), 2. 18 (s, 3H), 4. 15-4. 20 (m, 1H),

5. 83-5. 96 (d, 2H), 5. 92-5. 94 (d, 1H), 6. 71 (s, 1H),

2

7. 19-7. 36 (m, 3H), 7 · 82- 7 · 84 (d, 1H), 8. 46 (s, 1H),

10. 06 (s, 1H)

2. 16 (s, 3H), 2. 67 (s, 3H), 5. 85-5. 99 (d, 1H), 6. 93 (brs,

3 (Example 2) 236-237 1H), 7. 34 (s, 1H), 7. 45 (s, 1H), 7. 54-7. 57 (m, 1H),

8. 10-8. 47 (m, 3H), 10. 18 (brs, 1H)

1. 16-1. 20 (t, 3H), 2. 17 (s, 3H), 3. 37-3. 44 (m, 2H),

4 5. 83-5. 96 (d, 2H), 6. 15 (s, 1H), 6. 75 (s, 1H), 7. 19-7. 36

(M, 3H), 7. 82-7. 84 (d, 1H), 8. 44-8. 46 (m, 1H),

10. 00 (s, 1H)

0. 91-0. 95 (m, 3H), 1. 34-1. 60 (m, 4H), 2. 18 (s, 3H),

3. 34-3. 39 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 12 (s, 1H),

5 6. 71 (s, 1H), 7. 19-7. 36 (m, 3H), 7 · 81- 7 · 83 (d, 1H),

8. 44-8. 45 (d, 1H),

10. 00 (s, 1H)

1. 14-1. 96 (m, 10H), 1. 59 (s, 3H), 2. 18 (s, 3H), 3. 85-3. 87 (d, 1H), 5, 82-5. 96 (d, 2H), 5. 96 (s, 1H), 6. 69 (s, 1H),

6252-253

7. 19-7. 36 (m, 3H), 7. 81-7 · 83 (d, 1H), 8. 44-8 · 45 (d, 1H), 10. 03 (s, 1H)

2. 34 (s, 3H), 4. 54-4. 56 (d, 2H), 5. 83-5. 97 (d, 2H),

6. 28-6. 64

7

(M, 3H), 7. 34-7. 36 (d, 2H), 7 · 81- 7 · 83 (d, 1H),

8. 44-8. 45 (d, 1H), 9. 89 (s, 1H) (Ηΐ 's) 28 "6' (Ηΐ 'P) ff SZ" 8

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6

96 -9- £ 8 "9

'(HS' s) 6T 7 '(H9) 6S · ΐ-εε · ΐ' (Η £ ') 06 · 0-68 Ό

(Ηΐ 's) OT Όΐ' (Ηΐ 'Ρ) 9 8-

'(Ηΐ · 8-0ΐ · 8' (Η ^ 'ω) 89 "Ζ' (Ηΐ 's) S6" 9

822- LZZ

'(Η2' Ρ) Ζ6 " 9- ^ 8" 9 '(HS' s) 9T 7 '(H6' s) 92 "ΐ: 9 Ρ- OSMI

L \

OT8C.0 / llOZN3 / X3d co o Ζ OAV

Figure imgf000020_0001

81

Ol8C.0 / llOZN3 / X3d co o Ζ OAV 6. 73-6. 74 (d, IH), 7. 27-7. 86 (m, 5H), 8. 44-8. 45 (d, IH),

7. 77-7. 79 (d, IH)

214-215

DMS0-d 6:.. 0. 81-0 85 (m, 3H), 1. 40-1 45 (m, 2H), 2. 16

(S, 3H), 3. 06-3. 09 (m, 2H), 5. 85- 5. 98 (d, 2H), 6. 93 (s, IH),

7. 44-7. 59 (m, 3H), 8. 10-8. 46 (m, 3H), 10. 14 (s, IH)

0. 95-2. 22 (m, 10H), 2. 11 (s, 3H), 3. 32-3 · 75 (m, 2H),

4. 62-5. 02 (m, 2H), 5. 82-5. 95 (d, 2H), 6. 91-7. 35 (m, 4H),

7. 80-7. 82 (d, IH), 8. 42 (s, IH), 9. 88 (s, IH)

0. 64-2. 43 (m, 14H), 2. 05 (s, 3H), 3. 39-3. 75 (m, 2H),

135-136

4. 69-5. 03 (m, 2H), 5. 81-5. 94 (d, 2H), 6. 88-7. 35 (m, 4H),

7. 80-7. 82 (d, IH), 8. 42 (s, IH), 9. 69 (s, IH)

2. 23 (s, 3H), 2. 62 (s, 3H), 2. 89 (s, 3H), 5. 85- 5. 99 (d, 2H), 6. 92 (s, IH), 7 . 58-8. 49 (m, 5H), 10. 46 (s, IH)

DMS0-d 6:.. 89-0 95 (m, 3H), 1. 11-1 97 (m, 9H), 2. 20 (s, 3H),.

3. 60-3. 62 (m, IH), 5. 83-5. 97 (d, 2H), 6 · 67- 6 · 68 (d, IH), 7. 21-7. 37 (m, 3H ), 7 · 82- 7 · 84 (d, IH), 8 · 45- 8 · 46 (d, IH), 10. 05 (s, IH)

DMS0-d 6:.. 71-0 79 (m, 3H), 0 · 99- 1 · 79 (m, 9H), 2. 22 (s, 3H),

252-253

3. 26-3. 33 (m, IH), 5. 85- 5. 98 (d, 2H), 6. 95- 6. 97 (d, IH), 7. 54-8. 45 (m, 5H ), 10. 05 (s, IH)

DMS0-d 6:... 1. 08-1 74 (m, 10H), 2. 22 (s, 3H), 3. 59-3 61 (m, IH), 5. 86-5 99 (d, 2H), 6. 99 (s, IH), 7. 56-8. 46 (m, 5H),

10. 38 (s, IH)

DMS0-d 6:... 0. 83-0 86 (m, 3H), 1. 25-1 45 (m, 6H), 2. 21 (s, 3H), 3. 11-3 16 (m, 2H), 5. 86-5. 99 (d, 2H), 6. 95 (s, IH), 7. 55-8. 47 (m, 6H), 10. 42 (s, IH)

DMS0-d 6: 1. 27 ( s, 9H), 2. 21 (s, 3H), 5. 85- 5. 98 (d, 2H),

233-237

6. 96 (s, IH), 7. 55-8. 47 (m, 6H), 10. 33 (s, IH)

DMS0-d 6:. 2. 22 (s, 3H), 4. 34-4 36 (d, 2H), 5 · 86- 5 · 99 (d, 2H),

142-143

6. 26-6. 37 (d, 2H), 6. 92 (s, IH), 7. 53- 8. 85 (m, 7H),

10. 41 (s, IH)

DMS0-d 6: l 41-1 50 (m, 4H), 2. 30 (s, 3H), 2. 91-3 47 (m, 6H), 5. 85-5 98 (d,.... 2H), 6. 97 (s, IH), 7. 57- 7. 82 (m, 3H), 8. 13-8. 15 (d, IH), 8 · 46- 8 · 47 (d, IH)

181-182

0. 91-0. 96 (m, 3H), 1. 37-1. 64 (m, 2H), 2. 03 (s, 3H),

2. 92-3. 39 (m, 4H), 5. 81-5. 94 (d, 2H), 6. 93-7. 35

(M, 4H), 7. 80-7. 82 (d, IH), 8. 42- 8. 43 (d, IH)

234. 5-24 1. 14-1. 96 (m, 10H), 2. 36 (s, 3H), 3. 82-3. 87 (m, IH), 0 5. 83-5. 96 (d , 2H), 6. 67 (s, IH), 7. 33-7. 40 (m, 3H),

7. 81-7. 83 (d, IH), 8 · 44- 8 · 46 (d, IH), 10. 04 (s, IH)

223-224 2. 17 (s, 3H), 2. 93-2. 94 (d, 3H), 5 · 83- 5 · 96 (d, 2H),

6. 16 (s, IH), 99 τ

S9

(H2 'ω) ζζ τ- οζ τ (m <s) so' ζ (m <ι ") 99" ΐ-ΐ9 "ΐ 902- ^ 02

(Ηΐ 's) 06 "6 ' (Ηΐ c P) Z S-Zf" 8 '(Ηΐ' Ρ) 28 "Ζ-08" Ζ

'(Η2' ω) 9 £ · Ζ- "Ζ '(Ηΐ' s) 0ΐ" Ζ '(Ηΐ' s) 6 · 9 '(Η2' Ρ)

f6 "9-08" 9

29

(Η ') 8 ε-εο · ε' (HS 's) go 7' (Η9 6ΐ · ΐ- ε6 · ο 99Τ-29Ϊ

(Ηΐ 'Ρ) 90 ΌΙ-fO Όΐ' (Ηΐ 9 S- · 8

'(Ηΐ' ω) S8 "Ζ-Ϊ8" Ζ '(HS' ω) 0 '' (Ηΐ 'Ρ) £ L' 9-2 · 9

'(Η2' Ρ) 96 "9-28" 9 '(Ηΐ' Ρ) 09 Τ-89 Τ '(HS' s) 8ΐ · Ζ

ΐ9 (Ηΐ 'Ρ) 6 · ΐ- 06 · ΐ' (Η6 'm) SL' l-6fl '(HS' ^) S6 Ό-98 Ό

(Ηΐ 's) ZO Όΐ

(Ηΐ 'P) S · 8- · 8

(Η2 'Ρ) £ 8 "Ζ-Ϊ8" Ζ' (Ηΐ 's) · 9

(Ηΐ 's) 8T · 9 ' (Η2 'Ρ) 96 "9-28" 9 {wz' m) i £ τ-ζ £ τ

09

'OK' s) 9T · Ζ (Η9 <ι ") 99 · ΐ- ΐε · ΐ (HS 'ΐ6 Ό-88 Ό

(Ηΐ 's) 00 Όΐ' (Ηΐ 'Ρ) 9 · 8- · 8 (Ηΐ' Ρ) 8 "Ζ-Ϊ8 · ί

(HS 'ω) If' -εε '' (HI 's ^ q) 80 "9 {W,' Ρ) 96" 9-28 "9 9" Ζ

69 (HS '^) £ Ζ · ΐ- 6ΐ · ΐ

(Ηΐ 's) ZO Όΐ' (Ηΐ 'Ρ) 9 ^ S-ff "8' (Ηΐ 'Ρ) S8" Ζ-ΐ8 "Ζ

'(HS' ω) S "Ζ '(Ηΐ' s) fL · 9 '(Ηΐ' s) 96" 9 '(Η2' Ρ)

96 "9-28" 99

89

(Ηΐ 'ω) 6ΐ' f-fl 'f' (HS 's) T τ' (Η9'Ρ) 0Ζ · ΐ-6ΐ · ΐ "9ΐ2-9ΐ2

(Ηΐ 's) 8T Όΐ

(Ηΐ 'P) ff SZ · 8

(Η2 'Ρ) 28 "Ζ-08" Ζ (HS' ω) 9ε - - 6 '9' (Ηΐ 'sjq) TO · 9

Ζ9 {W, 'Ρ) 96 "9-28" 9' (H6 'S) 9S · ΐ Z-9ZZ

(Ηΐ 'sjq) T2 Όΐ' (Ηΐ 'Ρ) 8 · 8-' (Ηΐ 'Ρ) 9ΐ' 8-εΐ "8 '(HS' ω) 69" -SS '' (Ηΐ 's) 06 "9 9

