JPH0495068A - Arylpyrrole insecticide, acaricide and nematicide and preparation thereof - Google Patents

Abstract

NEW MATERIAL: A compound of formula I [X is H, F, Cl, Br, I or trifluoromethyl; Y is H, F, Cl, Br, I, trifluoromethyl, etc.; W is cyano or nitro; A is a 1-4C alkyl substd. by four halogen atoms, etc.; L is H, F, Cl or Br; M and R are each a 1-3C alkyl, a 1-3C alkoxy, a 1-5C alkylthio, a 1-3C alkylsulfinyl, etc.; if M and R are located at the adjacent positions, they together with the carbon atom to which they are attached form -OCH₂O-, etc.; Z is S(O)_n or O].

EXAMPLE: Methyl [2,3-dichloro-4-cyano-5-(3,4-dichlorophenyl)pyrrol-1-yl]-pivalate.

USE: The subject compound is useful as insecticides, acaricides and nematicides, and can protect agricultural products after harvest.

PROCESS: A compound of formula II is reacted with a compound of formula III in the presence of an alkali metal base and a solvent to give the compound of formula I.

COPYRIGHT: (C)1992,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to certain novel insecticidal, acaricidal and nematicidal arylvirol agents and methods of controlling insects, mites and nematodes using the same. The present invention also provides protection against insect, mite and nematode attack by applying insecticidal, acaricidal and nematicidal effective amounts of the novel arylpyrrole compounds to the plants or the soil in which they grow. on how to protect.

The present invention further relates to a method for synthesizing the arylvirole compound.

The present invention provides highly effective insecticidal and acaricidal agents that are effective for exterminating harmful insects, mites, and nematodes, and for protecting agricultural crops during growth and after harvest from damage by the harmful insects. and certain novel arylvirol compounds that are nematicidal agents.

The present invention further relates to a method for synthesizing the arylvirole compound.

The novel arylpyrrole compounds of the present invention have the structural formula shown in Formula I.

A (D Uni, X is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, or trifluoromethyl group; Y is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoro Methyl group or cyanogen group: W is a cyano group or a nitro group; A is a C8-C1 alkyl group substituted with 4 halogen atoms, 1 cyano group, 1 substituted with 1 to 3 halogen atoms or two optionally substituted alkoxy groups with one to three halogen atoms, one C1 to C6 carbalkoxy group,
one C1-C5 alkylcarbonyloxy group, one C2-C6 alkenylcarbonyloxy group, one benzenecarbonyloxy group or chloro, dichloro,
or methyl-substituted benzenecarbonyloxy group; L is
A hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and M and R each independently represent a hydrogen atom, a C1-C1 alkyl group, a CI-C1 alkoxy group, an 01-C1 alkylthio group, alkylsulfinyl group,
C, ~C3 alkylsulfonyl group, cyano group, fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group,
Trifluoromethyl group, R, CF! Z1R,CO or NR,R and when M and R are in adjacent positions and together with the carbon atoms to which they are bonded, M7M may form a ring represented by the following structure: Z is 5 (0) n or 0; R1 is a hydrogen atom, a fluorine atom, CHF, CHFCQ
, or trifluoromethyl group; R is CI''-C
3 alkyl group, C, to C, (7) alkoxy group, or NR, R,.

R1 is a hydrogen atom or a C1-C3 alkyl group; R4 is a hydrogen atom, a C1-C1 alkyl group, or R,
CO; R6 is a hydrogen atom or a C1-C3 alkyl group, and n is an integer of 0.1 or 2! 1'': However, when X and Y are hydrogen atoms and A is an alkyl group of C, -C, substituted with one cyano group, the substituent (I[) where A, L, M , R, W, X and Y are as described above.

Another preferred group of novel arylpyrroles of the invention is represented by: (III) is one of the two positions adjacent to the nitrogen atom on the pyrrole ring
must be combined with.

A preferred group of novel arylpyrroles of the invention are:
Represented by the formula (■): Here, A, L, M, R, W, X and Y are as described above.

Other preferred groups of novel arylpyrroles of the present invention are represented by: (mV) Uni A, L, M% R, W, X and Y It, as described above.

Yet another preferred group of novel arylpyrroles of the present invention is represented by the formula V (V):j::A, L, MIR, W, X and Yld, as described above.

Yet another preferable group of novel arylviroles of the present invention is represented by formulas ■ and ■: where A, L%
M%R%W1x and Y are as described above.

