DE2202942A1 - New condensation products - Google Patents

Description

CEIA-GESGY

CIBA-GEIGY AG, CH-4002 Basel Dt.itl'xy - ■ '., ■: ■■ ■■ .' ■■ ^: .; '.bvjer

Ui. F. Ζ-. ·. ■ - ■ · .: j ·: ι.

P β t β n I ι: υ ■■ / ί I It

8 monks 2, BrCluiiauiiirafla 4 / I1I

Case 5-7378 / 1 + 2 / -

New condensation products

The present invention relates to formamidines, their production and their use for pest control.

These formamidines, which can be present in the form of their free base or as salts of inorganic or organic acids / have the formula

R ₁ -N-CH-NR ₂ (I)

where R ^ is a substituted or unsubstituted phenyl radical, R _{2 is} hydrogen, alkyl, alkenyl or alkynyl and R, aralkyl

V ■. - ■ ■

interpret.

The alkyl, alkenyl or Alkynyl chains contain 1 to 18, respectively. 2 to l8, preferred option

■ but 1 to 4 resp. 2 to 4, carbon atoms. These leftovers can be branched or straight-chain, interrupted in the chain by heteroatoms such as e.g. 0, S, N, N-CH, unsubstituted

. or be substituted. Examples of such residues include Methyl, ethyl, methoxyethyl, methylthioethyl, propyl, isopropyl, n-, i-, sec ..-, tert-butyl, allyl, crotonyi, methallyl, chlorallyl, propargyl, tri fluorine thy 1, cyanomethyl, i-butynyl. The aralkyl radical for R, is composed of an aryl and alkylene group composed. Under an aryl radical are mononuclear and polynuclear, substituted or unsubstituted, to understand carbocyclic rings, especially the phenyl ring. The alkylene radicals have 1 to 4, preferably 1 to 2, substituted or unsubstituted chain links.

. The substituents on the alkyl, alkenyl ·? Alkynyl and phenyl radicals can be first or second order.

. Substituents of the first order include basicity-enhancing ones Understand electron donors. The following groups come into consideration, among others: Halogen atoms, such as Fluorine, chlorine * bromine or iodine; Alkoxy and alkylthio groups with 1 to 4 carbon atoms that are branched or unbranched can, and are preferably unbranched, and have 1 to 2 carbon atoms; lower alkoxyalkyl and alkyl groups,

209836/1219

where the definitions given above also apply here; prim., sec. and tert ·. Amino groups, with lower alkyl and " Alkenyl groups are preferred substituents; Hydroxyl and mercapto groups. The phenyl radical can also be replaced by alkyl, mono- and di-haloalkyl group may be substituted.

Second order substituents are to be understood as meaning acidifying electron acceptors. Among other things, the following groups are considered: nitro and cyano groups; tri- " Haloalkyl groups in which halogen is preferably P or Cl; lower alkylsulfinyl, lower alkylsulfonyl groups, which have a branched or unbranched alkyl radical with 1 to 4, preferably an unbranched alkyl radical with 1 or 2 carbon

S /

Fabrics; Sulfamyl and sulfamido groups, the Amino groups can carry one or two substituents, preferably lower alkyl groups, as defined above. - · ■.

Because of their effect, compounds of the formula 'are of particular importance.

s> ~ N = CH - N - R-. °

(II)

^R 5

209836/1219

wherein R ₄ to R _ß respectively. R ¹ . to R'g each hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, amino, C ₅ -C ₄ alkylamino, BiS-C ₃ -C ₄ alkylamino, nitro or cyano or R ' ₅ and R'g, respectively. R 'and R' together denote the groups -CH ₂ -O-CH ₂ - and R ₉ , R, _Q and R ₁₁ each denote hydrogen or C ₁ -C ₄ alkyl.

The one for R ₄ to

resp

R 'to R' standing

Alkyl, C _{1 -C 4} alkoxy, C 3 -C ₄ alkenyloxy or C ₃ -C ₄ alkynyloxy radicals can be branched or straight-chain, substituted or unsubstituted.

Preferred compounds of the formula II have the formulas

= CH - N - CH-

(in)

209836/1219

CH-N-CH, CH-CH ₃

R.

(IV)

N = CH -

(V)

where rJ to Rg have the meaning given for formula II

, R ,, and

per hydrogen,

Alkyl, F, Cl,

have and

Represent Br or J. ·. *

Examples of compounds' of formulas III to V are;

= CH-N -R

= CH - N - CH R

20983S / 1219

N = CH - H - ■ CH

where R

N = CH - N ■ - CH ₃

Cl

SS- N = CH-N-CH ₃

N = CH - N - CH-

__> - li = CH-fF-CH

-CH ₉ - <\ .

-CH, Cl

209836/1219

CH ₂

Cl

OCH

- CH ₂

Cl

- 'CH ₂

CH ₃

Cl

. CH, Cl

-CH ₂

ci

Cl

- CH,

Cl

Cl

CH-

209836/1219

- CH - <v

CH,

The compounds of the formula I can be prepared by methods known per se, for example as follows

+ O = CH-:

a) SO Cl

b) COCl ₂

c) POCl ₃ + d) PCI,

θ)

₃ g) Cl -

(D

CH,

2. R ₁ -N = C = O + O = CH-N (^ temperature

- CO

(D

3. R ^ CH-O-alkyl + ΗΝ ' ² temperature

R _x -alkyl-Oi { (D.

+ (Alkyl

^X _R. -Alkyl-

209836/1219 (D

_ Q -

Rp

5. R ₁ -N = CU-N ^ * + HaI-R \ (I)

In the above schemes, R, R and R have the meaning given for formula I and alkyl is C ₁ -C ₁ , alkyl, preferably methyl or ethyl.

The reactions 1-5 can conveniently be carried out in the following inert solvents: aromatic hydrocarbons, such as benzene, toluene, benzines, chlorobenzene, polychlorobenzenes, bromobenzene; chlorinated alkanes with 1 to 3 carbon atoms: Ethers such as dioxane, tetrahydrofuran; Esters, such as ethyl acetate; Ketones such as methyl ethyl ketone, diethyl ketone. Nitriles such as acetonitrile.

The starting materials, some of which are known compounds, can be described according to known compounds in the literature Establish methods.

The compounds of the formula I have a broad range

biocidal action and can be used to combat various types of plant and animal pests, for example as bactericides, viricides, growth regulators, abscess agents, molluscicides and anthelmintics.

In particular, the compounds of formula I have insecticidal and acaricidal properties and can be used against all stages of development such as eggs, larvae, pupae, nymphs and Adults used by insects and representatives of the Akarina order e.g. against insects of the families Teltigonidae, Oryllidae, Gryllotalpidae, Blattldae, Peduvildae, Phyrrohocoriae, Cimicidao, Delphacldae, Aphididae, Diaspidldae, Pseudococcldae,

209836/1219

- OK -

Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chryso-

melidae, Bruchidae, Tineidae, Noctindae, Lymatriidae, Pyralidae, Culcidae, Tipulidae, Stotnoxydae, - Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Ixodidae, Argasidae, Tetranychidae and Dermanyssidae. ■

The insecticidal or acaricidal effect can be achieved 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:

209836/1219

- ΑΛ "-

Bis-OjO-diethylphosphoric anhydride (TEPP) -

.OlEethy1 (2 _J 2,2-trichloro-l-hydroxyethyl) phosphonate (TR ICHLOSFON) l _t 2 D1broa-2,2-dichloräihyIdir ₁ ethyl phosphate (MLED) 2,2-Dichlorvinyldkethylphcsphat (DICHLCRPHOS).