99 (Η2 'Ρ) 86 " 9- ^ 8" 9' (HS 's) 88' Ζ '(HS' s) 297: 9 Ρ- OSMI '9 -ε

(Ηΐ 's) W · 0ΐ ' (Ηΐ 'Ρ) 9 8- S 8' (Ηΐ: s) 8T · 8

: (Ηΐ 'Ρ) Οΐ · 8- 60 · 8' (HS '^) 89' L- £ "Ζ '(Ηΐ: s) 26 · 9

'(Η2' Ρ) 86 "9-98" 9 '(Η2 9ΐ · ε- Όΐ' £: (Η £ 's)

ΐ 'Ζ (m <lu) W \ -ZZ' \ '(HS' ω) 98 Ό-28 Ό: 99

'P-OSHQ 1 Ζ

(Ηΐ 'Ρ) 8 · 8- 9 · 8

(Ηΐ 'ΡΡ) 9ΐ · 8- Π · 8' (Η £ ') £ 8 · Ζ' (Ηΐ 'Ρ) 9ΐ · 8- Π · 8

'(HS' ω) S8 "Ζ-Ζ9" Ζ '(Ηΐ' s) Ζ6 · 9 '(Η2' Ρ) 86 "9-98" 9 ζ

(Η ^ 'ω) οε -ε -ζο τ' (HS'S) 9 '(Η' hem) · Ϊ- 9 · Ϊ: 9 Ρ- OS I LZ- 'ΟΙΖ

(Ηΐ 'Ρ) 9 · 8- · 8

'(Ηΐ' Ρ) ΖΙ "8-0ΐ" 8 '(Η £') 06 · Ζ- · Ζ '(Ηΐ' s) Z6 "9

S9 (Η2 'Ρ) 66 " 9-98" 9' (HS 's) 29 Τ' (HS 's) 6T 7: 9 Ρ- OSMI

(Ηΐ 's) · 0ΐ' (Ηΐ 'Ρ) Lf · 8- 9 · 8' (Ηΐ 'Ρ) fl' 8 ~ ΖΙ · 8

(HS 'ω) S8 "Ζ-99' ί '(Ηΐ' s) £ 6 · 9 '(Η2' Ρ) Ζ6" 9- £ 8 "9 '(Η 9

Ζ

ίΖ · ε- ΐ6 · Ζ '( HS' s) 02 · Ζ '(Η9) W) · Η8 Ό: 9 Ρ- OSMI' 0ΖΖ-ί \ Ζ

(Ηΐ 's) 86 · 6 (Ηΐ' Ρ)

8- * 8

(Ηΐ 'Ρ) 8 Ί- Ζ8' ί (Ηε 'ω) 6ε' (ΗΤ S) 0Z · 9

Figure imgf000022_0001

Ol8C.0 / llOZN3 / X3d co o ζ OAV

Figure imgf000023_0001

Ol8C.0 / llOZN3 / X3d co o Ζ OAV

Figure imgf000024_0001

(Ηΐ 's) l · 6

'(Ηΐ') '(Ηΐ' ω) ^ 8 Ί-ZS 'ί' (Η2 '^) Ιζ Ί ~ η' ί

'(Ηΐ' s) 92 'I' (Ηΐ 's) 8' 9 '(Ηΐ' Ρ) 80 · 9_90 · 9

'(Η2' Ρ) 96 "9-28" 9 '(Ηΐ' ^) ^ 8 '£ ~ Ζ8' £ '(Η2' ^) 06 "ΐ-Ζ8" ΐ

'(Η £') ^ ΐ- 99 · ΐ '(Η2' ω) "ΐ- ^ ε" ΐ '(Η £') 8ΐ · ΐ- 80 · ΐ S6

(Ηΐ 's) g0 Όΐ' (Ηΐ 'Ρ) 9 · 8- · 8 (Ηΐ' Ρ) ΖΙ · 8- Οΐ · 8

'(Ηΐ' s) Z6 "Ζ '(Ηΐ' ω) 89" Ζ-99 "Ζ (Ηΐ 'P) S -L- £' I

'(Ηΐ' P) 2S '-θε "Ζ' (HI 'S) 96" 9 (Η2' Ρ) 66 "9-98" 9

'(Ηΐ') 09 · ε '(HS' s) 027 (Η ^ '^) l "ΐ-99" ΐ

(Ηΐ 'ω) 89 "ΐ -99" ΐ' (Η9 "ΐ-ΖΟ" ΐ: 9 Ρ- OSMI 26

(Ηΐ 's) 0T Όΐ' (Ηΐ 'Ρ) 9 · 8- · 8

'(Ηΐ' Ρ) ΖΙ "8-ΐΐ" 8 '(Ηΐ' s) T0 '8' (Ηΐ 's) g'

(Η2 'ω) 9 "-½" Ζ' (HT 's) 96 "9' (Η2 'Ρ) 86" 9-98 "9

'(Ηΐ' ω) 09 Τ-89 '£' (HS 's) gT' (Η) εΖ'ΐ-99 'ΐ

'(Ηΐ' ω) 89 " ΐ-99" ΐ '(Η9 LZ "ΐ-ΖΟ" ΐ: 9 Ρ- OSMI ΐ6

(Ηΐ 's) Tg ΐ' (Η2 'ω) ΐ9 · 8- ^ "8

'(Ηΐ' Ρ) 06 "Ζ-88" Ζ '(Η £') 6 £ · Ζ '(Ηΐ' ω) ΐΐ 'Z-80 "Ζ

'(Ηΐ' s) 99 "9 '(Ηΐ' P) fl -9-ΖΙ" 9 '(Η2' Ρ) 86 "9-98" 9

(Ηΐ ') ΐΟ · BU 66 Έ' (Η2 'ω) ΖΟ 7-90' Ζ '(Η2' ^) 28 "ΐ-6Ζ" ΐ

'(Η2' ω) 2 " ΐ-Ζ9" ΐ '(1Ε · τ -' (Η2 · ΐ- 02 · ΐ 06

(Ηΐ 's) 06 "6' (Ηΐ 'Ρ) · 8

- £ f · 8

'(ΗΪ' ρ) ^ 8 -L-ZS · 'ΟΕ' Kan) 9ε · ζ-οε · Ζ '(Ηΐ' s) \ Z 'I

(HT 's) 86 · 9 ' (Ηΐ 's) ZO "9' (Η2 'P) f6" 9-ΐ8 "9' (H6 'S) SS" ΐ 68

(Ηΐ 's) 0 ^ Όΐ

(Ηΐ 'P) S · 8- · 8' (Ηΐ 'P) S8 "Ζ-Ϊ8" Ζ' (Ηΐ

(Ηΐ 'Ρ) 02 "Ζ-8ΐ · ί' (Ηΐ 'Ρ) ΖΟ" Ζ-90 · ί' (Ηΐ 's) 26 · 9

'(Ηΐ' s) 96 "9

'(Η2' Ρ) 96 " 9-28" 9 '(HS' s) 9T '(H6' S) 9S "ΐ 88

(Ηΐ 's) T2 ΐ' (Η2 'Ρ) ΐ9 "8-6 ^" 8

(Ηΐ 'Ρ) 06 "Ζ-88" Ζ' (Η £ ') 9 £ · Ζ' (Ηΐ 'ω) 60 "Ζ-90" Ζ

'(Ηΐ' s) g9 · 9

Ζ8

'(Ηΐ' s) 60 " 9 '(Η2' Ρ) 86" 9-98 "9 '(H6' s) 09" ΐ

(Ηΐ "· 8- '(IE' hem) 8 £ · 8-

1 (Η2 'ω) 8ΐ "8-80" 8' (Ηΐ '^) 09 "-½' '(Ηΐ' s) gO" Ζ

98 (Η2 'Ρ) 00 " 9- ^ 8" 9' (HS 's) 9g' (H6 'S) 9S "ΐ: 9 Ρ- OSMI 29Τ-09Ϊ

(Ηΐ 's) 9T Όΐ

'(Ηΐ' Ρ) ^ S- £ "8 '(Ηΐ' P) S8" Ζ-Ϊ8 "Ζ '(Ηΐ' s) T9

(Ηΐ 's) l' I '(Ηΐ' ω) 9ε '' (Ηΐ 's) 26 "9' (Ηΐ 's) 86" 9

98 '(Η2' Ρ) 96 "9-28" 9 '(HS' s) gT '(H6' S) 9S "ΐ

(Ηΐ 's) T · 0ΐ' (Ηΐ 'Ρ) Lf · 8- 9 · 8

'(Ηΐ' ω) Π · 8- Οΐ · 8 '(Ηΐ' s) 8Ζ '' (Η2 89 "Ζ-ΐ9 '

'(Ηΐ' s) g6 · 9

(Ηΐ 's) 0 · 9' (Η2 'Ρ) 86 "9-98" 9' (Η2 Π - 80 '

^ 8

(Η2 'P) f6' £ -Z6 '£' (HS 's) ZZ' Ζ '(HS' ^) 92 "ΐ-9ΐ" ΐ: 9 Ρ- OSMI

Ol8C.0 / llOZN3 / X3d co o Ζ OAV '(Ηΐ' s) L '' (HS 's) U "Z' (Ηΐ 's) ½" 9' (HT 's) 8 · 9

W, 'P) TS "9-92" 9 W,' P) S8 "9-Ϊ8" 9 '(Η2' P) Z9 ^ -29 f £ ZZ £ Z LOT

(Ηΐ 's) 66 "6' (Ηΐ 'Ρ) ε · 8-' (Ηΐ 'Ρ) 28" Ζ-08 "Ζ

'(Ηΐ' ^) η 'ί' (Η2 'ω) 90 "Ζ-86" 9' (Η2 'Ρ) S6 "9-08" 9

'0κ') 8ε · ε '(Η2' ω) go -ε-ε6 τ 'κ ΐ9 Ί- Ί

'(Ηΐ 8ΐ · ΐ- ΐ · ΐ' (HS 'ω) 96 Ό-26 Ό' (Ηΐ 'ω) 0 Ό-99 Ό SLI-LLI 90ΐ

(Ηΐ 's) 69 "6' (Ηΐ 'Ρ) · 8- · 8' (Ηΐ 'P) S8" Ζ-ΐ8 "Ζ' (Η2

<Lu) gg "Ζ '( Ηΐ' s) S8" 9 '(Ηΐ' s) 62 "9 '(Η2' P) f6" 9-ΐ8 "9

'(Η2' ω) ΐε τ-9ζ τ 'ΟΕ' ^ Ή · ΐ '(Hd) ε6 · Ο-06 · ο ΐΖΐ-ΟΖΐ 90ΐ

(Ηΐ 's) gg Όΐ' (Ηΐ 'Ρ) 9 · 8- · 8

'ΟΕ' Ρ) ΐΐ · 8- Οΐ · 8 '(Ηΐ' s) 08 "Ζ '(Ηΐ' ^) 89" -½ '

