DE2301327A1 - NEW ETHERS - Google Patents

Description

CIBA-GEIGYAG, CH-4002 Basel

Ci

φ · ¹ 5 λ

α- <ί!

Case 5-7975 / 1 + 2 / = Germany

D ;. F. Zur: si .-: n ion. - Dr. ti. Assmf.nn Dr.R. ! "OyninEbcrfiOr - Dipl. Γ; - .; · ;, l ^. U-lzbauer

D .. r. Zv.rr.:z:.Ar. j; in.

Pütentanv / olt «

8 Monday on 2, Bräuhausstraße 4 / Ul

New ethers

The invention relates to the phenyl nuclei unsubstituted or substituted ^ -alkoxy-benKophenon- • Derivatej their production and use for the control of insects and representatives of the order Akarina. The compounds correspond to the formula

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CLBA-GEIGY AG - 2 -

R, hydrogen, halogen, C-. -Cj, -alkyl, vinyl or Ethynyl,

R ~ hydrogen, halogen, methyl or ethyl or R-, and Rp together the cyclopentyl or cyclohexyl ring, R ,, hydrogen, halogen, methyl, ethyl or C ₁ -CjI-alkoxy,

Rj, hydrogen, halogen or methyl, Rp- hydrogen or halogen or R-7 and Rj- together form a carbon-carbon bond

or an oxygen bridge,
Rg hydrogen, methyl or ethyl, R ₇ hydrogen, halogen, C ₁ -Cj, -alkyl or C -C ^ -alkoxy, Υ oxygen or the group -CHpO-, where the CHp-

Group is bonded to the phenyl nucleus and η and m are each the numbers 0 or 1.

Halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, but especially chlorine. ~ The for R ,, R ^ and R in question alkyl and

Alkoxy groups can be straight-chain or branched. Examples of such groups include: methyl, ethyl, propyl, isopropyl, i-, n-, sec-, tert-butyl, methoxy, Ethoxy.

A preferred group is formed by the compounds of the formula I in which

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R hydrogen, chlorine, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec-, tert-butyl, vinyl or ethynyl,

R is hydrogen, chlorine, methyl or ethyl or

R ₁ and R ₀ together form the cyclopentyl or cyclohexyl ring,

R _{3 is} hydrogen, methyl, ethyl, methoxy or alkoxy,

R ^ hydrogen, chlorine or methyl,

R ₁ - hydrogen or

R and R _r together form a carbon-carbon bond

or an oxygen bridge,
R / r hydrogen or methyl,
R _{7 is} hydrogen, chlorine, methyl or methoxy, Y is oxygen or the group -CHpO-, where the CHU-

Group is bonded to the phenyl nucleus and m and η each denote the numbers 0 or 1.

Particularly noteworthy for their effect are the compounds of the formula I in which
R ₁ hydrogen, chlorine, methyl, ethyl, n-propyl, iso-

propyl, n-, i-, sec-butyl or ethynyl, R hydrogen, chlorine, methyl or ethyl, R, hydrogen, methyl, methoxy or ethoxy, R |, hydrogen or chlorine,
R ₁ - hydrogen, or
R ^ and R ₁ - together a carbon-carbon bond

or an oxygen bridge,
R ^ hydrogen or methyl,

3 0 3: "'- / 119 7

CIBA-GEIGY AG

_ Ij. _

R ₇ hydrogen,

Y is oxygen and η and m are each the numbers 0 or 1.

• The compounds of the formula I are prepared in a manner known per se using the following methods: l) Formation of the ether (O-alkylation) by condensation of a halide with a 4-hydroxybenzophenone derivative:

(II)

YM + X

N a

(in)

R_

Base \ γ

3 rows

+ KDC

to R, Y, m and

where in the formulas II and III η also have the meaning given for the formula I; X represents chlorine, bromine or iodine, preferably chlorine or bromine; M is a metal especially I. or

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CIBA-GErGY AG

Main group of the periodic table or hydrogen.

2) Epoxidation of a 4-alkenyloxy-benzophenone derivative:

Il C.

(IB)

τα.

(ic)

3) Addition of hydrogen halide to the olefinic double bond of a 4-alkenyloxy-benzophenone derivative:

+ HX

(IB)

¹ m

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CIBA-GEtGY AG

ϊη

T)

-η

■ τ

where in the formulas (IB) and (ID) R ₁ , R _2, ZR _2. , R>, R ", Yj m 'and η have the meanings given for the formula I; X represents halogen but preferably represents chlorine.

4) Epoxidation of an unsaturated halide to an epoxy halide and condensation of the same with a Λ- hydroxybenzophenone derivative "

309 8 29 /

CIBA-GEiGY AG

- 1 -

(H)

+ Base

V, epoxidizing ^K l medium

(IV)

-> ■

Hi

TX

(V)

(IC)

—M ^L -n

where in the formulas IC, II, IV and VR ₁ , R ₃ , R ^, Rg, IL-Y-, m, η, M have the meaning given above; X stands for halogen, in particular for bromine or chlorine,

5) Hydrogenation of a 4-alkenyloxybenzophenone derivative: O

(IB)

catalyst

309S29 / 1197

CIBA-GEIGY AG

(IE)

where fL> Rp, R ₂ ,, Rg, R ", Y, m, η have the meaning given for the formula I.

6) Addition of an alcohol or water to a double bond: .

(IB)

E 'OH

^R l Hg (II) -SaIz ^

R,

¹ in

Hg-A R.

ίι R

4 OR!

Complex hydride

OH ⁰ water

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CLBA-GEIGY AG

- Q -

- η

OR!

where R ₁ , Rp, R ₂ , R ^, R ₇ , Y, m and η have the meaning given for the formula I, A is the anion of an Hg (II) salt and R 'is a C ₁ -C ₂ .-Alkylre st or hydrogen.

7) Production of alcohol and etherification of the OH group:

(IG)

R,

XL

l) Strong base ^R l 2) R 'X

Rr

OR! L ^R i

where R ₁ , R ₂ , R ₂ ^ R ₆ , R γ, m and η have the meanings given for the formula I, X is a halogen atom and R ^{1 is} a C ₁ -C ^ -alkyl radical.

309829/1197

CiBA-GEIGYAG '-10 -

The 0-alkylations of the 4-hydroxy resp. of 4-hydroxymethyl-benzophenone or their derivatives substituted in the nucleus can be sown with the various. _: saturated or unsaturated halides, depending on the reac-, - _r . activity of the applied halide, in different. Solvents and at different reaction temperatures -but always in the presence of at least one mole of one of the bases mentioned below- are carried out *

Particularly suitable solvents are acetone, .. ·. . Methyl ethyl ketone, cyclohexanone, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, dialkyl ether, dimethylformamide,. Dimethyl sulfoxide, hexamethylphosphoric acid triamide, suIfolane, inert hydrocarbons such as toluene, benzene, xylene and the like. However, other solvents can also be used, _o .

As a necessary bases or acid _o a cc ept or s in which ■ A-ether formation of the 4-hydroxybenzophenone derivative, and -; a halide find mainly alkali or alkaline earth,. hydroxides, alkali or alkaline earth carbonates, alkali or alkaline earth hydrides and alkali alkoxides use; it can . but also 'organic bases, such as "triethylamine, = pyridine-iisWhere are used as acid acceptors.

The reaction temperatures for the formation of aryl ether are between -10 and 140 ° C, mostly between 5 and 70 ° C (e.g. when using solvents such as dimethylsul-

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CIBA-GEIGYAG ^; - 11 -

foxide, dimethylformamide, sulfolane, hexamethylphosphoric acid triamide, 1,2-dimethylethane etc), or in the Boiling temperature of the solvent used (e.g. for ketones).

The benzophenone alkenyl ethers are preferably converted into the corresponding epoxy derivatives in an inert solvent, conveniently a chlorinated hydrocarbon between -25 ° C. and room temperature, usually between -5 and +5 ° C. with the aid of an epoxidizing agent such as a peracid «, The Epoxyderiva.te of the formula IB can also be obtained via the corresponding halohydrins, by splitting off hydrogen halide, by mixing a benzophenonalkenyl ether with an N-halosuccinimide, for example with N-bromosuccinimide in a mixture of water with a solvent such as tetrahydrofuran, 1 , 2-dimethoxyethane, dioxane or tert "butanol are converted into the bromohydrin in a homogeneous or heterogeneous phase between -5 C and room temperature and the desired epoxy derivative is obtained by subsequent treatment of the bromohydrin with an alkaline agent such as alkali carbonate, alkali alkoxide or an alkali hydroxide« Under alkali are in particular sodium and potassium z u understand. -_r-

The term “peracid” primarily refers to lower peralkanoic acids with 1 to 6 carbon atoms, such as ZoB ₀ peracetic acid, and aromatic peracids such as

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CIBA-GEIGY AG - 12 -

Perbenzoic acid, monoperphthalic acid, but especially 3-chloroperbenzoic acid understood.,

.The up and isolation of compounds of formula I is carried out by known techniques, Z ₀ B ₀ adding to the reaction mixture with water or ice, followed by extraction with a suitable solvent, for example _o ether; Washing the organic phase Z ₀ B ₀ with dilute alkali lye, drying the solution over anhydrous sodium sulfate. After the solvent has been removed, the compound of the formula I which remains can be purified, if necessary, by crystallization, vacuum distillation or chromatography on silica gel or aluminum oxide.