2-kethoxycarba = yl-l -.? Ethylvinyldi = ethylphosphate (XEVIKPHOS) Dteethyl-1-ethyl-2- (nethykarba :: oyl) vinyl phosphate ice (KOKOCROTOPHOS) MDiBethwyphosphinyloxyJ-Vi-direthyl-cis-crotona-.id (0! CRCTOPHOS) Z-Chloro ^ -diäihylcarba ^ oyl-l-Eethylvir.yldiireihylphosphat (PHOSFHASIDOfJ) 0,6-0ilthy] -0 (or S) -2-iäthylthio) -äthylthicphosphat (DEKETCN) S-ethylthioethyl-O.O-dicethyl-dithiophosphate (THIOMETCN) O.O-OJäthyl-S-ethyb.ercaptocethyldiihiophosphat (FhORATE) 0,0-0iethyl-S-2-6thylthio) ethyl dithiophosphate (DISULFOTCfJ) 0.0-0iEethyl-S-2- (äthylsu] finyl) ethyl thiophosphate (OXYOESETCSSETHYL) 0,0-DSBethyl-S - (], 2-dicarbaihoxy'Sihy! Dithiophosphate (BALATHION) 0, O, O, O-tetraethyl-S, S'-ethylene bis-dithiophosphate (ETHICN) O-ethyl-S.S-dipropyldithiophosphate O.O-DlBethyl-S-iK-Eethyl-S-foraylcarbaaoylniethyD-dithiophosphat (F03EOTHIOH) OiO-Dinethyl-S-ifl-EethylcarbanoylEethyDdithiophosphat (0IKETHOAT)

CO-Oicethyl-O-p-nitrophenylthiophosphate (PARATHICN-ÜETHYL) '

0,0-ethyl-O-p-nitrophenylthiophosphate (PARATHICiI) O-ethyl-O-p-nltrophenylphenylthiophosphonate (EPN)

0,0-D1nethyl-0- (4-nitro-a-tolyl) thiophosphate (FEHITROTHION) '

O _f O-ClBethyl-0-2,4-5-trichlorophenylthiophosphate (ROÜiiEL) 0-Aethyl-p, 2, *, 5-trichloropheny] ethylthiophosphonate (TRICHLOROiJAT)

O.O-DiBethyl-O ^ .S-dichloro-i-broaphenylthicphosphate (BRCKOPHOS)

0.0-0Ji! EthyI-0- (2,5-dichIoM-iodophenyl) -thiophos? Hat (IODOFEHPHOS) 4-tert. Butyl-2-chlorpher.yl-fl-Bethyl-O-ethyianidophosphate (CRUFOiAT) Q, O-D1eethy! -O- (3-ü: ethyI-A-oethylcercaptophenyl) thiophosphate (FENTHION) Isopropylaaino-O-ethyl-O- ii-cethylaercapto-S-ethyl phenyl) phosphate 0, (MH2thyl-0-p -. (sethy! sul.finyl) phenyl thiophosphate (FEHSULFOTHICH) 0-p- (D «r.ethylsulfaaido) phenyl 0.0- dicethylthiophosphate (FAKPHUR) O ₁ O ₁ O ¹ , 0'-tetra &ethyl-OjO'-thiodi-p-phenylene thiophosphate O-ethyl-S-phenyl-ethyl-dihiophosphonate 0,0-dinethyl-0-4 ^ methylbenzyl-3-hydroxycrotony1) phosphate

2-chloro-1- (2,4-dichlorophenyl) vinyl diethy1phosphate (CHLOROFEIIVIfJPHOS).

2-chloro-1- (2, A, 5-trichlorophenyl) vinyl-dinethy! Phosphate

O ^ Whlor-l-U.S-dichlorophenylilvinyl-O.O-diethylthiophosphate ', ■ PhenylgJyoxylonitriloxiD-OO-diethyühiophosphat (PHOXlSl) ■. ^; "

OjO-OJathyl-O-iS-chloM-nethyl ^ -oxo ^ -H-l-benzopyran-T-yl) -thiophosphate (COUMAPHOS) 2,3-p-01oxanedithiol-5, S-bis (0,0-diethyldithiophosphate) (DIOXATHIOiJ). '"

5 - [(6-chloro-2-oxo-3-ben2oxazolinyl / diethyl] 0.0- <ethyldithiophosphate (PHOSALCN) 2- (Ethoxyphosphinyliaino) -l, 3-dithiolane:

0,0-OJBethyl-S- [2-cethoxy-1,3, A-thiadiazo1-5- (4H) -onyl- (4) -methyl] dH1ophosphate 0,0-OiBethyl-SrphthaUnidosethyl-dHhiophosphat (IKIOAH) - -

0,0-Oiithyi-0- (3,5,6-trichloro-2-pyridyl) thiophosphate 0,0-diethyl-0-2-pyrazinylthiophosphate (THIONAZINE) 0 _l 0-0läthyl-0- (2-isopropyl-Wethyl-6-pyrJBidyI) thiophosphate (DIAZINON) 0, O-0iithyI-0- (2-quinoxaIyl) thiophosphate O ^ lBethyl-S-ii-oxo-l ^ .a-benzotrUzin-SfiHj-ylcethyn-dithiophosphat (AZIf.'PHOSKETHYL) 0,0-D {ethyl-S- (A-oxo-1,2,3-benzotriazine-3 «H) -ylrethyl) -duhiophosphate (AZIFHOSAETHYL) S-ttA.ß-diaaino-s-triazin ^ -yHcethyll-O ^ -di.Tethyldithiophosphat (ffi.'AZON) 0,0-DUethyl-0- (3-ch! Or-A-nHrophenyI) thiopho5? H3t (CHLCRTH I CN)

O, 0-D »oethyl-O (or S) -2- (ethyithiolthy!) Thiophosphate (OEKETCS-S-JiETHYL)

2- (0,0-0icethyI-phccphoryJ-thior.ethyl) -5-ncthoxy-pyrcn-4-3 _> 4-dichlorohenzyl-triphynylphosphonium chloride 0,0-diethyI-S- (2,5-dichlorofhchylth'.o: ethyl ) dithiophosphate (PHENKAPTON)

209836/1219

O.O-DJälhyl-O-fi-tethyl-euaarfnyl-Tj-thiophosphate (POTASAN) 2202942

5-AiJno-bis (dicethyla3ido) phosphinyl-3-ph6nyl-1,2, <- trJazol (TRIASIPHOS) »tW *« ¹ »«

Hl! Ethy! -5- (0 _f 0-dkeihylihiolphosphoryl) -3-thtavaler3.iiid (VAYIOOTHfON) 0,0-0iethyl-0- [2-dir.ethyla =: ino-4 - ': ethylpyriaidyl- (6) ] -thiophosphate (DIOCTHYL) OO-DlMthyl-S-ynethylcarbanoylrethyD-thiophosphate (OVETKOAT) 0-Ethy! -0- (8-chlnolinyl) -phenylthiophosphonate (OXCiOTHICPHOS) O-Keihyl-S-thiophos ) O-tethyl-O-tZ.S-dichloro-i-brocphenyD-benzothiophosphonate (PHOSVEL)

209836/1219

β, Ρ, Ο, Ο-Teirapropyldiihiopyrophosphat 2202942

3- (0lEelhoxyphosphiny1oxy} -? T-.rethyJ-? I-c; eihoxy-cis-crotonaraid

O ^ Icethyl-S-ft-äthylcarbaMyliethyUdithicphosphat (ETHOAT-ÜETHYL)

©, O-OiSthyl-S-iS-isoprcpylearfaa-oylceihyD-dithiophosphat (FROTKOAT)

S-Ml-Cyar.o-l-iethyllthyDcarba ^ oylreihyldiäthylthiolphosphat (CYAf.'TKOÄT) S- (2-aceiaridoethy1) -O, C-dire + h / ldithiophosphate Hemethylphosphoric Acid Triasid (KEüPA) O.CWMrethyl-O-tt-chloro-A-nitrcphenyOthiophosphate (DICAPTHON)

0,0-OUethyi-O-p-cyancpher.yl thiophosphate (CYAWX)

O-ethyl-O-p -cyanophenyl thiophosphonate

0,0-OI2thyl-0-2 ^ -dichlorphenylihiophosphat (DICHLORFENTHICiJ) 0,2,4> dichlorophenyl-0-rethy] isopropyla :: idothiophosphate e, 0-diithyl-0-2,5-chloro-4-bro = phenyl thiophosphate (6R020PH0S-AETHYL)

Dio "thyl-p- (cethylthio) phenylphosphate"

• 0, f-Qisethyl-0-p ~ su: i33idoDher.y1thiophcisphat (4p- (p-chlorophenyl>; ophenyljC, C-dicethylihiophosphai (AZOTHOAT)

O-ethyl-S-V-chlorophenyl-ethyldithiophosphonate D-l $ obuiyl-Sp_ £ hi-phenyl-ethyldithiophosphonate

Ο, Ο-Dfqethyl-S-p-chlorpher.yHicphosphat

O ^ O-Oieethy l * -S- (p-ch1 orpheny I th i o = e thy I) -d Uh i ophospha t

0, (M) ethyl-p-chlorophenylationcapto = ethyl-dithicprcsph3t (CARBOPHEÜOTHION)

OjO-olethyl-S-p-chlorophenylihio-ethyl-thiophosphate

0, (M) Uethyl-S- (carbäthoxy-pr, enyhethyl) qithiophosphate (PHENTHOAT) 0, O-Di3thyl-S- (carbof1uorithoxy-phenylceihyl) -dithiophosphate

O ^ Oicethyl-S-icarbolsopropoxy-phenyleethy I) -d1 thiophosphate

OfO-OiSthyl-T-hydroxy-a ^ -tetra ^ ethylene-cc-jxarinyl-thiophosphate (COLfidiTHOAT) '2-iethoxy - <- H-J, 3,2.-ben2odJcx2? Hosphorin-2-tj! FU. "

0, O-0iithy! -0- (5-phenyl-3-isocxazolyl) thlophosphate ·. ·

2- (Oiithoxyptiosphinyliaino) - <- j.ethyl-1,3-dlthiolane ^:

Trfs-U-cethyM-aziridinyU-phosphirioxyd (LlETEPA)

$. (2-Ch! Or-l-phthaliEidoIthy)) - 0,0-diethyldithiophosphate l-hydroxynaphthalenido diethyl phosphate iittthyl-3,5,6-trichloro-2-pyridy] phosphate

0.0> Olcethy] -0- (3 _t 5 _t C-trichloro-2-pyr1dyl) thiophosphate ^:.

