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Home , Aldicarb, Aminocarb, Fenitrothion, Mevinphos, Mipafox, Pest control

United States Patent (19) 11 3,941,829 Pissiotas et al. (45) Mar. 2, 1976

54 N-PHENYL-N'-CARBOPHENOXY FORMAMIDINES 57 ABSTRACT (75) Inventors: Georg Pissiotas, Lorrach, Germany; Phenylformamidines of the formula Dieter Dürr, Bottmingen, Switzerland 4 R3 (73) Assignee: Ciba-Geigy Corporation, Ardsley, R N.Y. R5 NiccH-N / (22 Filed: Dec. 1, 1972 N (21) Appl. No.: 311,058 COOR2 R6 R7 30 Foreign Application Priority Data Dec. 7, 1971 Switzerland...... 17790/7 wherein R represents , alkyl, alkenyl or al Dec. 7, 1971 Switzerland...... 1779/7 kynyl, R represents a-naphthyl, Jan. 26, 1972 Switzerland...... 1224/72 Oct. 27, 1972 Switzerland...... 5729/72 52) U.S. Cl...... 260f471 C; 260/240 G; 260/465 D; 260/470; 260/472; 424/277; 424/278; 424/285; 424/300 (51) int. Cl...... C07C 125/06 (58) Field of Search..... 260/471 C, 472, 470, 240 G 56 References Cited or substituted phenyl, FOREIGN PATENTS OR APPLICATIONS wherein the phenyl group is not substituted simulta 890,922 lf 972 Canada neously in the 2-position by a methyl group and in the 2,202,034 | 972 Germany 4-position by a chlorine atom, R. R. R. R. and R. 2,123,001 81972 France represent one or more radicals which are the same or 778,383 7/1972 Belgium different, such as hydrogen or halogen atoms or alkyl, alkoxy, alkylthio, alkenyloxy, alkynyloxy, alkoxycar Primary Examiner-Anton H. Sutto bonyl, CFs, cyano or nitro groups, their process for Assistant Examiner-Michael Shippen the manufacture and their use in control. Attorney, Agent, or Firm-Harry Falber; Frederick H. Rabin; Philip P. Berestecki 6. Claims, No Drawings 3,941,829 1 : 2 N-PHENYL-N'-CARBOPHENOXY FORMAMIDINES Preferred compounds on account of their action are those of the formula I, wherein R represents methyl, The present invention relates to phenylformami R represents o-naphthyl, 5 dines, a process for their manufacture and their use in . The phenyformamidines have the formula

10

COOR2 2-methylphenyl, 3-methylphenyl, 2-chlorophenyl, 2 - 15 isopropylphenyl, 3-isopropylphenyl, 3-methyl-5-iso propylphenyl, 2-chloro-5-tert.butylphenyl, 3,4-dime wherein R, represents hydrogen, alkyl, alkenyl or alky thylphenyl,methyltiophenyl, 3,4,5-trimethylpheryl, 3i Elenji, 3,5-dimethyl-4- 2-isopropox nyl, R, represents o-naphthyl, yphenyl, 2-allyloxyphenyl, 3-methyl-4-dime - 20 thylaminophenyl, 3,5-dimethyl-4-dimethylaminophe nyl, 3,5-dimethyl-4-diallylaminophenyl, i. 1,3-dioxolan 2-yl-phenyl, 1,3-diothiolan-2-yl-phenyl, (4,5-dimethyl 3-dioxolan-2-yl)-phenyl, 3-(1-methylbutyl)-phenyl, 2-sec.butylphenyl, 3-(1-ethylpropyl)-phenyl, 2,3-xylyl, 25 3-tert, butylphenyl, 3-sec.butylphenyl, 3,5-diisopropyl phenyl, 2-chloro-5-isopropylphenyl, 3,5-dimethyl-4- methoxyphenyl, 3-allyloxyphenyl, 2-propargyloxyme or substituted phenyl, thoxyphenyl, 2-Y-methylthiopropylphenyl, 3-(a- wherein the phenyl group is not substituted simulta methoxymethyl)-2-propenylphenyl, 4-(methyl-propar neously in the 2-position by a methyl group and in the 30 gylamino)-3,5-xylyl, 4-(methyl-Y-chloroallylamino)- 4-position by a chlorine atom, R., R., Rs, R and R. 3,5-xylyl, 2-(ethyl-propargylamino)phenyl, 2-chloro represent one or more radicals which are the same or 4,5-dimethylphenyl, 2-(2-propynyloxy)-phenyl, 3-(2- different, such as hydrogen or halogen atoms or alkyl, propynyloxy)-phenyl, 2-dimethylaminophenyl, 2-dial alkoxy, alkylthio, alkenyloxy, alkynyloxy, alkoxycar lylaminophenyl; ' ' 3-methyl-4-dimethylaminome bonyl, CF, cyano or nitro groups. 35 thyleneiminophenyl, 3-dimethylaminome The alkyl, alkyloxy, alkylthio, alkenyl, alkenyloxy, thyleneiminophenyl, 3-isopropyl-4-methylthiophenyl, alkynyl or alkynyloxy groups represented by R and Ra, 5,6,7,8-tetrahydronaphthyl, 2-(methyl-propar R. R., R and R contain l to 18, preferably l to 4, gylamino)-phenyl, 2-(dipropargylamino)-phenyl, 4 atoms in the chain; the alkenyl and alkynyl (dipropargylarnino)-3-tolyl, 4-(dipropargylamino)-3,5- chains contain 3 to 18, preferably 3 to 5, carbon atoms. 40 xylyl, 2-(allyl-isopropylamino)-phenyl, 3-(allyl-iso These groups may be straight-chain or branched, sub propylamino)-phenyl, 3-methoxymethoxy-phenyl, 2 stituted or unsubstituted. Possible substituents are cyclopentylphenyl, 2-(1-butyn-3-yl-oxy)phenyl or 2 halogen atoms. By halogen is meant fluorine, chlorine, (1-methoxy-2-propoxy)-phenyl, Rs, R, Rs, R and R. bromine and/or iodine. Examples of such groups in represent radicals which are the same or different, such clude: methyl, methoxy, methylthio, ethyl, ethoxy, tri .45 as hydrogen, fluorine, chlorine and/or bromine atoms, fluoromethyl, chloroethyl, propyl, isopropyl, n-, i-, sec. or methyl, methoxy, methylthio, trifluoromethyl, and tert. butyl, allyl, methallyl, propargyl, n-butynyl, ethoxycarbonyl, ethylpropyl, isopropyl, n-butyl, al isobutynyl. - lyloxy, propargyloxy, NC or O,N groups, and n is 1 to Possible substituents at the phenyl group represented 3. by R, are chiefly one or more similar or different halo 50 gen atoms, such as fluorine, chlorine, bromine and/or Examples of suitable compounds of the formula I iodine and/or alkyl with 1 to 5 carbon atoms, haloalkyl include: with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon CH. atoms, alkoxyalkyl with 1 to 4 carbon atoms in each of 3 R the moieties, alkylthio with 1 to 4 carbon atoms, al 55 C NCH-N". kynyloxy with 3 to 4 carbon atoms, dialkylamino with 1 N to 4 carbon atoms, dialkenylamino, dialkynylamino, COOR N-alkyl-N-alknylamino, N-alkyl-N-alkenylamino, HO, NC and/or ON groups, as well as cyclopentyl, mo CH noalkylaminomethyleneimino, dialkylaminome 60 3 R thyleneimino, cyclopenityl B cCH-N N COOR O. O. , S S and O O CH 65 3 Rh CHCH CH, N=CH-N 33 N groups. COOR