Various reaction sequences can be used to obtain epoxidized benzophenone alkyl ethers of the formula IC lead to the goal: Either the 4-hydroxy or 4-hydroxymethylbenzophenone compound is used first according to the manufacturing process mentioned etherified in the presence of a base with an alkenyl halide and then in this aryl-alkenyl-ether the olefinic double bond . As described above converted into an epoxy or else first the alkenyl halide with exclusion of moisture in an inert solvent, conveniently in a chlorinated hydrocarbon, between -25 ° C and room temperature with the help of an epoxidizing agent such as

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CiBA-GEIGYAG - 13 -

ZoBo expodes a peracid and this epoxy halide in the subsequent reaction with the 4-hydroxy resp. h- Hydroxymethyl-benzophenone in the presence of an acid reac- tor to the end product, an epoxidized benzophenone alkyl ether.

.The addition of hydrogen halide, especially hydrogen chloride or bromide to the aliphatic .Doppelbindung, is preferably carried out by the action of anhydrous hydrogen halide at a benzophenone-alkenyl- ether in a suitable solvent such as, for _o example, methanol, ethanol, another alcohol, a Dialkyl ether, 1,2-dimethoxyethane, glacial acetic acid, etc. The addition of the hydrogen halide is carried out at a temperature between -30 and +25 C.

The isolation of the halides formed takes place, as mentioned, by known techniques, such as adding water to the reaction mixture, extraction with an organic Solvent and removal of the excess hydrogen halide by neutralization with a weak base or by washing with water, the remaining halide after removal of the solvent by crystallization, high vacuum distillation or Chromatography can be further purified.

Unsaturated araliphatic ethers of the formula IB can be converted into saturated araliphatic ethers in a known manner Aethorn of the formula IE hydrogenated with

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CiBA-GElGYAG - l4 -

catalytically excited hydrogen, expediently between-space- and the boiling point of the reaction mixture at normal or elevated pressure. Suitable as catalysts Raney nickel or precious metals such as platinum are preferred or palladium »The main solvents are methyl and ethyl acetate, dioxane or alcohols such as methanol., Ethanol into consideration «.

The reactions to the active ingredient of the formula I, wherein R ^ is a C, -Cjr, alkoxy group, are at normal .Druck and in an anhydrous alcohol R * OH and optionally in teinelimern with respect to the Reka ons .. inert solution and Diluents carried out, · for example in ethers such as tetrahydrofuran, dioxane, ■ diethyl ether, 1,2-dimethyoxyethane, etc. In the 1st stage: -if R '= H- and in the 2nd stage, water can also be used as. ; Solvents are used ₀ ..-.-

The mercury (II) salts used are preferably mercury (II) acetate and Q, mercury (II) trifluoroacetate. The complex hydride used is MeBHj, in which Me is an alkali or alkaline earth metal atom Reaction with complex borohydride takes place in the presence of alkali hydroxide and water. The reaction ^{temperatures are in the range from -10 to + 2} IO ⁰ C, preferably between 0 and + 25 ° CO ·

As further methods of obtaining the connections

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CIBA-GEIGYAG - 15 -

of the formula I, where PL is a C -C ₁ alkoxy group, the etherification of an alcohol of the formula IG by reaction with a halide, depending on the reactivity of the halide used, in various solvents and at different reaction temperatures - but always in The presence of at least one mole of one of the bases mentioned above can be carried out.

The compounds obtained fall - wherever this in principle is possible as cis / trans isomer mixtures. An isomer mixture can, for example, with the help of chromatographic Separation methods are separated into the isomeric forms, e.g. by adsorption on a separating material selective adsorption activity, such as'. Silica gel, aluminum oxide, and subsequent elution of the separated Isomers with a suitable solvent, ZoB. Diethyl ether, hexane, methyl or ethyl acetate. Another chromatographic separation method is gas chromatography. In certain cases a Isomer mixture can also be separated by fractional distillation or fractional crystallization.

The starting materials of the formulas II to V are known "Compounds which are prepared analogously to known methods described in the literature .-metric tons.

The compounds of the formula I are suitable for combating various types of animal and

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CIBA-X3EIGYAG

vegetable pests; They are suitable for combating insects and representatives of the order Akarina but above all to combat insects,

For example, the compounds of the formula I can be used against insects of the following orders and families will:

Orthoptera

Isoptera
Hemiptera

Coleoptera

Lepidoptora

Acrididae

Gryllidae

Blattidae

Kalotermxtxdae

Miridae

Piesmidae

Lygaeidae

Pyrrhocorxdae

Pentatomidae

Cimicidae

Reduviidae

Jassidae

Eriosomatidae

Lecaniidae

Carabidae

Elateridae

Coccinellidae

Tenebrionidae

.Derinestidae

Cucujidae

Chrysomelidae

Curculionidae

Scolytidae

Scarabaexdae

Pyralidae

Phyticidae

30 98 2 j / I

CiBA-GEIGYAG ~ ¹ ^ "*

Pyraustidae Crambidae Tortricidae Gallerildae Lyonetiidae Yponomeutidae Pieridae Plutellidae tymantriidae Noctuidae

Diptera Culicidae

Simullidae Tipulidae

The insecticidal or acaricidal effect can be increased by adding other insecticides and / or acaricides widen it considerably and adapt it to the given circumstances.

The following active ingredients are suitable as additives:

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CIBA-GEiGYAG - / l & ~

Organic Phosphoryerbiniuigsn
Bis-0, O-diethylphosphoric anhydride (TEPP) dimethyl (2,2,2-trichloro-1-hydroxyethyl) phosphonate (TRICHLORFON) 1,2-dibroi? -2,2-dichloroethyldine; ethyl phosphate (NALED) 2,2-dichlorovinyldixethylphosphate (DICHLORFHOS) 2-Kethoxycarbanyl-1-EethylvinyldiiEethylphosphat (MEVINPHOS) BiEethyl-1-itßthyl ^ -fEethylcarbaisoyDvinylphcsphat ^ Is. (KOKOCRQTOPHOS) S-iDimethoxyphosphinyloxyJ-UK-dicethyl-cis-crotonanid (D1CR0T0PH.0S) 2-ehloro-2-diethylcarbaisoyl-1-rr.ethylviny] diniethylphosphate (PKOSPHAMIDON) O, 0-diethyl- - (ÄihyllhJo) -äthyIthiophosphat (DEhIETOfI) S-Aßthy) thioäthy] -0,0-dirnethyl-dithiophosphat (THICiODN) OfC-dietiiyl-S -äthykercaptomethyldithiophosphat (PHORATE) O, O-diethyl-S-thiophosphate (DISULFOTON) 0 _f 0-DimeihyI-S-2- (3thylsulfiny]) ethyl thiophosphate (OXYDEIiETONIiETHYL) 0,0-DlBethyl-S - (], 2-dicarbäthoxyathyI dithiophosphat (MALATHION) O, O, O, O-S , S'-methylene bis-dithiophosphate (ETHIOfI) 'O-ethyl-SjS-dipropyldithiophosphate

