WO2012034403A1

WO2012034403A1 - Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof

Info

Publication number: WO2012034403A1
Application number: PCT/CN2011/073810
Authority: WO
Inventors: 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
Original assignee: 中化蓝天集团有限公司; 浙江省化工研究院有限公司
Priority date: 2010-09-14
Filing date: 2011-05-09
Publication date: 2012-03-22
Also published as: CN101967139B; CN101967139A

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

Instruction manual

O-formylaminobenzamide compound containing monofluoromethoxypyrazole, synthesis method and application thereof

The present invention provides an o-formylaminobenzamide compound. Background technique

O-formylaminobenzamides (Finedine Receptor Inhibitors) are effective insecticides developed in recent years to control pests without ridges.

The PCT patent application WO2003/015519 discloses the following compounds having insecticidal activity:

R=CF ₃ , Cl, Br or OCH ₂ CF ₃

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

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

PCT patent application WO2006/080311 discloses compounds having insecticidal activity as follows:

The PCT patent application WO 2008/134969 discloses the following compounds having insecticidal activity:

All of the compounds disclosed in the above PCT patent application have certain similarities with the compounds of the present invention, but none of them have a homologous one containing a fluoromethoxypyrazole represented by the formula (I) of the present invention. Formylaminobenzamides. Although many products for controlling invertebrate pests can be purchased, there is still a need for new compounds that are more effective, less toxic, less costly, and environmentally safe. Summary of the invention

The object of the present invention is to provide a novel pest control agent which can prevent various pests which are problems in the field of agriculture and horticulture, or pests which are parasitic on animals, and which have high pests at low doses. Control effect.

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

A fluoromethoxypyrazole-containing orthoamidobenzamide compound represented by the formula (I) or an agriculturally applicable salt thereof,

Its towel:

A is N or CH;

R ¹ is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;

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

R ³ is hydrogen, alkyl or alkoxy;

R ⁴ is hydrogen, cyano, alkyl, alkoxy, alkylamino, alkyl, alkoxy, alkylamino, cyanoalkyl, cycloalkyl, cycloalkyl, hydroxy An alkyl group, an alkoxycarbonylmethyl group, an alkoxyamide group, an alkylamido group, an alkylalkylamide group, a cyano substituted alkylamido group or an arylheterocyclic methyl group;

Or R ³ and R ⁴ form a ternary, quaternary, five- or six-membered ring with the N-linked group;

m is an integer from 0 to 4;

n is an integer of 0 to 4. In a preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):

R ¹ is hydrogen, halogen, cyano, nitro, d-Ce fluorenyl, d-Ce haloalkyl, cyano d-Ce alkyl, C ₂ _C ₆ alkenyl,

C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ block, halo C ₃ -C ₆ block, (-(: ₆ alkoxy, dC ₆ cyanoalkoxy, dC ₆ haloalkoxy) , d-Ce alkylthio, d-Ce haloalkylthio, d-Ce alkylsulfonyl, CfCe alkylcarbonyl, halogenated CfCe alkylcarbonyl, (ce alkoxycarbonyl, ^dC ₆ alkoxycarbonyl) Or an amino dC ₆ alkyl group;

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

R ³ is hydrogen or an alkyl group;

R ⁴ is hydrogen, cyano, d-Ce alkyl, d-Ce alkoxy, d-Ce alkylamino, halogenated CfCe alkyl, halogenated CfCe alkoxy, halo (-(: ₆ alkylamino, Cyano dC ₆ alkyl, (: ₃ _(: ₆ cycloalkyl, halo (: ₃ _: ₆ cycloalkyl, hydroxy (-(: ₆ alkyl, dc ₆ alkoxycarbonylmethyl, (^ -(: ₆ alkoxyamido group, dc ₆ alkyl amide group, ^ dc ₆ alkyl amide group, cyano substituted dc ₆ alkyl amide group or aryl heterocyclic methyl group;

m is 2;

n is 1. In a further preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):

A is N;

R ¹ is hydrogen, halogen, cyano, CfCe alkyl, d-haloalkyl or d-alkylcarbonyl;

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

In a still further preferred mode, the monofluoroamidobenzoylamine compound containing a monofluoromethoxypyrazole represented by the formula (I):

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

R ² is a halogen or a cyano group.

As a most preferred mode, the fluoroformylpyrazole-containing o-formylaminobenzamide represented by the formula (I)

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

Examples of the halogen in the RR ² or R ⁴ or the halogen as the substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogens as a substituent may be 1 or 2 or more, and when it is 2 or more, each halogen may be the same or different. In addition, the halogen substitution position can be at any position.

The alkyl or alkyl moiety in RR ² , R ³ or R ⁴ may be straight or branched. Specific examples thereof include a d- ₆ alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group or a hexyl group.

The alkenyl or alkenyl moiety in R ¹ may be either a straight chain or a branched chain. Specific examples thereof include C ₂ such as a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 1, 3-butadienyl group, and a 1-hexenyl group. ₆ The block group or the block group portion in R ¹ may be either a straight chain or a branched chain. 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.

In the orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), an isomer such as an optical isomer or a geometric isomer may be present, and the present invention encompasses various forms. Both the conformation and the mixture of isomers. Further, the present invention also encompasses various isomers other than the above within the scope of technical knowledge in the technical field. Further, although a chemical structure different from the above structural formula (I) may be formed depending on the kind of the isomer, as long as those skilled in the art can fully recognize that the isomer exists, it is apparent that Within the scope of the invention.

The present invention also provides an orthoylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), which has the following structural formula (Π):

Among them, A, R ¹ and R ² groups and! ! ! with! Corresponding to a group in the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), namely:

A is N or CH;

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

m is an integer from 0 to 4;

n is an integer of 0 to 4.