In the preferred arylpyrrole of the present invention represented by formula I, W is a cyano group or a nitro group; L is a hydrogen atom; X and Y are each a chlorine atom, a bromine atom, or +1)'
) Fluoromethyl group: M is a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and R is a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group or a trifluoromethoxy group.

belongs to.

Preferred compound of formula (1) which is very effective as an insecticidal, acaricidal and/or nematicidal agent +1, L is a hydrogen atom; M is a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom; R is a fluorine atom, A chlorine atom, a bromine atom, a trifluoromethyl group, or a trifluoromethoxy group; W is a cyano group, and X and Y are each independently a chlorine atom, a bromine atom, or a trifluoromethyl group.

belongs to.

In the compound 2, which is very effective as another insecticidal, acaricidal, and/or nematicidal agent, L is a hydrogen atom; M is a hydrogen atom, a fluorine atom, a chlorine atom, or a bromine atom; and R is a fluorine atom. , a chlorine atom, a bromine atom, a trifluoromethyl group or a trifluoromethoxy group; W is a nitro group;
and X is a chlorine atom, a bromine atom, or a trifluoromethyl group, and Y is a hydrogen atom, a chlorine atom, a bromine atom, or a trifluoromethyl group.

Some specific examples of the insecticidal, acaricidal and nematicidal arylvirols of the present invention are: [2,3-dichloro-4-cyano-5-(3,4-dichlorophenyl)virol-1-yl] ]-pivalic acid, methyl ester, melting point 143°C-145°C: 4.5-dichloro-1-(hydroxymethyl)-2-1
1+ I! *σ-trifluoro-p-tolyl)virol-3-carbonitrile, acetic acid (ester): 4-bromo-2-(p-chlorophenyl-1-hydroxymethyl)-5-(trifluoromethyl)virol-3-carbonyl Tolyl, pivalic acid (ester), melting point 127.5
°C; 4-bromo3-(3,4-dichlorophenyl)-1-
(Hydroxymethyl)-5-(trifluoromethyl)virol-2-carbonitrile, pivalic acid ester, melting point 93°C-94°C: 3.4-dibromo-5-(p-chlorophenyl)-1-
(Hydroxymethyl)-virol-2-carponitrile, pivalic acid (ester), melting point 130°C-132°C
: [2,3-dichloro-4-cyano-5-(g, a.

a-Trifluoro-p-tolyl)pyrrol-1-ylcopivalic acid, methyl ester, 1l 153°C-157°C
: 3-bromo-5-cyano-4-(3,4-dichlorophenyl)-2-(trifluoromethyl)pyrrole-1-acetonitrile, mp 95°C-97°C; 2,3-dichloro-4-cyano-5 -(α,ff,ff-trifluoro-p-tolyl)pyrrole-1-acetonitrile, melting point 1
37.5°C-139°C: 3-bromo-5-(p-chlorophenyl)-4-cyano-2-(trifluoromethyl)
Pyrrole-1-acetonitrile, melting point 142°C! -1
44℃2.3-dichloro-4-cyano-(3,4-dichlorophenyl)pyrrole-1-acetonitrile, melting point 1
97°0-199°C; [2-(3,4-dichlorophenyl)3-nitro-5-
()Lifluoromethyl)pyrrol-1-yl]benzoic acid, methyl ester; [2,3-dichloro-4-cyano-5-(3,4-dichlorophenyl)pyrrol-1-yl]-benzoic acid, Methyl ester; 3-bromo-5-(p-bromophenyl)-4-cyano-2-()lifluoromethyl)pyrrole-1-acetonitrile, melting point 110.5°C-113°C; [3, bromo-5- Chloro-4-cyano-2-(3,4
-dichlorophenyl)virol-1-yl]piparic acid, methyl ester, melting point 119°C-122°C: [2,3-dichloro-4-cyano-5-Cara.

a-trifluoro-p-tolyl)pyrrol-1-yl]
p-chlorobenzoic acid, methyl ester; 4-bromo-2
-(p-chlorophenyl)-1-hydromethyl)-5-
trifluoromethyl)pyrrole-3-carbonitrile,
p-chlorobenzoic acid (ester): 2.3-dichloro-5-(p-chlorophenyl)-4-
Cyano-pyrrole-1-acetonitrile, melting point 175°C
-177°C; [2-(3,4-dichlorophenyl)-3-nitro5
-(trifluoromethyl)pyrrol-1-ylcopivalic acid, methyl ester, mp 116°C-119°C; 3-bromo-2-(p-chlorophenyl)-1-[2,
2,2-)lifluoroethoxy)-methyl]5-(trifluoromethyl)pyrrole-3-carbonitrile and 3-bromo-5-chloro-2-(p-chlorophenyl)
-4-cyano-pyrrole-3-carbonitrile, melting point 1
44°C-150°C A method for synthesizing the arylpyrrole compound of formula I in which A is a hydrogen atom is described in co-pending European Patent Application Publication No. 0 30
3 863.

