CS252469B2 - Method of 1-(alkylphenoxyaryl)-3-benzoyl ureas production - Google Patents

Abstract

A novel process for the preparation of 1- (alkylphenoxyphenyl) -3-benzoylurea is disclosed. New urea are useful as insecticidal active ingredients means.

Description

The present invention generally relates to a novel process for the preparation of 1- (alkylphenoxyaryl) -3-benzoylureas.

Prior to this invention, several benzoylureas having a pesticidal effect have been described in the patent literature. For example, U.S. Patent No. 3,992,553, issued November 16, 1976, and U.S. Patent No. 4,041,177, issued August 9, 1977, disclose certain benzoylureidodiphenyl ethers which have been found to have insecticidal properties.

Similarly, U.S. Patent Nos. 3,748,356 and 3,933,908 also disclose certain substituted benzoylureas and disclose that the compositions have potent insecticidal activity. U.S. Pat. No. 4,148,902, issued April 10, 1979, mentions substituted (phenylamino) carbonyl pyridine carboxamides and protects the method of controlling insects and, moreover, the composition of the composition itself.

Further details of the benzoylureas in the patent literature can be found in U.S. Patent Nos. 4,166,124, 4,083,977, 4,160,834, 4,264,605, 4,064,267, 4,005,223, 4,1 123,449, 4,068,002,

194,005, 4,275,077, 4,173,639, 3,989,842 and German DOS 29 01 334 (EP 013-414) and DE 31 04 407 (EP 57-888).

In carrying out the invention, the following object of the invention can be achieved, which is a novel process for the production of new 1- (alkylphenoxyaryl) -3-benzoylureas.

Broadly, the present invention relates to a novel process for the preparation of 1- (alkylphenoxyaryl) -3-benzoylurea.

The benzoyl ureas obtainable according to the invention can be represented by the general formula I

where

X and X 'are independently from each other hydrogen, halogen, alkyl, haloalkyl, polyhaloalkyl, alkoxy or polyhaloalkoxy, wherein the alkyl moiety of each group contains 1 to 4 carbon atoms;

Y is oxygen or sulfur, and man is 0 to 4,

R1 is hydrogen, halogen, alkyl, haloalkyl, polyhaloalkyl or alkoxy, wherein the alkyl moiety of each group contains 1 to 4 carbon atoms, is hydrogen, halogen, alkyl, polyhaloalkyl, polyhaloalkoxy, wherein the alkyl moiety of each group contains 1 to 4 carbon atoms, alkylsulfonyl , alkoxy, alkylthio, dialkylamino, wherein the alkyl moiety of each group contains 1 to 8 carbon atoms, CN, NO 2, CC (R 4), CONHR (4), wherein R 4 is alkyl of 1 to 8 carbon atoms,

R 1 is C 1 -C 12 alkyl, provided that m cannot be 0 or 1 when n is less than 2.

As mentioned above, the invention relates to a novel process for the preparation of 1- (alkylphenoxyaryl) -3-benzoyl ureas which find use in insecticidal compositions.

Preferred benzoylurea derivatives within the scope of formula I are compounds of formulas II to IV

ΝΗ ' ^χϋχ ΝΗ

(ΐϊ),

where

X, X ', Y, R, R 2' ^R 3 ^{'to R a is as} defined above it.

Particularly preferred benzoylureas are compounds of formulas V to VIII

ΝΗ χ '

Υ

Λ

(VII),

where

X, X, Υ, R1, R1 and R1 are as defined above.

The following benzoylurea derivatives are illustrative of the compounds included in the above formulas, which can be prepared by the process of the present invention:

1- [4- (2-methyl-3,4-dichlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea.

1- [4- (2-methyl-3,4-dichlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) (urea)

1- [4- (2-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-dichlorobenzoyl) urea,

1- [4- (2-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (2-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (2-methylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-dimethylbenzoyl) urea,

1- / 4- (2-methylphenoxy) -2,3,5,6-tetramethylphenyl) -3- (2,6-methylbenzoyl) thiourea,

1- [4- (2-methylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea

1- [4- (2-methylphenoxy) 2,3,5,6-tetramethylphenyl] -3- (2,6-dichlorobenzoyl) urea,

1- [4- (2-methylphenoxy) -2,3,5-trimethylphenyl] -3- (2,6-dichlorobenzoyl) urea,

1- [4- (2-methylphenoxy) -3,5-dichlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-bromophenoxy) -3,3-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-Methyl-4-bromophenoxy) -3,6-diethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-Methyl-4-bromophenoxy) -3, 1'-tert-thiyl-5-chlorophenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (2-methyl-4-bromo-phenoxy) -1H-n-methyl-5-chlorophenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (2-methyl-4-bromophenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-bronphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-bromophenoxy) -3,5-dimethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-bromophenoxy) -3,5-dichlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-bromo-4-methylphenoxy) -3,6-diethyl-5-chlorophenyl] -3- (2,6-dichlorobenzoyl) urea,

1- [4- (2-bromo-4-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-bromo-4-methylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-bromo-4-methylphenoxy) -3,5-dichlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-bromo-4-methylphenoxy) -3,5-dimethylphenyl] -3- (2-methylbenzoyl) thiourea,

1- / 4- (2-methyl-4-tert-butylphenoxy) -3,6-dimethyl-5-chlorophenyl) -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-tert-butylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-methyl-4-tert-butylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-tert-butylphenoxy) -3,5-dichlorophenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (2-methyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-chlorophenoxy) -3,5-dichlorophenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (2-methyl-4-chlorophenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-dimethoxybenzoyl) urea,

1- / 4- (4-nonylphenoxy) -3,6-dimethyl-5-chlorophenyl) -3- (2,6-difluorobenzoyl) urea,

1- [4- (4-nonylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (4-nonylphenoxy) -3,5-dichlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (4-nonylphenoxy) -3,5-dimethylphenyl] -3- (2-methylbenzoyl) urea,

1- [4- (2-chloro-4-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-chloro-4-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (2-chloro-4-methylphenoxy) -3,5-dichlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-chloro-4-methylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (3,4,5-trimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (3,4,5-trimethylphenoxy) [3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (3,4,5-trimethylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (3,4,5-trimethylphenoxy) -3,5-dichlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,3,5-trimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-dimethoxybenzoyl) urea,

1- [4- (2,3,5-trimethylphenoxy) -2,3,5,6-tetramethylphenyl] -3- (2,6-difluorobenzoyl (urea,

1- [4- (2,3,5-trimethylphenoxy) -3-isopropylphenyl] -3- (2-methylbenzoyl) thiourea,

1- [4- (2,3,5-trimethylphenoxy) -3-trifluoromethylphenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-trifluoromethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-trifluoromethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) thiourea,

1- [4- (2-methyl-4-trifluoromethylphenoxy) -3,5-dichlorophenyl] -3- (2,6-dimethoxybenzoyl) (urea,

1- [4- (2-methyl-4-trifluoromethylphenoxy) -2,3,5-trimethylphenyl] -3- (2-methylbenzoyl) thiourea,

1- / 4- (2,4-dimethylphenoxy) -2,3,6-trimethylphenyl] -3- (2-chlorobenzoyl (urea,

1- / 4- (3,5-dimethylphenoxy) -2,6-dimethylphenyl] -3- (2,6-difluorobenzoyl (urea,

1- [4- (2-methyl-4-methoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl (urea,

1- [4- (2-methyl-4-dimethylaminophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-methylthiophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-methylsulfonylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- / 4- (2-methyl-4-dimethylaminophenoxy, -3,5-dimethylphenyl) -3- (2-methylbenzoyl)

1- [4- (2-methyl-4-methoxyphenoxy) -3-chloro-6-methylphenyl] -3- (2-methylbenzoyl) urea,

1- [4- (2-methyl-4-methoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (3,4-dichloro * benzoyl) urea,

1- [4- (2,3-dimethyl-4-bromophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-ethoxycarbonylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-ethoxycarbonylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-methyl-4-trifluoromethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-trifluoromethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-trifluoromethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-trifluoromethoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-trifluoromethoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-methoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-methoxyphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (3,5-dimethyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,4,5-trimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,4,5-trimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-bromophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-cyanophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,5-dimethyl-4-cyanophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2-methyl-4-cyanophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4-cyanophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- [4- (2,4-dimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2,4-dimethylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) urea,

1- / 4- (2,5-dichloro-4-methylphenoxy) -3,6-dimethyl-5-chlorophenyl (-3- (2,6-difluorobenzoyl) urea),

1- [4- (2,5-dichloro-4-methylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2-chlorobenzoyl) (urea,

1- [4- (2-methyl-4,5-dichlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea,

1- [4- (2-methyl-4,5-dichlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2'-chlorobenzoyl (urea,

1- [4- (2,5-dimethyl-4-chlorophenoxy) -3-methylphenyl] -3- (2,6-difluorobenzoyl) urea and the like.

