PH26832A - Benzoylurea derivative and its production - Google Patents

Description

tore basis . O) el

Wo 1 The present invention relates to a novel benzoylurea derivative represented by the formula (I) described below, its production and an insecticidal and acaricidal composition containing it as an active ingredient:

Ry 0 X Fy R, Cl {I or Cb oon (1)

Ry Re wherein Ry is a chlorine or fluorine atom, each of R, and Rr which may be the same or different, is a fluorine or hydrogen atom, R, is a chlorine or hydrogen atom, Re is a halogen atom or a methyl or trifluoromethyl group, and X is an oxygen or sulfur atom.

The present inventors have extensively studied to develop a benzoylurea compound having excellent insecticidal and acaricidal activity, and as a result, have found that the benzoylurea derivative represented by the formula (I) (hereinafter referred to as present compound) has a very high insecticidal and acaricidal activity, particularly a high lethal activity against 7 : the larvae and nymphs of spider mites and a sterilization - activity against the female adults of spider mites as well as an ovicidal activity, and also that it can be I produced at a relatively low cost. The present i i . ii Les i dis gl Sal 1 aii iii ini ais AA aaa niin dsc

Boones cn ar Stn LU ddl i

CL | oo

Lot O ( Y i 1 inventors thus attained to the present invention.

Among the present compounds represented by the formula (I), preferred ones include those in which

Ry is a chlorine or fluorine atom, R, is a hydrogen atom, R, is a hydrogen atom when Ry is a chlorine atom, and a fluorine atom when Ry is a fluorine atom, R, is a hydrogen atom, Rg is a halogen atom or a methyl or / trifluoromethyl group, and X is an oxygen atom.

US-A-3933908 discloses benzoylurea compounds which are efficacious against insect pests, and among these compounds, diflubenzuron is already on the market.

Also, it is known that compounds disclosed in EP-Al- 161019 have not only an insecticidal activity, but also an acaricidal activity.

Although these compounds exhibit an insecticidal activity against insect pests belonging to Lepidoptera, etc., their acaricidal activity is so poor that they i are not always satisfactory as an acaricide. Contrary to this, it has been found that the present compounds have excellent insecticidal and acaricidal activity. j - For specific examples of insect pests against which the present compounds are particularly efficacious, ; there may be given the following insects and mites: j

Larvae of Lepidoptera such as diamond-back moth (Plutella xylostella), rice stem borer (chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), armyworms and cutworms, etc.; larvae of Diptera such as house mosquitoes (Culex spp.) [e.g. common mosquito mnie: ep pA Wat eid Ca da i Ee Lr te Ae A RN

ST . - To i ) 1 (Culex pipiens pallens)], Anopheline mosquitoes (Anopheles spp.), Aedes mosquitoes (Aedes spp.), chironomid midges (Chironomidae), houseflies (Muscidae) [e.g. Musca domestica], blow flies (Calliphoridae), flesh flies (Sarcophagidae), tabanid flies (Tabanidae), Co blackflies (Simulidae), etc.; nymphs of Dictyoptera e.g. German cockroach (Blattella germanica)]; larvae J of Coleoptera; and spider mites (Tetranychidae) such as two-spotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus cinnabarinus), Kanzawa spider mite (Tetranychus kanzawai), citrus red mite (Panonychus citri), European red mite (Panonychus ulmi), etc.; cheyletid mites (Cheyletidae); tarsonemid mites (Tarsonemidae); acarid mites (Acaridae) [e.g. mold mite (Tyrophagus putrescentiae)]; pyroglyphid mites (Pyroglyphidae) [e.g. Dermatophagoides farinael; etc.

Also, the present compounds are low in toxicity to warm-blooded animals so that it can be orally administered mixed with feeds for animals to domestic animals such as cattle, pigs, horses, sheep, goats, chickens, etc. As a result, the present compounds are excreted from animals as undecomposed, so that the x larvae of insects living in the excrements of domestic : animals [e.g. housefly, false stablefly (Muscina stabulans), little housefly (Fannia canicularis), blow flies (Calliphoridae), flesh flies (Sarcophagidae), sepsid flies (Sepsidae)), can be exterminated.