The synthesis of N-substituted arylpyrroles of formula I comprises a suitably substituted arylpyrrole of formula I in which A is a hydrogen atom and MIR, W% X and Y are as described above; This can be achieved by reaction of an alkylating agent and a suitable base, for example a haloalkyl ether of chloromethyl C8-C4, with potassium hydride.

This reaction provides an arylpyrrole having the same substituents as the starting material, but in addition, the nitrogen atom is substituted with an 01-C4 haloalkoxymethyl group.

A similar reaction in which a-bromoacetonitrile is replaced by a chloromethyl C8-C4 haloalkyl ether produces arylviroles of formula I with an acetonitrile substituent on the nitrogen.

The reaction is shown below.

, :, :II: L, M, R, W, X and Y are as described in the above formula I, and A is 1) a C1-C1 haloalkoxymethyl group, or 2) CH, CN .

The examples set forth below for illustrative purposes utilize the reaction system described above and provide methods for synthesizing other compounds of the invention not specifically described herein. Pyrrole is effective in controlling insects, mites and nematodes. These compounds are also effective in protecting agricultural crops during growth or after harvest from attack by the pests mentioned above.

from about 10 ppm to about 10,000 ppm and preferably when applied to the plant, the crop or the soil in which the plant is growing to protect said crop from practical insect, mite and/or nematode attack. 100 to 50
00 ppm of an arylpyrrole of formula I, for which formula ■
, ■, ■, V, Vt, and ■, all of which are included, are suspended in water or other inexpensive liquid carriers.

These compounds are also effective in protecting lawn turf from attack by pests such as grubs and stink bugs.

The arylpyrroles of formula I of the present invention may also be used in the leaves of the plant and/or in the soil or soil in which the plant is grown to provide the active ingredient at a rate of from about 0-100 kg/ha to about 4.0 kg/ha. When applied in sufficient quantities, it is effective in controlling insects, mites and nematodes. Obviously, the use of arylpyrroles of formula I in higher proportions can be used to protect crops from insect, mite and nematode attacks, but the use in higher proportions is generally unnecessary and wasteful. .

Although the arylpyrroles of the present invention are effective in controlling insects, mites, and nematodes when used alone, other insecticides,
It can be used in combination with other biological agents including acaricides and nematocides. For example, the arylpyrroles of the present invention can be effectively used with or in combination with phosphates, carbamates, pyrethroids, formamidines, chlorinated hydrocarbons, halobenzoylureas, and the like.

Conveniently, the arylpyrroles can be formulated into dry solid granules, free-flowing plastics, granular dosage forms, wettable powders, dusts, dust concentrates, microemulsions, etc., all of which can be formulated into soil, water and /or can be used on leaves,
Provide essential plant protection. Such formulations include a compound of the invention mixed with an inert, pharmacologically acceptable solid or liquid diluent.

For example, the formulation layer of the wettable powders, dusts, powder concentrates of the present invention may contain from about 3% to 20% by weight of the arylpyrrole compound of Formula I and from about 3% to 20% by weight of the solid anionic surfactant. It can be prepared by crushing the drug together with the drug. One suitable anionic surfactant is the dioctyl ester of sodium sulfosuccinate, especially American cyanamide.
The aerosol (Aero) distributed by the company
sol) OTB is a surfactant. Montmorillonite, attapulgite, chalk, talc, kaolin,
About 60% to 94% by weight of diatomaceous earth, limestone, silicates, or other inert solid diluents can also be used in such agent layers.

Solid granules particularly useful for soil or water applications can be prepared by grinding about equal parts of arylpyrrole and solid surfactant, usually about 3 to 20 parts, with about 60 to 94 parts of gypsum. . Then the mixture is approximately 24/48
Consolidated into small granules of mesh size or larger.