The novel benzoylureas of the present invention can be conveniently prepared by the method described below.

The novel compounds can be prepared by reacting an alkylphenoxyphenylisocyanate of formula XII with a benzamide of formula XI according to Scheme I.

Scheme I

(I) where

X, X, Y, R 1, R ₂ , R 1, m and n are as defined in formula (I).

In general, the reaction illustrated in Scheme I may be carried out in organic solvents such as aromatic hydrocarbons, halogenated hydrocarbons and the like. Solvents such as toluene and 1,2-dichloroethane are preferred. These reactions take place at temperatures ranging from room temperature to 150 ° C.

The intermediates shown in Scheme I may be prepared according to generally acceptable procedures.

AND

Aniline can be prepared according to Scheme II below.

Scheme II

0 ₂ N

O

Cl

(IX) where

R 1, R 2, R 1, m, and n are as defined in formula (I).

The reaction of a substituted chloronitrobenzene of formula XIII with a substituted phenol of formula XXV takes place in the presence of a base at elevated temperature to give a substituted nitroether of formula XV. The reduction of the nitroether of formula XV to the aniline of formula IX can be achieved under a hydrogen atmosphere using a heterogeneous hydrogenation catalyst. Suitable catalysts include platinum or palladium on carbon or Raney nickel.

Pressure ranging from 14 to 689 kPa may be used at room temperature. Suitable solvents include an aromatic hydrocarbon or alcohol. The reduction of the nitroether of formula XV to the aniline of formula IX can also be achieved by a chemical method using the procedure of E. Enders et al. in British Patent No. 1,456,964.

Intermediates such as substituted chloronitrobenzene and substituted phenol are commercially available or can be prepared by a method well known in the chemical literature.

The specific chloronitrobenzene of formula XVI is prepared as outlined in the scheme

III.

Scheme III

(XVI)

Aniline can be converted to the isocyanate or isothiocyanate of formula (XI) by reaction with phosgene or thiophosgene as shown below:

where

Y, R 1, R 2, R ₃ , m and n are as defined in formula I.

The compounds encompassed by this invention can be used as insecticides by methods known to those skilled in the art. Insecticidal compositions containing the compounds as active ingredient will usually contain a carrier and / or diluent, either in a liquid or solid state. '

Suitable liquid diluents or carriers include water, petroleum distillates or other liquid carriers, with or without a surfactant. Liquid concentrates may be prepared by diluting one of these compounds with a non-phytotoxic solvent, such as acetone, xylene, nitrobenzene, oyclohexanone or dimethylformamide, and dispersing the active ingredient in water with suitable surfactant emulsifiers and dispersants.

The choice of dispersing or emulsifying agent and the amount used will depend on the nature of the agent and the ability of the agent to facilitate dispersion of the active agent. Usually, it is desirable to use as little dispersing or emulsifying agent as possible to provide the desired dispersion of the active ingredient in the spray so that rain cannot re-emulsify the active ingredient after it has been applied to and washed out of the plant.

Nonionic, anionic or cationic dispersing or emulsifying agents can be used, such as the condensation products of alkylene oxide with phenol or organic acids, alkylarylsulfonates, complex ether-alcohols, quaternary ammonium compounds and the like.

In preparing a wettable powder, dust or granular composition, the active ingredient is dispersed in and appropriately comminuted in a solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth and the like.

In the preparation of wettable powders, the above-mentioned dispersants as well as lignin sulfonates may be present.

The required amount of active ingredient in the composition may be used per hectare to be treated in the form of from 11.2 to 22,460 liters or more of liquid carrier and / or diluent or in the form of about 5.6 to 560 kg of inert solid carrier and / or diluent. Concentrations in liquid concentrates will typically vary from about 10 to about 95 weight percent and in solid compositions will range from about 10 to about 95 weight percent.

0.5 to 90% by weight.

Satisfactory sprays, dusts or granules for normal use contain from about 0.26 to 16.8 kg active ingredient per hectare.

The insecticides included herein protect from the insect attack the plants or other material that have been used. These insecticides have a relatively high residual toxicity. With regard to plants, they have a high margin of safety when used in sufficient quantities to kill or repel insects, do not burn or damage plants, and withstand weather conditions, including rainwash, ultraviolet degradation, oxidation or hydrolysis in the presence or at least such degradation , oxidation and hydrolysis, which would materially reduce the desired pesticidal properties of the active ingredients or cause undesirable properties, for example phytotoxicity, of the active ingredients.

The active ingredients are chemically so inert that they are wettable with substantially all of the other components of the spray compositions and can be applied to the soil after sowing or to the roots of the plants without damaging the seeds or the roots of the plants. Mixtures of the active compounds may be used, if desired, as well as combinations of the active compounds of the invention with other biologically active compounds or additives.

The following examples illustrate the best embodiment of the invention.

Example 1

A process for the preparation of 3-chloro-2,5-dimethyl-4- (2,4-dimethylphenoxy) phenyl isocyanate

A 1 liter 3-neck round bottom flask equipped with a thermometer, an additional pressure equalization funnel, a dry ice condenser and a nitrogen and gas discharge tube is charged with a 12.5% solution of phosgene in toluene (198 mL, 21.4 g, 216.3 mmol phosgene).

The reaction vessel was cooled to 0 ° C and a solution of 3-chloro-2,5-dimethyl-4- (2,4-dimethylphenoxy) aniline (20.0 g, 72.5 mmol) in toluene (30 ml) was added dropwise over 30 minutes. 200 ml). The resulting heterogeneous mixture was allowed to warm to room temperature and then refluxed for 3 hours. During this time, the reaction medium becomes homogeneous.

The reaction mixture is then purified of excess phosgene. The solution was then allowed to cool and evaporated under reduced pressure. Obtained as a slightly off-white solid. Distillation at a boiling point of 138-155 ° C at 0.2 mm Hg affords pure isocyanate 9 (21.8 g, 72.2 mmol,

63-66 ° C as a waxy white solid.

Example2

1- (4- (2,4-Dimethylphenoxy) -3-chloro-2,5-dimethylphenyl) -3- (2,6-difluorobenzoyl) urea

3-Chloro-2,5-dimethyl-4- (2,4-dimethylphenoxy) phenyl isocyanate (3.84 g, 12.73 mmol) was added to a suspension of 2,6-difluorobenzamide (2.00 g, 12.73). mmol) in toluene (25 mL) at room temperature. The mixture was then heated at reflux for 17 hours. During this time, the amide dissolves. The reaction vessel was then cooled and the solvent was evaporated under reduced pressure. This gives crude urea as a white powder in a yield of 89%.

Examples 3 to 216

In a similar manner to that used in the previous examples, other urea derivatives were prepared using one of the synthetic schemes described above. The identity of the substituents in the general formula and the analytical data are given in the following Table I.

