DD259782A5 - INSECTICIDE COMPOSITION - Google Patents

Abstract

The invention relates to insecticidal agents for use in horticulture and agriculture for the control of noxious insects. According to the invention, the novel insecticidal compositions contain as active ingredient an effective amount of at least one 3 (2H) -pyridazinone derivative of the formula (I) wherein, for example: X is halogen, alkyl, a haloalkoxy group and the like. al .; n 1 to 4; A is hydrogen, halogen, alkyl, an alkoxy group, and the like. al .; B1 CX1 (where X1 is H or a halogen) or N; R1 and R2 independently of one another are H or an alkyl; E is H, halogen, an alkoxy group or OH, Q represents Y, halogen, alkyl, an alkoxy group, and the like; al .; m 1 to 5. Formula (I)

Description

wherein R 'represents, for example, an alkyl; A 'is a halogen and R ³ and R _{4 are} hydrogen or a lower alkyl. One of the key features of these known compounds is that R 'is an alkyl. On the other hand, British Patent No. 917849 discloses 3 (2H) -pyridazinone derivatives of the formula (V):

(V)

This publication also describes that the known compound A mentioned below is contained in the compounds of the formula (V)

 Connection A:

OCH,

However, the two phenyl rings in compound A are unsubstituted. In addition, there is no description in this publication of the use as an insecticide as intended in the present invention, although the publication states that the compounds A are used for agricultural preparations which affect the growth of plants. -

Furthermore, JP-OS No. 09344/67 describes 3 (2H) -pyridazinone derivatives of the formula (VI):

(Vl) ₁

wherein R7 is, for example, benzyl or 4-chlorobenzyl.

However, one of the main features of these known compounds (VI) is that the compounds have a thioether group. In addition, no compounds are described in which both phenyl rings are substituted. The physiological activities described therein are limited to fungicidal activity and depressed central nervous system activity. Thus, the compounds (VI) obviously differ from the compounds of the present invention.

Object of the invention

The aim of the invention is the provision of new agents with a strong insecticidal action, which can be used to control noxious insects in horticulture and in agriculture.

Explanation of the essence of the invention

The object of the invention is to find novel 3 (2H) -pyridazinone derivatives having the desired properties and processes for their preparation, which are suitable as active ingredient in insecticidal compositions. According to the invention, novel 3 (2H) -pyridazinone derivatives of the general formula (I):

(D

in which X is a halogen, an alkyl having 1 to 6 carbon atoms, a haloalkyl having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, nitro, an alkoxy group having 1 to 4 carbon atoms or

(wherein R is an alkyl of 1 to 4 carbon atoms);

η is an integer from 1 to 4;

A represents a halogen, an alkyl of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms or hydrogen;

B is CX ₁ (wherein X _{1 is} hydrogen or a halogen) or nitrogen;

Each of R ¹ and R ² is independently hydrogen or an alkyl of 1 to 4 carbon atoms; E is hydrogen, a halogen, an alkoxy group having 1 to 4 carbon atoms or hydrexyl; and Q represents the following.

-or

Ym

-0 "

TY ' "-

or

-O-

- 6 - ZÖ9 / HZ

(wherein Y is a halogen, an alkyl of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a haloalkyl of 1 to 4 carbon atoms, a haloalkoxy group of 1 to 4 carbon atoms, cyano

OCH,

or

\  J

(wherein Z is a halogen, an alkyl of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms or a haloalkyl of 1 to 4 carbon atoms and L is 0 or an integer of 1 to 5, wherein this Z is the same or different may be when L is an integer of 2 to 5 and m is an integer of 1 to 5, wherein Y may be the same or different when m is an integer of 2 to 5), wherein X is the same or different can be when η is an integer of 2 to 4. The authors have conducted intensive research on the insecticidal activity of the novel 3 (2H) -pyridazinone derivatives having the formula (I) described above, and found that the compounds of the invention have excellent and effective activity in controlling insect pests In order to realize the present invention. The compounds of the invention differ significantly from conventional insecticides in that they have an extremely strong and specific action against certain types of pest insects, and also have excellent residual activity to very effectively combat insect pests.

The compounds of the present invention greatly impair the physiological process of transformation (metamorphosis) and ecdysis of insect pests caused by insect hormone, resulting in malformations of the insect pests and inhibition of ecdysis, thus completely differentiating the compounds from the conventional ones which act on the nervous system of insect pests, for example, organic chlorine insecticides, organic phosphorus insecticides, carbamate insecticides and pyrethroid insecticides of the known solutions. This inhibition of ecdysis causes some of the insect pests to die, thus the compounds of the invention having the excellent residual activity of the present compounds have excellent and highly effective activity in the control of pest insects.

Such selective control, which is in contrast to the known solutions, is very useful in protecting crops without destroying the ecosystem because of the effects on natural enemies of insect pests including predatory mites (eg Amblyseius longispinosus) and also on beneficial insects are very low. In addition, the compounds of the invention have excellent safety because of their low toxicity to warm-blooded animals and fish. Due to their insecticidal activity, the following compounds of the invention are particularly advantageous. Compounds of the general formula (IA):

(IA)

N.

OCH,

wherein E represents hydrogen, chlorine or a methoxy group; A is hydrogen, chloro, bromo or methyl; B represents nitrogen or CXi (wherein X _{1 is} hydrogen or a halogen); X represents a halogen, an alkyl of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, NO ₂ , CO ₂ R (wherein R is an alkyl of 1 to 4 carbon atoms) or a haloalkoxy group of 1 to 4 carbon atoms; η is an integer from 1 to 4, Q represents:

or

wherein Y represents a halogen, an alkyl having 1 to 4 carbon atoms, a haloalkyl having 1 to 3 carbon atoms, a haloalkoxy group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and m is an integer from 1 to 5, wherein X may be the same or different when η is an integer of 2 to 4, and Y may be the same or different when m is an integer of 2 to 5.

More preferred are the compounds of formula (IB):

wherein E represents hydrogen; A represents hydrogen, chlorine or bromine; X _{2 is} a halogen, hydrogen or nitro group; X ³ and X ^{4 are} each independently hydrogen, a halogen, nitro or an alkyl of 1 to 3 carbon atoms; Q represents the following:

Ym

-he

Ym

he

wherein Y is a halogen or a haloalkyl of 1 to 3 carbon atoms and m is an integer 1 or 2, wherein Y may be the same or different when m is 2.

Particular preference is given to the compounds of the formula (IC):

wherein E represents hydrogen; A is chlorine or bromine; X _{5 represents} hydrogen, halogen or nitro; X _{6 represents} hydrogen, nitro or halogen; Q is:

or

-Cs- χ,

Υ, represents a halogen; Y ₂ is hydrogen or a halogen.

In particular, among the compounds listed in Tables 1-a and 1-b given below, particularly preferred compounds are those listed in Table 6. Among them, the most preferred compounds are given under numbers 340, 341, 393, 507, 582, 583, 607 and 608.

The compounds of the invention can be prepared by the following reaction:

-J

(H)

On.

wherein R ¹ , R ² , A, B, E, X, Q and η are as defined above and X 'and X "represent a halogen or-OM (wherein M is hydrogen or an alkali metal), provided that X" is a Represents halogen when X 'is -OM and X "represents -OM when X' is a halogen

 More specifically, the compounds of the invention can be prepared by the following reaction (1) or (2).

Reaction (1)

R I

-C-

room

(VII)

TV;

Reaction (2)

SA

hai

(VIII)

-u

OM

(IX)

(X)

0- C-

R ²

(D

In the reactions (1) and (2), R ¹ , R ² , A, B, E, X, Q, m, and η are as defined above, and hai is a halogen.

The compounds of the invention can be prepared by reacting one of the starting materials, a 3 (2H) -pyridazinone derivative represented by the above formula (VII) or (IX), with another starting compound represented by the above formula (VIII) or (X) in one suitable solvent in the presence of a hydrogen halide absorbing agent. It should be noted, however, that the hydrogen halide absorbing agent does not

is always needed when M represents an alkali metal.

As solvents, lower alcohols such as methanol and ethanol, ketones ₍ such as acetone and methyl ethyl ketone,

Hydrocarbons ₍ such as benzene and toluene, ethers ₍ such as isopropyl ether, tetrahydrofuran and 1,4-dioxane, amides such as N, N)

Dimethylformamide and hexamethylphosphortriamid and halogenated hydrocarbons such as dichloroethane can be used. If necessary, these solvents can be used as a mixture with water.

As the hydrogen halide absorbing agent, inorganic base such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate, and organic bases such as sodium methoxide, sodium ethoxide, triethylamine and pyridine can be used. If necessary, the reaction system may contain a catalyst such as tetraammonium salts

(eg, triethylbenzylammonium chloride).

The reaction temperature is between -20 ⁰ C and the boiling point of the solvent used for the reaction.

However, desirable is a reaction temperature in the range of -5 ⁰ C and the boiling point of the used

Solvent. "" "

The molar ratio of the starting materials can be selected according to option. However, it is advantageous to carry out the reaction using equimolar or approximately equimolar amounts of the substances.

Initially, the compounds of formula (IX) can be prepared by a process according to the following reaction:

R ^J OH / jvIOH / HO Z

hl

ITOH / MOH / H

wherein X, A, B, E, m, η and hai are as defined above and R ^{3 is} methyl or ethyl.

The compounds embodying the invention are exemplified by the compounds in Tables 1-a and 1-b below. It should be noted, however, that the compounds in Tables 1a and 1b only illustrate, not limit, the invention.

First, a compound of the invention containing an asymmetric carbon atom (asymmetric carbon atoms) includes the optically active (+) compound and the (- (- compound.

embodiment

The invention is explained in more detail below with reference to some examples.

Preparation of compounds (I) of the invention and of compounds of formula (IX) which may be used as one of the starting materials are described in detail by the following examples, which are not to be construed as limiting the invention.

Reference Example 1

Synthesis of 4-chloro-5-hydroxy-2- (4-chlorophenyl) -3 (2H) -pyridazinone

In 140 ml of water was dissolved 18.3 g (0.28 mol) of potassium hydroxide, to which was added 25.6 g (0.093 mol) of 4,5-dichloro-2- (4-chlorophenyl) -3 (2H) -pyridazinone and 140 ml of ethanol , The reaction mixture was refluxed for 6 hours. After cooling, ethanol was distilled out of the mixture under reduced pressure, then 300 ml of water was added to the mixture. Insoluble matter was removed by filtering, and the filtrate was acidified with hydrochloric acid. The solid thus precipitated was collected by filtration, washed with water and recrystallized from ethanol to give 11.1 g of the intended compound having a melting point of 270 ° C-271 ° C.

Synthetic Example 1 Synthesis of 4-chloro-5- (4-chlorobenzyloxy) -2- (4-chlorophenyl) -3 (2H) -pyridazinone (Compound No. 27)

In 70 ml of Ν, Ν-dimethylformamide were dissolved 7.1 g (0.028 mol) of 4-chloro-2- (4-chlorophenyl) -5-hydroxy-3 (2H) -pyridazinone, to which was added 4.5 g of p-chlorobenzyl chloride and Added 5.4g of anhydrous potassium carbonate. The resulting reaction mixture was heated with stirring on an oil bath at 120 ° C to 13O ⁰ C for two hours. After cooling, the reaction mixture was poured into 500 ml of water. The thus precipitated solid was collected by filtration, washed with water, dried, and then recrystallized from an ethyl acetate-benzene mixture to give 6.3 g of the intended compound.

Melting point 184.5 ° C-186.0 ° C.

'H nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.39 (2H, s) 7.30-7.69 (8H, m), 8.00 (1H, s).

Synthesis Example 2

Synthesis of 4-bromo-5- (4-chlorobenzyloxy) -2- (4-chlorophenyl) -3 (2H) -pyridazinone (Compound No. 28) In 35 ml of Ν, Ν-dimethylformamide was added 1.5 g (4.1 mmol ) 2- (4-chlorophenyl) -4,5-dibromo-3 (2H) -pyridazinone and 0.59 g (4.1 mmol) of p-chlorobenzyl alcohol were dissolved, to which 0.27 g of powdery potassium hydroxide was added. The reaction mixture was stirred for one day at room temperature. The resulting solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate and freed from the solvent by distillation under reduced pressure. The crystals thus obtained were recrystallized from ethyl acetate-benzene to give 1.4 g of the intended compound.

Melting point 168.5 ° C-175.1 ⁰ C.

¹ H nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.29 (1H, s), 7.30-7.65 (8H, m), 7.74 (1H, s).

Synthesis Example 3 Synthesis of 4-chloro-5- (4-chloro-a-methylbenzyloxy) -2- (4-chlorophenyl) -3 (2H) -pyridazinone (Compound No. 29)

In 30 ml of Ν, Ν-dimethylformamide were added 1.0 g (3.6 mmol) of 2- (4-chlorophenyl) -4,5-dichloro-3 (2H) -pyridazinone and 0.57 g

(3.6 mmol) of p-chloro-α-methylenebenzyl alcohol was dissolved, to which 0.24 g of powdery potassium hydroxide was added. The reaction mixture was stirred at room temperature for two days.

The resulting solution was poured into water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate and freed from the ethyl acetate by distillation under reduced pressure. The oil thus obtained was purified by column chromatography (on silica gel, eluting with benzene / ethyl acetate = 15/1) and recrystallization (from benzene / n-hexane) to give 300 mg of the intended compound.

Melting point: 135.0 ° C-138.0 ° C. -.

¹ H nuclear magnetic resonance spectrum (δ, TMS) 1.72 (3H, d, J = 6.2Hz), 5.55 (1 H, q, J = 6.2Hz), 7.19-7.62 ( 8H, m), 7.66 (1H,

Synthesis Example 4 Synthesis of 4-chloro-2- (4-chlorophenyl) -5- (4-trifluoromethylbenzyloxy) -3 (2H) -pyridazinone (Compound No.49).

In 30 ml of Ν, Ν-dimethylformamide were dissolved 1.0 g (3.6 mmol) of 2- (4-chlorophenyl) -4,5-dichloro-3 (2H) -pyridazonine and 0.64 g (3.6 mmol) of p-trifluoromethylbenzyl alcohol, To this was added 0.24 g of powdered potassium hydroxide. The reaction mixture was run at room temperature for one day. Then, the steps in Synthetic Example 2 - "" were repeated to obtain 900 mg of the intended compound.

Melting point 186.0 ° C-188.0 ° C.

¹ H nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.37 (2H, s), 7.21-7.81 (8H, m), 7.88 (1H, s).

