WO2012034472A1 - Cyano benzenedicarboxamide compounds, preparing methods and as agricultural insecticides uses thereof - Google Patents

Abstract

Cyano benzenedicarboxamide compounds of formula (I), preparing methods and as agricultural insecticides uses thereof. The compounds have broad-spectrum insecticidal activities.

Description

 Cyano group-containing phthalamide compound, preparation method and use as agrochemical insecticide

 The present invention relates to a phthalic acid amide compound, a preparation method and use as an agrochemical insecticide.

 Say

Background technique

 There is an increasing demand for ecological and economical books on disease and pest control agents, especially for application rates, composition of residues, selectivity, toxicity and production methods. Since insecticides and fungicides are resistant to pests and germicides after a period of use, it is necessary to develop novel compounds and compositions having insecticidal and bactericidal activity.

 A variety of phthalamide compounds (nidindin receptor inhibitors) are known to have insecticidal activity (see EP0919542A2, W02004/018410AK W02010/012442A2), in which phthalate is jointly developed by the Japanese pesticide company and Bayer. The formamide compound flubendiamide has good insecticidal activity against a variety of agricultural and horticultural lepidopteran pests (J. Pesticide Sci., 2005, 30(4): 354-360). At present, the replacement of phthalamides as pesticides has caused widespread concern among researchers of pesticide creation and has become a hot spot in the research of new insecticides.

 In the prior art, the preparation of the cyano group-containing phthalamide compound as shown in the present invention and its insecticidal activity have not been disclosed. Summary of the invention

 SUMMARY OF THE INVENTION An object of the present invention is to provide a cyano group-containing phthalic acid amide compound which can control various pests and diseases at a small dose, and which can be applied to agriculture to control crop diseases and insect pests.

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

a cyano group-containing phthalamide compound represented by the formula (I) or an agriculturally applicable salt thereof,

 among them:

RR ^{2 is} independently selected from hydrogen, dC ₆ ortho, cycloalkyl, C ₂ -C ₆ alkenyl or ^-alkynyl, and the hydrogen on the group may also be halogen, cyano, nitro, dC _{a 6-} methoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, a substituted phenoxy group, an alkylthio group, an alkylsulfinyl group or a decylsulfonyl group;

Or R ¹ and R ² together with the attached carbon form a cycloalkyl group;

R ^{3 is} selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC ₆ fluorenyl, halogenated dC ₆ fluorenyl, dC ₆ decyloxy or halodecyloxy;

R ^{4 is} selected from hydrogen or (^-(: ₆ fluorenyl);

X is selected from a methylene group, a dC ₆ alkyl group, a cyano substituted methylene group or a direct bond;

Or X and R ⁴ are bonded to the N to form a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a five-membered heterocyclic ring or a six-membered heterocyclic ring; Y is selected from the group consisting of hydrogen, halogen, cyano, nitro, a hydroxy group, a dC ₆ alkyl group, a halogenated dC ₆ fluorenyl group, a dC ₃ decyloxy group, a halogenated dC ₃ decyloxy group, a phenyl group, a substituted phenyl group, a heterocyclic aryl group or a substituted heterocyclic aryl group;

 A is CH or N;

 m is an integer from 0 to 4.

 In a preferred embodiment, the cyano group-containing phthalamide compound represented by the above (I):

RR ^{2 is} independently selected from hydrogen, alkyl, C ₃ -C ₆ cyclodecyl or ( ₂ -(: ₃ alkenyl), phenyl, substituted phenoxy which may also be substituted by hydrogen on the group Further substituted with thiol, decylsulfinyl or decylsulfonyl;

Or R ¹ and R ² together with the attached carbon form a cyclohexyl group;

R ^{3 is} selected from hydrogen or halogen;

R ^{4 is} selected from hydrogen or ^-^ fluorenyl;

Or X and R ⁴ are bonded to the N to form a five-membered heterocyclic ring or a six-membered heterocyclic ring;

Y is selected from hydrogen, a halogen atom, nitro, hydroxy, burning dC _3-yl, fluorinated alkyl with dC _3, dC ₃ alkoxy or fluoro - embankment group;

 m is an integer of 1 to 3.

In a further preferred embodiment, in the cyano group-containing phthalamide compound represented by the above (I): RR ^{2 is} independently selected from hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allylic. a group, the hydrogen on the group can also be a group such as a substituted phenyl group, a substituted phenoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group or the like;

R ^{3 is} selected from fluorine, chlorine, bromine or iodine, and R ³ is at the 3 or 4 position of the benzene ring;

R ⁴ is hydrogen or methyl;

 X is a methylene group, a methyl group, a cyano substituted methylene group or a direct bond;

Or X and R ⁴ are bonded to the N to form an oxygen-containing six-membered heterocyclic ring;

 Y is selected from the group consisting of hydrogen, fluorine, chlorine, nitro, hydroxy, methyl, methoxy, trifluoromethyl, trifluoromethoxy or heptafluoroisopropyl. As a most preferred embodiment, the structural formula of the cyano group-containing phthalamide compound represented by the above (I) is:

 Or its salt.

In the cyano group-containing phthalamide compound represented by the above formula (I), RR ² , R ³ , R \ A, X, Y and m are defined as a fluorenyl group, which is a linear or branched form, for example, a Bases such as ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Cyclodecyl is meant to include cyclic chain forms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl means straight-chain or branched form, such as ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1, 3-butadienyl, 1-hexenyl, etc. Group. An alkynyl group means a straight or branched chain form such as an ethynyl group, a 2-butynyl group, a 2-pentynyl group, a 3-hexynyl group or the like. Halogenated fluorenyl refers to a group wherein the fluorenyl group is substituted by one or more halogen atoms. The methoxy group means a group having an oxygen atom bonded to the terminal of the oxime group, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a tetrabutoxy group or the like. The haloalkoxy group means a group in which a mercapto group is substituted by one or more halogen atoms and an oxygen atom is bonded to the terminal. The thiol group is a group having a sulfur atom attached to the end of the thiol group, such as a methylthio group, an ethylthio group or the like. The mercaptosulfinyl group means a group having a terminal group of (S0-), such as a methylsulfinyl group. The mercaptosulfonyl group means a group having a terminal (S0 ₂ - ) at the alkyl group, such as a methylsulfonyl group. Halogen means fluorine, chlorine, bromine or iodine.

 The cyano group-containing phthalamide compound represented by the formula (I) of the present invention may have, in some cases, one or more asymmetric centers in its structural formula, and in some cases, two or more optical isomerisms. Bulk and diastereomers. The invention also includes all individual optical isomers and mixtures of these isomers in any ratio.

The present invention also provides an intermediate for preparing a cyano group-containing phthalamide compound represented by the formula (I), which has the following formula (II) or (III):

 (II) (III)

 among them:

RR ^{2 is} independently selected from hydrogen, d-alkyl, C ₃ -C ₆ cyclodecyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, and the hydrogen on the group may also be halogen , cyano, nitro, (^-[: ₆ methoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, alkylthio, alkylsulfinyl or decylsulfonyl further Replace

Or R ¹ and R ² together with the attached carbon form a cyclodecyl group;

R ^{3 is} selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC ₆ alkyl, halogenated d-Ce fluorenyl, alkoxy or halo-c decyloxy.

 In a preferred embodiment, the structural formula of the compound represented by the above formula (II) or (III):

RR ^{2 is} independently selected from hydrogen, dC ₃ fluorenyl, C ₃ -C ₆ cyclodecyl or C ₂ -C ₃ alkenyl, and the hydrogen on the group may also be substituted phenyl, substituted phenoxy Further substituted with a thiol group, a fluorenylsulfinyl group or an alkylsulfonyl group;

Or R ¹ and R ² together with the attached carbon form a cyclohexyl group;

R ^{3 is} selected from hydrogen or halogen.

 As a further preferred embodiment, in the structural formula of the compound represented by the above formula (II) or (III):

RR ² are independently selected from hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allyl, hydrogens on the group may also be substituted phenyl, substituted phenoxy, methylthio a group such as a methylsulfinyl group or a methylsulfonyl group;

R ^{3 is} selected from fluorine, chlorine, bromine or iodine, and R ³ is located at the 3 or 4 position of the benzene ring.

 The cyano group-containing phthalamide compound represented by (I) of the present invention can be produced by the following method:

即包括如下步骤：

That includes the following steps:

 (1) The substituted phthalic anhydride represented by the formula (VI) and the substituted aminoacetonitrile represented by the formula (V) are subjected to an N-acylation reaction in an inert solvent in the presence or absence of a base to give a structural formula ( Substituted o-amidobenzoic acid represented by III);

 (2) reacting an substituted o-amidobenzoic acid represented by the formula (I I I) with an acylating reagent in an inert solvent to obtain a substituted phthalimyl isoimide represented by the formula (I I );

 (3) a substituted phthalimide represented by the formula (II) is reacted with a substituted amine represented by the formula (IV) in an inert solvent in the presence or absence of an acid to give a structural formula (I). a cyano group-containing phthalamide compound;

Among the compounds represented by the structural formulae (IV) to (VI), RR ² , R ³ , R ⁴ , Y and m define a cyano group-containing phthalamide compound represented by the above structural formula (I).