For example, the following compounds may be

Ca bo i i DUBIN © aire a St AS A A Re Le a el Sh a alee ta Lan Si lia et ili miei ' 1 : yD e OC a 1 given as the present compound:

N-2,6-difluorobenzoyl-N'-[2,5-difluoro-4-{2- chloro-4- (trifluoromethyl) phenylthio} phenylurea

N-2-chlorobenzoyl}N'-[2,5-difluoro-4-1{2- chloro-4- (trifluoromethyl) phenylthio} phenyljurea

N-2,4,6-trifluorobenzoyl-N'-[2,5-difluoro-4- {2-chloro-4- (trifluoromethyl) phenylthio} phenylurea

N-{2,6-difluorobenzoyl}N'~[2,5-difluoro-4- {2-chloro-4- (trifluoromethyl) phenylthio} phenyljthiourea

N-2, 6-difluorobenzoyl}N'~[3-chloro-2, 5- difluoro-4-{2-chloro-4- (trifluoromethyl) phenylthio) - phenyljurea

N-f, 6-difluorobenzoyl N'-[3,5-dichloro-2- fluoro-4-{2-chloro-4- (trifluoromethyl) phenylthio} - phenylurea

N-2, 6-difluorobenzoyl}-N'-[5-bromo-2-fluoro-4- . {2-chloro-4- (trifluoromethyl) phenylthio} phenyljurea

N-{2, 6-difluorobenzoylFN'-[2-fluoro-5- trifluoromethyl-4-{2-chloro-4- (trifluoromethyl) - : phenylthio} phenyilurea

N-@2,6-difluorobenzoyl}N'-[5-bromo-3-chloro-2- fluoro-4-{2-chloro-4- (trifluoromethyl) phenylthio} - ; } phenylurea E

N+2,6-difluorobenzoyl}N'-[3-chloro-2-fluoro-5- trifluoromethyl-4-{2-chloro-4- (trifluoromethyl) - phenylthio} phenylurea

N-2,6-difluorobenzoyl}-N'-{[5-chloro-2-fluoro-4- {2-chloro-4- (trifluoromethyl) phenylthio} phenylurea i RE SAL ILS 1 Thor IX ms et pea LE AEE i win di ame ii Le aE ! Co R gn hol oo O ( ye i 1 N~2, 6-difluorobenzoyl-N '—{2-fluoro-5-methyl-4- {2-chloro-4- (trifluoromethyl) phenylthio} phenylurea

N{2-chlorobenzoyl}yN'~[5-chloro-2-fluoro-4- {2-chloro-4- (trifluoromethyl) phenylthio} phenyllurea

N-2,4,6-trifluorobenzoyl}-N'-[5-chloro-2- fluoro-4-{2-chloro-4- (trifluoromethyl) phenylthio} - phenylurea s

N~2,6-difluorobenzoy -N'-[5-chloro-2-fluoro- 4-{2-chloro-4- (trifluoromethyl) phenylthio) phenyljthio- urea

The present compounds represented by the formula (I) can be produced by the following methods.

Method A:

A method of reacting a benzoyl isocyanate compound or benzoyl isothiocyanate compound represented by the formula (II),

R10

Il : i

R, C-N=C=X CS (11) "3 wherein ISK Ry, Ry and X are the same as described Li above, with an aniline compound represented by the i formula (III), .

F R, Cl i mY Yer, (III) - 6 - t i. shasta Li it J a EC AS a ——— eR I EE CN ET EC NE CI * 1 . f ), ) . . : : N oe pn !

C C p 1 wherein R, and Re are the same as described above.

Method B:

A method of reacting a benzamide compound represented by the formula (IV),

Ry 0 ~ i | ]

R, C-NH,, (Iv)

R3 wherein Ry R, and Ry are the same as described above, with an isocyanate compound or isothiocyanate compound represented by the formula (V),

F R 4 Cl

X=C=N a Ty CF (v) > wherein Ry» Re and X are the same as described above.

In the foregoing Methods A and B, the reaction is usually carried out in the presence of an inert solvent. The solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene, xylene), o halogenated hydrocarbons (e.g. chlorobenzene, carbon tetrachloride, chloroform, methylene chloride, 1,2- dichloroethane), ethers (e.g. diethyl ether, tetra- hydrofuran, dioxane), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethyl oq , ! .

\ coh 1 sulfoxide, dimethylformamide, nitromethane and mixtures thereof.