'(Ηΐ' s) ^ · '(Ηΐ' s) 20 "Ζ '(Η2' Ρ) 86" 9-98 "9

'(Ηΐ' ω) 26 Τ '(Η9'Ρ) Μ) · ΐ-¾) · ΐ: 9 Ρ- OSMI 002-Ζ6Ϊ

(Ηΐ 's) 99' 6 '(Ηΐ "· 8- · 8' (Ηΐ 'Ρ)

^ 8 Ί-ZS 'ί W ,' m) L £ "-9ε" Ζ '(Ηΐ' s) 08 "9 '(Ηΐ' s) 92" 9

'(Η2' Ρ) 96 "9-28" 9 '(Η2' ^) ~ η '£' (HS '^) 9ΐ Ί-ΖΙ Ί Ζ8Ϊ-98Ϊ εοτ

{WZ 'Ρ) 8 · 8- 9 · 8

'(Ηΐ' Ρ) Ζ \ · 8- Οΐ · 8 '(Ηΐ' s) 8Ζ "Ζ '(Ηΐ 89" Ζ-99 "Ζ

'(Ηΐ' s) 9 ^ Ί '(Ηΐ' s) 00 Ί '(Η2' Ρ) 66 "9-98" 9 '(Ηΐ' ^) ΐθ '

002-66Ϊ ΐθΐ '(Ηΐ' ^) 29 Ό-Ϊ9 Ό '(Η2' ^) 99 Ό '(Η2' ^) Ό: 9 Ρ- OSMI

(Ηΐ 's) 02 Όΐ' (Ηΐ 'Ρ) 6 · 8- 8 · 8' (Ηΐ 'Ρ) 9ΐ · 8- Π · 8

'(Ηΐ' s) 6Z "Ζ '(Ηΐ' ω) 09" Ζ-Ζ9 "Ζ '(Ηΐ' s) 9 ^ Ί

'(Ηΐ' s) Z6 "9 '(Η2' Ρ) 86" 9-98 "9 '(HS' s) 68 'Ζ' (HS 's) Z97 ΟΟΐ

(Ηΐ 's) 89 "6' (Ηΐ 'Ρ) 8 8-' (Ηΐ 'Ρ) \ Ζ" 8-0ΐ "8

'(Ηΐ' s) T "Ζ '(Ηΐ' ω) 29" Ζ-99 "Ζ '(Ηΐ' s) 9 ^ 'ί' (Ηΐ 's) 06" 9

'(Η2' Ρ) 86 " 9- ^ 8" 9 '(HS' s) 887 '(HS' s) T9: 9 Ρ- OSMI 66

(Ηΐ 's) 02 · 0ΐ

'(Ηΐ' Ρ) 6 · 8- 8 · 8 '(Ηΐ' Ρ) 9ΐ · 8- ΐ · 8 '(Ηΐ

9 "Ζ-Ζ9" Ζ '(Η2' s) 8S "Ζ '(Η2' ^) Ζ £ 'ί' (Ηΐ 's) 06" 9

'(Η2' Ρ) ΐΟ " 9-98" 9 '(HS' s) 087 '(HS' s) Z9 'Ζ: 9 Ρ- OSMI 99Τ-99Ϊ 86

(Ηΐ 's) 9S Όΐ' (Ηΐ 'P · 8- 9 · 8

'(Ηΐ' s) 82 · 8 '(Ηΐ' Ρ) Ζ \ · 8- Οΐ · 8 '(Ηΐ' s) 6Ζ '

'(Ηΐ' ω) 9 "Ζ-99" Ζ '(Ηΐ' s) 09 "Ζ '(Ηΐ' s) 86" 9

'(Η2' Ρ) 86 " 9-98" 9 '(HS' Ρ) Ζ97-997: 9 Ρ- OSMI Ζ6

(Ηΐ 's) OT Όΐ' (Ηΐ 'Ρ) 6 8- 9 8

'(Η2' Ρ) Π · 8- ΐ ΐ · 8 '(Ηΐ 89 "Ζ-99" Ζ' (Ηΐ Lf Ί-ff Ί

'(Ηΐ' ω) 9ε -LZ "Ζ '(Ηΐ' s) 96" 9 '(Η2' Ρ) 66 "9-98" 9

'(HS' Ρ) 697-897 ' (HS' s) 6T: 9 Ρ- OSMI 96

(Ηΐ 's) 90 Όΐ' (Ηΐ 'Ρ) 8 8-' (Ηΐ 's) 8T "8

'(Ηΐ' Ρ) Π · 8- Οΐ · 8 '(Ηΐ' s) l Ί '(Ηΐ' s) T9 '

'(Ηΐ' ω) 89 "-½" Ζ '(Ηΐ' s) S6 "9 '(Η2' Ρ) 66" 9-98 "9

'(HS' Ρ) Ζ97-99 ' (H £' s) n, 2: 9 Ρ- OSMI 96

(Ηΐ 's) T \' (Ηΐ 's) ^ 8 "8

'(Ηΐ' Ρ) 29 '8-ΐ9 "8' (Η2 ίΖ" 8-6ΐ "8 '(Ηΐ' Ρ) S8" Ζ-ΐ8 "Ζ

'(Ηΐ' ω) 99 "Ζ-Ϊ9 'ί' (Ηΐ 'ω) 09" Ζ' (Ηΐ '^) ΖΖ' LSI 'ί

'(Ηΐ' s) 2 ' 9' (Η2 'Ρ) ΐΟ "9-88" 9' (HS 'Ρ) 987- ^ 87: 9 Ρ- OSMI f6

OT8C.0 / llOZN3 / X3d co o Ζ OAV 7. 82-7. 84 (d, IH), 8 · 44- 8 · 45 (d, IH), 9. 35 (s, IH)

108 186-187 1. 28-1. 32 (t, 3H), 4 · 09- 4 · 10 (d, 2H), 4. 21-4. 26 (m, 2H),

5. 81-5. 96 (d, 2H), 6. 69 (s, IH), 6. 87 (s, IH), 7. 26 (s, IH), 7. 41-7. 47 (m, 2H), 7. 82-7. 84 (m, IH), 8 · 41- 8 · 42 (d, IH), 9. 41 (s, IH)

109 122-123 1. 38 (s, 6H), 2. 10 (s, 3H), 2. 93 (s, 2H), 5 · 80- 5 · 94 (d, 2H),

6. 20 (s, IH), 6. 84 (s, IH), 7. 26- 7. 34 (m, 3H),

7. 82-7. 84 (d, IH), 8 · 43- 8 · 44 (d, IH), 9. 68 (s, IH)

DMS0-d 6:.. 0. 45-0 48 (m, IH), 0. 58-0 65 (m, 3H), 2. 21 (s, 3H),

110148-149

2. 70-2. 71 (m, IH), 5. 86- 5. 99 (d, 2H), 6. 97 (s, IH),

7. 55-7. 58 (m, IH), 7. 72 (s, IH), 7. 84 (s, IH),

8. 10-8. 13 (d, IH), 8. 46-8. 47 (m, 2H)

190-192 DMS0-d 6:. 1. 17 (d, 3H), 2. 15 (s, 3H), 3. 24-3 27 (d, 3H),

111

3. 88-3. 94 (m, IH), 5 · 85- 5 · 98 (d, 2H), 6. 95 (s, IH),

7. 54-7. 57 (m, 2H), 7. 73 (s, IH), 7 · 99- 8 · 01 (d, IH),

8. 09-8. 11 (d, IH), 8. 44-8 · 46 (d, IH), 10. 11 (s, IH)

153-155 1. 17-1. 21 (t, 3H), 2. 15 (s, 3H), 3. 38-3. 43 (m, 2H),

112

5. 82-5. 96

(D, 2H), 6. 20 (s, IH), 6. 70 (s, IH), 7. 26- 7. 36 (m, IH), 7. 58-7. 59 (d, 2H), 7. 81-7 · 83 (d, IH), 8. 44-8 · 46 (d, IH)

230-231 0. 93-0. 97 (t, 3H), 1. 54-1. 59 (m, 2H), 2. 15 (s, 3H),

113

3. 30-3. 35 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 15 (s, IH),

6. 72 (s, IH), 7. 26-7. 36 (m, IH), 7 · 51- 7 · 59 (d, 2H),

7. 81-7. 83 (d, IH), 8 · 44- 8 · 46 (d, IH), 10. 07 (s, IH)

DMS0-d 6:. 2. 18 (s, 3H), 2. 50 (s, 3H), 2. 87-2 90 (s, 3H),

114230-231

5. 85-5. 98 (d, 2H), 6. 91 (s, IH), 7. 15- 7. 17 (d, IH), 7. 45-

7. 47 (d, IH), 7. 56-7. 59 (m, IH), 8 · 13- 8 · 15 (d, IH),

8. 48-8. 49 (d, IH), 10. 05 (s, IH)

DMS0-d 6:. 2. 09 (s, 3H), 3. 85 (brs, IH), 3. 97-4 01 (m, 2H),

116

4. 59-4. 61 (m, 2H), 5. 88-6. 01 (d, 2H), 6. 48 (s, IH),

7. 23-7. 25

(M, IH), 7. 57 (s, IH), 7 · 90- 7 · 92 (d, IH), 8. 12-8. 13 (m, IH),

8. 22 (s, IH)

4. 36-4. 37 (d, 2H), 5. 85-5 · 98 (d, 2H), 6. 62 (s, IH), 6. 99 (brs,

117

IH), 7. 09 (m, 4H), 7. 91-7 · 93 (d, IH), 8. 47-8 · 53 (m, 2H)

201-203 2. 95-2. 96 (d, 3H), 5. 82-5 · 95 (d, 2H), 6. 34 (brs, IH), 7. 19-7 ·

118

37 (m, 3H), 7. 86 (s, IH), 8. 44-8 · 45 (d, IH)

142-146 1. 17-1. 20 (t, 3H), 3. 36-3. 43 (m, 2H), 5. 81-5. 94 (d, 2H),

119

6. 36 (brs, IH), 6. 66 (s, IH), 7. 15-7 · 36 (m, 3H), 7. 83-7 · 84 (d, 1H), 8. 43-8. 44 (d, IH)

132-135 0. 95-0. 99 (t, 3H), 1. 56-1. 60 (m, 2H), 3. 33 (m, 2H),

120

5. 83-5. 96 (d, 2H), 6. 25 (brs, IH), 6. 63 (s, IH),

7. 13-7. 46 (m, 3H), 7. 84-7 · 86 (d, IH), 8. 45-8 · 46 (d, IH)

162-165 1. 22-1. 24 (d, 6H), 4. 16-4 · 21 (m, IH), 5. 82-5 · 95 (d, 2H),

121

6. 00-6. 02 (d, IH), 6. 64 (s, IH), 7. 13-7. 47 (m, 2H),

7. 84-7. 86 (d, IH), 8. 45-8. 46 (d, IH), 186-189 0. 94-0. 96 (t, 3H), 1. 35-1. 80 ( m, 4H), 3. 37-3. 42 (m, 2H),

122

5. 83-5. 96 (d, 2H), 6. 22 (brs, IH), 6. 63 (s, IH), 7. 21-7 · 38 (m,

3H), 7. 85-7. 86 (d, IH), 8. 46-8 · 47 (d, IH)