 In a preferred embodiment, the inert solvent in the above step (1) is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide. Or a combination of one or more of toluene or methylene chloride, the base comprising an organic base and an inorganic base, the organic base being selected from the group consisting of triethylamine, pyridine or 3-methylpyridine, the inorganic base being selected From potassium carbonate, sodium hydrogencarbonate, sodium hydroxide or anhydrous sodium acetate; the inert solvent in the above step (2) is selected from the group consisting of toluene, 1,2-dichloroethane, ethyl acetate, tetrahydrofuran, acetonitrile, 1, One or a combination of two or more of 4-dioxane or dichloromethane, the acylating reagent being methyl chloroformate, acetic anhydride or trifluoroacetic anhydride, for each mole of the amide of the formula (Ι) The benzoic acid, the acylating agent may be used in an amount of from 1 mole to the excess mole; the inert solvent in the above step (3) is selected from the group consisting of tetrahydrofuran, dichloromethane, 1,2-dichloroacetamidine. One of diethyl ether, 1, 4-dioxane, acetonitrile or toluene or In combination of two or more, the acid includes an organic acid selected from the group consisting of acetic acid, trifluoroacetic acid or p-toluenesulfonic acid, and the inorganic acid is hydrochloric acid or sulfuric acid; the reaction temperature is 0° C. Between the boiling points of the inert solvent used.

 The reaction time varies depending on the reaction scale and the reaction temperature, and is preferably 2 to 12 hours.

 After the completion of the reaction, the product of the formula (I) can be separated from the reaction mixture by a conventional filtration or the like, and if necessary, separation means such as recrystallization or column chromatography can be used.

 The product in the above step (1) is acidified, extracted, and concentrated to precipitate a solid, which is washed with a solvent, filtered, and then separated.

 The substituted phthalic anhydride represented by the formula (VI) used in the above production method is a known compound which can be produced by a number of known methods.

Typical compounds represented by the formula (I) of the present invention are listed in the index table 1 and the index table 2, but they are in no way intended to limit the scope of the invention. In the index table 1, a typical compound represented by the formula (I), when R ⁴ is hydrogen and X is a direct bond, a typical compound such as Da) shows:

化合物 熔点

Compound melting point

R ¹ R ² R ³ A Ym

 Number (° C)

