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    US5438070A

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    Alfredo Méndez

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    © All Rights Reserved
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    HAA ‘US00S438070A, United States Patent 11 [11] Patent Number: 5,438,070 Eicken et al. [45] Date of Patent: Aug. 1, 1995 [5] CARBOXANILIDES, THEIR PREPARATION R 1 AND COMPOSITIONS CONTAINING THEM FOR CONTROLLING HARMFUL FUNGI [75] Inventors: Karl Eicken, Wachenheim; Hartmann Koenig, Limburgethof, Eberhard Ammermann, Heppenheim; Gisela Lorenz, Neustadt, all of Germany [73] Assignee: BASF Aktiengesellschaft, Ludwigshafen, Germany [21] Appl. No: 121,549 Sep. 16, 1993 30} Foreign Application Priority Data Sep. 21, 1992 [DE] [51] Int, cus [2] Us.a. Germany sevanen 42.31 S17 . COTD 231/14; AOIN 43/56 514/403; 548/194; 548/364. 548/369.7; 514/403 [58] Field of Search (56) References Cited U.S. PATENT DOCUMENTS 3,505,085 4/1970 Vonschmeling .... nyo 4134987 1/1979 Huppatz 5,223,526 6/1993 McLoughlin 314/406 FOREIGN PATENT DOCUMENTS 371950 6/1990 European Pat. Off - 545099, 6/1993 European Pat. Off. - WOS3I1II7 10/1983 WIPO 91/01311 2/1991 WIPO OTHER PUBLICATIONS Chem. Abst, vol. 94, No. 15, Apr. 13 1981, Acta Phytophathalogica Academiai Scientiarum Hun- garicae, vol. 8 (3-4)l, pp. 269-282 (1973) ‘Thiphene Carboxamide Fungicides ..., Pesticide Bio- chemistry and Physiology 15, 188-204 (1986) White et al Primary Examiner—Robert Gerstl Attorney, Agent, or Firm—Keil & Weinkaut (1 ABSTRACT Carboxanilides of the formula I NH-COmA where the substituents have the following meanings: R is substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, ‘cycloalkyl, cy: eee pac ears : Rr Aas oe : » c BN hh = es R2is halogen or alky! R3is alkyl or haloalkyl; nis tor 2, methods of manufacturing them, and agents containing them and their use for controlling harmful fungi. 6 Claims, No Drawings 5,438,070 1 CARBOXANILIDES, THEIR PREPARATION AND ‘COMPOSITIONS CONTAINING THEM FOR ‘CONTROLLING HARMFUL FUNGI ‘The present invention relates to carboxanilides of the formula 1 10 NH—CO—A where the substituents have the following meanings: R is Cy-Cizalkyl, Co-Crzalkoxy, C3-Crralkenyl, Cs-Cizalkenyloxy, —C3-Cealkeynyl, — C3-Co- alkynyloxy, where these groups can be partially or completely halogenated; C3-Cr-cycloalkyl, Cs-Crcycloalkenyl, C3-Cr- ‘eycloalkyloxy or Cy-Cr-cycloalkenyloxy, where these rings can carry one to three C1-Cy-alkyls; phenyl, which can carry one to five halogens and- Zor one to three of the following radicals: C1-Ce- alkyl, C,-Cs-haloalkyl, C)-Cyalkoxy, Ci-Cy- hhaloalkoxy, C1-Cy-alkylthio or C1-Cy-haloal- kylthio; Aisa cyclic radical from the group consisting of the formulae Al to AS: 35 2 “a 45 50 35 ‘where the substituents have the following meanings: Rl is hydrogen or C)-Cyalkyl; Reis halogen or C;-Cealkyl; R3 is Cj-Ce-alkyl or C)-Cerhaloalkyl; nis | or 2, where the radicals R! can be different ifthe value of is 2, where R is not phenyl if A is 3-methylthien-2-yl, ex- 65, cluding compounds I where A is AS and R? is methyl if R is cyclopentyl, cyclohexyl or cy- cloheptyl or where 2 R3is difluoromethyl if R is cyclohexyl, 4-t-butyley- clohexyl, eyciohexyloxy, cyclohex-L-en-L-yl, 2,6 dimethyleyclohex-I-en-I-yl, 4-ethyleyclohex-I-en- Ley], 4t-butyleyclohex-len-I-yl, cyclopentyl, 1- methylcyclopentyl, I-methylcyclopentoxy, 5,5 dimethyloyclopent-I-en-l-yi, 4-methylcyclopent- L-en-L-yl, cycloheptyl or cyclohept-l-en-I-yl or where R? is chlorodifluoromethyl if R is cyclopentyl or eyeloheptyl or where R}is trifluoromethyl if R is cyclohexyl, 3-methyley- clohexyl, 4-t-butyleyciohexyl, cyclohexyloxy, 