DE3109262A1 - "(ALPHA) -ISOPROPYL RESPECTIVE (ALPHA) -CYCLOPROPYL- (ALPHA) - (4-CHLORPHENYL) -ACetic Acid- (ALPHA) -HALOGENAETHINYL-M-PHENOXYBENZYLESTER, METHOD FOR THE PRODUCTION THEREOF ITS MANUFACTURE - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. Li. Aosmenn - ¹ Jr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Drpl.-iug. P. K: ingseise ~ - Dr. F. Zumstein jun.

PATENT LAWYERS

80OO Munich 2 ■ B räuhaus straße 4 -Telephone, collective no. 2253 41 -Telegrams Zumpat -Telex 529979

CIBA-GEIGY AG 5-12762 / 1 + 2 / +

Basel, Switzerland)

cc-isopropyl or a-cyclopropyl-a- (4-chlorophenyl) -acetic acid-ahalogenäthinyl-m-phenoxybenzyl ester, Process for their production and their use in pest control

The present invention relates to α-isopropyl and α-cyclopropyl-α-CA-chlorophenyl / acetic acid-α-haloethinyl-m-phenoxybenzyl ester the formula

( R ₁ -COO-CH- / \ -0-f \
¹ C \ / '\ / ^λ
III
C.
I. and ^x i (D, where R y * ~ CH ~ or Cl
de. CH π- / Fluorine, chlorine, bromine, methyl, - < ₌ / - ^CH -
^ 2 ^H 2 R- hydrogen, Trifluoromethyl Methoxy mean. X halogen

Halogen is fluorine, chlorine, bromine or iodine, but in particular Bromine or iodine, understand. Because of their action of particular importance are compounds of the formula I in which

· - ■ · - ·

R ₁ ^C1 ~ '\ / * ~ ^CH " ^or Cl- / ^« - CH-,

^CH / ^CH \

CH ₃ ^C ^

R "hydrogen, fluorine, chlorine, bromine or trifluoromethyl and X mean bromine or iodine.

Of particular importance, however, are compounds of the formula I in which

X /

or

CH ₃ CH ₃

—GH

R “hydrogen and

X mean bromine or iodine.

The compounds of the formula I are made according to methods known per se e.g. manufactured as follows:

1) R-COOH

C III

I Λ \ A \

acid binding

(II)

(III)

2) R-COX

C III C

I *

i ¹ y

acid binding agent

(IV)

(V)

C M!

I A \ A \

3) R-COOH + HO-CH-f », -0- \ MI

(ID

(V)

water-binding agent

G ΙΠ

4) R-COOR + HO-CH-: ^ \ -O-f

¹ I ¹ J i T2

V V

(VI) (V)

In formulas II to VI, R, R- and X have those for formula I. given meaning.

In the formulas III and IV, X stands for a halogen atom, in particular for chlorine or bromine, and in the formula VI R stands for C -C -alkyl, in particular methyl or ethyl. Particularly suitable acid-binding agents for processes 1 and 2 are tertiary amines, such as trialkylamine and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates such as potassium t-butoxide and sodium methylate. Dicyclohexylcarbodiimide, for example, can be used as a water-binding agent for process 3. Processes 1 to 4 are carried out at a reaction ^{temperature between -10 and 120 °} C., usually between 20 and 80 ^° C. at normal or elevated pressure and preferably in an inert solvent or diluent. Suitable solvents or diluents are, for example, ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Amides, such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone.

The starting materials of the formulas II, IV and VI are known or can be prepared analogously to known methods. The starting materials of formulas III and V are new. They are analogous to Tetrahedron Letters, 1448 (1978) (cf. also Example IA).

The compounds of formula I are available as a mixture of different optically active isomers exist if optically active starting materials were not used uniformly in the preparation. The different Mixtures of isomers can be separated into the individual isomers by known methods. The compound of the formula I is understood to mean both the individual isomers and their mixtures.

The compounds of the formula I are suitable for combating various types of disease animal and vegetable pests.