1 C3⁄4 iC ₃ H ₇ 3- CI CH 2, 4-Cl ₂ 187-190

2 CH ₃ iC ₃ H ₇ 3- CI CH 3, 5- Cl ₂ 229-231

3 c3⁄4 iC ₃ H ₇ 3- CI CH 2,6- (CH ₃ ) ₂ - 4-CF(CF ₃ ) ₂ 156-158

4 CH ₃ i- C ₃ H ₇ 3- CI CH 2- CH ₃ - 4- CF(CF ₃ ) ₂ 136-139

5 CH ₃ C ₂ H ₅ 3- CI CH 2-0H-4-CF (CF ₃ ) ₂ 240-241

6 CH ₃ C ₂ H ₆ 3- CI CH 2,6- (CH ₃ ) ₂ - 4-CF(CF ₃ ) ₂ 168-170

7 CH ₃ C ₂ H ₅ 3- CI CH 2,5-(CH ₃ ) ₂ -4-CF(CF ₃ ) ₂ 193-195

8 CH ₃ CH ₃ 3- CI CH 2-F 221-223

9 CH ₃ CH ₃ 3- CI CH 2-CH ₃ -4-CF(CF ₃ ) ₂ 213-215

10 CH ₃ CH ₃ 3- CI CH 2, 5- Cl ₂ 196-198

11 c3⁄4 CH ₃ 3- CI CH 2,5— (C3⁄4) ₂ — 4— CF(CF ₃ ) ₂ 248-250

12 C3⁄4 CH ₃ 3- CI CH 2-Cl-4-N0 ₂ 205-207

13 CH ₃ CH ₃ 3- CI CH 3-CH ₃ -4-CF(CF ₃ ) ₂ 233-235

14 c3⁄4 CH ₃ 3- CI CH 4-CF(CF ₃ ) ₂ 268-271

15 CH ₃ CH ₂ (4-0CH ₃ -Ph) 3- CI CH 2,6-(CH ₃ ) ₂ -4-CF(CF ₃ ) ₂ 119-121

16 CH ₃ CH ₃ 3- CI CH 2- CI 178-180

17 CH ₃ CH ₃ 3- CI CH 2-0CH ₃ -4-CF(CF ₃ ) ₂ 164-166

18 CH ₃ CH ₃ 3- CI CH 2, 6- Cl ₂ 155-157

19 CH ₃ CH ₃ 3- CI CH 2,6- (CH ₃ ) ₂ - 4-CF(CF ₃ ) ₂ 259-261

20 CH ₃ CH ₃ 3- CI CH 3, 5- Cl ₂ 237-239

21 CH ₃ CH ₃ 3- CI CH 2-OCH3 148-150

22 c3⁄4 CH ₃ 3- CI CH 2-0H-4-CF (CF ₃ ) ₂ 209-211

23 C3⁄4 CH ₃ 3-1 CH 4-CF(CF ₃ ) ₂

24 CH ₃ CH ₃ 3-1 CH 2-CH ₃ -4-CF(CF ₃ ) ₂ 243-245

25 c3⁄4 CH ₃ 3-1 CH 2-CH3 191-193

26 CH ₃ CH ₂ 0(4-Cl-Ph) 3-1 CH 2-CH ₃ -4-CF(CF ₃ ) ₂

27 CH ₃ CH(CH ₂ ) ₂ 3-1 CH 2-CH ₃ -4-CF(CF ₃ ) ₂

28 H C3⁄4CH ⁼ C3⁄4 3-1 CH 2-CH ₃ -4-CF(CF ₃ ) ₂

29 CH ₃ CH ₃ 3-1 CH 2,5—(CH ₃ ) ₂ — 4—CF(CF ₃ ) ₂

_{30 CH 3 CH 2 SCH 3 3-1} CH 2, 4- Cl 2

31 CH ₃ C ₂ H ₆ 3-1 CH 3-CH ₃ -4-CF(CF ₃ ) ₂ C3⁄4 CH ₃ 3-F CH 2,6-(CH ₃ ) ₂ -4-CF(CF ₃ ) ₂ 247-249

CH ₃ CH ₃ 3-F CH 3, 5- Cl ₂ 188-190

CH ₃ CH ₃ 3-F CH 2-CH ₃ -4-CF(CF ₃ ) ₂ 214-216

(c3⁄4) ₄ 3-F CH 3-CH ₃ -4-CF(CF ₃ ) ₂

CH ₃ CH ₂ (4- 0CH ₃ -Ph) 3-F CH 2, 4- F ₂

CH ₃ CH(CH ₂ ) ₂ 3-F CH 2, 4- Cl ₂

CH ₃ CH ₃ 3-F CH 2,5—(CH ₃ ) ₂ — 4—CF(CF ₃ ) ₂ 227-229

CH ₃ CH ₃ 3-N0 ₂ CH 3, 5- Cl ₂ 202-204

CH ₃ CH ₃ 3-N0 ₂ CH 3, 5- F ₂ 186-188

CH ₃ CH ₃ 3-N0 ₂ CH 2,6- (CH ₃ ) ₂ - 4-CF(CF ₃ ) ₂ 151-153

CH ₃ CH ₃ 3-N0 ₂ CH 2, 4, 5-F ₃

H C3⁄4CH=C3⁄4 3-N0 ₂ CH 2-F-5-CF ₃

CH ₃ i - C ₃ 3-N0 ₂ CH 2-CH3-3-CF3

CH ₃ i~C ₃ H ₇ 3-N0 ₂ CH 4-CF(CF ₃ ) ₂

C3⁄4 CH ₃ 4- CI CH 2,6- (CH ₃ ) ₂ - 4-CF(CF ₃ ) ₂ 272-274

CH ₃ CH ₃ 4- CI CH 2-CH ₃ -4-CF(CF ₃ ) ₂ 207-209

CH ₃ CH ₃ 4- CI CH 2, 4- Cl ₂ 176-178

CH ₃ CH ₃ 4- CI CH 3, 5- Cl ₂ 226-228

CH ₃ CH ₃ 4- CI CH 4-CF(CF ₃ ) ₂ 245-247 c3⁄4 CH ₃ 4- CI CH 2-0H-4-CF (CF ₃ ) ₂ 217-218

CH ₃ CH ₃ 4- CI CH 2,5—(CH ₃ ) ₂ — 4—CF(CF ₃ ) ₂ 166-168

CH ₃ CH ₃ 4- CI CH 2- 0C3⁄4- 4- CF(CF ₃ ) ₂ 178-180 c3⁄4 CH ₃ 4- CI CH 3-CH ₃ -4-CF(CF ₃ ) ₂ 229-231

C3⁄4 CH ₃ 4- CI CH 2, 5- Cl ₂ 205-207

CH ₃ CH ₃ 4- CI CH 3, 4- F ₂ 208-210 c3⁄4 CH ₃ 4- CI CH 2, 6- Cl ₂ 246-248

CH ₃ CH ₃ 4- CI CH 2, 4- F ₂ 187-190

CH ₃ CH ₃ 4- CI CH 2, 4, 5 188-191

CH ₃ CH ₃ 4- CI CH 3-CF3 220-222

CH ₃ CH ₃ 4- CI CH 2-CF3 239-241 c3⁄4 CH ₃ 4- CI CH 2-CH3-3-CF3 190-193

CH ₃ CH ₃ 4- CI CH 2-F-5-CF ₃ 219-221

CH ₃ CH ₃ 4- CI CH 3, 5- F ₂ 229-231 c3⁄4 CH ₃ 4- CI CH 4-CH3 221-223

C3⁄4 CH ₃ 4- CI CH 2-CH3 195-197

CH ₃ CH ₃ 4- CI CH 2- CI 185-187 c3⁄4 CH ₃ 4- CI CH 3,4- (CH ₃ ) ₂ 209-211

CH ₃ CH ₃ 4- CI CH 2, 3- Cl ₂ 190-192

CH ₃ CH ₃ 4- CI CH 2-F 154-156

CH ₃ CH ₃ 4- Br CH 4-CF(CF ₃ ) ₂ 241-243

CH ₃ CH ₃ 4- Br CH 2-0H-4-CF (CF ₃ ) ₂ 225-227 c3⁄4 CH ₃ 4- Br CH 2,5—(C3⁄4) ₂ — 4—CF(CF ₃ ) ₂ 227-229

CH ₃ CH ₃ 4- Br CH 3-CH ₃ -4-CF(CF ₃ ) ₂ 226-228

122 CH₃ 4- CI CH 3-CH₃-4-CF(CF₃)₂ 213-215CH ₃ CH ₃ 4- Br CH 2, 4-Cl ₂ 221-223 c3⁄4 CH ₃ 4- Br CH 2, 5- Cl ₂ 188-190

122 CH ₃ 4- CI CH 3-CH ₃ -4-CF(CF ₃ ) ₂ 213-215

123 CH ₃ I-C3H7 4- CI CH 2, 4-Cl ₂ 202-204

124 CH ₃ i - C ₃ 4- CI CH 2-0CH ₃ -4-CF(CF ₃ ) ₂ 194-196

125 CH ₃ c3⁄4 3-F CH 3-CH ₃ -4-CF(CF ₃ ) ₂ 262-264

_{126 CH 3 CH 3 3-F} CH 3, 5- Cl 2 206-208

127 c3⁄4 CH ₃ 3-F CH 2, 4- F ₂ 199-201

128 CH ₃ CH ₃ 3-F CH 2-0CH ₃ -4-CF(CF ₃ ) ₂ 191-193

129 CH ₃ CH ₃ 3-F CH 2, 4-Cl ₂ 188-190

130 c3⁄4 C ₂ H ₅ 3-F CH 2,6- (C3⁄4) ₂ - 4-CF(CF ₃ ) ₂ 245-247

131 CH ₃ C ₂ H ₅ 3-F CH 2-CH ₃ -4-CF(CF ₃ ) ₂ 210-212

Typical compounds 4- CF (CF _{3) 2} 253-255 Table 2 Index of formula (I), when A is CH, X is methylene, A _{- 132 CH 3 C 2 H 5} 3-F CH 3- C When a cyano-substituted methylene group or N XR ^{4 is} cyclized, a typical compound is represented by the formula (lb):

索引表 2

Index table 2

以下表 3为索引表 1和索引表 2中所述部分化合物的核磁数据。

Table 3 below shows the nuclear magnetic data of some of the compounds described in Index Table 1 and Index Table 2.

 Note: The compound numbers described in Table 3 correspond to the compound numbers described in Tables 1 and 2. Where s is a single peak, brs is a broad single peak, d is a double peak, dd is a double doublet, t is a triplet, q is a quartet, and m is a multiplet. Table 3 compound nuclear magnetic data

 Compound Number Nuclear Magnetic (400MHz, DMS0-4)

 10.13-10.06 (1H, d), 8.80-8.75 (1H, d), 7.73-7.66 (4H, m),

 1

7.61-7.58 (1H, m), 7.48- 7.46 (1H, d), 2.40-2.35 (1H, m) , 1.53-1.52 (3H, d) , 1.07— L 05 (3H, dd) , 0.97—0· 95 (3H, dd)

10.71-10.68 (IH, d), 8.84-8.80 (IH, d), 7.78-7.60 (5H, m), 7.32 (IH, s), 2.40-2.34 (IH, m), 1.54- 1.53 (3H, d ) , 1.07-1.06 (3H, dd), 0.98-0.97 (3H, dd)

 10.72-10.69 (IH, d), 8.84-8. 82 (1H, d), 7.78-7.53 (3H, m), 7.40 (2H, s), 2.38 (6H, s), 2.37-2.34 (IH, m ),

 1.53-1.52 (3H, d), 1.08—L 06 (3H, dd), 0.97-0· 96 (3H, dd)

10.82-10.79 (IH, d), 8.82-8.78 (IH, d), 7.79-7.54 (6H, m), 2.39 (3H, s), 2.39-2.38 (IH, m), 1.54-1.52 (3H, d ), 1.07-1.05 (3H, dd), 0.97-0.95 (3H, dd)

 10.42 (IH, s), 9.69 (IH, s), 8.83 (IH, s), 8·16- 8.10 (1H, m), 7.77-7.59 (3H, m), 7.17-7.13 (2H, m), 1.96-1.86 (2H, m), 1.57 (3H, s), 1.00-0.96 (3H, t)

 10.09-10.03 (IH, d), 8.89- 8.86 (1H, d), 7.87-7.58 (3H, m), 7.41 (2H, s), 2.39 (6H, s), 2.00-1.88 (2H, m),

 1.59-1.58 (3H, d), 1.03- L 00 (3H, t)

 10.06-10.00 (IH, d), 8, 88— 8.83 (1H, d), 7.77-7.57 (4H, m), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.32 (3H, s ),

 1.96-1.88 (2H, m), 1.60- 1.59 (3H, d), 1.02-0.99 (3H, t)

10.17-10.11 (IH, d), 8, 92- 8.86 (1H, d), 7.81-7.58 (4H, m), 7.29-7.21 (3H, m), 1.63- L 61 (6H, d)

 10.08-10.03 (IH, d), 8.98-8.93 (IH, d), 7.79-7.62 (4H, m), 7.54-7.50 (2H, m), 3.89 (3H, s), 1.63 (6H, s)

 10.17-10.10 (IH, d), 8.98- 8.92 (1H, d), 7.84 (IH, s),

 7.72-7.62 (3H, m), 7.59-7.56 (IH, m), 7.35-7.32 (IH, m) , 1.65-1.64 (6H, d)

 10.00 (IH, s), 8.98 (IH, s), 7.70- 7.67 (3H, m), 7.56 (IH, s), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.31 (3H, s), 1.65 (6H, s)

10.37-10.31 (IH, d), 9.00- 8.95 (1H, d), 8.27- 8.16 (2H, m),

 7.76-7.66 (4H, m), L 64- 1.63 (6H, d)

 10.65-10.62 (IH, d), 8.96- 8.92 (1H, d), 7.73-7.61 (5H, m), 7.51-7.49 (IH, m), 2.47-2.44 (3H, m), 1.62 (6H, s )

 10.75 (lH, s), 8.93 (IH, s), 7.94-7.92 (2H, m),

 7.75-7.62 (5H, m), 1.63— 1.62 (6H, d)

 10.12-10.06 (IH, d), 8.96-8.93 (IH, d), 7.79-7.68 (2H, m), 7.55-7.53 (IH, d), 7.41 (IH, s), 7.29-7.27 (2H, d ), 6.90-6.84 (2H, m), 3.74 (3H, s), 3.26-3.18 (2H, m), 2.42-2.41 (6H, d), 1.51—L 50 (3H, d)

 10.03-9.96 (IH, d) , 8.94- 8.89 (1H, d), 7.71-7.59 (4H, m), 7.54-7.52 (IH, d), 7.38-7.26 (2H, m), 1.63- 1.62 (6H , d)

9.73-9.63 (IH, d), 8.97-8.91 (IH, d), 8.26-8.24 (IH, d),

 7.70-7.59 (3H, m), 7.29-7.27 (IH, d), 7.20 (IH, s), 3.91 (3H, s), 1.61-1.60 (6H, d)

 10.45-10.37 (IH, d), 8.88— 8.84 (1H, d), 7.89-7.56 (4H, m), 7.42-7.37 (2H, m), 1.62- L 61 (6H, d)

10.08-10.01 (IH, d), 8· 98- 8.95 (1H, d), 7.78-7.58 (3H, m) , 7.40 (2H, s), 2.38 (3H, s), 1.63 (3H, s)

 10.70-10.68 (IH, d), 8.99— 8.94 (IH, d), 7.74-7.62 (5H, m),

20

 7.32-7.31 (IH, m), 1.63 (6H, s)

 9.39-9.29 (IH, d), 8.95-8.88 (IH, d), 7.98-7.96 (IH, m),

21 7.65-7.56 (2H, m), 7.13-6.95 (4H, m), 3.83 (3H, s),

 1.61 (6H, s)

 10.45-10.40 (IH, d), 9.69— 9.57 (1H, d), 8.99- 8.93 (1H, d),

22 8.09-8.07 (IH, m), 7.76-7.59 (3H, m), 7.16-7.12 (2H, m) ,

 1.61 (6H, s)

 10.59 (IH, s), 8.96 (IH, s), 8.05- 8, 03 (1H, d),

 23 7.93-7.92 (2H, d), 7.71-7.65 (3H, m), 7.30 (IH, t),

 1.60 (6H, s)

 9.85 (IH, s), 8.99 (IH, s), 8.05- 8.03 (1H, d),

 24 7.79-7.77 (2H, d), 7.53-7.49 (2H, t), 7.33-7.29 (IH, t),

 2.36 (3H, s), 1.61 (6H, s)

 9.63 (IH, s), 8.92 (IH, s), 8.01 (IH, d), 7.75 (IH, m),

 25

 7.40-7.22 (5H, m), 2.25 (3H, s), 1.60 (6H, s)

10.02 (IH, s), 9.11 (IH, s), 7.65-7.63 (2H, m),

 32

 7.49-7.45 (IH, m), 7.41 (2H, s), 2.35 (6H, s), 1.61 (6H, s)

10.68 (IH, s), 9.13 (IH, s), 7.77-7.61 (4H, m), 7.33 (2H, s),

33

 1.62 (6H, s)

 10.05 (IH, s), 9.13 (IH, s), 7·55— 7.45 (6H, m), 2.38 (3H, s),

34

 1.61 (6H, s)

 10.79 (IH, s), 9.16 (IH, s), 7.89-7.73 (4H, m),

 39

 7.37-7.34 (2H, m), 1.62 (6H, s)

 10.86 (IH, s), 9.17 (IH, s), 7.92- 7.80 (3H, m),

 40

 7.30-7.25 (3H, m), 1.57 (6H, s)