In Methods A and B, the reaction can generally be carried out under normal pressure, and the reaction will be completed usually in from 1 to 50 hours. The amounts of the compounds which are a raw material are generally in an equimolar ratio, but one of the compounds may be used in excess.

In Methods A and B, the reaction temperature is not particularly limited, but it is in a range of generally from 0° to 80°C, usually from room temperature to 60°C for Method A, and generally from room temper- ature to 160°C, usually from 80° to 130°C for Method B.

The present compounds thus obtained can be purified if necessary by means such as column chromatography, recrystallization, etc.

Both the benzoyl isocyanate compound or benzoyl isothiocyanate compound represented by the formula (II) and the benzamide compound represented by the formula (IV), used in the methods of the present invention, are a known compound. The aniline compound represented by the formula (III) is a novel compound, and it can be : produced, for example, by the following method: : i

Cy

I ieee A Nini

Beit ie aE ets ts - Cra bie en —iin os on [, - FE ee o JO LLL . , ! ! / { hh ) ! pe. yU - ( i i :

F R, Cl wig yo + ar Her,

Rs (VI) (VII)

F R, Cl

Basic substance and solvent ; _—_—m-— 0N—(/ S / CF , ° ° 2 3 0 -150 C, 0.1-24 hours

Rs (I11) 1 wherein R, and Rg are the same as described above.

The basic substance used includes for example sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, triethylamine, etc. The solvent used includes for example aprotic polar solvents such as dimethyl- formamide, dimethyl sulfoxide, hexamethylphosphoroamide, acetonitrile, etc.

In carrying out this reaction, the amount of the basic substance used is from about 0.5 to about 3 times by mole, preferably from about 1 to about 1.2 times by mole based on 1 mole of the aminothiophenol compound (VI), and the amount of the 3,4-dichloro- J benzotrifluoride (VII) used is from about 0.5 to about F 3 times by mole, preferably from about 1 to about 2 : : . times by mole based on 1 mole of the same. ! The reaction product thus obtained may be purified if necessary by means such as column : chromatography, recrystallization, etc. i t i - 9 -

\ : e ") 1 The aminothiophenol compound (VI) described : in the foregoing reaction formula can be produced, for example, by the method disclosed in 3P-A-60-181067, etc.

The isocyanate compound or isothiocyanate compound represented by the formula (V) can easily be { produced by reacting an aniline compound represented by / the formula (III) with phosgene Or thiophosgene accord- ing to the usual method. This reaction is usually carried out under the following condition: The amount of phosgene or thiophosgene used is usually from 0.2 to 20 times based on the aniline compound, and an inert solvent is usually used. Normally, such the solvent includes for example hydrocarbons (e.g. hexane, heptane, benzene, toluene), halogenated hydrocarbons (e.g.dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene) and mixtures of two or more of them. :

This reaction well proceeds in a range of from room temperature to the boiling point of the solvent. The reaction product thus obtained may easily be purified if necessary by distillation, etc.

When the present compounds are used as an . active ingredient for insecticidal and acaricidal com- - positions, they may be used as they are without adding any other ingredients. Usually, however, they are formulated into emulsifiable concentrates, wettable powders, dusts, granules, flowable formulations, oil sprays, aerosols, poisonous baits, etc. by mixing with i

C10 - ]

Ee i dA TEE ETE 3 LCL br dae 25 iin Hoitbo Ladi dea be eben oie sooo Sota noi t+ eter en , . } ~ yo 3 oo 6 ( : 0 1 solid carriers, liquid carriers, gaseous carriers, surface active agents, other auxiliaries for formulation, baits, etc.

In these preparations, the content of the present compounds, which are an active ingredient, is from 0.01 to 95% by weight. The solid carrier includes for example fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra abla, pyrophyllite, talc, diatomaceous earth, calcite, corn stalk powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide and the like. The liquid carrier includes for example aliphatic hydrocarbons (e.g. kerosene), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, - carbon tetrachloride), alcohols (e.g. ethylene glycol, cellosolve), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone, isophorone), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), esters (e.g. ethyl acetate), nitriles (e.g. acetonitrile, isobutyro- nitrile), acid amides (e.g. dimethylformamide, dimethyl- acetamide), dimethyl sulfoxide, vegetable oils (e.g. soybean oil, cotton seed o0il) and the like. The gaseous carrier includes for example freon gas, LPG (liquefied petroleum gas), dimethyl ether and the like. The surface active agent used for emulsification, dispersion, wetting, etc. includes for example anionic surface active agents such as the salt of alkyl sulfates, i

