NL8120075A - PHENOXYPHENYLISOTHIOUREA, PHENOXYPHENYLTHIOUREA AS INTERMEDIATES, PREPARATION AND USE THEREOF IN COMBATING HARMFUL ORGANISMS. - Google Patents

Description

'N.o. 311 (80 1 Ο <i „,. R. _„ B i £ l * υ / 9

Phenoxyphenylisothiourea, phenoxyphenylthiourea as intermediates, their preparation and use in the control of harmful organisms.

The present invention relates to N-phenoxyphenylisothiourea, methods of preparation thereof, pesticides for harmful organisms, containing the compounds according to the invention as active component and use for controlling harmful organisms in animals and plants.

The N-phenoxyphenylisothiourea correspond to the formula VWvAj <> where R ^, R ^ and R ^ each contain hydrogen, halogen, C ^ -C ^ alkyl, C ^ -C ^ alkoxy, trifluoromethyl or nitro, R ^ and R ^ each C 2 -C 8 -alkyl, 10 Rg C 1 -C 8 -alkyl, C 1 -C 8 alkenyl or C 1 -C 8 -alkynyl

Rr, C 1 -C 2 -alkyl, C 1 -C 2 -alkenyl or C 1 -C 8 cycloalkyl and

R 9 represent hydrogen or C 1 -C 20 C alkyl.

Halogen is to be understood to mean fluorine, chlorine, bromine or iodine, but in particular chlorine.

The R 1 to R 8 eligible alkyl, alkoxy, alkenyl and alkynyl groups may be straight or branched. Examples of such groups include methyl, methoxy, ethyl, propyl, isopropyl, η-, i-, sec.-, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -nonyl, n-decyl and their isomers, allyl, methallyl, propargyl.

Cyclopropyl and cyclohexyl are the preferred cycloalkyl groups at R 1.

Because of their activity, compounds of the formula I are preferred in which R 1 is hydrogen, chlorine, methoxy, trifluoromethyl or nitro, R 1 and R 1 are each hydrogen or chlorine, and R 5 is each ethyl 3 isopropyl, 1-butyl, sec. butyl or tert-butyl, R 6 S “C 6” alkyl * allyl or propargyl, 30 R 1, C 1 -C 8 alkyl, cyclopropyl or cyclohexyl and 8120075 2

Rg represent hydrogen.

Especially preferred, however, are compounds of formula I, wherein hydrogen, chlorine or trifluoromethyl, R 2 hydrogen or chlorine, R 2 hydrogen, R 1 and R 1. any isopropyl or R-ethyl and sec-butyl,

Rg represents methyl, Rl tert-butyl or isopropyl and 10 Rg hydrogen.

The compounds of the formula I are also present in the form of acid addition salts, for example mineral salts, and can be used according to the invention in the form of their salts. The concept of the present invention is therefore understood to mean both the free compounds of the formula I ale 00k and their acid addition salts, which are non-toxic to warm-blooded animals.

The compounds of the formula I can be converted into their acid salts by methods known per se. For the formation of addition salts, for example, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, phosphoric acid, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, malic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, suitable benzoic acid, phthalic acid, cinnamic acid and salicylic acid.

The compounds of the formula I are prepared analogously to known processes by, for example, using a thiourea of the formula v [.../*, (IX) with a halide of the formula

Rg - Hal (HI) 30, wherein in the formulas II and III R 1 to R g have the meanings already indicated for the formula I and "Hal" represents a halogen atom, in particular a chlorine or bromine atom.

The process is expediently carried out at a temperature between 0 and 100 ° C, at normal or slightly elevated pressure, and preferably in the presence of a solvent or diluent which is inert towards the reaction participants. Examples of solvents or diluents are ethers and ether-like compounds such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; Aromatic hydrocarbons such as benzene, toluene and xylenes and ketones such as acetone, methyl ethyl ketone and cyclohexanone are suitable.

The compounds of formula II to be used as starting materials are new. They can be easily obtained from known precursors, for example, by using an isothiocyanate of the formula IV

i1 A

\ ia «aX \ / \ * ίβ / (IV) i3 \

with an amine of the formula V.

R? - nh2 (V) turnover, where in formulas IV and V R 'to R_ and R_ have the meanings already mentioned. (See example 1). · The process for preparing the starting materials of the formula II is preferably used in the presence of a solvent or diluent which is inert towards the reactants (at a reaction temperature of 0 to 100 ° C under normal pressure Solvents and diluents suitable for this process are those already mentioned for the process for the preparation of the final product in Formula I.

The compounds of the formula I as well as the starting materials of the formula II are suitable for the control of harmful organisms in animals and plants.

In particular, the compounds of formulas I and II

suitable for the control of insects, phytopathogenic mites and ticks, for example of the order Lepidoptera, Coleoptera, Homoptera »Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera» Mallophaga, Thysanura, Isoptera, Psoooptera and Hymenoptera.