S-2- (Aethylsulfor, yl) ethyl direthylthiolphosphate (DIOXYDEKETOK-S-KETHYL) Olithyl-S-2- (äthy | sulflnyl) ethyl dithiophosphate (OXYDISULFOTO. ^{1. 1} ) '..'.

lU-O.O-diethylthlophofphorsJureanhydrid (SULFOTEP)

methyl-1,3-di (carboaethoxy) -l-propen-2-yl-phosphate V.

Methyl (2,2,2-trichloro-1-butyroyloxyethyl) phosphonate (BUTOÜAT) "."

0,0-0kethyl-0- (2,2-dichloro -] - ir.ethoxy-viny!) Phosphate. ■ '■'.

BU - (<Mcethylasido} fluorophosphate (DIKEFOX) S ^ tflchtorbcnzyl-irlphenylphosphoniu ^ chtorid ■, '■ Oleethyl-u-rethoxyrethylcirbaroyltethyl-dihiophosphate ^ (FORKOCARBAM) ■ ■ O _f O-DJSthyl-0- (2,2-dichloro-1-cii! Oratr.oxyvinyl) phosphate

0,0-0ieethyl-0- (2,2-dichloro-1-chloroethoxyvinyl) phosphate

O-ethyl-S.S-diphynyldithiolphasphate. ·

fr-ethyl-S-beni / l-phepyldithiophoiphonate

O.e-ethyl-S-tcnzyl-thiol phosphate O.O-Oiceifiyl-j-fA-chlorphcr.ylthiorethyDdilhiophosphat (KLTIffLCARGOPIIEIiOTIIICfl) O.O-Ethyl-C-Fäthylihic-EihyDdithiophosphat

Ollsopropyh-: nof! Uorpho; phat (! ÜIP / .FOX) 'O.e-Dieeti.yl-i-itorpriolinylearbaaoylrethylJdilhiüphosphat (MRPIiOTHICN)

Blsce Ihy U- i Ίο-phcny I phocpha t O.O-Olrelhyl-'i-ibcr. / Oliulfcr.yDdithiophoc.'ihat O, O-0icetKyl _: (j and O) -äUiylsulfinyläthylthioplio: phat

5flQfl ^ R / 1 O 1 O

Triethoxy-isopropoxy-bis (thto? Hosphiny]) disulfide. . . ■

2-Keihoxy-4H-] _f 3 _f 2-tenzcdioxaphosphorin-2-oxide

Octayethylpyropfcosphorasid (SCHSADAfi). BIs (disethczyihiophosphinylsulfidol-phenybeihan IJfy'J / K'-tetri-ethylduridofluorophosphate (DIKtFOX) "> O-phenyl-O-p-nitrophenyl-tethane thiophosphonate (CCLEP)

0-KethyI-0- (2-chloM-tert.tutyl-phenyO-N-rethylaaidothiophosphat (KARLEKE) 0-Ethy] -0- (2 _f 4-dichlorophenyl) -phenylthiephosphonate

O.O-Diethyl-C - ^ - ireihylcercapto-a ^ -direthylphenyD-thiophosphate

4.4 ^l -Bis- (0,0-direthylthlcpHo $ phoryloxy) -d1phenyldisulf1d

O.O-Oi-tp-chloroethyD-O-O-chloro-A-ceihyl-eusarinyl -7) phosphate S- (1-phihalinidoethyl) -0, C-diethy! Dithlophosphate

0,0-DiEethyl-0- (3-chloro-4-diethylsutfa »y! Phenyl) thiophosphate

O-KethylO-CZ-carbisopropoxyphenyD-asidothiophosphate MO.O-DiKeihylphoöphoryU-S-chlor-bkycloO ^ .O-heptadiend.S)

0-Kethyl-0 - (?> L-propoxycarbonyI -l-BethylvinyUSihylasidoihiophosphat

Htrophcnole I Ocrlvate Na salt [dinitrocresol]

trlethanolain salt)

2 cyclohexyl- <, 6-dinitrophenol [Dinex] 2- (l-KoihylhcptylM, 6 dinitrophenyl-crotonate [Oinocap] 2 scc-butyl-4,6-dinitrophynyl-3-ethylbutyl-butylate [binapacryl] 2 $ cc.-butyM, 6-dlnHrophcnyl-cycloproplonate 2 »cc-butyl- ^ o-dinltrophenyl-isopropyl-carbonate [Olnobuion]

Terschlcdene Pyrethrin I. . .'... '. . * Fyrethrln Il ' ■ [ _m - "

3-Λ1lyl-2-ethyl-i-oxo-Z-cyclopcnlcn-l-yl-chrysantheeüiai (A] lethrln) 6-chloripcronyl-chrysanthcauut (barthrin)

2,4-diiothylbenzyl-chrysanthciuMt (dinethrin) *.

2,3,4,5-ietrahydrophthalic bisoacthylchrysanthic butate.

4-chlorobenzyl-4-chlorophenyl sulfide [chlorine surfactant]. "

6> Hethy! -2-oxo-1,3-dithfolo- [4 _f 5-b] -quinox »Hn [QuinonetMonat]. \

(l) -3- (2-Furfuryl) -2-ethyl-4-oxocyclopcnt-2-cnyl (l) - (cis + trans) chrysanthium aonocarboxylate [Furothr 2-Pfvaloyl-1ndan-1,3-d1on [Pindon]

M'-i ^ -chlor ^ -oethylphcnyD-N.N-diaelhylfornaaidin (chlorophenaiidin) 4-chlorobenzyne-4-fluorophenyl sulfide (fluorobenzide) SjC-Olchlor-l-phcnoxycarbanyl ^ -trifluorKethyl-benzUlda / ol (Fenozaflor) p ^ -Chlorophenyl-p-chlorobenzenesulfonate (Ovex), ·

p-chlorophenyl benzenesulfonate (Fenson). ',. '· ·

p-Chlorophenyl-Z ^ jS-trtehlorphenylsulfon (Tciradlfon) "

P-ChIorphcny1-2,4,5-trichlorophony1 sulfide (Tctrasul) ■ ν ■

p-chlorobenzyl-p-chlorophenyl sulfide (chlorine surfactants) 2-ThJo-1,3-dithiolo - (, 5-6) quinoxaline (Thioquinox)

Prop-2-yny1 - (<- t-buty! Phenoxy) -cycIohcxylsulfit (Propargil)

- -15

l-ethyl-2- (2'-Bo (hyM'-broapiicnyn-formMiaidln

1-n-Bulyl-1-acthyl-2- (2'-Pctfiyl-V-chlorophynyl) -iornaialdin Mfethyi-i-tt'-ethyM'-chloranmno-incthylen) 2- (2 "-BethyM ^M -chlorphenyl) - foraanidin ln-butyl - ^ - iZ'-eethyM'-chlorophenyl-laincO-pyrroHdln

Urea *

K ^ -Mhyl-Uhlorphcnyl-I ^ N'-dUethyMhiourea:

Carbamates

l-thiaphyl-N-ethylcarbaate (CARBARYL) 2-bullnyl-i-chlorophynylcarbaate 4-DiMthy1aaino-3 _f 5-xytyl-li-ethylcarb3oate (-OlBethylaRinoO-toiyi-li-aelhyicarbaDat (ASiIKOCARB)

A-iethytthio-3,5-xy] yl-K-Delhylcarba _a 3t (IiE III I OCARB)

3, ^, 5-trilhylphenyl-H-ethylcarbaeate

Z-Chlorphenyi-K-aethyicarbaiat (CPXC) S-Chloro-B-oxo - ^ - norbornane-carbonitrile-O-methylcarbanioyU-oxia