3,941,829 S 6 in the presence of an acid binding agent. In the formu Cl CH 3 R lae II and III, R to R, have the same meanings as given N=CH-N for the formula I. N Examples of suitable acid binding agents are: for mamidines of the formula II; tertiary , such as COOR , dimethylaniline, pyridine, inorganic wherein R represents alkyl with 1 to 12 carbon atoms, bases, such as hydroxides and carbonates of alkali and allyl or propargyl, and R represents a-naphthyl, alkaline earth metals, preferably sodium and potassium carbonate. 10 The reaction is carried out preferably in or diluents which are inert towards the reactants. Exam ples of suitable solvents or diluents are: aromatic hy O drocarbons, such as , , benzines, halo 15 genated hydrocarbone, , polychloroben zenes, bromobenzene, chlorinated alkanes with 1 to 3 carbon atoms; ethers, such as dioxan, tetrahydrofuran; CH CH esters, such as ethyl acetate, ketones, such as methyl ethyl ketone, diethyl ketone, nitriles etc. 2-methylphenyl, 3-methylphenyl, 2-chlorophenyl, 2 20 Some of the starting materials of the formula II and isopropylphenyl, 3-isopropylphenyl, 3-methyl-5-iso III are known compounds which can be manufactured propylphenyl, 2-chloro-5-tert.butylphenyl, 3,4-dime by methods which are known perse. The compounds of thylphenyl, 3,4,5-trimethylphenyl, 3,5-dimethyl-4- the formula I display a broad biocidal activity and can methylthiophenyl, 3,5-di-tert, butylphenyl, 2-iso propoxyphenyl, 2-allyloxyphenyl, 3-methyl-4-dime be used for combating diverse and animal pests. thylaminophenyl, 3,5-dimethyl-4-dimethylaminophe 25 In particular, however, they possess insecticidal and nyl, 3,5-dimethyl-4-diallylaminophenyl, 1,3-dioxolan acaricidal properties and may be used against all devel 2-yl-phenyl, 1,3-dithiolan-2-yl-phenyl, (4,5-dimethyl opment states, e.g. eggs, larvae, pupae, nymphs and 1,3-dioxolan-2-yl)-phenyl, 3-(1-methylbutyl)-phenyl, adults, of and representatives of the order Aca 2-sec.butylphenyl, 3-(1-ethylpropyl)-phenyl, 2,3-xylyl, rina, for example against insects of the families: 3-tert.butylphenyl, 3-sec.butylphenyl, 3,5-diisopropyl 30 Tettigoniida Tenebrionidae phenyl, 2-chloro-5-isopropylphenyl, 3,5-dimethyl-4- Gryllidae Chrysomelidae methoxyphenyl, 3-allyloxyphenyl, 2-propargyloxyme Gryllor alpidae Bruchidae Blariidae Tineidae thoxyphenyl, 2-Y-methylthiopropylphenyl, 3-(a- Reduviidae Noctuidae methoxymethyl)-2-propenylphenyl, 4-(methyl-propar 35 Phyrrhocoridae Lymatriidae gylamino)-3,5-xylyl, 4-(methyl-Y-chloroallylamino)- Cinicidae Pyralidae Delphacidae Cuicidae 3,5-xylyl, 2-(ethyl-propargylamino)phenyl, 2-chloro Aphidiidae Tipulidae 4,5-dimethylphenyl, 2-(2-propynyloxy)-phenyl, 3-(2- Diaspididae Stonoxydae propynyloxy)-phenyl, 2-dimethylaminophenyl, 2-dial Pseudococcidae Tryperidae lylaminophenyl, 3-methyl-4-dimethylaminome Scarabacidae Muscidae thyleneiminophenyl, 3-dimethylaminome 40 Dernestidae Caliphoridae and thyleneiminophenyl, 3-isopropyl-4-methylthiophenyl, Pulicidae 5,6,7,8-tetrahydronaphthyl, 2-(methyl-propar gylamino)-phenyl, 2-(dipropargylamino)-phenyl, 4 Acarida of the families: (dipropargylamino)-3-tolyl, 4-(dipropargylamino)-3,5- 45 Ixodidae xylyl, 2-(allyl-isopropylamino)-phenyl, 3-(allyl-iso Argasidae propylamino)-phenyl, 3-methoxymethoxy-phenyl, 2 Tetranychidae and cyclopentylphenyl, 2-(1-butyn-3-yl-oxy)phenyl or 2 Dermanyssidae. (l-methoxy-2-propoxy)-phenyl. The insecticidal and/or acaricidal action can be sub The compounds of the formula I can be manufac 50 stantially broadened and adapted to suit the particular tured by methods which are known per se, e.g. by re circumstances by the addition of other acting formamidines of the formula and/or , among such other insecticides and acaricides are included the following. 55 Organic phosphorus compounds Bis-O-O-diethylphosphoricDimethyl-(2,2,2-trichloro-1-hydroxyethyl)-phos acid anhydride (TEPP) 60 1,2-dibromo-2,2-dichloroethyldimethylphosphatephonate TRICHLORFON) R. R7 () 2,2-dichlorovinyldimethylphosphate (DICHLOR with a chloroformic ester of the formula 2-methoxycarbamyl-1-methylvinyldimethylphosVOS) 65 phate () Cl-C-OR (III) Dimethyl-1-methyl-2-(methylcarbamoyl)-vinylphos O phate cis () 3,941,829 7 8 3-(dimethoxyphosphinyloxy)-N,N-dimethyl-cis 5-(6-chloro-2-oxo-3-benzoxazolinyl)methyl)0,0- crotonamide () diethyldithiophosphate () 2-chloro-2-diethylcarbamoyl-1-methylvinyldimethyl 2-(diethoxyphosphinylimino)-1,3-dithiolane phosphate () 0,0-dimethyl-S-2-methoxy-1,3,4-thiadiazol-5-(4H)- 0,0-diethyl-0(or S)-2-(ethylthio)-ethylthiophosphate onyl-(4)methyldithiophosphate () 0,0-dimethyl-S-phthalimidomethyl-dithiophosphate S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THI (IMIDAN) - OMETON) 0.0-diethyl-O-(3,5,6-trichloro-2-pyridyl)thiophos 0,0-diethyl-S-ethylmercaptomethyldithiophosphate phate () O 0,0-diethyl-0-2-pyrazinylthiophosphate (THIONA 0,0-diethyl-S-2-(ethylthio)ethyidithiophosphate (DI ZIN) SULFOTON) 0,0-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)thi 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate ophosphate () (OXYDEMETON METHYL) 0,0-diethyl-O-(2-quinoxalyl)thiosphosphate 0,0-dimethyl-S-(1,2-dicarbethoxyethyldithiophos 5 0,0-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3-(4H)- phate () ylmethyl)dithiophosphate (AZINPHOSMETHYL) 0,0,0,0-tetraethyl-S,S'-methylene-bis-dithiophos 0,0-diethyl-S-(4-oxo-1,2,3-benzotriazin-3-(4H)- phate () ylmethyl)dithiophosphate (AZINPHOSETHYL) 0-ethyl-S,S-dipropyldithiophosphate 20 S-(4,6-diamino-s-triazin-2-yl)methyl)-0,0-dimethyl 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylme dithiophosphate (MENAZON) thyl)-dithiophosphate () 0,0-dimethyl-O-(3-chloro-4-nitrophenyl)thiophos 0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithio phate (CHLORTHION) phosphate () 0,0-dimethyl-O(or S)-2-(ethylthioethyl)thiophos 0,0-dimethyl-0-p-nitrophenylthiophosphate (PA 25 phate (DEMETON-S-METHYL) RATHION-METHYL) 2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxy 0,0-diethyl-0-p-nitrophenylthiophosphate (PARA pyrone-4-3,4-dichlorobenzyl-triphenylphosphoni THION) umchloride O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN) 0,0-diethyl-S-(2,5-dichlorophenylthiomethyl)dithio 0,0-dimethyl-O-(4-nitro-m-tolyl) 30 phosphate (PHENKAPTON) () 0,0-diethyl-O-(4-methyl-cumarinyl-7-)-thiophos 0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate phate (POTASAN) (RONNEL) 5-amino-bis(dimethylamido)phosphinyl-3-phenyl 0-ethyl-0,2,4,5-trichlorophenylethylthiophosphate 1,2,4-triazole (TRAMIPHOS) () 35 N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiav 0,0-dimethyl-O-2,5-dichloro-4-bromophenylthio aleramide (WAMIDOTHION) phosphate (BROMOPHOS) 0,0-diethyl-O-(2-dimethylamino-4-methylpyrimidyl 