In particular, compounds of formulas I and II

suitable for controlling plant-damaging insects, in particular plant-damaging insects, in ornamental plants and useful plants, in particular in cotton cultures (for example against Spodoptera littoralis and Heliothis virescens) and vegetable cultures (for example, Leptinotarsa decemlineata).

8 1 1 0 0 7 5 if

Active substances with formulas I and II also show a very favorable effect against flies, such as Musca domestica and mosquito larvae.

The acaricidal activity of the compounds of the formula I 5 extends both to plant-damaging acari (mites: for example from the families Tetranychidae, Tarsonemidae, Eriophydae, Tyroglyphidae and Glycyphagidae) as well as against ecto-parasitic acari (mites and ticks: for example of the families Ixodidae, Argasidae, Sarcoptidae and Dermanyssidae), which damage 10 useful animals.

With particular advantage, compounds of formulas I and II are also combined with substances which exert a synergistic or enhancing effect. Examples of such compounds are, inter alia, piperonyl butoxide, propynyl ethers, propynyl oximes, propynyl carbamates and propynyl phosphates, 2- (3t-1-methylenedioxyphenoxy) -3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-tribothyphosphoryl 1,2-methylenedioxy-if- (2- (octylsulfonyl) -propyl) -benzene

The compounds of formulas I and II may be in unchanged form or together with the auxiliaries customary in the formulation technique as formulations, such as, for example, emulsion concentrates, suspension concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts granules, also very fine encapsulations in polymeric materials and the like, are used in known manner. The application methods, such as spraying, atomizing, spraying, spreading or pouring, are entirely aimed at the application purposes. In doing so, it should be noted that due to the method of use and the nature and amount of auxiliary substances used for the composition of the formulation, the biological behavior of the active substance of the formula I or II is not essential. is affected.

The formulations are prepared in a known manner, for example by intimate mixing and / or grinding of the active substances with extenders, i.e. with solvents, solid carriers and optionally using surfactants (tensides). Suitable solvents are: aromatic hydrocarbons, preferably the fractions Cg to Ct, ie xylene mixtures to substituted naphthalenes, aliphatic hydrocarbons such as cyclo-ifO hexane or alkanes, alcohols and glycols, their ethers and their esters. highly polar solvents such as dimethylsulfoxide or dimethylformamide, as water. As solid carriers, for example for dusts and dispersible powders, naturally ground stones are usually used. Chemically, in particular, calcite, talc, kaolinite, raw morillonite or atta-pulgite are suitable here. To improve the physical properties, highly dispersed silicas or highly disperse absorbent polyraes can also be added. Suitable granular carriers are porous types, such as, for example, pumice stone, crushed brick, sepiolite and bentonite, as well as non-sorbent carrier materials, such as, for example, calcite or sand. In addition, a variety of pre-granulated materials of an inorganic or organic nature, from dolomite to comminuted nut shells or corncobs, can be used.

Non-ionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties are suitable as surfactants in accordance with the polarity of the active compound of the formula I or II to be formulated.

Suitable anionic surfactants are, for example, quaternary ammonium compounds, such as, for example, cetyl trimethyl ammonium bromide. Suitable anionic surfactants are, for example, soaps, salts of aliphatic monoesters of sulfuric acid, such as, for example, sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as, for example, sodium dodecylbenzene sulfonate, sodium, calcium or ammonium lignin sulfonate, butylnaphthalene sulfonate or a mixture of the sodium salts of di-sodium salts and triisopropylnaphthalene sulfonate. Suitable non-ionic surfactants are, for example, the condensation products of ethylene oxide with fatty alcohols, such as, for example, oleyl alcohol or cetyl alcohol, or with alkyl phenols, such as, for example, octylphenol, nonylphenol or octylresol. Other nonionic compounds are the partial esters which are derived from long-chain fatty acids and bexitol anhydrides, the condensation products of these partial esters with ethylene oxide or lecithin.

The nonionic, anionic and cationic surfactants customary in the formulation technique are described, for example, in the following publications:

• "Me Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringewood, New Jersey, CO

8120075 6

Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., New York.

The formulations generally contain 0.1 to 99, in particular 0.1 to 95%, active substance of the formula I or II and 50 to 25% of a surfactant, and 1 to 99.9% of a solid or liquid additive.

The formulations may also contain additives such as stabilizers, anti-foaming agents, viscosity control agents, binders, adhesives as well as fertilizers for effecting special effects.

For example, the active substances of the formula I or II can be formulated as follows: (percentages by weight): Formulation examples for liquid active substances of the formula I or II 15 Emulsion concentrates a) active substance 20%

Ca-dodecylbenzene sulfonate 5% castor oil polyglycol ether (36 mol EO) 5% 20 xylene mixture 70% b) active substance 40%

Ca-dodecylbenzene sulfonate 8% tributylphenol polyglycol ether (30 mol EO) 12% 25 cyclohexanone 15% xylene mixture 25% c) active substance 50% tributylphenol polyglycol ether 4f2% calcium dodecylbenzene sulfonate 5.8% 30 cyclohexanone 20% xylene mixture 20%

Emulsions of any desired concentration can be prepared from such concentrates by diluting with water.