 10.32 (IH, s), 9.11 (IH, s), 7.87-7.74 (2H, m), 7.74 (2H, s),

41

 7.42 (lH, s), 2.37 (6H, s), 1.58 (6H, s)

 9.99 (IH, s), 9.08 (IH, s), 7.86-7.78 (IH, m),

 46 7.73-7.69 (IH, t), 7.63-7.59 (IH, t), 7.42 (2H, s),

 2.35 (6H, s), 1.62 (6H, s)

 9.97 (IH, s), 9.10 (IH, s), 7.78-7.72 (2H, m) ,

 47

 7.61-7.51 (4H, m), 2.38 (3H, s), 1.62 (6H, s)

9.96 (IH, s), 9.08 (IH, s), 7·85—7· 70 (4H, m),

 48

 7.67-7.55 (IH, m), 7.49-7.41 (IH, m), 1.61 (6H, s)

 10.63 (IH, s), 9.10(1H, s), 7.77-7.70 (4H, m),

 49

 7.62-7.60 (IH, m), 7.34 (IH, s), 1.62 (6H, s)

10.66 (IH, s), 9.07 (IH, s), 7.95-7.92 (2H, d),

 50

 7.72-7.64 (4H, m), 7.60-7.56 (IH, m), 1.60 (6H, s)

 10.62(1H, s), 9.36 (IH, s), 9.14 (IH, s), 8.17- 8.15 (IH, d),

51 7.73-7.69 (2H, m), 7.60- 7· 56 (1H, m), 7· 16- 7· 12 (2H, m),

 1.58-1.56 (6H, d)

 9.93 (IH, s), 9.10 (IH, s), 7.74-7.63 (2H, m) ,

 52 7.60-7.55 (2H, m), 7.33 (IH, s), 2.44-2.42 (3H, m),

2.29 (3H, s), 1.62 (6H, s) '(ω 'H9)C9 'L-LL 'ί ' ( ^s Ήΐ)80 "6 ' ( ^s Ήΐ)80 Όΐ 69

 (s 'Η9)ΐ9 'Τ '(Ρ 'Η9)02 Ύ-ΙΖ Ύ

 '(Ρ 'Ηΐ)80 " -Οΐ Ί '(ω 3⁄4)6C " -^ "Ζ '(ΐ 3⁄4T)C9 "Ζ- 9 " 89

'(Ρ 'Η2)99 ·Ζ-Ζ9"'( ^δ 'Ηΐ)ΐΟ·6 ' ( ^s Ήΐ)90 Όΐ

 (s 'Η9)ΐ9 ·ΐ

 '(ω 'Ηΐ)92 'ί-0£ 'ί 3⁄4T)ZS " -Ο^ "Ζ ' ( 'ffi) ·Ζ- ΐ9 · L9

'(ω 'Ηδ)69 ' -9Z "Ζ '( ^s 'Ηΐ)90 '6 '( ^s 'Ηΐ)98 '6

 (s 'Η9)ΐ9 ·ΐ

 '(s 3⁄4ε) 27 '(ω 'HC)CT 'ί-ΙΖ "Ζ ' (Ρ 'Ηΐ) 0 ·Ζ- ΐ 99

 '(ω 'Ηδ)29 'L- L "Ζ '(s 3⁄4ΐ)^0 '6 '(s 3⁄4ΐ)9 "6

( ^s 'Η9) 09 ·ΐ

 '(s 'Ηδ)8^ 'Ζ '(Ρ 'W,) "Ζ-9ΐ "Ζ '(ω 3⁄4C)^9 'Z- 9 'Ζ 99

'(ω 3⁄4)99 " -Ζ9 "' (s Ήΐ)ΐΟ "6 ' ( ^s Ήΐ)9Τ Όΐ

( ^s 'Η9) S9 ,ΐ

'( ^ω 'Ηΐ)1⁄2 "9-86 "9 ' (ω 'Η2) WZ— ·Ζ '(ω 3⁄4ΐ)Ζ9 'Z-C9 "Ζ f9

'(ω 'HC)69 "Ζ-9Ζ "'(s'HT)60'6' ( ^s Ήΐ)89 Όΐ

( ^s 'Η9)Τ9 "ΐ '( ^ω 'HC)S9 "Z-29'Z ' ( ^m 'ΗΖ)Ο ' -^ 'Ζ

 S9

 '(Ρ'1Π)ε2·8- ·8 '(s Ήΐ)80 "6 '(s Ήτ)εε Όΐ

 (s 'Η9)ΐ9 ·ΐ

 '(s 'HC) g "2 ' 'Ηΐ)ΐ Ζ — S Z ' (ω 'm) 99 'Z-69 ' 29

'(Ρ 'ΗΤ) Ζ - -8 ''( ^s Ήΐ)ΖΟ "6 ' ( ^s Ήΐ)ΖΟ Όΐ

 (s 'Η9)ΐ9 "Τ '(ω 'Η2)ΐ9 'Ζ-1⁄2 'Ζ

 Ϊ́9

'(ω 'Η9)69 "Ζ-08"' (s 3⁄4T)SO "6 ' ( ^s 'Ηΐ)90 Όΐ

( ^s 'Η9) 09 ,ΐ

 '(Ρ 'ΗΤ)^ 'L-9f Ί '(ω 'Η2)99 "Ζ-Τ9 'Ζ '(ω 'Η2)89 "Z-CZ 'Ζ 09

 '(Ρ 'HT)T6 -Z-C6" '(s 3⁄4ΐ)ετ "8 '(s Ήΐ)ΖΟ "6 ' (s Ήΐ)09 Όΐ

( ^s 'Η9)Τ9 "ΐ 'Ηΐ)99 "Z-6S 'Ζ '( ^ω 'HC)C9 'Ζ-ΟΖ 'Ζ

 69

'(ω 'HT)S8 -Z-88"' (s Ήΐ)90 "6 ' ( ^s Ήΐ)ΐ2 Όΐ

 (s 'Η9) 69 ·ΐ

 '(ω 'Ηΐ)80 'Ζ '(TM 'Ηΐ)Ζ2 'Z-TC 'Ζ '(ω 3⁄4ΐ)^9 'Z-89 ' 89

'(ω 'H0 9 - -Ο ''(δ'Ηΐ)ΐΟ·6' ( ^s Ήΐ) £0 Όΐ

 (s 'Η9) 69 ·ΐ

 '(ω 'HT)9g " -6δ " '(ω 3⁄4S) 99 "Ζ-09 'Ζ '(ω 3⁄4ΐ)Ο "Z-CZ " Ζ9

'(ω 'HT)C8 - -g8"' ( ^s 'HT)^6"8 ' ( ^s Ήΐ)82 Όΐ

 (s 'Η9) 09 ·ΐ

 '(ω 3⁄4)8C Ί- 'ί '(m 3⁄4ΐ)99 -Ζ-ΐ9 'Ζ '(ω 'Η2) 9 'Z-8Z ' 99

'(ω 'ΗΤ)08 ' -^8 "' ( ^s 'Ηΐ)90 "6 ' ( ^s 'Ηΐ)ΐ9 Όΐ

 (s 'Η9)ΐ9 'T-C9 ·ΐ

 '(ω 'HT)Cg " -6S "Ζ '(ω 3⁄4)Ζ9 "Ζ-Τ9 'Ζ '(ω 'Η2)69 "Ζ-8Ζ ' 99

 '(ω 'HT)T8 ' -28" ' (s 3⁄4ΐ)86 "6 ' (s 3⁄4T)OS Όΐ

( ^s 'Η9)ΐ9 ·ΐ

'( ^ω 'Ηδ)^ - ^ '(Ρ 'Ηΐ)6^ "Ζ-Τ9 'Ζ '(ω 3⁄4ΐ)99 'Ζ-ΐ9 "

 '(ω 3⁄4)89 " -ΖΖ " '(s Ήΐ)90 "6 ' (s Ήΐ)99 Όΐ

( ^s 'Η9) 91 '( ^s 'HC)26 "C

 '(ω 'Η2)02 'ί-6Ζ " '(ΐ 'Ηΐ)99 "Ζ-09 'Ζ '(∞ 3⁄4Ζ)69 'Ζ-ΐΖ 'Ζ

'(Ρ ^c )9Z "8-82 "8 '(s 'Ηΐ)^ΐ '6 '(s 'Ηΐ)9^ '6

Ll.8.0/llOZN3/X3d Z^WO/ZIOZ OAV 7.43-7.39 (IH, t), 1.61 (6H, s)

 10.00 (IH, s), 9.03 (IH, s), 7.78-7.68 (3H, m),

 70

 7.59-7.55 (IH, t), 7.31-7.19 (3H, m), 1.61 (6H, s)

 10.75 (IH, s), 8.93 (IH, s), 8. 05- 8.03 (1H, d),

 71 7.95-7.92 (3H, m), 7.66-7.64 (IH, m), 7.60- 7.58 (2H, d),

 7.56-7.54 (IH, m), 1.62 (6H, s)

 10.45-10.40 (IH, d), 9.82— 9.70 (1H, d), 8.93 (IH, s),

 72 8.09-8.07 (IH, m), 7.79 (IH, s), 7.76- 7.74 (1H, d),

 7.55-7.52 (IH, m), 7.16— 7.12 (2H, m), 1.62-1.61 (6H, d)

10.05-9.99 (IH, d) , 8.98- 8, 94 (1H, d), 7.82-7.79 (2H, m),

73 7.60-7.53 (2H, m), 7.33 (IH, s), 2.44-2.42 (3H, d),

 2.31 (3H, s), 1.65-1.64 (6H, d)

 10.66-10.63 (IH, d), 8, 98- 8· 93 (IH, d), 7.86- 7.69 (4H, m),

74

 7.61-7.52 (2H, m), 2.48-2.46 (3H, d), 1.64-1.63 (6H, d)