4 methyicyclohexylony, 2,6-dimethyleyclohexyloxy, eyclohex-l-en-I-yi, 4-ethyleyclohex-I-en-I-yl, 2° isopropylcyclohex-1-en-I-yl, 6isopropylcyciohex- -en-l-yl, 4t-butylcyclohex-I-en-I-yl, G-ethyl2- methylcyclohex-I-en-I-yl, 6.isopropyleyclohex-1- cyclopentyl, I-methyicyclopentyl, methylcyclopentoxy, 2-methylcyclopent-I-en-1 S.methyleyclopent-I-en-I-yl, 4methyleyclopent- -en-1-yl, cycloheptyl or cyclohept-L-en-I-yl. The invention additionally relates to the preparation of these compounds, compositions containing them and their use for controlling harmful fungi, in particular Botrytis. 'N-@-Methyiphenyl)-3-methyithiophene-2-carboxa- mide, _N-@-methylphenyl)-2,5-dimethylthiophene-3- carboxamide and N-@-methylphenyl1,3,5-trimethyl- yrazole-4-carboxamide are known from the literature as fungicidal active compounds (DE-A 2 701 091; Pes- tic, Biochem. Physiol., 25 (2), (1986) 188-204) ‘The subsequently published application WO-A 95/11,117 additionally describes the pyrazolecarboxani- lides excluded from the compounds I as being fungicid- ally active. It is an object of the present invention to provide novel fungicidally active compounds having an im- proved spectrum of action. ‘We have found that this object is achieved by the compounds I defined at the beginning. We have additionally found processes for preparing, these compounds, compositions containing them and their use for controlling harmful fungi ‘The compounds I are in general obtained by reacting, a carboxylic acid halide of the formula II in a manner known per se (eg. J. March, Advanced Organic Chem- istry, 2nd E4., 1977, 382 ff, McGraw-Hill) with an aniline of the formula IIT in the presence of a base. R Ha—co—A + Ni —> NH—CO—A 1 ‘The radical Hal in the formula ITs a halogen such as chlorine, bromine or iodine, in particular chlorine or bromine. This reaction is customarily carried out at 5,438,070 3 temperatures from —20* C. to 100° C., preferably 0° C. 10 50°C. Suitable solvents are aliphatic hydrocarbons such as, pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p- 5 xylene, halogenated hydrocarbons such as dichloro- methane, chloroform and chlorobenzene, ethers such a3 diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, ‘methyl ethyl Ketone, diethyl ketone and tert-butyl ‘methyl Ketone, alcohols such 2s methanol, ethanol, n-propancl, isopropanol, n-butanol and tert-butanol, and also dimethyl sulfoxide and dimethylformamide, particularly preferably toluene and tetrahydrofuran, Mixtures of the solvents mentioned can also be used. Suitable bases are generally inorganic compounds stuch as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potas- sium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, so- dium oxide, calcium oxide and magnesium oxide, alkali ‘metal and alkaline earth metal hydrides such as lithium hhydride, sodium hydride, potassium hydride and cal- ‘cium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium cerbon- ate and calcium carbonate and also alkali metal hydro- ‘gencarbonates such as sodium hydrogencarbonate, and organometallic compounds, in particular alkali metal alkyls such as methylithium, butyllithium and phenyli thium, alkylmagnesium halides such as methylmagne- sium chloride and also alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, additionally organic bases, eg, tertiary amines such as trimethylamine, triethylam ine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine,Iutidine and 4-dimethylaminopyridine and also bieyclic amines. Triethylamine and pyridine are particularly prefera- by used. ‘The bases are in general employed in equimolar amounts based on the compound Il. However, they can also be used in an excess of from $ mol % to 30 