In a preferred embodiment, the compound represented by the structural formula (Π) is:

A is N;

R ¹ is hydrogen, halogen, 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, halogenated C ₃ -C ₆ block, -C ₆ alkoxy, dC ₆ cyanoalkoxy, -C ₆ haloalkoxy, ^-alkyl 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 or amino-C ₆ alkyl;

R ² is hydrogen, halogen, C _r C ₆ alkyl, halogenated C _r C ₆ alkyl, C _r C ₆ alkoxy, halogenated C _r C ₆ alkoxy or cyano; m is 2; n is 1.

As a further preferred mode, among the compounds represented by the structural formula (Π):

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

R ² is halogen, cyano, CfCe alkyl or halogenated dC ₃ alkyl.

In a more preferred manner, among the compounds represented by the structural formula (Π):

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

R ² is a halogen or a cyano group.

The present invention also provides a method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I).

A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), comprising the steps of:

(1) In an aprotic solvent, a compound represented by the formula (VI) is reacted with a monofluoromethane bromide under an action of an acid binding agent to give a structural formula (W) to represent a compound;

(2) In a protic solvent, the structural formula (W) indicates that the compound is hydrolyzed under a base to give a monofluoromethoxypyrazolecarboxylic acid represented by the formula (III);

CHPF

Yesterday

(VI) (VD) (III)

(3) In a non-protic solvent, a base and an alkylsulfonyl chloride are added, and the monofluoro-aminopyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid represented by the formula (V) are reacted to obtain a structural formula ( 4 ) represented by a monofluoro-pyridazole-containing 4H-benzo[1,3]oxazin-4-one compound;

(4) A 4-fluorenyl-benzo[Z,3-oxazin-4-one-based compound containing a monofluoromethoxypyrazole represented by the formula (Π) and a compound represented by the formula (IV) in an aprotic solvent Reacting the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I);

(II) (IV) (I)

The definitions and preferred forms of the A, RR ² , R ³ , R ⁴ and R ⁵ groups and m and n in the compounds represented by the formulae (II) to (YD) are as defined above for the monofluoromethoxy group represented by the formula (I). An orthoformylbenzamide compound of pyrazole, wherein the compound represented by the formula (VI) is in the compound! ^ is ^ _-6 alkyl.

The compound represented by the above formula (VI) is a known compound, and its preparation method can be referred to PCT Patent Application No. WO03015519 and WO2006023783.

In a preferred embodiment, in the step (1) of the synthesis method, the ratio of the compound represented by the formula (VI) to the material of the monofluoromethane bromide and the acid binding agent is 1: 1.1 to 2: 1.1 to 2, further preferably 1: 1.1~1.5: 1.1~1.5; The aprotic solvent is selected from one or a combination of two or more of tetrahydrofuran, acetonitrile, 1,4-dioxane or acetone; the reaction temperature is 10 to 90 ° C Further preferably 20 to 80° (:.

Step (1) The post-treatment of the compound represented by the structural formula (W) is: filtration, the filter cake is washed with a small amount of an organic solvent, and the filtrate is combined and concentrated. The hydrolysis reaction is carried out directly in the step (2) without isolation and purification.

In a preferred embodiment, in the step (2) of the above synthesis method, the structural formula (W) represents an amount ratio of the compound to the base material to be 1:1 to 1.5, further preferably 1:1 to 1.2; and the protic solvent is Methanol and/or ethanol; reaction temperature is 10 to 90 ° C, further preferably 20 to 80 ° (:.

The post-treatment of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III) in the step (2) is: after evaporating the organic solvent, adding water, extracting with diethyl ether, and then adding acidic hydrochloric acid to the aqueous phase to make it acidic. A large amount of solid precipitated, filtered, washed with water, and dried by an infrared lamp to give the above formula (III) a solid containing a monofluoromethoxypyrazolecarboxylic acid.

In a preferred embodiment, in the step (3) of the above synthesis method, the fluorine-containing methoxypyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid and alkylsulfonyl chloride represented by the structural formula (V) are charged. The amount ratio of the substance is 1:1 to 1.5: 2 to 3, further preferably 1:1 to 1.2: 2 to 2.5; the alkylsulfonyl chloride is methylsulfonyl chloride; and the aprotic solvent is selected from tetrahydrofuran and acetonitrile. One or a combination of two or more of 1, 4-dioxane, diethyl ether or toluene; the base is an organic base, and the organic base is further preferably one selected from the group consisting of triethylamine, pyridine or 3-methylpyridine. Or a combination of two or more; the reaction temperature is -30 to 80 ° C, and more preferably -15 to 30 ° C. The volume of the organic base is 1 to 4 times (ml/g), preferably 1 to 2 times (ml/g), based on the mass of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III).

The post-treatment of the step (3) is: the end of the reaction, filtration, the filter cake is washed with water, a mixed solvent of an organic solvent and water, and a small amount of an organic solvent to obtain a first solid; the filtrate is distilled off, and then extracted with an organic solvent, After the sodium sulfate is dried, Filtration, concentration, recrystallization from ethanol to give a second crop of solids; and two batches of solids combined to give the compound of formula (II).

The substituted anthranilic acid represented by the structural formula (V) is a known compound and can be produced by a number of methods, and can be referred to the following literature: Organic Synthesis, Coll. Vol. 79, pl 96 (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 .

In a preferred embodiment, in the step (4) of the above synthesis method, a tetrafluoromethoxypyrazole-containing 4H-benzo[1,3]oxazin-4-one compound represented by the formula (Π) and a structural formula ( The amount of the compound to be represented by IV) is 1:1 to 5, more preferably 1:1 to 2; the aprotic solvent is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, diethyl ether, toluene One or a combination of two or more of dichloromethane or chloroform. The volume of the aprotic solvent is 5 to 60 times the mass of the 4H-benzo[1,3]oxazin-4-one compound containing the monofluoromethoxypyrazole represented by the structural formula (Π) (ml/ g ) is preferably 5 to 20 times (ml/g).