Solutions 35 a) active substance 8% ethylene glycol monomethyl ether 20% b) active substance 10% polyethylene glycol ^ 00 70% N-methyl-2-pyrrolidone 20% 8120075 7 c) active substance 5% epoxidized vegetable oil 1% petrol (boiling limits 160 -190 ° C) 9k% d) active substance 95% 5 epoxidized vegetable oil 5%

These solutions are suitable for use in the form of very small drops.

Granules a) active substance 5% 10 kaolin 0.2-0.8 mm 9½% highly dispersed silica 1% b) active substance 10% attapulgite 90%

The active substance is sprayed onto the carrier dissolved in methylene chloride * and then the solvent is evaporated under vacuum.

Dusts a) active substance 2% highly dispersed silica 1% 20 talc 97% b) active substance 5% strongly dispersed silica 5% kaolin finely divided 90%

By intimately mixing the carriers with the active ingredient, ready-to-use dusts are obtained.

Formulation examples for solid active substances of the formula

I or II

Spray powders a) active substance 20 # 30 Na-lignin sulfonate 5%

Na lauryl sulfate 3% silicic acid 5% kaolin 67% 8120075 8 b) active substance 60%

Na lignin sulfonate 5%

Na-diisobutylnaphthalene sulfonate 6% octylphenol polyglycol ether 5 (7.8 mol EO) 2% strong diapers silica 27%

The active substance is mixed well with the additives and ground well in a suitable mill. Spray powders are obtained, which can be diluted with water to form suspensions of any desired concentration.

Emulsion concentrate active substance 10% octylphenol polyglycol ether (4-5 mol EO) 3% 15 Ca-dodecylbenzene sulfonate 3% castor oil polyglycol ether (36 mol EO) 4% cyclohexanone 30% xylene mixture 50% 20 Emulsions of any desired concentration can be prepared from this concentrate turn into.

Dusts a) active substance 5% talc 95% 25 b) active substance 8% kaolin finely divided 92%

Ready-to-use dusts are obtained by mixing the active compound with the carriers and grinding it on a suitable mill.

30 Granules from an extruder active substance 10%

Na lignin sulfonate 2% carboxymethyl cellulose 1% kaolin finely divided 87%. The active substance is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in the air stream.

Qhulling granulate active substance 3% 40 polyethylene glycol 200 3% kaolin (0.3-0.8 mm) 94% 8120075 9

The finely ground active substance is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. Dust-free coating granulates are thus obtained. Suspension concentrate 5 active substance 40% ethylene glycol 10% nonylphenol polyglycol ether (15 mol EO) 6%

Na-lignin sulfonate 10% 10 carboxymethyl cellulose 1% formalin (35% b formaldehyde solution) 0.2% silicone oil in the form of a 75% emulsion 0.8% 15 water 32%

The finely ground active substance is intimately mixed with the additives. In this way a suspension concentrate is obtained, from which suspensions of any desired concentration can be prepared by diluting with water.

Example 1; a) Preparation of 2,6-diisopropyl-4-phenoxyaniline 48.9 g of phenol are dissolved in 500 ml of xylene. In a nitrogen atmosphere, 30.2 g of powdered potassium hydroxide are added to this solution. The reaction mixture is heated to boiling point with stirring and the water formed is continuously distilled off.

After the addition of 0.6 g of copper chloride and 100 g of 2,6-diisopropyl-4-bromoaniline, the mixture is stirred at 150-155 ° C for 8 hours, then cooled and filtered off. The filtrate is washed with 15% sodium hydroxide solution (150 ml) and twice with 150 ml of water each time. The organic phase is separated, dried with sodium sulfate, the solvent is distilled off and the product is distilled.

The compound of the formula • mm · 8120075 10 having a boiling point of 103-101 + 0 / 0.01 Torr and a melting point of 71-72 ° C (recrystallized from hexane) is obtained.

The following anilines are also prepared in an analogous manner: - / »: 11 + 6-150 ° C / 0.03 Torr C1" \) ^%) -8¾

X

“S X

V ^ 3 bps: 151-155 ° 0 / 0.02 Torr

C1 'X

CHj

®3 \ X

• a· · "· / \ . / \ ΛΤΤΤ • v.-0-. - NH- O, 2pt .: 123-125 C / 0.02 Torr

X

ra3 X.

/ 2¾ · * · · ΜΦ

Cl— \ \ -o- / \ -. Ίη bpt .: 165-168 ° C / 0.03 Torr V J \ S * 2 C4S9 (sec.) / 2¾ • a · «a ·

Cl— () -0- /) .- ^) cH bpt .: 11 + 2-1 If6 ° C / 0.03 Torr CH ^ OHj 8120075 11 bpt .: 1 56-164 ° C / 0.02 Torr * * · »= · Vo

XXjX

Λ x

·· · «· CH

CS, - \ -o— {\ -1-nh bpt: 160oC / 0.02 Torr 3 2

X

CH3 CH3 b) Preparation of N- (2,6-diisopropyl-1-phenoxyphenyl) isothiocyanate 8.9 g Thiophosgene and 13 * 7 g calcium carbonate are stirred in 60 ml methylene chloride and 35 ml water. At 0 to 5 ° C, 17 ** 1 g of 2,6-diisopropyl-1-phenoxyaniline are added dropwise to this mixture. The reaction mixture is brought to a boil and stirred under reflux for two hours. After cooling, the mixture is filtered off. The organic phase is separated from the filtrate, washed twice with 50 ml of water each time, dried over sodium sulfate and evaporated. The crude product (oil) is used for further conversion without purification.