Other suitable solid surfactants useful in such preparations include the anionic dioctyl ester of sodium sulfosuccinate as well as nonionic block copolymers of ethylene oxide and propylene oxide. Such block copolymers are available from BASF Wyandotte Corporation as Pluronic.
l OR8■ 17R8■ 25R8■, F38■,
It is commercially available as F1a[F], F77■ or F87@ and is particularly useful for producing solid granules.

In addition to the powder and concentrate formulations described above, wettable powders and fluids are used because they can be suspended in water.

Preferably, such a fluid is applied to the foliage of the plant to be protected where the aqueous composition is to be sprayed. These sprays can be applied to the breeding grounds, food or habitat of the insects and mites to be exterminated.

When a solid formulation of a compound of the invention is used in combination with other pest control agents, the formulation can be used as a mixture of the components or can be used sequentially.

Similarly, liquid formulations of arylpyrroles in combination with other pest control agents can be tank mixed or used separately or sequentially as a spray solution.

Liquid spray formulations of the compounds of this invention should contain from about 0.001% to about 0.1% by weight of active arylpyrrole.

The following examples are intended to illustrate the invention.

Example 1 Ponitrile r CN CH! OCR, A sample of CF3 3-bromo-2-(p-chlorophenyl)-5-(trifluoromethyltolyl (1.0 g, 0.003 mol) was dissolved in dry tetrahydrofuran and hydrogenated columnum (1.25 mol) was dissolved in dry tetrahydrofuran.
equal volume) of tetrahydrofuran suspension. The reaction mixture was stirred for 10 minutes and added: chloromethyl (trifluoromethyl) ether (0.5 4 g, 0.0 3
6 mol), stirred at room temperature for about 48 hours, then poured into a large volume of water and extracted with water. The ether extract is washed with brine, dried (magnesium sulfate) and concentrated in vacuo to give a residue. After flash chromatography (silica and l=1 methylene chloride:hexane) the title product is obtained as a white solid.
g (68% yield), melting point 124.6°C-125, 3°
C0 The above procedure was repeated except that appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2-(substituted)phenylpyrrole and the appropriate alkylating agent were used to obtain the following compound.

CHz COOC x Hs CH20OC,H.

CH20OCaHs-p-CI2 CHzOCOC(CHs)s CH, OCOCR.

CH,CN CH. C.N. CH　2CN CH20COC(CH)s CH x OCOC @Hs -CQ -CQ -CI2 -CI2 -CQ -CQ 4-CF.

-CQ 4-CF.

-CI2 -CF3 -Br -CQ -CQ Melting point °C Example 2 Insecticide and acaricide evaluation All tests were performed using industrial products. All concentrations reported here are for the active ingredient. All tests are kept at 27°C.

Spodoptera eridania
eridania), third instar, Souther armyworm (
southerarmyworm) Sieval lima (southeramyworm), which grows to 7-8 cm in length.
lima) Bean leaves are immersed in the stirred test suspension for 3 seconds and placed in a hood to dry. The leaves are then placed in a 100XIO petri dish with moist filter paper at the bottom and ten third instar larvae are added. The dishes are kept for five days before observations are made for mortality, reduced feeding, or any interference with normal molting.

Spodoptera eridania
eridania), 7 days residue The plants treated in the above test are kept under a high intensity lamp at room temperature for 7 days. These lamps recreate the effect of a bright, sunny June day in the New Jersey and are kept on for 14 hours a day. 7 days later,
Leaves are harvested and evaluated as in the test above.

Aphis fabae
, mixed age, approximately 5 cm tall with one bean apex (Tropae
alum sp,) in a pot containing approx.
00-200 Arimaki caught. Winter break is #154
Use a Devilbiss sprayer,
The test agent is sprayed in the hood during two revolutions of a 4 rpa+ turntable. The spray tip was kept approximately 15 cm from the plants and the sprayer was directed to completely cover the plants and aphids. The sprayed pots are kept on their sides on white enamel trays for 2 days, after which mortality is assessed.

Tetranychus urticae (7etranychus)
urticae) (P-resistant strain), two-star spider mite (
2-5potted 5pider site)7
- Siev lima with primary leaves that grow to 8 cm.
a lima) bean plants are selected and l per pot.
Trim it to become a plant. A small piece is cut from a leaf taken from the main colony and placed on top of each leaf of the test plant. This is done 2 hours before treatment to allow the mites to migrate to the test plants and lay their eggs. The section size is varied to obtain a collection of approximately 100 mites. During treatment, the leaves used for mite migration are removed and discarded.