239-242 1. 42 (s, 9H), 5. 83-5. 96 (d, 2H), 5. 91 (s, IH), 6. 67 (s, IH), 7. 1

123

6-7. 38 (m, 3H), 7. 84-7 · 86 (d, IH), 8. 47-8 · 48 (d, IH)

150-154 0. 58-0. 62 (m, 2H), 0. 86-0. 91 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 54

124

(S, IH), 6. 64 (s, IH), 7. 19-7 · 47 (m, 3H), 7. 84-7 · 86 (d, IH), 8. 46-8. 47 (d , IH), 9. 96 (s, IH)

218-220 2. 83 (s, 3H), 3. 07 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 90-7. 38 (m, 4H

125

), 7. 84-7. 86 (d, IH), 8. 46-8. 47 (d, IH), 9. 90 (s, IH)

170-173 0. 90-0. 96 (dd, 3H), 1. 11-1. 79 (m, 9H), 5. 82-5. 96 (d, 2H), 6. 6

127

0 (s, IH), 7. 21-7. 37 (m, 3H), 7. 83-7. 85 (d, IH), 8. 46-8. 47 (d,

IH)

223-227 1. 15-1. 97 (m, 10H), 3. 86-3. 88 (m, IH), 5. 82-5. 95 (d, 2H), 6. 0

128

3-6. 05 (d, IH), 6. 64 (s, IH), 7. 18-7. 37 (m, 3H), 7. 83-7. 85 (d, IH), 8. 45- 8. 46 (d, IH), 10. 00 (s, IH)

152-155 4. 21-4. 22 (d, 2H), 5. 81-5 · 94 (d, 2H), 6. 62 (s, IH), 7. 27-7 · 38

129

(M, 3H), 7. 86-7. 88 (d, IH), 8. 43-8 · 44 (d, IH),

128-131 2. 2. 86 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 44 (s, IH), 6. 88 (s, IH), 7

130

• 28-7. 88 (m, 4H), 8. 45-8 · 46 (d, IH)

175-178 1. 04-1. 07 (t, 3H), 3. 29-3. 36 (m, 2H), 5. 82-5. 95 (d, 2H), 6. 40

131

(S, IH), 6. 96-7. 85 (m, 5H), 8. 42-8 · 43 (d, IH), 9. 73 (s, IH)

179-181 0. 84-0. 85 (m, 3H), 3. 23-3. 28 (m, 2H), 5. 79-5 · 93 (d, 2H), 6. 45

132

(Brs, IH), 7. 27-7. 85 (m, 4H), 8. 42-8 · 43 (d, IH), 9. 74 (s, IH)

215-219 1. 06-1. 07 (d, 6H), 4. 05-4. 10 (m, IH), 5. 82-5. 95 (d, 2H), 6. 25

133

-6. 27 (d, IH), 6. 98 (s, IH), 7. 34-7. 85 (m, 5H), 8. 42-8 · 43 (d, 1

H)

207-210 0. 85-0. 88 (m, 3H), 1. 19-1. 43 (m, 4H), 3. 26-3. 31 (m, 2H), 5. 82

134

-5. 92

(D, 2H), 6. 40 (brs, IH), 6. 94 (s, IH), 7. 33-7 · 86 (m, 4H), 8. 41- 8. 43 (d, IH)

124-126 1. 26 (s, 9H), 5. 78-5. 92 (d, 2H), 6. 25-6. 27 (d, IH), 7. 13-7. 60

135

(M, 4H), 7. 81-7. 82 (d, IH), 8. 40-8 · 41 (d, IH),

0. 94-0. 97 (t, 3H), 1. 54-1. 56 (m, 2H), 2. 21 (s, 3H),

136

3. 32-3. 37

(M, 2H), 5. 83-5. 96 (d, 2H), 6. 14-6. 15 (m, IH), 6. 64 (s, IH), 7. 12-7. 16 (m , IH), 7. 23-7 · 29 (m, IH), 7. 32-7 · 35 (m, 2H), 7. 81-7. 83 (d, IH), 8. 44-8. 46 (d, IH),

2. 12 (s, 3H), 2. 81 (s, 3H), 3. 07 (s, 3H), 5. 82- 5. 95 (d, 2H),

137

6. 74 (s, IH), 7. 02-7. 04 (m, IH), 7. 12-7. 13 (m, 2H),

7. 32-7. 35 (m, IH), 7 · 81- 7 · 83 (d, IH), 8 · 44- 8 · 46 (d, IH), 9. 34 (s, IH)

3. 30-3. 71 (m, 8H), 5. 71-5 · 84 (d, 2H), 6. 89-6 · 94 (m, 3H), 7. 37

142216-218

-7. 40 (m, IH), 7. 85-7. 87 (d, IH), 8. 46-8. 47 (dlH)

1. 37-1. 60 (m, 6H), 3. 19-3. 65 (m, 4H), 5. 78-5. 91 (d, 2H), 6. 85

143208-210

-7. 37 (m, 4H), 7. 83-7 · 85 (d, IH), 8. 44-8 · 45 (d, IH) 1. 31-1. 32 (m, 3H), 4. 14-4. 16 (d, 2H), 4. 17-4. 28 (m, 4H), 5. 83

145158-161

-5. 96

(D, 2H), 6. 59 (s, IH), 6. 74 (brs, IH), 7. 13-7 · 34 (m, 3H), 7. 85- 7. 87 (d, 1H), 8. 44-8. 45 (d, IH)

193-195 4. 56-4. 57 (d, 2H), 5. 83-5. 96 (d, 2H), 6. 30-6. 59 (m, 4H), 7. 21

146

-7. 38 (m, 3H), 7. 83-7. 85 (d, IH), 8. 44-8. 45 (d, IH), 9. 36 (s, 1

H)

169-173 0. 93-1. 66 (m, 8H), 3. 07--3. 51 (m, 4H), 5. 80-5. 93 (d, 2H), 6. 8

147

5-7. 36 (m, 4H), 7. 82-7 · 84 (d, IH), 8. 44-8 · 45 (d, IH)

130-134 0. 91-1. 66 (m, 10H), 2. 98-3. 50 (m, 2H), 5. 80-5. 94 (d, 2H), 6. 8

148

7-7. 36 (m, 4H), 7. 82-7 · 84 (d, IH), 8. 44-8 · 45 (d, IH)

195-196 0. 97-1. 00 (m, 3H), 1. 42-1. 66 (m, 6H), 3. 43-3. 48 (m, 2H), 5. 90

149

-6 03

(D, 2H), 6. 24 (brs, IH), 6. 69 (s, IH), 7. 28-7. 43 (m, 3H), 7. 91- 7. 93 (d, IH), 8. 52-8. 54 (d, IH), 10. 05 (brs, IH)

251-255 1. 00-1. 80 (m, 10H), 5. 79-5 · 96 (d, 2H), 6. 86 (s, IH), 7. 35-7. 8

154

7 (m, 4H), 8. 42-8. 43 (d, IH)

196-199 4. 45-4. 16 (d, 2H), 5. 82-5. 95 (d, 2H), 6. 72 (s, IH), 7. 19-7. 92

155

(M, 5H), 8. 42-8. 43 (d, 2H), 8. 94 (s, IH)

2. 98-3. 00 (s, 3H), 5. 87-6. 00 (d, 2H), 6. 37 (s, IH), 6. 67 (s, IH

161

), 7. 23- 7. 40 (m, 4H), 7. 88-7 · 90 (d, IH), 8. 49- 8. 50 (d, IH), 10. 19 (s, IH)

1. 47 (s, 9H), 5. 88-6. 01 (d, 2H), 6. 01 (s, IH), 6. 68 (s, IH),

163

7. 20-7. 38 (m, 4H), 7. 88-7 · 89 (d, IH), 8. 51-8 · 52 (d, IH), 10. 07 (s, IH)

3. 32 (s, 3H), 3. 49 (s, 3H), 5. 84-5. 97 (d, 2H), 6. 74 (s, IH), 7. 3

180

1-7. 46

(M, 3H), 7. 86-7. 88 (d, IH), 8. 48-8. 49 (d, IH) 8. 95 (brs, IH)

129-132 2. 96-2. 97 (s, 3H), 5. 86-6 · 00 (d, 2H), 6. 20 (brs, IH), 7. 02 (s,

182

IH), 7. 23-7. 39 (m, 3H), 7. 86-7 · 88 (d, IH), 8. 48-8 · 49 (d, IH)

130-135 1. 19-1. 23 (t, 3H), 3. 44-3 · 49 (m, 2H), 5. 90-6 · 03 (d, 2H), 6. 21

183

(Brs,

IH), 7. 00 (s, IH), 7. 29-7. 43 (m, 3H), 7. 90-7 · 92 (d, IH), 8. 52- 8. 53 (d, IH) , 9. 73 (brs, IH)

218-220 0. 90-0. 94 (m, 3H), 1. 49-1 · 51 (m, 2H), 3. 30-3 · 35 (m, 2H), 5. 83

184

-5. 96

(D, 2H), 6. 16 (brs, IH), 6. 99 (s, IH), 7. 19-7 · 35 (m, 3H), 7. 82- 7. 84 (d, IH), 8. 43-8. 45 (d, IH), 9. 82 (brs, IH)

123-126 1. 13-1. 15 (d, 6H), 4. 15-4. 21 (m, IH), 5. 82-5. 95 (d, 2H), 6. 94

185

-6 96

(D, IH), 7. 20-7. 36 (m, 3H), 7. 83-7 · 85 (d, IH), 8. 43-8 · 44 (d,

IH)

110-113 0. 86-0. 92 (m, 3H), 1. 27-1. 47 (m, 4H), 3. 34-3. 39 (m, 2H), 5. 83

186

-5. 96

(D, 2H), 6. 18 (brs, IH), 6. 98 (s, IH), 7. 20-7. 36 (m, 3H), 7. 83- 7. 85 (d, 1H), 8. 44-8. 45 (d, IH) 239-243 1. 42 (s, 9H), 5. 80-5. 94 (d, 2H), 5. 97 (brs, IH), 7. 04- 7 · 33 (m,

187

4H), 7. 80-7. 82 (d, IH), 8 · 41- 8 · 42 (d, IH)

137-139 0. 54-0. 84 (m, 4H), 2. 81-2 · 83 (m, IH), 5. 82-5 · 96 (d, 2H), 6. 31

188

(S, IH), 6. 99-7. 36 (m, 3H), 7. 83-7 · 85 (d, IH), 8. 45-8 · 47 (d, 1 H), 9. 68 ( brs, IH)

220-221 0. 86-0. 90 (m, 3H), 1. 30-1. 50 (m, 6H), 3. 32-3. 37 (m, 2H), 5. 82

189

-5. 96

(D, 2H), 6. 18 (brs, IH), 6. 94-7 · 35 (m, 4H), 7. 82-7 · 84 (d, IH), 8. 44- 8. 45 (d , 1H), 9. 72 (brs, IH)

0. 82-0. 84 (m, 3H), 0. 91-1 · 61 ((m, 9H), 3. 54-4 · 20 (m, IH), 5. 8

190

2-5. 95 (d, 2H), 7. 02-7. 34 (m, 4H), 7. 80-7. 82 (d, IH), 8. 42-8. 43 (d, IH), 10. 00 (brs, IH)