The compounds of the formula I are particularly suitable for combating from representatives of the Arthropoda Division e.g. of the Insecta class, e.g. of the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera as well as the class Arachnoidea e.g. the order Acarina.

In particular, compounds of the formula I are suitable for combating Plant-damaging insects, in particular plant-damaging feeding insects, in ornamental and useful plants, in particular in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).

Active ingredients of the formula I also show a very beneficial effect against Flies such as Musca domestica and mosquito larvae.

The acaricidal action of the compounds of the formula I extends both for plant-damaging acarines (mites: e.g. of the families Tetranychidae, Tarsonemidae, Eriophydae, Tyroglyphidae and Glycyphagidae) as well as against ectoparasitic acarines (mites and ticks: e.g. of the families Ixodidae, Argasidae, Sarcoptidae and Dermanyssidae), which cause harm to farm animals.

The acaricidal or insecticidal effect can be achieved by adding with other insecticides and / or acaricides adapt to given circumstances. Org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidine; chlorinated hydrocarbons.

Compounds of the formula I are also particularly advantageous with substances combined, which have a synergistic or potentiating effect on pyrethroids. Examples of such compounds are including piperonyl butoxide, propynyl ether, propyny oxime, propynyl carbamate and propynyl phosphates, 2- (3,4-methylenedioxy-phenoxy) -3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-Tributylphosphorotrithioate, 1,2-methylenedioxy-4- (2-octylsulfinyl) propyl benzene.

The compounds of the formula I can either be used in unchanged form or together with the usual aids in the formulation technique as formulations, such as emulsion concentrates, suspension concentrates, directly sprayable or dilutable solutions, diluted emulsions, Wettable powders, soluble powders, dusts, granules, including finest encapsulation in polymeric substances and the like, in known Way to be used. The methods of application such as spraying, misting, dusting, scattering or pouring depend entirely on the desired goals. It should be noted that by the application method as well as the type and amount of auxiliary materials used for the preparation of the formulation the biological behavior of the Active ingredients of the formula I is not adversely affected.

The formulations are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredients with extenders, such as, for example, with solvents, solid carriers and, if appropriate, surface-active substances (surfactants). Possible solvents are: aromatic hydrocarbons, preferably the fractions C_ to C ^ ₂ , ie xylene mixtures or substituted naphthalenes, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and

Glycols and their ethers and esters, strongly polar solvents such as Dimethyl sulfoxide or dimethylformamide, and water. Solid carriers, e.g. for dusts and dispersible powders, are mostly used natural rock flour is used, such as calcite, talc, kaolinite, montmorrillonite or attapulgite. To improve physical Highly disperse silicas or highly disperse absorbent polymers can also be added to properties. As granular adsorptive Granulate carriers come from porous types such as pumice stone, broken bricks, Sepiolite and bentonite, as non-sorptive carrier materials e.g. calcite or sand. It can also be a variety of granulated Materials of an inorganic or organic nature, such as dolomite in particular, up to crushed plant residues can be used.

As surface-active substances, depending on the polarity of the formulating active ingredient of the formula I non-ionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties into consideration. Surfactants are also to be understood as meaning mixtures of surfactants.

Suitable cationic surfactants are, for example, quaternary ammonium compounds, such as cetyl trimethyl ammonium bromide. Suitable anion-active surfactants include soaps, salts of aliphatic monomers of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds such as sodium dodecylbenzenesulfonate, sodium, calcium and ammonium lignin sulfonate, butylnaphthalene sulfonate or a mixture of the sodium salts of diisopropyl and triisopropyl naphthalene sulfonate. Suitable nonionic surfactants are for example the condensation products of ethylene oxide with fatty alcohols, such as oleyl alcohol or cetyl alcohol, or with alkylphenols, such as octylphenol, nonylphenol or octyl cresol. Other non-ionic agents are the partial esters, which differ from long chain Fatty acids and hexitanhydrides derive the condensation products this partial ester with ethylene oxide and lecithins.