The following compounds are prepared in an analogous manner: / HiO! ) 2 Φ SX9 »= ·

CH3 ° "\ ^ *" NCS mp .: 39-42 ° C

NCH (CH3) 2 / h (ch3) 2 = tse

™ 3 * \> -NCS

..... NCH (CH3) 2 mp-! 63-65 ° c

c) Preparation of compounds of formula II

19 * 2 g of N-2,6-diisopropyl-t-phenoxyphenyl isothiocyanate are diluted with 10 ml of toluene and then 13 * 7 g of tert-butyl-15 amine are added. The reaction mixture is then stirred at 8120075 12 20-25 ° C for 12 hours. After evaporation and recrystallization from hexane, the compound of the formula \ _0-7 SB -! - SHC.H (Cert.) Mp .: 11.1) -11.7¾ V / w CH, Cl3 is obtained

The following compounds are also prepared in an analogous manner: 8120075 13 A. / V / \ _ \ v_> · _____

R 'R "R" "R1V RV

c4Vtert) c3H7 (i) C3H7 (i) 4_cl H 'smpt: 146-148 ° C

C4H9 (tert.) C3H7 (i) C3H7 (i) 3-CF3 H mp <83-85 ° C

C4H9 (tert.) C2H5 C ^ CseQ.) 4-C1 HSp, 9i-92 ° C

C4H9 (tert.) C2H5 C3H7 (i) 4-C1 H smp.tc 127-129eC

C3H7 (i) C3H7 (i) C3H7 (i) 4-OCH 3 H mp; 187eC

c4H9 (tert.) C3H? (i) C3Hy (i) 4-OCH3 H mp .: 178 ° C

c 4 H 9 (tert.) C 3 H? (i) C3 H? (i) 4-CH 3 H mp ^; 168-170 ° C

C3H7 (i) C3H7 (i) C3H7 (i) 4 "CH3 H smpt: 146—147 eC |

CH3 C3H7 (i) C3H7 (i) H H mp: 130-131 ° C

^ 3 ^ 7 (i) ^ 3 ^ 7 (1) ^ ® mp: 148-149 ° C

° 3H7 (n) C3H7 (i) C3H7 (i> H H «1-1WC

C3H7 (.i> C3H7 (i) C3H7 (i) H H 3mpt-; 160-161 ”C

C4H9 (u) C3H7 (1) C3H7 (i) H H 3mpt "U" -IWC

C4H9 (i> C3H7 (i) C3H7 (i) H H 3mpt-: 152-153 "C

C4H9 (s®.) C3H7 (i) C3H7 (i) Η H 3mpt .: 157-158 ° C

C5Hll (n) C3H7 (i) C3H7 (i) H H 3mpt "« I'l ^ ’C

CH3 C3H7 (i) C3H7 (i) H CH3 m.p .; 149-150 ° C

C2H5 C3H7 (i) C3H7 (i) H C2H5 mp: 161-162 ° C

C3H7 (n) C3H7 (x) C3H7 (i) H C3H7 (a) Smpt ': 152-153 "C

8120075 14

R 'R "R"' R1V RF

VW C3H7 (i) C3H7 (i) 1 C4H9 (n) -pt, 153-154 ° C

c4H9 (Sec.) C3H? (i) C3H7 (i) 4-CH3 H mp, 156-157 ° C

CH3 C3H7 (i) C3H7 (i) 4_OCH3 H mp "156-157" C

C2H5 C3H7 (i) C3H7 (i) ^ -OCH3 H smptt i54-155eC

C3H7 (n) C3H7 (i) C3H7 (i) 4-OCH3 H mp <155-156 ° C

C4H9 (i) C3H7 (i) C3H7 (i) 4-OCH3 H m.p. H2-113 ° C

C4H9 (seo.) C3H7 (i) C3H7 (i) 4-OCH3 H mp * 170-171 ° C

C7H15 (n) C3H7 (i) C3H7 (i) H Mp * ^ 98 ° 0

C3H7 (i) C3H7 (i) C3H7 (i) 4 ° ch3 h «apt, 187oQ

/ ίΗ2

~ c \\ CH3 C3H7 (i) 4_C1 H mp * 143-145 ° C

✓9H2

-CH ^ C2H5 C3H7 (i) 4-C1 H mp {80 ° 85 ° C

CH3 C 2 H 5 C 2 HgCsec, 4-C 1 H mp 109-110eC

C3H7 (i) C2H5 C4H9 (seG,) H H smp-

C4Hg (tert.) C2H5 C4Hg (seC,) Η H mp. 97-100oC

εΛω ° 3H7 (i) C3H7 (i) 4- ° CH3 H smpi: 1W-H4-C

C6H13 ()) ° 3H7 (i) C3H7 Ci) HH

C7H15 (n) C3H7 (i) C3H7 (i> H H