! • (DUethyicarbaaoyD-S-flethyl-B-pyrazoiyl-N.N-dinethylcarbaQat (DlMETILAN)

Z.S-Oihydro-Z ^ -diaeihyl-T-ber.zofuranyl-N-ynethylcarbaxate (CARBGFURAN) Z-Methyl-Z-Bcthylthlo-proplonaldehyd-O-dsethylcarbanoyD-oxini (ALOICARB) B-Chinaldyi-N-aethyicarbacate and its salts Methyl 2-isopropyl - <- (scthylcarbaBoyloxy) carbanilate M-d'AethylpropyDphcnyl-MnKthylcarbaoate S.S-Oi-tert.butyl-n-ethyicarbaoate

- (1-ethylbutylphenyl-methyl-ethylcarbate 2-Isopropylphenyl-f! -R.ctliylcarbaaat 2-sec.Butylphynyl-K-methylcarbanate

a-loiyl-N-alkylcarbaate - ''

2,3-xylyl-K-ethytcarbaat '

S-Uopropylphynyl-N-acthylcarbaate

3-tert-butylphynyl-K-octhylcarbaate 3-cec.-Rutytophynyl-N-Ethylcarb.ivat

S-hopropyl-S-Bcthylphcnyl-H-aethylcarbaaat (PROMECARO)

3,5-0 U sopropy 1 phcny 1 -H-ce thy I carbaaa t 2-chloro-5-isopropylphynyl-fi-ethylcarbanate

2-chloro-4,5-dtBethylphenyl-H-acthylcarb3aat *

2- (l _t 3-0ioxolan-2-yl) phenyl-II-BcthylcarbaGat (DIOXACARB)

2-0,3-0l _u iolan-2-yl) phcnyl-N, N- <JiBcthylcarba _B at

, y | { _f {di _et iylcr 2- (l _t 3-0ilhlnlat> -2-yl) | im-v | -ri _l t: -d <zethylcarbanate 2-liopropoxyphenyi-tJ-ethylcarbaoate (ARPROCARB) 2- (2-propynyoxy) phenyI-N-ethy1carbavate 3- (2-propynyloxy) phcriyl-i .'-ccU.ylcarba «ai 2-DlBethylaolr.oplathylcarbavate % Dtally] artlnophcr> yl-fl-Kethylcarbarat ^ Olallylanlno-JS-xylyl-C-teihylcarbanat (ALLYXICARB) i-Benzothlenyl-fl-eethylcarbaiat _2f 3-DUiydro-2-ecthyl-7-bcn / ofur3hy1carbanat. 3- (ethyl-l-phcnylpyra2ot-5-yl- " _v n-dlr.cil! Y] cnrhncat l-isopropyl-S-methylpyrazol-S-yl-NH-dir. 6-ditcthylpyriBld! N-4-yl-fi _l N ^t -dlocthyl-cart) amat 3-fa thy I-4-di nc t hy 1 ae I nooc tliy 1 cn t ■ I ηωΙιβηϊΙ jli-xelhyj cj.-bj ω L

S-Oliüethylaraino-r.ethylenJnincpher.yl-fi-rethylcarbanat (FORKcTAiUUE) and its salts l-fethylthlo-sthyllnino-fi-aethyUarbanat (KEIHCJiYL)

2-ethylcarba-oyioxi .-! "Ino-l _f 3-dithioIan 2202942

5-! Iethyl-2-eihylcarb3coy] ox? Aino-1,3-oxy thiolane 2- (l-i'ethoxy-2-pro? Oxv) chenyl- ^l i-ie {ethyl carbarate. . .

l-0icethylcarba ^ yl-1-ethylthio-O- ^ ethylcarfcanyl-forooxime

1- (2'-CyancäthyHhio) -0-ethylcarbanyl-3cetaldoxio '■

l-Kethylthio-O-cartaryl-acetaldoxia

O- (3-sec-B'jtylphenyI) -! I-phenylthio-N -ethylcarbanate. ·.

2,5-Dkcihyl-1,3-aithicland-M0-: ethylcarbar, y1) -a1doxie).

O-2-D5phenyl-N-.Tethylcarba.Tat

2- (K-Kethylcarb3.Tyl-oxi! R, ino) -3-chlorobicyclo [2.2.l] heptane.

2- (K-! Iethylcarb3-yl-oxiniino) -bicyclo [2.2.l] heptane S-lxopropylphenyl-N-irethyl-ü-chloraceiyl-carba ^ at 3-! Sopropylphenyl-'i - e {hyl-ii- r; ethylthic-.ethyl-carbaEat 0- (2,2-0iir: ethyl-A-chler-2,3-dihydro-7-benzofuranyU-f; -i !! ethylcarbaEat _> 0- (2 _l 2,4- Tricethyl2,3-dihydro-7-beniofuranylM -niethylcarbanate

O-naphthyl-H- ^ ethyl-'i-acetyl-carbasate ■ .... ·

0-5 _J 6.7 _l 3-Tetrahydrer.aphthyl-N -.-. Ethyl-carbai; at. »

S-Isopropyl-'i-cethylthio-phenyl-N-Rethylcarbamate ' S ^ -Olcethyl - ^ - rethoxy-phenyl-il-r.ethylcarbanate

3-Hethoxycethoxy-pherjyl-f! _{-R i} ethylcarbaii! At ... .

S-ailyloxyphenyl-'l-irethylcarbasate. .

i-propargyloxy ethoxy-phenyl-fl-rethyl-carbaiaate.

2 ~ A1 lyloxyphenyl-fi-reihyl-carbanate

f-Kcthoxycarbonylaaino-S-tsopropylphenyl-N-cethyl-carbair.at SjS-Dlcethyl-i-ihoxycarbonylanino-phenyl-N -. 'Ethyl-carbaaat 2-γ-Μβ thy 1 th ΐ opropy I pheny 1 -fJ — τβ thy I -ca rbasa t

3- (a-KethoxyGethyl -? - propenyl) -pfcenyl-H-pethyi-carbanate · ·

2-Chl or-S-tert-bu ty 1-pheny 1-fl-se ihy 1-carbariate

4- (Kethyl-propargyla3ino) -3,5-xylyl-N-! Methyl-carbacate

A- (Hethyl-y-choral lyiar, lno) -3,5-xylyl-N-! Nethyl-carba »at MKethyl-p-chlorallylajinoJ ^ .S-xylyl-fJ-r.ethyl-carbanate 1- (ß-ethoxycarbonylethyl J-S-cethyl-S-pyrazolyl-fl.N-dioethyl-carbaate J-Kethyl-A-fd'Eethylafiino-Cethybercapto-NethylenenklnoJphenyl-K-isethylcarbainat !, S-B'sfcdrba ^ oylthiol ^ -dJjN-diceihylaainoJ-propane hydrochloride SjS.Dkethylhydroresorcinoldlcethylcarbaisate

2- ^ ethyl-propaPäyla ^ ino] -phenyl-! I-r; ethylcarba! R.3t ...

2- [Kethyl-prcpargyla3ino] -phenyl - '! - ciethylcarbar.at · · .. "'

2- [0Jpropargylaniinu] -phenyl -! «- nethy karbarst 4- [0ipropargylaffiino] -3-tolyl- * i-S: ethyl chloride

4- [0lpropargyla. «! Ino] 3,5-xylyl - (! - iethylcarbanate '·

2-f Alyl-isopropyl-aino] -phenyl-f! -! R> ethyl carbate S-iAllyl-Isopropylaninoj-phenyl-fl-methylcarbainate

Chlorinated hydrocarbons

t-Hexachlcrcydchexan (.GiSxXANE; LIÜDÄÜ; γ HCH] -

1,2,4,5,6,7, e.B-Cctachlor- ^ s ^ JJo'tetrahydro-AJ-rethyleneindan [CHLORDAN] 1,4,5,6,7,3,8-Hepiachloro, 3a, iJJo-tetr-hydro - ^^ - nethylenindan [HCPTACKLOR] ! • 2,3, *, 10, in-hexach1cr-J, 4,4a, 5,8, Sa-hcxahydro- € ndo-l _t 4-exo-5,8-dl! RethanonaphthaUn [ALDRIN]

! [DIELC

209836/1219

. The compounds of the formula I also show · ·: herbicidal properties and are particularly suitable for combating grass-like and broad-leaved weeds in various crops. When used in high concentrations, the new compounds act as total herbicides, while in lower concentrations they act as selective herbicides. Of the compounds of formula "I will be difficult to control and deep-rooted, annual or perennial weeds successfully damaged or destroyed in growth. The application of the new drugs can with the same good success before emergence (preemergence) and after emergence (postemergence Field weeds such as millet species (Panicum spp.), mustard species (Sinapis ερρ.), goose foot species (Chenopodicea), black foxtail (Alcpercurus spp.) and other foxtail species, e.g. Amarantus spp., grasses, e.g. Lolium spp., Aster family, e.g. Taraxacum spp., Chamomile species (Matricaria spp.), Are destroyed or their growth is hindered without causing damage to crops such as cereals, maize, rice, cotton, soybeans or sugar beets. The application rates vary and depend on the time of application and are between 0.1 to 10 and more kg of active ingredient per hectare reprimand take place.