0,0-dimethyl-O-(2,5-dichloro-4-iodophenyl)-thio (6))-thiophosphate (DIOCTHYL) phosphate (JODOFENPHOS) 0,0-dimethyl-S-(methylcarbamoylmethyl)-thiophos 4-tert.butyl-2-chlorophenyl-N-methyl-0- 40 phate () methylamidophosphate (CRUFOMATE) 0-ethyl-O-(8-quinolinyl)-phenylthiophosphonate 0,0-dimethyl-O-(3-methyl-4-methylmercapto (OXINOTHIOPHOS) phenyl)thiophosphate () 0-methyl-S-methyl-amidothiophosphate (MONI Isopropylamino-O-ethyl-O-(4-methylmercapto-3- TOR) methylphenyl)phosphate 45 0-methyl-O-(2,5-dichloro-4-bromophenyl)-benzothi 0,0-diethyl ophosphate (PHOSVEL) -0-p-(methylsulphinyl)phenyl-thiophosphate 0,0,0,0-tetrapropyldithiophosphate (FENSULFOTHION) 3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy 0-p-(dimethylsulphamido)phenyl-0,0-dimethylthio cis-crotonamide phosphate (FAMPHUR) 50 0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithio 0,0,0,0'-tetramethyl-0,0'-thiodi-p-phenylenethio phosphate (ETHOATE-METHYL) phosphate 0,0-diethyl-S-(N-isopropylcarbamoylmethyl)-dithio 0-ethyl-S-phenyl-ethylthiophosphate phosphate () 0,0-dimethyl-O-(-methylbenzyl-3-hydroxycrotonyl)- S-N-(1-cyano-1-methylethyl)carbamoylmethyldie phosphate 55 thylthiolphosphate (CYANTHOATE) 2-chloro-1-(2,4-dichlorophenyl) vinyl-diethylphos S-(2-acetamidoethyl)-0,0-dimethyldithiophosphate phate ) 1-chloro-1-(2,4,5- Hexamethylphosphoric acid triamide (HEMPA) trichlorophenyl) vinyl-dimethylphosphate 0,0-dimethyl-O-(2-chloro-4-nitrophenyl)thiophos 0-(2-chloro-1-(2,5-dichlorophenyl) vinyl-0,0-die phate (DICAPTHON) thylthiophosphate 60 0,0-dimethyl-0-p-cyanophenylthiophosphate (CYA Phenylglyoxylonitriloxime-0,0-diethylthiophosphate NOX) () 0-ethyl-0-p-cyanophenylthiophosphonate 0,0-diethyl-O-(3-chloro-4-methyl-2-oxo-2-H-1-ben 0,0-diethyl-0-2,4-dichlorophenylthiophosphate (DI zopyran-7-yl)thiophosphate () CHLORFENTHION) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophos 65 0,2,4-dichlorophenyl-O-methylisopropylamidothio phate) () phosphate 3,941,829 10 9 bismethylamido-phenylphosphate 0,0-diethyl-O-2,5-dichloro-4-bromophenylthiophos 0,0-dimethyl-S-(benzenesulphonyl)dithiophosphate dimethyl-p-(methylthio)phenylphosphatephate (BROMOPHOS-ETHYL) 0,0-dimethyl-(S and 0)-ethylsulphinylethylthiophos phate 0,0-dimethyl-0-p-sulphamidophenylthiophosphate 0,0-diethyl-0-4-nitrophenylphosphate 0-p-(p-chlorophenyl)azophenyl)0,0-dimethylthio triethoxy-isopropoxy-bis(thiophosphinyl)disulphide 0-ethyl-S-4-chlorophenyl-ethyldithiophosphatephosphate (AZOTHOATE) 2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide 0-isobutyl-S-p-chlorophenyl-ethyldithiophosphate octamethylpyrophosphoramide () 0,0-dimethyl-S-p-chlorophenylthiophosphate O bis-(dimethoxythiophosphinylsulphido)-phenylme 0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithio thane phosphate N,N,N',N'-tetramethyldiamidofluorophosphate 0,0-diethyl-p-chlorophenylmercaptomethyl-dithio () phosphate () 0-phenyl-0-p-nitrophenyl-methanethiophosphonate 0,0-diethyl-S-p-chlorophenylthiomethyl-thiophos- 15 (COLEP) phate 0-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N- 0,0-dimethyl-S-(carbethoxy-phenylmethyl)dithio methylamidothiophosphate (NARLENE) phosphate () - O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphon 0,0-diethyl-S-(carbofluorethoxy-phenylmethyl)- ate dithiophosphate 20 0,0-diethyl-O-(4-methylmercapto-3,5-dimethyl 0,0-dimethyl-S-carboisopropoxy-phenylmethyl)- phenyl)-thiophosphate dithiophosphate 4,4'-bis-(G,0-dimethylthiophosphoryloxy)-diphenyl 0,0-diethyl-7-hydroxy-3,4-tetramethylene-coumari disulphide nyl-thiophosphate (COUMITHOATE) 0,0-di-((3-chloroethyl)-0-(3-chloro-4-methyl 2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sul- 25 coumarinyl-7)phosphate phide S-(1-phthalimidoethyl)-0,0-diethyldithiophosphate 0,0-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate 0,0-dimethyl-O-(3-chloro-4-diethylsulphamyl 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithio phenyl)-thiophosphate lane tris-(2-methyl-l-aziridinyl)-phosphine oxide 0-methyl-O-(2-carbisopropoxyphenyl)-amidothio (METEPA) 30 phosphate S-(2-chloro-1-phthalimidoethyl)-0,0-diethyldithio 5-(0,0-dimethylphosphoryl)-6-chloro-bicy phosphate N-hydroxynaphthalimido-diethylphosphate clo(3.2.0)-heptadiene(1.5) dimethyl-3,5,6-trichloro-2-pyridylphosphate 0-methyl-O-(2-i-propoxycarbonyl-1-methylvinyl)- 0,0-dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophos- 35 ethylamidothiophosphate. phate S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate Nitrophenols and derivatives (DIOXYDEMETON-S-METHYL) diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate 4,6-dinitro-6-methylphenol, sodium Dinitrocre (OXIDISULFOTON) 40 sol) dinitrobutylphenol-(2,2',2')-triethanolamine bis-0,0-diethylthiophosphoric acid anhydride (SUL salt FOTEP) 2-cyclohexyl-4,6-dinitrophenyl (Dinex) dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phos 2-(1-methylheptyl)-4,6-dinitrophenyl-crotonate phate Dinocap) dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phos- 45 2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate 0,0-dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phosphate (BUTONATE) Binapacryl) phate 2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate bis-(dimethylamido) fluorphosphate (DIMEFOX) 2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate 3,4-dichlorobenzyl-triphenylphosphoniumchloride 50 Dinobuton dimethyl-N-methoxymethylcarbamoylmethyl-dithio phosphate (FORMOCARBAM) 0,0-diethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)- Miscellaneous phosphate I 0,0-dimethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)- pyrethrin II phosphate 3-allyl-2-methyl-4-oxo-2-cyclopentan-1-yl-chrysan 0-ethyl-S,S-diphenyldithiolphosphate themumate (Allethrin) 0-ethyl-S-benzyl-phenyldithiophosphonate 6-chloropiperonyl-chrysanthemumate (Barthrin) 2,4-dimethylbenzyl-chrysanthemumate (Dimethrin) 0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithio.0,0-diethyl-S-benzyl-thiolphosphate " 2,3,4,5-tetrahydrophthalimidomethylchrysanthemu mate 0,0-dimethyl-S-(ethylthiomethyl)dithiophosphatephosphate (METHYLCARBOPHENOTHION) 4-chlorobenzyl-4-chlorophenylsulphide (Chloroben diisopropylaminofluorophosphate () sid 0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithi- 65 6-methyl-2-oxo-1,3-dithiolo-4,5-b-quinoxaline ophosphate (MORPHOTHION) (Quinomethionate) 3,941,829 11 12 (I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl m-tolyl-N-methylcarbamate (I)-(cis-trans) -monocarboxylate 2,3-xylyl-N-methylcarbamate Furethrin) 3-isopropylphenyl-N-methylcarbamate 2-pivaloyl-indane-1,3-dione Pindon 3-tert.butylphenyl-N-methylcarbamate N'-(4-chloro-2-methylphenyl)-N,N-dimethylfor 5 3-sec.butylphenyl-N-methylcarbamate mamidine (Chlorophenamidin 