Below, the invention is involved

The following abbreviations used in the following Table 1 are as follows: t is unterminated, n is positive, i is hetero, s is secondary, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl; corresponding i- Pr is an isopropyl group or the like. In the index table 1, R ² = 3_C1, n = 1, R ^: and R ⁴ may be independent substituents, or may be connected as a whole.

The following index table 2 shows the physical and chemical properties and nuclear magnetic data of some of the compounds described in Table 1. Note: The numbers described in Index Table 2 correspond to the compound numbers described in Table 1. Where s is a single peak, d is a doublet, t is a triplet, q is a quartet, m is a multiplet, and brs is a broad singlet. Index table 2

No. Melting point / °c 3⁄4 NMR (Reagents are CDC1 ₃ unless otherwise stated)

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) ,

6 252-253

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

'(Ηΐ 'Ρ)98 "Z-S8 'ί '(HS '^) 9S 'ί-ίΖ 'ί ' (Η2 '^) Ζ9 "9-09 "9

'ΟΕ 'Ρ)96 -9-£8 "9

'ΟΕ 'Ρ) 8ΐ ·卜 9ΐ '(HS 's)08 Τ '(HS ^)\Ζ 'Ζ 06ΐ 8ΐ

(Ηΐ 's)09 "6 '(Ηΐ 'Ρ)9 8- S 8 '(Ηΐ 'Ρ)98 "Ζ

'(Η2 'ω) S " -εε "Ζ '(HI 'S)99 "9 '(HI ^)ίΖ "9 '(ΙΕ'Ρ)

96 -9-£8 "9

ΐ

'(Η2 's)g Τ '(HS 's)T6 τ '(HS 's)T2 '(H9' ^S )S9"T

(Ηΐ 's)T6 ·6 '(Ηΐ 'Ρ) 9f ·8- ·8

' (Η2 'Ρ) 8 Ί-ZS 'ί ' (Η2 9S 'L-7Z Ί ' (Ηΐ 's) U ·9

9ΐ '(Η2 'Ρ)96 -9-£8 "9 ' (HS ^) Ζ ' (HS 's)TT '(H9' ^s )^l

(Ηΐ 's)66 ·6

'(HT 's)9 ·8 '(Ηΐ 'Ρ)98 'ί ' (Η9 '^) 9S "Ζ-06 "9

9ΐ ' (Η2 'ΡΡ) S6 '9 ' (Η8 ΐθ -6ΐ Τ ' (HS 's) ΐθ ·Ζ

(Ηΐ 's) '6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ) 8 ·Ζ

' (Η^ 'ω) S "Ζ-06 "9 '(Η2 'Ρ)96 "9-28 "9 ' (Η^ '^) 9 SO Έ

'(Η£ 's)80 'Ζ '(HS 'ω)02 "ΐ-Ζΐ "ΐ ' (HS '^) 86 Ό-96 Ό

(Ηΐ 's)98 "6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ)

S8 "Ζ-Ϊ8"Ζ '(Ηΐ 'ω)9ε " -2S "Ζ '(Ηΐ 's)90 "Ζ ' (Η2 's)96 "9

'(Η2 'Ρ)1⁄2 "9-Ϊ8 "9 '(HS 's)ZO Τ ' (HS 's)9Z 7 ' (HS 's)^07

(Ηΐ 's)OT Όΐ ' (Ηΐ 'Ρ) ff S-£ "8 ' (Ηΐ 'Ρ) 28 "Ζ-08 Ί ' (Η2

'冚)

9S "Ζ ' (HS 'ω) 20 "Ζ-86 "9 ' (Η2 'Ρ) 06 "9-ΖΖ "9 ' (Η2 '^) 2ΐ w, ' ^m ) z τ-ιζ τ '(HS ' s)go τ '(m ^<IU )T61-WT

(Ηΐ 's)^8 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'Ρ)98 " -S8 Ί

' (HS 'ω) 9£ "Ζ ' (Η2 99 "9-69 ·9 ' (Η2 'Ρ)

Ϊ́ΐ

96 -9-£8 "9

'(Η 'Ρ)8Ζ · - ΐ · '(HS 's)T2 '(Η£ '冚)££ ·ΐ- 62 ·ΐ

(Ηΐ 'Ρ)00 Όΐ-96 ·6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)

8 "Ζ-08 "Ζ '(Η ' εΉ6·9 '(Η2 'P)f6 "9-ΐ8 "9 ' (Η^ '^)

98ΐ- 8ΐ Οΐ

'(HS 's)207 '(Η2 'ω)ΐ9 "ΐ- ε 'ΐ ' (HS '^) 96 Ό-Τ6 Ό

(Ηΐ 's)20 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 ' (Ηΐ 'Ρ) 8 ·Ζ

'(Η2 'ω) ε "Ζ '(Ηΐ 's)89 "9 ' (Ηΐ 's) £ "9 ' (Η2 'Ρ)

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

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 '' (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

Ϊ́9 (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 ·

(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" 9 9

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 S-Z ·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 '冚) ·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

Ζ ε ε ΐ 6 · Ζ ' (HS 's) 02 · Ζ ' (Η9 ) W) · Η 8 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

Ol8C.0/llOZN3/X3d co o ζ OAV

Ol8C.0/llOZN3/X3d co o Ζ OAV

(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 " -1⁄2 "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 ΐ 6

(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 ·卜 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 '冚) 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 '冚) 8£ ·8—

1 (Η2 'ω) 8ΐ "8-80 "8 ' (Ηΐ '^)09 " -1⁄2 ' ' (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)1⁄2"9'(HT's)8 ·9

W, 'P)TS "9-92 "9 W, 'P)S8 "9-Ϊ8 "9 '(Η2 'P)Z9 ^-29 f£Z-Z£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 " -1⁄2 '

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

'(Ηΐ 'ω)26 Τ '(Η9'Ρ)Μ)·ΐ-3⁄4)·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 -L-Z "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 " -1⁄2 "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 Ζ "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) ,

110 148-149

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) ,

114 230-231

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

142 216-218

-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

143 208-210

-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

145 158-161

-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)

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) The compounds represented by the structural formula (I) of the present invention listed in the index table 1 and the index table 2 can be used according to the present patent specification. The synthesis methods described and the preparation methods described in Synthesis Examples 1-3 were synthesized.