209836/1219

To widen the spectrum of action, other herbicides can be added to the active ingredients of the formula I, for example from the series of triazines, such as halo-diamino-striazines, Alkoxy- and alkylthio-diamino-s-triazines, triazoles, diazines, such as uracils, aliphatic carboxylic acids and halocarboxylic acids, halogenated benzoic acids and phenylacetic acids, aryl- I qxyalkanecarboxylic acids, hydrazides, amides, nitriles, esters of such Carboxylic acids, carbamic and thiocarbamic esters, ureas, etc.

Representatives of such additive herbicidal active ingredients are, for example, the following compounds:

209836/1219

2-chloro-t, 6-bis- (Sthyi3nino) -s-triaztn,

Z-Chlor-A-äthylaaino-S-Jscprcry'aiino-E-triazine,

2-chloro-t, 6-bis- (rethoxypröpyla-ino) -s-triazine, 2-? Ethoxy - *, 6-bis- {isc? Ro? Yla ^ irio) -s-triazine, 2-0läthylaiinc-4-iso? Ropylaceta3ido-o-rethoxy-s-triazine, 2-isopropyla ».lno-4-5ethoxy prcDylasino-6-rethylthio-s-triazine, 2 - »! Ethylthio-4,6-bis (isopropyia-ino) -s-triazine, i-Kethylthio-AjC-bis-iäthyle-iinoJ-s-triazine, 2-üethyHhio-4-ä * hyla ^ ino-6-isciroDylanino-s-triazine, 2-Keihoxy-i-ethyla ~ ino-6-iso3ropyla ~ ino-s-triazine 2-kethoxy-4,6-bis- {äth / laiir.o) -s-triazine, 2-Ch1oM, 6-b! S - (! Socro2ylariino) -s-tri3zin,

Oinltro-sec-fcutyl-pher.pl urd its salts Pentachlorophenol and its salts, trichloroacetic acid and its salts, 2,2-dichloropropionates and their salts, 2-chloro-fl, IJ-diallylacetic acid aaid, Maielns Surehydrazide,

2,3, Ε-ΤΓίοΗ1θΓΟεηζοβ5ΐ ^ Γβ and their salts 2,3,5,5-Tetrachloride benzoic acid and its seeds, Z-Methexy-SjS.Ö-trichlorbenzcesSure and its salts, 2-kethoxy-3,6-dichlorobenzoic acid and its salts, 3-Aa! No-2,5-dichlorobenzoic acid and its salts, 3-nitro-2,5-dichlorobenzoic acid: jre and its salts, 2-Kethyl-3,6-dichlorobenzoic acid and its salts,

t, 6-dichloro-thiobes: aQid, 2,3,6-irichlorophenoxyacetic acid and its salts, 2,4-dichlorophenoxyacetic acid and its salts, 2 | 1,5-trilophenoxyacetic acid, its salts and esters, (2- Ssethyl-A-chlorophenoxy) -acetic acid, its salts and esters, 2- {2,4,5-trichlorophenox ^ -propionic acid _f its salts and esters, 2- (2 _l 4,5-trichlorophenoxy) -3thyl- 2,2-dichlorpropiofi3t, 4- (2,4-D5chlorphenoxy) -b ⁱ jttersäi «re, their salts and esters, 4- (2-EethyM-ch! orphenoxy} -butyric acid, its salts and esters, 2,3, 5-trichlorobenzyloxyprcp2nol,

ü'-Cyclooctyl-R.n-dicethylurea, S-phenyl-l.i-direthylurea, S-ti'-chlorophenyU-J.l-diirethylurea, i

^ (S'.i'-OichlcrphenyD-l.l-dinethyl-urea, S-O'.V-Oichlorpher.yD-l-n-Sutyl-l-rethyl-urea,

S-U'.V-Oichlorpher.yD-l.l-diethyl urea, 3- (4'-chlorophenyl) -l-; ethoxy-I-ethyl urea,

yy, 3f- (V-bror; phenyl) -l-i: et'noxy-l-r.e: nyl-hanrs {off, S-Ü'.V-Oichlorpher.yUO-rethoxy-'J-direthyl-hai-nstoff,

N.S-O '.- in-propyD -'- äthyl-thiocarta-insäarccs'.Kr, K, K-Oi-in-propy I i -'-'.- proF '/ l-thiocarbanic acid ester, H-Aethyl-fi-tn-tutyD-S-n-propyl-thiocartanintiurecstEr,

209836/1219

The favorable toxicity to warm-blooded animals should also be emphasized of the compounds of formula 1 or agents containing them.

The active ingredients of the formula I are also fungicidal Properties against phytopathogenic fungi on various crops such as cereals, maize, rice, vegetables, ornamental plants, Fruit trees, vines, field crops, etc ..

The new active ingredients can be used on fruits, flowers, Foliage, stalks, tubers and roots occurring fungi can be contained or destroyed, with later overgrowing Plant parts are spared from such infections. the Active ingredients of the formula I are particularly effective against the phytopathogenic fungi belonging to the following classes, orders or species effective:

Oomycctes, such as Plasmodiophora species, Aphanomyces species,

Pythium species, Phytopthora species (Phytophthora Infestans, Phytophthora cactorum), Plasmopara species (Plasmopara viticola), Bremia species (Bremia lactucae Peronospora species (Peronospora tabacina), Pseudoperonospora species (Pseudoperonospora humuli).

Zyftomycetes, such as Rhizopus species.

Ascomycetes, such as Eurotiales, for example Aspergillus species, Penicilliuni species (Penicillium digitatum, Penicillium italicuni), Taphrinales, e.g. Taphrina species (Taphrina dcformans Erysiphales, e.g. Erysiphe species (Erysiphe cichorace arum, Erysiphe graminis),

209836/1219

Sphaerotheca species (Sphacrotheca pannocaj, unclnula-

Species (Uncinula necator),

· 'Helotiales, such as Monilinia species (Monilinia [Sclerotinia] • fructicola, Monilinia laxa), Dlplocarpon species (Diplocarpon rosae), Pseudopeziza species,

Sphaeriales, such as Nectria species (Nectria galligena), Ceratocystis species,

• '·. Pseudosphaeriales, such as Venturia species (Venturia inaequalis), Mycosphaerella species, Ophiobolus species

'(Ophiobolus graminus), Cochliobolus species [Helminthos- * porium] miyabeanus), Cercospora species (Cercospora beticola, Cercospora musae).

Basidiomycetos .. such as Aphyllophorales, e.g. Pellicularia species (Pellicularia filamentora = [Rhizoctonia sonlani]),

Uredinales, e.g. Puccinia species (Puccinia triticina), . · · ·

Uromyces species (Uromyces phaseoli), Hemileia species; ';.' (Henr.ileia vastatrix), Cronartium species (Cronartium ribicola), Phragmidium species (Phraßmidium subcorticium),

ta

Oymno s porangium species.
Dentcromycctes = (Fungi imperfecti)

e.g. Piricularia species (Piricularia Species. Thielaviopsis species, Clasteri tis species (Botrytis cinerea), Cladosporium species, Alternaria species (Alternaria solani), Verticillium Ar » ·. . ten (Vcrtlcilliurn albo ~ atrum), Phialophora species,

Molanconiales, e.g. Colletotrichum species,

. 209836/1219

u-

■ - - ■ "

Fusarium species (Fusarium oxysporum, Fusarium nivalc),

Glocosporium species (Cloeosporium fructigenum) , <■ · ■

Sphaeropsidales, e.g. Septoria species (Sepfcoria apicola).

Diplodia species (Diplodia natalensis), Mycelia sterilia, e.g. Sclerotium species (Sclerotium.

rolfsii).

Furthermore, the new active ingredients can be used to treat seeds, fruits, tubers, etc. to protect against fungal infections for example through all kinds of smut fungi, such as. Ustllaginales, e.g. Ustilago species (üstilage avenae), . Tilletia species (Tilletia üritici), Urocystis and Tuburcinia species.