1- (alkylphenoxyaryl) -3-benzoylurea of the formula

Table I

Example Formula

1 ^C 22 ^H 26 ^Cl 2 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,5-Cl _2-CH3 4-CH3 2 ^C 22 ^H 17 ^Cl 3 ^N 2 ° 3 2-C1 0 3,5-Cl _{2-CH3 4-CH3} 3 ^C 22 ^H 16 ^C 4 ^N 2 ° 3 2,6-Cl ₂ 0 3,5-Cl _2-CH3 4-CH3 4 ^C 24 ^H 22 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,5- _{(CH3) 2} 2-CH3 _4-CH3 5 ^C 24 ^H 22 ^ClFN 2 ° 3 2,6-ClF 0 3,5- _{(CH3) 2 2-CH3 4-CH3} 6- ^C 24 ^H 23 ^C 1 ^N 2 ° 3 2-C1 0 3,5- _{(CH3) 2 2-CH3} 4-CH3 7 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 2,6-Cl ₂ 0 3,5- _{(CH3) 2} 2-CH3 _4-CH2 8 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 2-C1 0 3,5,6-CH ₃ ClCH ₃ 2-CH3 4-CH3 9 ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,5,6-CH ₃ ClCH ₃ 2-CH3 4-CH3 10 ^C 24 ^H 21 ^C 2 ^FN 2 ° 3 2,6-ClF 0 3,5,6-CH ₃ ClCH ₃ 2-CH3 4-CH3 11 ^C 24 ^H 21 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,5,6-CH ₃ ClCH ₃ 2-CH 2 _4-CH3 12 ^C 22 ^H 15 ^C 5 ^N 2 ° 3 2-C1 0 3,5-Cl ₂ 2.3 4-CH ₃ ClCl 5-CH3 13 ^C 22 ^H 14 ^C 6 ^N 2 ° 3 2,6-Cl ₂ 0 3,5-Cl ₂ 2.3 4-CH ₃ ClCl 5-GHIj 14 ^C 22 ^H 14 ^C 5 ^FN 2 ° 3 2,6-ClF 0 3,5-Cl ₂ 2.3 , 4-CH 3 Cl 2 _5-CH3 15 Dec ^C 22 ^H 14 ^C 4 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,5-Cl ₂ 2.3 4-CH ₃ ClCl _5-CH3 16 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 2 ^N 2-C1 with 3,5,6-CH ₃ ClCH ₃ 2-CH3 4-CH3 17 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 2-C1 0 3,5,6-CH ₃ ClCH ₃ 3-CH ₃ 5-CH 3 18 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 2 ^N 2-C1 with 3,6- (CH ₃ ) ₂ -5-Cl 3-CH3 5-CH3 19 Dec ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 3-CH _{3 5-CH3} 20 May ^C 24 ^H 21 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 3-CH ₃ 5-CH3 21 ^C 26 ^H 26 ^Cl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl H 4-tero -butyl 22nd ^C 26 ^H 26 ^C 2 ^N 2 ° 2 ^N 2-C1 with 3,6- (CH ₃ ) ₂ -5-Cl H 4-tert -butyl

continuation of Table 1

Example Formula XX ' Y ^R 1 ^R 2 ^R 3 23 C ^ _C H _Cl N _{oc of} 26 0_ 25 325 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H 4-tert. -butyl 24 ^C 26 ^H 25 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- _{(CH3) 2} ~ 5-Cl H 4-terc, -butyl 25 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl H _4-CH3 26 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH 3) ₂ -5-Cl H _4-CH3 27 Mar: ^C 23 ^H 19 ^Cl 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H 4-C ^H 3 28 ^C 23 ^H 19 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H _4-CH3 29 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl H 2- _C H ₃ 30 ^C 23 ^H 19 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- _{(CH3) 2} ~ 5-Cl H _2-CH3 31 ^C 23 ^H 20 ^C 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl H _2-CH3 32 ^C 23 ^H 19 ^C 3 ^N 2 ^P 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H 2-CH3 33 ^C 23 ^H 19 ^BrC 1 ^L 2 ^N 2 ^O 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br _2-CH3 34 ^C 23 ^H 19 ^BrClFN 2 ° 2 ^N 2-F with 3,6- (GH 3) ₂ 5-Cl 4-Br _2-CH3 35 ^C 23 ^H 18 ^BrCl 3 ^N 2 ° 2 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br _2-CH3 36 ^C 23 ^H 19 ^BrCl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl 4-Br 2-CHij 37 ^C 23 ^H 18 ^BrClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br _2-CH3 38 ^C 23 ^H 19 ^BrCl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH 3) ₂ -5-Cl 2-Br 4-CH3 39 ^C 23 ^H 18 ^BrCl 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Br _4-CH3 40 ^C 23 ^H 18 ^BrClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Br _4-CH3 41 ^C 23 ^H 19 ^BrCl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH 3) ₂ -5-Cl 2-Br _4-CH3 42 ^C 23 ^H 19 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 4-C1 2-CH 2 43 ^C 23 ^H 18 ^C 4 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-C1 2-CH 2 44 ^C 23 ^H 18 ^Cl 2 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-C1 2-CH3 45 ^C 23 ^H 19 ^C1 3®2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl 4-C1 _2-CH3 46 ^C 23 ^H 19 ^Cl 3 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl 4-CH3 47 ^C 23 ^H 18 ^C 4 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl _4-CH3

continuation of Table

Example Formula XX ' Y ^R 1 ^R 2 ^R 3 48 ^C 23 ^H 18 ^Cl 2 ^F 2 ^N 2 ° 3 2,6-1 ·., 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl 4-CH 3 49 ^C 23 ^H 19 ^C 3 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl _4-CH3 50 ^C 31 ^H 36 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl H 4-n-OgHg 51 ^C 31 ^H 35 ^Cl 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H ^4_n “ ^C 9 ^H 19 52 ’ ^C 31 ^H 36 ^Cl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl H 4-nC _{19 g of} H 53 ^C 25 ^H 25 ^C1N 2 ^S 2 ° _2-CH3 with 3,6- (CH ₃ ) ₂ -5-Cl _{2-CH3 4-CH3} 54 ^C 24 ^H 22 ^C1FN 2 ^O i> ^S 2-F with 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 4-CH 3 55 ^C 31 ^H 35 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H 4-n-CgHjg 56 ^C 27 ^H 28 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH 2 4-terc.- -butyl 57 ^C 27 ^H 27 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH _3, 4-ťerc.- -butyl 58 ^C 27 ^H 28 ^C 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 4-terc.- -butyl 59 ^C 27 ^H 28 ^C 1 ^FN 2 ° 2 ^N 2-F with 3,6- (CH ₃ ) ₂ -5-Cl 2-CH 2 4-terc.- -butyl 60 ^C 25 ^H 24 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 2,3- (CH ₃₎ 2 5-CH 3 61 ^C 25 ^H 23 ^Cl 3 ^N 2 ° 3 2,6-Clj 0 3,6- (CH ₃ ) ₂ -5-Cl 2,3- (CH ₃₎ 2 5-CH3 62 ^C 25 ^H 23 ^C1 2 ™ 2 ⁰ 3 2,6-ClF 0 3,6- (CH ₃ ) ₂ -5-Cl 2,3- (CH ₃₎ 2 5-CH 3 63 ^C 25 ^H 23 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2,3- (CH ₃₎ Jž · ’ _5-CH3 64 ^C 25 ^H 24 ^C 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ ) ₂ -5-Cl 2,3- (CH 3) 2 5-CH3 65 ^C 25 ^H 24 ^ClFN 2 ° 2 ^N 2-F with 3,6- _(CH3) J-5-Cl 2,3- (CH ₃₎ 2 _5-CH3 66 ^C 26 ^H 27 ^C1N 2 ^S 2 ° _2-CH3 with 3,6- (CH 2 -5-Cl 2,3- (CH 3) 2 5-CH3 67 ^C 25 ^H 24 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH 3) ₂ -5-Cl 3,4- (CH 3) 2 5-CH3 68 ^C 25 ^H 23 ^Cl 3 ^N 2 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 3,4- (GH 2) 2 _5-CH3 69 ^C 25 ^H 23 ^C 2 ^FN 2 ° 3 2,6-ClF 0 3,6- (CH ₃ ) ₂ -5-Cl 3,4- (CH ₃₎ 2 _5-CH3 70 ^C 25 ^H 23 ^Cl 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 3,4- (CH 3) 2 5-CH 3 71 ^C 25 ^H 24 ^C 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH ₃ , ₂ -5-Cl 3,4- (CH ₃₎ 2 _5-CH3