Synthesis Example 5 Synthesis of 4-chloro-5- (4-chlorobenzyloxy) -2- (4-trifluoromethylphenyl) -3 (2H) -pyridazinone (Compound Ph. 109)

In 50 ml of Ν, Ν-dimethylformamide, 2.0 g (6.5 mmol) of 4,5-dichloro-2- (4-trifluoromethylphenyl) -3 (2H) -pyridazinone and 0.92 g (6.5 mmol) of p-chlorobenzyl alcohol were dissolved, To this was added 0.51 g of powdered potassium hydroxide. Then, the procedures of Synthetic Example 2 were repeated to obtain 1.94 g of the intended compound.

Melting point 171.0 ⁰ C-175.0 ° C.

'H nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.35 (2H, s), 7.37 (4H, s), 7.71 (4H, s), 7.89 (1H, s).

Mass spectrum m / e, 414 (M ⁺ ), 125.

Synthetic Example 6 Synthesis of 4-chloro-5- (4-chlorobenzenyloxy) -2- (2,4-difluorophenyl) -3 (2H) -pyridazinone (Compound No. 154)

In 20 ml of Ν, Ν-dimethylformamide, 1.03 g (7.2 mmol) of p-chlorobenzyl alcohol was dissolved, to which 0.31 g of 55% sodium hydride was added. The reaction mixture was stirred at room temperature for 30 minutes. To the resulting solution was added dropwise a solution of 2.0 g of 4,5-dichloro-2 (2,4-difluorophenyl) -3 (2H) -pyridzincone in 50 ml of Ν, Ν-dimethylformamide. After the reaction mixture was stirred at room temperature for one day, the procedures in Synthesis Example 1 were repeated to obtain 1.5 g of the intended product.

Melting point 166.6 ° C-166.9 ° C.

¹ H magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5,31- (2H, s), 6,28-7,57 (7H, m), 7,8,6 (1H, s).

Synthesis Example 7 *** "

In 30 ml of Ν, Ν-dimethylformamide were added 1.0 g (3.4 mmol) of 2- (4-chloro-2-fluorophenyl) -4,5-dichloro-3 (2H) -pyridazinone and 0.48 g (3.4 mmol) of p Chlorobenzyl alcohol, to which 0.22 g of powdery potassium hydroxide was added. Then, the procedures in Synthesis Example 2 were repeated to obtain 920 mg of the intended compound.

Melting point 167.3 ° C-167.9 ° C.

'H Magnetic Resonance Spectrum (CDCl ₃ , δ, TMS) 5.33 (2H, s), 7.20-7.40 (7H, m), 7.85 (1H, s).

Synthesis Example 8 Synthesis of 2- (5-chloropyridin-2-yl) -4-chloro-5- (4-chlorobenzyloxy) -3 (2H) -pyridazinone (Compound No. 235)

In 30 ml of Ν, Ν-dimethylformamide, 1.5 g (5.1 mmol) of 2- (5-chloropyridin-2-yl) -4,5-dichloropyridazinone and 0.73 g (5.1 mmol) of p-chlorobenzyl alcohol were dissolved thereto 0.34 g of powdered potassium hydroxide was added. Then, the procedures in Synthesis Example 2 were repeated to obtain 500 mg of the intended compound.

Melting point 166.7 ° C-169.0 ° C.

¹ H magnetic nuclear resonance spectrum (CDCl ₃ , δ, TMS) 5.34 (2H, s), 7.35 (4H, s), 7.67-7.84 (2H, m), 7.93 ( 1 H, s), 8.53 (1 H, d,

Synthetic Example 9 Synthesis of the compound prepared in Synthesis Example 7 (Compound No. 170) by another method

In 50 ml of Ν, Ν-dimethylformamide, 2.75 g (0.01 mmol) of 4-chloro-2- (4-chloro-2-fluorophenyl) -5-hydroxy-3r (2H) -pyridazinone was dissolved, and 0, 44g 55% sodium hydride. The mixture was stirred at room temperature for 10 minutes.

The resulting solution was incorporated in 1.6 g of p-chlorobenzyl chloride and then stirred at 100 ⁰ C to 110 ⁰ C for 2 hours.

Then, the procedures in Synthesis Example 1 were repeated to obtain 2.1 g of the intended product.

Synthetic Example 10 Synthesis of 4-bromo-5- (4-chloro-2-fluorobenzyloxy) -2- (3,4-dichlorophenyl) -3- (2H) -pyridazinone (Compound No. 522)

To a mixture of 2.0 g (5, OmMoI) of 4,5-dibromo-2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone and 0.84 g (5.2 mmol) of 4-chloro-2-fluorobenzyl alcohol 80 ml of Ν, Ν-dimethylformamide was added. The resulting mixture was cooled with ice, processed with 0.4 g of potassium hydroxide and then stirred for one day. Then, the procedures in Synthesis Example 2 were repeated to obtain a crude product. The crude product was recrystallized from benzene to give 1.3 g of the intended compound.

Melting point 172.0 ° C-173.0 ° C.

Magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.57 (2H, s), 7.25-7.95 (6H, m), 8.43 (1H, s). '

Synthetic Example 11 Synthesis of 4-chloro-2- (4-chlorophenyl) -5 - [(6-chloro-3-pyridyl) -methoxy] -3 (2H) -pyridazinone (Compound No. 340)

The procedures in Synthesis Example 2 were repeated to provide 2.00 g (7.2 mmol) of 2- (4-chlorophenyl) -4,5-dichloro-3 (2H) -pyridazinone, 1.1 g (7.7 mmol) of 6 Chloro-3-pyridinemethanol, 0.4 g of potassium hydroxide and 80 ml of Ν, Ν-dimethylformamide used, and there were obtained 1.7 g of the intended product (recrystallized from benzene / n-hexane).

Melting point 190.0 ° C-192.0 ° C.

Magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.51 (2H, s) 7.22-7.71 (5H, m), 7.90 (1H, dd, J = 2 Hz 8 Hz) , 8.34 (1H, s) 8.50 (1H, d, J = 2Hz).

Synthetic Example 12 Synthesis of 4-chloro-2- (4-chlorophenyl) -5 - [(5-methyl-2-thienyl) methoxy] -3 (2H) -pyridazinone (Compound No. 323)

The procedures in Synthesis Example 11 were repeated using 2.0 g (7.3 mmol) of 2- (4-chlorophenyl) -4,5-dichloro-3 (2H) -pyridazinone, 1.0 g (7.8 mmol) of 5-methyl 2-thiophene methanol, 0.4 g of potassium hydroxide and 80 ml of N, N-dimethylformamide, to give 2.0 g of the intended product.

Melting point 147.0 ° C-148.0 ° C.

¹ H nuclear magnetic resonance spectrum (CDCl ₃ , 5, TMS) 2.37 (3H, s), 5.58 (2H, s), 6.71 (1H, d, J = 3Hz), 7.07 (1 H, d, J = 3Hz),

Synthetic Example 13 Synthesis of 4-chloro-2- (4-chlorophenyl) -5- (2,4-dichlorobenzyloxy) -3 (2H) -pyridazinone (Compound No. 39)

In 50 ml of Ν, Ν-dimethylformamide was dissolved 1.5 g (5.9 mmol) of 4-chlorophenyl) -5-hydroxy-3 (2H) -pyridazinone and 1.3 g (6.6 mmol) of 2,4-dichlorobenzyl chloride, to which was added 0 , 7g triethylamine. The reaction mixture was heated with stirring on an oil bath at 100 ⁰ C to 120 ⁰ C for 7 hours. After cooling, the reaction mixture was poured into 200 ml of water, and the precipitated solid was removed by filtration, washed with water, dried, and then recrystallized from benzene. This gave 1.7 g of the intended compound.

Melting point 168.0 ° C-169, O ⁰ C.

Magnetic nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 5.53 (2H, s), 7.28-7.78 (7H, m), 8.45 (1H, s).

Synthetic Example 14

Synthesis of 2- (4-chlorophenyl) -5- (2,4-dichlorobenzyloxy) -4-methoxy-3 (2H) -pyridazinone (Compound IMr 311) In 60 mL toluene was added 1.0 g (2.4 mmol) 4 Chloro-2- (4-chlorophenyl) -5- (2,4-dichlorobenzyloxy) -3 (2H) pyridazinone, which in Synthesbeiispie! 13, and 0.13 g (2.4 mmol) of sodium methoxide was added. The resulting reaction liquid was treated with stirring and reflux for 12 hours. After cooling, the reaction liquid was washed with water, dried over anhydrous sodium sulfate, and freed from toluene by distillation to obtain a crude product. The crude product was purified by column chromatography (eluting with benzene / ethyl acetate = 18/1) to give 450 mg of the intended compound.

Melting point 148.0 ° C-150.0 ⁰ C.

¹ H nuclear magnetic resonance spectrum (CDCl ₃ , δ, TMS) 4.01 (3H, s), 5.33 (2H, s), 7.08-7.63 (7H, m), 7.60 (1 H, s).

Synthesis Example 15 -

Synthesis of 5- (4-chlorobenzyloxy) -2- (4-chlorophenyl) -3 (2H) -pyridazinone (Compound No. 305) In 50 ml of Ν, Ν-dimethylformamide was added 2.0 g (9, OmMoI) 2- (4-chlorophenyl) -5-hydroxy-3 (2H) -pyridazinone and 1.5 g (9.3 mmol) of p-chlorobenzyl chloride were dissolved, to which was added 1.7 g of anhydrous potassium carbonate. The reaction mixture was heated with stirring on an oil bath at 100 ° C-120 ° C for one hour. Then, the procedures in Synthetic Example 13 were repeated to obtain 2.5 g of the intended compound.

Melting point 203.0 ° C-204.0 ⁰ C.

Nuclear Magnetic Resonance Spectrum (CDCl ₃ , δ, TMS) 5.05 (2H, s), 6.36 (1H, d, J = 3Hz), 7.40-7.80 (8H, m), 7, 90 (1 H, d,

After each of the procedures in Synthetic Examples 1 to 15, some compounds were prepared. The melting point of each of these compounds is given in Tables 1-a and 1-b.

When the compounds of the invention are used for insecticidal purposes, they are generally mixed with a suitable carrier, for example solid carriers such as clay, talc, bentonite or diatomaceous earth, or liquid carriers such as water, alcohols (e.g., methanol and ethanol), aliphatic hydrocarbons, aromatic hydrocarbons (eg benzene, toluene and xylene), chlorinated hydrocarbons, ethers, ketones, esters (eg.

Ethyl acetate), acid amides (eg dimethylformamide) or nitriles. If desired, emulsifiers, dispersants, suspending agents, penetrating agents, dispersing agents, dispersing agents, stabilizers, synergists and the like may be added to these mixtures for use in the form of an oil solution, an emulsifiable concentrate, a wettable powder, a bar, a granule , to bring a tablet, a paste, a flowable medium or the like.

In addition, the blends may be contacted with other insecticides, various fungicides, herbicides, plant growth regulants, fertilizers and / or synergists during manufacture or their application, as required.

The amount of the compounds of the invention used as an active ingredient is advantageously in the range of 0.005 to 50 kg / ha, but varies depending on the place and season in which the application of the compounds takes place, the manner of application, the diseases and insect pests to be controlled, the crops to be protected, etc.

The amount of the compounds of the invention present in an insecticidal agent is advantageously, but not limited to, between 0.01 and 99.5% by weight.

The following are some examples of preparations of insecticidal compositions, said compositions containing the compounds of the present invention as an active ingredient. These examples are for illustration only and do not limit the invention. In the examples below, under "Share"

"Parts by weight" to understand.

Preparation Example 1 Emulsifiable Concentrates

Active ingredient 10 parts

Xylene 60 parts

Ν, Ν-dimethylformamide 20 parts

Solpol 2680 (trade name, a mixture of a nonionic, surface-active:

Agent and an anionic surfactant manufactured by Toho Chemicals Co., Ltd., Japan) is 10 parts

The said components are intimately mixed to form an emulsifiable concentrate. In use, the emulsifiable concentrate is diluted with water to a concentration of one-fiftieth to one-twenty-thousandth and applied at a rate of from 0.005 to 50 kg / ha of the active ingredient.

Preparation Example 2: Wettable Powder

Active ingredient> 10 parts

Siegreit PFP (trade name, a mixture of kaolinite and sericite, produced

from the Siegreit Mining Industries Co., Ltd.) '81 parts

Solpol 5039 (trade name, anionic surface active agent prepared

Toho Chemicals, Co., Ltd., Japan) 4 parts

Carplex No. 80 (trade name, white carbon, manufactured by

Shionogi Seiyaku K.K., Japan) 3 parts

Calcium lignosulfonate. 2 parts

The said components are homogeneously mixed together and ground to produce a wettable powder. In use, the wettable powder is diluted with water to a concentration of one fiftieth to one twenty thousandth and applied at a rate of from 0.005 to 50 kg of the active ingredient per hectare.

Preparation example 3: oil solutions

Active ingredient 5 parts

Methylzellosolve. 95 parts

The above components are homogeneously mixed together to form an oil solution. In use, the oil solution is applied at a rate of 0.005 to 50 kg of the active ingredient per hectare.

Preparation Example 4: Dust

Active ingredient '3 parts

Carplex No.80 (brand name). 0.5 part

Volume . 95 parts

Diisopropyl phosphate 1.5 parts

The above components are homogeneously mixed together and ground into a dust. In use, the dust is applied at a rate of 0.005 to 50 kg of the active ingredient per hectare.

Preparation Example 5: Granules

Active ingredient 5 parts

Bentonite. 54 parts

Talcum 40 parts

Calcium lignosulfonate. Part 1

The above components are intimately mixed and ground, processed with a small amount of water, and mixed with each other while stirring. The resulting mixture is granulated with an extrusion granulation apparatus and dried to form a granule. In use, the granules are applied at a rate of 0.005 to 50 kg of the active ingredient per hectare.

Preparation example 6: Flowable substances

Active ingredient 25 parts

Solpol 3353 (trade name, a nonionic, surfactant,

manufactured by Toho Chemicals Co., Ltd., Japan) 10 parts

Runox 1 00OC (trade name, an anionic surfactant,

manufactured by Toho Chemicals Co., Ltd., Japan) 0.5 parts

1% aqueous solution of xanthan gum (high natural molecular weight) 20 parts

Water 44.5 parts

The above-mentioned components except for the active ingredient are uniformly mixed together to form a solution, to which the active ingredient is added. The resulting mixture is thoroughly stirred, then wet-milled with a sand mill to form a flowable material. In use, the flowable material is diluted with water to a concentration of one fiftieth to one thousandth of a thousand and applied at a rate of from 0.005 to 50 kg of the active ingredient per hectare.