The present invention also provides the use of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) or an agriculturally applicable salt thereof, a pesticide preparation for controlling pests, and a control The method of pests.

A pest control agent containing a fluoromethoxypyrazole-containing orthoformylbenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof can be used for pest control on agricultural crops, for example It is particularly useful as a control agent for various pests that is a problem in the field of agriculture and horticulture, that is, an agricultural and horticultural pest control agent, or a pest control agent that is parasitic on animals, that is, an animal parasite control agent.

It is useful as a pest control agent for agricultural and horticultural purposes, for example, as a pesticidal or acaricide, in particular, for controlling plant parasitism such as two-spotted spider mites, red leafhopper, citrus scorpion, and whole claw scorpion. Anthraquinones, Plutella xylostella, Brassica chinensis, Spodoptera litura, Helicoverpa armigera, Helicoverpa armigera, Tobacco moth, Rice leaf roller, Wild rice moth, Apple small moth, Peach small moth, Pear , agricultural tiger pests such as small tigers, potato leaf beetles, yellow squash, locusts, whiteflies, thrips, locusts, and larvae. Among them, the agricultural and horticultural pest control agent containing the compound of the present invention is particularly effective for agricultural pests and the like. Further, the agricultural or horticultural pest control agent containing the fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof Various resistant pests of an agent such as an organophosphorus agent, a carbamate agent, or a pyrethroid agent are effective. Further, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof It has excellent osmotic transferability, so the soil can be treated by using an agricultural and horticultural pest control agent containing the compound represented by the structural formula (I) of the present invention, and can also be controlled while controlling soil harmful insects, mites and the like. Pests in the stems and leaves.

Other preferred embodiments of the pest control agent containing the monofluoroamidobenzamide compound containing the monofluoromethoxypyrazole represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof may be mentioned. A pest control agent for agricultural and horticultural pest control, such as plant parasitic mites, agricultural pests, and soil pests.

An agricultural and horticultural pest control agent containing the fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof, usually mixed with the compound and Auxiliary agent for various pesticides, forming a powder, granules, granule wettable powder, wettable powder, aqueous suspension, oily suspension, aqueous solvent, emulsion, paste, aerosol, microdispersion, etc. Various forms of preparation are used, but as long as it is suitable for the purpose of the present invention, it can be made into all preparation forms which are generally used in the field. Examples of the adjuvant used in the preparation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite mixture, clay, sodium carbonate, baking soda, thenardite, zeolite, starch. Solid support; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N a solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or the like; a fatty acid salt, a benzoate, an alkyl sulfosuccinate, a dialkyl sulfo amber Acid salt, polycarboxylate, alkyl sulfate salt, alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate salt, alkyl sulfonate, alkyl aryl Sulfonic acid salt, aryl sulfonate, lignosulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate salt, alkyl aryl phosphate, aryl phosphate Styrene aryl phosphate, polyoxyethylene alkyl ether phosphorus An anionic surfactant or developer such as a salt of a salt, a polyoxyethylene alkyl aryl phosphate or a naphthalene sulfonic acid formaldehyde condensate; a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride , fatty acid alcohol polyglycol ether, block diol, block alcohol, alkylene oxide block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, Polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hardened castor oil, polyoxypropylene Nonionic surfactants and developing agents such as fatty acid esters; olive oil, guava, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, groundnut oil, cottonseed oil, Vegetable oil or mineral oil such as soybean oil, rapeseed oil, linseed oil, tung oil, liquid paraffin, and the like. The various components of the above-mentioned auxiliary agents can be used singly or in combination of two or more kinds as long as they do not deviate from the object of the present invention. Further, it may be appropriately selected from those known in the art in addition to the above-mentioned auxiliary agents. Various adjuvants commonly used, such as extenders, thickeners, dustproofing agents, antifreeze agents, dispersion stabilizers, phytotoxicity reducing agents, and antifungal agents, can also be used.

The composition of the formula (I) represents a weight ratio of the compound and the various adjuvants, that is, the carrier, usually 0. 1: 99. 9~90: 10. When these preparations are actually used, they can be used directly or diluted with a diluent to a prescribed concentration. Use various developing agents (surfactants, vegetable oils, mineral oils, etc.) as needed.

The application of the agricultural and horticultural pest control agent containing the compound represented by the structural formula (I) of the present invention varies depending on the meteorological conditions, the form of the preparation, the application period, the application site, the type of the pest or the occurrence state, and the like, and cannot be generalized. The application is generally carried out at a concentration of the active ingredient of 0.05 to 800 ppm, preferably 0.5 to 500 ppm, and the application amount per unit is 1 to 5000 g, preferably 10 to 1000 g per 1 hectare of the compound of the invention. Further, the application of the agricultural and horticultural pest control agent containing the other preferred embodiment of the pest control agent of the present invention can be carried out according to the application of the above-mentioned pest control agent. The present invention also encompasses a method for controlling pests using such an application method, particularly a method for controlling plant parasitic mites and agricultural pests.

The application of various preparations, or dilutions thereof, of the agricultural and horticultural pest control agent containing the compound of the formula (I) of the present invention can be generally carried out by a usual application method such as spreading, spraying, misting, misting. _A tomizi _ng , granulation, surface application, soil application (mixing, infusion, etc.), surface application (coating, coating, coating, etc.), impregnation of baits, and the like. In addition, by mixing the above-mentioned active ingredients into the feed to the livestock, it is also possible to hinder the occurrence and growth of pests, particularly harmful insects, in the excrement, and it is also possible to use the so-called ultra low volume. Administration, in this method, may contain 100% of the active ingredient.