continuation of Table

Example Formula XX ' Y ^R 1 r ₂ ^R 3 72 ^C 25 ^H 24 ^ClFN 2 ° 2 ^N 2-F with 3,6- (CH ₃ ) ₂ -5-Cl 3,4- _{(CH3) 2 5-CH3} 73 ^C 26 ^H 27 ^C1N 2 ^S 2 ° 2- ^ch 3 with 3,6- (CH ₃ ) ₂ -5-Cl 3,4- _{(CH3) 2 5-CH3} 74 ^C 25 ^H 24 ^Cl 2 ^N 2 ° 3 2-6 0 3,6- (CH ₃ ) ₂ -5-Cl H 2-C ₃ H ₇ 75 ^C 25 ^H 23 ^ClF 2 ^N 2 ° 3 2,6- ^ 0 3,6- (CH ₃ ) ₂ -5-Cl H 2-C 3 -C 7 76 ^C 25 ^H 25 ^C1N 2 ° 3 _2-CH3 0 3,6- (CH ₃ ) ₂ -5-Cl _{2-CH3 4-CH3} 77 ^C 24 ^H 12 ° ^C ™ 2 ° 3 2-F 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH3 4-CH3 78 ^C 25 ^H 26 ^N 2 ° 3 2-C ^H 3 0 3,5- _{(CH3) 2 2-CH3} 4-C ^H 3 79 ^C 25 ^H 26 ^N 2 ° 2 ^N 2-CT3 0 3,5- _{(CH3) 2} ^2-CH3 _4-CH3 80 ^C 24 ^H 23 ^FN 2 ° 3 2-F 0 3,5- _{(CH3) 2 2-CH3 4-CH3} 81 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 4 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 2tO6H _{3 4-CH3} 82 ^C 24 ^H 21 ^C 3 ^N 2 ° 4 2,6-Cl ₂ 0 3,6- (CH ₃ ) -5-Cl 2-OCH ₃ 4-CH3 83 ^C 24 ^H 21 ^C 2 ^FN 2 ° 4 2,6-ClF 0 3,6- _{(CH3) 2} 2-OCH _{3 4-CH3} 84 ^C 24 ^H 21 ^ClF 2 ^H 2 ° 4 2,6-F ₂ 0 3,6- _{(CH3) 2} 2-OCH _{3 4-CH3} 85 ^C 25 ^H 25 ^C1N 2 ° 4 2-CHij 0 3,6- _{(CH3) 2} 2-OCH _{3 4-CH3} 86 ^C 24 ^C 22 ^C1FN 2 ° 3 ^N 2-F with 3,6- _{(CH3) 2} 2-OCH ₃ 4-C ^H 3 87 ^C 24 ^H 23 ^C 1 ^N 2 ° 2 ^N 2-Cl with 3,5- _{(CH3) 2} 2-CH3 _4-CH3 88 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 ^N 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl 4tSCH ₃ 3-CH ₃ 89 ^C 24 ^H 21 ^C1F 2 ^N 2 ° 3 ^N 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-SCH ₃ 3-CH3 90 ^C 26 ^H 27 ^C1 2 ¹⁴ 3 ^O 3 2-Cl 0 3,6- (CH 3) ₂ -5-Cl _3-CH3, 4-N _(CH3) ^l 2 ^5-ch 3 91 ^C 26 ^H 26 ^C1F 2 ^N ° 3 3 2,6- ^f 2 0 3,6- (CH ₃ ) ₂ -5-Cl 3-CH ₃ , 4-N (CH ₃ ) 2 ^{5 CH} 3 92 ^C 26 ^H 26 ^C 3 ^N 3 ° 3 2,6-Cl ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl N _{(CH3) 2 5-CH3} 93 ^C 26 ^H 26 ^C 2 ^FN 3 ° 3 2,6-ClF 0 3,6- (CH ₃ ) ₂ -5-Cl N _{(CH3) 2 5-CH3} 94 ^C 26 ^H 27 ^ClFN 3 ° 3 2-F 0 3,6- (CH ₃ ) ₂ -5-Cl N _{(CH3) 2 5-CH3} 95 ^C 27 ^H 30 ^C 1 ^N 3 ° 3 2-CH3 0 3,6- (CH ₃ ) ₂ -5-Cl ^N < ^CH3 > 2 _5-CH3 96 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-Cl 0 2-CH ₃ ~ 5-Cl _{2-CH3 4-CH3} 97 ^C 23 ^H 19 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0- 2-CH ₃ '5-Cl 2-CH3 _4-CH3

continuation of Table

Example Formula XX ' Ϊ ^R 1 ^R 2 ^R 3 98 ^C 22 ^H 17 ^BrCl 2 ^N 2 ° 3 2-Cl 0 2-CH ₃ -5-Cl 4-Br _2-CH3 99 ^ '22 ^B 16 ^{Br < 'F} ^ 2 ^ 2 ° 3 2,6-F., 0 C-CH ₃ -5-Cl 4-Br _2-CH3 100 ALIGN! ^C 23 ^H 20 ^BrClN 2 ° 3 2-Cl 0 3-CH ₃ 2-CH ₃ -4-Br _6-CH3 101 ^C 23 ^H 19 ^BrF 2 ^N 2 ° 3 2,6-P ₂ 0 3- ^CH 3 2-CH ₃ 4 -Br 6-CH3 102 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-CH 2 0 2-CH ₃ -5-Cl 4-C1 2-CH3 103 ^C 24 ^H 23 ^C 1 ^N 2 ° 3 _2-CH3 0 2-CH ₃ -5-Cl _{4-CH3 2-CH3} 104 ^C 23 ^H 20 ^ClFN 2 ° 3 2-F 0 2-CH ₃ ~ 5-Cl _{4-CH3 2-CH3} 105 ^C 22 ^H 17 ^Cl 3 ^FN 2 ° 3 2-F 0 2-CH ₃ -5-Cl 4-C1 _2-CH3 106 ^C 23 ^H 20 ^BrFN 2 ° 3 2-F 0 3-CH ₃ 4- -Br-6-CH3 _2-CH3 107 ^C 24 ^H 23 ^BrN 2 ° 3 2-CH 2 0 3-CH ₃ 4- _{Br-6-CH3 2-CH3} 108 C ₂₂ H ₁₇ BrClPN ₂ O ₃ 2-F 0 2-CH ₃ -5-Cl 4-Br- 2-CH3 109 ^C 23 ^H 20 ^BrClN 2 ° 3 _2-CH3 0 2-CH ₃ -5-Cl 4-Br _2-CH3 110 ^C 23 ^H 20 ^BrClN 2 ° 3 2-Cl 0 3,5- _{<CH3) 2} 4-Br _2-CH3 111 ^C 23 ^H 20 ^BrFN 2 ° 3 2-F 0 3,5- _{(CH3) 2} 4-Br _2-CH3 112 ^C 23 ^H 19 ^BrClFN 2 ° 3 2-C 1-6 -F 0 3,5- _{(CH3) 2} 4-Br 2-CH3 113 ^C 23 ^H 19 ^BrF 2 ^N 2 ° 3 2,6-F ₂ 0 3,5- _{(CH3) 2} 4-Br _2-CH3 114 ^C 23 ^H 19 ^BrClFN 2 ° 3 2,6-ClF 0 2,5- _{(CH3) 2} 4-Br 2-CH3 115 ^C 23 ^H 18 ^BrF 2 ^N 2 ° 3 2,6-F ₂ 0 2,5- _{(CH3) 2} 4-br _2-CH3 116 ^C 23 ^H 20 ^BrClN 2 ° 3 2-Cl 0 2,5- _{(CH3) 2} 4-Br _2-CH3 117 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-Cl 0 2,5- _{(CH3) 2} 2-Cl 4-CH 3 118 ^C 23 ^H 20 ^ClFN 2 ° 3 2-F 0 2,5- _{(CH3) 2} 2-Cl _4-CH3 119 ^C 24 ^H 23 ^C 1 ^N 2 ° 3 2- ^CH ii 0 2,5- _{(CH3) 2} 2-Cl 4-CH 3 120 ^C 24 ^H 23 ^C 1 ^N 2 ° 3 H ₂ 0 3,6- _(CH3) ^2-5-C1 _{2-CH3 4-CH3} 121 ^C 23 ^H 20 ^BrClN 2 ° 3 "and 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br 2-CB ₃ 122 ^C 24 ^H 22 ^ClFN 2 ° 3 2-F 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 5-CH3 123 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 2-Cl 0 3,6- (CH ₃ ) ₂ -5-Cl _{2-CH3 5-CH3}