mol %, preferably 5 mol % to 10 mol %, or—in the case of the use of tertiary amines—if appropriate as a solvent. ‘The starting materials are in general reacted with one another in equimolar amounts. It may be advantageous for the yield to employ IT in an excess of from 1 mol % 1020 mol %, preferably 1 mol % to 10 mol %, based on ML. ‘The starting substances of the formulae TI and IIT ss needed for preparing the compounds I are known or ccan be synthesized analogously to the known com- pounds (Helv. Chim. Acta, 60, (1977) 978; Zh. Org. Khim, 26, (1990) 1527; Heterocycles 26, (1987) 1885, Inv. Akad. Nauk. SSSR Ser. Khim., (1982) 2160; THL 28 593 (1987); THL 29, (1988) 5463). ‘Compounds I in which A is a2-aminothiazole A4 are obtained particularly advantageously by first preparing the corresponding N-phenyl-2-halothiazole-5-carbox- anilide V from a 2-halothiazole-S-carboxylic acid halide Of the formula IV and an aniline of the formula III and then reacting V with ammonia to give the correspond- ing carboxanilide 14. 10 2 30 35 0 0 4 5 hapa nar s ‘CO—Hal? » . ‘Hall and Hal? are in each case halogens such as chlo- rine, bromine and iodine, chlorine being preferred in the position Hal! and chlorine and bromine being preferred in the position Hal. The reaction of V with ammonia is carried out in a ‘manner known per se at from 50° C. to 200° C., at from 1 t0 200 atm, preferably $ to $0 atm, in an inert solvent in the presence of a catalyst. Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p- xylene, halogenated hydrocarbons such as dichloro- ‘methane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, ‘methyl ethyl ketone, diethyl ketone and tert-butyl ‘methyl Ketone, alcohols such as methanol, ethanol, ‘n-propanol, isopropanol, n-butanol and tert-butanol and. also dimethyl sulfoxide and dimethylformamide, partic- ularly preferably alcohols such as ethanol and isopropa- nol. “Mixtures of the solvents mentioned can also be used. Suitable catalysts are, for example, phenylsulfonic acid and hydroxybenzoic acid. ‘The catalyst is in general employed in amounts of from 0.1 mol % to 20 mol %, preferably from 0.5 mol % to 5 mol % based on V. With respect to their use in fungicidal compositions, suitable compounds of the formula I are those in which the substituents have the following meanings: R is Co-Cy-alkyl such as ethyl and straight-chain or branched propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,-decyl, undecyl and dodecyl, partic- ularly straight-chain or branched C3-Cjo-alkyl such a6 propyl, I-methylethyl, butyl, I-methyl- propyl, 2-methylpropyl, 1,l-dimethylethyl, n- pentyl, I-methylbutyl, 2-methylbutyl, 3-methyl- butyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, m-hexyl, 1 ‘methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyipentyi, 1,2-dimethylbutyl, 1,3-dimethyl- butyl, 1,3-dimethylbutyl, 2,3-dimethyIbutyl, 1, dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethyl- butyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpro- ; Om => 5,438,070 5 pyl, I-ethylbutyl, 2-ethylbutyl, L-ethyl-3-methyl- propyl, ncheptyl, I-methylhexyl, I-ethylpentyl, 2ethyipentyl, I-propylbutyl, octyl, I-methyl- heptyl, 2-methyiheptyl, I-ethylhexyl, 2-ethyl- hexyl, I-propylpentyl, 2-propylpentyl, nonyl, I-methyloctyl, 2-methyloctyl, —-ethylhepty!, 2ethylheptyl, I-propylhexyl,2-propylhexyl, decyl, I-methylnonyl, 2-methyinonyl, l-ethyloc- tyl, 2-ethyloctyl, {-propytheptyl and 2-propyl- heptyl, in particular propyl, I-methylethyl, bu- tyl, T-methylbutyl, 2-methyibutyl, 1,1-dime- thylethyl, pentyl, I-methylbutyl, hexyl, heptyl and I-methylheptyl, where these groups can be partially or completely halogenated, ie. the hy- Grogens of these groups can