Further, the structural formula (I) according to the present invention can be used in combination with one or two or more kinds of conventional insecticidal, bactericidal or herbicidal pesticides, and exhibits more advantageous effects and functions. In particular, one or more mixed pest control compositions of the compound of the formula (I) and the other active ingredients of the pesticidal compound of the present invention may be used in combination or in combination, and the scope of application, the period of treatment of the drug, and the control activity may be applied. Wait for a good direction to improve. Further, the compound of the present invention and other active ingredient compounds of the agricultural chemical may be used by mixing the separately prepared preparations at the time of dispersion, or may be used together as a preparation, and the present invention also encompasses such a mixed pest control composition. .

The structural formula (I) of the present invention represents a compound and a preparation thereof, and has the following advantages:

(1) The present invention introduces a monofluoromethoxy group for the first time in a pyrazole ring, and the structure of the compound is novel;

(2) The compound of the present invention and its preparation have a broad spectrum of insecticidal activity: against lepidopteran pests (Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera), Hemipteran pests (Peach and aphid), and the same wing The target pests (rice planthopper), the dipteran pests (Lepidoptera: Trifolium), and the leaf-like pests (Horse genus) have shown very good activity;

(3) The compound of the present invention and its preparation have an extremely high insecticidal activity: at a dose of 0.16 mg/L, it has a good effect on Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera; at a dose of 4 mg/L The lower aphids, trifolium and horseradish have also showed good results; at 20mg/L, the rice brown planthopper showed good effect;

(4) The compound of the present invention and its preparation have good safety, and are safe to some crops such as wheat, soybean, cotton, rice, etc., and are environmentally friendly;

(5) The compound of the present invention and its preparation have reasonable toxicity, ecotoxicity and environmental compatibility, and are low-toxic environmental friends. Good pesticides. The examples of the present invention are described below, but the present invention is not limited thereto, and a synthesis example of the compound of the present invention will be described first. detailed description

Example 1 N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyloxy Synthesis of -1H-pyrazole-5-carboxamide (Compound 8)

First step: Synthesis of 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid

In a 500 ml three-neck round bottom flask, 1-(3-chloro-2-pyridyl)-3-hydroxy-1H-pyrazole-5-carboxylic acid ethyl ester (13.35 g, 0.05 mol) was added sequentially, 300 ml of acetonitrile, solid carbonic acid Potassium (8.28 g, 0.06 mol), fluoro-bromomethane (8.48 g, 0.075 mol), then heated to reflux, the reaction was taken to complete disappearance, cooled to room temperature, filtered, and the filter cake was rinsed with acetonitrile 2*50 ml. Then, 200 ml of methanol was added to dissolve it, and then a 50 ml aqueous solution containing sodium hydroxide (2.4 g, 0.06 mol) was slowly added thereto at room temperature, and stirred at room temperature for about 30 minutes, the reaction was completed, the solvent was distilled off, water was added, and diethyl ether was used. *50ml extraction, the aqueous phase is diluted with hydrochloric acid to adjust the pH value, the system has a large amount of white solids formed, filtered, and dried by infrared light to give 3-fluoromethoxy-1-(3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid 11.05 g, melting point 149-151 ° C, yield 81.6%; 3⁄4 NMR (400 MHz, DMSO - d ₆ ) δ 5.84 - 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).

Second step: 6-chloro-2-[3_-fluoromethoxy-l-(3-chloro-2-Bpyridyl)-1H-5-pyrazolyl]-8-methyl-4H-[ Synthesis of d] [1, 3] benzoxazine-4-one

In a 250 ml three-neck round bottom flask, 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (3 g, O. Ollmol) (Example 1 - Synthesis One step product), 2-amino-5-chloro-3-methylbenzoic acid (2.04g, O. Ollmol), acetonitrile 150ml, pyridine 7ml, stir to dissolve all solids, and cool the system at _5°~- 10 ° dropwise addition of methylsulfonyl chloride (2ml, 2.96g, 0.026mol) / acetonitrile 20ml solution, after the completion of the addition, kept at _5 ° ~ -10 ° reaction lh, then naturally rise to room temperature for 3h, after the reaction is complete Add 30 ml of water, stir for 30 min, filter, and filter the cake with 2: 1 acetonitrile / water (2 * 40 ml), acetonitrile (2 * 20 ml) and diethyl ether (2 * 20 ml) to obtain the first solid; After the solvent, water was added, and the mixture was extracted with ethyl acetate (3*40 ml). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated, and then recrystallized from ethanol to obtain a second solid. -Chloro-2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl- 4H- [d] [1, 3] Benzoxazine-4-one 4.17g, melting point 206.0-207.5 ° C, yield 84.22%; 3⁄4 NMR (400ΜΗζ, CDC 1 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).

Step 3: 2-(3-Chloro-2-pyridinyl)-5--fluoromethoxy-2H-pyrazole-(2-tert-butylcarbamoyl-4-chloro-6-methyl Synthesis of -phenyl) 3-carboxamide