226-228 1. 07-1. 86 (m, 10H), 3. 83-3. 85 (m, IH), 5. 82-5. 96 (d, 2H), 7. 0

200

3-7. 34 (m, 4H), 7. 81-7 · 83 (d, IH), 8. 42-8 · 43 (d, IH)

166-169 0. 92-1. 28 (m, 8H), 2. 85-3. 52 (m, 4H), 5. 82-5. 95 (d, 2H), 6. 99

201

-7. 33 (m, 4H), 7. 81-7 · 82 (d, IH), 8. 42-8 · 43 (d, IH)

109-113 0. 91-1. 63 (m, 10H), 2. 86-3 · 73 (m, 4H), 5. 81-5 · 94 (d, 2H), 7. 0

202

1-7. 33 (m, 4H), 7. 81-7 · 83 (d, IH), 8. 41-8 · 42 (d, IH)

121-124 2. 71 (s, 3H), 3. 09 (s, 3H), 5. 82-5. 95 (d, 2H), 6. 98-7. 35 (m, 4H

203

), 7. 83-7. 84 (d, IH), 8. 44-8 · 45 (d, IH)

219-221 1. 13-1. 72 (m, 6H), 2. 96-3. 05 (m, 2H), 3. 68-3. 70 (m, 2H), 5. 80

204

-5. 93

(D, 2H), 6. 98-7. 32 (m, 4H), 7. 80-7 · 82 (d, IH), 8. 41-8 · 42 (d, 1

H)

171-174 0. 92-1. 28 (m, 8H), 2. 79-3. 39 (m, 4H), 5. 80-5. 93 (d, 2H), 6. 92

205

-7. 27 (m, 4H), 7. 81-7 · 82 (d, IH), 8. 43-8 · 44 (d, IH)

225-227 1. 10-1. 90 (m, 10H), 3. 83-3. 85 (m, IH), 5. 81-5. 95 (d, 2H), 6. 9

206

0-7. 36 (m, 4H), 7. 82-7 · 84 (d, IH), 8. 44-8 · 45 (d, IH)

223-225 0. 82-0. 84 (m, 3H), 0. 96-1. 54 ((m, 9H), 3. 55-4. 15 (m, IH), 5. 8

207

1-5. 94 (d, 2H), 6. 98-7. 34 (m, 4H), 7. 81-7. 82 (d, IH), 8. 43-8.

44 (d, IH)

214-216 0. 87-0. 90 (m, 3H), 1. 30-1 · 51 (m, 6H), 3. 29-3 · 34 (m, 2H), 5. 81

208

-5. 95

(D, 2H), 6. 25 (brs, IH), 6. 91-7 · 34 (m, 4H), 7. 82-7 · 84 (d, IH), 8. 44- 8. 45 (d , IH)

228-229 0. 48-0. 82 (m, 4H), 2. 75-2. 76 (m, IH), 5. 82-5. 95 (d, 2H), 6. 41

209

(S, IH), 6. 94-7. 36 (m, 3H), 7. 83-7 · 85 (d, IH), 8. 45-8 · 47 (d, 1 H), 10. 01 ( brs, IH)

215-219 1. 33 (s, 9H), 5. 82-5. 95 (d, 2H), 6. 04 (brs, IH), 7. 03-7 · 35 (m,

210

4H), 7. 82-7. 84 (d, IH), 8. 44-8 · 45 (d, IH)

180-183 0. 90-0. 94 (m, 3H), 1. 27-1. 48 (m, 4H), 3. 30-3. 35 (m, 2H), 5. 82

211

-5. 95

(D, 2H), 6. 27 (brs, IH), 6. 91 (s, IH), 7. 18-7 · 32 (m, 3H), 7. 83- 7. 85 (d, 1H), 8. 45-8. 46 (d, IH)

211-214 1. 13-1. 15 (d, 6H), 4. 15-4. 21 (m, IH), 5. 82-5. 95 (d, 2H), 6. 94

212

-6. 96 (d, 1H), 7. 20-7. 36 (m, 3H), 7. 83-7 · 85 (d, 1H), 8. 43-8 · 44 (d,

1H)

129-132 1. 14-1. 16 (d, 6H), 4. 13-4. 18 (m, 1H), 5. 82-5. 95 (d, 2H), 6. 04

213

(Brs,

1H), 6. 97 (s, 1H), 7. 14-7. 36 (m, 3H), 7. 83-7. 85 (d, 1H), 8. 45- 8. 46 (d, 1H)

168-170 2. 67 (s, 3H), 5. 86-5. 99 (d, 2H), 6. 99 (s, 1H), 7. 43-7. 56 (m, 3H

214

), 8. 10-8. 12 (d, 1H), 8. 46-8 · 47 (d, 1H)

190-193 1. 19-1. 23 (t, 3H), 3. 42-3. 48 (m, 2H), 5. 89-6. 02 (d, 2H), 6. 27

215

(Brs,

1H), 6. 96 (s, 1H), 7. 26-7. 39 (m, 3H), 7. 90-7. 92 (d, 1H), 8. 52- 8. 53 (d, 1H) , 10. 13 (brs, 1H)

211-214 1. 13-1. 15 (d, 6H), 4. 15-4. 21 (m, 1H), 5. 82-5. 95 (d, 2H), 6. 94

216

-6 96

(D, 1H), 7. 20-7. 36 (m, 3H), 7. 83-7 · 85 (d, 1H), 8. 43-8 · 44 (d,

1H)

218-220 0. 90-0. 94 (m, 3H), 1. 49-1 · 51 (m, 2H), 3. 30-3 · 35 (m, 2H), 5. 83

217

-5. 96

(D, 2H), 6. 16 (brs, 1H), 6. 99 (s, 1H), 7. 19-7 · 35 (m, 3H), 7. 82- 7. 84 (d, 1H), 8. 43-8. 45 (d, 1H), 9. 82 (brs, 1H) compound represented by the structural formula (I) according to the present invention, index table index table 1 and 2 may be listed according to the present patent specification preparation Example 1-3 synthesis and synthetic methods described embodiments synthesized.

The present invention further provides a containing ortho-carboxamido-benzoyl-pyrazol-difluoromethoxy-use of amine salts of a compound represented by the structural formula (I) or an agriculturally suitable pesticide formulation for controlling pests and a method for controlling harmful organisms.

O-aminobenzoyl carboxamido containing a difluoromethoxy-pyrazole amine compound or an agriculturally suitable salt of pest control agent comprising the present invention represented by the structural formula (I) can be used to control pests on crops, e.g. as a problem in the agricultural and horticultural fields of various pests control agent, namely agriculture gardening pest control agents, parasites or animal pest control agents, namely animal parasitic biocontrol agents are particularly useful.

As the agricultural and horticultural pest control agents such as insecticide, miticide, it is useful, in particular, for the prevention and treatment of mite Tetranychus urticae, Tetranychus urticae, citrus, Panonychus ulmi and other plant parasitic mites; Plutella xylostella, Mamestra brassicae, Spodoptera litura, cotton bollworm, tobacco budworm, tobacco moth, rice leafroller, rice Adoxophyes, codling moth, peach moth solid, Grapholita molesta , black cutworm, potato beetle, cucurbit, aphids, whiteflies, thrips, locusts, and other agricultural pests like leafminers class. Wherein the agricultural and horticultural use containing the compound of the present invention, pest control agents, particularly effective for agricultural insect pests and the like. Further, ortho-carboxamido benzamides agricultural and horticultural or agriculturally suitable salt containing a fluorine-containing-methoxy-pyrazolo the present invention represented by the structural formula (I) with the pest control agent for the prevention and treatment of organophosphorus agents, carbamate agents, various drug resistant pests pyrethroid active agent. Further, the present invention is represented by the structural formula (I) containing a difluoromethoxy-pyrazol o carboxamido benzamides or agriculturally suitable salt thereof having excellent penetration metastatic because, by containing it is present agricultural and horticultural compound of the invention represented by the structural formula (I) by treating the soil pest control agent, while the control of harmful soil insects, mites and the like can also control pests like stem portion.

Carboxamido-containing o-aminobenzoyl as a difluoromethoxy-pyrazole amine compound or other preferred aspect agriculturally suitable pest control agent containing a salt of the structural formula (I) of the present invention represented by the above the integrated control of the above-mentioned plant parasitic mites, agricultural insect pests, soil insect pests such as agricultural and horticultural pest control agents.

Carboxamido containing o-aminobenzoyl difluoromethoxy containing a pyrazole amine compounds suitable for agricultural and horticultural agriculturally the present invention represented by the structural formula (I) or a salt thereof with the pest control agent is typically mixed with the compound various adjuvants on pesticide i.e. carrier to form dusts, granules, wettable powders, granules, wettable powders, aqueous suspensions, oily suspensions, aqueous solutions, emulsions, pastes, aerosols, and the like dispersed in trace various forms of formulation is used, but the object of the present invention as is appropriate, the formulations may be made of all forms normally used in the art. As an adjuvant used in the formulation may include diatomaceous earth, mixture of slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite, starch other solid carriers; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, N, N - solvent dimethylformamide, dimethylacetamide, N- methyl-2-pyrrolidone, alcohol or the like; fatty acid salt, a benzoate, an alkyl sulfosuccinate, a dialkyl sulfosuccinate acid salts, polycarboxylic acid salts, alkyl sulfate salts, alkyl sulfates, alkylaryl sulfates, alkyl diglycol ether sulfates, salts of alcohol sulfuric acid esters, alkyl sulfonates, alkylaryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, a polystyrene sulfonate, alkyl phosphates, alkylaryl phosphates, aryl phosphates , styryl aryl phosphate, a polyoxyethylene alkyl ether phosphates, Such anionic salt of polyoxyethylene alkylaryl phosphoric acid ester salts, naphthalenesulfonic acid formaldehyde condensate surfactant or developing solvent; sorbitan fatty acid esters, glycerin fatty acid ester, polyglycerol fatty acid esters, fatty acid alcohol polyglycol ether, acetylene glycol, block belongs alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, a polyoxyethylene styryl aryl ether, polyoxyethylene ethylene glycol alkyl ethers, polyethylene glycol, a polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene hardened castor oil, a polyoxypropylene fatty acid such ester nonionic surfactant, developing solvent; olive oil, melon wow kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil , rapeseed oil, linseed oil, tung oil, liquid paraffin or a vegetable oil such as mineral oil. These various ingredients adjuvants, without departing from the object of the present invention can be appropriately selected or two or more kinds. Further, this may be selected from among materials known in the art suitable adjuvants in addition to the above. It may also be used, for example, extenders, thickeners, dust-reducing agents, antifreeze agents, dispersing various adjuvants conventionally used stabilizer, a phytotoxicity reducing agent, and a fungicide.

The present invention is represented by structural formula (I), i.e., various adjuvants and a blending ratio by weight of the carrier is usually 0.1: 9~90 99.: 10. When the actual use of these formulations can be used directly, or diluted to a predetermined concentration with a diluent, and various spreaders may be added as needed (a surfactant, a vegetable oil, mineral oil, etc.) used.