10.13-10.05 (IH, d), 8.96- 8.90 (1H, d), 7.82-7.79 (2H, m),

75

 7.73-7.69 (2H, m), 7.55- 7· 46 (2H, m), 1.64-1.62 (6H, d)

10.19-10.11 (IH, d), 8.99—8· 93 (1H, d), 7.84-7.81 (3H, m),

76

 7.59-7.55 (2H, m), 7.36-7.33 (IH, m), 1.65- 1.64 (6H, d)

10.71-10.68 (IH, d), 8.99- 8.95 (1H, d), 7.88-7.80 (2H, m),

77 7.74-7.72 (2H, m), 7.61-7.55 (IH, m), 7.32-7.31 (IH, m) ,

 1.64-1.63 (6H, d)

 9.75 (IH, s), 8.92 (IH, s), 8.26-8.24 (IH, d),

 78 7.84-7.79 (2H, m), 7, 55- 7· 53 (1H, d), 7.30-7.21 (2H, m) ,

 3.92 (IH, s), 1.61 (6H, s)

 10.20-10.13 (IH, d), 8.93-8.87 (IH, d), 7.85-7.77 (3H, m),

79 7.62-7.51 (IH, m), 7.35- 7· 30 (1H, t), 7.11 (IH, s),

 1.63-1.62 (6H, d)

 10.60-10.57 (IH, d), 8.96— 8.91 (1H, d), 7.85-7.79 (3H, m),

80

 7.60-7.53 (IH, m), 7.47— 7.38 (2H, m), L 63- 1· 62 (6H, d)

10.76-10.73 (IH, d), 8, 99— 8.94 (1H, d), 7.87-7.81 (2H, m) ,

81 7.61-7.55 (IH, m), 7.42-7.39 (2H, d), 6.97-6.93 (IH, m) ,

 1.64-1.63 (6H, d)

 10.39-10.33 (IH, d), 8, 96—8· 91 (IH, d), 7.90-7.80 (3H, m),

82

 7.69-7.54 (2H, m), 1.64- L 63 (6H, d)

 10.52-10.46 (IH, d), 8.97— 8.92 (1H, d), 8.36-8.25 (IH, m),

83

 8.08-7.81 (3H, m), 7.61-7.52 (3H, m), 1.64-1.63 (6H, d)

10.45-10.37 (IH, d), 8.88— 8.83 (1H, d), 7.79-7.72 (2H, m),

84

 7.60-7.57 (2H, dd), 7.50-7.40 (2H, m), 1.62- 1.61 (6H, d)

10.04 (IH, s), 8.91 (IH, s), 7.84-7.76 (2H, m),

 85

 7.49-7.47 (IH, d), 7.36 (2H, s), 2.34 (6H, s), 1.58 (6H, s)

10.05-10.01 (IH, d), 8.94- 8· 89 (1H, d), 7.78-7.76 (IH, m),

86 7.68-7.64 (2H, m), 7.57— 7.49 (2H, m), 7.39 (IH, s),

 1.60-1.59 (6H, d)

 10.65-10.62 (IH, d), 8.93— 8.88 (1H, d), 8.09-8.04 (IH, m),

87 7.85-7.75 (3H, m), 7.59-7.50 (2H, m), 7.42-7.40 (IH, m) ,

1.59-1.58 (6H, d) 9.82-9.76 (IH, d) , 8.89-8.84 (IH, d), 7.84-7.62 (2H, m),

88 7.47-7.37 (IH, m), 7.21-7.10 (3H, m), 6.88-6.82 (IH, m) ,

 2.24 (3H, s), 1.59- 1.58 (6H, d)

 10.18-10.09 (IH, d), 8.92—8· 87 (1H, d), 7.76-7.71 (4H, m),

89

 7.58-7.47 (3H, m), 1.60- L 59 (6H, d)

 9.85-9.78 (IH, d) , 8.94-8.90 (IH, d), 7.88-7.48 (3H, m) ,

90

 7.10 (3H, s), 2.27 (6H, s), 1.63- 1.62 (6H, d)

10.24-10.17 (IH, d), 8.97— 8.91 (1H, d), 7.84-7.80 (2H, m),

91

 7.69-7.51 (3H, m), 7.43-7· 41 (1H, m), 1.64-1.63 (6H, d)

10.05-9.96 (IH, d), 8.95- 8.89 (1H, d), 7.86-7.64 (3H, m),

92

 7.55-7.52 (2H, d), 7.38-7.20 (2H, m), 1.64-1.63 (6H, d)

9.90-9.85 (IH, d) , 8.92-8.87 (IH, d), 7.89-7.74 (2H, m),

93 7.51-7.49 (1H, d), 7.22-7.07 (3H, m),

 2.28 (3H, s), 2.16 (3H, s), 1.64—1.63 (6H, d)

10.19-10.12 (IH, d), 8.93— 8.87 (1H, d), 7.81-7.77 (3H, m),

94

 7.62-7.52 (IH, m), 7.28-7.22 (3H, m), 1.64- 1.62 (6H, d)

9.82-9.76 (IH, d) , 8.94-8.89 (IH, d), 7.88-7.50 (3H, m),

95 7.24 (IH, s), 7.13-7.12 (IH, d), 6.98- 6.96 (1H, d),

 2.28 (3H, s), 2.23 (3H, s), 1.65- L 63 (6H, d)

10.39-10.32 (IH, d), 9.01- 8.96 (1H, d), 8.40- 8.39 (1H, m),

96 8.30-8.26 (IH, m), 8.19- 8.16 (1H, m) , 7.90-7.83 (2H, m) ,

 7.68-7.59 (IH, m), 1.65- L 63 (6H, d)

 10.25-10.17 (IH, d), 8, 99—8· 94 (IH, d), 8.29 (IH, s),

 97 8.17-8.02 (IH, m), 7.88-7.76 (2H, m), 7.65-7.51 (2H, m),

 1.66-1.64 (6H, d)

 10.52-10.49 (IH, d), 8.96—8· 91 (1H, d), 7.86-7.79 (2H, m),

98 7.73-7.71 (2H, d), 7.62-7.53 (IH, m), 7.43-7.40 (2H, m) ,

 1.64-1.63 (6H, d)

 10.10-10.04 (IH, d), 9.00- 8.95 (lH, d), 7.92-7.78 (3H, m),

99

 7.68-7.52 (3H, m), 2, 41- 2.40 (3H, d), 1.66- 1.65 (6H, d)

9.42-9.30 (IH, d), 8.97-8.89 (IH, d), 7.96-7.74 (3H, m),

100 7.63-7.50 (IH, m), 7.18-7.08 (2H, m), 6· 98- 6· 95 (IH, t),

 3.85-3.84 (3H, d), 1.62—1.61 (6H, d)

 10.28-10.24 (IH, d), 8.92- 8.86 (1H, d), 7.81-7.76 (2H, m),

101 7.52-7.45 (2H, m), 7.23-7.19 (IH, m), 6.92-6.90 (IH, m),

 6.43-6.37 (IH, m), 2.24 (3H, s), 1.62-1.61 (6H, d)

 9.81 (IH, s), 9.03 (IH, s), 7.74-7.57 (3H, m),

 109

 7.18-7.08 (3H, m), 2.28 (3H, s), 2.14 (3H, s), 1.61 (6H, s)

9.16-9.12 (IH, d), 7.98-7.96 (IH, d), 7.69-7.54 (3H, m),

111 7.16-6.94 (3H, m), 6, 79- 6.51 (IH, m), 3.84 (3H, s), 1.56

 (6H, s)

 10.41 (IH, s), 9.05 (IH, s), 7.73-7.67 (4H, m),

 112

 7.59-7, 55 (1H, t), 7, 42-7· 40 (2H, d), 1.59 (6H, s)

 10.06 (IH, s), 9.06 (IH, s), 7.82-7.75 (IH, m),

 113 7.69-7.53 (3H, m), 7.36-7.32 (2H, m), 7.28-7.22 (IH, m) ,

2.28 (3H, s), 1.59 (6H, s) 10.16 (IH, s), 9.02 (IH, s), 7.66-7.45 (5H, m),

 7.23-7.19 (IH, m), 6.92- 6.90 (1H, d), 2.29 (3H, s),

1.60-1.57 (6H, d)

 9.44 (IH, s), 9.01 (IH, s), 8.29-8.27 (IH, d),

 7.70-7.69 (2H, d), 7.59- 7.55 (1H, t), 7.29-7.20 (2H, m) 3.91 (3H, s), 1.90-1.78 (2H, m), 1.52 (3H, s),

 0.96-0.92 (3H, t)

 10.13-9.98 (IH, d) , 8.93— 8.78 (1H, d) , 7.78-7.53 (3H, m), 7.40-7.36 (2H, d), 2.45-2.42 (3H, d), 2.33 (3H, s ), 1.97-1.81 (2H, m), 1, 57- L 56 (3H, d), 1.03-Q.96 (3H, m)

10.10-9.92 (IH, d), 8.98- 8.79 (1H, d), 7.73-7.56 (4H, m), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.34-2.29 (3H, d ),

2.00-1.86 (2H, m), 1, 60- L 57 (3H, d), 1.02-Q.98(3H, t) 10.57 (IH, s), 8.95 (IH, s), 7.77-7.67 (4H , m),

 7.59-7.49 (2H, m), 2.46-2.44 (3H, d), 1.97-1.83 (2H, m)

1.57 (3H, s), 1.02-0.98 (3H, t)

 10.16-9.94 (IH, d) , 8.94- 8, 71 (1H, d), 7.74-7.55 (5H, m),

7.48-7.46 (IH, d), 1.97-1.82 (2H, m), 1.57-1.56 (3H, d)

1.01-0. 98 (3H, t)

 10.14(1H, s), 8.75 (IH, s), 7.71- 7.69 (IH, t) ,

 7.56-7.55 (2H, d), 7.36 (2H, s), 2.46 (6H, s),

 2.41-2.38 (IH, m), 1.51 (3H, s), 1.06—1.04 (3H, d),

 0.95-0.93 (3H, d)