The mite-infested plants are immersed in the agitated test chemical for 3 seconds and placed in a hood to dry. Plants are kept for 2 days and the first leaves are used to assess adult mortality. The second leaf is left on the plant for an additional 5 days to observe egg death and/or newly born larvae.

3rd instar southern corn beetle (south)
Arn corn rootworm) lc of talc fine powder is placed in 30+m(2) wide-mouthed twist-stop glass bottles.A suitable acetone suspension of l+n(2) is placed on the talc to contain 1.25 and 0.25 mg of active ingredient per bottle. The bottle is placed under a gentle stream of air until the acetone evaporates. The dried talc is broken down, lCC of millet seeds are added and fed to the insects, and 25■ a. Moist soil is placed in each bin. The bins are capped and the contents are thoroughly mixed with a Vortex m1xer.
Stirred with

Next, 10 third instar beetles are placed in each jar and the jars are loosely capped to allow air exchange for the larvae. Treatments are held for 6 days and mortality determined.

Missing larvae are considered dead because their decomposition is rapid and undetectable. The concentrations used in this study correspond to approximately 50 and 10 kg/ha, respectively.

Rating scale: 〇-No effect 1-10-25% mortality 2-26-35% mortality 3-36-45% mortality 4 = 46-55% mortality 5-56-65% mortality 6-66-75% mortality 7 = 76-85% death 8 = 86-99% death 9-100% mortality R-feeding reduction The values obtained from the above evaluation are shown in Table ■.

Example 3 ns), third instar tobacco budworm (tobacco
budworm) Cotton cotyledons are soaked in the test agent and dried in a hood. Once dry, cut each into quarters and lO
Place the sections separately into a 30 mQ plastic medicinal cup containing a piece of moist dental gauze wick 5-7 mm long. One third instar larva is placed in each cup and a pole paper lid is placed on top of the cup. Treatments are kept for 3 days and mortality is calculated to estimate the damage caused by reduced feeding.

Empoasca ab
rupta), adult, western potato leafhopper (western potato leafhopper)
opper) approximately 5 cm long.
a) Immerse the bean leaves in the stirred test suspension for 3 seconds and place in the hood to dry.

Leaves were placed in a 10100X1o Petri dish with moist filter paper at the bottom. Approximately 10 adult leafhoppers are placed in each dish, the treatment is kept for 3 days, and mortality calculations are made.

Blattella Germani Force (Blattella ge)
rmanica), diet test, adult male German cockroach (1 g of corn meal in 30 m (2 broad robin) by pipetting 1 mQ of a solution of the test compound in acetone of 11000 pp. % bait. The bait is dried through a gentle stream of air in the jar. The bait is placed in a 1-bin wide Mason jar.
ar) and 10 adult male cockroaches were placed in it. A mesh lid is placed on top of the jar and a piece of cotton soaked in 10% honey is placed over the mesh lid. Mortality is calculated after 3 days.

Blattella Germani Force
rman:ca), residue test, adult male German
German cockroach A 1 ml solution of the test substance in I 000 ppm acetone was gradually pipetted onto the bottom of an I 50 x 15 mm Petri dish, making sure to cover the bottom as evenly as possible. After the sediment had dried, 10 adult worms were added. male cockroaches were placed in each dish;
The lid is placed. Mortality is calculated after 3 days.

Spodoptera x Ridania
eridania), third instar larvae, southern army+m Compounds were 0.1 g test substance, 0.2 g Emulphor E L-620 emulsifier, 10
It is prepared as an emulsion containing m+2 acetone and 90 mα water. Dilute this 10 times with water and use lO for the test.
ppm emulsion. Furthermore, a 10-fold dilution with water is made if necessary. Chemu. with primary leaves that grow to 7-8 cm.
Lima (Sieva li+aa) legume plants are cut at least 3 ci above soil level to prevent microbial contamination of the soil that could cause stem rot during the test.

The cut stems are placed in the test emulsion and the winter grass is covered with a little cotton to keep the stems off the bottom of the bottle and to limit evaporation and volatilization of the compound. The test is maintained at 27°C for 3 days to allow compound uptake into the plants. Following this, one leaf is removed from the plant and placed in a 100X10u+n+ Petri dish with 10 Southern Fall armyworms.

After 3 and 5 days, mortality calculations and feeding damage observations are made.