The compounds of the invention have a specific insecticidal activity on half-wing insects such as leaf and grasshopper; Beetle insects such as the red flour beetle (Tribolium castaneum), the yellow mealworm (Tenebrio molitor) and the 28-point sun bug (Henosepilachna vigintioctopunctata); sanitary harmful insects such as flies and mosquitoes and butterfly insects and they also have an excellent residual effect. Thus, the compounds of the invention are an excellent insecticide which enables highly effective control of noxious insects. Hereinafter, the effects of the present compounds as an insecticide will be explained in detail by way of experimental examples.

Experimental Example 1 Insectic test on green rice leafhopper (Nephotettix cincticeps)

A 10% emulsifiable concentrate (or a 10% wettable powder) of a compound of the invention was diluted with water containing a spreading agent to give a solution of the compound of 500 particles / mill. to surrender. On the stems and leaves of a rice plant in a 1/20000 tub, a sufficient amount of the resulting solution was applied, followed by drying in air. Subsequently, green rice hoppers (Nephotettix cincticeps) were placed in the tub, which are resistant to organic phosphorus insecticides and carbamate insecticides.

The rice plant thus treated was covered with a cylindrical wire gauze and held in a thermal chamber. After 30 days, the number of green rice leafhopper parasitic on the rice plant was counted and their mortality was determined according to the following equation:

Number of released insects minus number of parasitic insects on the rice plant (number of non-killed insects)

Mortality (%) = ^ * t £ H> _{χ 10Q}

Number of released insects

The experiment was performed twice for each compound

 The results are shown in Table 2.

Experimental Example 2:

Insecticidal experiment on brown rice plant hops (Nilaparvata lugens)

The procedures of Experimental Example 1 were repeated with the brown rice planthopper (Nilaparvata lugens) instead of the green rice leafhopper, which are resistant to organic phosphorus insecticides and carbamate insecticides. The results are shown in Table 3.

Experimental Example 3 Insecticidal experiment on red meal beetle (Tribolium casteneum)

To a clear brat tube was added 50 mg of a 10% emulsifiable concentrate of a compound of the invention (or a 10% wettable powder or a 10% oil solution) and acetone was added until an acetone solution of the compound of 500 particles / Mill. was made. Ten (10) cm ^{3 of} the acetone solution was added 10 g of wheat flour, which was in a laboratory vessel with a diameter of 9 cm. After stirring, the acetone was distilled out of the mixture. Then 10 mature adult male and female red meal beetles (Tribolium casteneum) were added to the jar. The adult beetle vessel was stored in a thermostatic chamber. After ninety days, the assessment was made by counting the number of adult beetles that were present.

The experiment was performed twice for each compound. As a result, it was found that no hatched animals were observed in the treated laboratory vessels at all in the following compounds: Compounds Nos. 27,28,175,235 and 283.

Experimental Example 4 Fish toxicity experiment on swordfish

A methanol solution containing a compound of the invention to be tested was added to 21 of water in a glass container having a diameter of 20 cm and a height of 10 cm, so that a solution of 0.5 part per mill. the connection arose. The vessel was kept at 25 ⁰ C in a thermostatic chamber, then 10 swordfish were placed therein. The fish was observed for some time. The mortality after 48 hours is given in Table 4.

Experimental Example 5 Examination of acute oral toxicity in mammals

Male ICR mice (Swiss Hauschka, CD-1, Ha / ICR) were purchased at 4 weeks of age from Clea Japan, Inc. and used as experimental animals after a one-week acclimatization period. The animals were kept in groups of 5 in stainless cages with a wire mesh floor. The pens of the animals were in a barrier system with a regulated temperature of 22 ° C ± 1 ° C, a humidity of ± 5% and light over 12 hours 3m days. Animals were fed (CE-2, Clea Japan, Inc.) and tap water ad libitum.

Groups of 5 animals were given a single oral dose of 300 mg / kg of the compound of the present invention by oral administration. The compounds were diluted with corn oil and the administration volumes were 10 ml / kg body weight each. Mortality was calculated seven days after oral administration. The result is shown in Table 5.

In the following table, Me is methyl, Et is ethyl, Pro is propyl, Bu is butyl, pen is pentyl, hex is hexyl, t represents a tertiary, i is an iso and s is a secondary compound.

Table 1-a

Y _m

Compound Na

R ¹ R ^:

Xn

m. ρ.

H H 2-C

4-Me CH Z £

173.0-174.2

Me H2-Cj2

2-Me CH Z £

H 2-C jg "4-s-Bu CH Z £

HH 2-C 4-CA CH Z £

187.1-187.9

H H 2-C

4-Br CH Z £

H. IT 2-Z £. 3-CF ₃ CH Z £

187.6-189.0

Compound Na .R ¹ R ² Xn Y _m B A m. p. ro • 7 H H 4-OMe CH br 8th H H 2-ZSL 3-0-i-Pro CH br 9 H H Z-ZS 4-Me CH ZS, 10 H H 3-C S 4-Pen CH ZH 11 H H' Z & Z 3-CAE CH ZSL 12 H H Z-ZSL i-Z CH ZS, 166.0-167.0 13 me H 3-.Ca 4-Br  CH ZS 14th H H 3-C ^ 4-t-Bu CH ZH 192.0-194.0 15 H ' H 3-C £ 4-OEt CH br 16 H H Z-ZS 4-OPRO CH Zi 17 H H 3-C SL 2,5- (Me) ₂ CH ZS, 18 H H Z-ZS 2A-ZH ζ CH ZS 19 H- H 3-C £ ZA ZS. ζ CH br

Compound No. R ¹ R ² Xn Ym B CH A CS πι. p. Vc) 20 H H A-Ci '4-C ₆ H ₅ CH ci 213.3-220.0 21 me H A-Ci 4- (4-CjZC ₆ H ₄₎ CH ci 22 H H A-Ci 4-Me CH C £ 214.0- 216.0 23 H H A-Ci 4-i-Bu " CH C £ 24 H H 4-C j2 , 3-Me CH C £ 25 H H A-C & 2-Me CH ci 26 me H 4-C i 2-Me. CH ci 27 H H A-Ci 4-C £ CH br 184.5-186.0 28 H H 4-C i A-Ci CH ci 168.5- 175.1 29 me H A-Ci , A-C £ CH ci 135.0- 138.0 30 H H A-Ci S-C CH br 31 H H A-Ci B-CP. CH ci 32 H H A-Ci 2-C

Compound - Να R ¹ R ² Xn Ym i 5 CH A m.p. cc) 33 H H 4-C £ 4-Br CH ^s C £ 184.6- 185.7 34 H H A-C £ 4-Br CH br 187.1 - 187.9 35 H H A-C £ 4-1 CH C £ , 195.0- 196.5 36 H H 4-C jg 2,5- (Me) ₂ CH C £ 204.0-206.0 37 H H 4-C, 4-t-Bu CH C £ 238.9- 240.2 38 H H. A-C £ 3,4-C ^ ζ CH ci 194.0- 196.0 39 H H 4-C £ 2> A-C £ ζ CH C £ 168.0- 169.0 40 H H 4-C jg 4-F , CH C., 41 H H 4-C £ 2,6- (Me) ₂ , 4-t Bu CH C jg , 42. H H 4-C £ 2,3,4,5,6-F ₅ CH C j2 43 H- H A-C £ 3-OBu CH C £ 44 H H A-C £ 4-0-s-Bu CH C £ 45 H H 4-C jg 4- (C ₆ H ₅ CH ₂ O) C £ 188.0-190.0

Table 1-a (cont'd)

Compound No. , R ¹ R ² Xn Ym B A m. p. cc) 46 H H 'A-C £ 4- (2-MeC ₆ H ₄ CH ₂ O) CH Zi 47 H H 4-CA 4- (3,4-CAZC ₆ H ₃ CH ₂ O) CH br , 48 H H 4-C i 4- (4-FC ₆ H ₄ CH ₂ O) CH Zi 49 H H 4-C jg 4-CF ₃ CH Zi 186.0-188.0 50, H H 4-C Jg 3-CF ₃ CH br 51 H H 4-C jg 4-0CHF ₂ CH C £ - 177.4-178.4 52 H H 4-C i 4-0CF ₃ CH Zi 53 et H 4-C £ 4-C jg CH Zi 54 H H   i-Zi 4-0CH ₂ CF ₃ CH Zi 55 H H i-Zi 4-CN CH br 218.2- 219.4 56 H H 2-Me 4-F CH Zi 182.0- 184.0 57 H H' 2-Me 4-C £ CH Zi 166.0-168.0 58 H H. 2-Me 3-C jg CH br

Compound _{rI rZ ß ft} -.p . , CC)

166.0 -

59 H H 2-Me 4-Br CH C ^

167.0

60 Me H 2-Me 4-1 CH Zi

61 H H-2-Me 4-Me'CH C H '~

146.0

62 H H 2-Me 4-i-Pro CH Zi 139.0-140.0 63 H H 2-Me 4-O-i-Pro CH br 64 H H 2-Me 4 C2.4-C Jg 2C ₆ H ₃ ) CH Zi 65 H- H 2-Me 3 - (2A-Z £ 2C ₆ H ₃ CH ₂ O) CH br 66 H H 2-Me 4-CF ₂ CH Zi 67 H H 2-Me- 4-0CHF ₂ CH Zi 68 H H 3-Me 3-Me CH Zi 154.4 - 155.8 -. ⁶⁹ H H 3-Me A-Zi CH ZH 176.0-177.0 70 me H 3-Me 4-Br CH Zi 71 H H 3-Me 4-Me CH Zi 126.0- 127.0

Table 1-a (cont ¹ d)

Compound No. R ¹ R ² Xn Y _m B A mp ( ⁰ C) 72 me H 3-Me 2-Zi CH - Zi 73 me H 3-Me 2,4-CjZ 2 CH br 74 tt H 3-Me 3,4-C £ 2 'CH zt 75 H H. 3-Me * 4-CH ₃ CH Zi 76 H H 3-Me 4-i-Pro CH   Zi 137.0-138.0 77 H H" 3-Me 3-CF ₃ • CH br 78 H H 3-Me 4-OBu CH Zi 79 H H 4-Me 4-t-Bu CH Zi 190.9-191.9 80 Per H 4-Me 4-Me CH Zi 81 H H 4-Me 3..4-C / 2 ζ CH Zi 218.0-220.0 82 H H 4-Me 4-Br CH Zi 225.0-226.0 ^: 83 H H 4-Me 4-C £ CH. Zi 84 H H 4-Me 3-C <2 CH Zi 196.0-197.0

Compound No. R ¹ R ² X _n Y _m B A m. ρ. rc) 85 me • Η 4-Me 4- (4-C 1 -C ₆ H ₄ ) CH Zi 86 H H 4-Me 4-OMe CH br 87 H H 4-Me 4-0CF ₃ CH C Jg 88 H H 4-Me 2, 4-C, δ ε CH ZH 164.0- 165.0 89 H H 4-Me 2,4- (Me) ₂ CH  zn 156.0- 157.0 90 H H 4-Me 2,5- (Me) ₂ CH zn 173.0-175.0 91 H H 4-Me 3-OMe, 4-0Pro CH C & B2 H 4-Br 4-Me CH ZZ 93 ' H H 4-Br 2-Me CH ZS. 94 H H 4-Br 4-t-Bu CH br 95 me H " 4-Br 4-Hex CH ze. 96 et H 4-Br 4-t-Bu CH zn 97 H H 4-Br 4-C £ CH zn 190.0-191.0

- ££ - C-J ^ l

Table 1-a (cont'd)

Compound No. R ¹ R ² Xn 4-Br B A m. p. ( "C) - 98 H H 4-Br 4- (4-MeC ₆ H ₄₎ CH Zi 99th me H 4-Br 3-OBu CH br 100 H H 4-Br 4-0CHF ₂ CH Zi 101 H H 4-Br 4-CF ₃ . CH, C i 102 H H 4-Br • 4-Me CH Zi 103 me H 3-CF ₃ 4-t-Bu CH Zi 104 Et. H 3-CF ₃ k Zi CH ' br 105 me H 3-CF ₃ 4-Br CH Zi 106 me H 3-CF ₃ 2,4-CjS 2 CH Zi 107 me H 3-CF ₃ 4-F CH Zi 171.0-175.0 .108 H H 4-CF ₃ A-Zi CH Zi 109 H H 4-CF ₃ A-Zi CH Zi 110 H H 4-CF ₃ CH br

Table 1-a (cont'd)

Compound No. R ¹ R ^z Xn Ym B A ^m - ^P - ro Ill H H 4-CF ₃ 4-Br CH Z £, 112 H H 4-CF ₃ 4 _: Br CH br 113 Per H 4-CF ₃ 4-Me CH ZH 114 me H 4-CF ₃ 4- (4-CjZC ₆ H ₄₎ CH ZZ , 115 - H H 4-CF ₃ 4-0-i-Pro CH br 116 H H '4-CF ₃ 4- (4-MeC ₆ H ₄ CH ₂ O) CH Z £ 117 H H 4-CF ₃ 4-0CHF ₂ . CH Zi 118 H H 4-CF ₃ 4'-0CHF ₂ CH Br ' 119 H H 4-CF ₃ 4-0CH ₂ CF ₃ CH C ^ 120 H H 4-CF ₃ 4-CF ₃ CH C Jg 121 H H 4-CF ₃ 4-CF ₃ CH br 122 H H 4-CF ₃ 2,4-C ^ ₂ CH Zi 123 H H 4-CF ₃ 3,4-C ^ ₂ CH zn

Table 1-a (cont'd)

Compound No. - R ¹ R ² X _n Y n, B A mp ( ⁰ O 124 ·. H H 4-CF ₃ 2,4- (Me) ₂ CH C £ 125 H H 4-CF ₃ 2,6- (Me) ₂ , 4-t Br CH C £ 126 H H 4-CF ₃ 2,3,4,5,6-F ₅ CH C ^ 127 H H 4-CF ₃ 2,3,4,5,6-F ₅ CH br 128th, H H 4-CF ₃ . 4-CN CH C 129 H H 2-Et 4-Me CH Z £ 130 H H 2-Et 4-C H CH C 131 H H 3-Et 4-CF ₃ CH 132 H H 4-Et 4-0CHF ₂ CH C i 133 · H H 4-Et 4-CJZ CH Cl 134 ' H H 4-i-Pro '2-C Jg CH br 135 me H-. 4-bu · 4-C £ CH C jess 136 H H 4-0CHF ₂ 4-C j2 CH C S.