.- OjO-DimethyJ-S-CH-reethyl-N-foriüylcarbaiBoylnsethyl) -dithiophosphat (FORMOTiMON) 0,0-Dimethyl-S- (N ^! -Inethylcarbamoylmethyl Idithiophosphat (DlliiETHOAT) 0,0-Dimethyl-0-p-ni ' tropheny] thiophosphate (PARATHION-METHYL) 0,0-Dϊäthy1-0-p-nitropheny1thiophosphat (PARATHlON) O-Ethy1-0-p-nitropheny1phenyIthiophosphonat (EPN) OO-Dkeihyl-O-iWntro-m-tolTHIophosphonate (FENIophosphate) D-DiEsthy] -0-2,4-5-trichlorophenylthiophosphate (ROfifiEL) 0-ethyl-0,2,4,5-trichloropheny] ethy] thiophosphoaate (TR (CHLORONATE) ojö-diiseihyl-O ^ jS-dichloM-broiiiphenylthiophosphate (BROMOPHOS) ß, ö-Oiinethyl-0- (2 ₎ 5-dichloro-4-iodophenyl) -thiophos? Has (IODOFENPHOS) 4-tert.butyl-2-chlorophenyl-N-diethyl-O-itethylaoiidophosphat (CRUFOMAT) 0 , 0-OiinethylrO- (3-methyl- ^/ yn! Ethyln! Ercaptophenyl) th5ophQsphat (FENTHION) isopropyla! Nino-0-ethy] -0- (4-ynethyln; ercapio-3t-fiiethylphenyl) phosphate 0, diethyl-0 -p -. (. methylsulfinyl) phenyl thiophosphate (FENSULFDTHION) 0-p- (DiEethylsulfamido) pheny] Q, 0-dimethyl amido phosphate (FAMPMUR) OjOjO'jO'-Tetrair.ethyl-OjO'-thiodi-p-phenylenethiophosphate O-ethyl-S-pheny] -ethyldithiophosphonate OO-diinethyl-O-gi-sißthylbenzyl-S-hydroxycrotonylphosphate 2-chloro-1- (2,4 -dichlorophenyl) vinyl diethyl phosphate (CHLORFENVINPHOS) 2-chloro-1- ( _2f 4,5-trichlorophyl) vinyl-dinethylphosphate 0- {2-chloro-1- (2,5-dichlorophenyl) jviny.l-0,0 -diäthy Hhiophosphat Phenylglyoxylonitriloxim-O ^ O-diethylthiophosphat (PHOXIM) &, 0-diethyl-0- (3-chloro-4-diethyl-2-oxo-2-Hl-benzopyran-7-yl) -thiophosphat (COUHAPHOS) 2 , 3-p-DJoxandiihiol-S, S-bis (0,0-diethyldithiophosphate) (OIOXATHIOfl) 5 - [(6-chloro-2-oxo-3-benzoxazolinyl) p-ethyl] 0,0-diet] dithiophosphate ( PJIOSALON) 2- {ethoxyphosphinylimino) - !, 3-dithiolane O, Q-DlBethyl-S- [2-methoxy-1,3,4-th fadiazol -5- (41f) -ony I - <4) -methy 1 ld i thiophosphate 0,0-diisthyl-STphthalimidQsiethyl-dithfophosphat (JMIDAN) 0,0-0iä'thyl-0- (3,5,6-trichlor-2-pyridyl) thiophosphate 0 _f D-Diäihyl-0-2- pyra2Jny] thiophosphate (TiIlONAZIN) O, 0-Diäihyl-0- (2-Isopropy1-4-i3ethyl-u-pyriEidyl) Hioph osph3t (DlAZINON) OO-Diäihyl-Q - ^ - quinoyalyJ Hhiophosphat 0,0-DiiBelhyl-S- (i-oxD-1,2,3-ben2otriazin-3 ( ^? .H) -y]? Iethyl) -dithiophosphate (AZIfJPHOSMETIiVL)

• 309829/1197

CLBA-GEIGYAG

0,0-0iäihyl-S- (4-oxo-l, 2 _J ^ 3-benzotriazin 3 (4H) -yl T.ethyl) -dithiophosphate (AZI'.PKQSAETHYl) S - [(6-i _J dia- iino-s-tria2ir, -2-yl) reihyl] -0 ₎ 0-di-ethyldithicr.! -. üSFhat (KtWZON) OjO-Diceihyl-OO-chloM-niirophenyDthiophosphat (CHLCRTHIOi;) Ö, O-Direthy] -O (Cder S) -2- {äthylihioäii.yl jihiophosphat (ϋΕϊ'ΞTOi, '- S-KETf! YL) 2- (O ₁ OD kejhyl-phosphoryl-thioneihyO-Sr.ethoxy-pzron-i-Sji-dichlorofcenzyl-triphenylphosphon i u. "chl orid

P, O-0i | thyl-S- (2,5-d; ch1orpher.ylthio ^ ihyl) dithiophosD! Iat ( ⁰ HENKAPTOfO 0,0-0i§ihyl-0- (4-ir, e {hyl-cur: arinyl-7) -thiophoGphat (FOTASAN) '5-ABino-bis (dinethyla!: idO) phosphinyl-3-phenyl-1 _J 2 _i ^/ . -triazole (IRIAMIPHOS) H-Keihy1-5- (0,0 »di-ethylthiolphosphoryl ) -3 - thiavaleranid (VAiIIDOTHICN) 0,0-Diäihyl-0- [2-dk, eihyla ", ino-ir.ethylpyriniidyl- (6)] - thiophosphate (DIOCTHYL) 0,0-Diiseihyl-S- (isethylcarbas ! oylir.ethylMhiophosphat (ObXTHOAT) 0-ethyl-0- (8-quinolinyl) -phenylthiophosphonate (OXINOTHIOPHOS) O-ethyl-S-ethyl-aiBidothiophosphat (KONITOR) 04iethy] -0- (2,5-dichloro-4-broirphenyl ) -benzothiophosphonate (PHOSVEL) 0,0,0,0-fetrapropyldihiopyrophosphate S-fOiniethoxyphosphinyloxyJ-N-iBethyl-N-ireihoxy-cis-crotonaniid 0,0-DiF.ethyl-S- (N-ethylcarbanoylmethyl) dithiophosphate (ETHYL ) OjO-Diäihyl-S-iN-isopropylcarbacioylirethyD-dithiophosphat (PKOTHOAT) SKO-Cyano-l-iethylilhyDcarbaiiioylEeihyldläthylihiolphosphat (CYANTHOAT) S- (2-Acetaiaidoäihy 1) -ethiEethosphat 1 o ylphosphoric acid triacid (HEMPA) 0,0-Dip.ethy1-0- (2-chloro-in? trophenyl) thlophosphate (DICAPTHON) 0,0-DiEethyl-Op-cyanophenyl thiophosphate (CYANOX) O-ethyl-0-p-cyanopheny] thiophosphonate 0,0-diethyl-0 ~ 2,4-dichlorophenylthiophosphate (DfCHLORFENTHION) 0,2,4-dichloropheriyl-O-ciethyl isopropylamidothiophosphate 0,0-diethy 1-O-2,5-dichloro-5-bronipheny 1 thiophosphate (BROHOPHOS-AETHYL) Dinethyl-p- (ciethyl thi o) phenyl phosphate 0, C ~ DΐEeihy 1 -0-p-su · f a-ni dopheny 1 thiophosphate Or [p- (p-chlorophenyl> zopheny]) ] C, 0-dimethyl thiophosphate (AZOTHOAT) 0-ethyl-Si-chloropheny] -ethyldi thiophosphonate 0-1sobuty1-spychloropheny T-ethy1d ithiophosphonate 0,0-di-ethyl-Sp-chlorophenyithiophosphate 0,0-dir.ethy ] -S- (p-chT orpheny 1 thi omethy]) - di thiophosphate Ο, Ο-diethyl-p- chlorophenylmercaptomethyl-dithiophosphate (CARBOPHENOTHIOIi) 0,0-dietliyl-Sp-chlorophenylthiomethyl-thiophosphate OO-dicethyl- S-icarbäthoxy-phenykethyDdithiophosphat (PHENTHOAT) OjO-diethyl-S-icarbofluoroethoxy-phenykethyD -di thiophosphate O , O-Dic-eihyl-S-icarboisopropoxy-phenylrrethyU-di thiophosphate OO-iiäthyM-hydroxy-jji-tetranethylene-counarin] -thiophosphate (COIiMITHOAT) 2-kethoxy-4-Hl, 3,2.-benzodioxaphosphorir.-2 -eu] fi <i 0,0-diethyl-0- {5-phsnyl-3-isooxazolyl) thiophosphate 2- {diethoxyphosphinylinino) -4-n, ethyl-1,3-dithiolane

Tris- (2-i.ethyl-l-aziridiny]) - phosphine oxide (HETEPA) S- (2-chloro-1-phthaliciidoethyl) -0,0-diethyldithiophosphate N-hydroxynaphthal i isido-d i ethyl phospha t Dii: ethyl] -3,5,6-trichloro-2-pyridyl phosphate

0,0-dip.ethyl-0- (3,5,6-irichlor-2-pyrid / l) thiophosphate

S- 2- (AethyIsulfonyl) ethyl direthylihiolphosphat (DinXY0O € TÜ, 'i-S-! UlHYl)

309 02 8/1197

Diethyl S- 2- (ethylsulfinyl) ethyl dithiophosphate (OXYDISULTOTOH) Bis-OO-diethylthiophosphoric anhydride (SULFOTEP) DiEethyl-1,3-di (carboaethoxy) -l-propen-2-yl-phosphate DiBethyl- {Z _f Z, 2 -trichlor-1-bu {yroyloxyethyl) phosphonate (BUTC (MT) O ^ -DiBethyl-O-iZjZ-dichloro-1-inethoxy-vinyl phosphate bis (dicetbylasido) fluorophosphate (DIMEFOX) S ^ -dichlorobenzyl-triphenylphosphoniusichiorethyl Eethoxys-ethylcarbaisoylinethyl-dithiophosphat (FORKOCARBAH) 0,0-diethyl4} - {2,2-dichloro-l-chloroethoxyvinyl) phosphate OjO-OiEethyl-O-iZjZ-dichloro-l-chlorothoxyvTnyDphosphat O-Ethy1-S, Sd i pheny1d ί th i ο1phos pha t O-ethyl-S-benzyl-phenyldithiophosphonate 0, O-diethy] -S-benzy] thiol phosphate.