3-isopropyl-5-methylphenyl-N-methylcarbamate 4-chlorobenzyl-4-fluorophenyl-sulphide Fluoroben () side 3,5-diisopropylphenyl-N-methylcarbamate 5,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl 2-chloro-5-isopropylphenyl-N-methylcarbamate benzimidazole Fenozaflor O 2-chloro-4,5-dimethylphenyl-N-methylcarbamate p-chlorophenyl-p-chlorobenzenesulphonate Ovex) 2-(1,3-dioxolan-2-yl)phenyl-N-methylcarbamate p-chlorophenyl-benzenesulphonate Fenson) (DIOXACARB) p-chlorophenyl-2,4,5-trichlorophenylsulphone Tet 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl-N-methyl radifon p-chlorophenyl-2,4,5-trichlorophenylsulphide (Tet 15 2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarba rasul late p-chlorobenzyl-p-chlorophenylsulphide Chloroben 2-(1,3-dithiolan-2-yl)-N,N-dimethylcarbamate side 2-(1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarba 2-thio-,3-dithiolo-(5,6)-quinoxaline Thiochinox rate prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite 20 2-isopropoxyphenyl-N-methylcarbamate Propargil). (APROCARB) 2-(2-propinyloxy)phenyl-N-methylcarbamate Formamidines 3-(2-propinyloxy)phenyl-N-methylcarbamate 1-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formami 2-dimethylaminophenyl-N-methylcarbamate dine (CHLORPHENAMIDIN) 25 2-diallylaminophenyl-N-methylcarbamate 1-methyl-2-(2'-methyl-4'-chlorophenyl)-formami 4-diallylamino-3,5-xylyl-N-methylcarbamate (AL dine LYXICARB) 1-methyl-2-(2'-methyl-4'-bromophenyl)-formami 4-benzothienyl-N-methylcarbamate dine 2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcar 1-methyl-2-(2',4'-dimethylphenyl)-formamidine 30 bamate 1-n-butyl-l-methyl-2-(2-methyl-4'-chlorophenyl)- 3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarba formamidine rate 1-methyl-1-(2-methyl-4'-chloroaniline-methylene)- 1-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcar formamidine bamate (ISOLAN) 2-(2'-methyl-4'-chlorophenyl-formamidine 35 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N- 1-n-butyl-2-(2-methyl-4'-chlorophenyl-imino)- dimethyl-carbamate pyrolidine. 3-methyl-4-dimethylaminomethyleneiminophenyl-N methylcarbamate Urea 3,4-dimethylphenyl-N-methylcarbamate N-2-methyl-4-chlorophenyl-N',N'-dimethyl-thi 40 2-cyclopentylphenyl-N-methylcarbamate OUT 3-dimethylamino-methyleneiminophenyl-N-methyl carbamate () and its 1-methylthio-ethylimino-N-methylcarbamate (ME a 1-naphthyl-N-methylcarbamate () THOMYL) 2-butinyl-4-chlorophenylcarbamate 45 2-methylcarbamoyloximino-1,3-dithiolane 4-dimethylamino-3,5-xylyl-N-methylcarbamate 5-methyl-2-methylcarbamoyloximino-1,3-oxythio 4-dimethylamino-3-tolyl-N-methylcarbamate lane () 2-(1-methoxy-2-propoxy)phenyl-N-methylcarba 4-methylthio-3,5-xylyl-N-methylcarbamate (ME rate THIOCARB) 50 2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate 3,4,5-trimethylphenyl-N-methylcarbamate 1-dimethylcarbamyl-1-methylthio-0-methylcarba 2-chlorophenyl-N-methylcarbamate (CPMC) myl-formoxime 5-chloro-6-oxo-2-norborane-carbonitrile-0-(methyl 1-(2'-cyanoethylthio)-0-methylcarbamyl-acetaldox carbamoyl)-oxime 1-(dimethylcarbamoyl)-5- e methyl-3-pyrazolyl-N,N-dimethylcarbamate 55 1-methylthio-0-carbamyl-acetaldoxime () 0-(3-sec.butylphenyl)-N-phenylthio-N-methylcarba 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methyl nate carbamate () 2,5-dimethyl-1,3-dithiolane-2-(0-methylcarbamyl)- 2-methyl-2-methylthio-propionaldehyde-0-(methyl aldoxime) carbamoyl)-oxime () 60 0-2-diphenyl-N-methylcarbamate 8-quinaldyl-N-methylcarbamate and its salts 2-(N-methylcarbamyl-oximino)-3-chloro-bicy methyl-2-isopropyl-4-(methylcarbamoyloxy)car clo2.2.1]heptane banilate 2-(N-methylcarbamyl-oximino)-bicyclo[2.2.1]hep m-(1-ethylpropyl)phenyl-N-methylcarbamate tane 3,5-di-tert, butyl-N-methylcarbamate 65 3-isopropylphenyl-N-methyl-N-chloroacetal-carba m-(1-methylbutyl)phenyl-N-methylcarbamate mate 2-isopropylphenyl-N-methylcarbamate 3-isopropylphenyl-N-methyl-N-methylthiomethyl 2-sec.butylphenyl-N-methylcarbamate carbamate 3,941,829 13 14 0-(2,2-dimethyl-4-chloro-2,3-dihydro-7-ben stems, tubers and roots, and from which parts of zofuranyl)-N-methylcarbamate which grow later then also remain free. The active 0-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N- substances of the formula I are active in particular methylcarbamate against phytophathogenic fungi belonging to the fol 0-naphthyl-N-methyl-N-acetal-carbamate 5 lowing classes: 0-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate Oomycetes, Zygomycetes, Ascomycetes, Basidiomy 3-isopropyl-4-methylthio-phenyl-N-methylcarba cetes, Denteromycetes. In addition, the new active substances can also be 3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamatemate used for treating seeds, fruit, tubers etc., and protecting 3-methoxymethoxy-phenyl-N-methylcarbamate them from fungus , for example from smut 3-allyloxyphenyl-N-methylcarbamate fungi of all kinds, such as Ustilaginales, e.g. Ustilago, 2-propargyloxymethoxy-phenyl-N-methyl-carbamate Tilletia, Urocystis, Turbicinia and Phoma types. 2-allyloxyphenyl-N-methyl-carbamate In addition to the above cited acaricides and insecti 4-methoxycarbonylamino-3-isopropylphenyl-N- cides, it is also possible to admix the active substances methyl-carbamate 15 of the formula I with, for example, bactericides, fungi 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- static agents, bacteriostatic agents, nematocides and/or methyl-carbamate e.g. the following , in order to broaden the 2-y-methylthiopropylphenyl-N-methyl-carbamate activity spectrum: 3-(o-methoxymethyl-2-propenyl)-phenyl-N-methyl dodecylguanidine acetate (DODINE) carbamate pentachloronitrobenzene (QUINTOZENE) 2-chloro-5-tert-butyl-phenyl-N-methyl-carbamate pentachlorophenol (PCP) 4-(methyl-propargylamino-3,5-xylyl-N-methyl-car 2-(1-methyl-n-propyl)-4,6-dinitrophenyl-2-methyl bamate crotonate (BINAPACRYL) 4-(methyl-y-chloroallylamino)-3,5-xylyl-N-methyl 2-(1-methyl-n-heptyl)-4,6-dinitrophenylcrotonate carbamate 25 (DINOCAP) 4-(methyl-g-chloroallylamino)-3,5-xylyl-N-methyl 2,6-dichloro-4-nitroaniline (DICHLORAN) carbamate 2,3,5,6-tetrachloro-benzoquinone (1,4) (CHLOR 1-((3-ethoxycarbonylethyl)-3-methyl-5-pyrazolyl ANIL) N,N-dimethylcarbamate 2,3-dichloro-naphthoquinone (1,4) (DICHLONE) 3-methyl-4-(dimethylamino-methylmercapto N-(trichloromethylthio) phthalimide (FOLPAT) methyleneimino)phenyl-N-methylcarbamate N-(trichloromethylthio) cyclohex-4-ene-1,2-dicar 1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)- boximide (CAPTAN) propanehydrochloride N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2- 5,5-dimethylhydroresorcinoldimethylcarbamate dicarboximide (CAPTAFOL) 2-ethyl-propargylamino]-phenyl-N-methylcarba 35 N-methansulfonal-N-trichloromethylthio-chloroani line 