C10H21 (n) C3H7 (i) C3H7 (i) H H

C ^ HgCtert.) CH3 C3H7 (i) 4-C1 E

2

-Cir CH, CH (tert.) 4-C1 H

ch2 3 4 9

C4H (tert.) CH3 C4H (tert.) 4-C1 H

C „H C„ H CH (sec.) 4-C1 H

4 5 4 3 4 9 8120075

R 'R "Rm RLV RV

15

CH, C0H_ C.H (se c J 4-Cl H

3 7 (n) 25 49

C3H7 (i) C2H5 C4H9 (sec0 4_C1 H

/ <? Η 2

-CK \ Δ C0H C .H (se c ·) 4-C1 H

\ L 2 5 4 9 CH2

C4H9 (n) C2H5 C4H9 (seC ° 4 "C1 H

C4H9 (i) C2H5 c4H9 (sec.) 4-C1H

C4H9 (sec.) C2H5 C4H (secii 4-C1 H

"* \ H / C2tt5 C4H9 (secJ 4-C1 H

· - ·

Vs

-O C2B5 C4H9 (seC ') 4'Cl H

iH ”CH 3 2H5

C4H9 (tert.) C3H7 (i) C3H7 (i) 4-C1; H

d) Preparation of the final product 11 * 54 g of N-2t6-diisopropyl-4- (phenoxyphenyl) -N'-tert-butyl thiourea are dissolved in 30 ml of dimethylformamide. 5 * 96 g of methyl iodide 5 are added dropwise to this solution at 40 ° C. After storage at room temperature for 12 hours, the reaction mixture is poured into an aqueous solution adjusted to pH 12 with potassium carbonate. The aqueous solution is extracted with methylene chloride, the organic phase is separated, dried over potassium carbonate and the methylene chloride is distilled off.

After recrystallization (hexane; cooling to -50 ° C) the compound of the formula 8120075 16 c / 3 / LaV SCH_ / - \ "C33 1 3 s-^ uS cert * * ~ V _ S is obtained ~ ^ 3 with a melting point of 89-92 ° C.

The following compounds are also prepared in an analogous manner: c / * 3 / c \ SCH _

• a \ CH, | 3 mp .: 80 ° C

/ 0- <> -— N = C—NH-C.Hn tert.

\ .s \ .J 4 9 - cufSmj Λ C1 \ / 0% SCH.

· «·. = · CH | 3 c>%> - »- <3 X = <^ NH-CA tert.

Mp .: 89 C

CH3 CH3 8120075 17 R '"R" / 1 * - · · = · c RV- \ / "- 0-v N = C-NHR" · - · · - ·

Yv

R 'R "R'M R1V RV

C.H (tert.) CH. Cl 3mpt .: 120 ° C

49 33 7 (i) 3 7 (i) C4Hg (tert.) CH3 ° 3Η7 (£) C3H7 (i) CH3 3mpt ': 86_87 ° c C3H? (I) CH3 ε3Η7 (£) C3H7 (i) CH3 3mpt, : 94-96 ° C C3H7 (i) CH3 CA (i> C3H7Ci) H ν'7'5 '"^ 5605

C3H? (I) CH3 C3Hy (i) C3H? (I) 0CH3 mp: 106-107 ° C

C3H7 (i) C2H5 C3H7 (i) C3H7 (i) 0CH3 'mpt ^ 67 “68 ° C

C4H9 (tert.) CH3 C3H? (I) C3H? (I) 0CH3 mp: 93-94 ° C

C4Hg (tert.) C2H5 C3H7 (i) 0CH3 3mpt,: 8120075 18

R 'R "R" "R1V RV

c4H9 (tert.) CH3 CH3 C3H7 (i) C1 smPt>: 99-100 ° C

CH

CA CH3 SH7 (i) 01 c4H9 (tert.) CH3 CH3 C4Hg (terL) Cl C4H9 (tert-) “O ^ -CaCH CH3 C4H9 (tert) Cl

CH

X '2 ch3 ° 2H5 Wa) 01 2 / H2 C2H5 C2H5 (i) C1

C4 Hg (tert.) CH 3 C 3 -C 3 H 7 (i) C 1 Mp: 65-68 ° C

C4H9 (tert.) -CH2-C = CH C2H5 α3Η7 (£) Cl CH3 CH3 SVi) 01 CH2 c3H7 (.) - ttJ CH3 C3H7 (i) C3H7 (i) CH3 mp I 189-190ec C4H9 (Seo.) CH3 C3H7 (i) 0¾