0,0-Dieeihyl-S- (4-chlorophenylthioisethy.l) dithiophosphate (HET HYLCARBOPHEHOTH IOK) 0,0-Dinethyl-S-iäihyIthioniethyi) dithiophosphate Diisopropylaainofluorophosphat (Ml PAFOX) OjO-Diaethyl-S-phosphate-i-DOPhophinyl-Diaethyl-S-phosphate (KOFOX) OjO-diaethyl-SOTHYDOPHOPphinyl-Diaethyl-S-phosph-i-DOPphinyl

BisEethylaiBido-phenyl phosphate "

OjO-Diaethyl-S-fbenzenesulfonylidithiophosphate 0, O-0imethyl- (S and 0) -ethylsulfiny1äthy1thiophosphat 0,0-diethyl-0-4-n-propheny] phosphate Triethoxy-isopropoxy-bis (thiophosphinyl) sulfide

Okiaaethylpyrophosphoramid (SCHRADAN) bis (diiaethoxyihiophosphinylsulfido) -phenylmethane ^ / H'-tetraBelhyiaiamidofluorophosphat (DIMEFOX) O-phenyl-0-p-nitrophenyl-inethane thiophosphonate (COLEP) O-Ksthyl-O-tert -chloro. butyl-phenyl) -N-raeihyTaraidothiophosphat (HARLEKE) 0-Ethy] -0- (2,4-dichloropheny]) -phenylthiophosphonate 0,0-DiSthyl-0- (4-aethylfflercapto-3,5-dimethylphenyl) -thiophosphate 4 , 4! -Bis- (0,0-diiiethylthiophosphory1oxy) -diphenyldisulphide 0,0-di- (B-ch] orethyl) -0- (3-chloro-4-methyl-cuni3rinyl-7) -phosphate S- (1 -Phihal inidoäthyl) -0,0-Di äthyldi thi ophosphat OjO-Oiaethyl-OO-chior-i-diethy lsulfamyl pheny l) -thiophosphat 0-Kethy1-0- (2-c3rbisopropropoxypher, yl) -a! 5ldothi ophosphat 5- (0,0-Diii: ethylpIiosphoryl) -6-chlorobicyclo (3.2.0) -heptadiene (!, 5) 0-5'ethyl-0- (Zi-propoxycarbonyi-1-methylvinyl) ethylamidothiophosphate

nitrophenols I. Derivatives

4,6-DinUro, 6-sethy] phenol, Na salt [Dinitrocresol] Dinitrobutyl phenol (2.2 ¹ ^ ¹¹ triethanolan salt) 2 Cyclohexyl-ijB-Dinitrophenol [Dinex] 2- (1-Kethylheptyl) -4,6 dinitrophenyl crotonate [dinocap] 2 sec-butyl-ijB-dinitrophenyl-S-iiethyl-butenoate [binapacryl] 2 sec-butyl-ijB-dinitrophenyl-cyclopropionate 2 sec-butyl-ijO-dinitrophenyl-isopropyl-carbonate [dinobutone]

309829/1197

CIBA-GElGY AG - 2 L -

Various pyrethrin I.
Pyrethrin II

S-Allyl-Z-Eethyl-i-oxo-Z-cyclopenten-l-yl-chrysantheauEat (Allethnn) ß-cHorpiptronyl-chrysantheireate (barthrin) 2,4-di-ethylbenzyl-chrysanthesiMat {dieethrin) 2,3,4,5- telrdhydrophthal ioido ^ ethylchrysaniheauicat i-chlorobenzyme chlorophenyl sulfide [chlorine surfactant] 6-methyl-2-oxo-1,3-dithiolo- [4,5-b] -quinox3line [quinonethionate] (l) -3- (2-Furiury1) - 2-ethyl-4-oxucyclapent-2-cnyl (I) - (cis + irans) chrysaitf-e- j -'- rr-gficcarboxylate [furethrin] 2-pivalcy] indane-1,3-dione [pindane] N * - (4-chl οΓ-2-Hiethylphenyl) -8, H-diBethylformam? D5n (chlorophenainfdin) 4-chlorobenzyl-4-fluorophenyl-sulphide (fluorosurfactants) Sjo-dichloro-I-phonoxycarbaayl-Z-trifluoriieihyl-fenoiizaidazoi ( ) p'-chlorophenyl-p-chlorobenzenesulfonate (Ovex) p-chlorophonylbenzenesulfonate (Fenson) p-chlorophenyl ^ jijS-trichlorophenyl sulfon (Teiradlfon) p-chloropheny1 -2, 4,5-trichlorophenyl sulfide (tetrasulfyl) p-chlorobenzyl chlorophenyl sulfide (chlorine surfactants) Z-thio-1,3-dithiolo- (5,6) quinoxaline (thioquinox) prop-2-ynyl- (4-t-butylphenoxy) cyclohexy isulf1t (propargil)

l-Dinethyl-2- (2-4 -Kthyl ^{I l} -chlorphcnyl) -foni asiidm (CHLORPHENAHIDIiI) 1 -:! ethyl-2- (2'-Reihyl-4 -chlorphenyI ^l) -fornai "idin 1- Methy1-2- (2'-niethyl-V-faroBphenyl) -forffia3i5din 1-Kethyl-2- (2 ', 4'-dimethylphenyl) -foraaaid1n In -Buty1-li «ethy] -2- (2 ^I -pethyl- 4 ^I -chJorphehyI) -foriiiamidin 1-Methy1-1- (2 ^l -i «othyl-4 ^I -chloroanilino-ethylene} 2- (2" -tiethyi-4 "-chlorophenyl) -forBa« idin In-Butyl-2 - (2'-nieiliyl-4 ^l -chlorophenyl-iBino} -pyrrolidine

urea

K-2-! Iiethy1-4-chloropheny Ϊ-Μ ¹ , M'-disethyl-thiourea

C arbar iate

1-Kaphthyi-H-Eeihylcarbaet (CARBARYL) 2-Buliny1-4-chlorophynylcarbsHat 4-niir, cthy1aniino-3,5-xyIy1-H-Ee {hylcarbaBat i-Diiiethylanyino ^ -toiyl-a-ethylcarbaARBat) (AMINOC {hyHhio-3,5-xy1yl-B-methylcarbasat (KTHIOCARB) 3,4,5-TriinethylphenyMJ-BefhylcarbaMt 2-Chl orpheny I -fl-ethy! carbaeate (CFEC) S-Chloro-G-oxo-Z-norbornan- carbonUril-O-iicDthylcarbaKoylJ-oxia! - ([JipethylcarbasiOyD-S-ieihyl-a-pyrazolyl-SjH-diiethylcarbasat (DIKElTSLAf;) 2,3-0ihydro-2 _> 2-dicieLhyl-7-benzofuranyl-K-DDtRAI) 2-! Iethy] -2-nethy] thio-propionaldehyde-0- (i! EHiyIc3rba? Ioyl) -oxiiii (ALDlCARB)

309829/1197

GiBA-GEIGYAG

fetftyl Z-isopropyl-M & ethyl carbai eoyloxy carbanilate e-Cl-AethylpropyOphenyT-fJ-ir.eihylcarbarcat