Table 1-a (cont'd)

Compound No. R ¹ R ² Xn Ym B A IU. P. (° c) 137 · H H 4-0CHF ₂ A-Z £ CH br 138 H H 4-0CHFz 3-CF ₃ Cll ZS 139 H II 4-OCHF ₂ 4-CF ₃ CH zn 140 H H 4-0CIfF ₂ 4-0CHF ₂ CH ce 141 H H 4-0CHF ₂ 4-0CH ₃ CH 142 H H 4-0CHF ₂ 4-Br CH br , 143 H H 4-0CHF ₂ 4-Br CH ze, 144 me H 4-0CHF ₂ 4- (4-C 1 -C ₆ H ₄ ) CH ZS, 145 H H 4-Me 4-0CHF ₂ CH ZS 146 H H 4-Me 4- (4-C 1 -C ₆ H ₄ ) CH Ci. 147 H H 2-E = 4-Me i-Z £ CH Z £ 148 H H 2-F, 4-Me 3-0-Bu CH br '149 H H- 2-F, 4-Me 4-0CHF ₂ CH. zn

Table 1-a (cont'd)

Compound. No. R ¹ R ² Xn Ym B- α ^m _{( c} ^p ; 150 H H 2,4-Br ₂ 2-CH ₃ CH. br 151 H H 2,4-Br ₂ 4-Cjü CH ZS 152 H H 2,4-Br ₂ 4-CF ₃ CH ZS 153 H H -2,4-Br ₂ . 4-C jg CH C S 154 -: H H 2,4-F ₂ A-C £ CH Zi ¹⁶⁶ ' ⁶ ~ 166.9 155 H H 2,4-F ₂ A-C £ CE br 156 H H 2,4-F ₂ 4-Br CH ZS 157 H H 2,4-F ₂ 4- (4-CAC ₆ H ₄₎ CH C £ 158 H H 2,4-F ₂ 4-0CHF ₂ CH Z £ 159 · H H 2,4-F ₂ 4-0CHF ₂ CH br "160 H  Η 2,4-F ₂ 4-CF ₃ CH Z £ 161 H H 2.-4-F ₂ 4-CF ₃ CH br 162 H H 2,6-F ₂ 4-C, CH ZS

Table 1-a (cont'd)

Compound No. R ¹ R ² Xn Y " B A m.p. CO 163 H Η ' 2,6-F ₂ 3,4,5- (HeO) ₃ CH Z £ 164 H H 4-Br, 2-Cjg 4-CF ₃ CH zn 165 H H 4-Br, 3-CF ₃ CH br 166 H H 4-Br, 2-F K-Z £ CH c / 180.0-. 181.0 167 H H 4-Br, 2-F A-Z η CH br 180.0-181.0 168 H H 4-Br, 2-F 4-0CHF ₂ CH ZZ 169 H H 4-Br, 2-F 4- (4-CJgC ₆ H ₄₎ CH zn 170 H H '2-F ' K-Zi CH · zn 167.3-167.9 171 H H , 2-F 4- " CH br 166.0-168.0 172 H H 2-F 4-Br CH zn 160.0- 162.0 173 H H 4-Cje ", 2-F 4-Br CH br 174 H H 2-F 4-F CH zn 172.4-173.0 175th H H- KZ &, 2 - F 4-Me CH zn. 172.0-173.0

Table 1-a (cont'd)

Compound No. R ¹ H R ² Xn y. B ni.p. ^A co 176 H H 2-F 4-CF ₃ CH Zi 177 H H 4-Cj2, 2-F 4-CF ₃ CH br 178 H H 4-C SL, 2-F 4-OCHF ₂ CH 164.0 ^ ^{C £} 165.2 179 H- H 4-cig. 2-F 4-0CHF ₂ CH br 180 H H 2-F 4- (4-CAC ₆ H ₄₎ CH C * 181 H Ή 4-C , 2-F 4- (4-C 1 -C ₆ H ₄ CH ₂ O) CH Zi 182 H H 4-Ci ₁ 2-F 4-CN CH Zi 183 H H 2-F i-Zi CH Zi 184 H H 3-Cjg, 2-F 4-CF ₃ CH Zi 185 H H 4-CF ₃ A-Zi CH Zi 186 H H 2-C &, 4-CF ₃ '4-C £ CH br , 187 H H 2-Zi, 4-CF ₃ 4-0CHF ₂ CH Zi 188 H 2-C , 4-CF ₃ 4-0CHF ₂ CH br

Table la (cont ^! D)

Compound No. R ¹ R ² Xn C ^ ₂ A-Z £ B A m.p. cc) 189 H H- 2,4- Z £ t / 4-Br CH Z £ 184.0 ~ 185.0 190 H- H 2,4- Cl ₁ 2-Me CH U 193.0- 195.0 191 H H 2,4- 4-C '£ ₃ 4-OCH ₂ CF ₃ CH Z £ 192 H H 2.3 5-C £ ₃ .4-CN CH 193 H H 2.4 6-C ^ ₃ 4-t-Bu CH 194. H H 2.4 6-Br ₃ 3,4-C j2 ₂ CH br 195 me H 2.4 6-Br ₃ 2-Me CH CI 196 me H 2.4 6-F ₃ A-Z £ CH Z £ 197 H H 2.4 6-F ₃ 4-Br CH Z £ - 198 H H 2.4 6-F ₃ 4-CF ₃ CH Z £ 199 H Η ' 2.4 6-F ₃ 4-CF ₃ CH Z £ 200 H H 2.4 6-F ₂ A-Z £ CH br 201 H H 2, CH Z £

Table 1-a (cont'd)

Compound Να » R ² X _n Y. B A- m.p. cc) 202 H r 4-CE, 2.6-F ₂ 4-0CF ₃ CH Cl 203 H H 4-Br, _r ^ 2,3-CS ₂ ^ό ' , 4-C ^ ₂ CH ₃ CH ₂ O) CH CS 204 me H 4-Br, 4-F CH CS 205 ' H H 2,3,4,5-F ₄ i-CS CH CS 206 H H 2, a, 4,5-F ₄ 4-0CHF ₂ CH CS 207 H H 2,3,4,6-F ₄ A-CS CH cn 208 me H 2,3,4,6-F ₄ 2A-C & ζ CH CS. 209 H H 2,3,5,6-F ₄ 4-CN CH CS 210 H H 2,3,5,6-F ₄ 4-Cjg CH CS 211 H H 2,3,4,5-Cj2 ₄ 4-C ₆ H ₅ CH, br 212th H H 4-0CH ₂ CF ₃ CH Γ O 213 H H 2,4-Br ₂₁ 5, -6-CA ₂ 4-CF ₃ - CH br 214 H H 2,3,4,5,6-F ₅ 4-C * CH CS

Compound No. R ¹ R ² X _n , 6-F ₅ Y _m B m.p. A CO 215 H H 2,3,4,5 , 6-F ₅ 4-C £ CH br '216 H H 2,3,4,5 , 6-F ₅   4-Br CH ZS. 217 me H , 2,3,4,5 , 6-F ₅ 4-t-Bu CH 218 me H 2,3,4,5 , 6-F ₅ 4-CH ₃ CH Zi 219 H H 2,3,4,5 , 6-F ₅ 4-0CHF ₂ CH Zi 220 H H 2,3,4,5 6-F ₅ 4-CF ₃ CII a 221 me H 2,3,4,5, , 6-F ₅ 4- (2,4-C ^ ₂ C ₆ H ₃ ) CH zn 222 H H 2,3,4,5 , 6-F ₅ 2,5- (Me) 2 CH Zi 223 H H . ' 2,3,4,5 2,3,4,5,6-F ₅ CH zn 224th H H 2-F 4-C £ CH ze, 225 H H 2-F 4-C j6 CH br , 226 H H 2-F 4-Br CH Zi 227 H , H 2-F 4-Me CH C jg

Table 1-a (cont'd)

Compound No. R ¹ R ² Xn Ym B mp ^S CO 228 H H , 2-F 4-Hex CH br 229 me H 2-F 4- (4-C 1 -C ₆ H ₄ ) CH C £ 230 H H 2-F 4-CF ₃ CH cn 231 H H   2-F 4-CF ₃ CH Br '* 232   H H 2-F 4-OCHFζ CH ZH 233 H H 2-F 4-0CHF ₂ CH br 234 H H 2-F 4-CN CH C jess 235 H H 4-C 4-C £ N c, ¹⁶⁶ · ⁷ ~ 169.0 236 H H 4-Cj2 4-C £ N br 237 H H 4-C £ 4-Br N C j2 238 H H 4-C £ "4-0CHF ₂ 'N 239 H H 4-CAE , 4-CF ₃ N C £ 240 H. H 4-Br 4-C £ N CSS

, Compound No. R ¹ R ² ' Xn Ym B m.p. br 24f H H 4-Br A-Ci N Zi 242 H H 4-Br 4-Br N ZH 243 H H 4-Br 4-0CHF ₂ N Z-LL 244 H H 4-CF ₃ 4-Cj2 N Zi 245 H H 4-CF ₃ 4-Me N zn 246 H H 4-CF 3 4-CF ₃ . N ZH 247 H H 4-CF ₃ 4-DCHF ₂ N Zi 248 me H- 2-Zi, • 4-CF3 4- (4-CAC ₆ H ₄₎ N Zi 249 H H 2-C &, 4-CF ₃ 4-0-Pro N Zi 250 H H 2-CjS, 4-CF ₃ 4-CAE. N Zi 251 H H i-Ci, 2-CF ₃ A-Zi N br 252 H H 4-CÄ, 2-CF3 A-Zi N Zi 253 H H i-Zi, 2-CF3 4-F N

Table 1-a (cont'd)

Compound No. R ¹ R ² Xn ν. , B a ¹ ^ 254 H H 4-CjS, 2-CF ₃ -3-CF ₃ , N C., 255 H H 4-CÄ, 2-CF ₃ 4-0CHF ₂ N Zi

Table 1-b

Compound No. Xn 2,4-C Q e H B CH A br m.p. ( ⁰ o 256 4-C A ' 4-I-C ^ ₂ -C ₆ H ₃ H CH br 148.7 - Ί52.1 257 i-ZSL 4-Me 0H4 , H CH br '258 4-C 'ig C ₆ H ₄

Compound Να Xn Ö e H B CH A br ItI.p. 259 4-C 4- (4-FC ₆ H ₄ ) C ₆ H ₄ H CH ci 203.0- 260 4-C 2-Me, 4-Ci-C ₆ H ₃ H CII Γ 0 261 4-CJZ 2,4,6-Ci ₃ -C ₆ H ₂ H CH br 262 4-M 2,4,6-Ci ₃ -C ₆ H ₂ H CH ci 263 J ₄ -C « 4- (4-CiC ₆ H ₄ CH ₂ O) C ₆ H ₄ H CH ci .CC) 264 4- " 2,4,5-Ci ₃ -C ₆ H ₂ H CH br '207.0 265 4 W 2,4-F ₂ -C ₆ H ₃ H CH ci 266 4-C • 2,4-F ₂ -C ₆ H ₃ H CH Br. 267 4-C 2,4,5-Ci ₂ -C ₆ H ₂ H CH ci 268 4- " 2,6-Ci ₂ -C ₆ H ₃ H CH br 190.0-191.5 269 4-c ". 2-Me, 4-Br-C ₆ H ₃ H CH br 270 4-CJZ 3,5-Ci ₂ -C ₆ H ₃ H CH br 271 4-C 2,3,4,5,6-F ₅ C ₆ 176.7-179.0 180.6- -185.8 201.0-203.0

Table 1-b (cont'd)

Compound Na Xn Q e B A m.p. CC) 272 4-Cj2 2-CÄ, 4-FC ₆ H ₃ H CH C £ 193.7-194.6 273 i-Zl 2-F, 4-C-jg -C ₆ H ₃ H CH CSS 176.2-178.1 274 i-Zi 2-F ₃ .4-C 1 -C ₆ H ₃ H CH br 145.9-158.9 275 K-Zi 4-PrO-C ₆ H ₄ H ' CH br 276 K-Zi 2,5-CjS ₂ -C ₆ H ₃ H CH Zi 176.0-180.0 277 4-C £ 2.F, 4-Br-C ₆ H ₃ H CH Zi . 176.6-178.3 278 ' i-Zi 2-F, 4-Br-C ₆ H ₃ H CH br 179.3-180.2 - 279 K-Zi ql H CH br 280 • 4-ProO-C ₆ H ₄ H CH br 170.0-171.0 281 K-Zi 4-HeX-C ₆ H ₄ H CH br 282 4-C £ 2-C, 4-CF ₃ -C ₆ H ₃ H CH br 283 4-C ^ 4-CF ₃ -C ₆ H ₄ H CH br 181.0-182.0 284 4-Cf 2-C-Ä, 4-Br-C ₆ H ₃ H CH Zi

Table 1-b (cont'd)

Compound No. Xn 2, Q e B A. in.p. CC) 285 A-C £ 9 2-Cjg, 4-Br-C ₆ H ₃ H. CH br 286 A-C £ 4-FC ₆ H ₄ H CH Br 174.0-175.5 287 4-C £ 2, 4-CACH ₂ CH ₂ -C ₆ H ₄ H CH C jg 288 2, 6-F ₂ , 4-CJi-C ₆ Hu H CH C £ 289 4-c £ 6-F ₂ , 4-C 1 -C ₆ H ₂ H CH br 290 A-Z £ Q2 H CH C £ 291 4-Cj2 4-Ci ₂ , 6-FC ₆ H ₂ H CH C £ 292 A-Z £ 6-F ₂₁ 4-Br-C ₆ H ₂ H CH C £ 293 A-Z £ 2-Cj, 4-Me-C ₆ H ₃ H CH C £ 294 4-C £ 2-F ₁ 4-Me-C ₆ H ₃ H CH br 295 4-C £ 2-Me, 4-CjZ-C ₆ H ₃ H CH br 296 4-C £ 2-MeO, 4-CA-C ₆ H ₃ H CH br - 297 4-C £ H GH br Q3 6

Table 1-b (cont'd)

Compound No. X _n Q e B A in.p. CC) 298 i-Zi 4-C 1 -C ₆ H ₄ OH CH C £ 299  4-Cjg 4-C 1 -C ₆ H ₄ C j2 CH Zi 300 4-C £ 4-Cg-C ₆ H ₄ OCH ₃ CH Zi 301 4-C jg 2,4-Ci ₂ -C ₆ H ₃ CH Zi 302 A-Zi 2,4-C ^ ₂ -C ₆ H ₃ . OCH ₃ CH Zi 303 4-CJS 4-Br-C ₆ H ₄ OCH ₃ CH Zi 304 4-CAE 2-F, 4-C 1 -C ₆ H ₃ C-i CH Zi 305. 4-C £ 4-C 1 -C ₆ H ₄ H , CH H 203..0-204.0 306 4-C £ 2,4-Ci ₂ -C ₆ H ₃ H CH K 221.5-222.8 307 C. E-4 2-F ·, 4-Cj2-C ₆ H ₃ H CH H 308 4-C-jg 4-C 1 -C ₆ H ₄ H CH OCH ₃ 309 4-ClZ 4-Br-C ₆ H ₄ H CH OCH ₃ 310 i-Zi 2-F, 4-C 1 -C ₆ H ₃ H CH- OCH ₃