 10.12-9.92 (IH, d) , 8.92- 8, 76 (1H, d), 7.72-7.53 (4H, m), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.33-2.29 (3H , d), 2.27-2.24 (IH, m), 1.53— 1.52 (3H, d) , 1.07— 1.05 (3H, d) 0.98-0.95 (3H, t)

 10.76-10.56 (IH, d), 8.89-8.74 (IH, d), 7.77-7.48 (6H, m), 2.46-2.44 (3H, d), 2.29-2.24 (IH, m), 1.51- 1.49 (3H , d) 1.07-1.04 (3H, d), 0.97-0.92 (3H, t)

 10.16-9.92 (IH, d) , 8.87— 8, 65 (1H, d), 7.87-7.45 (6H, m),

2.40-2.23 (IH, m), 1.51 (3H, s), 1.07- 1.04 (3H, d),

 0.97-0.92 (3H, t)

 8.83-8.76 (IH, d) , 8.66-8.58 (IH, m), 7.60- 7.58 (2H, m), ~~ 7.52-7.49 (IH, m), 7.24-7.21 (IH, m), 6.55 (IH , s), 6.50-6.47 (IH, m), 4.32-4.30 (2H, d), 3.80 (3H, s),

3.75 (3H, s), 1.61- 1.59 (6H, d)

 9.37-9.31 (IH, d), 8.83- 8.78 (1H, d), 7.65-7.45 (3H, m)

 3.65 (4H, s), 2.86 (4H, s), 1.65- L 64 (6H, d)

 9.54 (IH, s), 8.80 (IH, s), 7.75-7.64 (2H, m) ,

 7.56-7.46 (IH, m), 3, 67- 3· 65 (4H, t), 2.88-2.86 (4H, t) ,

1.64 (6H, s)

 8.84-8.77 (IH, d) , 8.66-8.58 (IH, dt), 7.74-7.65 (2H, m), 7.52-7.42 (IH, dd), 7.24-7.21 (IH, q), 6.58- 6.47 (2H , m) : 4.32-4.31 (2H, d), 3.81—3, 75 (6H, dd), 1.61-1.60 (6H, d)

8.89 (IH, s), 8.84 (IH, s), 7.99 (IH, d), 7.55 (IH, d) 7. 23 (1H, t) , 1. 65 (12H, s) A pest control agent containing the phthalamide compound represented by the above formula (I) as an active ingredient, and a pest at a low dose With super high control effect.

 The cyano group-containing phthalamide compound represented by the formula (I) of the present invention or an agriculturally applicable salt thereof can be used for an agrochemical insecticide.

 Specifically, for the control of Plutella xylostella, Brassica chinensis, Spodoptera litura, Spodoptera exigua, Spodoptera frugiperda, Helicoverpa armigera, Oriental armyworm, Nicotiana moth, Tobacco moth, Rice leaf roller, Rice brown belt Rolling moth, apple small moth, peach small moth, pear small heartworm, small tiger, potato leaf beetle, yellow squash, aphid, whitefly, thrips, aphids, scorpionfish and other agricultural pests. 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. In addition, the agricultural and horticultural pest control agent containing the cyano group-containing phthalamide compound represented by the formula (I) of the present invention is used for controlling organophosphorus, carbamate, pyrethroid, and benzoic acid. Resistant pests such as ureide are effective. Further, the cyano group-containing phthalamide compound represented by the formula (I) of the present invention has excellent osmotic transfer property, and therefore contains a cyano group represented by the formula (I) according to the present invention. The phthalate-based agricultural and horticultural pest control agent is used to treat the soil, and the pests of the stems and leaves can also be controlled while controlling the soil harmful insects, mites and the like.

 Other preferred embodiments of the pest control agent containing the cyano group-containing phthalamide compound represented by the formula (I) of the present invention include comprehensive control of the plant parasitic mites and agricultural pests. , pest control agents for agricultural and horticultural use such as soil pests.

 The cyano group-containing phthalic acid amide compound represented by the formula (I) of the present invention can be used as an active component of a chemical pesticide for pesticides, and is formulated into various liquid preparations, emulsifiable concentrates, suspension concentrates, aqueous suspensions, Microemulsions, (water) emulsions, powders, wettable powders, soluble powders, (water-dispersible) granules or capsules, for pest control of crops such as rice, soybeans, wheat, cotton, corn, vegetables and canola.

 When configured as a pesticide chemical pesticide, the weight percentage of the active component, that is, the weight percentage of the cyano group-containing phthalamide compound represented by the formula (I) of the present invention is preferably 0. 001%-99. 99% by weight, the balance being an agriculturally acceptable carrier.

The carrier can be a solid or a liquid. Suitable solid carriers include natural or synthetic clays and silicates such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminosilicates such as kaolinite, kaolin, montmorillonite and mica; , calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine. The liquid carrier includes water and an organic solvent, and when water is used as a solvent or a diluent, the organic solvent can also be used as an adjuvant or an antifreezing additive. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, Methylene chloride or the like; aliphatic hydrocarbons such as petroleum distillate, cyclohexane, light mineral oil; alcohols such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol; and ethers and esters thereof There are also ketones such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.

The carrier can also be a surfactant. Suitable surfactants can be emulsifiers, dispersants or wetting agents; they can be ionic or nonionic. Nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: agricultural milk 2201B, agricultural milk 0203B, agricultural milk 10 (f, agricultural milk 50 ( f, agricultural milk 600 agricultural milk 600- 2 ^# , agricultural milk 1601, agricultural milk 2201, agricultural milk NP-10, agricultural milk NP- 15, agricultural milk 507*, agricultural milk 0X- 635, agricultural milk 0X-622, agriculture Milk 0X-653, agricultural milk 0X-667, Ning milk 36 ^s . Dispersing agent includes sodium lignosulfonate, pull-up powder, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc. Wetting agent: laurel Sodium sulphate, sodium dodecyl benzene sulfonate, sodium decyl naphthalene sulfonate, and the like.

 The above pesticide chemical pesticides can be prepared by a general method. For example, the active substance may be mixed with a liquid solvent and/or a solid carrier, and a surfactant such as an emulsifier, a dispersant, a stabilizer, a wetting agent may be added, and other auxiliary agents such as a binder, an antifoaming agent, an oxidizing agent may also be added. Wait.

 The cyano group-containing phthalamide compound of the present invention can also be used in combination with herbicides, fungicides, nematicides, plant growth regulators, fertilizers, and other pesticides or other agricultural chemicals. .

 In the control of pests, when the pesticide preparation of the present invention is applied to a pest to be controlled or a medium for growth thereof, wherein the active component is a cyano group-containing phthalamide represented by formula (I) The effective amount of the compound is from 10 grams to 1000 grams per hectare.

 The cyano group-containing phthalamide compound represented by the formula (I) of the present invention or an agriculturally applicable salt thereof and a preparation thereof have the following advantages over the prior art:

 (1) The present invention introduces an α-amino nitrile functional group in the structure of phthalic acid for the first time, and the structure of the compound is novel;

(2) The compound of the present invention and its preparation have an extremely high insecticidal activity: a good effect on lepidopteran pests at a dose of 0.16 mg/L;

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

 (4) The compound of the present invention and its preparation have reasonable toxicity, ecotoxicity and environmental compatibility, and are low-toxic environmentally friendly pesticides. detailed description

 The following specific examples are intended to further illustrate the invention, but the invention is not limited thereto.

Synthesis example Example 1

Preparation of 3-iodo-N ¹ -(2methyl-tetrafluoropentylphenyl) N ² —(1methyl-l-cyanoethyl)phthalamide (Compound 24)

Step 1: Synthesis of 3-iodo-N-(1methyl-l-cyanoethyl)-amidobenzoic acid

A mixture of 2-amino-2-dimethylpropionitrile (0.88⁄2, 10 mmol) and triethylamine (0.20 g, 2 mmol) was dissolved in hydrazine, hydrazine-dimethylacetamide (DMA, 3 mL). Slowly added to a solution of 3-iodophthalic anhydride (2.74 g, 10 mmol) in DMA (8 mL) at room temperature. The reaction mixture was stirred for 1 h, poured into water and acidified with dilute hydrochloric acid. The aqueous layer was extracted with EtOAc. The solvent was removed under reduced pressure to give a brown oily product. The product was obtained as a white solid, 1.80 g (50%), m.p.: 141~ 143 ° C, and NMR data: ¹诵R (400 丽z, DMSO-c,): δ = 13.23 (1Η, brs), 8. 77 (1H, s) , 8· 09- 8. 07 (1H, d), 7. 93- 7· 91 (1H, d),

7. 28-7. 24 (1H, t) , 1. 64 (6H, s).

Step 2: Synthesis 3-Iodo-N-(1methyl-monocyanoethyl) phthalimide

Trifluoroacetic anhydride (0.76 g, 3. 6 mmol) was added to 3-iodo-N-(1methyl-l-cyanoethyl)-amidobenzoic acid (1.07 g, 3 mmol) in 10 mL of toluene In the suspension, the reaction mixture was stirred at room temperature for 30 min. The solvent was removed under reduced pressure to give the title compound. The melting point of the compound is 148~150 ° C, and the nuclear magnetic data is: 3⁄4 NMR (400MHz, CDC1 ₃ ): δ = 8. 30-8. 28 (1Η, d) , 7. 98-7· 96 (1H, d) ,

7. 45-7. 41 (1H, t) , 1. 85 (6H, s).