3 _f 5-di-ized. butyl-II-s-ethylcarbaniate ■

BO-methyl-butyl-phenyl-H-methylcarbaate, Z-isopropylphenyl-li-methylearbanate, Z-sec-butylphenyl-methyl-carbonate, -tolyl-N-methylcarbaate, 2-3-xyly1-N-methylcarbamate, 3-isopropylphenyl-ft-methyl carbapate. Butylphenyl-N-nethylcarbasat S-see.-Bulylphenyl-N-iTiethykarbaniat S-isopropyi-S-methylphenyl-H-methyTcarbamat (PROMECARB) SS-Diisopropylphenyl-N -sethylcarbaniat Z-Chlor-S-isopropyiphenyl -carbanat '2- N-iiethylcarbanat'Chloro-4,5-dimethylphenyT-N-methylcarfaan; ate "2-O, 3-dioxolan-2-yI) phenyl-fi-ethy1carbain3t (DfOXACARB) 2- (4,5« fliBi} thyUl, 3 ~ <11oxolane 2-yl iphenyl-fi-xethylcarbaiiat 2_ (l _ji 3_Dioxo1an-2-yl) phenyl-N, N-diirethyIcarbar? At 2-O _t 3-D! Thiolan-2-yl) - !!, fi-dirnethylcarba3iat 2- {1,3-Dithiolan-2-yl) phenyl-N, N-.dir, ethylcarbar _! at 2-fsopropoxypheny1-N-methylcarban: ate (ARPROCARB) Z-CZ-Propinyloxyiphenyl-ft'-iriethylcarbasat 3- (2- Propinyloxy) phenyl-fi! Nethylcarbanate 2-Bieethylaniinaphenyl- "- methyl carbaniat:? - Oiallylai! Iinophenyl-t! -N; eihylcarba! Nat i-Oiallylamino-SS-xyiyl-K'-is ethylcarbairiat (ALLYXICARB) i-Benzothieny'-N- ^ ^ at ethylcarbair 2,3-dihydro-2-i3eth / ¹ -7-benzofurany1-N ^l 3--r.ethylcarbaijiat Meihyi-l-yl-N-phenylpyrazo1-5 , N-dine; ethylcarba! T; at 1-Isopropyl-S-methylpyrazol-S-yl-fijN-dirriethylcarbapate (ISOLAN) Z-dicethylaniino-S ^ -dimethylpyririidin-'i-yl-NjK-diffiethylcarbaiate S-ethyl-i -dimethylaininoiethyleniminophenyl-fi- (ne thy lcarbaniat 3,4-DiEethylphenyl-H-rie thy 1 carbamat Z-Cyci open ty I pheny 1 -N-me thy 1 ca rbair.at 3-OϊBethyTamίno-ιπsthy ¹ eπ ^ πIΪnophenyl · - N-methylcarb3rπai: (FORMETANATE) and its salts ί-iethylthiö-ethyi 1mino-N-rr.eihylcarbainat (METH0WL) 2-Sethylcarbanioyl ox ifnino-l, 3-di thiolane 5-Keihyl-2-oxethyio-l , 3-oxy thiolane 2-Cl-kethoxy-2-propoxy) pheny 1 -N-methylcarbaniate 2 - {! - Butyn-3-yl-oxy) phenyl-ii-! Iiethy] carban! At 1-BiEethylcarbamyl- l-rr.ethyrthio-O-ir.ethylcarbanyl-foriüOxin! - (Z'-rCyanoäthylthioi-O-rethylcarbacyl-acetaldoxiin 1-iethylthio-O-carbair.yl-acetaldoxiin P- {3-sec.-Biityl pheny l) - N-phe nylthio-N-methylcarbanate 2 _a 5-0iEethyi-1,3-ditfno] an-2- (0-r, ethylcarbariyl) aldoxime} · - "O-2-diphenyl-H-methylcarbar: at 2- {K -Methylcarbanyl-oxir.ino) -3-chlorobicyclo [2.2.1] heptane 2- (fl-Eeihylcarba.7.yI-oxi.T.ino) -b5cyc! C [2.2.1 jheptane 3-! Sopropy 1 pheny 1 -'ί-re thy 1 -fi-chl orace ty 1 -carbar; 31

309829/1197

CIBA-GEIGYAG - 23 "

3-Isopropylphenyl-S-Rethyl-fi-rneihylthica-ethyl-carba ~ ai

O-iZ ^ -OineWiyl-i-chloro-Z.a-dihydro-T-ber.zofuranyD-fi- ^ ethylcarba-at

O-iZjZ ^ -lricethylZ ^ -dihydro-T-benzofuranyD-N'-rieihylcarba-ate O-fiaphihyl-N-ethyl-N-acceyl-carbaMt 0-5,6,7,8-tetrahydronaphthyl-N '- oüiyl -carbapat 3-isopropyl "-4-ir.ethylth5o-phenyl-! i-ir, ethylcarba [rat SjS-Diinethyl-i-rethoxy-pheRyi-N-'ethylcarbaniai S-MeihoxyRBthoxy-phenyl-li-ethyl carbonate 3-allyloxyphenyl -? ii? ethylcarban: at Z-Propargyloxycethcxy-phenyl-Hn-eihyl-carbanat 2-ATlyloxyphe-'iyI-K-rrrethyl-carbaTiat 4-Methoxycarbonylaraino-3-sopropylphenyl-N-ynethyl-carbafiät 3,5-Dime {hyl-4- ^ ethoxycarbor _! ylar _! inD-pheny] -N ⁱ -r.eihyl-carba "ial Ζ-γ-Kethy 1th i opropy1pheny1-S-Ee thy] -carbaia t S-ta-KethoxyEethyl-Z-propenyU-phenyl-fJ-jieihyl-carbaniat Z -ChI or-S-tert-butyl-phenyl-N-methyl-carbarsate 4- (Kethyl-propargyIanino) -3,5-xyly] -N-iiiethy] -carban! At i-ifieihyl-y-chlorallylariinoJ-SjS- xylyi-N-niethyl-carbanate 4- (methyl-p-chlorallylamino) -3,5-xylyl-N-methyl-carbamab! - (P-ADthoxycarbDnyläthyO-S-pethyl-S-pyrazolyl-Njfi-dirnethyl-carbamat S- Kethyl-i-tdiKethylanino-ßethylnercapto-meihyleniiriinoJphenyl-fJ-riBthylcarbaisat!, S-BisicarbanoylthioJ-Z-ffijK-dkethylaiiiinoJ-propaRhydrochloride Sjojuinethylhydroresorcinoldkethyl-zirroresorcinoldkethyl-nlacarbino] {A-yuuinethylhydroresorcinoldkethyl-nlacarbino-ethyl phenyl-fi-inethylcarbainat Z-fDipropargylaninoj-phenyl-N-üiethylcarbainat ^ [Dipropargylaaino ^ S-tolyi-N-methylcarbaircat 4- [Dipropargylaaino] 3,5-xylyl-N-iriethylcarba! nat 2 - ['Al lyl-isopropylan pberiyl-N-methylethylcarbaiate S-allyl-isopropylaBiinoj-phenyl-N-isethylcarbaisate

Chlorinated hydrocarbons

Y-kexachlorocyclohexane [GAfAMEXAfJE; LIHDAN; γ HCH]!, Z ^ jSjGjYjSjB-Octachlor- ^ a ^^ Jaltrahydro-i ^ -Mttiyienindan [CHLORDAN] 1,4,5,6,7,8,8-Keptachloro, 3c, i, 7,7o-tetrahydro- 4,7-nethylenindan [HEPTACHLCR] 1,2,3,4,10, in-hexachlor-iji ^ a.SjßjBa-hexahydro-endo ^^ - exo-Se-diirethar.cnaphthalin [ ALDRIK]

5,8-dißethanonaphthalin [DIELDRIf =] 1,2,3,4,10,10-hsxachlor-f), 7 "cpoxy-1,4, kn, 5,6,7,8, Ba-octahydro-endo- endo-5,8-diethanonaphtiialin [EiIORIN]

309829/1 1

CFBA-GEIGY AG

The compounds of the formula I can be used alone or together with suitable carriers and / or additives can be used. Suitable carriers and additives can be solid or liquid and correspond to those in the Substances commonly used in formulation technology such as natural or regenerated substances, solvents, dispersants, wetting agents, Adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be used Dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or slurries in the usual way Formulation used in application technology for General knowledge should be processed. Furthermore are "cattle dips", i.e. cattle baths, and "spray races" *, i.e. Spray courses in which aqueous preparations are used be to mention.

The agents according to the invention are produced in an known manner by intimate mixing and / or grinding of active ingredients of the formula I with the appropriate ones Carriers, if necessary with the addition of opposite dispersants or solvents that are inert to the active ingredients. The active ingredients can be used in the following working-up forms available and applied

30S829 / 1197

CIBA-GEIGYAG, gf

Forms of processing : dust, grit,

Granulates, coated granulates, Impregnation granules and homogeneous granules e

Liquid

Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions ;

b) Solutions

For the production of solid reconditioning forms (dust, Litter) the active ingredients are mixed with solid carriers. As a carrier, for example Kaolin, talc, bolus, loess, chalk, limestone, kaIkgries, Attapulgite, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (Feldspars and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea, ground vegetable products such as grain flour, tree bark flour, wood flour, nut shell flour, Cellulose powder, residues of plant extracts, activated charcoal etc., each individually or as mixtures with one another.

309829/1197

CIBA-GEIGY AG

Granules can be produced very easily by tnan an active ingredient of the formula I dissolves in an organic solvent and the resulting solution on a granulated Mineral, e.g. attapulgite, SiOp, granite aleium, bentonite etc. and then evaporate the organic solvent again.

Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable compounds (urea / formaldehyde; dicyandiamide / formaldehyde; melamine / formaldehyde or others), whereupon a gentle polymerization is carried out which does not affect the active substances , and V7obeherein the granulation is carried out during the gel formation. It is more favorable to impregnate finished, porous polymer granules (urea / formaldehyde, polyacrylonitrile, polyester and others) with a certain surface and a favorable, predeterminable adsorption / desorption ratio with the active ingredients, e.g. in the form of their solutions (in a low-boiling solvent) and the solvent to remove. Such polymer granules can also be applied in the form of micro-granules with debris weights of preferably 300 g / liter to 600 g / liter with the aid of atomizers. The atomization can be carried out previously over large areas of crops with the help of airplanes.

3 0 9 8 2 9/1197

CIBA-GEIGYAG

Granules are also made by contacting the carrier material with the active ingredients and additives and subsequent Zerkl I get one.