In a 50 ml single-mouth round bottom flask, 6-chloro-2-[3--fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl-4H - [d] [1, 3] benzoxazin-4-one (lg, 0. 00238 mol) (Example 1 - synthesis of the second step product) in tetrahydrofuran solution was slowly added dropwise t-butylamine (0. 21g, 0 00286摩尔), After stirring at room temperature overnight, the reaction was completed, the residue was evaporated under reduced pressure, and the residue was evaporated to dryness. -pyridyl)-5-fluoromethyloxy-2H-pyrazole-(2-tert-butylcarbamoyl-4-chloro-6-methyl-phenyl) 3-carboxamide, m.p. 227.0-228.0 ° C, The yield was 87·6%; 3⁄4 NMR (400 MHz, 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-(Methylcarbamoyl)-4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethoxy-1H - Synthesis of pyrazole-5-carboxamide (Compound 3) In a 50 ml single-neck round bottom flask to 6-chloro-2-[3-fluoromethoxy-1-(3-chloro-2-pyridinyl) - 1H_5_pyrazolyl]-8-methyl-4H-[d][1,3]benzoxazine-4-one (lg, 0.0000 238 mol) (Example 1 - synthesis of the second step product) Methylamine hydrochloride (0. 19g, 0.0000286 mol) and anhydrous sodium acetate (0. 24g, 0.0000286 mol) were added to the tetrahydrofuran solution. After stirring at room temperature overnight, the reaction was completed, and tetrahydrofuran was evaporated under reduced pressure. After adding water, the mixture was extracted with EtOAc. EtOAc (EtOAc m. 4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl-1H-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-(ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl- Synthesis of 1H-pyrazole-5-carboxamide (Compound 33) Step 1: 6-Cyano-2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5 Synthesis of pyrazolyl]-8-methyl-4H-[d] [1,3]benzoxazin-4-one

In a 250 ml three-neck round bottom flask, 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (5 g, 0. 0185 mol) (Example 1 - Synthesis The first step product), 2-amino-5-cyano-3-methylbenzoic acid (3. 24g, 0. 0185mol), acetonitrile 150ml, pyridine 15ml, stirring to dissolve all the solids, cooling the system, at _5 °~- 10° dropwise addition of methylsulfonyl chloride (4ml, 5.98g, 0.052mol) / acetonitrile 20ml solution, after the addition is completed, keep the reaction at _5 ° ~ - 10 ° lh, then naturally rise to room temperature for 3h, after the reaction is complete, add water 30ml, stir for 30min, filter, filter cake The first batch of solids was obtained by rinsing with 2:1 acetonitrile/water (2*40 ml), acetonitrile (2*30 ml) and diethyl ether (2*30 ml). After the solvent was distilled off, water was added and ethyl acetate was used. *40ml), the organic phase is dried over anhydrous sodium sulfate, filtered and concentrated, then recrystallized from ethanol to give a second crop of solids, which are combined to give a pale yellow solid, 4.17g, which is 6-cyano -2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl-4H-[d][1,3]benzo Oxazine-4-one, melting point 208.5-211.0 ° C, yield 54.87%; 3⁄4 NMR (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).

Second step: N-[2-(ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyloxy Synthesis of -1H-pyrazole-5-carboxamide

In a 50 ml single-neck round bottom flask, to 6-cyano-2-[3--fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl_ 4H-[d] [1,3] benzoxazine-4-one (0.4 g, 0.00097 mol) (Example 3 - synthesis of the first step product) in tetrahydrofuran solution was slowly added dropwise with ethylamine (65-70) %, 0.083g, 0.0012mol), after stirring at room temperature overnight, the reaction was completed, the tetrahydrofuran was evaporated under reduced pressure, and a little ethanol was added to the residue. After stirring for several minutes, it was filtered to give a light gray solid, 0.35 g, which was N-[2 - (ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl-1H-pyrazole-5- Formamide, melting point 151.0-152.5 ° C, yield 78.6%; 3⁄4 NMR (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 Examples 4 to 6 give practical examples in which the compound (I) of the present invention is used as an active material component to prepare and prepare several insecticide dosage forms, and it should be noted that the present invention is not limited only to the following examples. Within the scope. In these formulation examples, all "%" refer to weight percentage. Example 4 Wettable Powder Formulation

15% of compound (8) (index table 1), 3% sodium lignosulfonate (M _Q ), 2% lauryl polyoxyethylene ether (JFC), 40% diatomaceous earth and 40% The light calcium carbonate is thoroughly mixed and pulverized by an ultrafine pulverizer to obtain 15% wettable powder.

Π

Hey.

Example 5 Emulsion Formulation

10% of compound (8) (index table 1), 5% of agricultural milk 500 (calcium salt), 5% of agricultural milk 602, 5% of N-methyl-2-pyrrolidone and 75% of two The toluene is heated and stirred evenly to obtain a 10% cream product. Example 6 Water Dispersible Granule Formulation

60% of compound (8) (index table 1), 2% polyvinylpyrrolidone, 12% sodium naphthalene sulfonate formaldehyde condensate, 8% N-methyl-N-oleoyl-taurate sodium, 2% carboxymethyl cellulose, and 16% kaolin are uniformly mixed, pulverized, kneaded by water, and then granulated by adding a 10-100 mesh sieve granulator, followed by drying and sieving (screening) Net range). That is, 60% of water-dispersible granule products are obtained. The following Examples 7 to 14 give examples of the biological activity assays using the compounds of the present invention, and it should be noted that the present invention is not limited only to the scope of the following examples.

The insecticidal activity evaluation test was carried out according to the following methods:

After the test compound was dissolved in a mixed solvent of acetone/methanol (1:1), it was diluted to the desired concentration with distilled water containing 0.1% Tween 80.

The test targets were Plutella xylostella, Spodopterem f rug i per da), Helicoverpa armigera, Aphis medicaginis ^Myzus persicae ^

Ta lugens), Liriomyza trifolii (r /o ) and horseradish (Phaedon cochleariae).

The following "mg/L" refers to each mg of active substance per liter.

Test Statistics: The number of dead insects and live insects in each treatment was counted, and the mortality was calculated.