continued thrust

An example of formula XX 'Y R ^ R ^

124 ^C 24 ^Ií 21 ^í - ' ^ÍJ ''?\'% 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 5-CH3 125 C ,, U _{r, ir} ( '] W ^ () ₂₅ 25 23 _2-CH3 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH3 _5-CH3 1 26 t * 2 6 2 6 2 2 3 2-C1 0 2-CH ₃ -5-Cl _2-CH3 4-tert -butyl 127 ^C 26 '2fi ^{C; 1FN} 2 ^C, 3 2-F 0 2-CH ₃ -5-Cl _2-CH3 4-tert -butyl 128 ^C 26 ^H 25 ^Cl 2 ^N 2 ° 3 ^2, 6-F ₂ 0 2-CH ₃ -5-Cl _2-CH3 4-tert -butyl 129 ^C 27 ^H 29 ^C 1 ^N 2 ° 3 _2-CH3 0 2-CH ₃ -5-Cl _2-CH3 4-tert -butyl 130 ^C 26 ^H 26 ^Cl 2 ^N 2 ° 3 2-C1 0 3,6- _{(CH3) 2} 5-Cl H 2 sec. -butyl 131 ^C 26 ^H 26 ^ClFN 2 ° 3 2-F 0 3,6- (CH ₃ ) ₂ -5-Cl H 2 sec. -butyl 132 ^C 26 ^H 25 ^C 2 ^FN 2 ° 3 2-Cl, 6-F 0 3,6- (CH ₃ ) ₂ -5-Cl H 2 sec. -butyl 133 ^C 26 ^H 25 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl H 2 sec. -butyl 134 ^C 24 ^H 22 ^Cl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 3-CH ₃ 135 ^C 24 ^H 21 ^C 2 ^FN 2 ° 3 2-C1.6-F 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 3-CH3 136 ^C 24 ^H 21 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3 3-CH ₃ 137 ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2-C1 0 3,6- (CH 3) ₂ -5-Cl 2-CH ₃ -4-Cl 3-CH ₃ 138 ^C 24 ^H 20 ^C 3 ^FN 2 ° 3 2-C1.6-F 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Cl 3-CH ₃ 139 ^C 24 ^H 20 ^C 2 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Cl 3-CH ₃ 140 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-C1 0 3-CH ₃ 2-CH ₃ -4-Cl 3-CH ₃ 141 ^C 23 ^H 19 ^Cl 2 ^FN 2 ° 3 2-C 1-6 -F 0 3-CH ₃ 2-CH ₃ -4-Cl 3-CH ₃ 142 ^C 23 ^H 19 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3-CH ₃ 2-CH ₃ -4-Cl 3-CH ₃ 143 ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2-C1 0 3,6- _(CH3) ^2-5-Cl 2tCH ₃ -4-Cl _5-CH3 144 ^C 24 ^H 20 ^C 2 ^FN 2 ° 3 2-Cl, 6-F 0, ' -3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Cl _5-CH3 145 ^C 24 ^H 20 ^C 2 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Cl _5-CH3

continuation of Table

Example- Formula XX ' Y ^R 1 ^R 2 ^R 3 146 ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 3-CH ₃ -4-Cl _5-CH3 . ^{147 C} 24 ^H 20 ^C 2 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 3-CH ₃ -4-Cl _5-CH3 148 ^C 24 ^H 21 ^BrCl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Br 3- _C H ₃ 149 ^C 24 ^H 20 ^BrCl 2 ^F 2 ^5, 2 ^O 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2-CH ₃ -4-Br 3-CH 3 150 ^C 23 ^H 20 ^BrCl 2 ^N 2 ° 3 2-C1 0 3-CH ₃ 2-CH ₃ -4-Br 3-CH ₃ 151 ^C 23 ^H 19 ^BrF 2 ^N 2 ° 3 2,6-F ₂ 0 3-CK ₃ 2-CH ₃ -4-Br 3-CH ₃ 152 ^C 23 ^H 20 ^Cl 2 ^N 2 ° 3 2-C1 0 3-CH ₃ 2-CH ₃ -4-Cl _5-CH3 153 ^C 23 ^H 19 ^Cl 2 ^F 2 ^N 2 ° 3 ^2, 6-F ₂ 0 3-CH ₃ 2-CH ₃ -4-Cl 5- _C H ₃ 154 ^C 24 ^H 21 ^BrF 2 ^N 2 ° 3 2,6-F ₂ 0 3,5- _{<CH3) 2} 2-CH ₃ -4-Br 3-CH ₃ .155 ^C 26 ^H 25 ^BrCl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br 2 sec. -butyl 156 ^C 26 ^H 24 ^BrClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 4-Br 2 sec. -butyl 157 ^C 25 ^H 22 ^ClF 3 ^N 2 ° 3 2- _C F ₃ 0 3,6- (CH ₃ ) ₂ -5-Cl 2- ^CH 3 _4-CH3 158 ^C 25 ^H 24 ^Cl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 2,4- _{(CH3) 2 5-CH3} 159 ^C 25 ^H 23 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl 2,4- _{(CH3) 2 5-CH3} 160 ^C 24 ^H 21 ^C 3 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl, _{4-CH3 5-CH3} 161 ^C 24 ^H 20 ^C 2 ^F 2 ^N 2 ° 3 2,6- ^F 2 0 3,6- (CH ₃ ) ₂ -5-Cl 2-Cl, _4-CH3 5- _C H ₃ 162 ^C 23 ^H 18 ^Cl 4 ^N 2 ° 4 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl 2,4-Cl ₂ 5-CH 3 163 ^C 23 ^H 17 ^Cl 3 ^F 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- _{(CH3) 2,} -S-Cl 2,4-Cl _{2 5-CH3} 164 ^C 22 ^H 16 ^BrCl 3 ^N 2 ° 3 2-C1 0 3,5-Cl _{2 2-CH3,} 4-Br 5-CII ₃ 165 ^C 22 ^H 15 ^BrCl 2 ^F 2 ^N 2 ° 3 ² ' ⁶ - ^F 2 0 3,5-Cl _{2 2-CH3,} 4-Br _5-CH3 166 ^C 24 ^H 21 ^BrCl 2 ^N 2 ° 3 2-C1 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3, 4-Br 5- _C H ₃ 167 ^C 24 ^H 20 ^BrClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH ₃ ) ₂ -5-Cl _2-CH3, 4-Br ^{5 CH} 3 168 ^C 23 ^H 20 ^C 2 ^N 2 ° 2 ^N 2-C1 with 2-CH ₃ -5-C1 _{2-CH3 4-CH3} 169 ^C 22 ^H 17 ^C 3 ^N 2 ° 2 ^N 2-C1 with 2-CH ₃ ~ 5-Cl 4-C1 _2-CH3 170 ^C 23 ^H 20 ^C 2 ^N 2 ° 2 ^N 2-CH 2 with 2-CH ₃ -5-Cl 4-C1 _2-CH3