Step 3: Synthesis of 3-iodo-N ¹ -(2methyl-tetrafluoropentylphenyl) N ² —(1methyl-l-cyanoethyl)phthalamide

Add 2-methyl-4-heptafluoroacetate to 3-iodo-N-(1methyl-monocyanoethyl)isophthalimide (1. 02 g, 3 mmol) in acetonitrile (10 mL) Isopropylaniline (0. 80 g, 2.90 mmol) and trifluoroacetic acid (0.0 g). Filtration, collection of the precipitate, washing with a small amount of low-temperature acetonitrile to obtain the first product; after evaporation of the solvent, the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2 / 1-1 /1), the second batch of product is obtained, and the two batches of the product are combined to obtain 3-iodo-N ¹ -(2methyl-tetrafluoropentylphenyl) N ² - (1 methyl- 1 -cyanide) Base ethyl)phthalamide 1. 04g (60%), melting point 243~245° C, nuclear magnetic data: ¹诵R (400MHz, DMS0-4): δ = 9. 85 (1H, s), 8. 99 (1H, s) , 8. 05-8. 03 (1H, d) , 7. 79-7. 77 (2H, d) , 7. 53-7. 49 (2H, t) , 7. 33-7. 29 (1H, t) , 2. 36 (3H, s) , 1. 61 (6H, s). Example 2

Preparation of 4-chloro-N ¹ -(2,4-dichlorophenyl) N ² -(1methyl-l-cyanoethyl)phthalamide (Compound 48) Step 1: Synthesis of 4-chloro-N (1 methyl-l-cyanoethyl)-amidobenzoic acid

 A mixture of 2-amino-2-dimethylpropionitrile (0. 84 g, 10 mmol) and triethylamine (0.20 g, 2 mmol) was dissolved in hydrazine, hydrazine-dimethylacetamide (DMA, 3 mL). It was slowly added to a solution of 4-chlorophthalic anhydride (2.74 g, 10 mmol) in DMA (8 mL) at room temperature. The reaction mixture was stirred for 1 h, poured into water and acidified with dilute hydrochloric acid. The aqueous phase was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the product as crystals, crystals. The product obtained was 1.73 g (65%), m.p. 127.

Step 2: Synthesis of 4-chloro-N (1 methyl-mono-cyanoethyl) phthalimide

 Trifluoroacetic anhydride (1.0 g, 4. 8 mmol) was added to a suspension of 4-chloro-N (1methyl-l-cyanoethyl)-amidobenzoic acid (1. 06 g, 4 mmol) in 12 ml of toluene. The mixture was stirred at room temperature for 30 min. The solvent was removed under reduced pressure to give aq.

Step 3: Synthesis of 4-chloro-N ¹ - ( 2, 4 - dichlorophenyl) N ² (1 methyl- 1 - cyanoethyl) phthalic acid amide

In a solution of 4-chloro-N (1methyl-mono-cyanoethyl) phthalimide (0.19 g, 1⁄2 mol) in acetonitrile (12 mL), 2,4-dichloroaniline (0. 63 g, 3. 9 mmol) and trifluoroacetic acid (0.11 g). Filtration, collection of the precipitate, washing with a small amount of low-temperature acetonitrile to obtain the first product; after evaporation of the solvent, the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2 / 1-1 /1), the second batch of product is obtained, and the two batches are combined to obtain 4-chloro-N ¹ (2,4-dichlorophenyl) N ² (1 methyl-monocyanoethyl) phthalic acid Formamide 1.13g (71%), melting point 176~178° C, NMR data: ¹诵R (400MHz, DMS0- ): δ =9. 96 ( 1H, s), 9. 08 (1H, s) , 7. 85-7. 70 (4H, m) , 7. 67-7. 55 ( 1Η, m) , 7. 49- 7. 41 (1H, m), 1. 61 (6H, s). The compound (I) of the present invention listed in the index table 1, the index table 2, and the table 3 can be synthesized according to the production method described in the above Synthesis Example 1-2. The following Examples 3 to 5 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 "%" refers to weight percentage. Example 3 Wettable powder formula

15% of compound (24) (Table 1), 5% lignosulfonate (M _Q ), 1% lauryl polyoxyethylene ether (JFC), 40% diatomaceous earth and 44% light The calcium carbonate is uniformly mixed and pulverized to obtain a wettable powder. Example 4 Emulsion Formula

10% of the compound (24) (Table 1, 5% of the agricultural milk 500 (calcium salt), 5% of the agricultural milk 602, 5% of N-methyl-2-pyrrolidone and 75% of the two The toluene is heated and stirred uniformly to obtain an emulsifiable concentrate. Example ⁵ granule formula

 5% of compound (24) (Table 1), 1% polyvinyl alcohol (PVA), 4% sodium naphthalene sulfonate formaldehyde condensate (NM0) and 90% clay were uniformly mixed, pulverized, and then 100 The mixture was added to 20 parts of water, kneaded, and extruded into a granulator to prepare granules of 14 32 mesh, which were dried to obtain granules. Examples of biological activity assays using the compounds of the present invention are given below, 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:

 Weigh a certain amount of the preparation, and dilute with distilled water to prepare the liquid with the required concentration. The screening concentration was from 500, 100, 20, 4.0. 8, 0. 16, 0. 032 mg / L, and the amount of the drug treatment solution was lOmL. The test target was oriental worm (i 'mg separa ta), cotton bollworm (Helico this armigera), Aphis medicagini, PI u tell a xylostella, oofe ^'s litura Spodopterem frugiperda).

 (1) Oriental armyworm screening

 The corn leaves are fully infiltrated in the liquid, and then dried naturally. They are placed in a petri dish, and the 3rd instar larvae are picked up and placed in the observation room. The test was repeated 4 times. The results were checked after 72 hours. The brush is lightly touched by the worm, and no reaction is considered to be dead.

 (2) Cotton bollworm screening - spray method

 Potted cotton (2-3 leaf age) 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 Φ 9cm plastic petri dish, and the larvae of the genus Spodoptera or Helicoverpa armigera were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days.

 (3) Plutella xylostella screening - impregnation method

 Cut the cabbage slices, punch them into discs, and then immerse them in the liquid for 20s, put them in Φ9TM plastic culture dish (5 pieces/dish), and pick up the 2nd instar larvae of Plutella xylostella 15 pieces/dish, put a piece of filter paper, add cover. Incubate in a room at 26 °C. The test was repeated 4 times. Check the results after 72h. The tip of the scorpion touches the worm, and no response is considered to be dead.

 (4) 苜蓿蚜 screening - impregnation method

Cut the broad bean leaves to the ends, place the back side up on a small piece of cotton, place it in a plastic Petri dish, add a small amount of water, and connect the mash to the oyster. After 24 hours, the mites were removed. After the culturing for 2 days, the leaves were fully infiltrated in the medicinal solution for 5 s, and then placed on the cotton, and naturally dried. The results were checked after 24 hours. (5) Spiraea moth screening

 Cut the cabbage slices, use the puncher to beat the cabbage leaves, soak in the liquid for 20s, and dry. Place in a six-hole plastic box with a round hole (2cm), 3 pieces per hole. Access to Spodoptera litura 3 instar larvae 1 / hole, placed in the observation room. Repeated test

4 times. The results were checked after 72 hours. The tip of the scorpion touches the worm, and no response is considered to be dead.

 (6) Screening of Spodoptera frugiperda - Spray method

 Potted cotton (2-3 leaf age) 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 Φ 9cm plastic petri dish, and the larvae of the genus Spodoptera or Helicoverpa armigera were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days. Note: The numbers described in the biological activity assay examples correspond to the compound numbers described in Index Table 1, Index Table 2, and Table 3. Test Statistics: The number of dead insects and live insects in each treatment was counted, and the mortality was calculated.

c _r test number - live insect count _im

 Dead IT rate (%) = , x lOO

 Number of trials

 The CK control mortality was <20%, the test results were credible, the test results were corrected, and the CK control mortality was <5%. The results of the bioassay test indicate that the compound of the present invention has good insecticidal activity, especially for lepidopteran pests such as oriental armyworm, cotton bollworm, diamondback moth, Spodoptera litura, and Spodoptera litura. Active, also has a certain insecticidal activity against Homoptera pests. "mg/L" refers to each mg of active substance per liter.

 At a concentration of 500 mg/L, the mortality rates of compounds 23, 24 and 137 against oriental armyworms were 100%.

 At a concentration of 500 mg/L, the mortality of compound 32, 33 against guanidine was 100%.

 At a concentration of 500 mg/L, compounds 23, 24, 32, 33, 34, 40, 46, 47, 48, 137 have a mortality rate of more than 80% against Plutella xylostella, and at a concentration of 100 mg/L, compounds 23, 24, 33, 34 46, 47, 48, 137 have a mortality rate of more than 80% against Plutella xylostella. At 20 mg/L, the mortality of compounds 23, 24, 34, 46, 47, 48 against Plutella xylostella is greater than 80%, and the concentration of 4 mg/L is higher. The mortality rate of compound 23, 24, 34, 47, 48 against Plutella xylostella is more than 80%, and the mortality rate of compound 23, 24, 47 against Plutella xylostella is greater than 80%, 0. 16mg/ At the L concentration, the mortality of compounds 24, 47 against Plutella xylostella was 100%.

 At the concentration of 0.8 mg/L, the mortality rate of compounds 23 and 24 against cotton bollworm was 100%. At the concentration of 0.16 mg/L, the mortality rate of compound 24 against cotton bollworm was 100%.

 At the concentration of 0.8 mg/L, the mortality rate of compounds 23 and 24 against Spodoptera frugiperda was greater than 80%. At the concentration of 0.16 mg/L, the mortality rate of compound 24 against Spodoptera frugiperda was 100%.

 0. At a concentration of 16 mg/L, Compound 24 had a mortality rate of 100% against Spodoptera litura.

Comparing the insecticidal activity of the compound of the present invention with the control compound flubendiamide, the results are listed In Table 4.