2-methyl-propargylamino]-phenyl-N-methylcarbamate N'-dichlorofluoromethylthio-N,N-dimethyl-N'- phenylsulphamide (DICHLOFLUANID) 4-dipropargylamino)-3-tolyl-N-methylcarbamatemate 0-ethyl-S-benzyl-phenyldithiophosphate 4-dipropargylaminol-3,5-xylyl-N-methylcarbamate 40 0,0-diethyl-S-benzyl-thiolphosphate 2-allyl-isopropylamino)-phenyl-N-methylcarbamate disodium-ethylene-1,2-bis-dithiocarbamate 3-allyl-isopropylamino]-phenyl-N-methylcarbamate (NABAM) zinc-ethylene-1,2-bis-dithiocarbamate (ZINEB) Chlorinated Hydrocarbons manganese-ethylene-1,2-bis-dithiocarbamate y-hexachlorocyclohexane (GAMMEXANE; LIN- 45 (polymeric)(MANEB) tetramethylthiuramdisulphide () 1,2,4,5,6,7,8,8-octachloro-3o,4,7,7a'tetrahydro-4,7-DAN; y HCH) 1-oxy-3-acetyl-6-methyl--(5)dione-(2,4) (DEHYDRO-ACETIC ACID) 1,4,5,6,7,8,8-heptachloro,30,4,7,7a-tetrahydro-4,7-methylene indane (CHLORDAN) 8-hydroxyquinoline (8-QUINOLINOL) 50 2-dimethylamino-6-methyl-5-n-butyl-4-hydroxy 1,2,3,4,10,10-hexachloro-1,440,5,8,8a-hexahydromethylene indane () pyrimidine methyl-N-benzimidazole-2-yl-N-(butyl endo-1,4-exo-5,8-dimethanonaphthalene AL carbamoyl)carbamate (BENOMYL) DRIN) 2-ethylamino-6-methyl-5n-butyl-4-hydroxypyrimi 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4o,5,6,7,8- dine 8a-octahydro-exo-1,4,endo-5,8-dimethanonaph 55 2,3-dicyano-1,4-dithia-anthraquinone (DITHIA NON) 1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4o,5,6,7,8-thalene DIFLORIN) 2-(4-thiazolyl)-benzimidazole 8a-octyhydro-endo-endo-5,8-dimethanonaphtha 3,5-dimethyltetrahydro-1,3,5-thiadiazine-2-thione lene ( (DAZOMET) The active substances of the formula I are also suit 60 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine able for combating representatives of the division Thal pentachlorobenzyl . lophyta, e.g. viruses, bacteria and fungi. They thus Furthermore, the compounds of the formula I are possess fungicidal properties against phytopathogenic suitable for combating plant pathogenic . fungi on various cultivated plants, such as cereals, The compounds of the formula I may be used as pure maize, , vegetables, ornamental plants, fruit trees, 65 active substance or together with suitable carriers and vines, products, etc. for additives. Suitable carriers and additives can be With the new active substances it is possible to con solid or liquid and correspond to the substances con trol or destroy fungi occurring on fruit, blossom, leaves, ventionally used in formulation technique such, for 3,941,829 16 example, as solvents, dispersants, wetting agents, adhe ample, improve the adhesion of the active ingredients sives, thickeners, binders and/or fertilisers. on plants or parts of plants (adhesives and aggluti For application, the compounds of the formula I may nants) and/or ensure a better wettability (wetting be processed to dusts, emulsion concentrates, granules, agents) and dispersibility (dispersing agents). Exam dispersions, sprays, to , or suspensions, in the ples of suitable adhesives are the following: olein/chalk conventional formulation which is commonly em mixture, cellulose derivatives (methyl cellulose, car ployed in application technology. Mention may also be boxymethyl cellulose), hydroxyethyl glycol ethers of made of cattle dips and spray races, in which aqueous monoalkyl and dialkyl phenols having 5 to 15 ethylene preparations are used. oxide radicals per molecule and 8 to 9 carbon atoms in The agents according to the invention are manufac O the alkyl radical, lignin sulphonic acids, their alkali tured in known manner by intimately mixing and/or metal and alkaline earth metal salts, polyethylene gly grinding active substances of the formula I with the col ethers (carbowaxes), fatty alcohol polyethylene suitable carriers, optionally with the addition of disper glycol ethers having 5 to 20 ethylene oxide radicals per sants or solvents which are inert towards the active molecule and 8 to 18 carbon atoms in the fatty alcohol substances. The active substances may take, and be 15 moiety, condensation products of ethylene oxide? prop used in, the following forms: ylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, Solid forms: condensation products of urea and , and Dusts, tracking agents, granules, coated granules, also latex products. impregnated granules and homogeneous granules. The water-dispersible concentrates of the active sub Liquid forms: 20 stance, i.e. wettable powders, pastes and emulsifiable a. active substances which are dispersible in water: concentrates, are agents which can be diluted with wettable powders, pasts, emulsions; water to any concentration desired. They consist of b. solutions. active substance, carrier, optionally additives which To manufacture solid forms (dusts, tracking agents), stabilise the active substance, surface-active substance the active substances are mixed with solid carriers. 25 and anti-foam agents and, optionally, solvents. Suitable carriers are, for example: kaolin, talcum, bo Wettable powders and pastes are obtained by mixing lus, loess, chalk, limestone, ground limestone, attaclay, and grinding the active substances with dispersing dolomite, , precipitated silica, alka agents and pulverulent carriers in suitable apparatus line earth silicates, sodium and potassium aluminium until homogeneity is attained. Suitable carriers are, for silicates (feldspar and mica), calcium and magnesium 30 example, those mentioned for the solid forms of appli sulphates, magnesium oxide, ground synthetic materi cation. In some cases it is advantageous to use mixtures als, fertilisers, for example ammonium sulphate, ammo of different carriers. As dispersing agents there can be nium phosphate, ammonium nitrate, urea, ground veg used, for example, condensation products of sulpho etable products, such as corn meal, bark dust, sawdust, nated naphthalene and sulphonated naphthalene deriv nutshell meal, cellulose powder, residues of plant ex 35 atives with formaldehyde, condensation products of tractions, activated charcoal etc. These substances can naphthalene or naphthalene sulphonic acids with phe either be used singly or in admixture with one another. nol and formaldehyde, as well as alkali, ammonium and Granules can be very easily manufactured by dis alkaline earth metal salts of lignin sulphonic acid, in solving an active substance of the formula I in an or addition, alkylary sulphonates, alkali and alkaline ganic and applying the resulting to a 40 earth metal salts of dibutyl naphthalene sulphonic acid, granulated material, for example attapulgite, SIO, fatty alcohol sulphates such as salts of sulphated hex granicalcium, bentonite etc. and then evaporating the adecanols, heptadecanols, octadecanols, and salts of