These mixtures can also contain additives stabilizing the active ingredient and / or nonionic, anionic and active substances Cation-active substances are added, for example, the adhesive strength of the active ingredients on plants and Improve plant parts (adhesives and adhesives) and / or better wettability (wetting agents) and dispersibility (Dispersants). For example, the following substances come into question: Olein / Lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), Hydroxyä'thylenenglykoläther of mono- • and dialkylphenolen with 5-15 ethylene oxide residues per Molecule and 8-9 carbon atoms in the alkyl radical, lignosulfonic acid, their alkali and alkaline earth salts, Polya'thylenglykol'ather (Carbowaxes), fatty alcohol polyglycol ethers with 5-20 ethylene oxide residues per molecule and 8-18 Carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, Polyvinyl alcohols, condensation products of urea / formaldehyde and latex products.

Active ingredient concentrates dispersible in water, i.e. wettable powders (xtfettable powders) Pastes and emulsion concentrates are agents that can be mixed with water to any desired level

30982S / 1197

CLBA-GEIGY AG -

Concentration can be diluted. They consist of an active ingredient, a carrier and, if applicable, the active ingredient stabilizing additives, surface-active substances and anti-foaming agents and, if necessary, solvents. The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and powdery carriers mixed and ground in suitable devices until homogeneous. as Carriers are, for example, those mentioned above for the solid work-up forms. In In some cases it is advantageous to use mixed breeds of different carriers. Can be used as dispersants for example: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and Formaldehyde as well as alkali, ammonium and alkaline earth salts of ligninsulphonic acid, further alkylarylsulphonates, alkali and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, Fatty alcohol sulfates, such as salts of sulfated hexadecanols, Heptadecanols, octadecanols and salts of sulfated Fatty alcohol glycol ethers, the sodium salt of oleyl ethyl tauride, ditertiary ethylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

309829/1197

Silicone balls, for example, can be used as antifoam agents Question. The active ingredients are mixed, ground, sieved and strained with the additives listed above, that in the case of wettable powders the solid portion has a particle size of 0.02 to 0.04 mm and in the case of pastes 0.03 mm does not exceed. For the production of emulsion concentrates and pastes, dispersants such as those in the in the previous sections, organic solvents and water were used. As a solvent For example, alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and those boiling in the range from 120 to 350.degree. C. come Mineral oil fractions in question. The solvents should be practically odorless and inert towards the active ingredients be.

The agents according to the invention can also be used in the form of Solutions are applied. For this purpose, the active ingredient or several active ingredients of the general formula I are used dissolved in suitable organic solvents, solvent mixtures or water. As an organic solvent can aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkyl naphthalenes, mineral oils can be used alone or as a mixture with one another. The content of active ingredient in the means described above is between 0.1 and 95%, it should be mentioned that when applying from the aircraft or by other means

309829/1197

CIBA-GEIQYAG - 30 ~

suitable application devices concentrations up to 99.5% or even pure active ingredient can be used. The active ingredients of the formula I can, for example, such as can be formulated as follows:

Dust : The following substances are used to produce a) .5% and b) 2% dust:

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc

The active ingredients are mixed with the carriers and marry.

• Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient
- 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm). The active ingredient is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The thus obtained Solution is sprayed onto kaolin and then the

309829/1197

ClGA-GEIGY AG - 31 -

Acetone evaporated in vacuo.

Wettable powder; For the preparation of a a) 407oigen, b) and c) 25% d) 10 ^r wettable powder The following constituents are verwent-:

a) 40 parts of active ingredient

5 parts of lignosulfonic acid ^ sodium salt,

1 part dibutylnaphthalenesulfonic acid sodium salt,

Parts of silica;

b) 25 parts of active ingredient

4.5 parts calcium ligin sulfonate,

1.9 parts of champagne-chalk / hydroxy-athylellulose mixture (1: 1),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts Champagne chalk / HydroxySthylcellulose-

Mixture (1: 1), 8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr, parts of kaolin;

3 0 S 6 2 3/1 1 9

CIBA-GEIGYAG

d) 10 parts of active ingredient

3 parts mixture of sodium salts of saturated

Fatty alcohol sulfates,
5 parts napthalenesulfonic acid / formaldehyde condensate

sat,

82 parts of kaolin.

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. One receives wettable powder that can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate:

a) IO parts active ingredient

3.4 parts epoxidized vegetable oil,

13.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylaryl stilfonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

. 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

309829/1197

. ... - 230132?

5 parts of dimethylformamide,
57.5 parts of xylene.

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water will *

Spray: The following ingredients are used to produce a 5% spray:

5 parts active ingredient,

1 part epichlorohydrin,
94 parts of gasoline (boiling limits 160 - 190 ⁰ C), '

309829/1197

CIBA-GEIGYAG Example I.

In a solution of! 9.8 g of 4-hydroxybenzophenon and 20.5 g of 2-brora-6-methyl-3 "oeten in 200 ml of pyranium sulfoxide were at 10-15 ° C in portions within 5 hours 6.7 g of 90 $ iges powdered potassium hydroxide added in portions with vigorous stirring. After the potassium hydroxide had been added, the mixture was stirred for 16 hours at room temperature. For work-up, the reaction mixture was stirred in 1 liter of ice water, the organic phase was separated off and the aqueous layer was extracted four times with diethyl ether. The combined organic phases were then repeated with ice-cold aqueous solution potassium hydroxide solution and finally washed with water until neutral, dried and the solvent and the volatile components completely under reduced pressure abdestllliert over sodium sulfate to give the analytically pure, colorless 4- (I _1, 5-dimethyl-4-heptenyl-l-oxy) benzophenone remained. i 1.5680.

Example 2

A) To a solution of 19.8 g of 4-hydroxybenzophenone and 16.4 g of l-bromo-3-methyl-2-pentene in 150 ml of 1,2-t) imethoxyethane was at room temperature with stirring within

309829/1197

CLBA-GEIGY AG - 35 "-

for 6 hours the solution of 6.5 g of approx. 86% potassium hydroid dropped into 100 ml of absolute ethanol "After the addition the base was stirred for 15 hours at room temperature. The resulting potassium bromide was used for working up the filtrate is filtered off, the residue is concentrated in vacuo taken up in ether-n-hexane (1: 2), three times with ice-cold 10 ^ potassium hydroxide solution and then with water After drying the organic phase over sodium sulfate, the filtration and the complete Removal of the solvent left the colorless, analytically pure 4- (3-methyl-cis / trans-2-pentenyl-oxy) -benzophenone back, which solidified in crystalline form after some time and was recrystallized from η-hexane. ■

B) To a solution of 14 g of 4- (3-methyl-2-pentenyl-loxy) -benzophenone in 150 ml of methylene chloride was added dropwise at -2 to ⁰ C within 4 hours, the solution of 10.15 g of 85% 3 ~ chloroperbenzoic acid in 100 ml of methylene chloride diethyl ether (9: 1). After stirring for 2 hours at ⁰ ° C., the reaction mixture was treated with η-hexane, three times with ice-cold above potassium hydroxide solution and then washed neutral with water Residue recrystallized from cyclohexane,

309329/1197

CIBA-GEIGY AG

whereby pure 4- (2 _J 3 ~ Ep ° ^x y-3- ^m ethyl-pent-1-oxy) -benzophenone was obtained. M.p. ": 66-67 C.

Example 3

A mixture of 19.8 g of 4-hydroxybenzophenone and 20 g of powdered, anhydrous potassium carbonate in 150 ml of acetone was added dropwise at 55 ° C. in the course of 30 minutes at reflux temperature. The reaction solution was then filtered off from the sediment and the acetone was largely removed from the filtrate in vacuo. The residue was taken up in diethyl ether and the ether solution was washed six times with 10% potassium hydroxide solution and four times with water. After the organic phase had been dried over sodium sulfate, the solvent was completely removed and the residue, which solidified in crystalline form, was recrystallized from methanol, giving ice, trans-4- (3-chloro-2-propenyl-1-oxy) -benzophenone with a melting point of 56 -59 ⁰ C was obtained »

Example 4

To a cooled to -5 ⁰ C suspension of 19.1 g of powdered mercury (il) acetate in 120 ml of abs. Methanol was added with vigorous stirring in 8 minutes, the solution of 14.1 g of 4 ~ (3 ~ methyl-2-pentenyl-1-oxy) -benzo-

30982 9/1197

CIBA-GEIGYAG - 3? "

phenone in 7.0 ^m l abs "methanol. Two hours after the access

Before the olefin, the reaction mixture was cooled to -Io C and treated with 60 ml of a 3 molar aqueous sodium hydroxide solution, whereby the temperature rose to -5 ° C (cooling bath -20 ° C). 15 minutes after the addition of the sodium hydroxide solution is added to the reaction mixture at about -8 C with 60 ml of 0.5 N sodium borohydride solution in 3 N sodium hydroxide solution and allowing the temperature gradually to 'O ⁰ C ansteigenο 2 * 5 hours after the addition of the Borohydride solution, the reaction gel was decanted from the precipitated mercury sludge by pouring the supernatant solution onto 600 ml of saturated sodium chloride solution and extracting it four times in a separating funnel with 200 ml of diethyl ether. The combined ether solutions were washed four times with sodium chloride solution, dried over sodium sulfate and completely freed from the solvent in vacuo. The oily residue was purified by chromatography on silica gel (eluent: diethyl ether-hexane 1: 3), whereby pure 4- (3-methyl-3-methoxypent-1-oxy) -benzophenone was obtained. n "20:!