Empoasca ab
rupta)s adult, western potato leafhopper (western potato leafhopper)
opper), systemic uptake compounds were O, 1 g test substance, 0.2 g Emulphor
E L-620 emulsifier, lomQ acetone and 9
Prepared as an emulsion containing 0 ml of water. Add this with water 1
Dilute to 0 times to obtain a 100 ppro emulsion for testing. A further 10x water diluent is made if necessary. 7-8c1
Sieva Lima has primary leaves that have grown to 1+.
lima) The legume plants are cut at least 3 cm above the soil level to prevent microbial contamination of the soil which could cause rot of the test stems. The cut stems are placed in the test emulsion and the winter grass is covered with a little cotton to keep the stems off the bottom of the bottle and to limit evaporation and volatilization of the compound. The test was maintained at 27°C for 3 days to allow compound uptake into the plants. Following this, one leaf was removed from the plant and 10 adult Western potato leafhoppers were removed.
A 10,100×10 Petri dish apparatus with 1000 pper) was prepared. Mortality calculations are performed after 3 days.

The evaluation scale for the above evaluation is the same as that described in Example 2.

The obtained values are listed in Table ■.

Table■ The answer is ζ−μ.

Tobacco side (ppm) (ppm) (ppm) (ppm)
(ppm) (ppm) (ppnl)
2. 3-dichloro-4-cyano-(3,4-dichlorophenyl)-virol-1-acetonitrile 3-promo 5-(p-chlorotuunyl)-4-cyano-2-(trifluoromethyl) Pyrrole-1-acetonitrile 4,5-dichloro-1-(hydroxymethyl)-
2-tt, α, ff -trifluoro-p-)lyl)pyrrole-3-carbonitrile, acetic acid (ester) 2.3-dichloro-4-cyano-5-Car, a, tt
-Trifluoro-p-)lyl)pyrrole-1-acetonitrile Table TIER) Evaluation as an insecticide Tobacco leafhopper (ppm) (ppm) (ppm) (pp
rn) (ppm) (ppm) (ppm
) 泗 YO 4 reverse fall 100 1000 10
00[2,3-dichloro-4-cyano-5-(3,4-
dichlorophenyl)pyrrol-1-yl]-pivalic acid, methyl ester 3-bromo-5-cyano-4-(3,
4-dichlorophenyl)-2-(trifluoromethyl)
Pyrrole-1-acetonitrile 4-bromo-3-(3,
4-dichlorophenyl)-1-(hydroxymethyl)-
5-(trifluoromethyl)pyrrole-2-carbonitrile, pivalic acid ester 2,3-dichloro-5-(p-chlorophenyl)-4-
Cyano-pyrrole-1-acetonitrile table ■ (line) Tobacco (ppm) (ppm) (ppn+) (p
pm) (ppm) (ppn+) (pp
m) 4-bromo-2-(p-chlorophenyl-1-hydroxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile, pivalic acid (ester) 3.4-dibromo-5-(p-chlorophenyl )-1-
(hydroxymethyl)-pyrrole-2-carbonitrile, pivalic acid (ester) [2,3-dichloro-4-cyano-5-(tr, a, a
-trifluoro-p-)lyl)pyrrol-1-yl]pivalic acid, methyl ester [2-(3,4-dichlorophenyl)-3-nitro-5-(trifluoromethyl)
Pyrrole-■-yl 1 pivalic acid, methyl ester Example 4 Evaluation of test compounds as nematicides Maintenance of cultures: Q, elegans (
Bristol from J. Lewis
strain) is maintained at 20 °C on E, co1i1NII on NG agar plates.

New cultures are established weekly.

The test nematodes were fresh Ascaris Ringer's solution (F
resh Ascaris Ringers 5
(FAR5) from 4-5 day old cultures. The nematodes are further washed with FAR5 containing gentamicin to reduce bacterial contamination and centrifuged to separate the worms from the wash solution.

Repeat this process three times. The washed worms were then grown from GIBCOa supplemented with gentamicin (600 units/m ) and mycostatin (0,5 mg/m
bMM).

Tests were then performed on mixtures of the three compounds, piggy-baked from other high-performance selection programs to reduce additional labor and compound consumption.
be done.

The compound is dissolved in acetone and brought up to volume with equal parts of water. The final tested concentration of each compound in the mixture was 150 p
It is pm. The test substance is micropipetted (25 uQ) into one compartment of a 96-compartment sterile tissue culture plate (CO5TAR)' and the solvent is allowed to evaporate. These "processed" plates can be used immediately or stored in a freezer without any obvious adverse effects on the compounds.

A freshly prepared volume (50 ug) of CbMMIC, elegans, is micropipetted into each treated compartment and several control compartments per plate. Solvent plates are incubated at 20°C.