C4H9 (tert.) -CH2-CH5CH2, CH3 mp, 84-86 ° C

i 8120075

R 'R "R" "RLV RV

19

CH (tart.) * HJ CH, C, H, / M C-H ,, .. CH, smpti69-170eC

49 3 3 7 (i) 3 7 (i) 3

C4H9 (tert.) C2H5 C3H7 (i) C3H7 (i) CH3 mp .: U1-113 ° C

CH (tert.) * HBr -CH.-CH = »CH_ C, H_, .., C, H_,., CH, mp. ; 124-126 ° C - 49 223 7 (i) 3 7 (i) 3 CH3 CH3 C3H7 (i) C3H7 (i) 0CH3 mp *: l20 “l2l ° c

CH HJ CH_ C, H, v C. H, v OCH, m.p .: 176-177eG

3 3 3 / (i) 3 7 (i) 3

CjH. ca3 C3H7 (i) C3H7 (i) ° ®3 s "pt": 100-102 ° C

c2h5.ej ch3 οΛα) 0Λ (1) OCH3 mp,: 176-177 ° C

C3H7Cn) CH3 C3H7 (i) C3H7U> 0CH3

• VW "CH3 C3H7 (U c3? 7 (i) OCH3 -Pt, 171-172" C

'3 * 7 (1) ^ 3 «Λα» «Λ (1> m.p .: 106-107eC

C4H9 (u) CH3 C3H7 (i) <¥ 7 (1) 0CH3 “pt- ^ 72 ° 0

C4H9 (n) * HJ CH3 C3H7 (i) C3H7 (i) 0CH3 Mp: 142-145'C

C4H9 (x) CH3 C3H7 (i) C3H7 (i) 0CH3 mp C4R9 (i) * HJ CH3 C3H7 (i) C3H7 (i) 0CH3 mp <l36-140 ° c

C4Hg (sas.) CH3 C3H7 (i) C3H7 (i) 0CH3 smpti 83 ”84 <, C

C4H9 (SeC,). HJ CH3 C3H7 (i) 0Λα) OCHj C7H15 (n) “3 C3H7 (i) C3H7 (i) ° ®3 ^ 5513 C7H 15 (,) - 1 °« 3 C3H7 (i) C3 * 7 (i) ° 3 m.p. l9-122.c CH. CH. C-H_ ,. v C H ... H smptrl09_110oc 3 3 3 7 (i) 3 7 (i) 8120075

R 'R "R" "R1V RV

20

CH3 «HJ CH3 C3H7 (i) C3H7Ci) H smpttl90-192eC

C2H5 CH3 C3H7 (i) C3H7 (i) H mp: 75-76eC

C2H5 «HJ CH3 C3H7 (i) C3H7 (i) H mp *: 189” 190 ° C

40 ° C 3 H 7 (n) CH 3 C & C 3 H 7 (i) H% = 5650

C3H7 (n) “3 C3H7 (i) C3H7 (i) H ™ P ^ 190-m" C

C3a7 (.). RJ CH3 «Λ (1) C3H7 (u h ™ t-.183-184 * C

C4H9 (n) CH3 = 3 ^ (1) «3 * 7 (0 H = T = l5544 C4H9 (n), HJ CH3 C3a7U> C3H7 (i) H == ^ 185-187-0 4Ωβ C4H9 (i > CH3 ° 3H7 C1) S4H) H = 1.5569

C4H9 (i) -HJ CH3 C3H7 {i> C3a7U) H == mpt j 170-171 ”C

50® C4H9 ^ seC * ^ CH3 C3H7 (i) C3H7 (i) 'H ° D: 1.5512

C ^, Hg (sec> HJ CH3 C3H7 (i) C3H7 (i) H mp il48-150®C

C5aU (") CH3 C3H7 (i> C3H7 (i) E% °" = 1.5548

VlKn) * 81 CH3 C3H7 (i) C3H7U) H

C6ai3 (n) CH3 «3 * 7 (0 C3« 7 (i) B ”Γ = ^ 5524 C6H13 (n), EJ ^ 3 C3a7 (i) C3H7 (i) B == ^ = 111-1 ^ 0 C7H15 (n) CH3 C3H7 (i) C3H7 (i) H “d: 1.5461 C7H15 (n), HJ CH3 C3H7 (i) C3B7 (i) H = Ϊ * · = 100-101 · 0 40® | C10H21 ( n) CH3 C3H7 (i) C3H7 (i) H Λ: 1.5392 8120075 R 'R "R"' R1V Rv 21