The non-ionic, anionic and cationic surfactants are described in the following publications, among others:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringewood, New Jersey, 1979.

The formulated agents usually contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I and 0 to 25% of a surfactant and 1 to 99.9% of a solid or liquid additive.

The agents can also contain other additives such as stabilizers, defoamers, Contains viscosity regulators, binders, adhesives and fertilizers or other active ingredients to create special effects.

The active ingredients of the formula I can, for example, be formulated as follows are: (data in percent by weight),

Formulation examples for liquid active ingredients of the formula I emulsion concentrates

Active ingredient 20% Ca-dodecylbenzenesulfonate 5% Castor oil polyglycol ethers
(36 moles of AeO) 5% Xylene mixture 70% Active ingredient 40% Ca-dodecylbenzenesulfonate 8th% Tributylphenol polyglycol ethers
(30 moles of AeO) 12% Cyclohexanone 15% Xylene mixture 25%

c) active ingredient 50%

Trifautylphenol polyglycol ether 4.2%

Calcium dodecylbenzenesulfonate 5.8%

Cyclohexanone 20%

Xylene mixture 20%

Such concentrates can be diluted with water to produce emulsions any desired concentration can be produced.

solutions

a) Active ingredient 80% Ethylene glycol monomethyl ether 20% b) Active ingredient 10% Polyethylene glycol 400 70% N-methyl-2-pyrrolidone 20% c) Active ingredient 5% Epoxidized vegetable oil 1% Petrol (boiling limits 16O-19O ^e C) 94% d) Active ingredient 95% Epoxidized vegetable oil 5%

These solutions are suitable for use in the form of tiny drops. Granules

a) active ingredient 5%

Kaolin 0.2-0.8 mm - 94%

Highly disperse silica 1%

b) active ingredient 10%

Attapulgite 90%

The active ingredient is dissolved in methylene chloride and applied to the carrier sprayed and the solvent then evaporated in vacuo.

Dust

a) Active ingredient 2% Highly disperse silica 1% Talc 97%

b) Active ingredient 5% highly disperse silica 5% kaolin finely divided 90%

Obtained by intimately mixing the carrier with the active ingredient one ready-to-use dusts.

Formulation examples for solid active ingredients of the formula I.

Wettable powder 20% a) Active ingredient 5% Na lignin sulfonate 3% Na lauryl sulfate 5% Silica 67% kaolin 60% b) active ingredient 5% Na lignin sulfonate 6% Na diisobutylnaphthalene sulfonate 2% Octylphenol polyglycol ethers
(7-8 moles AeO) 27% Highly dispersed silica

The active ingredient is mixed well with the additives and in one grind a suitable mill. You get wettable powder that deals with Allow water to dilute into suspensions of any desired concentration.

Emulsion concentrate

Active ingredient 10%

Octylphenol polyglycol ethers

(4-5 mol AeO) 3%

Ca-Dodecylbenzölsulfonat 3%

Castor oil polyglycol ether

(36 mol AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

This concentrate can be diluted with water to produce emulsions any desired concentration can be produced.

Dust

a) active ingredient 5% talc 95%

b) Active ingredient 8% kaolin finely divided 92%

Ready-to-use dusts are obtained by adding the active ingredient the carriers is mixed and ground on a suitable mill.

Extruder granulate

Active ingredient 10%

Na lignin sulfonate 2%

Carboxymethyl cellulose 1%

Kaolin finely divided 87%

The active ingredient is mixed with the additives, ground and with Moistened with water. This mixture is extruded and then dried in a stream of air.

Coating granules

Active ingredient 3%

Polyethylene glycol 3%

Kaolin (0.3-0.8 mm) 94%

The finely ground active ingredient is mixed with polyethylene glycol in a mixer moistened kaolin applied evenly. In this way, dust-free coating granules are obtained.