Compound Na X η .Q e B A π. p. CC) 311 i-ZSt 2,4-C ^ ₂ -C ₆ H ₃ H CH OCH ₃ 148.0-150.0 312 4-C? 3-C 1 -C ₆ H ₄ H CH Oi-Bu 313 4-CJZ 4-Pen-C ₆ H ₄ H CH OEt 314 4-Cjg 2,4-CjS ₂ -C ₆ H ₃ H N br 315 4-C £ 2-F ₅ 4-CjS-C ₆ H ₃ H N Cj2 316 i-ZZ 2-F ₁ 4-CjS-C ₆ H ₃ H N br 317 4-C j2 4-Br-C ₆ H ₄ H N br 318 4-C 2,4-C ^ ₂ -C ₆ H ₃ H. N. C £ 319 4-C £ 4-C 1 -C ₆ H ₄ H  N H- 320 4-C Q3 H CH zn 321st i-ZZ • Q 3 H 'CH br 322 4-Cjg Q4 H CH Zi 323 4-C £ V. Q 5 H CH Zi 147.0-148.0

Table 1-b (cont'd)

Compound No. X _n Q * e B A m.p. CO 324 4-C £ _s Q 6 H CH br 325 A-C £ Q7 H CH C £ 326 4-C jess Q8 H CH C £ 327 A-C £ Q9 H- CH br 328 4-C £ ql 0 H CH br 329 4-C £ ql 0 H CH C £ 330 4-CJZ ql 1 H CH br 331 4-C £ ql 2 H CH C £ 332 4-C £ ql 3 H CH ci 333 4-C £ ql 4 H CH C £ 334 4-Cjß ql 2 H CH br 335 A-C £ ql 5 H CH C £ 336 A-C £ ql 6 H CH CU 135.0-136.5

Table 1-b (cont'd)

Compound Na. Xn a 7 e B A m.p. rc) 337 4-C i ql 8th ' H CH Zi 190.0- -195.0 338 A-Zi .Ql 9 H CH br 339 A-Zl ql 0 H CH Zi 340 A-Zi Q '2 0 H CH Zi 190.0-192.0 341 A-C & Q2 1 H CH br 195.0 ' 342 A-Zi Q2 1 H CH Zi 343 A-Zi Q2 2 H CH br 344 4-C i Q2 2 H- CH Zi 345 A-Zi Q2 3 H CH br 346 A-ZS, Q2 4 H CH Zi 347 4-C i Q2 4 H CH Zi 348 A-Zi Q2 5 · H CH br 349 A-Zi Q2 ' H CH Zi -197.0

Table 1-b (cont'd)

Compound Na Xn Q e B A in.P. CC) 350 A-C £ Q2 5 H CH br 351 4-C ^ Q 2 6 H CH C £ 352 4-Cj2 Q2 8 H CH C £ 187.6-188.1 353 A-C £ Q2 7 H CH C £ 354 A-C £ Q2 0 C £ CH C £ 355 A-C £ Q2 0 H N C £ - 356 A-C £ Q2 0 H CH H 357 A-C £ Q 2 9 H CH br 358 A-C £ '' Q 3 0 .. H CH br 359 A-C £ Q 3 1 H CH br 360 3-Cjg 4-CJg-C ₆ H ₄ H CH br 171.3-172.0 361 3-C £ 2,4-C ^ ₂ -C ₆ H ₃ H- CH br 155.0-156.0 .362 3-C £ 2-F ₁ 4-C 1 -C ₆ H ₃ H CH C £

Compound No. , Xn 2-F, Q iC ₆ H ₃ e B - * A in.p. CC) 363 3-C   4-C 4-C 6H4 H CH br 364 4-Br Z-Z H CH - br

365 4-Br 4-Br-C ₆ H ₄ H CH Br

366 4-Br 2,4-Ci ₂ -C ₆ H ₃ H CH Ci 167.0 ~ 168.5

367 4-Br 2,4-Cjg Z-Ci ₁ H ₃ . H CH Br

368 4-Br 2-F, 4-Ci-C ₆ H ₃ ZS. CH ZH

369 4-Br 4-Ci-C ₆ H ₄ OCH ₃ CH Zi

370 4-Br "2-F ₁ 4-Ci-C ₆ H ₃ H CH Ci 185.2 ~ 185.7

371 4-Br 2-F, 4-Ci-C ₆ H ₃ H CH Br 168.7 ~ 169.9

372 4-Br 2,4-Ci ₂ -C ₆ H ₃ OCH ₃ CH Ci

373 4-Br 4-Ci-C ₆ H ₄ H CH OCH ₃

374 4-Br 4-1-C ₆ H ₄ H CH- Br .375 4-Br Q2 0 HN Br

Compound Να X η Q 0 e B A m. P. CO 376 4-Br Q2 1 H CH br 194th 7- -195.4 377 4-Br Q2 4 H CH 378 4-Br Q2 H ~ CH . "

379 4-Br Q2 5 H CH Cj?

380 4-Br 2,6-Fz, 4-C Jg-C ₆ H ₂ H CH Cjg 381 4-Br 2,4,6-CJg ₃ -Ci ₁ Hz H CH br 382 4-Br 2,4, 5-CjS ₃ -C ₆ H ₂ H CH Cjg 383 4-Br Q3 .H CH br 384 4-Br Q6 H CH Cjg 385 2-NO ₂ 4-CjS-CeH ₄ H CH Cjg 386 2-NOz 2,4-C ^ zC ₆ H ₃ H . CH Cj2 387 3-NOz 4-CiK-C ₆ H ₄ H CH Br 197.5-198.5 .388 3-NOz 4-Br-C ₆ H ₄ H CH br

Compound Na X _n Q e B A m.p. cc) 0 389 3-NO ₂ 2-F ₁ J-CA-C ₆ H ₃ H CH Z £ 390 3-NO ₂ 4-HeX-C ₆ H ₄ H CH- Zi 0 391 3-NO ₂ 4-CF ₃ -C ₆ H ₄ H CH br 392 4-NO ₂ 4-CjZ-C ₆ H ₄ H CH Zi 5 393 4-NO ₂ 4-CjS-C ₆ H ₄ H CH br 202.0- -209. 394 4-NO ₂ 2,4-CA ₂ -C ₆ H ₃ H- CH C Jg 395 4-NO ₂ 2,4-Ci ₂ -C ₆ H ₃ H CH Br. 231.0- -239. 396, 4-NO ₂ 2-F, 4-C 1 -C ₆ H ₃ H CH ZS, 0 , 397 4-NO ₂ 2-F, 4-CJE-C ₆ H ₃ H CH Br 189.0- -190. 398 4-NO ₂ 4-Br-C ₆ H ₄ - H " CH br 399 4-NO ₂   Q20 H CH Z & 400 4-NO ₂ Q2 1 H CH Z £ 401 4-NO ₂ Q2 0 H CH br 211.0- -212.

-to- £ .99 IOC

Table 1-b (cont'd)

Compound Na X _n Q- Έ B A m.p. cc) 402 4-NO ₂ Q 2 4 H CH ci 403 4-N0 _z Q2 5 H CH br 404 4-NO ₂ Q3 2 H CH ci 405 2-0CH ₃ 4-CJe-C ₆ H ₄ , H CH ci 406 2-0CH ₃ 4-Ci-C ₆ H ₄ H QH br 407 3-0CH ₃ 4-C 1 -C ₆ H ₄ H CH ci 408 .3-0CH ₃ 4-Br-C ₆ H ₄ H CH br 409 · 3-0CH ₃ 2,4-Ci ₂ -C ₆ H ₃ H CH · ci 410 4-0CH ₃ 4-Ci-C ₆ H ₄ H CH ci 165.5- -166.1 411 4-0CH ₃ 4-Ci-C ₆ H ₄ H H br 412 4-0CH ₃ 4-Br-C ₆ H ₄ H CH- ci 223.6- -224.5 413 4-0CH ₃ 2,4-Ci ₂ -C ₆ H ₃ • H CH ci 217.2- -218.2 414 4-0CH ₃ 2-F, 4-Ci-C ₆ H ₃ H CH ci

Compound,,

X _n Q EBA. mp ( ⁰ C)

N / A ,

415 4-OCH ₃ Q2 0 H CH Z £

416 4-OCH ₃ Q 2 2 H "CH ZZ

417 4-0CH ₃ Q 2 1 H CH Br

418 4-0CH ₃ 4-CF ₃ -C 6H4 H CH H 419 4-0CH ₃ 4-I-C H CH br 420 2-CF ₃ 2-F ₁ AZ & -C ₆ H ₃ H CH br 421 2-CF ₃ 2-F, A-ZH -C ₆ H ₃ ' H CH ZS, 422 3-CF ₃ 4-C £ -C H CH br 423 .3-CF ₃ 4-Br-C ₆ Η * H CH br  424 3-CF ₃ , Q2 0 H CH br 425 3-CF ₃ Q3 2 H CH br 426 3-CF ₃ Q2 5 H CH br 427 3-CF ₃ Q2 2 H CH br

-48- Zi) V / ISZ

Table 1-b (cont'd)

Compound. '

X _n Q EBA mp CC)

428 · 4-CF ₃ . 2,4-Ci ₂ -C ₆ H ₃ H CH Br

429 4-CF ₃ 2-F ₁ 4-Ci-C ₆ H ₃ H CH Br

430 4-CF ₃ 4-Ci-C ₆ H ₄ Ci CH Ci

431 4-CF ₃ 4-C 1 -C ₆ H ₄ OPro CH Ci

432 4-CF ₃ 4-Ci-C ₆ H ₄ H N br 433 4-CF ₃ 2,4-CiZz-C ₆ H ₃ H Ν ' ci 434 4-CF ₃ 4-Ci-C ₆ H ₄ · H CH OEt 435 4-CF ₃ 4-Br-C ₆ H ₄ H CH OBu 436 4-CF ₃ 4-Ci-C ₆ H ₄ H CH OCH ₃ 437 4-CO ₂ CH ₃ 4-Ci-C ₆ H ₄ H CH br 438 4-CO ₂ CH ₃ '4-Me-C ₆ H ₄ H CE br 439 4-CO ₂ CH ₃ , 4-Br-C ₆ H ₄ H CH br 440 4-CO ₂ CH ₃ 2,4-Ci ₂ -C ₆ H ₃ H CH ci

Compound Να 4-CO ₂ CH ₃ Q e B A mp ( ⁰ C) 441. 4-CO ₂ Et 2-F ₁ 4-CJg-C ₆ H ₃ H CH Zi 442 4-CO ₂ Et H CH Zi 195.0-196.0 443 4-CO ₂ Et 4-Ci-C ₆ H ₄ H CH br 444 4-CO ₂ Et 2,4-Ci ₂ -C ₆ H ₃ H CH Zi 445 4-COzEt 2-Me ₁ 4-Ci-C ₆ H ₃ H CH br 446 4-CO ₂ Et 4-Br-C ₆ H ₄ H CH Zi 447 4-CO ₂ Et 4-Me-C ₆ H ₄ , H CH Zi 448 4-CO ₂ Et 2-F ₁ 4-Ci-C ₆ H ₃ H CH bf 449 4-CO ₂ Et 2-F, 4-Br-C ₆ H ₃ H CH br 450 '' 4-CO ₂ Et Q2 0 H CH Zi 451 4-CO ₂ Et Q2 0   H CH br 452 4-CO ₂ i-Pro G3 H CH br 453. 4-Ci-C ₆ H ₄ H CH Zi

Compound Na Xn Q E. B A mp ( ⁰ C) 454 4-COzPro 4-Ci-C ₆ H ₄ H .CH ci 455 4-CO ₂ Bu 4-Ci-C ₆ H ₄ H CH ci 456 2,3-CiS ₂ 4-Ci-C ₆ H ₄ H CH ci 457 2,3-Ci ₂ 4-Ci-C ₆ H ₄ H CH br 458 2,4-Ci ₂ 4-Ci-C ₆ H ₄ H CH Br 175.0-176.0 459 2,4-Ci ₂ 4-Br-C ₆ H ₄ H CH br 460 2,4-Ci ₂ 2,4-Ci ₂ -C ₆ H ₃ H CH br 461 2,4-CjK ₂ 2-F, 4-Ci-C ₆ H ₃ H CH br 462 2,4-CjK ₂ 2-F ₅ 4-Br-C ₆ H ₃ H CH ci 463 2,4-Ci ₂ 4-Pe _n -C ₆ H ₄ H CH ci 464 2,4-Ci ₂ 4-1-Bu-C ₆ H ₄ H CH br 465 W 2,4-Ci ₂ Q2 0 - H CH ci 466 2,4-Ci ₂ Q2 4 H CH ci

Compound Na Xn Q- e B A m.p.CO 467 2,4-Ci ₂ Q2 1 H CH br 468th 2,4-CJg ₂ Q4 H CH br 469 2A-C £ ζ Ql 1 H CH br 470 2,4-Ci ₂ 4-Ci-C ₆ H ₄ OCH ₃ CH ci 471 2,4-CjS ₂ 4-Ci-C ₆ H ₄ OH CH ci 472 2,4-Cjg ₂ 4-Ci-C ₆ H ₄ br CH br 473. 2,4-Ci ₂ 4-Ci-C ₆ H ₄ H N ci 474 2,4-Ci ₂ 4-Br-C ₆ H ₄ H N ci 475 2,4-Ci ₂ 2,4-Ci ₂ -C ₆ H ₃ H CH H 476 2,4-Ci ₂ 4-FC ₆ H ₄ H CH OCH ₃ 477 2A-CHz 4-Br-C ₆ H ₄ H CH OBu 478 2,4-Ci ₂ Q2 0 H N ci 479 2,4-Ci ₂ Q2 0 B CH H

Compound Na 2.5-C £ ζ Q e B A mp ( ⁰ C) 480 2,5-Ci ₂ 4-Ci-C ₆ H ₄ H CH ci 171.5-172.5 481 2,5-CJg ₂ 4-Ci-C ₆ H ₄ H CH br 185.0-186.0 482 2,5-Ci ₂ 2,4-Ci ₂ -C ₆ H ₃ H CH ci 483 2,5-C ^ ₂ 4-Br-C ₆ H ₄ H CH ci 484 2,5-C ^ ₂ 4-Et-C ₆ H ₄ H CH br 485 2,5-CjS ₂ 2-Me ₁ 4-PrO-C ₆ H ₃ Ή CH br 486 2,5-Ci ₂ Q2 1 H CH ci 487 · 2,6-CjS ₂ Q 8 H CH br 488 2,6-Ci ₂ 4-Me-C ₆ H ₄ H CH ci 489 2,6-C jg ₂ 4- (4-CiC ₆ H ₄ ) C ₆ H ₄ H CH ci 490 2,6-Ci ₂ 4-HexO-C ₆ H ₄ H CH ci 491 3,4-CjE ₂ 4- (4-CiC ₆ H ₄ CH ₂ ) C ₆ H ₄ H CH ci 492 4-Me-C ₆ H ₄ H CH br