Ne Ps EN i LA . . .L REE . . To T . A . : NER

Co e C Na 1 alkyl(aryl)sulfonates, dialkyl sulfosuccinates, the - salt of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalenesulfonic acid/formalin condensates, etc., and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxy- propylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The ’ auxiliary for formulation such as fixing agents, dispersing agents, etc. includes for example ligno- sulfonates, alginates, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethyl cellulose), pine oil, agar, etc. The stabilizer includes for i example alkyl phosphates (e.g. PAP (isopropyl acid phosphate), TCP (tricresyl phosphate) ], vegetable oils, epoxidized oils, the foregoing surface active agents, antioxidants (e.g. BHT, BHA), fatty acid salts (e.g. sodium oleate, calcium stearate), fatty acid esters : (e.g. methyl oleate, methyl stearate) and the like.

The preparations thus obtained may be used as they are or in dilution with water. Also, they may be used in mixture with other insecticides, acaricides, nematocides, fungicides, herbicides, plant growth i regulators, fertilizers, soil improvers, feeds for : animals, etc.

When the present compounds are put to practical use as an insecticidal and acaricidal composition, their dosage rate is usually from 0.1 to 100 g per 10 ares, and their application concentration is from 10 to

C12

: Loh!

So ® oS yin 1 500 PpPm when emulsifiable COncentrates, wettable

Powders, flowable formulations, etc. are useg diluted

With water, Dusts, granules, oi} Sprays, aerosols, etc. are useqd as they are without dilution.

The present invention will be illustrateq in more detail with reference to the following Production €Xamples, formulation examples and test examples, byt it is not limited to these examples. Firstly, production examples will pe given,

Production example 1 [Production of the Present compound (1) 0.21 Gram of >~Chloro-2-f1luoro-4- (2-ch1ope. #- (trifluoromethyl) phenylthio) ani 11mne was dissolved it in 6 ml of toluene, and to this solution was added dropwise a solution of 0.11 g of 2,6-difluorobenzoy1 isocyanate in 4 m1 of toluene with ice-cooling and

Stirring. After completion of addition, the reaction solution was stirreq overnight at room temperature.

Thereafter, ¢ ml of n-hexane was added, the Precipitateqg crystals were filtered off and dried to obtain 0.20 g 3 of 6d luoronenzoy Jon (5-ohloro-2-t1uoroy. go. i eh1oTo-4- (trifluoromethyl) pheny1tnio; phenyJurea as - white crystais.

Yield 64% } m.p. 193.7°¢

1 Production example 2 [Production of the present 7 compound (1)] 0.32 Gram of S5-chloro-2-fluoro-4-[2-chloro-4- F (trifluoromethyl) phenylthiolaniline was added to 30 ml a of a 5% phosgene-toluene solution, and the mixture was i heated under reflux for 3 hours. After concentrating " the reaction solution, the residue obtained was LL dissolved in 20 ml of xylene, and 0.14 g of 2,6- 4 difluorobenzamide was added. The solution was then ; : 10 stirred under reflux for 24 hours. Thereafter, the 3 reaction solution was cooled and concentrated to obtain ; a crude product. This crude product was subjected to : chromatography on silica gel to obtain 0.40 g of NA2,6- L difluorobenzoyl-N'-5-chloro-2-fluoro-4-{2-chloro-4- - (trifluoromethyl) phenylthio} phenyfurea as white crystals. 3

Yield 83% 3 m.p. 193° - 194°C :

Some of the present compounds thus obtained . will be collectively shown in Table 1. :

Ribs ie Ss a ad oa a te ped Mi rte a nie el Ia Le rm tbr ak nea Ls JSS ™

Co Ny i. N (: ) CYL ) : - yb pO oo . lus}

HP

: mn Co oA 0 0 .