Comprising the present invention represented by structural formula (I) agricultural and horticultural compound with administration of pest control agent, in accordance with weather conditions, preparation form, application time, the kind of application properties, pests or condition like occurs varies, not uniformly It is, but generally 0. 05~800ppm, preferably 0. 5~500ppm concentration of active ingredient to be administered, it is administered in an amount per unit per 1 hectare compounds of the invention l~5000g, preferably 10~1000g. Further, another preferred embodiment of the agricultural and horticultural pest control agent of the present invention comprising administering pest control agent, may be administered in accordance with the above-described pest control agent. The present invention also includes pest control methods using such methods of administration, especially plant parasitic mites, agricultural insect pests of the control methods.

Comprising the structural formula (I) of the present invention is a compound represented by the agricultural and horticultural pest control agents of various formulations used, or a dilution thereof is administered usually be administered using a method generally performed for example spreading, spraying, spraying (misting), fog of (a tomizi ng), granule applicators, submerged application method, soil application (such as mixing or irrigation) or surface application, dipping bait (as coating, dust coating or covering) or the like. Further, the above-described mixing the active ingredient administered to livestock feed servo, it may also hinder the pests in their excrement, especially the occurrence of harmful insects and fertility, may additionally use a small amount of a so-called ultra-high concentration walking method (ultra low volume) administration, in the method, the formulation may contain 100% of the active ingredient.

Further, the present invention comprises the structural formula (I) compounds may be represented by the use of a conventional insecticidal, fungicidal or herbicidal pesticides, or combination of two kinds or more, show more beneficial effects of the action. In particular the mix or combination of the present invention of formula (I) and a compound represented by other pesticide active ingredient compound of one kind or a mixture of two or more pest control composition, the scope of application may be, during the chemical treatment, prevention activity other improvements in the right direction. Further, the compounds of the present invention and the other active ingredient compound of the pesticide can be mixed formulations were prepared at the time of spreading, together may also be formulated using both, the present invention also includes such a mixed pest control composition .

Represented the structural formula (I) compounds and their preparations of the present invention has the following advantages:

(1) The present invention is first introduced in a difluoromethoxy pyrazole ring, a compound having a novel structure;

(2) preparation of a compound of the present invention and possess broad spectrum insecticidal activity: to lepidopterous pests (diamondback moth, Spodoptera frugiperda and Helicoverpa armigera), Hemiptera (Aphis and Myzus persicae), Homoptera head pests (rice brown planthopper), Diptera pests (clover leaf miner) and CPI leaf pests (Phaedon) have shown very good activity;

(3) preparation of compounds of the present invention has ultra-high insecticidal activity: at 0. 16mg / L dosage on the diamondback moth, Spodoptera frugiperda and H. armigera showed good results; at 4mg / L dose under aphids, leafminers, and clover Phaedon also exhibited good results; at 20mg / L dosage on rice brown planthopper exhibited good results;

(4) a compound of the invention and formulation with good security, security for some crops, such as wheat, soybean, cotton, rice and the like is good, and having a resistance to the environment;

Compound (5) of the present invention and the formulation has reasonably Toxicity, Ecotoxicity and environmental compatibility, low toxicity and environment-friendly pesticide. Embodiments of the invention described below, but the present invention is not limited thereto, first described the synthesis of compounds of the embodiment of the present invention. detailed description

Example 1 N- [2- (tert-butylcarbamoyl) -4-chloro-6-methyl - phenyl] -1- (3-chloro-2-pyridinyl) -3-- fluoromethoxy -1H- pyrazole-5-carboxamide (compound 8)

Step: 3-- difluoromethoxy-1- (3_-chloro-2-pyridinyl) lH-pyrazole-5-carboxylic acid Synthesis of

In 500ml three neck round bottom flask were added 1- (3-chloro-2-pyridinyl) -1H- pyrazole-3-hydroxy-5-carboxylate (13.35g, 0.05mol), 300ml of acetonitrile, the solid carbonate potassium (8.28g, 0.06mol), a fluorine monobromomethane (8.48g, 0.075mol), then heated to reflux until starting material disappeared the reaction was cooled to room temperature, filtered, the filter cake was rinsed with 2 * 50ml acetonitrile, and the filtrate was concentrated after the addition of methanol to dissolve 200ml, then slowly added dropwise 50ml containing aqueous sodium hydroxide (2.4g, 0.06mol) at room temperature, stirred at room temperature for about 30min, the reaction was complete, solvent was distilled off, water was added with diethyl ether 2 * 50ml extraction, the addition of dilute aqueous hydrochloric acidic PH value, the system generates a large amount of white solid was filtered, dried infrared lamp to give 3-- difluoromethoxy-1- (3-chloro-2-pyridinyl) -1H- pyrazole-5-carboxylic acid 11.05g, m.p. 149-151 ° C, yield 81.6%; ¾NMR (400MHz, DMSO- d 6) δ5.84-5 · 98 (d, 2H), 6.74 (s , 1H), 7.62-7 · 65 (m, 1H), 8. 19-8 · 21 (d, 1H), 8.53-8.54 (d, 1H), 13.65 (br, 1H); m (%): 270 (100).

Step Two: 6-Chloro-2- [3_- difluoromethoxy -l- (3- chloro -2-B ratio piperidyl) - 1H-5- pyrazolyl] -8-methyl -4H- [ synthesis d] [1, 3] benzoxazin-4-one

In 250ml three neck round bottom flask, 3-- fluoro-methoxy-1- (3_-chloro-2-pyridinyl) lH-pyrazole-5-carboxylic acid (3g, O. Ollmol) (1- Synthesis Example step product), 2-amino --5- chloro --3- methylbenzoic acid (2.04g, O. Ollmol), acetonitrile 150ml, 7 ml of pyridine, was stirred to dissolve all the solids, the system was cooled at _5 ° ~- 10 ° was added dropwise methanesulfonyl chloride (2ml, 2.96g, 0.026mol) / 20ml acetonitrile solution, after the addition was complete, kept at _5 ° ~- 10 ° LH reaction, then naturally raised to room temperature for 3h, after completion of the reaction , add water 30ml, stirred for 30min, filtered, the filter cake was washed with 2: 1 acetonitrile / water (2 * 40ml), acetonitrile (2 * 20ml) and ether (2 * 20ml) was rinsed to give the first batch of solid; the filtrate was evaporated after the solvent, water was added, extracted with ethyl acetate (3 * 40ml), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated and recrystallized from ethanol to give a second crop of solid, two batches of solid were combined to give 6 - chloro-2- [3_- difluoromethoxy-1- (3_-chloro-2-pyridinyl) - 1H-5- pyrazolyl] -8-methyl - 4H- [d] [1, 3] benzoxazin-4-one 4. 17g, m.p. 206.0-207.5 ° C, yield 84.22%; ¾NMR (400ΜΗζ, CDC1 3) ^ 1.81 (s, 3H), 5.83-5.97 (d, 2H), 6.85 (s, lH), 7.46-7.49 (m, 2H), 7.84-7.99 (m, 2H), 8.54-8.56 (d , 1H); M (%): 421.0 (100).

Third Step: 2- (3-chloro-2-pyridinyl) -2H- pyrazol -5-- difluoromethoxy-yl - (2-tert-butyl-carbamoyl-4-chloro-6-methyl - phenyl ) synthesis of 3-carboxamide

In 50ml single neck round bottom flask, 6-chloro-2- [3-- difluoromethoxy-1- (3-chloro-2-pyridyl) - 1H_5_ pyrazol-yl] -8-methyl _4H - [d] [1, 3] tetrahydrofuran-benzoxazin-4-one (lg, 0. 00238mol) (product of Step embodiment synthesis Example 1_) was slowly added dropwise tert-butylamine (0. 21g, 0 . 00286mol), stirred overnight at room temperature, the reaction was completed, tetrahydrofuran was evaporated under reduced pressure, the residue was added with a little ethanol. after stirring a few minutes, filtered to give a white solid 1. 02 g, namely 2- (3-chloro-2 - pyridinyl) -2H- pyrazol -5-- difluoromethoxy-yl - (2-tert-butyl-carbamoyl-4-chloro-6-methyl-phenyl) - 3_ carboxamide, m.p. 227.0-228.0 ° C, The yield was 87 · 6%; ¾NMR (400MHz , DMS0_d 6) ^ 1.26 (s, 9H), 2.16 (s, 3H), 5.84-5.98 (d, 2H), 6.93 (s, lH), 7.26-7.58 ( m, 4H), 8.10-8.13 (m , lH), 8.45-8.46 (d, 1H), 10.10 (S, 1H); m (%): 492. 5 (100).

Example 2 N- [2- (methylamino) -4-chloro - 6-methyl - phenyl] -1- (3-chloro - 2-pyridyl) -1H -3-- fluoromethoxy - pyrazole-5-carboxamide (compound 3) in 50ml single-necked round-bottomed flask, 6-chloro-2- [3-- difluoromethoxy-1- (3-chloro-2-pyridinyl) - 1H_5_ pyrazol-yl] -8-methyl _4H- [d] [1, 3] benzoxazin-4-one (lg, 0. 00238mol) (synthesis Example 1_ second stage product) in tetrahydrofuran was added methylamine hydrochloride (0. 19g, 0. 00286mol) and anhydrous sodium acetate (0. 24g, 0. 00286mol), stirred overnight at room temperature, the reaction was completed, tetrahydrofuran was evaporated under reduced pressure, the residue was water was added, extracted with ethyl acetate, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated to give crude product, a white solid was recrystallized from ethanol to give 0. 87 g, namely N- [2- (methylcarbamoyl) 4-chloro-6-methyl-phenyl] -1 - (3_-chloro-2-pyridinyl) -1H- -3-- difluoromethoxy-pyrazole-5-carboxamide, m.p. 236.0-237.4 ° C, yield 82. 7%; ¾NMR (400MHz, DMSO- d 6) δ 2.18 (s, 3H), 2.93-2.94 (d, 2H), 5.83-5.96 (d, 2H), 6.16-6.17 (d , lH), 6.70 (s, lH), 7.20-7.36 ( m, 4H), 7.82-7.84 (d, lH), 8.44-8.45 (d 1H), 9.96 (S, 1H); M (%):. 450. 0 (100).