309829/1197

CIBA-GEIGYAG

-30-

The following connections are also established in the same way:

Active ingredient physical data

/ ° ^Η 3

0-CH ₀ -CH-C 2 \ ₀ / \

0-CH ₂ -CH ₂ -CH = C-CH ₂ -CH

OH ₅

0-CH ₀ -CH-CH-C 2 2 V ₀ / \

CH-CH

M.p .: 59-60 ° C

M.p .: 63-65 ° C.

1.5814

1.5751

309829/1197

CIBA-GEIGYAG

Active ingredient χ / 0
π J 0
π VCH -CH -C j / ^CH 3
O-CH-C = C
2 \ C.
oc ^H 3 _x CH ₃
H-CH ₀ -CH ₀ -CH = C
2 2 ν CH ^
\ / 3
0-CH ₂ -CH = C Physical
data 11
C.
Π Il
C. 3
t — riTT CH ₃ 3 CH ₃ - J I Il CH NS / 0
Il 0
Il ? h πη
ν I ³ / ^CH 3
0-CH-CH ₀ -CH ₀ -CH-C
2 N ₀ / ν n _D ²⁰ . 1.5697 11 11
C.
( Ύ 2 3 r \ Mp .: 94-96 ⁰ C n _D ²⁰ : 1.5721 \ y n _D ²⁰ : 1.5693 / \ \ / M.p .: 31-33 ° C / \ ^/ i 0
π I!
C.

3OSß23 / 1197

CIBA-GEIGYAG

- ir © -

Active ingredient

Physical data

HC

0-CH ₀ -CH-C

CH ₂ -CH

CH.

0-CH ₂ -CH = C

0-CH ₂ -CH = C

M.p .: 41-43 C m.p .: 36-38 C m.p .: 60-62 C M.p .: 99-100 C m.p .: 85-87 ° C

309C :: G / 1197

CIBA-GEIGYAG

Active ingredient XXy 0
H I. 0
Il ^^ O-CH ₂ -CH = C Cl 0
H / ^CH 3
0-CH ₀ -CH-C
C. \ _Λ / X Physical
data Il Il Il
( Γ * ir
^υ C = CH X / M.p .: 54-56 C XX / 0
Il Il
C / χ Tl 1 he M.p .: 74-75 ° C ^^ C-CH-CH = CH NX / 0 cl
Μ Il / 7 \ M.p .: 53-57 ° C XX p M.p .: 80-81 ° C V \ \ x χ n _D ²⁰ : 1.5954

309823/1197

CLBA-GEIGY AG

Active ingredient

Physical data

CH "

0-CH ₂ -CH = C

C = CH

0-CH ₀ -CfH ₀ -CH 2 2 \

CH

/ ^0H 3

CH ₂ -CH n _D ²⁰ : 1.614

1.5762

ι 1.5738

20th

: 1.5571

H ₀ ²⁰ '. 1.5678

309829/1

CLBA-GEIGY AG

Active ingredient

0-CH ₂ -CH ₂ -CO-CH ₂ -CH
CH.,

0-CH ₂ -CH =

CH = C

CH

OH

CH ₂ -O-CH ₂ -CH ₂ -C-OCH

CIBA-GEIGY AG. - Example 5

Inhibitory effect on larvae Dysdercus fasciatus IO Dysdercus fasciatus larvae, which are 8-10 days before adult moult, were treated topically with acetone solutions. The larvae are then kept at 28 ^° C. and a relative humidity of 80-90%. The animals received meal from pre-swollen cotton seeds as putters. After about 10 days, that is, as soon as the control animals have completed their adult moult, the test animals were examined.

In addition to normal adults and moulting dead, special forms such as extra larvae (larvae with an additional Larval moult) and adultoids (adults with larval characteristics).

The special forms were non-viable stages of development, which frindo cannot be found in the normal development cycle

The compounds according to Examples 1 to 4 show good effect in the above test.

3 0 9 G 2 '■: ■: ι 1 9 7

CIBA-GEIGY AG Example 6

in the gas phase on eggs

of Spodoptera littoralis

40 mg Active ingredient (tel-quel), in another of 175 ml Contents of a clutch of 100 eggs of Spodoptera littoralis brought »The two flasks were with an intermediate piece connected and left at 25 C »

The evaluation of the inhibitory effect took place after 5 to 6 Days.

The compounds according to Examples 1 to 4 show good effect in the above test.

30 98 29/1197

Claims (3)