solvent. sulphated fatty alcohol glycol ethers, the sodium salt of Polymer granules can also be manufactured by mix oleoyl ethionate, the sodium salts of oleoyl methyl ing the active substances of the formula I with polymer 45 tauride, ditertiary acetylene glycols, dialkyl dilauryl isable compounds (urea/formaldehyde; dicyan ammonium chloride and fatty acid alkali and alkaline diamide/formaldehyde; melaminefformaldehyde or earth metal salts. others), whereupon a mild polymerisation is carried Suitable anti-foam agents are silicones. out that does not affect the active substances and in the The active substances are mixed, ground, sieved and process of which the granulation is carried out during 50 strained with the additives cited hereinabove in such a the gel formation. It is more advantageous to impreg manner that, the size of the solid particles does not nate finished, porous polymer granules (ureafformalde exceed 0.02 to 0.044 in wettable powders, and 0.03 u. hyde, polyacrylonitrile, polyester or others) which have in pastes. To produce emulsifiable concentrates and a specific surface area and a favourable predetermina pastes, dispersing agents such as those cited above, ble adsorption/desorption ratio, with the active sub 55 organic solvents, and water are used. Examples of suit stances, for example in the form of their solutions (in a able solvents are: alcohols, benzene, , toluene, low boiling solvent) and to remove the solvent. Poly dimethyl sulphoxide, and mineral oil fractions which mer granules of this kind in the form of microgranules boil between 120' and 350°C. The solvents must be having a bulk density of 300 g/liter to 600 g/liter can practically odourless, not phytotoxic, and inert to the also be manufactured with the aid of atomisers. The 60 active substances. dusting can be carried out from aircraft over extensive Furthermore, the agents according to the invention areas of cultures of useful plants. can be applied in the form of solutions. For this pur It is also possible to obtain granules by compacting pose the active substances, or several active substances the carrier with the active substance and carriers and of the general formula I, are dissolved in suitable or subsequently comminuting the product. 65 ganic solvents, mixtures of solvents or in water. Ali To these mixtures can also be added additives which phatic and aromatic hydrocarbons, chlorinated deriva stabilise the active substance and/or non-ionic, anionic tives thereof, alkyl naphthalenes, and mineral oils, sin and cationic surface active substances, which, for ex gly or in admixture with each other, can be used as 3,941,829 17 18 organic solvents. 46 parts of kaolin. The content of active substance in the above de scribed agents is between 0.1 to 95%, in which connec d. tion it should be mentioned that, in the case of applica 10 parts of active substance, tion from aircraft or some other suitable means of ap 5 3 parts of a mixture of the sodium salts of saturated plication, it is possible to use concentrations of up to fatty alcohol sulphates, 99.5% or even pure active substance. 5 parts of naphthalenesulphonic acid/formaldehyde The active substances of the formula I can, for exam condensate, ple, be formulated as follows: 82 parts of kaolin. O The active substances are intimately mixed, in suit Dusts able mixers, with the additives, the mixture being then The following substances are used to manufacture ground in the appropriate mills and rollers. Wettable (a) a 5% and (b) a 2% dust: powders are obtained which can be diluted with water to give suspensions of any desired concentration. a. 5 5 parts of active substance Emulsifiable concentrates: 95 parts of talcum The following substances are used to produce (a) a b. 10% and (b) a 25% emulsifiable concentrate: 2 parts of active substance 20 a. 1 part of highly disperse silicic acid 10 parts of active substance, 97 parts of talcum. 3.4 parts of epoxidised vegetable oil, The active substances are mixed with the carriers and 13.4 parts of a combination emulsifier consisting of ground. fatty alcohol polyglycol ether and alkylarylsul 25 phonate calcium salt, Granules 40 parts of dimethylformamide, The following substances are used to produce 5% 43.2 parts of xylene, granules: 5 parts of active substance, b. 0.25 parts of epichlorohydrin, 30 25 parts of active substance, 0.25 parts of cetyl polyglycol ether, 2.5 parts of epoxidised vegetable oil, 3.50 parts of polyethylene glycol, 10 parts of an alkylarylsulphonateffatty alcoholpoly 91 parts of kaolin (particle size 0.3 - 0.8 mm). glycol ether mixture The active substance is mixed with epichlorohydrin 5 parts of dimethylformamide, and dissolved with 6 parts of ; the polyethylene 35 57.5 parts of xylene. glycol and cetyl polyglycol ether are then added. The From these concentrates it is possible to produce, by thus obtained solution is sprayed on kaolin, and the dilution with water, emulsions of any desired concen acetone subsequently evaporated in vacuo. tration. Wettable powder: 40 Spray: The following constituents are used for the prepara The following constituents are used to prepare a 5% tion of (a) a 40%, (b) and (c) a 25%, and (d) a 10% spray: wettable powder: 5 parts of active substance, 1 part of epichlorohydrin, a. 45 94 parts of benzine (boiling limits 160 - 190°C). 40 parts of active substance, 5 parts of sodium lignin sulphonate, EXAMPLE 1. 1 part of sodium dibutyl-naphthalene sulphonate, N-(2-methyl-4-chlorophenyl)-N'-methyl-N'-(2- 54 parts of silicic acid. - 50 methylphenoxycarbonyl)-formamidine. b. To a solution of 54.8 g of N-(2-methyl-4-chloro 25 parts of active substance, phenyl)-N'-methyl-formamidine in 400 ml of dry ben 4.5 parts of calcium lignin sulphonate, zene are added dropwise, while stirring, 25.5 g of chlo 1.9 parts of Champagne chalk/hydroxyethyl cellulose roformic-o-tolyl ester, the temperature being kept be mixture (1:1), 55 tween 5-10°C. After the mixture has been stirred con 1.5 parts of sodium dibutyl naphthalene sulphonate, stantly for 12 hours at room temperature, the resulting 19.5 parts of silicic acid, hydrochloride salt of the formamidine used simulta 19.5 parts of Champagne chalk, neously as base is filtered off, washed with benzene, 28.1 parts of kaolin. and the benzene solution evaporated in vacuo. Recrys 60 tallisation from yields the product of the C. formula 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene , 1.7 parts of Champagne chalk/hydroxyethyl cellulose 65 (H, CH, mixture (1:1), 8.3 parts of sodium aluminium silicate, ol-(X-sch 16.5 parts of kieselguhr, CH O 3,941,829 19 20 with a of 68-70°C. The following compounds are manufactured in anal ogous manner:

ch 3 c C 1 NCH-N N coor,

R R

O ->- Smp. 132-33 C. C S. S.

d

O O -(- Smp. 72-73'c H ch c"." 3 -> n26 : 1,5609 -{X CH 3. CH 1chch c(CH) ch, ch C (c) -(x C chc(ch -> c ch S ch, Smp. : 115-16'c ch ch -(e- N (CH) Smp O3 O5C ch ch N (ch) <> n26 : 1,5673 St. 37 ( ) <> n26 : 1,5663

{n}ch, -CH-CH CH 3 S-CH-CH-CH 2

H. C. 2's HC-O-CH-CH-CH=CH

3,941,829

Rt. Physical R Physical Dot a Dotc.

C ch

CHC Chi CH 2 C 2 3. CH C CH

CF 3 c-(>Sh

O Re-Na CH-N-c-

CH 3 CH-CH 25 CH

Rir Physical R. r Physicol do to do to

f

26 : 1,5666

CHCH ch 3 26 : 1,5694 ck D C. c. C C s O 26 : 5447 sC s {X- " 25 : 5713 ch 37 (i) {s n23 : 1,5588 O 3. ch C h N 2 (a) c."<>- C 37 (i) Nc-{X- CH37 (i) CH 3. CHCH-CH,- o-(X

C chuc-cho-SX2

3,941,829 47 48

Physical t Physical do to Do to

CH, CH

R it Physicol Rf Physical Do to Do to

CH K- n24 : 1,573 CH

37 ()