Ol 4 mo arma oOo oo ~ Mm OW MN ~ OO WwW ™M ~N Mm NN mH / © o I~ Oy I~ 0 0 O Ow ~ aA OO

OD -A ~~ ~~ ~~ NN — A : [sa] oH fq nu oO > QO o EB [aT] ~— —

L > oO 0O oO woo own Ooo Oo : 0 < | in [44 oo ™ ™ nN — oH oH Tu Bm fe Non ! m UO Vv Lo Ov VU Mm oO ! ~~ i

Q Pe : y

Q xT =x mom om omomom mom Am oon ' ol Zz [a4 |®] i

Ee x=0 : x . , = A BU 0=0 0 Bg 0 fo fy om BR fu fry Ff [my Du ~~ ™ a4 - [24 24 oe mom mom am Bm mo mom oN [a4 —~ fro BR fy mA mB By Be Be ~ 0 oO Co oF > = bs eld NN co «nw r~ ooo HN :

Oo 0 —r nr nr er er nr ar =~ ~~ A ~~ 0, z ~— ~— . ;

E . 0 . oO ee A 0 { Lime es Ce SR : Co : ’ : sN/ oo C - a 1 Production example 3 (Production of an intermediate aniline compound) 5.00 Grams of 5-chloro-2-fluoro-4-mercapto- aniline, 12.2 g of 3,4-dichlorobenzotrifluoride and 5S 4.31 g of potassium carbonate were dissolved in 30 ml of dimethylformamide, and the resulting solution was } stirred for 2 hours at a temperature of from 100° to 110°C in an oil bath. Thereafter, the reaction solution was poured into water and extracted with three 200-ml portions of diethyl ether. The extract obtained was washed with water, dried, filtered and concentrated.

The residue obtained was subjected to chromatography on ‘silica gel to obtain 6.57 g of 5-chloro-2-fluoro-4-[2- chloro-4- (trifluoromethyl) phenylthiolaniline. vield 66% m.p. 80.8°C 1h-nMR (cpcly) : §(ppm) 4.13(2H, br.) 6.67(1H, 4. J=8.0 Hz) 6.94(1H, 4d. J=8.0 Hz) 7.25(1H, 4. J=10.0 Hz) 7.57 (1H, br. s) i

Production example 4 (Production of an intermediate aniline compound) i 3.00 Grams of 2,5-difluoro-4-mercaptoaniline hydrochloride, 6.60 g of 3,4-dichlorobenzotrifluoride and 4.90 g of potassium carbonate were dissolved in

SRA diisbai Liataciatt 4 = (iii diiiodk cilia REA A Ee eri as : | Liv! : oo ( a Ni ; 1 30 ml of dimethylformamide, and the resulting solution was stirred for 6 hours at a temperature of from 100° to 110°C in an oil bath. Thereafter, the reaction solution was poured into water and extracted with three © 5 100-ml portions of diethyl ether. The extract obtained was washed with water, dried, filtered and concentrated.

The residue obtained was subjected to chromatography on ’ silica gel to obtain 3.60 g of 2,5-difluoro-4-1{2- chloro-4- (trifluoromethyl) phenylthiolanilince.

Yield 69% m.p. 95.9°C lh-nmRr (CDC1,) : 8 (ppm) 4.17(2H, br.) 6.62 (1H, dd. J=8.0, 10.0 Hz) : 15 6.70(1H, 4. J=8.0 Hz) 7.17 (1H, ad. J=6.0, 10.0 Hz) 7.56 (1H, br. s)

Production example 5 (Production of an intermediate aniline compound) 1.00 Gram of 2-fluoro-5-methyl-4-mercapto- aniline hydrochloride, 2.24 g of 3,4-dichlorobenzotri- fluoride and 1.59 g of potassium carbonate were i dissolved in 10 ml of dimethylformamide, and the resulting solution was stirred for 6 hours at a temper- ; ature of from 110° to 120°C in an oil bath. Thereafter, the reaction solution was poured into water and extracted with two 100-ml portions of diethyl ether.

Co Lon

IE c AE 1 The extract obtained was washed with water, dried, filtered and concentrated. The residue obtained was subjected to chromatography on silica gel to obtain 1.27 g of 2-fluoro-5-methyl-4-[2-chloro-4-(trifluoro- methyl)phenylthiolaniline. . yield 73% } n2%0 1.592 ’ 1h-NMR (cpCly) : § {ppm) 3.95(2H, br.) 6.58(1H, 4. J=8.0 Hz) 6.76 (1H, 4d. J=9.0 Hz) 7.18(1H, 4d. J=11.0 Hz) oo 7.25(1H, 4d. J=2.0, 8.0 Hz) 7.55(1H, br. s)

Some of the intermediate aniline compounds thus obtained will be shown below.