continuation of Table

Example Formula XX ' Y ^R 1 ^R 2 ^K 3 171 ^C 24 ^H 23 ^BrN 2 ° 2 ^N 2-C ^H 3 with 3-CH3 _2-CH3, 4-Br 6-CII ₃ 172 ^C 22 ^H 17 ^BrCl 2 ^N 2 ° 2 ^N 2-Cl with 2-CH ₃ , 5-Cl 4-Br _2-CH3 173 ^C 23 ^H 20 ^BrClN 2 ° 2 ^N 2-Cl with 3-CH ₃ 2-CH ₃ -4-Br _6-CH3 174 ^C 24 ^H 23 ^C 1 ^N 2 ° 2 ^N «2 with 3,6- (CH _{3) 2} -5-d _{2-CH3 4-CH3} 175 ^C 23 ^H 20 ^C 2 ^N 2 ° 2 ^{N H} 2 with 3,6- (CH _{3) 2} -5-Cl 4-C1 _2-CH3 176 ^C 24 ^H 21 ^C 3 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH _{3) 2} - ₅ - ^c1 3-CH. J-4-C1 5- _C h ₃ 177 ^C 24 ^H 21 ^BrCl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH _{3) 2} -5-Cl! 2-CH ₃ -4-Br 3-CK ₃ 178 ^C 23 ^H 20 ^BrClN 2 ° 2 ^N 2-Cl with 3-CH3 2-CH ₃ -4-Br 3-C ^H 3 179 ^C 20 ^H 20 ^Cl 2 ^N 2 ° 2 ^N 2-Cl with 3-CH ₃ 2-CH ₃ -4-Cl _5-CH3 180 ^C 26 ^H 25 ^BrCl 2 ^N 2 ° 2 ^N 2-Cl with 3,6- (CH _{3) 2} -5-Cl 4-Br 2 sec. -butyl 181 ^C 24 ^H 21 ^C1F 2 ^N 2 ° 2 ^N 2,6-F ₂ with 3,6- (CH _{3) 2} -5-Cl _{2-CH3 4-CH3} 182 ^C 24 ^H 19 ^Cl 2 ^N 3 ° 3 2-Cl 0 3,6- (CH _{3) 2} -5-Cl 4-CN _2-CH3 183 ^C 24 ^H 18 ^ClF 2 ^N 2 ° 3 2,6-F ₂ 0 3,6- (CH _{3) 2} -5-Cl 4-CN _2-CH3 184 ^C 25 ^H 21 ^CI 2 ^N 3 ^P 3 2-Cl 0 3,6- (CH ₃₎ 2-5-Cl 4-CN, _5-CH3 2-CB ₃ 185 ^C 25 ^H 20 ^ClF 2 ^N 3 ° 3 2,6- ^p 2 0 3,6- (CH _{3) 2} -5-Cl 4-CN, _{5-CH3 2-CH3} 186 ^C 26 ^H 23 ^ClF 2 ^N 2 ° 5 2,6-F ₂ 0 3,6- (CH ₃₎ 2-5-Cl 4-CO ₂ C ₂ ^H 5 _2-CH3 187 ^C 26 ^H 24 ^Cl 2 ^N 2 ° 5 2-Cl 0 3,6- (CH ₃₎ 2-5-d _4-O2 C ₂ H ₅ C _2-CH3

Table I - continued: II. part Example C % calculated H N % C found H N 1 56.79 3.47 6.02 56.61 3.35 6.08 2 56.97 3.70 6.04 56.84 3.61 6.02 3 53.03 3.24 5.62 52.38 3.15 5.72 4 67.91 5.23 6.60 67.23 5.10 6.62 5 65.35 5.03 6.35 65.22 5.03 6.29 6 68.16 5.47 6.63 68.12 5.58 6.48 7 63.02 4.85 6.13 58.72 4.16 6.33 8 63.03 4.85 6.12 63.33 4.94 6.09 9 58.61 4.30 5.70 58.28 4.21 5.64 10 60.64 4.45 5.89 60.79 4.42 5.82 11 62.82 4.61 6.10 62.94 4.88 6.03

continuation of Table 1: II. part

Example C % calculated Η N C % found H : N

12 49.61 2.84 5.26 49.99 2.90 5.21 13 46.60 2.49 4.94 46.74 2.53 4.94 14 47.99 2.56 5.09 47.21 2.80 5.01 15 Dec 49.47 2.64 5.24. 49.44 2.74 5.17 16 60.89 4.68 5.92 61.13 4.83 6.05 17 63.03 4.85 6.12 62.64 4.73 6.40 18 60.89 4.68 5.92 61.12 4.73 5.94 19 Dec 58.61 4.30 5.70 58.41 4.26 5.71 20 May 62.82 4.61 6.10 63.23 4.67 6.08 21 64.34 5.40 5.77 64.03 5.36 5.98 22nd 62.27 5.23 5.59 62.06 5.43 5.79 23 60.07 4.85 5.39 60.25 4.92 5.50 24 64.14 5; 17 5.75 64.60 5.32 5.73 25 62.31 4.55 6.32 62.22 4.66 6.23 26 60.13 4.39 6.10 59.84 4.38 5.98 27 Mar: 57.82 4.01 5.86 58.09 4.02 5.85 28 62.10 4.30 6.30 62.05 4.41 6.19 29 62.31 4.55 6.32 61.83 4,56 6.34 30 62.10 4.30 6.30 62.02 4.50 6.79 31 60.13 4.39 6.10 60.72 4.66 6.08 32 57.82 4.01 5.86 57.95 4.22 5.95 33 52.90 3.67 5.36 53.18 3.68 5.47 34 52.94 3.67 5.37 53.13 3.68 5.37 35 49.62 3.26 5.03 49.60 3.29 4.99 36 51.32 3.56 5.20 51.63 3.53 5.20 37 52.75 3.46 5.35 52.27 3.40 5.43 38 52.90 3.67 5.36 52.43 3.68 5.31 39 49.62 3.26 5.03 49.75 3.23 5.00 40 52.75 3.46 5.35 52.97 3.49 5.31 41 51.32 3.56 5.20 50.70 3.55 5.00 42 57.82 4.01 5.86 57.51 4.00 5.66 43 53.93 3.54 5.49 54.22 3.55 5.55 44 57.64 3.78 5.84 57.50 3.84 5.81 45 55.94 3.88 5.67 55.98 3.94 5.60 46 57.82 4.01 5.86 58.20 4.17 5.72 47 53.93 3.54 5.49 53.91 3.51 5.50 48 57.64 3.78 5.84 57.82 3.84 5.73 49 55.94 3.88 5.67 55.78 3.91 5.55 50 67.02 6.53 5.04 66.06 6.47 5.14 51 63.11 5.98 4.75 60.04 5.58 5.03 52 65.14 6.35 4.90 64.36 6.35 4.86 53 66.28 5,56 6.18 65.12 5.73 5.98 54 63.08 4.85 6.13 62.91 4.83 6.14 55 66.84 6.33 5.03 66.16 6.48 4.78 56 64.93 5.65 5.61 64.84 5.71 5,56 57 64.74 5.43 5.59 64.70 5.73 5.65 58 62.91 5.48 5.43 62.96 5.58 5.38 59 64.98 5.66 5.61 65.24 5.85 5,52 60 63.69 5.13 5.94 63.68 5.30 5.99 61 59.36 4.58 5.54 59.52 4.82 5.47 62 61.35 4.74 5.72 61.49 4.81 5.77

Ti

continuation Example Table I; C II. part % calculated H N % found C H N 63 63.49 4.90 5.92 63.58 5.20 5.92 64 61) 4.96 5.75 61.78 5.12 5.77 65 63.74 5.14 5.95 63.85 5.22 5.94 66 66.86 5.83 6.00 67.35 5.86 5.91 67 63.69 5.13 5.94 63.68 5.21 5.87 68 59.36 4.58. 5.54 59.68 4.80 5.31 69 61.35 4.74 5.72 61.60 4.84 5.79 70 63.49 4.90 5.92 63.35 4.97 5.83 71 61.59 4.96 5.75 61.65 5,05 5.70 72 63.74 5.14 5.95 64.29 5.17 5.91 73 66.86 5.83 6.00 67.60 6.13 6.13 74 63.70 5.13 5.94 63.94 5.26 5.87 75 63.50 4.90 5.92 63.36 5.08 5.80 76 68.72 5.77 6.41 67.84 5.65 6.30 77 65.38 5.03 6.35 65.25 5.13 6.21 78 74.60 6.51 6.96 74.81 6.66 6.88 79 71.74 6.26 6.69 72.14 6.42 6.54 80 70.92 5.70 6.89 71.09 5.70 6.98 81 60.90 4.68 5.92 60.85 4.57 5.84 82 56.77 4.17 5,52 56.53 4.14 5.37 83 58.67 4.31 5.70 59.07 4.47 5.63 84 60.70 4.46 5.90 60.98 4.19 5.72 85 66.29 5,56 6.18 66.57 5,56 6.29 86 60.95 4.69 5.93 60.63 4.58 5.71 87 65.67 5.28 6.38 66.09 5.50 6.27 88 58.90 5.43 5.72 58.63 4.58 5.68 89 58.72 4.31 5.71 58.62 4.29 5.91 90 62.40 5.44 8.40 62.56 5.44 8.52 91 62.22 5.22 8.37 62.81 4.93 8.20 92 58.38 4.90 7.86 58.28 5.02 7.99 93 60.24 5.06 8.10 60.15 5.13 7.77 94 64.52 5.62 8.68 64.57 5.63 8.64 95 67.56 6.30 8.75 67.21 6.38 8.38 96 62.31 4.55 6.32 62.65 4.92 6.27 97 62.10 4.31 6.30 62.45 4.78 6.30 98 51.99 3.37 5,51 52.51 3.49 5,56 99 51.84 3.16 5.50 51.70 3.32 5.37 100 ALIGN! 56.58 4.13 5.74 57.19 4.34 5.77 101 56.41 3.91 5.72 56.96 4.14 5.66 102 62.31 4.55 6.32 62.36 4.51 6.38 103 68.16 5.48 6.62 68.37 5.55 6.53 104 64.72 4.72 6.56 65.29 4.77 6.63 105 59.08 3.83 6.26 59.48 3.80 6.24 106 58.56 4.27 5.94 59.37 4.43 5.82 107 61.62 4.96 5.99 62.83 5.22 5.85 108 53.74 3.48 5.70 53.75 3.59 5.43 109 56.63 4.13 5.74 56.84 4.09 5.64 110 56.63 4.13 5.74 56.64 4.16 5.64 111 58.61 4.28 5.94 58.59 4.54 5.79 112 54.62 3.79 5.54 54.66 3.82 5.50 113 56.46 3.91 5.72 56.61 4.30 5.61