3,941,829 59 60

R R

c

C

HC=C-CH -o

(D- c O-ch ch Hcc-CH - O Y 2 CCH

N-CH -3CH CH- CECH o-ch 2 choch,

N (CH-C=CH),CH - C

O C.H. O. cho-c NCH-N-C- Smp. ; 58-59'c N 7

40 EXAMPLE 2 EXAMPLE 3 A. Insecticidal ingest action Action against Chilo suppresalis Tobacco and plants were sprayed with a Six rice plants at a time of the variety Caloro' were 0.05% aqueous emulsion (obtained from a 10% emulsi 45 transplanted into plastic pots (diameter at the top - 17 fiable concentrate). cm) and reared to a height of about 60 cm. Infestation After the coating had dried, the tobacco plants were with Chilo suppressalis larvae (L: 3-4 mm long) took populated with Egyptian cotton leaf worms (Spodoptera place 2 days after the active substance had been ap littoraralis) and the potato plants with Colorado potato plied in granule form to the paddy water (rate of appli beetle larvae (Leptinotarsa decemlineata). The test was 50 cation: 8 kg of active substance per hectare). Evalua carried out at 24°C and 60% relative humidity. In the tion of the insecticidal action took place 10 days after above test, the compounds according to Example 1 application of the granules. displayed good ingest poison action against Spodoptera The compounds according to Example l were active littoralis and Leptinotarsa decenlineata. in the above test against Chilo suppressalis. B. Systemic insecticidal action 55 EXAMPLE 4 To determine the systemic action, rooted bean plants Action against soil insects (Vicia fabae) were put into a 0.01% aqueous active Sterilised compost earth was homogeneously mixed substance solution (obtained from a 10% emulsifiable with a wettable powder containing 25% of active sub concentrate). After 24 hours, (Aphis fabae) 60 stance so that there resulted a rate of application of 8 were placed on the parts of the plant above the soil. kg of active substance per hectare. The aphids were protected from contact and gas action Young zucchetti plants (Cucumis pepo) were put into by means of a special device. The test was carried out plastic pots with the treated soil (3plants per pot; diam at 24°C and 70% relative humidity. In the above tests eter of pot = 7 cm). Each pot was infected immediately the compounds according to Example I displayed good afterwards with 5 Aulacophora femoralis and Pachmoda insecticidal ingest poison and systemic insecticidal ac or Chortophila larvae. The control was carried out 4, 8, tion. 16 and 32 days after depositing the larvae. 3,941,829 61 62 At 80-100% kill after the first control, a fresh infesta present on the roots are counted 28 days after planting tion with 5 larvae each was carried out in the same soil and sowing respectively. In this test the compounds sample with 3 new zucchetti plants. If the activity was according to Example 1 display good action against less than 80%, the remaining larvae remained in the soil Meloidgyne Avenaria. sample until the control immediatedly following. If an We claim: active substance at a rate of application of 8 kg/ha still 1. A compound of the formula effected a 100% kill, a further control with 4 and 2 kg of active substance per hectare was carried out. In the above test, the compounds according to Exam O ple 1 displayed action against Aulacophora fermoralis, Pachmoda and Chortophila larvae. EXAMPLE 5 Action against ticks 15 A. Rhicephalus bursa Five adult ticks and 50 tick larvae were counted into a glass tube and immersed for 1 to 2 minutes in 2 ml of wherein R represents hydrogen, C-C alkyl, Ca-C an aqueous emulsion from an emulsion series each alkenyl or CCs alkynyl, R represents a-naphthyl, or containing 100, 10, 1 and 0.1 ppm of test substance. phenyl substituted by halogen, C-C alkyl, C-C halo The tube was then sealed with a standardised cotton alkyl, C-C alkoxy, alkoxyalkyl having 1 to 4 carbon atoms in each of the alkyl moieties, C-C alkylthio, wool plug and placed on its head, so that the active Ca-C alkynyloxy, dialkylamino having C-C alkyl substance emulsion could be adsorbed by the cotton groups, dialkenylamino having C-C alkenyl groups, wool. 25 dialkynylamino having CC alkynyl groups, N-lower In the case of the adults evaluation took place after 2 alkyl-N-(CaCl)alkynylamino, N-lower alkyl-N-(C weeks, and in that of the larvae after 2 days. Each test C.)alkenylamino, OH, CN, NO, cyclopentyl, was repeated twice. monomethylaminomethyleneimino, dimethylaminome B. Boophilus microplus (larvae) 30 thyleneimino, 1,3-dioxolan, 1,3-dithiolan, and 4,5- Tests were carried out in each case with 20 OP-sensi dimethyl-1,3-dioxolan tive larvae using an analogous dilution series as in the wherein the phenyl group is not substituted simulta case of test A. (The resistence refers to the tolerability neously in the 2-position by a methyl group and in of Diazinon). the 4-position by a chlorine atom, and R. R. Rs, The compounds according to Example 1 acted in 35 Rs and R represent one or more radicals which are these tests against adults and larvae of Rhicephalus the same or different, selected from hydrogen, bursa sensitive and OP-resistent larvae of Boophilus halogen atoms or C1-C alkyl, C-C alkoxy, C-C, microplus. alkylthio, Ca-Cs alkenyloxy, Ca-C alkynyloxy, CF, or nitro groups. EXAMPLE 6 40 2. A compound according to claim 1, wherein R represents methyl, R. represents a-naphthyl, 2-methyl Acaracidal action phenyl, 3-methylphenyl, 2-chlorophenyl, 2-isopropyl Phaseolus vulgaris (dwarf beans) have an infested phenyl, 3-isopropylphenyl, 3-methyl-5-isopropylphe piece of leaf from a mass culture of Tetranychus urticae nyl, 2-chloro-5-tert.butylphenyl, 3,4-dimethylphenyl, placed on them 12 hours before the test for the 45 3,4,5-trimethylphenyl, 3,5-dimethyl-4-methylthiophe cidal action. The mobile stages which have migrated nyl, 3,5-di-tert.butylphenyl, 2-isopropoxyphenyl, 3 are sprayed with the emulsified test preparations from methyl-4-dimethyl-aminophenyl, 3,5-dimethyl-4-dime a chromatography atomiser so that the spray broth thylaminophenyl, 3,5-dimethyl-4-diallylaminophenyl, does not run off. The number of living and dead larvae, 1,3-dioxolan-2-yl-phenyl, 1,3-dithiolan-2-yl-phenyl, adults and eggs are evaluated after 2 to 7 days under a 50 (4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl, 3-(1-methyl stereoscopic microscope. During the "interim', the butyl)-phenyl, 2-sec.butylphenyl, 3-(1-ethylpropyl)- treated plants are kept in greenhouse compartments at phenyl, 2,3-xylyl, 3-tert.butylphenyl, 3-sec.butylphe 25°C. nyl, 3,5-diisopropylphenyl, 2-chloro-5-isopropylphe The compounds according to Example 1 were active nyl, 3,5-dimethyl-4-methoxyphenyl, 4-(methyl-propar in the above test against eggs, larvae and adults of 5 gylamino)-3,5-xylyl, 4-(methyl-a-chloroallylamino)- Tetranychus urticae. 3,5-xylyl, 2-(ethyl-propargylamino)phenyl, 2-chloro 4,5-dimethylphenyl, 2-(2-propynyloxy)-phenyl, 3-(2- EXAMPLE 7 propynyloxy)-phenyl, 2-dimethylaminophenyl, 2-dial Action against soil nematodes lylaminophenyl, 3-methyl-4-dimethylaminome To test the action against soil nematodes, the active 60 thyleneiminophenyl, 3-dimethylaminome substance (in the concentration indicated in each case thyleneiminophenyl, 3-isopropyl-4-methylthiophenyl, is applied to and intimately mixed with soil infected 2-(methylpropargylamino)-phenyl, 2-(dipropar with root gall nematodes (Meloidgyne Avenaria). Im gylamino)-phenyl, 4-(dipropargylamino)-3-tolyl, 4-(di mediately afterwards, tomato cuttings are planted in propargylamino)-3,5-xylyl, 2-(allylisopropylamino)- the thus prepared soil in a series of tests and after a 65 phenyl, 3-(allyl-isopropylamino)-phenyl, 3-methox waiting time of 8 days tomato seeds are sown in another ymethoxyphenyl, 2-cyclopentylphenyl, 2-(1-butyn test series. 3-yl-oxy)-phenyl or 2-(1-methoxy-2-propoxy)-phenyl, In order to assess the nematocidal action, the galls and Ra, R., Rs, Rs, R, represent radicals which are the 3,941,829 63 same or different, selected from hydrogen, fluorine, chlorine or bromine atoms, or methyl, methoxy, meth ylthio, trifluoroethyl, ethylpropyl, isopropyl, n-butyl, allyloxy, propargyloxy or ON groups. 3. Compounds according to claim 2 of the formulae 5 CCCR 2

CH A st f C

COO 2 C R / c CH-N

B NChrCH-N 5 2 Coor 9.25 R / CH N=CH-N 3 l, Coor, ch Nich-N 20 ch, R Coor K> NCHN-o-g w C '3. 1. H Coor, ch R R 25 / 1 {> NCHN / C 3 o-g>=CH-NY N Co COOR 2 c" ch CH R 30 n Ch4 9 <>N=CH-NN N=CH-N/ COOR coor R CH RCH 35 HCEC-CH 2-O-(X-N=CH N 3. C 3. COOR 25 R Cl CH R NCH-N / <>ic / ch Coor, 40 oor, R wherein / R represents methyl, and NC H-N R2 has the same meaning as in claim 2. coor 4. A compound according to claim 3 of the formula 45 CHN YlR CH ch {> i-CH-N C CH-N CH, coor N 2 CO SO CH 3

N <>CF -- coor 5. A compound according to claim 3 of theCH, formula 3 CH 55 23 ch Necreen C NCH N

H coor, 60 CH 3 co->e C5 R C C Narch-N 6. A compound according to claim 3 of the formula w COOR CH ch, N C". 2 C =CH-N? 5 ch R 65 N C Nic-N / CH COO-(X-CH 5 Y 3 COOR sk s: : sk

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 3,941, 829 DATED March 2, 1976 NVENTOR(S) Georg Pissiotas and Dieter Duerr It is Certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Column 63, Claim 2, line 3, change "trifluoroethyl" to -- trifluoromethyl -- . eigned and Sealed this Nineteenth Day of October 1976 SEAL Attest.

RUTH C. MASON C. MARSHALL DANN 4t testing Officer Crn in is starter of Patents and Trademarks