S-Bromo-2-fluoro-4-[2-chloro-4-(trifluoro- methyl) phenylthiolaniline

La-nmR (CDC1,) = § (ppm) 4.08 (2H, br.) 6.70(1H, 4d. J=8.0 Hz) 7.13(1H, d. J=8.0 Hz) fh 7.28(1H, 4. J=10.0 Hz) - 7.30(1H, 44. J=2.0, 8.0 Hz) 7.57(1H, br. s) ; 3,5-Dichloro-2-fluoro-4-{2-chloro-4- (trifluoromethyl) phenylthiolaniline

Ch !

CG ( at : 1 'u-NMR (CDCl) : § (ppm) 4.28(2H, br.) 6.65(1H, d. J=8.0 Hz) 6.98(1H, 4. J=8.0 Hz) 7.35(1H, dd. J=2.0, 8.0 Hz) 7.65(1H, br. s) 2-Fluoro-5-trifluoromethyl-4-[2-chloro-4- : ! (trifluoromethyl) phenylthio]aniline i-nmr (CDC15) :

S{ppm) = 4.21 (2H, br.) 6.63(1H, 4d. J=8.5 Hz) 7.22(1H, 4. J=7.0 Hz) 7.25(1H, 4. J=10.0 Hz) 7.27(1H, dd. J=2.0, 8.5 Hz) : 15 7.55(1H, br. s)

Formulation examples will be shown. In the examples, the present compounds are shown by Compound :

No. in Table 1, and parts are by weight.

Formulation example 1

Ten parts of each of the present compounds (1) x to (12), 14 parts of polyoxyethylene styrylphenyl ether, i 6 parts of calcium dodecylbenzenesulfonate, 35 parts of a xylene and 35 parts of dimethylformamide are well mixed to obtain an emulsifiable concentrate of each compound. i

Formulation example 2

Twenty parts of each of the present compounds :

CC -19 -

Co $ ( ge 1 (1) to (12), 10 parts of Fenitrothion, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 65 parts of synthetic hydrated silicon dioxide are well pulverized and mixed to obtain a wettable powder of each compound.

Formulation example 3 /

One part of each of the present compounds (1) to (12), 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a dust of each compound.

Formulation example 4

Twenty parts of each of the present compounds (1) to (12), 3 parts of a sodium naphthalenesulfonate/ : formalin condensate and 75 parts of water are well 1s pulverized and mixed, and 2 parts of methyl cellulose is added and mixed as a thickening agent to obtain a flowable formulation of each compound.

Test examples will be shown. The present compounds are shown by Compound No. in Table 1, and compounds used as a control are shown by compound symbol LL in Table 2. E fis: oe -~ EL = Sad i ial NL hot Sid hig ~ ~ Ri - jaan AE chy ht gi i Sed al cain Sti ana PILAR ToL Cs in

Co ' ! “ + / h )

C 3 ( yo

Table 2

Compound

Structural formula Remark symbol

F . oO © Diflubenzuron 1 n N\ (A) CNHCNH-{ >- C1 (compound described

F in US-A-3933908). cl : 0 O , / hon Compound described (B) - Ene Ys) = == in US-A-3933908. cl

F F Cl ! 0 Q Flufenoxuron i : ! (Cc) S-band yo Yer, (compound described \

F in EP-Al1-161019). i

CH,

J _~CHg (D) Cl N=CH-N Chlordimeform — ~N

CH, : } . i ! . 1 Test example 1

The emulsifiable concentrates of the following test compounds obtained according to Formulation example : 1 were each diluted with water to a concentration of 1 ppm. Thereafter, 100 ml of each dilute solution thus obtained was put in a 180-ml polyethylene cup, and 20 " last instar larvae of common mosquito (Culex pipiens pallens) were liberated therein. The larvae were bred on a bait until emergence to obtain an emergency ! inhibitory ratio (two replications).