Mortality ( _% ) = number of live insects 试 Κ)0

Number of test insects Note: The numbers described in the biological activity measurement examples correspond to the compound numbers described in the index table 1 and the index table 2. Example 7 Effect test on Plutella xylostella)

Cut the cabbage slices, punch them into discs, then immerse them in the liquid for 20s, place them in a 09cm plastic dish (5 pieces/dish), and pick up the second instar larvae of the diamondback moth 15 pieces/dish, put a piece of filter paper, cover . The cells were cultured at 26 ° C, and the results were checked after 72 hours. The test was repeated 4 times. The tip of the scorpion touches the worm, and no response is considered to be dead. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 1-27, 33-63, 85-86, 89, 93, 99-106, 110-112 in Table 1 gave 100% mortality at 4 mg/L. Further, compounds 1, 3, 4, 8, 33, 49-51, 57-58, 59, 83, 89, 101, 103, 106 gave a mortality rate of at least 80% at 0.16 mg/L. Example ⁸ Effect test on Spodoptera frugiperda) Potted cotton (2-3 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the leaves were cut with scissors, placed in a 09 cm plastic petri dish, and the larvae of Spodoptera litura were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 49, 50, 51 in Table 1 gave 100% mortality at 4 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 0.8 mg/L. Compounds 8, 33, 51 gave at least 80% mortality at 0.16 mg/L. Example 9 Effect Test on Helicoverpa armigera Heliconia

Potted cotton (2-3 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, connect the cotton bollworm larvae, put a piece of filter paper, and cover. Place in the observation room and check the results after 6 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as dead. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 8, 10, 33, and 51 gave 100% mortality at 4 mg/L.

Compound 8 gave 100% mortality at 0.16 mg/L. Example 10 Effect Test on 苜蓿蚜 phis medicaginis)

Cut the leaves of broad bean into the ends, place the back side up on a small piece of cotton, place it in a petri dish, add a small amount of water, and connect it into a pot. After 24 hours, the mites were removed. After 2 days of culture, the leaves were infiltrated in the liquid for 5 s and then placed on cotton and dried. Check the results after 24h. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33-37, 39, 27, 47, 51, 83, 85, 89, 95, 101 in Table 1 gave at least 90% mortality at 20 mg/L. Compounds 3, 8, 33, 34, 35, 36, 51, 83, 101 gave at least 80% mortality at 4 mg/L. Example 11 Effect Test for Myzus Myz _U s persicae) embodiment

Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, use the nymphs respectively. Place in the observation room and check the results after 7-10d. Mortality is calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 51 in Index Table 1 achieved 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L. Example 12 Effect test on rice brown planthopper Nilaparvata lugens)

The rice seedlings were fixed in a petri dish with white quartz sand, and the 3rd instar nymph was anesthetized with C0 ₂ and placed in the POTTER spray tower. Spray down. Cover with a clear plastic cup after spraying, mark and place in the observation room. The results were checked after 72 hours. The test was repeated 4 times. The tip of the scorpion touches the worm, and no response is considered to be dead. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 8, 33, 36, 51-53, 57, 58 in Table 1 gave at least 90% mortality at 100 _mg /L. Compounds 8, 33, 51 gave at least 80% mortality at 20 mg/L. Example 13 Effect test on Iriomza trifoliD

Potted broad beans (3-4 leaf ages) were sprayed with chemicals and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the larvae of Liriomyza sativa were separately used. Place in the observation room and check the results after 7 days. Mortality is calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 8, 9, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 8, 10, 49, 51 gave 100% mortality at 4 mg/L. Example 14 Effect test on horseradish Phaedon cochleariae)

Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, and connect the 2nd instar larvae of horseradish or Plutella xylostella, put a piece of filter paper, and cover. Place in the observation room and check the results after 6-7 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L. Compound 8 gave at least 90% mortality at 0.8 mg/L. According to the above method, compound 8 and the known compound chlorantraniliprole were selected for killing the diamondback moth, cockroach and rice brown fly fruit as shown in Table 3.

Parallel comparison of chlorfenapyr compound 8 and known compound chlorantraniliprole (mortality, %) concentration concentration

Compound number Plutella xylostella concentration (mg/L) 苜蓿蚜 rice brown planthopper

(mg/L) (mg/L)

0.8 100 20 100 100 100

8 (Example 1) 0.16 100 4 90 20 80

0.032 80 0.8 30 4 0 Chlorantamide 0.8 100 20 70 100 80

0.16 80 4 0 20 10 0.032 20 0.8 0 4 0 Conclusion: For Lepidoptera pests, P. xylostella, at a dose of 0.16 mg/L, for Hemiptera pests at a dose of 4 mg/L, for Homoptera pests at a dose of 20 mg/L Rice brown planthopper; the insecticidal activity of the present compound 8 (Example 1) is significantly better than the known compound chlorantraniliprole.

Claims

Claim

1. An o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) or an agriculturally applicable salt thereof,

Its towel:

A is N or CH;

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

R ³ is hydrogen, alkyl or alkoxy;

m is an integer from 0 to 4;

n is an integer of 0 to 4.

The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 1, which is characterized by the structural formula (I):

R ³ is hydrogen or an alkyl group;

R ⁴ is hydrogen, cyano, d-Ce alkyl, d-Ce alkoxy, d-Ce alkylamino, halogenated CfCe alkyl, halogenated CfCe alkoxy , halo dc ₆ alkylamino, cyano dc ₆ alkyl, c ₃ -c ₆ cycloalkyl, halo c ₃ -c ₆ cycloalkyl, hydroxy-(: ₆ alkyl, dc ₆ alkoxycarbonyl a group, (;-(: ₆ alkoxyamido group, dc ₆ alkyl amide group, ^ dc ₆ alkyl amide group, cyano substituted dc ₆ alkyl amide group or aryl heterocyclic methyl group;

m is 2;

n is 1.

The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 2, which is characterized by the structural formula (I):

A is N;

R ² is halogen, cyano, CfCe alkyl or halogenated dC ₃ alkyl.

The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 3, which is characterized in that the structural formula (I):

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

R ² is a halogen or a cyano group.

The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 4, wherein the compound I) is:

An intermediate for the preparation of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to any one of claims 1 to 5, which has the following structural formula (Π):

Its towel:

A is N or CH;

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

m is an integer from 0 to 4;

n is an integer of 0 to 4.