Phoma species (Phoma bctae) ". ·

can be used. ·

The active ingredients of the formula I can be used for broadening of the spectrum of activity in addition to acaricides and

Insecticides for example - also bactericides, Fungistatikay bacteriostatics, Nematocides and / or e.g. the following fungicides are added:. .

209836/1219

Dodecylgjanidin Acetate (DCOIKE) PentacMcrniirclenrol (CJlMCiZESE) Pentachlorophenol (PC?)

2_ (| _ »'eihyl-n-pröpyl) i, C-dir.Jtroph £ r, y1-2-rct: -ylcfctor ₁ a {(GIWPACRYL) Zd-i'eir.yl-n-hepiyD-iE- dinitrcphcnylcrotc-iat (DINC ¹ CA?) 2, C-DichloM-hitro = r-, ilin (DICKLCRA ?;) ZSSe-Telrachlor-benzc-chincn (1, A) (C: -: ¹ .CWSIL) 2,3 -Dichlor-aaphthcchiKc.i (1,0 (GIC ^ C'.E) MTrlchlorrethylthio) pr.ir.al inld (rCLFEI) K- (Tr? Chlcrrelhyllhio) cyc! Cr.cx-i-er.-l ,? -dic; r: r; xir.id (CAPliü) H- (l, l,?,? - ielrachlorä ⁱ J.yHhio) cyclcr.cx-icr ₁ -! _J 2-dicar! .Ixi-.id (CAPTAFOL) K-Üethylsul f cnal-K-iricii! & rreih / l iiii oc.M crar: ί 1 in K'-OichloriluorEeUiylihio-l .'- dir.iihyl-N'-phcriylsuliaiid (I) ICuLCSfLUAKIO) O-Aeihy1-S-benzyI-phcny1di thicphosphate! -S-ben? Yl-thio] phosphate OJnatriun-ethylene-lP-bis-dithiccartarai (!, 'E ^) Zlnk-ä "t! Iyler> -l, 2-bis-dithiocarbarate (ZlfiEB) rangan (M) - Jlhylen-l,? - bis-ditlnccarba-.at (ΪΑΚΕΒ) letracelhyHhiurardisuliid (TnIRAS!)

1-0xy-3-8ceiyl-6-fcihyl-cyclohexen- (5) dior .- (2, O (DEHYCROACETIC ACID) 8-hydroxyquinoline (E-Cülfiui! '. CL)

2-0irelf: ylaniino-6-csThy 1-5-n-tuiy l-i-hydro / y-pyrinidine Kethyl-K-benziaidazol-Z-yl-il-ftütylcarLs-c / Dcarba-at (Efi.QVYL)

2- (M5: iazolyl) -benzir-it'32ol

3 _t 5-0ireliiyMelrahydro-l, 3,5-ihi3diazir -? - {hion (CAZCiIT)?, 3-dihydro-5-carboxar, i1 idc-Cr.e thy I -Ι, ί-oxaihin Pcntachlorbenzy! Alcohol

209836/1219

A-

. . In addition, connections have '<% <j _ft * j _O #ij

of formula (i) nematocidal properties

and can, for example, be used to combat the following plant parasites Nematodes are used: Meloidogyne spp., Heterodera spp., Ditylenchus spp., Pratylenchus spp., Paratylenchus spp., Anguina spp., Helicotylenchus spp., Tylenchorhynchus spp., Rotylenchulus spp., Tylenchulus semipenetrans, Rado-

• *

pholus similus, Belonolaismus spp., Trichodorus spp., Longi-

dorus spp .; Aphelenchoides spp., Xyiphinema spp ..: The compounds of the formula I can ode by themselves

• ■ * *

. Eingeset together with suitable carriers and / or additives are :: "Suitable carriers and additives can be solid or flux leg and correspond to the usual in formulation technology Sto.Cf: for example natural or regenerated substances, solvents, dispersants, yaw, network -, adhesives, thickeners, binders and / or fertilizers.

•, · The connections of the

Formula (i) for dusts, emulsion concentrates,.

• · ■

Granules, dispersions, sprays, solutions or

Slurries in the usual formulation contained in the

; Application technology is part of general knowledge, processed

• · ■. ■■ · ■ ♦

.will. Furthermore, "cattle dips", ie cattle baths, and apply "spray races", ie Sprühgänge in which aqueous preparations verwen- det to mention.

The production of present invention are obtained in a known per se V / else by intimately mixing and / or grinding of active substances of the formula I etoffen with suitable carriers, optionally with the addition of inert towards the Wirkstoffer Dispergicr- or solvents. The active ingredients can be present and used in the following working-up forms:

20983B / 1219

.solid forms of processing: dust, grit,

Granulates, coated granulates,

■ '. · Impregnation granules and

Homogeneous granules

"liquid processing forms:

a) dispersible in water

Active ingredient concentrates: wettable powders, ■ * 'pastes, emulsions;

b) Solutions

For the production of solid processing forms (dust center Litter) the active ingredients are mixed with solid carriers. Carrier materials include, for example, kaolin, talc, Bolus, loess, chalk, limestone, lime grit, ataclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and Potassium aluminum silicates (feldspar and mica), calcium and Magnesium sulfate, 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 extractions, activated charcoal, etc., each individually or as mixtures with one another.

Granules can be produced very easily by adding an active ingredient of the formula T in an organic solvent dissolves and the solution thus obtained on a granulated mineral, e.g. attapulgite, SiO, gran / calcium, bentonite etc. brings and then evaporates the organic solvent again.

It can also be used to produce synthetic granules

been that the V / irkstoffc of the formula I with polymerizable

209836/1310

Compounds are mixed (urea / formaldehyde; dicyandia-formaldehyde; Melamine / formaldehyde or other), before a gentle polymerization is carried out, from which the active substance. remain untouched, and while still continuing. · the gel formation the granulation is made. It is cheaper to have finished, porous pole; • meric granules (urea / formaldehyde, polyacrylonitrile, polycste:

and others) with a specific surface area and a favorable, predeterminable adsorption / desorption ratio with the active ingredients E.g. in the form of their solutions (in a low-boiling solvent) to impregnate and remove the solvent. Of the-

. like polymer granules can be used in the form of micro-granules Bulk weight of preferably 300 g / liter to 600 g / liter as well m3fc can be applied with the aid of atomizers. Can atomize Be carried out over large areas of crops with the help of airplanes

Granules can also be obtained by contacting the carrier material.

. rials with the active ingredients and additives and then crushing available · * •. These mixtures can also stabilize the active substance Additives and / or non-ionic, anion-active and cation-active substances are added which, for example, improve the adhesive strength improve the active ingredients on plants and parts of plants (adhesives and adhesives) and / or improve wettability (wetting agents) and ensure dispersibility (dispersants).

For example, the following substances are possible: olein / lime mixture, cellulose derivatives (.'- '. Ethylcolluloce, carboxymethyl cellulose), Hydroxyäthylcnclykoläthor of Mono- and Dialkylphcnolo with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms

209836/1219.

- 27

in the alkyl radical, lignin sulfonic acids, their alkali and alkaline earth salts, Polyethylene glycol ether (Carbov / achs), fatty alcohol polyglycol ether rr .: 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms ir. ■ fatty alcohol part, condensation products of ethylene oxide, propylene · oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea / formaldehyde and latex products.

Active ingredient concentrates that are dispersible in water, ie wettable powders , pastes and emulsion concentrates "represent agents that can be diluted with water to any desired concentration. They consist of active ingredient, carrier, and optionally the active ingredient stabilizing additives, CFC-Ξ 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. Examples of carriers are used those mentioned above for the fixed work-up forums in question. In -naidien. In cases it is advantageous to mix different dener carriers to use. As dispersants, for example wise 'are used: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, Condensing products. of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde as well as alkali, ammonium and alkaline earth salts of lignin sulfonic acid, further alkylarylsulfonates, alkali and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, fatty al alcohol sulfato, such as salts of sulfated hexadccanols, heptadecanols,

209836/1219

- ■

Octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oils ylmethyltauride, ditertiary ethylene glycols Dialkyldilaurylammonium chloride ^ and fatty acid alkali and alkaline earth salts. " ·.

Silicone oils, for example, can be used as antifoam agents. ·. '■' ..

The active ingredients are grounded with the additives listed above: mixed, ground, sieved and passed in such a way that the solid fraction of the fuel powders does not have a grain size of 0.02 to 0.04 and the pastes of 0.03 ^mm exceeds. For the production of emulsion concentrates and pastes, dispersants such as those listed in the previous sections, organic solvents and solvents are used. The solvents used are, for example, alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and mineral oil fractions boiling in the range from 120 to 350 ° C. The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.