Suspension concentrate

Active ingredient 40% Ethylene Glyco 1 10% NonyIp hanoI polyglycol ether
(15 moles AeO) 6%. Na-Li gninsulfonat 10% Carboxymethyl cellulose 1% Formalin (37% formaldehyde solution) 0.2% Silicone oil in the form of a 75%
emulsion 0.8% tap water 32%

The finely ground active ingredient is intimately mixed with the additives. A suspension concentrate is obtained in this way, from which suspensions of any desired concentration are prepared by dilution with water can be.

Example 1 ; A) To 10 g of α-ethynyl-m-phenoxybenzyl alcohol in 500 ml of ether are dissolved 0.1 mol of methyl lithium over 20 minutes under argon and at -50 to -60 ⁰ C were added dropwise in 50 ml of ether. After a further 10 minutes, 5.63 g of iodine, dissolved in 100 ml of ether, are added dropwise and the mixture is stirred at room temperature for 10 hours. 2 ml of isopropanol are then slowly added dropwise and 20 ml of saturated ammonium chloride solution are added. The ether phase is washed with saturated sodium chloride solution and dried over magnesium sulfate. After the solvent has been removed, the residue is chromatographed on silica gel using ether / hexane (1: 2). The compound of the formula is obtained

I A ^m \ a '\ 20 °

^H0 ti V ° "i Π ^ = 1.6237

III · ·

Nuclear Magnetic Resonance Spectrum (60 MHz) in CDC1 / TMS S 3.1: d IH S 5.4: d IH δ 6.7-7.7: m 9H

B) Preparation of a-isopropyl-a- (4-chlorophenyl) -acetic acid-a-iodäthinyl-m-phenoxy-benzyl ester

To an ice-cold solution of 1.8 g of a-isopropyl-a- (4-chlorophenylacetic acid chloride and 1.2 ml of pyridine in 50 ml of toluene, a solution of 4.1 g of a-iodoethinyl-m-phenoxybenzyl alcohol in 20 ml of toluene is added dropwise. The reaction mixture is stirred for 16 hours at room temperature and under nitrogen and then mixed with ether. The ether extract is washed once with water, once with 2N hydrochloric acid and three times with saturated sodium chloride solution, then over sodium sulfate dried, filtered and concentrated. The product is chromatographed over silica gel with ether / hexane (1:10) as the eluent.

The compound of the formula is obtained

I I * T M

£ \ y \ y 20 °
4 = 1.5829

The following connections are also established in the same way:

Cl -. (> -CH-COO-CH- ^ \ -0- / \

III ^. ^ -

Br

CH "20

= 1.5827

-On ₁

C C 20 °

1.5729

^ -CH-COOCH- ¹ · '

- C

--0-i

CH

C = C-Br 1.5779

\ - CH-COOCH- ·. , »- 0-i S

^CH

CC-20 °

1.5703

27

= 1.5953

C = C-J

"S-CH-COO-CH- ·. J» -O-i J'-CF.

tl ° = 1.5518

C = C-Br

1.5607

(-1TT

CH

₃ C = CJ

1.6027

Example 2: Insecticidal feed poison effect

Cotton plants were each with an aqueous active substance emulsion containing 100, 200, 400 or 800 parts by weight of active substance per 10 parts by weight of additives, respectively. Sprayed suspension, each of which has been produced from one of the exemplary emulsifiable concentrates, wettable powders, granules or sprays. After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis and Heliothis virescens L. larvae. The test was carried out at 25 ^° C. and 60% relative humidity.

Compounds according to Example 1 showed good insecticidal properties in the above test Food poison effect against Spodoptera and Heliothis larvae.

Example 3: acaricidal effect

Pieces of phaseolus leaf infested with Tetranychus urticae larvae vulgaris plants were each with a 100, 200, 400 or 800 parts by weight of active ingredient per 10 parts by weight of additives sprayed aqueous emulsion, each consisting of one of the examples of emulsifiable concentrates, wettable powders, granules or spray

means has been produced. After 2 days the larvae were up living and dead individuals are evaluated and the minimum concentration for 100% destruction is determined.

Compounds according to Example 1 worked in the above Te-. t against larvae of Tetranychus urticae.