Example 3 N- [2- (ethylamino) -4-cyano-6-methyl - phenyl] -1- (3-chloro-2-pyridinyl) -3-- difluoromethoxy - 1H- pyrazole-5-carboxamide (compound 33) Step 1: 6-cyano-2- [3_- difluoromethoxy-1- (3_-chloro-2-pyridinyl) - 1H-5 - pyrazol-yl] -8-methyl -4H- [d] [1, 3 synthesis] benzoxazin-4-one

In 250ml three neck round bottom flask, 3-- difluoromethoxy-1- (3-chloro-2-pyridinyl) lH-pyrazole _5_ acid (5g, 0. 0185mol) (Synthesis Example 1_ first stage product), 2-amino-cyano _3_ _5_ methylbenzoic acid (3. 24g, 0. 0185mol), acetonitrile 150ml, pyridine 15ml, and stirred to dissolve all solids, the system was cooled, _5 ° ~- 10 ° was added dropwise methanesulfonyl chloride (4ml, 5.98g, 0.052mol) / 20ml acetonitrile solution, after completion of the dropwise addition, reaction was maintained lh at _5 ° ~- 10 °, then naturally raised to room temperature for 3h, after completion of the reaction, water 30ml, stirred for 30min, filtered, the filter cake was washed with 2: 1 acetonitrile / water (2 * 40ml), acetonitrile (2 * 30ml) and ether (2 * 30ml) was rinsed to give the first batch of solid; the filtrate was distilled off the solvent, water was added, extracted with ethyl acetate (3 * 40ml), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated and recrystallized from ethanol to give a second crop of solid, two batches of solid were combined to give a light yellow solid 4.17 g, namely 6-cyano-2- [3_- difluoromethoxy-1- (3_-chloro-2-pyridinyl) - 1H-5- pyrazolyl] 8- yl _4H- [d] [1,3] benzoxazin-4-one, m.p. 208.5-211.0 ° C Yield 54.87%; ¾NMR (400MHz, CDC1 3) δ 1.86 (s, 3H), 5.84-5.97 (d, 2H), 6.90 (s, lH), 7.27-7.98 (m, 3H), 8.32 (s, lH), 8.55-8.56 (d, lH); M (%): 411.1 (100).

Step: N- [2- (ethylamino) -4-cyano-6-methyl - phenyl] -1- (3-chloro-2-pyridinyl) -3-- fluoromethoxy -1H- pyrazole-5-carboxamide

In 50ml single neck round bottom flask, 6-cyano-2- [3-- difluoromethoxy-1- (3-chloro _2_ pyridinyl) - 1H_5_ pyrazol-yl] -8-methyl-_ 4H- [d] [1,3] tetrahydrofuran-benzoxazin-4-one (0.4g, 0.00097mol) (synthesis Example 3_ first stage product) was slowly added dropwise ethylamine (65-70 %, 0.083g, 0.0012mol), was stirred overnight at room temperature, the reaction was completed, tetrahydrofuran was evaporated under reduced pressure, the residue was added with a little ethanol. after stirring a few minutes, filtered to give a light gray solid 0.35g, namely N- [2 - (ethylamino) -4-cyano-6-methyl-phenyl] -1 - (3_-chloro-2-pyridinyl) -3-- difluoromethoxy--1H- pyrazol-5 carboxamide, m.p. 151.0-152.5 ° C, yield 78.6%; ¾NMR (400MHz, DMSO- d 6) ^ i.23-1.27 (m, 3H), 2.26 (s, 3H), 3.45-3.48 (m, 2H),

5.84-5.98 (d, 2H), 6.23 (s, lH), 6.64 (s, lH), 7.36-8.48 (m, 5H), 10.52 (s, lH); M (%): 457.1 (100). The following Example 4 to Example 6 to give the compound (I) of the present invention as an active ingredient group of substances, the preparation process of several practical examples of pesticide formulations, it is noted that the present invention is not limited to the following Examples range. In the examples of these formulations, all "%" are by weight. Example 4 Wettable Powder Formulation

15% of the compound (8) (index table 1), 3% of sodium ligninsulfonate salt (M Q), 2% of the polyoxyethylene lauryl alcohol (the JFC), 40% of diatomaceous earth and 40% precipitated calcium carbonate intimately mixed, the ultrafine grinder, to obtain 15% wettable powder yield

Π

ΡΠ.

Formulation Example 5 Emulsifiable concentrates

10% of compound (8) (index table 1), 5% milk farmers, 500 (calcium salt), 5% milk farmers 602, 5% N- methyl-2-pyrrolidone and 75% titanium toluene was heated and stirred uniformly to obtain a 10% emulsifiable concentrate products. Example 6 Water dispersible granule formulation

60% of Compound (8) (index table 1), 2% polyvinyl pyrrolidone, 12% sodium naphthalene sulfonate formaldehyde condensate, 8% N- methyl -N- oleoyl - taurate, 2% of carboxymethylcellulose, and 16% kaolin clay were uniformly mixed, smash, kneaded together with the water added for granulation 10-100 mesh sieve granulator, and then dried, sieved (mesh network range). To obtain 60% water dispersible granule product. Example 7 The following Example 14 to give compounds of the invention are given below bioassay were instances, be noted that the present invention is not limited within the scope of the following examples.

Evaluation of pesticidal activity test was carried out according to the following method:

Test compound with acetone / methanol: After dissolving (11) in a mixed solvent, diluted with distilled water containing 0.1% Tween 80 to the desired concentration.

Test targets for diamondback moth Plutella xylostella, Spodoptera frugiperda Spodoptem f rug i per da), bollworm iHeliothis armigera), alfalfa fine cavities (Aphis medicaginis ^ peach cavities {Myzus persicae ^ rice brown planthopper (

Figure imgf000037_0001
ta lugens), clover leaf miner (r / o) and Phaedon (Phaedon cochleariae.

Hereinafter "mg / L" are per mg of active substance / l.

Test statistics: statistical dead insects were each treated and the number of live insects, mortality was calculated.

Mortality (%) = number of live insects Number of test insects χ Κ) 0

Note the number of test insects: Example number index table index Table 1 Compound No. 2, and the corresponding bioactivity embodiment. Example 7 Effect Test for Plutella xylostella Plutella xylostella) embodiment

Cabbage cut sheet, punching into a circle, and then immersed in liquid in 20s, put in a plastic Petri dish 09cm (5 / dish), then 15 2nd instar Plutella xylostella / dish and put on a filter paper, stamped . Chamber was placed 26 ° C incubation, test results after 72h. The experiment was repeated four times. Pointed tweezers to touch the worms, dead insects treated as non-responders. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Table 1 Index Compound 1-27, 33-63, 85-86, 89, 93, 99-106, 110-112 to give 100% mortality in 4mg / L while. Further compounds 1, 3, 4, 8, 33, 49-51, 57-58, 59, 83, 89, 101, 103, 106 to obtain a mortality of at least 80% 0. 16mg / L time. Example 8 For Spodoptera frugiperda i Spodoptera frugiperda) the test results of potted cotton (2-3 single leaf stage) for spraying agent, dry. Into the culture room and cultured normal. 5, 12, the blade 19d cut with scissors, placed in 09cm plastic dish, then frugiperda larvae, a release paper, stamped. Placed under observation room, test results after 6d. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 3 Compound 1, 8, 10, 33, 49, 50, 51 to give 100% mortality in 4mg / L while. Compound 3, 8, 33, 51 to obtain a mortality of at least 90% of 0. 8mg / L time. Compound 8, 33, 51 to obtain a mortality of at least 80% 0. 16mg / L time. Test results for Example 9 bollworm Heliothis armigera) embodiment

Potted cotton (2-3 single leaf stage) spray of the agent processing, dry. Into the culture room and cultured normal. 5, 12, the blade 19d cut with scissors, placed in 09cm plastic dish, then cotton bollworm, a release paper, stamped. Placed under observation room, test results after 6d. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 3 Compound 1, 8, 10, 33, 36, 49, 51 to give 100% mortality at 20mg / L time. Compound 8, 10, 33, 51 to give 100% mortality in 4mg / L while.

Compound 8 0. 16mg / L obtained when 100% mortality. Example 10 Test for Effect Aphis phis medicaginis) embodiment

The cut ends Vicia back up on the small piece of cotton and placed in a Petri dish, add a little water, then aphid Aphis as to produce nymphs. 24h after removing the adult aphids, culture was continued after 2d placed on the cotton leaves and air dried after infiltration of the chemical solution 5s. Test results for 24h. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 3 Compound 1, 8, 10, 33-37, 39, 27, 47, 51, 83, 85, 89, 95, 101 to give at least 90% mortality at 20mg / L time. Compound 3, 8, 33, 34, 35, 36, 51, 83, 101 to give at least 80% mortality at 4mg / L while. Example 11 Effect Test for Myzus Myz U s persicae) embodiment

The potted cabbage (photos 3-4 leaf stage) spray of the agent processing, dry. Into the culture room and cultured normal. After 5, 12, 19d, respectively, with access nymphs of Myzus persicae. Placed under observation room, test results after 7-10d. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 3 Compound 1, 8, 10, 33, 51 to give 100% mortality at 20mg / L time. Compound 3, 8, 33, 51 to obtain at least 90% mortality at 4mg / L while. Example 12 Test for Effect of Rice brown planthopper Nilaparvata lugens) in the embodiment

The white quartz sand, rice plants in a petri dish is fixed, then anesthetized with C0 2 3 mid-instar nymphs placed in a spray tower by spraying the POTTER. After spraying with a transparent plastic cup hooded, put in the observation room after labeling. Check the results after 72h. The experiment was repeated four times. Pointed tweezers to touch the worms, dead insects treated as non-responders. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 1 Compound 8, 33, 36, 51-53, 57, 58 to obtain at least 90% mortality at 100m g / L time. Compound 8, 33, 51 to obtain at least 80% mortality at 20mg / L time. Example 13 Effect for Test clover leaf miner iriomyza TrifoliD

Potted bean (sheets 3-4 leaf stage) for spraying agent, dry. Into the culture room and cultured normal. After 5, 12, 19d are respectively connected clover leaf miner larvae. Placed under observation room, test results after 7d. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 1 Compound 8, 9, 10, 33, 36, 49, 51 to give 100% mortality at 20mg / L time. Compound 8, 10, 49, 51 to give 100% mortality in 4mg / L while. Example 14 Test for Effect Phaedon Phaedon cochleariae) embodiment

The potted cabbage (photos 3-4 leaf stage) spray of the agent processing, dry. Into the culture room and cultured normal. 5, 12, the blade 19d cut with scissors, placed in 09cm plastic dish, then Phaedon or 2 instar larvae of Plutella xylostella, a release paper, stamped. Placed under observation room, examination results 6_7d. The mortality was calculated according to the above formula mortality. Insect also be seen as abnormal death. Index Table 3 Compound 1, 8, 10, 33, 36, 49, 51 to give 100% mortality at 20mg / L time. Compound 3, 8, 33, 51 to obtain at least 90% mortality at 4mg / L while. Compound 8 0. 8mg / L obtained when at least 90% mortality. According to the above method, the compound 8 and selection known compound chlorantraniliprole Plutella xylostella were killed, brown rice and alfalfa aphid fly results in Table 3.

Figure imgf000039_0001

Active compound chlorantraniliprole and parallel to the known compound chlorantraniliprole (mortality%) comparing the concentration 8

Compound No. Plutella concentration (mg / L) Aphis rice brown planthopper

(Mg / L) (mg / L)

0.8 10020100100100

8 (Example 1) 0.16 1004902080

80 0.032 3040 0.8 0.8 chlorantraniliprole 100207010080

0.16 80,402,010 20 0.032 0.8 040 Conclusion: lepidopterous pests Plutella respectively, of Hemiptera Aphis at 20mg / L at a dose of 4mg / L at a dose of 0. 16mg / L dose of the Homoptera rice brown planthopper; compound 8 of the present invention (Example 1) was superior to known pesticidal active compound chlorantraniliprole.