continuation of Table I: II. part

Example % calculated % found C H N C H N

114 54.62 3.79 5.54 54.96 3.90 5.36 115 56.46 3.91 5.72 56.76 4.07 5.59 116 56.63 4.13 5.74 56.64 4.20 5.64 117 62.31 4.55 6.32 62.21 4.69 6.09 118 64.72 4.55 6.32 64.93 4.82 6.54 119 68.16 5.48 6.62 68.20 5.61 6.62 120 68.16 5.48 6.62 68.01 5.78 6.42 121 56.63 4.13 5.74 57.07 4,56 5.69 122 65.38 5.03 6.35 65.74 5.17 6.25 123 63.03 4.85 6.12 63.14 5.13 6.06 124 62.86 4.62 6.11 62.90 4.67 6.01 125 68.72 5.77 6.41 68.94 5.66 6.27 126 64.34 5.40 5.77 64.93 5.49 5.73 127 66.59 5.59 5.97 66.81 5.72 5.91 128 64.13 5.18 5.75 64.36 5.24 5.72 129 69.74 6.29 6.02 69.85 6.41 5.98 130 64.34 5.40 5.77 63.51 5.28 6.07 131 66.59 5.59 5.97 65.73 6.30 6.36 132 62.04 5.00 5,56 61.06 4.86 5.79 133 64.13 5.18 5.75 64.51 5.35 5.85 134 63.03 4.85 6.12 63.35 5.39 6.36 135 60.64 4.45 5.89 61.29 4.46 5.78 136 62.82 4.61 6.10 63.04 4.89 6.21 137 58.61 4.30 5.70 58.87 4.53 5.70 138 56.54 3.95 5.50 57.41 4.27 5,57 139 58.43 4.09 5.68 58.59 4.27 5.65 140 62.31 4.55 6.32 62.63 4.62 6.38 141 59.88 4.15 6.07 60.54 4.54 6.06 142 62.10 4.30 6.30 62.55 4.62 6.27 143 58.61 4.30 5.70 - 58.47 4.30 5.63 144 56.54 3.95 5.50 56.88 4.05 5.39 145 58.43 4.09 5.68 58.72 4.18 5.68 146 58.61 4.30 5.70 58.59 4.34 5.53 147 58.43 4.09 5.68 58.38 4.17 5.53 148 53.75 3.95 5.22 53.72 4.03 5.53 149 53,60 3.75 5.21 53.27 3.78 5,07 150 56.63 4.13 5.74 56.52 4.22 5.76 15.1 56.46 3.91 5.72 56.65 4.09 5.94 152 62.31 4.55 6.32 62.17 4.65 6.30 153 62.10 4.30 . 6.30 61.95 4.42 6.19 154 temperature melting 194 mp 197 ° C 155 55.34 4.46 4.96 55.49 4.42 4.87 156 55.19 4.28 4.95 55.78 4.28 4.81 157 61.17 4.52 5.71 61.45 4.66 5.63 158 63.70 5.13 5.94 63.64 5.24 6.03 139 63.50 4.90 5.92 63.75 5.18 6.63 160 58.61 4.30 5.70 59.19 4.68 5.60 161 58.43 4.09 5.68 58.64 4.36 5.64 162 53.93 3.54 5.47 54.16 3.79 5.41 163 53.77 3.34 5.45 53.57 3.42 5.58 164 48.69 2.97 5.16 49.39 3.01 5,07

continuation of Table I: Part II

Example% calculated% found

C H N C H N 165 ' 48.56 2.78 5.15 49.05 2.86 5.08 166 53.75 3.76 5.22 53.96 4.04 5.20 167 53,60 3.75 5.21 53.69 3.78 5.16 168 60.13 4.39 6.10 60.58 4.55 6.05 169 55.07 3.57 5.84 55.86 3.61 5.64 170 60.13 4.39 6.10 60.14 4.32 6.08 171 59.58 4.79 5.79 60.48 5.04 5.71 172 50,40 3.27 5.34 50.32 3.37 5.22 173 54.78 4.00 5,56 55.82 4.37 5.04 174 65.67 5.28 6.38 66.57 5.41 6.35 175 60.13 4.39 6.10 60.39 4.69 6.13 176 56.76 4.17 5,52 59.96 4.25 5,57 177 52.19 3.83 5,07 52.61 3.92 4.91 178 54.83 4.00 5,56 54.98 4,18, 5,57 179 60.13 4.39 6.10 60.62 4.61 6.13 180 53.81 4.34 4.83 54.16 4.36 5.20 181 60.69 4.46 5.90 60.35 4.57 5.98 182 61.55 4.09 8.79 61.68 4.48 8.32 183 61.35 3.86 8.94 63.16 4.42 8.35 184 62.25 4.39 8.71 62.21 4.59 8.50 185 62.06 4.17 8.68 61.72 4.46 8.49 186 temperature melting 176 mp 179 ° C 187 temperature melting 188 to 190 ° C

Certain representative examples of the novel compounds have been tested to determine their insectioid activity against certain insect species, including caterpillars and beetles. The novel compounds have also been tested for phytotoxicity for economically important crop plants, including bean, soybean, furry, corn, tomato and cotton. The new compounds were further evaluated for mammalian toxicity.

A test compound suspension was prepared by dissolving 1 g of the compound in 50 ml of acetone in which 0.1 g (10% by weight of the compound) of an alkylphenoxypolyethoxyethanol surfactant was dissolved as an emulsifying or dispersing agent.

The resulting solution was stirred into 150 mL of water to give about 200 mL of a suspension containing the compound in finely divided form. The stock suspension thus prepared contained 0.5% by weight of the compound.

Test concentrations in parts per million parts, by weight, used in the tests described below were obtained by appropriately diluting the stock suspension with water. The test procedures were as follows:

Test on leaves sprayed with bait for Spodoptera eridania (Cram.)

The test insects consist of Spodoptera eridania (Cram.) Moth larvae grown on Tendergreen bean plants at 26.5-3 ° C and 50-5% relative humidity.

Test compounds are adjusted by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Standard height and age potted Tendergreen bean plants are placed on a rotary table and sprayed with 100-110 ml of a composition containing test compounds using a De Vilbis sprayer at an air pressure of 27.6 KPa. This app, which lasts 25 seconds, is enough to moisten the plants until you drop. For the control determination, 100 to 110 ml of a solution of water, acetone and emulsifier not containing the test compound are also sprayed on the infested plants.

When the paired leaves have dried and separated, they are each placed in a 9 cm Petri dish lined with wet filter paper. Five randomly selected larvae are introduced into each dish and sealed.

The sealed dishes are labeled and maintained at 26.5-29.5 ° C for three days. Although larvae could easily consume the entire leaf within 24 hours, they do not add more food. Larvae that were unable to move along the length of the body or after plucking are considered dead. Percent mortality is recorded at various concentration levels. Spray test for Epilachna varivestie (Muls.).

The test insect consists of the larvae of the beetle Epilachna varivestis (Mulsl) in the fourth instar stage grown on Tendergreen bay plants at a temperature of 26.5-3 ° C and a relative humidity of 50-5%.