Example 4: a) Rhipicephalus bursa

5 adult ticks or 50 tick larvae were placed in a glass tube counted and for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series with 100, 10, 1 or 0.1 ppm test substance each submerged. The tube was then closed with a standardized cotton ball and turned upside down to form the active ingredient emulsion could be absorbed by the wadding.

The evaluation was carried out after 2 weeks for the adults and after 2 days for the larvae. Two repetitions were run for each attempt.

b) Boophilus microplus (larvae)

With an analogous dilution series as in test a), 20 sensitive resp. OP-resistant larval experiments were carried out. (The resistance refers to the tolerance of Diazinon).

Compounds according to Example 1 were effective against adults in this test and larvae of Rhipicephalus bursa and sensitive resp. 0P-resistant larvae of Boophilus microplus.

Minimum concentration in parts by weight of active substance per 10 parts by weight of additives for 100% killing of

Spodoptera littoralis larvae

Heliothis virescens larvae

Tetranychus

urticae

Larvae

Rhipicephalus
burs a
Larvae

-CH-COO-CH- .CH C "

SS

Br

IN
C.

sX

h ^CH 3 C = C-Br

rci

200

100

200

200

400

200

400

200

400

10

10

10

CD

»-CH-COOCH-i

. CH ₀

3 3 C = C-Br

200

200

400

10

O CD NJ CD NJ

Minimum concentration in parts by weight of active substance per 10 parts by weight of additives for 100% killing of

Spodoptera littoralis larvae

Heliothis virescens larvae

Tetranychus urticae larvae

Rhipicephalus

bursa

Larvae

/ \ -CH-COO-CH-i J

100

100

200

100

100

200

CH ₃ C = CJ

Cl- '^ .- CH-COO-CH-v
CH ₃ CH ₃ C = C-Br

200

200

400

10

Minimum concentration in parts by weight of active substance per 10
Parts by weight of additives for 100% destruction of

Spodoptera littoralis larvae

Heliothis
virescens
Larvae

Tetranychus urticae larvae

Rhipicephalus

bursa

Larvae

Cl- <> - CH-COO-CH-f : r ° "i Γι

\ / ι ι Π Ι Ι ·

^ 3 ^CH 3 C = CJ

100

200

200

10

> = CH-CiI - CH-COOCH ₂ - / \ -0-f \

³ 4V ν ν

400

400

800

Phenothrin

(Dutch patent specification No. 7 409 256)

Claims (10)

Patent claims 1. ' A compound of the formula where R Cl- · ^ V-CH- or Cl- · ^ tfl, CH, 3 3 Δ Δ R "hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl or Methoxy and
X mean halogen. 2. A compound according to claim 1, wherein R Cl- ^ ^ -CH- or ^cl ~ * \ / ^# ~? ^H "' R is hydrogen, fluorine, chlorine, bromine or trifluoromethyl and X mean bromine or iodine. 3. A compound according to claim 2, wherein ^C1 "% )"? ' ° ^{the C1} "% S" '" / ^Ca *""/ ^CH \ fi ^N CH R “hydrogen and X mean bromine or iodine. 4. The compound according to claim 3 of the formula _cl _. / X-CH-COO-CH-./.-Ο-. ' . 5. The compound according to claim 3 of the formula Cl- /.-CH-COO-CH-. --Ο- · - , -CH ₂ '{«· 6. The compound according to claim 3 of the formula ⁰ K ^ f yy ^x Br 7. A process for the preparation of compounds according to claim 1, characterized in that a compound of the formula R-COX
in the presence of an acid-binding agent with the compound of the formula HO-CH- / ^N _r 0- / X « c \ / \ / III · Γ reacted, in which R ₁ , R ₂ and X _{1 have} the meaning given in claim 1 and X stands for a halogen atom. 8. A pesticide which as active component a compound according to claim 1 and suitable carrier and / or contains other aggregates. 9. Use of a compound according to claim 1 for combating various animal and vegetable pests. 10. Use according to claim 9 for combating insects and representatives of the order Akarina.