Claims

Claims
1, a fluorine-containing o-methoxy-pyrazol-carboxamido benzamides represented by a structural formula (I) or an agriculturally suitable salt thereof,
Figure imgf000041_0001
Its towel:
A is N or CH;
R 1 is hydrogen, halo, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block groups, block groups halo, alkoxy, cyano, alkoxy group, ^ alkoxy group, an alkylthio group, on behalf of ^ alkylthio, alkylsulfonyl, alkylcarbonyl, substituting ^ alkylcarbonyl, alkoxycarbonyl, substituting ^ alkoxycarbonyl or an amino group;
R 2 is hydrogen, halo, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
R 3 is hydrogen, alkyl or alkoxy;
R 4 is hydrogen, cyano, alkyl, alkoxy, alkylamino, ^ alkyl group, alkoxy group ^, ^ alkane amino, cyano, cycloalkyl, substituting ^ cycloalkyl, hydroxyalkyl alkyl group, an alkoxycarbonyl group, an alkoxy group, an amide group, an alkyl amide group, an amide group ^ substituted alkyl, cyano-substituted aromatic heterocyclic alkyl group or an amide group;
Or R 3 and R 4 form a ternary starting with N- attached, quaternary, five- or six-membered ring;
m is an integer of 0~4;
n is an integer of 0~4.
2, according to a fluorine-containing o-methoxy-pyrazol-carboxamido benzamides according to claim 1, wherein said structural formula (I):
R 1 is hydrogen, halo, cyano, nitro, d-Ce-wan group, d-Ce-haloalkyl, cyano-d-Ce-alkyl, C 2 _C 6 alkenyl group,
C 2 _C 6 haloalkenyl, C 2 -C 6 block basis, C 3 -C 6 halo-block basis, (- (: 6 alkoxy, cyano dC 6 alkoxy, haloalkoxy dC 6 , d-Ce-alkylthio, d-Ce-haloalkylthio, d-Ce-alkyl sulfonyl group, a carbonyl group CFCE alkyl, haloalkyl CFCE alkylcarbonyl, (of Ce alkoxycarbonyl, substituting ^ dC 6 alkoxycarbonyl dC 6 alkyl or amino;
R 2 is hydrogen, halogen, d-Ce-alkyl, halo-d-Ce-alkyl, d-Ce alkoxy, haloalkoxy CfCe alkoxy or cyano;
R 3 is hydrogen or alkyl;
R 4 is hydrogen, cyano, d-Ce-alkyl, d-Ce-alkoxy, d-Ce-alkylamino, haloalkyl CfCe alkyl, halo CfCe alkoxy, dc. 6 halogenated alkylamino group, a cyano group dc 6 alkyl, c 3 -c 6 cycloalkyl, c 3 -c 6 halo-cycloalkyl, hydroxyalkyl, - (: 6 alkyl, DC 6 alkoxycarbonyl group, (;-(: 6 alkoxylactam group, dc 6 alkylamido, substituting dc 6 ^ alkyl amide group, cyano dc 6 alkylamide group or aromatic heterocyclic group;
m is 2;
n is 1.
3, according to a fluorine-containing o-methoxy-pyrazol-carboxamido benzamides according to claim 2, wherein said structural formula (I):
A is N;
R 1 is hydrogen, halo, cyano, dC 6 alkyl, haloalkyl or dC 6 dC 6 alkylcarbonyl;
R 2 is halogen, cyano, alkyl or haloalkyl CFCE dC 3 alkyl.
4, according to a fluorine-containing o-methoxy-pyrazol-carboxamido benzamides according to claim 3, wherein said structural formula (I):
R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R 2 is halogen or cyano.
5, according to claim containing a difluoromethoxy-pyrazol o carboxamido benzamides claim 4, wherein said I) compound:
Figure imgf000042_0001
6, an intermediate o-difluoromethoxy-carboxamido a pyrazole-containing benzamides according to any one of claim 1 prepared according to claim 5, characterized by having the following structural formula (Π):
Figure imgf000043_0001
Its towel:
A is N or CH;
R 1 is hydrogen, halo, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block groups, block groups halo, alkoxy, cyano, alkoxy group, ^ alkoxy group, an alkylthio group, on behalf of ^ alkylthio, alkylsulfonyl, alkylcarbonyl, substituting ^ alkylcarbonyl, alkoxycarbonyl, substituting ^ alkoxycarbonyl or an amino group;
R 2 is hydrogen, halo, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
m is an integer of 0~4;
n is an integer of 0~4.
7, prepared as claimed in claim 6 o claim carboxamido-containing intermediate is a benzamides difluoromethoxy-pyrazole claim 1 to 5, characterized in that the structural formulas ([pi) in:
A is N;
R 1 is hydrogen, halo, cyano, nitro, -Ce alkyl, dC 6 haloalkyl, cyano dC 6 alkyl, (: 2 - (: 6 alkenyl, C 2 _C 6 haloalkenyl , C 2 -C 6 block basis, C 3 -C 6 halo-block basis, dC 6 alkoxy group, a cyano group 6 alkoxy dC, dC 6 haloalkoxy, (;-(: 6 alkylthio, dC 6 haloalkylthio, alkylsulfonyl 6 dC, dC 6 alkylcarbonyl, halo-dC 6 alkylcarbonyl, alkoxycarbonyl 6 dC, dC ^ substituting 6 alkoxycarbonyl group or an amino group dC 6;
R 2 is hydrogen, halo, alkyl CFCE, dC 6 haloalkyl group, (- (: 6 alkoxy, halo (- (: 6 alkoxy or cyano; m is 2;
n is 1.
8, prepared as claimed in claim 7 according to claim ortho-carboxamido-containing intermediate is a benzamides difluoromethoxy-pyrazole claim 1 to 5, characterized in that the structural formulas ([pi) in:
R 1 is hydrogen, halo, cyano, dC 6 alkyl, haloalkyl or dC 6 dC 6 alkylcarbonyl;
R 2 is halogen, cyano, alkyl or haloalkyl CFCE dC 3 alkyl.
9, prepared as claimed in claim 8 according to claim carboxamido-containing intermediate o benzamides of a difluoromethoxy-pyrazole claim 1 to 5, characterized in that the structural formulas ([pi) in:
R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R 2 is halogen or cyano.
10 A method according to claim ortho-carboxamido-containing synthetic benzamides a difluoromethoxy-pyrazole according to claim 1, characterized by the following steps:
Compound (1) in an aprotic solvent, represented by the structural formula (VI) with a fluorine bromide in a acid binding agent to act, reaction of formula (W) a compound represented by;
(2) in a protic solvent of formula (W) a compound represented by the action of an alkali hydrolysis to give a fluorine-containing carboxylic acid methoxy pyrazole represented by the formula (III);
(3) in an aprotic solvent, adding a base, and an alkylsulfonyl chloride, a fluorine-containing carboxylic acid, and methoxy pyrazole of formula (V) represents a substituted anthranilic acid represented by the structural formula (III) reacted formula ( [pi) containing a fluorine-methoxy-4H- benzo pyrazole represented by [1, 3] oxazin-4-ones;
A fluorine-containing pyrazole methoxy 4H- benzo [1,3] oxazin-4-ones represented by the compound of formula (IV) (4) in an aprotic solvent, represented by the formula ([pi) a fluorine-containing o-methoxy-pyrazol-carboxamido benzamide compound represented by formula reacted (the I);
Wherein the structural formula (Π), (111), (IV), (V), (VI) and (YD) compound represented by the following:
Figure imgf000044_0001
A, RR 2, R 3, R 5 groups, and m and n are as defined and R 4 of claim 1.
11. The ortho-carboxamido-containing synthetic benzamides a difluoromethoxy-pyrazole according to claim 10, wherein:
Step (1) a compound represented by the structural formula (VI) with a ratio of fluorine and an acid-binding agent is methyl bromide feed was 1: 1.1~2: 1.1~2, the aprotic solvent is selected from tetrahydrofuran, acetonitrile, 1, 4-dioxane, acetone or a combination of one or two or more, the reaction temperature is 10~90 ° C;
Said step of formula (W) (2) represents the ratio of the compound with a base in the feed was 1: ~ 1.5, said protic solvent is methanol and / or ethanol, the reaction temperature is 10~90 ° C;
Ratio and containing a substituted anthranilate alkylsulfonyl chloride feed material and a fluorine-carboxylic acid represented by formula (V) methoxy pyrazole in step (3) in the structural formula (III) is represented by 1: 1 5 ~ 1: 2 ~ 3, the alkylsulfonyl chloride is methanesulfonyl chloride, the aprotic solvent is selected from tetrahydrofuran, acetonitrile, 1,4-dioxane, diethyl ether or toluene or a two or more thereof, said base is an organic base, the reaction temperature is -30~80 ° C;
Compound feed material in step (4) containing a fluorine-methoxy-4H- benzo pyrazole represented by the structural formula (Π) [1, 3] oxazin-4-ones and structural formula (IV) represented by the equivalent ratio of 1: 1 ~ 5, the aprotic solvent is selected from tetrahydrofuran, acetonitrile, 1,4-dioxane, diethyl ether, toluene, chloroform, dichloromethane, or one or two or more thereof.
12. A benzamides o-carboxamido-containing a synthetic difluoromethoxy-pyrazole according to claim 11, wherein:
Compound of step (1) in the structural formula (VI) represented by a ratio of fluorine with a bromide feed material and the acid binding agent is 1: 5 1. 1~1: 1~1 1. 5, the reaction temperature is 20~80 ° C;
Said step of formula (VD) (2) represents the ratio of the feed material with a base of 1: 1~1 2, the reaction temperature is 20~80 ° C;
Ratio and containing a substituted anthranilate alkylsulfonyl chloride feed material and a fluorine-carboxylic acid represented by formula (V) methoxy pyrazole in step (3) in the structural formula (III) is represented by 1: 1 .. 2 ~ 1: 2~2 5, the organic base is selected from triethylamine, pyridine or 3-methylpyridine one or two or more thereof, the reaction temperature is -15~30 ° C;
Compound feed material in step (4) containing a fluorine-methoxy-4H- benzo pyrazole represented by the structural formula (Π) [1, 3] oxazin-4-ones and structural formula (IV) represented by the equivalent ratio of 1: 1 ~.
13, o-aminobenzoyl carboxamido containing a difluoromethoxy-pyrazole amine compound or an agriculturally suitable salt thereof, such as the use of a formula (I) according to claims 1 to 12 represented by their characterized in that the structure (I) are used to control pests on crops.
14. A pesticide formulation of pest control, comprising: an amine-containing compound containing an ortho-carboxamido-aminobenzoyl difluoromethoxy-pyrazole or a salt thereof according to structural formula (I) according to claim 1 represented by as an active ingredient and pharmaceutically agriculture, forestry, public health carrier, wherein the weight ratio of the active ingredient and the carrier is 0.1: 99. 9~90: 10.
15. A method for controlling pests, characterized in that: according to claim 14 pesticide formulation applied to the medium to be controlled or the growth of harmful organisms, wherein the effective amount of active ingredient is from 10 to 1000 grams per hectare g.
16. A method of controlling pests, which Laid wherein: containing a fluorine-containing o-methoxy-pyrazol-carboxamido benzamide compound represented by the structure according to formula (I) according to claim 1 and conventional kill one kind of insects, pesticides bactericidal or herbicidal or in combination of two or two or more.
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