The results are shown in Table 3.

a ’ ' gL 3 ! oo C ( "

Table 3

Emergence inhibitory

Test compound | ratio (%)* (1) A (2) A { (3) A } (4) A (5) n (6) A (7) A (8) A (9) A (10) A (11) A (12) A

No treatment | C * Emergence inhibitory ratio (%):

A: More than 90%

B: From 80 to 90%

C: Less than 80% b 1 Test example 2

The emulsifiable concentrates of the following test compounds obtained according to Formulation example 1 were each diluted with water to a concentration of 15 ppm. . Two milliliters of each dilute solution thus - 22 - i

Co yy) BR o ® Re 0 1 obtained was applied onto 13 g of artificial diet for = tabacco cutworm (Spodoptera litura) which were then put id = 4 in a polyethylene cup of 11 cm in diameter. Then, ten 5 fourth instar larvae of tabacco cutworm were liberated io in the cup. After six days, the dead and alive were a examined to obtain mortality (two replications). I

The results are shown in Table 4. .

Table 4 ~

Test compound | Mortality (3) - (1) 100 i (2) 100 . (3) 100 (4) 100 F (5) 100 : (6) 100 3 (7) 100 . . (8) 100 ; (10) 100 2 (11) 100 3 (12) 100 ig

No treatment 5 Fo a A SS MA ic

Bl sie cach nih mes ati di a Li ll —

Co 1 Test example 3

The emulsifiable concentrates of the following test compounds obtained according to Formulation example 1 were each diluted with water to a concentration of } 100 ppm to obtain a dilute solution. From 20 to 60 deutonymphs of carmine spider mite (Tetranychus ’ cinnabarinus) were transferred onto leaves in a petri : i dish, and 3 ml of the dilute solution was sprayed thereon. After three days, the number of adults was counted to obtain an adult emergence inhibitory ratio.

The results are shown in Table 5.

Test example 4

The emulsifiable concentrates of the following test compounds obtained according to Formulation example 1 were each diluted with water to a concentration of 100 ppm to obtain a dilute solution. Thirty female adults of carmine spider mite (Tetranychus cinnabarinus) were transferred onto a leaf in a petri dish, and 3 ml of the dilute solution was sprayed thereon. After air-drying, 18 female adults were transferred onto untreated leaves in a petri dish, and allowed to i; oviposit for three days. The eggs obtained were stored 3 in a chamber controlled at 27°C in an artificial weather room. After six days, hatchability of the eggs was examined to obtain a sterilization ratio.

The results are shown in Table 5.

a . } : » . o ey ’ Cen er ! . , Pp) CY . 5 ’ ® ( i

Table 5

Test Adult emergence Sterilization compound inhibitory ratio (%)* ratio (%)** (1) 100 95 (2) 100 - (3) 100 - (4) 100 _ (5) 100 99 (6) 100 96 ; (7) 100 99 (8) 100 95 (9) 97 - (10) 98 72 i (11) 100 - (12) 100 - — i (A) 5 0 (B) 2 0 (C) 60 0 : adult emergence ratio « in the plot treated :

Adult emergence with chemicals

Saas x 100 inhibitory =f -—— : ratio (%) adult emergence ratio in the plot treated with water hatchability in the I plot treated with i, * 4% i el

Sterilization -|1 - chemicals x 100 oo ratio (%) hatchability in the plot treated with water or i Ha ne amen eo ea ee a ( ; of ; 1 Test example 5

The emulsifiable concentrates of the following test compounds obtained according to Formulation example 1 were each diluted with water to a concentration of © 5 100 ppm to obtain a dilute solution. The female adults of carmine spider mite (Tetranychus cinnabarinus) were j transferred onto leaves and allowed to oviposit for 24 hours. The eggs obtained were dipped for 5 seconds in the dilute solution. After treatment, the eggs were stored in a chamber controlled at 27°C in an artificial weather room. After six days, the number of unhatched eggs was examined to obtain an ovicidal ratio.

The results are shown in Table 6. }

Table 6

Test compound Ovicidal ratio (%) | - (1) 100 (5) 98 : (10) 95 (11) 100 (12) 100 - (A) 5 (B) 3 (C) 10 i

\ . C i pet 3 1 Test example 6

Ten female adults of carmine spider mite (Tetranychus cinnabarinus) were transferred onto each leaf of potted kidney bean in a primary leaf stage, : which had elapsed seven days after sowing, and stored in a constant-temperature room kept at 25°C. After six days, the emulsifiable concentrate of the following ‘ test compounds obtained according to Formulation example 1 was diluted with water sO that the active ingredient concentration was 500 ppm. Ten ml of the dilute solution was sprayed onto the plant on a turn table by a spray gun, and 2 ml of the diluted solution was treated on the pot soil. After 20 days, the degree of damage of each kidney bean by spider mites was examined.