Observations of efficacy are made under a dissecting microscope 4.24 and 48 hours after immersion.

Just before examining the plate, tap it lightly to stimulate insect movement. Although activity is determined subjectively, it is evaluated semi-quantitatively based on the effect of the drug on adult and larval movement.

The criteria are as follows.

8 = no movement, 7 = markedly reduced movement of almost 95% of the worms, 6 = reduced movement, 5 - slightly reduced movement, 0 - normal movement, equivalent to control. Other elements that indicate motility are death,
It is easily manifested by rigor mortis, shrinkage, coiling, paralysis, abnormal spasticity, decreased number of worms within 48 hours, and other deviations from normal behavior.

CAENORHAB
DITIs ELEGANS) evaluation method Day 0
E, Co11-NG agar plate was inoculated with 30-50 of 9. elegans.

Culture at 20°C.

Day 4 - Collection of new C. elegans population Washed with antibiotics Transferred to CbMM Q. x elegans (25-100
UL) was added to the "drug-treated" plot 1. Observation of activity 4 hours after immersion Day 5 Observation of activity Day 6 Observation of activity 1 Drug-treated plots were freshly prepared or previously prepared. and stored in the freezer.

The values obtained from these tests are shown in Table ■.

Table■ C.Elegance (elegans) activity level Nistil pivalic acid (esthenolytic acid) Pivalic acid, methyl ester a-active Not tested -1-acetonitrile acetonitrile The main features and aspects of the invention are as follows.

1. Compound 1-acetonitrile-1-acetonitrile pivalic acid, methyl ester 〇-inactive (I) having the structure shown in formula 1, where X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or trifluoromethyl group; Y is a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, or cyano group; W is a cyano group or a nitro group; A is four halogen atoms an alkyl group of 01 to C, substituted with one cyan group, one alkokino group substituted with one to three halogen atoms, or two optionally substituted with one to three halogen atoms; an alkoxy group, one 01 to C4 carbalkoxy group,
one C1-C6 alkylcarbonyloxy group, one C2-C6 alkenylcarbonyloxy group, one benzenecarbonyloxy group or chloro, dichloro,
or methyl-substituted benzenecarbonyloxy group: L is
A hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and M and R are each independently an alkyl group of 01 to C1,
C1-C1 alkoxy group, C1-C1 alkylthio group, C1-C1 alkylsulfinyl group, C1-C1
an alkylsulfonyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a trifluoromethyl group, R, CF2ZSR2CO or NR,R, and M and R are adjacent positions and they bond When together with a carbon atom, M and MR may form a ring represented by the following structure: 2 is 5(0)n or O: R1 is a hydrogen atom, a fluorine atom, CHF, CHFCQ
, or a trifluoromethyl group; R2 is a C1-C1 alkyl group, a 01-C1 alkoxy group, or NR,
R,; R1 is a hydrogen atom or a 01-C1 alkyl group; R6 is a hydrogen atom, a 01-C3 alkyl group, or R,
CO; R5 is a hydrogen atom or an alkyl group of 01 to C3; and n is an integer of 0, ■ or 2; provided that X and Y are hydrogen atoms and A is substituted with one cyan group, is an alkyl group, the substituents include 1 of the two positions adjacent to the nitrogen atom on the pyrrole ring.
must be combined with.

2. W is a cyano group or a nitro group; X and Y are each a chlorine atom, a trifluoromethyl group, or a bromine atom; R is a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, or a trifluoromethoxy group; M or hydrogen atom, fluorine atom, chlorine atom or bromine atom, and L is a hydrogen atom or a fluorine atom.

The compound according to 1 above, which is

3. The compound according to claim 1 having the following structural formula: and A, L, MXR% W, X and Y are as described in 1 above.

4. The compound described in I above having the following structural formula: and
A, L%M%RSW, X and Y are as described in 1 above.

5. Insects, mites and nematodes, their breeding grounds, food or habitat, with formula I, where x, y, w.

A method for controlling insects, mites, and nematodes, comprising contacting an insecticidal, acaricidal, and nematocidal effective amount of a compound in which ASL, M, and R are as described in I above.

61. The method according to 5 above, wherein the compound of formula I has the structure described in 2 above.

7. In the plant population or in the soil or water in which the plants are grown, a compound of formula I, where X, Y%W, A, L%M and R are as defined in claim l. For killing insects,
A method for protecting plant growth from insect, mite and nematode attack comprising applying an effective amount of acaricide and nematicide.