The agents according to the invention can also be used in the form of Solutions are applied. For this purpose, the active ingredient or will: several active ingredients of the general formula I in suitable organic Solvents, solvent mixtures or water soluble As organic solvents, aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alky! Naphthalenes, Mineral oils are used alone or as a mixture with one another:

The content of active ingredient in the middle described above: lies between 0.1 and 955 «, it should be mentioned that the Application from the aircraft or by means of other suitable Λρρΐ:

cation device concentrations up to 99.5 / ί or even more pure

209836/1219

Active ingredient can be used. OOnOQ / 0

t) he active ingredients of the formula T can, for example, like
be formulated as follows:.

Dusting agent: For the production of a) 5 # .gen and b) 25oigen Släutemittels the following substances are used:

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

b) '2 parts of active ingredient,

1 part of highly dispersed silica,

'-97 parts of talc.

The active ingredients are mixed with the carrier substances
and marry.

Granulate: To produce a 5 # granulate, the following Substances used:

^ 5 parts of active ingredient

0.25 part of epichlorohydrin,.
'·· ■ .Ό> 25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol · ■ · '".
9 ^ parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and
Cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone is evaporated in vacuo. Spray powder: The following ingredients are used to produce a) JlOJ & Lgen, b) and c) 25% d) 10 # spray powder:

209836/1219

So

a). 40 parts of active ingredient

- 5 parts of lignin sulfonic acid sodium salt,

1 part dibutylnaphthalenesulfonic acid sodium salt, 54 parts of silica;

b) 25 parts of active ingredient

4.5 parts of C.alcium lignin sulfonate, 1.9 parts of champagne chalk / hydroxyethyl cellulose

Mixture (l: l),

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 of champagne chalk / hydroxyethyl cellulose

Mixture (1: 1), - ·

8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, ': -. · ■. · ■ · ·'

46 'parts of kaolin; - -... '". ^. *

d) 10 parts of active ingredient

3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates, ....

5 parts of naphthalenesulfonic acid ^ ormaldehyde condensate, Share kaolin.

The active ingredients are in gceicneten mixers with the The aggregates are intimately mixed and ground on the appropriate mills and rollers. You get wettable powder, which can be mixed with water

209836/1219

■■ · ■■■■■ - 22029A2

Allow suspensions to be diluted to any desired concentration. Emulsifiable concentrates: For the production of a) lO ^ igen and b) 25 # emulsifiable concentrate, the following substances are used:

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 alkylarylsulfonate 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 poly-

glycol ether mixture,
5 parts of dimethylformamide, 57.5 parts of xylene.

These concentrates can be diluted with V / assc Emulsions of any desired concentration can be prepared. Spray: To produce a 5 # spray ....... ν ·· '■:

by means of the following ingredients are used: 5 parts of active ingredient,
1 part epichlorohydrin,
94 parts petrol (boiling limits l60 ^o -l90 ° C);

209836/1219

example 1

a) 1200 g of 2-amino-5-chloro-toluene are mixed with 2000 ml of triethyl orthoformate boiled on reflux.

The alcohol which forms is distilled off via a column. Towards the end the reaction begins by a few drops of conc. Sulfuric acid accelerates.

4-chloro-2-methyl-phenyl-imino-ethyl formate is obtained by vacuum distillation with a boiling point of 123'-127 ° C at 10 mmHg.

b) 1.97 kg of ethyl 4-chloro-2-methyl-phenyl-imino-formate wer-the with 1.4 kg of N-methylbenzylamine and 2 l of toluene for 10 hours boiled on reflux. After the solvent has evaporated, the residue is distilled in vacuo. N-4-chloro-2-methyl-phenyl-N-methyl-N-benzyl-formamidine is obtained with a boiling point of 16 ° C at 0.05 mmHg

The following connections are also established in the same way:

= CH

Bp 165 ° C / 0.3

209836/1219

Cl- <f? -N = CH-N

CH

OCIL

N = CH-N

/ ° 3 ^H 7 (n)

CH. 1.5986

1.5943

C _o H 2

_o H _r 2

N = CH-N

CH,

1.6041

CH,

N - CH - N

N) H ₂ - m.p .: -103-104

CH.

a H ₀ / \ 4 9 (n)

N = CH - N 1.5786

CIL

N = CH-N

C "H _r / 25

L> fl "V ——>

1.6068

> —N =

^N =

N = CH-N

CIL 1.5696

209836/1219

• H

V — M -

■ Ν = CH - N

\ / Xl _o ~ V_y

CH.

N = CH-N

M.p. 99-100

M.p. 107 -

• Ν = CH - N

V> tl ~~ N. y

119-120

V-N = CH-N

Cl

^CH 3 JL

V-N = CH-N

M.p. 125-126

M.p. 72-73

N = CH -N

CH,

M.p. 85-87

N = CH-N

Njh, m.p. 131-132

Bi ~ <f Vn = ch - n

CH,

3 cl

209836/1219 m.p. 128-129

N = CH-N

H.

NiH,

Cl

■ Ν =

M.p. 90-99

M.p. 88-89

■ Ν = CH - N

CH.

1.5954

/ ° ^Η 3

■ Ν = CH - N

Cl

N) H ..

Cl

CH_ / 3

■ Ν = CH -N

^^ - Cl-H ₂ SO ₄ m.p. 22Q-222 ⁽

Cl

/ ^CH 3

= CH-N

CH,

ν rip> = r> Cl n ₂₅ 1.6178

/ 3

= CH - N

IH

207-208

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/> - N = ^CH ""

CH, / 3

CE,

/ 3

-N = CH -

IL,

1.6218

CH ^

Cl-s ^ /> - N = CH -

CH.

Vn = cn - ν

CH,

/ J

IL

n _oc 1.6100

Ci-C Vn = cn - ν

CH, / 3

CIL,

CIL / -

^N C1L

1.5903

CII

= OH -

Fp: 82-

Br- < Vn = CH-N

/ n ₂₅ 1.6173

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CH - N

CH

<f

CH, / 3

= CH - N

CPL

CIL

ci- <f Vn = ch - ν

CH

OCH _V

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■ Ν = CH - N

CPL,

^CII 2

1.6152

N = - CH - N

cn

CIL 1.5914

CH _V 3

N = CH-N

CH.

1.5976

^αι ί

-N - CII - N

CH _V

(UT

Xm _ν

1.5776

σΗ ₃ - ^ ζ_ Vn = CH - ν

-CH.

N = CH-N

CH.

CH, ^ Vn = ch - ν

CH - <VN = CH - Ν— GE ^ - € ^

CH.

= CH - N

uri "\ ->

CH.

• Ν = CH - N

/ ^CH 3

CH.

η.

1.5898

^Χ 3 χ

CH "- ^ r> -Ν = CH - Ν — CH,

CH.

CH.

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κ

• Ν = CH-N

Nm,

. κ -GH NlH,

N = CH-N

= CH - N

VyXl ₀ X /

CH

= CH - N

Cl

Cl-C> -N = CH-N

CH,

Xrtip K S.

Cl

Cl- <f __> - Ν = CH - N CH,

Cl

V-N = CH-N

Cl

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■ Ν = CH-N

CH,

= CH - N

\ JH

= CH - N

= CH - N

CH,

= CH-N

Ζ— κ-ci

Cl m.p. 94 -

= CH-N

Njh, IW 1.6102

J Nc =

V-N = CH-N

CH ₂ -CH ₂ -OH n ₂₅ 1.5946

209836/1219

A) Insecticides Frasssri ft-VMrkuna;

Tobacco and potato plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10 yo emulsifiable concentrate).

After the coating had dried on, the tobacco plants were populated with owl caterpillars (Spodoptera litoralis) and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata). The experiment was carried out at 24 C and 60 \ ' relative humidity.

In the above test, the compounds according to Example 1 showed a food poison action against Spodoptera litoralis and Leptinotarsa decemlineata. .

B) Systemic insecticidal effect

To determine the systemic action rooted bean plants (Vicia faba) in a 0.01 #ige aqueous solution of active substance (obtained from a 10 $ aqueous emulsifiable concentrate cash) is set. After 24 hours, the

. plant parts of aphids (Aphis fabae) set above ground.

were by a special facility / the animals before the contact

and gas circulation protected. The experiment was carried out at 24 ° C and 70% relative humidity.

·· · The compounds according to Example 1 acted systemically against Aphis fabae in the above test.