C10H21 (n), HJ CH3 C3H7 (i) C3H7 (i) H

^ 3 CH3 c2S5 C4Hg (sec) Cl

CH3 «HJ CH3 C2H5 C4Hg (sec.) Cl mp .; 165-170eC

CH3 C3H7 (n) C2H5 W0 '* C1 C2H5 ra3 c2H5 c4H9 (seC,) C1 l5731

G2H3 * HJ CH3 C2H5 C4Hg (sec,) Cl smpti40-14SeC

G2H5 C4H9 (n) C2H5 C ^ sec.) Cl C3H7 (n) CH3 c2H5 c4Vse ° 0 C1 '1.5681 C3H7 * HJ CH3 C2H5 C4Hg (8ftO.) Cl smpt .. 87.90oc C3H7 (η) -CH2-C = CH C2H5 C ^ sec.) Cl n £ ° *: 1 * 5734 G3H7 (i) GH3 C2H5 C4H9 (sec,) ci ι ^ 0 * 1.5528 C3H7 (i) * HJ GH3 C2H5 C4H9 (sec ^ Cl smpt 133-135-0 G 3 H 7 (i) -CH 2 -CH = CH 2 C 2 H 5 C 2 C sec.) Cl n £ °. 1.5631 CH ** '^ CE C2H5 C4H ^ eC ·) C1 C': 1> 5721

CH

'KL2 C2H5 C2a5 W ”* 0 01 l5560 2 C4H9 (n) CH3 c2H5 C ^ isec.) C1 C4H9 (n), HJ CH3 c2hS V9 (Stc.) Cl | C4H9 (i) ^ 3 C2H3 c4Vse0,) C1 1¾0% 1.5563 8120075 22

a 'R "R"' R1V RF

C4H9 (i) #HJ CH3 C2H5 C4H9 (seC1) 1.5734 C4H9 (i) -CH2-C = CH C2H. C ^ UecO Cl C4H9Csec.) CH3 C2H5 C ^ Csec.) Cl njj0 *: 1,5562 c4VSeC,), HJ CH3 C2H5 C4H9 (seC.) Cl -CH2-CH = CH2 C2H5 C4H9 (seC.) Cl n ^ 0 1.5547 C4H9 (tert. CH 3 C 2 H 5 C 2 sec) c 1> 5591 C4Hg (tert. -CH 2 -C = CH C 2 C 2 C sec.) Cl n 2 °. 1.5596 • - · CH3 C2H5 C ^ gisec.) · Cl 1.5643 · - «* (βΗ / '# ΐυ CH3 C2H5 C4Hg (sec.) Cl · - ·" \ 0 *. -CH2C = CH C2H5 C4Hg (sec.) Cl njj ° °: 1.5721 W “rt · 5 ^ Η. * 3 * 7 (i) E njj0 ': 1.5750 0Α (“ * ·) C2H5, EI * 3 * 7 (0 1

c4H9 (tert.) c3H7 (n) C3H7 (i) C3H7 (i) H “-« ’C

c4H9 (l: ert.) C3H7 (a) 'F' C3H7 (i) C3S7 (i) H

C4H9 (Cert ·) C4H9 (n> C3H7 (i) C3H7 (i) H 3mpt ”S7 ~ 60 ° C

C4E9 (text.) C4H9.HBr Η

C4H9 (tert) C4H9 (i) C3H7 (i) C3H7 (i) H smpt7 80-82 "C

8120075 23

R 'R "R" "R1V RV

C4H3 (t, rt.) C4H9 (i) .HJ C3K7 (i) C3H7 (i) H n £ ° \ 1,5672 C4Hg (cert.) -CH2-CH-CH2 α3Η7 (ΐ) C3H7 (i) H 3Ifipt *: 78 “8 ° ec

C4Hg (tert.) -CH2CH-CH2 * HBr C3H7 (i) C3H? (I) H

C4H9 (tert.) -CH2-C = CH3 C3H7 (i) C3H7 (i) H ipt: 79-8l ° c

C4H9 (tert.) -CH2C = CH.HBr C3H? (I) H

«Αω -cs2ch-ch2 Cj ^ a) c3h7 (,) h

C3H7 (i) -CH2-CH = CH2 * HBr H mp: 171-172'C

H »C4H (tert.) CH3 C2H5 C4H9 (sec.) H: 1.5549 C3H7 (i) CH3 C2H5 C4H9 (sec.) H: 1.5662

Example 2: Insecticidal feeding activity: Spodoptera littoralis, Dysdercus fasciatus and Heliothis virescens

Cotton plants were sprayed with an aqueous emulsion containing 0.05% of the test compound (obtained from a 10-5 percent emulsifiable concentrate).

After the scale had dried, the plants were each occupied with larvae of the species Spodoptera littoralis (L3 stage), Dysdercus fasciatus (L4) or Heliothis virescens (L3). Two plants were used per test compound and per test species and the killing percentages obtained were measured after 2, 4, 24 and 48 hours. The test was performed at 24 ° C and a relative humidity of 60 #.

Compounds according to example 1 showed a good action against larvae of the species Spodoptera littoralis, Dysdercus fasciatus and Heliothis virescens in the previous test.

/ 8120075 24

Example 3- Insecticidal feeding activity: Leptinotarsa decemlineata_

In a similar procedure using larvae of the species Leptinotarsa decemlineata (Lj5) and potato plants instead of cotton plants, the test method described in example 2 was repeated.

Compounds according to example 1 had a good effect against larvae of the species Leptinotarsa decemlineata.