Compound Na 3,4-C £ ₂ Q • E B A m.p. cc) 493 3,4-CA ₂ 3-Me-C ₆ H ₄ H CH ci 494 3,4-Ci ₂ 3-Me-C ₆ H ₄ H CH br 495 3,4-Ci ₂ 2-Me-C ₆ H ₄ H CH br 496 3,4-Ci ₂ 4-MeO-C ₆ H ₄ H CH br 497 3,4-Ci ₂ 4- (4-BrC ₆ H ₄ CO) C ₆ H ₄ H CH ci 498 3,4-Ci ₂ 3-PeIiO-C ₆ H ₄ H CH br 499 3,4-Ci ₂ 4-Ci-C ₆ H ₄ H. CH ci • 178.3- -179.4 500 3,4-Ci ₂ 4-Ci-C ₆ H ₄ H CH br 178.0- -179.0 501 3,4-Ci ₂ 2-Ci-C ₆ H ₄ H CH ci 502 -3,4-Ci ₂ ql H CH br 503 3,4-Ci ₂ 4-Br-C ₆ H ₄ H CH ci 175.0 ' -176.0 504 3,4-Ci ₂ 4-Br-C ₆ H ₄ H CH br 505 4-FC ₆ H ₄ - H CH br

Compound Na ^Xn 3,4-Ci ₂ Q e B A m.p. CC) · - *> 506 3,4-Ciss ₂ 3-FC ₆ H ₄ H CH br 507 3,4-Ci ₂ 2,4-Ci ₂ -C ₆ H ₃ H CH ci 166.0- -167.0 508 3,4-Ci ₂ 2,4-Ci ₂ -C ₆ H ₃ . H CH br , 167.0- -171.0 509 3,4-Ci ₂ Q3 3 H CH ci 510- 3,4-Ci ₂ 4-1-C ₆ H ₄ H CH ci 182.3- -183.2 , 511 3,4-Ci ₂ 4-1-C ₆ H ₄ H CH br 512 3,4-Ci ₂ 4-CF ₃ -C ₆ H ₄ H CH ci 513 3,4-Ci ₂ 4-CF ₃ -C ₆ H ₄ H CH br 514 3,4-Ci ₂ 4-CF ₃ CH ₂ OC ₆ H ₄ H CH br 515 3,4-Ci ₂ 4 CHF ₂ CF ₂ CH ₂ OC ₆ H ₄ H CH ci 516 3,4-Ci ₂ 4 CHF ₂ OC ₆ H ₄ ' H CH- br 517 3,4-Ci ₂ 2,4-Br ₂ -C ₆ H ₃ H CH ci 518 2,4-Br ₂ -C ₆ H ₃ H CH br

Compound Na 3,4-CiZ ₂  2, Q 4-Br-C ₆ H ₃ e B , A m.p. cc) - 519 3,4Ci ₂ 2, 2-Cl, 4-Br-C ₆ H ₃ H CH ci 175.2-176.1 520 3,4-Ci ₂ 2, 2-Cj2, 4-Ci-C ₆ H ₃ H CH br 172.0- 521 3,4-Ci ₂ 2-F ₅ 4-Ci-C ₆ H ₃ H CH ci 522 3,4-CiS ₂ 2-F, 4-FC ₆ H ₃ H CH br 523 3,4-Ci ₂ 2-Cl, 4-FC ₆ H ₃ H CH ci 186.2- 524 3,4-Ci ₂ 2-Cl, 4-Br-C ₆ H ₃ H CH br 177.0- 525 3,4-C ^ _z 2-F, 4-Br-C ₆ H ₃ H CH ci 526 3,4-Ci ₂ 2-F, 4-Ci-C ₆ H ₂ H CH br 527 3,4-Ci ₂ 6-F ₂ , 4-Ci-C ₆ H ₂ H CH ci 528 3,4-Ci ₂ 6-F ₂ , :, 6-FC ₆ H ₂ H CH br 529 3,4-Cjß ₂ 4-Ci ₂ Ci ₃ -C ₆ H ₂ H CH br 530 3,4-Ci ₂ 2,4,5 4-CN-C ₆ H ₄ H CH br -173.0 531 H CH ci -187.4 -178.1

Compound Να 3, U Q e B A m.p. CC) · 532 3, 4- " 4-HeX-C ₆ H ₄ H CH br 533 3, 4-C " Q7 H CH Br. 534 3, 4-CI. 4- (4-MeC ₆ H ₄ ) C ₆ H ₄ H CH C " 535 O j 4-Ci ₂ 4- (4-MeC ₆ H ₄ CH ₂ O) C ₆ H ₄ H CH C., 536 3, mm, 4- (4-C 1 -C ₆ H ₄ ) C ₆ H ₄ H CH br 537 3, 4-C jg 2 4- (4-CF ₃ C ₆ H ₄ CH ₂ O) C ₆ H ₄ H CH C., 538 3, ' " -4- (4-EtOC ₆ H ₄ CH ₂ O) C ₆ H ₄ Ή CH C., 539 3, 4-C Jg ₂ 4- (4-BrC ₆ H ₄ CH ₂ ) C ₆ H ₄ H CH br 540 3, 4-C Jg ₂ 4-Cjg -C ₆ H ₄ H CH H 541 3, 4-C Jg ₂ - 2,4-CJg ₂ -C ₆ H ₃ H CH OCH ₃ 542 3, 4-C Jg ₂ 4-CiT-C ₆ H ₄ H CH 0-i-Pro 543 3, 4-C jg ζ 4-CJg-C ₆ H ₄ Cjg .CH Cjg 544 4-Cjg ₂ 2,4-CJg ₂ -C ₆ H ₃ CS CH

Compound Να 3, 4-Ci ₂ 8th e B CH A m.p. ("C) 545 3, 4-Ci ₂ 4-C, -C ₆ H ₄ OH CH ci 546 3, 4-Ci ₂ 4-CjS-C ₆ H ₄ OCH ₃ CH ci 547 3, 4-C *. 4-Br-C ₆ H ₄ OCH ₃ CH ci 548 3, i-cs ₂ , 4-Me-C ₆ H ₄ ci CH ci 549 3, A-CS ₂ 4-EtO-C ₆ H ₄ OEt CH Ci · 550 3, 4-C j2 ₂ 2-F, 4-Ci-C ₆ H ₃ ci CH ci , 551 3, 4-Ci ₂ 2-F ₁ 4-CjS-C ₆ H ₃ H CH OCH ₃ 552 3, 4-CjS ₂ 2-F, 4-Ci-C ₆ H ₃ H CH H 553 3, 4-Ci ₂ 2-F, 4-Br-C ₆ H ₃ ci CH ci 554 3, 4-C jg. ₂ 2-F, 4-Br-C ₆ H ₃ H CH H 555 3, 4-Ci ₂ - 2-Me, 4-Ci-C ₆ H ₃ H CH br 556 3, 4-C S ₂ 2-Me, 4-Br-C ₆ H ₃ H CH ci 557 4-Ci-C ₆ H ₄ H 0-s-Bu

Compound No. 3,4-Ci ₂ Q- e B A m.p. CC) 558 3,4-CjZ ₂ 4-Br-C ₆ H ₄ H CH OEt 559 3,4-Cje ₂ 4-Br-C ₆ H ₄ H CH OBu 560 3, .4-Ci ₂ Q3 H CH ' ci 561 3,4-Ci ₂ Q3 H CH Br 562 3,4-Ci ₂ Q4 CH br 563 3,4-Ci? ₂ Q4 ci CH Ci - 564 3,4-Ci ₂ Ql 5 H CH ci 565 3,4-Ci ₂ Ql 2 H CH ci 566 3,4-Ci ₂ Q3 4 H CH br 567 3,4-Ci ₂ Q5 -.H- CH br 568 3,4-Ci ₂ Q8 H CH br 569 3,4-Ci ₂ Q6 H CH br 570 Q6 H CH ci

Compound Na X _n Q 0 e B A m.p.Cc) 571 3,4-CJg ₂ ql H CH br 572 3,4-CjZ ₂ Q9 H CH br 573 3,4-Ci ₂ Q9 1 CJZ CH C £ 574 ql 2 H CH br 575 3,4-Cjg ₂ ql 5 H CH br 576 3A-CH ₂ Q3 3 C jg CH ZS. 577 3,4-C ζ ql 4 H CH C £ '578 3,4-Ci 2 ql 6 H CH br 579 3,4-C £ ₂ Q3 6 H CH br 580 3,4-Cj2 ₂ ql 8th H CH br 581 3,4-C £ ₂ Q-I 0 H CH br 582 3,4-C £ z Q2 0 H CH ZS 173.0-176.0 583 3,4-CjS ₂ Q 2 H CH Br 193.0-194.0

Compound Na X _n Ö 1 e B A in.p. ( "C) 584 3,4-CjS ₂ Q2 1 H CH CU 585 3,4-Cg ₂ 0.2 2 H CH br 586 3,4-Cj2 ₂ Q2 2 H CH CU 587 3,4-CiJ ₂ Q2 7 H CH br 588 3,4-C ^ ₂ Q3 7 H CH ci 589 ZA-Ci ₂ Q3 4 H CH br 590 3,4-Ci ₂ Q2 4 H- CH ca 591 3,4-C £ 2 Q 2 2 H CH br 592 3,4-Ci ₂ Q3 2 H CH ci 593 Q3 5 H CH br 594 ZA-CJi ₂ Q2 5 H CH ci 595 3,4-Ci ₂ Q-2 3 H CH br 596 3,4-Ci ₂ Q2 H CH a

X η Table 1-b (Cont ' d) B A m.p. ( "C) .8th 3,4-Cg ₂ CH ci .0 Compound Να 3,4-CjZ ₂ Q e CH br .2 597 3,4-Cjg 2 Q3 8 H CH br .0   598 3,5-Ci ₂ Q3 9 H CH ci .4 599 3,5-Cg ₂ Q3 0 H CH Br 600 3,5-Ci ₂ 4-Ci-C ₆ H ₄ H CH br 601 3,5-Ci ₂ 4-CiS-C ₆ H ₄ H CH br 602 3.5-CjS 2 4-Br-C ₆ H ₄ H CH br 603 4-Ci, 2-F 2-F, 4-Ci-C ₆ H 3 H CH ci 189.7- 190 604 4-Ci, 2-F. Q2 0 H CH br '183.0- 185 605 4-Ci, 2-F 2,4-CJg ₂ -C ₆ H ₃ H CH zn 175.7- 177 606 - 4-C £. 2-F 2,4-CJg ₂ -C ₆ H ₃ H CH br 171.0- 172 607 A-Ci, 2-F 2-F, 4-CjK-C ₆ H 3 H CH TO 179.9- 186 608 2-F, 4-Ci-C ₆ H 3 H 609 4-1-C ₆ H ₄ H

Compound No. 4-Cj2, 2-F Q e B A m.p. cc) • 9 610 A-C, 2-F 4-1-C ₆ H ₄ H CH br .0 611 A-C, 2-F 2,4-F ₂ -C _n H ₃ - H CH ci 162.0- -162 .1 612 A-C, 2-F 2,4-F ₂ -C ₆ H ₃ H CH br 179.6- -181 2 613 A-C, 2-F 2-CÄ, 4-FC ₆ H ₃ H CH br 163.3-164 .6 614 A-C, 2-F 2-F, 4-Br-C ₆ H ₃ H CH ci 185.7- 615 A-C, 2-F 2-F, 4-Br-C ₆ H ₃ H CH br 177.3- 616 A-C, 2-F 4-Bu-C ₆ H ₄ . H CH Cl 617 A-C, 2-F 4-1-BuO-C ₆ H ₄ H CH ci 618 A-C, 2-F 2,6-F ₂₃ 4-C 1 -C ₆ H ₂ H CH br 619 OH, 2-F 2,6-F ₂₁ 4-CjK-C ₆ H ₂ H CH ci 620 OH, 2-F 2-Me ₁ 4-Ci-C ₆ H ₃ H CH br 621 A-C, 2-F 2-Me, 4-Br-C ₆ H ₃ H CH br 622 Ql 2 H CH ci -187 -178

Compound Na ^Xn 4-C i , 2-F a E. B A m.p. ( "C) 623 4-Cl, 2-F Ql 2 H CH br 624 4-Cl, 2-F 4-C, -C ₆ H ₄ OH CH ci 625 4-C i, 2-F 4-C 1 -C ₆ H ₄ OCH ₃ CH ci 626 4-Cl, 2-F 4-Br-C ₆ H ₄ OEt CH ci 627 4-Cl, 2-F 4-C 1 -C ₆ H ₄ ci CH ci 628 4-CjS, 2-F 4-C 1 -C ₆ H ₄ , H CH H 629 4-C SL, 2-F 2,4-Cjβ Z-Ci ₁ H ₃ H CH H 630 4-Cl, 2-F 4-CJg-C ₆ H ₄ H CH OCH ₃ 631 4-Cl, 2-F 2,4-CJe ₂ -C ₆ H ₃   H CH OCH ₃ 632 4-Cl, 2-F 4-CiS-C ₆ H ₄ H CH Opro 633 4-Cl, 2-F 2,4-Ci ₂ -C ₆ H ₃ H CH 0-i-Bu 634 4-Cl, 2-F 4-Me-C ₆ H ₄ H CH OCH ₃ 635 4-Ci-C ₆ H ₄ • H N ci

Table 1-b (cont'd) ·

Compound Να 4-C £. 2-F Q j. - 0 Έ B A m.p. CC) 636 4-CJE ,. 2-F 4-C i2 -C ^ CJ. H N br 637 4-CÄ, 2-F 2-F, 4-C 1 3 H N CJS 638 4-C, 2-F Q3 H ' CH Br. 639 4-Cj2, 2-F Q4 H CH Br 148.0-150.0 640 AC £, 2-F Q4 5 H CH ci 641 4-C £. 2-F ql 0 H CH br 642 4-C, 2-F Q4 H. CH br 643 A-Ci, 2-F Q5   H CH br 644 4-Cs, 2-F Q8 H CH br 645 4-CÄ, 2-F Q6 H CH ci 646 4-Cjg, 2-F ql H CH br 647 4-CAE. 2-F Q9 H CH CZ 648 ql H CH br

-65- Züy / HZ

Table 1-b (cont'd)

Compound VT ^ ⁿ Na A-Z £, 2-F Q 5 e B A m.p. CC) 649 A-C £, 2-F. Q3 4 ' H CH br 650 A-C &, 2-F ql 1 H CH ZS, 651 A-C &. 2-F Q4 0 H CH zn 652. A-C &, 2-F Q2 0 H CH ZH 157.0 ~ 158.0 653 A-C £, 2-F Q2 1 H CH Br 189.0-191.0 654 K-BR, 2-F Q2 1 Ή CH ZH 655 K Zii. 2-F Q2 2 H CH br 656 A-BR, 2-F Q2 7 H CH br 657 A-C Ii, 2-F- Q3 2 H CH br 658 A-C &, 2-F Q4 8th H CH br 659 We. 2-F ql 3 H CH br 660 A-BR, 2-F Q4 4 H CH br 661 Q4 H CH ZS.