8. Add about 0 to the plants or the soil in which they are growing.
．． 7. The method of claim 7, comprising applying said compound at a rate of 125 kg to about 4.0 kg.

9. The compound of formula (I) is applied to the leaves of the plant or to the soil or water in which the plant is growing in the form of a solution composition containing from about 10 ppm to about 10,000 ppm of the compound of formula I. the method of.

10. Compound of formula (■) is mixed with at least 1 molar equivalent of reagent A -h of formula (■)
ajogen (U) in which A is as defined above, and reacting with at least one molar equivalent of an alkali metal base and a solvent to give the desired compound of formula I I) Here, A is C I substituted with four halogen atoms
'-C- alkyl group, one cyano group, one alkoxy group substituted with one to three halogen atoms, or two alkoxy groups optionally substituted with one to three halogen atoms , one C1-C4 carbalkoxy group, one C, -C, alkylcarbonyloxy group, one C2-C, alkenylcarbonyloxy group or one benzenecarbonyloxy group or chloro, dichloro or methyl substituted benzenecarbonyl The oxy group, and Y, W, L, M and R are as described in 1 above.

Claims (1)

[Claims] 1. A compound having the structure shown in formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Here, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom , or a trifluoromethyl group; Y is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, or a cyano group; W is a cyano group or a nitro group; A is four halogen atoms Replaced C_1 to C_4
an alkyl group, one cyano group, one alkoxy group substituted with one to three halogen atoms, or two alkoxy groups optionally substituted with one to three halogen atoms, one C_1 ~C_4 carbalkoxy group, one C_1 to C_6 alkylcarbonyloxy group, one C_2 to C_6 alkenylcarbonyloxy group, one benzenecarbonyloxy group or chloro, dichloro, or methyl substituted benzenecarbonyloxy group; L is A hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and M and R are each independently an alkyl group of C_1 to C_3, an alkoxy group of C_1 to C_3, an alkylthio group of C_1 to C_3, an alkylsulfinyl group of C_1 to C_3 , C_1 to C_3 alkylsulfonyl group, cyano group, fluorine atom, chlorine atom, bromine atom, iodine atom,
Nitro group, trifluoromethyl group, R_1CF_2Z,
When R_2CO or NR_3R_4 and M and R are in adjacent positions with the carbon atoms to which they are attached, M and MR may form a ring represented by the following structure: -OCH_2O-, -OCF_2O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼; Z is S(O)_n or O; R_1 is hydrogen atom, fluorine atom, CHF_2, CHF
Cl or trifluoromethyl group; R_2 is a C_1 to C_3 alkyl group, C_1 to C_
3 alkoxy group, or NR_3R_4; R_3 is a hydrogen atom or a C_1 to C_3 alkyl group; R_4 is a hydrogen atom, a C_1 to C_3 alkyl group, or R_5CO; R_5 is a hydrogen atom or a C_1 to C_3 alkyl group, and n is an integer of 0, 1 or 2; However, when X and Y are hydrogen atoms and A is an alkyl group of C_1 to C_4 substituted with one cyano group,
The substituents are 1 of the two positions adjacent to the nitrogen atom on the pyrrole ring.
must be combined with. 2. Insects, mites and nematodes, their breeding grounds, food or growth environments, with the formula I, where X, Y, W, A, L, M
and R is the compound according to claim 1, and a method for controlling insects, mites, and nematodes, comprising contacting an effective amount of the compound for insecticidal, acaricidal, and nematicidal purposes. 3. VIII ▲Mathematical formulas, chemical formulas, tables, etc.▼ Add the compound of (VIII) to at least 1 molar equivalent of the reagent A-ha of formula IX
logen(IX) where A is as defined above, and reacting in the presence of at least one molar equivalent of an alkali metal base and a solvent to give the desired compound of formula I ▲Formula , chemical formulas, tables, etc. ▼ (I) Here, A is C_1 substituted with four halogen atoms.
~C_4 alkyl group, one cyano group, one alkoxy group substituted with one to three halogen atoms, or two alkoxy groups optionally substituted with one to three halogen atoms, 1 one C_1-C_4 carbalkoxy group, one C_1-C_6 alkylcarbonyloxy group, one C_2-C_6 alkenylcarbonyloxy group or one benzenecarbonyloxy group or chloro, dichloro or methyl substituted benzenecarbonyloxy group, and Y , W, L, M and R are those according to claim 1.