Example 4: Action against plant damaging acari: 10 Tetranychus urticae (OP sensitive) and Tetranychus cinnabarinus (OP tolerant) _

The primary leaves of Phaseolus vulgaris plants were occupied 16 hours before the acaricidal activity test with an infected leaf culture mass mass of Tetranychus urticae (OP-sens.) Or Tetranychus cinnabarinus (OP-toll.). (The tolerance refers to the diazinon tolerability).

The infected plants thus treated were sprayed with a test solution containing 400 or 200 ppm of the test compound until dripping wet.

After 24 hours and again after 7 days, images and larvae (all movable stages) were evaluated under the microscope on living and dead organisms.

A plant was used per concentration and per test type. During the test run, the plants were kept in greenhouse booths at 25 ° C.

Compounds according to Example 1 showed a positive effect against organisms of the species Tetranychus urticae and Tetranychus cinnabarinus in this test.

Example 3- Action against ectoparasitic acari (ticks) 30 Rhipicephalus bursa (images and larvae), Amblyomma hebraeum (+ images, pupae and larvae) and Boophilus microplus (larvae -OP-sensitive and OP-tolerant) _

As test objects, larvae (about 50 each), pupae (about 25 each) or images (about 10 each) 35 of the tick species Rhipicephalus bursa, Amblyomma hebraeum and

Boophilus microplus applied. The test animals were placed in an aqueous emulsion or solution containing 0.1; 1.0; 10; 5 ° or 100 ppm of the compound to be tested, immersed.

40 The emulsions resp. solutions 8120075 are then taken up with cotton wool and the moistened test animals are left in the thus contaminated tubes.

A valuation of the kill rate achieved at each concentration occurred for larvae after 3 days and for pupae and imagoes after 11f days.

Compounds according to example 1 showed in this test a good effect against larvae, pupae and images of the species Rhipicephalus bursa and Amblyomma hebraeum as well as against larvae (OP-res. And OP-sens.) Of the species Boophilus microplus.

8120075

Claims (17)

A compound of formula \ K 4 p'A S 3 \ 8 wherein, R 1 and R 2 each are hydrogen, halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, trifluoromethyl or nitro, 5 R ^ and R1. any C 1 -C 2 -alkyl, Rg C 1 -C 8 -alkyl, C 1 -C 8 -alkenyl or C 1 -C 2 -alkynyl, Ry-C 1 -C 4 alkyl, C 1 -C-(alkenyl or C C 1 -C 8 cycloalkyl and R 8 represent hydrogen or C 1 -C 8 Q alkyl. A compound according to claim 1, wherein R 1 hydrogen, chlorine, methoxy, trifluoromethyl or nitro * R 2 and R 1 each hydrogen or chlorine, R 1 and R 1 each ethyl, isopropyl, i-butyl, sec-butyl or tert .-butyl, Rg allyl or propargyl, R 3 represent C 1 -C 8 alkyl, cyclopropyl or cyclohexyl and Rg hydrogen. A compound according to claim 2, wherein R 1 is hydrogen, chlorine or trifluoromethyl, R 2 is hydrogen or chlorine, R 2 hydrogen, R 2 and R (each is isopropyl or R 2 ethyl and R 2 sec-butyl, R 9 methyl, R y tert-butyl or isopropyl and R 9 represent hydrogen. 25 k Compound according to claim 3 of the formula y ° K cm • mm • mm ''% / -0-% / -NH-CH tert.> 3 ^ 3 3ι3 8120075 A compound according to claim 3 of the formula ..... -X 6. A compound according to claim 3 having the formula c / ®3 / \ / - \ W | ®3 ^ h-c4h, e. <4 X = ¾ x A compound according to claim 3 of the formula} = ¾ ^ X,? Ca, ··· * m · C3_ T 3 Cl— (\ -0-v ^ -HH-CH tart. X CEj 8. Process for the preparation of compounds according to claim 1, characterized in that a compound of the formula R3 * 8 is reacted with a compound of the formula R6 - Hal, in which R1 to R8 are as specified in claim 1. meaning 10 and Hal represents a halogen atom. 9. Means for controlling harmful organisms, which in addition to a suitable carrier and / or another additive as active component, contains a compound according to claim 1 · 8120075 ♦ Use of a compound according to claim 1 for the control of various animal and vegetable harmful organisms. Use according to claim 10 for the control of insects and representatives of the order Acarina. 12. Compound of the formula R1 r2 \ 4. / m \ 4 sa, R3 8 Wherein, and R ^ each hydrogen, halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, trifluoromethyl or nitro, R, and Rc each C 1 -C-alkyl , 4 p ά 4 C 1 -C 10 alkyl, C 1 -C 20 alkenyl or C 1 -C 12. cycloalkyl and Rg represent hydrogen or (C 1 -C 2 alkyl). 13. Agent for controlling harmful organisms, which in addition to a suitable carrier and / or another additive as active component contains a compound according to claim 12. H. Use of a compound according to claim 12 for controlling various animal and vegetable harmful organisms. 8120075