209636/1219

Example ? 2202942 Effect of free ChiIo suooressalis

In each case 6 rice plants of the Caloro variety were transplanted into plastic pots which had an upper diameter of 17 cm and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis larvae (L, J> -k mm long) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg active ingredient per hectare) in the paddy water. The evaluation for insecticidal action was carried out 10 days after the addition of the granules. .

The compounds according to Example 1 were effective against Chilo suppressalis in the above test.

209836 / 121.9

Ii

Sterilized compost was mixed homogeneously with a wettable powder containing 25 pounds of active ingredient, so that an application rate of 8 kg of active substance per hectare resulted.

The treated soil became young zucchetti plants (Cucumis pepo) potted in plastic pots (three plants per pot with a diameter of 7 cm). Everyone Pot was immediately afterwards with 5 Aulacophora femoralis larvae, respectively. Pachmoda or Chortophila larvae infected.

The control became 4, 8, 16 and 32 days after the onset of the Larvae carried.

At 80-100 % kill after the first control, a new infestation was carried out with 5 larvae each in the same soil pattern with 3 new courgette plants. If the effect was less than $ 80>, the remaining animals remained in the test earth to the next control. If a substance still caused a kill of $ 100 at an amount of 8 kg / ha, then a check was carried out with k resp. 2 kg of active substance / ha.

The compounds according to Example 1 showed in the above Test effect against Aulacophora fermoralis, Pachmoda and Chortophila larvae. -

209836/1219

Wlrkune; against ticks

A) Rhiplcephalus bursa

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

The evaluation takes place ^ in the case of the adults after 2 weeks

if and in the larvae after 2 days. For every attempt were made

. . Performed 2 repetitions. ...

.. The compounds of Example 1 acted in the above test against adults and larvae of Rhipicephalus bursa.

B) Boophilus T.icroolus (larvae)

With an analogous dilution series as in test A, tests were carried out with 20 0P-sensitive larvae each. * · I

The compounds according to Example 1 acted ¹ Im

above test against sensitive larvae of Boophilus microplus.

209836/1219

Example 6 ·.

Acaricidal effect

Phaseolus vulgaris (French beans) were coated with an infected piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The mobile stages that had overflowed were dusted with the emulsified test preparations from a chromate graphic atomizer so that the spray mixture did not run off. After two to 7 days, larvae, adults and eggs were evaluated for living and dead individuals under the dissecting microscope, and the result was expressed as a percentage. During the “holding time”, the treated plants stood in greenhouse cabins at 25.degree.

In the above test, the compounds according to Example 1 were effective against eggs, larvae and adults of Tetranychus urticae.

209836/1219

. ■ ·
Fungicidal effect; . .

a) Action against Plricularia oryzae Bri. et Cav. Protective effect: ■

Rice plants were grown in the greenhouse and sprayed once with an aqueous spray mixture containing 0.05% active ingredient. Two days later, the plants treated in this way were infected with conidia of Piricularia oryzae Bri. et Cav. infected and checked for fungal attack after an incubation period of 5 days in a • humid chamber.

Curative effect; ·. ■ '".'."

■ · Rice plants were grown in the greenhouse that were grown with

Conidia of Piricularia orycae Bri. et Cav. were infected. Two days after infection, the plants were sprayed with an aqueous spray mixture containing 0.05% active substance. ... ·

After an incubation period of 5 days in a humid chamber

was checked for fungal attack. . · '.. ■ =' ····

b) Effect of gecen Phytoohthora infestans on Solanum Lycopersicum

S. Lycopersicum plants of the same cultivar and in the same stage of development were treated with a broth containing 0.05% active ingredient (made from the active ingredient which had been worked up into a wettable powder). After the spray coating had dried on, the dry plants were sprayed to runoff with a zoospore suspension of Ph. Infestans. They then stayed for 6 days in the greenhouse at 18-20 ⁰ C and high air

feuohtiekeit (95 - loo $) 209836/1219

and after this time showed typical leaf spots. Due to their large number and the evaluation of the tested substance was carried out.

• The compounds according to Example 1 showed a good fungicidal action in the above tests a) and b).

209836/1219

HS

Example 8 Effect against soil rgmatodes

To test the effect against soil nematodes * mrde the active ingredient at a concentration of 50 ppm in root knot nematodes (Meloidogyne Avenaria) given infected soil and mixed thoroughly. In the earth so prepared were in In one test series tomato seedlings were planted immediately afterwards and in another test series tomato seeds were planted after 8 days sown.

To assess the nematocidal effect, the galls present on the roots were counted 28 days after planting or after sowing. The compounds according to Example 1 showed nematocidal activity in the above test.

209836/1219

Claims (1)

Claims 1. Formamidines / which in the form of their free base or as Salts of inorganic or organic acids are present, of the formula R ₁ - N = CH - N - R ₀ 1λ wherein R. is a substituted or unsubstituted phenyl radical, R _{2 is} hydrogen, alkyl, alkenyl or alkynyl and R-aralkyl be .
2. Compounds according to claim 1 of the formula wherein R. to R _0, respectively. R 'to R' _Q each hydrogen, fluorine, 4 ο 4 b Chlorine, bromine, iodine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, amino, C ₁ -C ₄ alkylamino, BiS-C ₁ -C ₄ alkylamino, nitro or cyano or R ' ₅ and R' respectively. R 'and R ¹ - together denote the groups -CH ₂ -O-CH ₂ - and R _g , R ₁₀ and R ₁₁ each denote hydrogen or C ₁ -C ₄ alkyl . 3. Compounds according to claim 1 of the formula 209836/1219 wherein R ¹ - to R ' _ß each hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, -SO ₃ NH ₂ , -SO ₃ N (C ₁ -C ₄ alkyl) ₂ , -SO ₃ (C _1- C ₄ alkyl), -NO ₃ or -CN and R ₁₂ , R ₁₃ and R _{14 are} each hydrogen C ₁ -C _{4 represent} alkyl, F, Cl, Br or I. 4. Compounds according to claim 2 of the formula f. Vn = CH -N- CH 14th wherein R ' ₄ to R' _{8 are} each hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, -SO ₃ NH ₂ , -SO ₂ N (C ₁ -C ₄ alkyl) ₂ , .- SO ₂ (C ₁ -C ₄ alkyl) -NO ₃ or -CN and R ₁₂ , R ₁₃ and R ₁₄ each hydrogen, C ₁ - Represent C ₄ alkyl, F, Cl, Br or J. 209836/1219 5. Compounds according to claim 2 of the formula ^R l N = OH - H - OH, ^H 8 *1 ^R 4 ^H 5 wherein R ¹ . to R ' _ß each hydrogen, fluorine, chlorine, bromine, iodine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, ,, -SO ₃ N ( C ₁ -C ₄ alkyl) ₂ , -SO ₂ (C ₁ -C ₄ alkyl), -NO ₃ or -CN and R. ,, R.- and R
or represent J. per hydrogen, Alkyl, F, Cl, Br 6. A compound according to claim 3 of the formula / ^CH 3 N = CH - 7. A compound according to claim 3 of the formula Vn = CH 8. Process for the preparation of formamidines, which in the form their free base or as a salt of inorganic or organic acids, of the formula R ₁ N = CH - N - R ₂ ' wherein R 'is a substituted or unsubstituted phenyl radical, R _{2 is} hydrogen, alkyl, alkenyl or alkynyl and R is aralkyl 209836/1219 mean characterized by having a connection the formula R ₁ -N = CH - 0 - alkyl, in which R. has the meaning given above, and alkyl is C ₁ -C ₄ alkyl, preferably methyl or ethyl, with a compound of the formula HN in which R- and R- have the meaning given above, brings about the reaction. 9.. Pesticides which act as the active component a compound , which is in the form of its free base or as a salt of inorganic or organic acids, of the formula R.-N = CH-N-R- ^R 3 wherein R, a substituted or unsubstituted phenyl radical, R ₂ signify hate, alkyl, alkenyl or alkynyl and R-aralkyl and contain suitable carriers and / or other additives. 10. Use of the compounds which are present in the form of their free base or as a salt of inorganic or organic acids, the formula R ₁ -H-CH-NR, ^R 3 wherein R, a substituted or unsubstituted phenyl radical R _{2 is} hydrogen, alkyl, alkenyl or alkynyl and R-aralkyl, for combating various types of plant and animal pests. 209836/1219 11. Use according to claim 10 for combating Insects and representatives of the order Akarina. 12. Use according to claim 11 for combating phytopathogenic fungi. 13. Use according to claim 11 for combating plant-parasitic nematodes. 209836/1219