 Comparison of insecticidal activity

表 4显示， 与现有化合物氟虫酰胺相比， 当浓度大于 0. 16 mg/L时， 本发明化合物对小 菜蛾的杀虫活性基本相当， 对斜纹夜蛾发挥了较高的杀虫作用， 特别是在低施用率下 (0. 032Mg/L), 本发明化合物要比现有化合物优异， 远远高于毒死蜱和氯氰菊酯的活性。 基 于这些化合物结构上的相似性， 这种提高的结果是出人意料的。

Table 4 shows that compared with the existing compound flubendiamide, when the concentration is greater than 0.16 mg / L, the compound of the present invention has substantially the same insecticidal activity against Plutella xylostella, and exerts a high insecticidal action against Spodoptera litura. Especially at low application rates (0.032 Mg/L), the compounds of the invention are superior to the existing compounds and much higher than the activity of chlorpyrifos and cypermethrin. Based on the structural similarity of these compounds, the result of this increase is unexpected.

 Compound 24 was subjected to a greenhouse residual activity test, and the results are shown in Table 5. The test results showed that: at 0. 8mg/L, the compound 24 was treated with the test insects 19 days after the drug, and the mortality rate of Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera was still 100%; at 0. 16mg/L, With the prolongation of treatment time, the efficacy was reduced. After 12 days, the drug could still reach 100%. After 19 days, the mortality of Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera decreased to 60%, 55 % and 80 %, respectively. At 0. 032 mg/L, the efficacy against all three test insects was low. It has a high residual activity on compound 24. Table 5 Compound 24 residual activity test results

 Mortality rate (%)

 Concentration

 Compound Plutella xylostella, Spodoptera frugiperda, Helicoverpa armigera

 (mg/L)

 5 12 19 5 12 19 5 12 19

0. 8 100 100 100 100 100 100 100 100 100

24 0. 16 80 100 60 100 100 55 100 100 80

0. 032 60 70 0 0 20 20 0 50 30

Claims

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

RR ^{2 is} independently selected from the group consisting of hydrogen, Cf, C ₃ - (cyclodecyl, C ₂ -C ₆ alkenyl or (: ₂ -(: ₆ alkynyl), the hydrogen on the group may also be halogen Further substituted with cyano, nitro, dC ₆ methoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, sulfonylthio, decylsulfinyl or alkylsulfonyl; Or R ¹ and R ² together with the attached carbon form a cyclodecyl group; R ^{3 is} selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC ₆ fluorenyl, halogenated dC ₆ fluorenyl, dC ₆ decyloxy or halooxy; R ^{4 is} selected from hydrogen or (^-( ₆垸; X is selected from a methylene group, a dC ₆ fluorenyl group, a cyano substituted methylene group or a direct bond; Or X and R ⁴ are bonded to the N to form a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a five-membered heterocyclic ring or a six-membered heterocyclic ring; Y is selected from the group consisting of hydrogen, halogen, cyano, nitro, Hydroxy, dC ₆ fluorenyl, halogenated dC ₆ fluorenyl, d-C ₃ decyloxy, halogenated dC ₃ decyloxy, phenyl, substituted phenyl, heterocyclic aryl or substituted heteroaryl;  A is CH or N;  m is an integer from 0 to 4.  2. The cyano group-containing phthalamide compound according to claim 1, wherein: RR ^{2 is} independently selected from the group consisting of hydrogen, dC ₃ , or ( _{3 -6} (cyclohexyl) or (: ₂ _ ( ₃ alkenyl), a phenyl group on the group may also be substituted, a substituted benzene An oxo group, an alkylthio group, an alkylsulfinyl group or a decylsulfonyl group; Or R ¹ and R ² together with the attached carbon form a cyclohexyl group; R ^{3 is} selected from hydrogen or halogen; R ^{4 is} selected from hydrogen or ^-(: ₃ fluorenyl; Or X and R ⁴ are bonded to the N to form a five-membered heterocyclic ring or a six-membered heterocyclic ring; Y is selected from the group consisting of hydrogen, a halogen atom, a nitro group, a hydroxyl group, a fluorenyl group, a fluorinated dC ₃ fluorenyl group, a dC ₃ decyloxy group or a fluorinated dC _{3 group.} Oxygen  m is an integer of 1 to 3.  The cyano group-containing phthalamide compound according to claim 2, which is characterized in that: RR ² are independently selected from hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allyl, hydrogens on the group may also be substituted phenyl, substituted phenoxy, methylthio a group such as a methylsulfinyl group or a methylsulfonyl group; R ^{3 is} selected from fluorine, chlorine, bromine or iodine, and R ³ is at the 3 or 4 position of the benzene ring; R ⁴ is hydrogen or methyl;  X is a methylene group, a methyl group, a cyano substituted methylene group or a direct bond; Or X and R ⁴ are bonded to the N to form an oxygen-containing six-membered heterocyclic ring;  Y is selected from the group consisting of hydrogen, fluorine, chlorine, nitro, hydroxy, methyl, methoxy, trifluoromethyl, trifluoromethoxy or heptafluoroisopropyl.  The cyano group-containing phthalamide compound according to claim 3, characterized in that said phthalamide compound

 The cyano group-containing phthalic acid amide compound according to claim 1, which comprises R and/or S optical isomers in any ratio.  An intermediate for preparing a cyano group-containing phthalamide compound according to claim 1, which has the following formula (Π) or (

 ( I I ) ( III )  among them: RR ^{2 is} independently selected from the group consisting of hydrogen, C "C ₆ alkyl, ( ₃ - (: ₆ cyclodecyl, C ₂ - C ₆ alkenyl or C ₂ - C ₅ alkynyl, hydrogen on the group) May be halogen, cyano, nitro, (^-[: ₆ methoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, thiol, fluorenylsulfinyl or fluorenyl) Further substitution of a sulfonyl group; Or R ¹ and R ² together with the attached carbon form a cycloalkyl group; R ^{3 is} selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC ₆ fluorenyl, halogenated dC ₆ alkyl, dC ₆ decyloxy or halodecyloxy.  7. An intermediate for the preparation of a phthalamide compound according to claim 1 according to claim 6, wherein: RR ^{2 is} independently selected from hydrogen, dC ₃ alkyl, C ₃ -C ₆ cyclodecyl or C ₂ -C ₃ alkenyl, and the hydrogen on the group may also be substituted phenyl, substituted phenoxy Further substituted with a thiol group, a fluorenylsulfinyl group or a decylsulfonyl group; Or R ¹ and R ² together with the attached carbon form a cyclohexyl group; R ^{3 is} selected from hydrogen or halogen.  8. An intermediate for the preparation of a phthalamide compound according to claim 1 according to claim 7, wherein: RR ^{2 is} independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allyl, and the hydrogen on the group may also be substituted with a phenyl group, a substituted phenoxy group, a methylthio group. Further, a group such as a methylsulfinyl group or a methylsulfonyl group is substituted with one oxime; R ^{3 is} selected from fluorine, chlorine, bromine or iodine, and R ³ is at the 3- or 4-position of the benzene ring.  A method for producing a cyano group-containing phthalamide compound according to claim 1, which comprises the steps of:  (1) The substituted phthalic anhydride represented by the formula (VI) and the substituted aminoacetonitrile represented by the formula (V) are subjected to an N-acylation reaction in an inert solvent in the presence or absence of a base to give a structural formula ( Substituted o-amidobenzoic acid represented by III);

 (2) In an inert solvent, the substituted o-amidobenzoic acid represented by the formula (I I I) is reacted with an acylating reagent to obtain a substituted phthalimyl group represented by the formula (I I).

(3) Substituted phthalic acid represented by the formula (Π) in an inert solvent in the presence or absence of an acid The formylisoimide is reacted with a substituted amine represented by the formula (IV) to obtain a cyano group-containing phthalamide compound represented by the formula α);

Wherein: RR ² , RR\A, X, Y and m are defined as claimed in claim 1.  10. A process for the preparation of a cyano group-containing phthalamide compound according to claim 9, wherein:  The inert solvent described in the step (1) is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, N,N-dimethylformamide, One or a combination of two or more of N,N-dimethylacetamide, toluene or dichloromethane, the base comprising an organic base and an inorganic base selected from the group consisting of triethylamine, pyridine or 3- a methylpyridine, the inorganic base being selected from the group consisting of potassium carbonate, sodium hydrogencarbonate, sodium hydroxide or anhydrous sodium acetate;  The inert solvent in the step (2) is one or two selected from the group consisting of toluene, 1,2-dichloroethane, ethyl acetate, tetrahydrofuran, acetonitrile, 1,4-dioxane or dichloromethane. In the above combination, the acylating reagent is methyl chloroformate, acetic anhydride or trifluoroacetic anhydride;  The inert solvent in the step (3) is one or more selected from the group consisting of tetrahydrofuran, dichloromethane, 1,2-dichloroethane, diethyl ether, 1, 4-dioxane, acetonitrile or toluene. The acid includes an organic acid and a mineral acid, and the organic acid is selected from the group consisting of acetic acid, trifluoroacetic acid or p-toluenesulfonic acid, and the inorganic acid is hydrochloric acid or sulfuric acid;  The reaction temperature is between 0 ° C and the boiling point of the inert solvent used.  A use of a cyano group-containing phthalamide compound represented by the formula (I) according to any one of claims 1 to 10 or an agriculturally applicable salt thereof, which is characterized in that it is used for agrochemical killing Insecticide.  And a cyano group-containing phthalic acid amide compound represented by the structural formula (I) according to claim 1 or a compound thereof (or 0.001%-99. 99% by weight) or Agriculturally applicable salts, as well as agriculturally acceptable carriers. A method for controlling pests, characterized in that: the pesticide preparation according to claim 12 is applied to a pest to be controlled or a medium for growth thereof, wherein the active component contains a cyano group phthalamide The effective amount of the compound is from 10 grams to 1000 grams per hectare.