-66- 2ba / uz Table 1-b (cont'd)

Compound Na 4-C £. 2-F Q e B A m.p. ⁽¹ C) 4 662 4-Cjg, 2-F Q2 4 H CH C £ 5 663 4-C "j2, 2-F Q2 4 H CH br 8th 664 4-CAE 2-F Q3 2 H CH br 5 665 4-Ci ₁ 2-F Q 2 5 H CH Zi 666 4-Cl, 2-F Q2 5 H CH br 667 4-C £, 2-F Q 3 0 H CH Cjg 668 4-CAE 2-F _ Q2 3 H CH Zi 669 '' 4-Br, 2-F Q2 0 Zi CH zn 670 4-Br, 2-F 4-1-C ₆ H ₄ H CH br 671 4-Br ₁ 2-F 4-Br-C ₆ H ₄ H CH zn 188.4- -189. 672 4-Br, 2-F 4-Br-C ₆ H ₄ H CH br 175.0- -176. 673 4-Br ₃ 2-F 2-F, 4-CJg-C ₆ H ₃ H CH Zi 188.2- -189. 674 2-F, 4-Ci-C ₆ H ₃ H CH br 190.0- -191.

Compound Na 4-Br, η 2-F a) e B A m.p. ("O 675 4-Br ₁ 2-F 2,4-Ci-C ₆ H ₄ H CH ci 212.0- -212.6 676 4-Br, 2-F 2,4-CA-C ₆ H ₄ H CH br 206.0- -207.0: 677 4-Br, 2-F Q2 0 H CH ci 185.0- -189.0 678 4-Br ₁ 2-F Q2 0 H CH br 187.4- -188.4 679 4-C , 2-CH ₃ 4-CjK-C ₆ H ₄ ci CH ci 680 A-CS, , 2-CH ₃ 4-Ci-C ₆ H ₄ H ar ci 175.0- - 177.0 681 A-C £ , 2-CH ₃ 4-Ci-C ₆ H ₄ H CH br 188.0- - 189.8 682 A-C & , 2-CH ₃ 2-F, 4-Ci-C ₆ H ₃ H CH ci 187.0 - -188.5 683 A-Cl , 2-CH ₃ 2-F, 4-Ci-C ₆ H ₃ H CH br 199.5- - 200.6 684 4-Br, 2-CH ₃ Q2'0 H CH br 207.0- -208.0 685 4-Br, 2-CH ₃ 4-Ci-C ₆ H ₄ H CH br 686 A-C £ , 3-CH ₃ 2,3,4,5,6-F ₅ C ₆ H CH br 687 4-Ci-C ₆ H ₄ H CH ci

Compound No. 4-Cjg, 3-CH ₃ 2, Q e B A mp ( ⁰ C) 688 A-Ci, 3-CH ₃ 3, 4-Ci-C ₆ H ₄ H CH br 689 A-Ci, 3-CH ₃ 4-C ₆ H ₅ -C ₆ H ₄ H CH ci 690 4-Br ₁ 3-CH ₃ 3, 4-BuO-C ₆ H ₄ H CH br 691 4-Br, 3-CH ₃ 4-Me-C ₆ H ₄ H CH 692 4-Br, 3-CH ₃ 4-CN-C ₆ H ₄ H CH br 693 3-Ci, 4-F 4-CF ₃ -C ₆ H ₄ H CH br 694 "3-Cjg, 4-F 4- (Me) ₂ -C ₆ H ₃ H CH Br. 695 3-Ci, 4-F 4- (Me) ₂ -C ₆ H ₃ H CH ci 696 3-Ci ₁ 4-F 4-Ci-C ₆ H ₄ H CH Br. 152.4-153.2 697 3-Ci, 4-F 4-Ci ₂ -C ₆ H ₃ H CH br 698 3-Ci, 4-F 4-Me-C ₆ H ₄ Zi CH. ci 699 4-Cjg, 3-F Q6 H CH br 700 4-Ci-C ₆ H ₄ H CH Ci '

Table 1-b (cont'd)

Compound Na ⁿ 4-Cjg, 3-F Q e B A m.p. CC) 701 4-Cj2, 3-F 4-CJg-C ₆ H ₄ H CH br 702 4-Br, 3-F 2-F ₁ 4-C 1 -C ₆ H ₃ H CH br 703 4-Br, 3-F 4-Br-C ₆ H ₄ ' H CH br 704 4-Br ₁ 3-F 2,4-C ^ ₂ -C ₆ H ₃ H CH C £ 705 4-Br, 3-C £ Q2 0 H CH br 706 4-Br, SC £ 4-C 1 -C ₆ H ₄ H CH Ci ". 707 4-Br, 3-Ze. 4-C 1 -C ₆ H ₄ H CH br 708 4-Br, 3-C £ 4-Pr ₀ -C ₆ H ₄ H CH 709 2,4-Br ₂ Q2 1 H CH C £ 710 2,4-Br ₂ 4-1-C ₆ H ₄ H CH cn 711 2,4-Br ₂ 2, '4-C ^ ₂ -C ₆ H ₃ H CH br 712 3,4-Br ₂ 4-HeX-C ₆ H ₄ H CH ci 713 4-C 1 -C ₆ H ₄ H CH CU

Compound X Να Π , 3-CF ₃ , Q e B A m.p. CC) 714 3,4-Br ₂ , 3-CF ₃ 4-Br-C ₆ H ₄ H CH br 715 3,4-Br ₂ , 3-CF ₃ 4-Me-C ₆ H ₄ ; H CH br 716 3,4-Br ₂ , 3-CF ₃ 3-Br-C ₆ H ₄ H CH ci 717 4-C , 3-CF ₃ 4-Ci-C ₆ H ₄ H CH ci 718 4-C , 3-CF ₃ 4-Ci-C ₆ H ₄ H CH br 719 4-C , 3-CP ₁ 2-F ₁ 4-Ci-C ₆ H ₃ H CH br 720 4-C , 3-CF ₃ 2-F ₁ 4-Ci-C ₆ H ₃ H CH 721 4-C , 3-CF ₃ 2,4-Ci ₂ -C ₆ H ₃ H CH ci 722 4-C , 3-CF ₃ 2-Ci, 4-Br-C ₆ H ₃ H CH br 723 4-C * 2-F ₁ 4-Br-C ₆ H ₃ H CH br 724 '4-Ci 4-Me-C ₆ H ₄ · H CH br 725 4-C 4-CF ₃ -C ₆ H ₄ H CH br 726 4-C Ql 1 H CH br

Compound Na · ^Xn 4-Ci, 3-CF ₃ Q e B A m.p.CO 727 4-Ci, 3-CF ₃ Q2 0 H CH ci 728 4-C, 3-CF ₃ Q2 1 H CH br 729 2-C, 4-CF ₃ Q2 3 H CH br 730 2-C, 4-CF ₃ 2,4-Cjg 2-C ₆ H ₃ H CH br 731 2,3,4-Cβ 3 4-Br-C ₆ H ₄ H N br 732 2,3,4-Ci ₃ 4-Ci-C ₆ H ₄ H CH ci 733 2,3,4-Ci ₃ 4-Ci-C ₆ H ₄ H CH br 734 2,3,4-Cg ₃ 2-F, 4-Ci-C ₆ H ₃ H CH br 735 2,3,4-Ci ₃ 2-F ₁ 4-Ci-C ₆ H ₃ H CH ci 736 2,3, -4-Ca ₃ 2,4-Ci ₂ -C ₆ H ₃ H CH ci 737 2,4,5-Ci ₃ , 4-Br-C ₆ H ₄ H CH br 738 2,4,5-Ci ₃ 4-Ci-C ₆ H ₄ H CH Ci 189.1-191.5 739 4-Ci-C ₆ H ₄ H CH Br 161.0-162.0.

Compound NO. 2,4,5-c'jg 3 Q e B A m.p. ( "C) 740 2,4,5-C ^ ₃ 4-Br-C ₆ H ₄ H CH ci 202.0 · -204.0 741 2,4,5-Ci ₃ 4-Br-C ₆ H ₄ .H CH br 184.2 -185.0 742 2 * 4.5-0 4 a 2,4-CJg ₂ -C ₆ H ₃ H CH ci 224.8 · -226.2 743 2,4,5-CJg ₃ 2-F, 4-CJg-C ₆ H ₃ H CH Cjg 195.0 -196.0 744 2,4,5-CjZ ₃ 2-F, 4-Ci-C ₆ H ₃ H CH br 189.5 -190.3 745 2,4,5-Ci ₃ Q 1 2 H CH ci 746 4-Ci, 2,6-F ₂ Q3 H CH br 747 4-Ci, 2,6-F ₂ 4-Ci-C ₆ H ₄ H CH br 748 4-C £ ₃ .2,6-F ₂ 4-Me-C ₆ H ₄ H CH ci 749 3-Ci, 4-F .2-Ci-C ₆ H ₄ , H CH br 750 3-Ci, 4-F 4-Ci ^ C ₆ H ₄ H CH ci 151.0 -154.0 751 3-Ci, 4-F 4-Br-C ₆ H ₄ H CH ci 150.0 -153.0 752 4-Br-C ₆ H ₄ H CH br 140.0 -143.0

Compound Na 3-Ci, 4-F 2, Q e B A in.p. (Ic) 753 3-Ci, 4-F 2, 4-Ci ₂ -C ₆ H ₃ H CH ci 161.1-166.8. 754 3-Ci, 4-F 2-F 4-Ci ₂ -C ₆ H ₃ H CH br 154.0- 755 3-Ci, 4-F 2-F , 4-Ci-C ₆ H ₃ H CH ci -156.0 756 3-Ci, 4-F , 4-Ci-C ₆ H ₃ H CH br 154.9-156.4 757 3-Ci, 4-F 4-1-C ₆ H ₄ H CH ci 147; 0-148.5 758 4-Br ₅ 2-F 4-1-C ₆ H ₄ H CH br 145.1- 759 2,3,4-Ci 3 4-1-C ₆ H ₄ H CH ci 157.0- 760 2,3,4-Ci ₃ 2, 4-Br-C ₆ H ₄ H CH ci 761 2,3,4-Ci ₃ 4-Ci ₂ -C ₆ H ₃ H CH br 762 2,3,4-Ci ₃ 4-1-C ₆ H ₄ H CH ci 763 2,4,5-Ci ₃ 2, 4-1-C ₆ H ₄ H CH br 764 2,4,5-Ci ₃ 4-Ci ₂ -C ₆ H ₃ H CH br 765 4-1-CIH * H CH ci -150.0 -159.0 202.9-203.7

Compound Na 2,4,5-C ^ ₃ Q e B A m.p. cc) 766 i-Ci 4- 4-1-C ₆ H ₄ H CH br 767 2,3,4-C ^ ₃ (4-CiC ₆ H ₄ CO) C ₆ H ₄ H CH C £ 212.5 -248.2 768 2,3,4-Cg 3 Q2 0 H CH Zi 223.0 -224.0 769 2,4,5-C £ ₃ Q2 0 H CH br 229.0 -230.0 770 2,4,5-C £ ₃ Q2 0 H CH ci 182.0 -183.0 .771 i-Ci, 2-CH ₃ Q2 0 H CH br 175.2 -176.7 772 4 - C £, 2-CH ₃ Q2 0 H CH ci  198.0 -199.0 773 4-C, 2-CH ₃ Q2 1 H CH br 774 A-Ci ₁ 2-CH ₃ 4-Br-C ₆ H ₄ H CH ci 184.0 -185.0 775 A-Ci ₁ 2-CF ₃ Q2 4 H CH ci '776 A-Ci, 2-CF ₃ Q2 0 H CH ci 777 '4-Br Q 2 2 H CH ci 778 Q2 0 H CH ci 202.4 -203.4

Compound No. 4-Br, 2-F Q e B A m.p. (° C) 779 4-Br, 2-F 2F ₁ 4-Br-C ₆ H ₃ H CH Zi 188.6-190.4 780 4-C £ 2F, 4-Br-C ₆ H ₃ H CH Br 185.6 ~ 186.3 781 4-C £ 4-C, -C ₆ H ₄ H CH CH ₃ 782 4-C Q2 0 H CH CH ₃ 783 3,4-CA ₂ Q2 4 H CH CH ₃ 784 3,4-CjS ₂ 4-C 1 -C ₆ H ₄ H CH et 785 ΖΛ-ZS. _z Q2 0 H CH Et · 786 4-Br ·. 4-C 1 -C ₆ H ₄ H CH Per  787 4-NO ₂ 4-Me-C ₆ H ₄ H CH i-Pro 788 4-CH ₃ 4-Br-C ₆ H ₄ H CH i-Pro 789 2,4-Cjg ₂ 2,4-C ^ ₂ -C ₆ H ₃ H CH Bu 790 4-C j2 Q2 1 H CH s-Bu 791 Q3 3 H CH

Compound Na 4-C Q 3 e B A m.p.Cc) 792 4-C i Q3 6 H CH br 793 3,4-CA ₂ Q3 3 H CH ci 794 3,4-Ci ₂ Q3 6 H CH br 795 3,4,5-Ci ₃ Q3 -C6H4 H CH ci 796 3,4,5-Ci ₃ 4-C 0 H CH. ci 797 3,4,5-Ci ₃ -Q2 0 H CH ci 798 4-Ci, 3-CH ₃ Q 2 0 H CH br 799 4-Br, 3-CH ₃ Q2 0 H CH ci 800 4-Br ₁ 3-F Q2 -0 H CH ci 801 4-Ci, 3-F Q2 0 H CH Ci> 802 4-Ci ₁ 3-F Q 2 0 H CH ci 803 4-Br ₁ 3-Ci Q-2 0 H CH br 804 Q2 H CH " ci

Table 1-b (cont'd)

Compound Na 4-Br,; 3-CF ₃ Q 0 e H B A m.p.CC) 805 3-Br Q2 0 H CH br 806 3-Cjg 3-Br Q2 0 H CH C £ 807 3,4-Br ₂ 3-NO ₂ Q2 0 H CH br 808 .3,4-Br ₂ 3-NO ₂ .. Q 2 0 H CH br 809 A-C, 3-0CH ₃ Q2 0 H CH P D 810 A-Ci ₁ 3-0CH ₃ Q2 0 H CH br 811 A-C, 3-Br Q2 0 H CH " 812 A-C,  3-F Q2 O" H CH br 813 A-C, 3,4-Ci> ₂ Q2 0 H CH Cl. 814 A-C, Q2 "CA .. H CH br 815 A-C £, A-C £ -C ₆ H ₄ H CH C £ 816 A-C, A-C £ H CH ci 817 4-Br, ZA-Ci CH Ci 180.0-181.0

Compound No. Xn Hz Q e B A in.p. CC) 818 3,4-C 3,4-C Ji ₂ -C ₆ H ₃ " CH Br 189.0-190.0 819 4-F inn r H CH C jg 820 ' 4-F 4-C 1 -C ₆ H ₄ H CH br 821 4-F. Q2 0 H. CH CU 822 4-F 4-F Q2 0 H CH br 823 3-Br ₁ 4-F ACO ΓΗ H CH 824 3-Br, 4-F 4-Ci-C ₆ H ₄ H CH br 825 3-Br, 4-F Q2 0 H CH C., 826 3-Br, Q2 0 H CH Br '

Ql to Q4 ^ hown in the above-mentioned Tables are groups represented by the following formulas.