Claims Rp hydrogen, halogen, methyl or ethyl or R ₁ and Rp together the cyclopentyl or cyclohexyl ring, R ^ hydrogen, halogen, methyl, ethyl or C ₁ -C ₂ , - Alkoxy, R ₂ , hydrogen, halogen or methyl, Rp- hydrogen or halogen or Rj and R ₁ - together a carbon-carbon bond or an oxygen bridge, Rg hydrogen, methyl or ethyl, R _{7 is} hydrogen, halogen, C-, -C ₂ ^ -alkyl or C -C ^ -alkoxy, Y is oxygen or the group -CHpO-, where the CHp- Group is bonded to the phenyl nucleus and η and m are each the numbers 0 or 1. .309829 / 1 197 CIBA-GEiGYAG ^ 2. Compounds according to claim 1, wherein R is hydrogen, chlorine, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec "-, tert-butyl, vinyl or ethynyl, R _{p is} hydrogen, chlorine, methyl or ethyl or R-, and Rp together is the cyclopentyl or cyclohexyl ring, R is hydrogen, methyl, ethyl, methoxy or ethoxy, Rh is hydrogen, chlorine or methyl, Rp is hydrogen, or
R ^ and Rp- together form a carbon-carbon bond or an oxygen bridge,
R ^ hydrogen or methyl,
R ₇ . Hydrogen, chlorine, methyl or methoxy, Y oxygen or the group -CHpO-, where the CHg- Group is bonded to the phenyl nucleus and m and η each denote the numbers 0 or 1. 3 »Compounds according to claim 2, in which R- is hydrogen, chlorine, methyl, ethyl, n-propyl, iso- propyl, n-, i-, sec "-butyl or ethynyl, Rp hydrogen, chlorine, methyl or ethyl, R ^ hydrogen, methyl, methoxy or ethoxy, Rh hydrogen or chlorine, Rc- hydrogen or R-, and R ₁ - together a carbon-5 3 5 Carbon bond or an oxygen bridge, R ^ hydrogen or methyl, 3 0 "r ^; f λ ι 9 7 CIBA-GEIGYAG - tj $ - R ₇ hydrogen, Y oxygen and η and m each denote the numbers O or 1. 4. 4- (2,3 ~ dichloro-2-propenyl-l-oxy) -benzophenone in water Claim 3 * 5 «4- (3,3- ^ iehlor-2-propenyl-1-oxy) -benzophenone geraäss Claim 3 ° " 6o ■ 4- (2, 3-epoxy-3-methyl-4-pentynyl-l-oxy) -benzophenone according to claim 3 «7 · 4- (3-methyl-2-penten-4-ynyl-l-oxy) -benzophenone according to claim 3 8ο 4- (l, 5-E> imethyl ~ 4-heptenyl ~ l-oxy) -benzophenone according to claim 3 9. 4- (ljS-Dimethyl ^^ - epoxy-heptyl-l-oxy) -benzophenone according to claim 3 · 10o 4- (l, 5-dimethyl ~ 4-hexenyl-l-oxy) -benzophenone according to Claim 3 ° 11. 4- (3-Chloro-3-methyl-2-propene-1-oxy) -benzophenone according to claim 3 « 12. 4- (2,3-Epoxy-3-methyl-pentyl-1-oxy) -benzophenone according to claim 3 · 13 "4- (3-methyl-2-pentenyl ~ l-oxy) -benzophenone according to Claim 3 ° 14. CiSj trans-4- (3-chloro-2-propenyl-1-oxy) -benzophenone according to claim q η ο c -> c! .- 1 1 Q CIBA-GEIGYAG - 49 - 15 »4- (3i5-dimethyl-2-hexenyl-1-oxy) -benzophenone according to Claim 3 16. 4- (3-Methyl-3-methoxy-pentyl-1-oxy) -benzophenone according to claim 3 « 17. Process for the preparation of compounds of formula R, in - -h R 3 rows wherein R _{1 is} hydrogen, halogen, CjC ^ -alkyl, vinyl or ethynyl, Rp is hydrogen, halogen, methyl or ethyl or R ₁ and Rp together represent the cyclopentyl or cyclohexyl ring, R, hydrogen, halogen, methyl, ethyl or C ₁ -C ₂ alkoxy, Rj, hydrogen, halogen or methyl, Rp- hydrogen or halogen or R-, and Rp- together a carbon-carbon bond or an oxygen bridge, R ^ hydrogen, methyl or ethyl, R "hydrogen, halogen, CjC ^ -alkyl or C ₁ -Ch Y oxygen or the group -CHpO- where the CHp- 309829/1197 CIBA-GEIGYAG Group is bonded to the phenyl nucleus and η and in each denote the numbers O or 1, characterized in that that a compound of the formula '0 with a compound of the formula. 3 rows lets react in what R ^ to R ", Y, m and η have the meaning given above and X stands for fluorine, chlorine, bromine or iodine and M stands for a metal or hydrogen. l8. Process for the preparation of compounds of the formula 309829/1197 CIBA-GEIGYAG wherein R _{1 is} hydrogen, halogen, C ₁ -C _i . -Alkyl, vinyl or ethynyl, Rp hydrogen, halogen, methyl or ethyl or R-, and Rp together the cyclopentyl or cyclohexyl ring, J- CZ. Rj, hydrogen, halogen or methyl, R / - hydrogen, methyl or ethyl, "hydrogen, halogen, C, -C ₂ , -alkyl or C, -C ₁ , -alkoxy, Y oxygen or the group -CHpO-, where the Group is bonded to the phenyl nucleus and η and m each denote the numbers 0 or 1, characterized in that that you have a compound of formula 0 epoxidized, wherein R ,, Rp, R; ,, R ^ -, R ", Y, m and η die have the meaning given above. 19. Process for the preparation of compounds of 3 rows 3Λ Λ - ■■ 'ti · ■ "■" CIBA-GEIGYAG wherein PL hydrogen, halogen, C, -C ₁ -alkyl, vinyl or ethynyl, R is hydrogen, halogen, methyl or ethyl or R-, and Rp together the cyclopentyl or cyclohexyl ring, R, halogen, and R ₁ - hydrogen or R-, hydrogen and Ri- halogen, Hydrogen, halogen or methyl, Hydrogen, methyl or ethyl, "Hydrogen, halogen, C-j -Cj. -Alkyl or O, -Cj, -alkoxy, Y oxygen or the group -CHpO-, where the CHp group is bound to the phenyl nucleus and η and m are the numbers O or 1, characterized in that that a compound of the formula O • ^B c R, -m / N .2 a hydrogen halide of the formula HX is added, in which R ₁ , Rp, R ₂ ,, Rg, R ₇ , Y, m and η have the meanings given above and X stands for fluorine, chlorine, bromine or iodine " 3098 2 9/1197 CIBA-GEIGY AG 20. Process for the preparation of compounds of the formula R _{1 is} hydrogen, halogen, C ₁ -Cj -alkyl, vinyl or ethynyl, R _{p is} hydrogen, halogen, methyl or ethyl or R-. and Rp together is the cyclopentyl or cyclohexyl ring, Rl is hydrogen, halogen or methyl, Rg is hydrogen, methyl or ethyl, R is hydrogen, halogen, (^ - (X-alkyl or C ₁ -C ₁ J-alkoxy Y is oxygen or the group -CHpO-, the CHp group being bonded to the phenyl nucleus and η and m denote the numbers 0 or 1, characterized in that that you get the compound of the formula with a compound of the formula 309 6 2 9/1197 CiBA-GEIGYAG 5 »- lets react, where R. ,, R _p , Rj, R ^ ₃ R,. ,, Y, m and η have the meaning given above and X stands for fluorine, chlorine, bromine or iodine and M for a metal <. 21 · - Process for the preparation of compounds of the formula R, R. 3 rows R _{1 is} hydrogen, halogen, C ₁ -C ^ -alkyl, vinyl or ethynyl, Rp hydrogen, halogen, methyl or ethyl or R-, and Rp together the cyclopentyl or cyclohexyl ring, R ^ and Rj- each hydrogen,
R21 is hydrogen, halogen or methyl, Rg is hydrogen, methyl or ethyl, R "is hydrogen, halogen, O ^ C ^ -alkyl or C ₁ -C, -alkoxy, Y is oxygen or the group -CH ₀ O-, where the CH ₀ - 3Q9629 / 1 19th CIBA-GEIGYAG 5Γ- Group is bonded to the phenyl nucleus and η and m are the numbers O and 1, characterized., that a compound of the formula O R, hydrogenated, in which R ₁ , R _g , Ru, Rg, R, Y, m and η have the meanings given above. 22. Process for the preparation of compounds of the formula 7 \ y \ C n / \ R. ^ / R η R ₅ 3 R-, wherein R is hydrogen, halogen, C ₁ -C ^ -alkyl, vinyl or ethynyl, Rp hydrogen, halogen, methyl or ethyl or R-, and Rp together the cyclopentyl or cyclohexyl ring, Ru hydrogen, halogen or methyl, R ₁ - hydrogen,
5 . 3 0 9 i i C / 1 ΐ 9 7 CIBA-GEIGY AG Hydrogen, methyl or ethylj. R is hydrogen, halogen, C -C alkyl or C -C alkoxy. Y is oxygen or the group -CHpO-, the CHp group being bonded to the phenyl nucleus and η and m denote the numbers 0 or 1, characterized in that that you have a compound of formula 0 ¹ m / s R-, can react with a compound of the formula R '^ OH in the presence of a mercury-II salt and then reacts the intermediate product with complex borohydride in the presence of alkali hydroxide and water, wherein R-,, Rp, R ^., R ^, R " , Y, m and η have the meaning given above and R ¹ ^ is a C, -C ^ -alkyl group. 23. Process for the preparation of compounds of the formula 3 rows 309 t23 / 11 CIBA-GEIGY AG R-, hydrogen, halogen-C, -Cj-alkyl., Vinyl or Aethlnyl, R is hydrogen, halogen, methyl or ethyl or R ₁ and R together form the cyeloperityl or cyclohexyl ring, R-, C ₁ -C ₂ I. Ru hydrogen, halogen or methyl, Rp- hydrogen, R _{6 is} hydrogen, methyl or ethyl, R _{7 is} hydrogen, halogen, C ₁ -C ₁ , -alkyl or CjC ^ Y is oxygen or the group -CH 0-, where the group is bonded to the phenyl nucleus and η and m denote the numbers 0 or 1, characterized in that that you have a compound of formula 0 OH with a compound of the formula R ¹ ^ ₂ -X in the presence of a strong base, wherein R- ,, R _pi R ₂ ,, R / -, R ₇ , Y> m and η have the meaning given above, R 'a C ₁ -C ₂ , * AIky! Group and X stands for fluorine, chlorine, bromine or iodine. .309823 / 1 19.7 CLBA-GEIGY AG 24. Pesticides containing a compound of the formula as the active component 3 R ₁ Hydrogen, halogen, C ₁ -C ₂ J _- -alkyl, vinyl or ethynyl, Hydrogen, halogen, methyl or ethyl or and Rp together the cyclopentyl or cyclohexyl ring, hydrogen, halogen, methyl, ethyl or C ₁ -C ₂ alkoxy, n ■ hydrogen, halogen or methyl, p. Hydrogen or halogen or ^ and R ₁ - together a carbon-carbon bond or an oxygen bridge, g hydrogen, methyl or ethyl, hydrogen, halogen, C ₁ -G ₂ , -alkyl or C ₁ -C ^ Ϋ oxygen or the group -CHpO-, where the C örüppe is bonded to the phenyl nucleus and h and m are the numbers 0 or 1, and suitable question and / or wasted aggregates contain » 3Ö9 & 29/1197 CLBA-GEIGY AG 25. Agent according to claim 24, which is a compound according to any one of claims 2 to as the active component l6 included. - 26. Use of compounds of the formula wherein Around Hydrogen, halogen, C ^ -C ^ -alkyl, vinyl or Ethynyl, Hydrogen, halogen, methyl or ethyl or ₂ together the cyclopentyl or cyclohexyl ring, hydrogen, halogen, methyl, ethyl or C - ^ - Cj.- Alkoxy,
R ₁ , hydrogen, halogen or methyl, R, - hydrogen or halogen or D R ^ and R ₁ - together a carbon-carbon bond or an oxygen bridge,
Rg hydrogen, methyl or ethyl, R _{7 is} hydrogen, halogen, C ^ -C ^ -alkyl or C ^ -C ^ -alkoxy, Y is oxygen or the group -CH ₂ O- where the CH ₃ - group is bonded to the phenyl nucleus and 3 0 3 L I \ i I 1 1 a 7 CIBA-GEIGYAG _ £ Q η and m each mean the numbers O or 1, for combating of insects and representatives of the order Akarina. 309629/1197