The intermediate for preparing a fluoromethoxypyrazole-containing orthoformylbenzamide compound according to any one of claims 1 to 5, which is characterized in that the structural formula (Π) Medium:

A is N;

R ¹ is hydrogen, halogen, cyano, nitro, -Ce alkyl, dC ₆ haloalkyl, cyano dC ₆ alkyl, (: ₂ -(: ₆ alkenyl, C ₂ -C ₆ haloalkenyl) , C ₂ -C ₆ block, halo C ₃ -C ₆ block, dC ₆ alkoxy, dC ₆ cyanoalkoxy, dC ₆ haloalkoxy, (;-(: ₆ alkylthio, dC ₆ haloalkylthio, dC ₆ alkylsulfonyl, dC ₆ alkylcarbonyl, halo dC ₆ alkylcarbonyl, dC ₆ alkoxycarbonyl, ^d _{6 6} alkoxycarbonyl or amino dC ₆ alkyl;

R ² is hydrogen, halogen, CfCe alkyl, halogenated dC ₆ alkyl, (-(: ₆ alkoxy, halo (-(: ₆ alkoxy or cyano; m is 2;

n is 1.

R ² is halogen, cyano, CfCe alkyl or halogenated dC ₃ alkyl.

The intermediate for preparing a fluoromethoxypyrazole-containing orthoylaminobenzamide compound according to any one of claims 1 to 5, which is characterized in that the structural formula (Π) Medium:

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

R ² is a halogen or a cyano group.

10. Synthesis of an o-formylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim The method is characterized by the following steps:

(1) In an aprotic solvent, a compound represented by the formula (VI) and a monofluoro-bromomethane are reacted under the action of an acid binding agent to give a structural formula (W) to represent a compound;

(3) In a non-protic solvent, a base and an alkylsulfonyl chloride are added, and the monofluoro-aminopyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid represented by the formula (V) are reacted to obtain a structural formula ( 4) a 4H-benzo[1,3]oxazin-4-one compound containing a monofluoromethoxypyrazole;

(4) A tetrafluoromethoxypyrazole-containing 4H-benzo[1,3]oxazin-4-one compound represented by the formula (Π) in an aprotic solvent and a compound represented by the formula (IV) Reacting the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I);

The compounds represented by the structural formulas (Π), (111), (IV), (V), (VI) and (YD) are as follows:

The definitions of A, RR ² , R ³ , R ⁴ and R ⁵ and m and n are as defined in claim 1.

A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to claim 10, which is characterized in that:

The ratio of the compound represented by the structural formula (VI) to the material of the monofluoromethane bromide and the acid binding agent in the step (1) is 1: 1.1 to 2: 1.1 to 2, and the aprotic solvent is selected from tetrahydrofuran. One or a combination of two or more of acetonitrile, 1,4-dioxane or acetone, the reaction temperature is 10 to 90 ° C;

The structural formula (W) in the step (2) represents that the ratio of the compound to the base is 1: 1 to 1.5, the protic solvent is methanol and/or ethanol, and the reaction temperature is 10 to 90 ° C;

The monofluoropyrazole-containing carboxylic acid represented by the structural formula (III) represented by the formula (III) and the substitution represented by the structural formula (V) The ratio of the amount of the anthranilic acid and the alkylsulfonyl chloride to be charged is 1:1 to 1. 5: 2 to 3, the alkylsulfonyl chloride is methylsulfonyl chloride, and the aprotic solvent is selected from tetrahydrofuran. One or a combination of two or more of acetonitrile, 1,4-dioxane, diethyl ether or toluene, the base is an organic base, and the reaction temperature is -30 to 80 ° C;

a material of the compound represented by the structural formula (IV) and a compound represented by the formula (IV) represented by the structural formula (Π) represented by the formula (4): 4H-benzo[1,3]oxazin-4-one compound represented by the formula (IV) The amount ratio is 1:1 to 5, and the aprotic solvent is selected from one or a combination of two or more of tetrahydrofuran, acetonitrile, 1,4-dioxane, diethyl ether, toluene, dichloromethane or chloroform.

A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to claim 11, wherein:

The reaction temperature of the compound of the formula (VI) and the amount of the material of the fluoromonobromomethane and the acid-binding agent in the step (1) is 1: 1. 1~1. 5: 1. 1~1. For 20~80 °C;

The reaction formula (VD) in the step (2) represents a ratio of the compound to the base material: 1: 1~1. 2, the reaction temperature is 20 to 80 ° C;

The ratio of the content of the substituted fluoroaminopyrazolecarboxylic acid represented by the structural formula (III) and the substituted anthranilic acid represented by the structural formula (V) and the alkylsulfonyl chloride represented by the formula (III) in the step (3) is 1:1. 〜2. 2〜2. 5, the organic base is selected from one or a combination of two or more of triethylamine, pyridine or 3-methylpyridine, the reaction temperature is -15~30 ° C;

a material of the compound represented by the structural formula (IV) and a compound represented by the structural formula (IV) represented by the structural formula (Π) represented by the formula (4): 4H-benzo[1,3]oxazin-4-one compound represented by the formula (IV) The ratio is 1:1~2.

13. Use of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) according to any one of claims 1 to 12, or an agriculturally applicable salt thereof, It is characterized in that the compound of structure (I) is used for pest control on crops.

A pesticidal preparation for controlling pests, comprising: a fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the formula (I) according to Claim 1 or a salt thereof至9. 9〜90: 10。 The weight ratio of the active ingredient to the carrier is 0. 1: 99. 9~90: 10.

A method for controlling pests, characterized in that: the pesticide preparation according to claim 14 is applied to a pest to be controlled or a medium for growth thereof, wherein the effective amount of the active ingredient is from 10 g to 1000 per hectare Gram.

A method for controlling pests, comprising: an o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) according to claim 1 and an existing killing agent One or two or more kinds of pesticides for worm, sterilizing or weeding are used in combination.