Ql:

CU Q 2:

br

Q3:

TO

Q4: Br

, J

br

Q6:

Q7:

W //

For example,

ZiL. Q 8:

Q9:

S Br

qlo:

S Zi

br

Q13:

Q14:

Q16:

OPro Q18:

me

Bu Q20:

Zi

Zi

Br Q22:

CF ₃ Q24

zl

Zi Q26

Per

Me Q28: - < ^/ V "OCH

Q29:

Q31:

Hex Q30: - <( V- Bu

Et Q32:

br

Q33:

Br Q34:

Bu

Q35:

br

Q36:

Q37:

Q39:

Et Q40:

Bu -t

 Q41:

me

Q42:

CF ₃

Table 2

Mortality of Green Ri- Mortality of Green Ri-

Compound ce leafhopper ( Nepho- compound ce leafhopper (Nepho No. tettix cincticeps) (%) No. tettix cincticeps) (%).

1 2 1 O O 9 ImI 2 1 O O 2 7 1 O O 2 8th 1 O O 3 3 1 O O 3 4 , 1 O O • 3 5 1 O O 4 9 1 O O 5 1 1 O O 9 7 1 O O 1 5 • 4 1 O O

1 6 7 1 O O 1 7 O 1 O O 1 7 1 1 O O 1 7 2   1 O O 1 7 4 1 O O 1 7 5 1 O O 1 7 8th 1 O O 1 8th 9 1 O O 1 9 O 1 O O '. 2 Third 5 1 O ο / 2 5 6 1 O

1 6 6

1 OO

2 7 3

1 OO

Table 2 (cont'd)

Mortality of Green

Compound ce leafhopper ( Nepho-

No. tettix cincticeps ) (%)

CNl 7 4 1 O O 2 8th 6 1 O O. 3 4 O 1 O O 3 4 1 1 O O 3 6 O 1 O O 3 6 1 1 O O 3 7 O 1 O O 3 I 1 1 O O 3 7 6 1 O O 3 9 3 1 O O 3 9 7 1 O O

Mortality of Green ri-Compound ce leafhopper (Nepho No. tettix cincticeps) (%)

4 1 CNl 1 0 0 4 5 8th 1 0 0 4 8th O. 1 0 , 0 4 8th 1 . 1 0 0. 4 9 9 1 0 0 5 O 0 1 0 0 δ O 3 1 0 0 5 O 7 1 0 0 5 O 8th 1 0 0 5 1 0 ' 1 0 0 5 2 1 1 0 0

4 0 1

• 10 0

5 2 2

1 0 0

-84- Z59 78Z

Table 2 (cont'd)

Mortality of Green ri-Compound ce leafhopper (Nepho- No. tettix cincticeps (X)

5 8th 2 1 O O 5 8th 3 1 O O 6 O 5 1 O O 6 O 6 1 O O 6 O 7 1 O O. -6 O 8th 1 O O 6 O 9 1 O O 6 3 9 1 O Q 6 5 2 1 O O 6 5 3 1 O O 6 7 1 1 O O

Mortality of Green ri-Compound ce leafhopper (Nepho- No. tettix cincticeps (X)

6 7 3 1 O O 6 7 4 1 O O 6 7 5 1 O O 6 7 6 1 O O 6 7 7 1 O O 6 7 8th 1 O O. 6 8th 4 1 O 0 6 9 6 1 O 0 .7 3 8th 1 O 0 7 3 9 1 O 0 7 4 O 1 O 0

6 7 2

1 0 0

74 1

1 0 0

Mortality of Green Ri- Mortality of Green Ri-

Compound ce leafhopper (Nepho- compound ce leafhopper (Nepho No. tettix cincticeps) (%) No. tettix cincticeps) (X)

.7 5 O 1 O 0 7 5 1 1 .0 0 7 5 2 1 0 0 7 5 5 1 0 0 7 · 5 6 1 0 0

7 5 7 1 0 0 7 5 8th 1 0 0 7 7 0 1 0 0 7 7 1 1 0 Q 7 7 8th 1 0 0 known compound A ο

Table

Mortality of brown ri-compound ce planthopper ( NiIa -No. Parvata lugens) (%)

4 1 O O 2 8th 1 O O 3 4 1 O O 3 9 1 O O 7 9 1 O O 8th 1 1 O O 8th 2 1 O O 8th 4 1 O O 8th 8th 1 O O 1 O 9 1 O O υ 7 1 O O 1 7 1 1 O O

Mortality of brown ri-compound ce planthopper ( NiIa -No parvata lugens) (X)

2 5 6 1 O O 2 7 2 1 O O 2 7 3 1 O O 2 7 4 1 O O 3 4 O 1 O O 3 4 1 · 1 O O 3 6 1 1 O O 3 6 6 1 O O 3 7 O 1 O O 3 7 1 1 O O 3 7 6 1 O O 3 9 7 1 O O

Table 3 (cont'd)

Mortality of brown ri-compound ce planthopper ( NiIa -No parvata lugens) (X)

4 O 1 1 O ο · 4 1 2 1 O O 4 4 2 1 O O. 4 8th 1 1 O 0 δ O O 1 O 0 δ O 7 1 O 0 δ O 8th . 1 O 0 δ 2 1 1 O 0 δ 2 2 1 O 0 δ 8th 2 1 O 0 δ 8th 3 1 O 0 6 O δ 1 O 0

Mortality of brown ri-compound ce planthopper ( NiIa -No. Parvata lugens) (%)

6 0 7 1 0 0 6 0 8th 1 0 0 6 0 9 1 0 0 6 1 1 1 0 0 6 1 3 1 0 0 6 δ 2 1 0 0 6 δ 3 " 1 0 0 .6 7 2 1 0 0 6 7 4 1 0 ο. 6 7 δ 1 0 0 6 7 6 1 0 0 6 7 7 1 0 0

6 0 6

1 0 0 678

1 0 0

Table 3 (cont'd)

Mortality of brown ri-compound ce planthopper ( NiIa -No. Parvata lugens) (%)

6 8 4

7 3 9

1 OO

1 OO

Mortality of brown ri-compound ce planthopper ( NiIa -No. Parvata lugens) (%)

7 7 O A 1 O O 7 7 8th 1 O O known compound O

Table 4 Mortality (X) Compound No. 0 22 0 27 0 28     ο 29 0 36 0 38 , 0 39 0 49 0 82 0 89 0 109 • 0 · 170 ' 0 175 0 366

Table Compound No. 5 Mor ta 1 i ty (%) 27 0 33 0 97 0 170 0 172 0 le 6 tab

Compound No.

Chemical Formula

27

C £

OCH ₂

28

C £ -

OCH ₂

33

C & -

34

C l-

Br

• OCH2

> Br

-AU-

Table 6 (cont'd) Compound No.

Chemical Formula

C £ -

C Q.

OCH ₂

C £ -

ZS.

 0CH2

c &

br

C £

OCH ₂

170

-Q-

Table 6 (cont'd)

Compound No.

Chemical Formula

171

C £ -

/ Br

OCHj

172

C £ -

F · 0

C &

-OCH ₂

256

C £ -

Br

OCH ₂

C £

272

C £ -

C £

OCH ₂

Table 6 (cont'd)

Compound No.

Chemical Formula

273

C £ -

C £

OCH ₂

274

C £ - -

Br

OCH ₂

340

C £

C £

OCH ₂

341 Ci

• Br

OCH ₂

Table 6 (cont'd )

Compound N'o.

360

Chemical Formula

OCHj

366

br

C B.

OCH ₂

C Ά

371

br

N N

br

OCH ₂

376

OCH ₂

Table 6 (cont'd)

Compound No.

Chemical Formula

393 NO:

br

-OCH ₂

397

NO ₂ -

OCH

C £

401

458

C £ - OCH ₂

br

OCH ₂

Z &

Table 6 (cont'd)

compound No. C H C £ - 499

500

503 507

C ζ

C S, Chemical Formula

C £

OCH ₂

br

ZS.

OCH ₂

C &

Table 6 (cont'd) Compound No.

Chemical Formula

508

OCH;

510

521

P

c a OCH ₂

522

OCH ₂

Table 6 (cont'd)

Compound No.

Chemical Formula

582

583

Z £

C £

OCH ₂

605

OCH ₂

606

, Br

C £

OCH ₂

-9Ö- <£ D »

Table 6 (cont'd) Compound No. Chemical Formula

C &

C £

OCH ₂

OCH,

OCH ₂

Table 6 (cont'd)

Compound No.

Chemical Formula

652

C £ OCH ₂

653

-OCH ₂

C £

696

OCH ₂

750

Compound No.

Table 6 (Cont'd) Chemical Formula

OCH ₂

Claims (5)

Claim: An insecticidal composition, characterized in that it contains as active ingredient an effective amount of at least one of the 3 (2H) -pyridazinone derivatives of the formula (I) contains, in which X is a halogen, an alkyl of 1 to 6 carbon atoms, a haloalkyl of 1 to 4 Carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, a nitro group, an alkoxy group having 1 to 4 carbon atoms or - C - 0 - R represents,. (where R is alkyl of 1 to 4 carbon atoms);
η is an integer of 1 to 4;
A is hydrogen, a halogen, an alkyl having 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms; B represents FUrCX ₁ (wherein XI represents hydrogen or a halogen) or nitrogen;
R ¹ and R ^{2 are} each independently hydrogen or an alkyl 1 to 4 carbon atoms;
E is hydrogen, a halogen, an alkoxy group of 1 to 4 carbon atoms or hydroxyl represents and
Q represents the following: -C " in the jm vr. Ti ΪΙ Ym "f or ^v 0 (wherein Y represents a halogen, an alkyl of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a haloalkyl of 1 to 4 carbon atoms, a haloalkoxy group of 1 to 4 carbon atoms, a cyano group, or the like) έ, ΌΖΙ / Ο £. C O CH; or (wherein Z represents halogen, an alkyl of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms or a haloalkyl of 4 to 4 carbon atoms, and / 0 or an integer of 1 to 5, where Z is the same or different when the integer is from 2 to 4 5); and m is an integer of 1 to 5, wherein Y may be the same or different (when m is an integer of 2 to 5), where X may be the same or different when η is an integer of 2 to 5 , together with a suitable vehicle and an aid. Composition according to Claim 1, characterized in that the compound is represented by the formula (IA): O ^ wherein E represents hydrogen, chlorine or a methoxy group; A represents hydrogen, chlorine, bromine or methyl; B is nitrogen or CX-I (wherein Xi is hydrogen or a halogen); X represents a halogen, an alkyl of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, NO ₂ , a haloalkoxy group of 1 to 4 carbon atoms or CO ₂ R (wherein R represents an alkyl of one to four carbon atoms); η is an integer of 1 to 4; - Q stands for Ym Ym Ym Ym Π -Ν or ° Ym Y represents a halogen, an alkyl of 1 to 4 carbon atoms, a haloalkyl of 1 to 3 carbon atoms, a haloalkoxy group of 1 to 3 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, and rh is an integer of 1 to 5, wherein X is the same or different when η is 2 to 4, and. Y is the same or different when m is 2 to 5. 3. Composition according to claim 1, characterized in that the compound is represented by the formula (IB): (IB) OCH, E represents hydrogen; A represents hydrogen, chlorine or bromine; X _{2 represents} hydrogen, a halogen or NO ₂ ; X ₃ and X _{4 are} each independently hydrogen, a halogen, an alkyl with 1 to 3 carbon atoms or NO ₂ ; Q represents the following: Ym'm. Ym or Y represents a halogen or haloalkyl of 1 to 3 carbon atoms and m is an integer ί or 2, where Y is the same or different when m is 2. 4. The composition according to claim 1, characterized in that the compound is represented by the formula (IC): DCH (IC) wherein E represents hydrogen; A represents chlorine or bromine; X _{5 represents} hydrogen, a halogen or NO ₂ ; X _{6 represents} hydrogen, a halogen or NO ₂ ; Q represents the following: Y _{1 represents} a halogen and Y _{2 represents} hydrogen or a halogen. 5. A method for controlling noxious insects, characterized in that an insecticidally effective amount of a 3 (2 H) -pyridazinone derivative having the formula (!) According to claim 1 is applied. 6. Process for the preparation of a 3 (2H) -pyridazinone derivative of the formula (I) according to item 1, characterized in that a compound of the formula (II) Xn (M) is reacted with a compound of formula (III) (III) R ² wherein R ¹ , R ₂ , A, B, E, X, Q and η are as defined in item 1 and X 'and X "represent a halogen or OM (wherein is hydrogen or an alkali metal), provided that X" OM represents when X 'is a halogen and X "represents a halogen when X'OM is. Field of application of the invention This invention relates to insecticidal compositions containing novel 3 (2H) -pyridazinone derivatives, to a method of controlling pest insects using the compositions of the present invention, and to a method of the novel 3 (2H) -pyridazinone derivatives used as the active ingredient. Characteristic of the known state of the art The authors have already stated earlier that some of the compounds having the general formula (IV) mentioned below have insecticidal, acaricidal, nematicidal and fungicidal activity in agricultural and horticultural use (see EP-OS No. 0088384): Y'ra '