Test compounds are adjusted by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Tendergreen bean plants of standard height and age grown in pots were placed on a turntable and sprayed with 100-110 ml of a composition containing test compounds using a De \ Vilbris sprayer at an air pressure of 27.6 kPa.

This app that lasts 25 seconds is enough to moisten the plants until you drop. For the control determination, 100 to 110 ml of a solution of water, acetone and emulsifier not containing the test compound are also sprayed on the infested plants.

When the paired leaves have thinned), they are separated and each is placed on a 9 cm Petri dish lined with wet filter paper. Five randomly selected larvae are introduced into each dish and sealed. The sealed dishes are labeled and kept at 26.5-3 ° C for three days.

Although larvae could easily consume the entire leaf within 24 to 48 hours, they do not add more food. Larvae that were unable to move along the length of the body or after plucking, considered dead.

Test on bait-sprayed leaves for Heliothis virescens, F. and Haliothis zea (Boddie).

The test insects consist of larvae of Heliothis virescens, F. of about 4.5 mg and of Heliothis zea (Boddie) of about 2.5 mg each at the second instar stage, obtained on the market and grown on an artificial diet at 26, 5 - 3 ° C and relative humidity 50 5%.

Using a similar procedure as above, but replacing the young bean with cotton plants, treated and dried cotton leaves are placed in 9-inch Petri dishes, which are arranged in groups of 10 dishes. Ten randomly selected larvae are introduced into each and the dishes are sealed. The sealed dishes were labeled and held at 26.5-3 ° C for five days.

The biological properties of certain representative examples of compounds of the invention are shown in Table II below.

Severography, n

Price 2,40 Kčs

Table II

Biological properties of representative benzoyl ureas

Example

S. e

Effect 500 (1) ppm

E (2)

9

21 22

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

A of Table II

S. e

Effect 500 (1) ppm

E (2)

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

C

C

AND

AND

C

C

C

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND.

AND

AND

C

AND

C

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

C

AND

A of Table II

Effect 500 (1) ppm

E (2)

(B)

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

(B)

AND

AND

AND

AND

(B)

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

C

AND

C

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

And continuation of Table II

Example

Effect 500 ppm (2) (2)

152

153 A

154 A

155 A

156 A

157 A

158 A

159 A

160 A

161 A

162 A

163 A

164 A

165 A

166 A

167 A

168 A

169 A

170 A

172 A

174 A

175 A

176 C

177 A

178 A

179 A

180 A

181 A

182 A

183 A

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

AND

C

AND

AND

AND

Explanatory notes

(1) Spodoptera eridania (Cram.)

2) Epilachna varivestis (Muls.)

3) Rating: A = complete suppression

B = partial suppression C = suppression did not occur

Examples 212-217

In order to demonstrate a greater biological effect against Spodoptera eridania (Cram.), Representative benzoylureas are compared with known products. The results are shown in Table III below:

Table III

Comparison of representative benzoylureas with previously known closely related compounds against Spodoptera eridania (Cram.)

Severography, n. P., MOST

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Compound Dose used (ppm) Percent suppression after 5 days 1- (4-chlorophenyl) -3- (2,6-difluoro- 10 100 ALIGN! benzoyl) urea ¹ * 5 40 1- (4- (4-methylphenylthio) phenyl) - 500 40 2) -3- (2,6-dichlorobenzoyl) urea 125 30 31 10 1- / 4- (2,4-Dimethylphenoxy) - 125 100 ALIGN! -3-chlorophenyl / -3- (2-chloro- 31 30 benzoyl) urea 8 20 May 1- / 4- (2,4-Dimethyl-phenoxy) - 2 100 ALIGN! -3,6-Dimethyl-5-chlorophenyl) - 1 100 ALIGN! -3- (2-chlorobenzoyl) urea (Example 8) 1- / 4- (2,4-Dimethylphenoxy) - 2 100 ALIGN! -2,5-dimethyl-3-chlorophenyl / - 1 90 -3- (2-chlorobenzoyl) thiourea guilt (example 16) 1- / 4- (2,4-dimethylphenoxy) -3,5- 8 100 ALIGN! -dimethylphenyl / -3- (2,6-difluoro- 2 100 ALIGN!

benzoyl) urea (Example 4)

Explanatory notes:

1) Dimilin, a known compound

2) a compound previously known from German Publication No. 2,901,334

3) a compound previously known from DE 3 104 407 ¹ (EP 57-888)

Examples 218 to 220

Representative benzoylureas are compared to known products in order to demonstrate a greater biological effect against the gris. The results are shown in Tables IV and V below.

Table IV

Comparison of representative benzoylureas with previously known closely related compounds against Heliothis zea (Boddie)

Compound ^LD 50

Heliothis Zea Boddie

1- (4-Chloro-phenyl) -3- (2,6-difluorobenzoyl-urea ¹ → 500)

1- [4- (4-methylphenylthio) phenyl] -3-100

2)

- (2,6-dichlorobenzoyl) urea

Compound ^LD 50 (PP ^m )

Heliothis zea (Boddie) continuation of Table IV

1- / 4- (2,4-dimethylphenoxy) -3- chlorophenyl / -3- (2,6-difluorobenzoyl) - _the. 3) urea 100 ALIGN! 1- / 4- (2,4,5-trimethylphenoxy) -3,6- -dimethyl-5-chlorophenyl / -3- (3,6-difluorobenzoyl) urea (Example 159) 0.4 1- [4- (2,5-dimethyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea (Example 145) 0.7 Explanatory notes: 1) Dimilin, a known compound 2) a compound previously known from German 3) a compound previously known from German (EP 57-888) publication file No 2 DE č, 901 334 . 3,104,407 Table V Comparison of representative benzoylureas by us against Heliothis virescens, F. with previously known closely relatives- Compound LD ₅₀ (ppm) Heliothis virescens F. 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea 31 1- [4- (4-methylphenylthio) phenyl] -32) - (2,6-diohlorobenzoyl) urea 100 ALIGN! 1- / 4- (2,4-dimethylphenoxy) -3-chloro- phenyl-3- (2,6-difluorobenzoyl) urea • 3) fault 100 ALIGN! 1- [4- (2,5-dimethyl-4-chlorophenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea (Example 145) 0.63 1- [4- (2-methyl-4-tert-butylphenoxy) -3,6-dimethyl-5-chlorophenyl] -3- (2,6-difluorobenzoyl) urea (Example 157) 2.4

Explanatory notes:

1) Dimilin, a known compound

2) a compound previously known from German Publication No. 2,901,334

3) a compound already known from DE 3 104 407 (EP 57-888)

While the invention has been illustrated by the preceding examples, it is not to be construed as limiting the materials used herein. The invention generally encompasses the field as set forth below. Various modifications and embodiments can be made without departing from the spirit and scope of the invention.

Claims (1)

Process for the preparation of 1- (alkylphenoxyaryl) -3-benzoylureas of the general formula "A NH (R ₂ > _n where X and X 'are each independently hydrogen, halogen, alkyl, haloalkyl, polyhaloalkyl, alkoxy or polyhaloalkoxy, wherein the alkyl moiety of each group contains 1 to 4 carbon atoms, Y is oxygen or sulfur, and m is 0 to 4, is hydrogen, halogen, alkyl, haloalkyl, polyhaloalkyl or alkoxy, wherein the alkyl portion of each group contains 1 to 4 carbon atoms, R 2 is hydrogen, halogen, alkyl, polyhaloalkyl, polyhaloalkoxy, wherein the alkyl moiety of each group contains 1 to 4 carbon atoms, alkylsulfonyl, alkoxy, alkylthio, dialkylamino, wherein the alkyl moiety of each group contains 1 to 8 carbon atoms, CN, NO 2, CO _n R ^ _R ^ CONHR in which represents alkyl having 1 to 8 carbon atoms, R 1 represents an alkyl of 1 to 12 carbon atoms, with the proviso that m cannot be 0 or 1 when n is less than 2, characterized in that an alkylphenoxyphenylisocyanate or an alkylphenoxyphenylisothiocyanate of the general formula (phylm wherein> R1, R2 / Rg, m and n are as defined above. with a benzamide of the formula wherein X ' NH, X and X 'are as defined above. and then isolating the prepared compound.