The degree of damage was classified into three stages, -, + and ++. i - : Little damage is observed. | i + : Slight damage is observed. : ++: Same damage as in the untreated plot is observed.

The results are shown in Table 7. -

F

© ce Na de a a

T Y

‘ : ~ , So . : ( ; , 3!

Table 7

Test compound Degree of damage (1) - (2) - to + . (3) - (4) - to + (5) - (8) - (10) - to + (11) - to + (12) - (D) ++

N° treatment ++ t . ! i

Claims (1)

1. CL : gs 0

   - . A rs ro : : w LL . . Lae white pha . Co EL Cite tm Gq allw a eT a ge Sohn oy fr BEE FU ITT TESTE TF mazory ma met ETT seed Lm ET a Bg Eyam Le Sea) 1 Seta mar bed Do Ee pera 2 drt TL Yn TSE id SLEpalaeE smo ron © Shier er uss sey San WAALS oe ay Le TE RE man AT RN IRS For SAPS 2 boll pw aan re ag REIT ded RIT RE RNR T(E Ee ee Sr A Eee re Ee ara SFT1k - Oey Ih 2a LE EE Word iat AT Tape SAT STEER AT Ee Rea se ; &3 ATES RR IR NILE nT REG FEI Ts ra A TST I TR SRR a TL a rT ETE TR nT mera mer GE gost aT (TT 2 CYC Em RTOS Fg TESTE Te PTTETLUTIR TT RE TR SE iE we SE nen Tl ae TT E= Sammi 0 2 Wt o- EE Soo Tan Ta se ) Co = Co - oo - oC r - 0 NR. . . ce em -4 : LD C= = - 2 = : : {: | = Ol w 3 - -—t . i . ~ ~ ] Ng i = CLAIMS: i ol : 1. An aniline compound represented by the % ¥ formula, 5 F R cl x 4 & : 7 = NH, — S / CF so 2 3 . tH ES R i } ~ . ° 5 ‘ 3 . wherein R, is a chlorine or hydrogen atom, and Rg is a Ey Eyl [ro halogen atom or a methyl or trifluoromethyl group. Lp

   - 2. The aniline compound according to Claim 1 ¥ . Bs ) wherein R, is a hydrogen or chlorine atom, and Rg is a hi ¥ To fluorine, chlorine or bromine atom or a methyl or pie : trifluoromethyl group, provided that when R, is a & 2 -10 chlorine atom, Rg is a chlorine atom. : A] =z : EE £3 - - 29 - - TT I 1 14 i iE i Lt 4 :

   i Si PLA diiiiiniint aki wee alsdater assis Sata Sk RL i ARR A ch RE A dea GL SERED Loh? - - - . 1 0) ( 0)

   3. The aniline compound according to Claim 1 : represented by the formula, F cl \ cl

   J

   4. The aniline compound according to Claim 1 represented by the formula, F Cl \ HN J Vs CF,

   F

   5. The aniline compound according to Claim 1 represented by the formula, F cl \ HN ~ M- s CF, { Br ’

   6. The aniline compound according to Claim 1 represented by the formula, i F Cl \ \ 7 4 CF, :

   7. The aniline compound according to Claim 1 represented by the formula, i

   REE ose SIs te prt nobus PA 4 a } / ny bos - Le N F cl \ \ a mse CHg

   8. The aniline compound according to Claim 1 represented by the formula, { : { / F Cl cl HN os {)- CF, \ Cl

   9. A method for producing an aniline compound represented by the formula, F R, cl N / H, S CFq Rs wherein R, is a chlorine or hydrogen atom, and Rg is a . halogen atom or a methyl or trifluoromethyl group, which comprises reacting a mercaptoaniline compound represented by the formula, F R4 wpe E. Rs wherein R, and Rg are the same as described above, with 3,4-dichlorobenzotrifluoride in the presence of a base. NORIYASU SAKAMOTO THZ5UYA MORI TADASHI OHSUMI HIROAKI FUJIMOTO ‘ IZUMI FUJIMOTO Inventors