be partially or com- pletely replaced by halogens such as fluorine, Chlorine and bromine, in particular fluorine and chlorine, for example haloalkyl such as chloro- methyl, dichloromethyl, trichloromethyl, fluo- romethyl, difluoromethyl, trifluoromethyl, chlo- rofluoromethyl, dichlorofiuoromethyl, chiorodi- fluoromethyl, I-fiuoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2rifluoroethyl, 2-chlor0-2- fluoroethyl, | 2-chloro-2,2-difluoroethyl, 2,2- Gichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; CxCiralkony sich a ethoxy and straight-chain or ‘oranched propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, deeyloxy, un- decyloxy and dodecylony, particularly stright- chain or branched Cz-Cioalkoxy such as eth- Oxy, propory, I-methylethoxy, —butoxy,—1- methylpropoxy, 2-methylpropoxy, -.t-dime- tylethoxy, mpentoxy, L-methyibutoxy, 2- methylbutoxy, methylbutoxy, -12-dimethyl- propoxy, I-thylpropoxy, n-hexyloxy, -methyl- pentoxy, 2-methylpentoxy, -}methylpentoxy, ‘SEmethyipentoxy, 12-dimethylbutoxy, 1,-dime- thylbutoxy,2.3-dimethylbutoxy, 1,2-dimethyl- butory, 2,2-buteay EMh2-pentens) LeDimetbyl2 peony] 2BuyAy! SBaynyl Ethory Propory |Methyethory mButoxy TPMethylpropoxy 2-Mathylpropony 1 LDimethyetnary mPentyioxy ‘Hexjlory 2Ethythexyloxy 2 Propenylony 2-Batenyioxy 2-Methyb2propenylony 2-Femeayloxy Senteniony 3-Chloroz-propenyioxy 2.3Dichloro2propenyloxy 23,3ichloropropenylony 2Buyayloxy SBarymytony LeMethyt2-propynylony Gyelopropyt Gyelobuty Gyelopentyt Gyeloberst 3-Gyelopenteny! 1G yclopenteny S.Gyelahexeay! .eyelohexeny] Gyelopentyony Cyclokenslony 3-Gyelopentenyloxy S.Cyelohexenylosy Phesy! 2-Flsorophensl 7 TABLE B 3 >. R SCH ror cH nay sem Cas seu eCity SoH ECatip SoH tert-Cally 50m csi SCH; scotty, scH Cats 5,438,070 13 4 TABLE Beoontinued TABLE Cecontinved ; LL ree sco 5 ee yy Ry a Pe ee espe a of & ue casey ce eco aon eee nes ee ‘Cyclopenty! be H H CHy eCsHy caret Bobo g@ sy. wa Ho Es BS Serer Bob @ Se, ofc ne en Cyclopentyloxy 23 H H CH; ‘Propoxy ame Pn eo Beer iy Hoe eS eS ae ees ce oo See ees ie 2 4 8 oe as oo Ber Oe eS eh, ee BS or =a mee. aoe Si 2 =e oy eo Soe, hepa Se ee ‘2-Methylpropoxy am CH) H CH; se0-CsHiy yore eee es io mci 3 a f EE & & Tape c se eine ‘NH—CO” s RE CH; i CH ‘Cyclopeatyl ae: & See S : 8 so a ceecee cre a tapLeD one eee es HOH ees aa i H a a iCall vi se eee a A H H cl seo CsHit "NH—CO" s "NE fee 2 : eo ns cee ens od 8 Bie es 5,438,070 15 16 TABLE D-continued TABLE D-contiaued = @ 5 . i RW w ® N A 5 A NH—co~™ 5 “NH NH—cO7™ 5 ~~ N ® R ® R Fy ee 10 cm ‘LeDinatiiaony cr meaty a Pension os seecestinn cs THolony or ents cn Seton cr roms cas elope os sees cH Sjelchent & Thaeuyayt 6 cus 1 Eiyipeopony crs 2Methsviy! cH Eqetopetiony os ain cas SEyelonxenony Ss aust con ZMtewyt2sropenlony oH Enya Sith, Press es {eto curs 2 Fuoropenyl cs By a or Met? beeny es iBaytoment cot ‘eprops! TABLE EB cr magi tateyl . is cs UMetytpetenst —n os LaDineigh penteny] os i oH Hopes! Nec or 2s) NE=CO os Sbayest cs Bihowy cs Propory os PNetethony oy Baton » or oath cs ces SOR os ce Bo cr cH secCally oF cH fea os cH ee cy oH Zeagtbexoxy 38 on ort es ZPropeniony cH fees & 2Btenyony cs ate os Mey propenyony cs roy & 2entenions co) sess or remem cs Tate cr 3 Chlore -prpenyloxy o 8 2Methpvig & 2 Dicker? propenony cr ‘Any ce TiS trchiorpropeniony & 2 Matty! oa bropynylony cs Shyiyh es 2butastony cs {Metts or 3 Batmptony oe Pen) cs Meth popynytory 45 & 1 Meyl2bateny a Grlorrons & Ethyl buen? os Srtoboet & sopropyueny ce ‘Gietopentyt cs os Sieben & crs ‘Syetopemeayt cs es 1:Gyelopenten a 3 oS SGyetoheney cr 2Beyay! cost iGjettereyl S Bayt cs Greopenyiosy cr Ethony cs Greshension os Propons cs SGoctopenessony & Methetbony oS 2.Gjlcbenenyony & ato ci ich ss & EMetitprepory an cr & TMethiprepors oe Bo cs TDimetylctory oe woGih & sbenplon? cH: inp & EHewiony as teecatty cs Zetex cu ron © oe 2 Propenlony ae dhs co 2bacyiony oe os & 2 Meng propenyony ce noms & Penni ch sits cr SPemeylony ce Eihony ca 3Chloro 2 propenlony re Propony 6 or 2:eDenoce 2 propery cas TMetyietiony cs 253 rehleropopenion ca Bary or Ztropyeony ee {Exes fropony & Zoeomiony ae 2Metispeopory & Engeleny 5,438,070 7 TABLE E-continued R we Ts x Q N—cHs NH—co Tatil pepo Gxclopronst Syelbuen Sycopentens 1-jlopentenyl 3jtohexenyt Syelpeniviony XEyclopenenyony 3-Gjeohexenyiony oh Ch Cab seecCatly ica tects nest feeesFi meets Oms vee.Cilhs Ebony Propory EMenytetioxy TMetigropoxy 2Methyipropony Tebimetletony Penplory Hexylony Gyetopectnyt Ey propoxy Eselopentsons SE ctoketesloxy EMansh-propemony ese Cath Propory [EMethylthoxy Baton [UMets¥propony 2 Methlpropery EhDietisletony BPentlony EHeryloxy yclopenteny! Cyclery Ethyl propory Gyclopentylony 2oyelobexenvlony 2-Methyl2-propenylony Press! 2Flvoropheny! Pheayt 2 Fluoropheny! Phenyt 2Foropheny! ‘The novel active ingredients are particularly suitable for protecting various materials against degradation or destruction by bacteria or fungi or from being attacked by and covered with microorganisms. Examples of ‘materials which can be preserved or microbicidally 10 15 25 30 35 50 55 6 18 finished with the novel active ingredients are glues and adhesives, starch solutions, wax emulsions, clay emul- sions, sizes, finishes, spinning baths, gelatine formula- tions, putty, joint sealants, cooling lubricants, drilling oils, fuels, plastic dispersions, emulsion paints, textiles, leather, raw hides and cosmetics. The compounds are also suitable as anti-slime agents in the paper industry, in cooling towers and in air moistening units. ‘The compounds I are also suitable for protecting the following plant species against attack by microorgan- isms: cereals (e-g., wheat, barley, rye, oats, rice, sorghum and related species); beets (eg, sugar and fodder beets); pomes, drupes and aggregate fruit (©. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and. blackberries); leg” ‘umes (€.g, beans, Ientils, peas, soybeans); ol-yield- ing erops (e-., rape, mustard, poppies, olives, sun- flowers, coconuts, castor-oil beans, cocoa beans, groundnuts); eucurbits (¢g., pumpkins, cucumbers, melons); fiber-vielding plants (eg., cotton, flax, hhemp, jute), citrus fruit (eg., oranges, lemons, arapeftvit, tangerines); vegetables (e.g, spinach, lettuce, asparagus, cabbage varieties, carrots, on- ions, tomatoes, potatoes, paprika); laurel species (eg, avocado, cinnamomum, camphor) or plants such as Indian corn, tobacco, nuts, coffee, sugar cane, tea, grapes, hops, and banana and rubber trees. For the purposes ofthe present invention, the term “plants” is also taken to mean all types of other green growth, whether ornamentals, grassy areas, embankments, or generally low-growing cover crops For example the following microorganisms may be ‘combatted with the novel compounds I: Straphylococcus aureus, Escherichia coll, Klebselle pneumoniae, Citrobacter freundii, Proteus vulgaris, Pseudomonas aeruginose, Desulfovibrio. desulfur- ‘cans, Streptovertcilium rubrireticull.. Aspergillus niger, Aspergillus versicolor, Penicillium funiculosum, Penicillium expansum, Penicillium glaucum, Po- ‘ecilomyces variati, Trichoderma viride, Chaetomium slobosum. Aspergillus amstelodami, Phoma pigmen- ‘ovore, Phoma violacea, Aureobasidium pultulans, Saccharomyces cerevisiae, Alteraria tenuis, Stem- iylium macrosporoideum, Cladosporium herbarum, ‘Cladosporium resinae, Candida albicans, Trichophy- ton mentagrophytes, Geotrickum candidans, Monilia ‘stophila, Seenedesmus quadricauda, Chlorella vulga- 1s, Nostoe muscorium, Oscillatoria limosa and Ana- baena constricta. ‘The novel substances can be converted into coaven- tional formulations such as solutions, emulsions, suspen sions, dusts, powders, pastes and granules. The applica- tion forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for exam- ple by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, itis also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are sol- vents such as aromatics (@.g., xylene), chlorinated aro- ‘matics (¢g., chlorobenzenes), paraffins (eg, crude oil fractions), alcohols (€.g., methanol, butanol), ketones (eg, cyclohexanone), amines (eg., ethanolamine, dic 5,438,070 19 ‘methylformamide), and water; carriers such as ground natural minerals (c.g, kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e-g., polyoxyethylene fatty alcohol 5 ethers, alkyl sulfonates and ary] sulfonates); and disper- ‘sants such as lignin-sulfite waste liquors and methyleel- Iulose. The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient. ‘The active ingredients are used in a purity of from 90 to 100, and preferably from 95 to 100, % (according to the NMR/HPLC/GC spectrum). Usual application concentrations are—based on the ‘weight of the material to be protected—from 0.001 to 5, and preferably from 0.01 to 2, wt % of active ingredi- cent; when the active ingredients are used for treating water, in oil production, in drilling and cutting oils, fuels, in swimming baths, cooling towers, air moistening units or in the paper industry, amounts of from 5 to 00 ppm are sufficient. Ready-to-use disinfectant solutions contain for instance from 0.5 to 10 wt % of active ingre- dient. ‘Examples of such formulations are given below: L.A solution of 90 parts by weight of compound no. 7 and 10 parts by weight of N-methyl-a-pyrrolidone, which is suitable for application in the form of very fine drops. IL. A mixture of 20 parts by weight of compound no. 2, 80 parts by weight of aylene, 10 parts by weight of 30 the adduct of 8 to 10 moles of ethylene oxide and I mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the ‘mixture in 100,000 parts by weight of water, an aqueous dispersion is obtained. IIL. An aqueous dispersion of 20 parts by weight of compound no. 4, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of 40 the adduct of 40 moles of ethylene oxide and I mole of, castor oil. A mixture of this dispersion with 100,000 parts by weight of water contains 0.02 wt % of the active ingredient. TV. An aqueous dispersion of 20 parts by weight of 45 compound no. 3, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. The mixture of this dispersion with 100,000 50 parts by weight of water contains 0.02 wt % of the active ingredient, ‘V. A hammer-milled mixture of 80 parts by weight of compound no. 1, 3 parts by weight of the sodium salt of diisobutyinaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid ob- tained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in 20,000 parts by weight of water, a spray liquor con- taining 0.1 wt % of the active ingredient is obtained. VI. An intimate mixture of 3 parts by weight of com- pound no. Sand 97 parts by weight of particulate kaolin. ‘The dust contains 3 wt % of the active ingredient. ‘VIL. An intimate mixture of 30 parts by weight of ‘compound no. 6, 92 parts by weight of powdered silica gel and & parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence. 10 1s 2s 35 55 6 20 VIII A stable aqueous dispersion of 40 parts by ‘weight of compound no. 4,10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which disper- sion can be further diluted. TX. A stable ily dispersion of 20 parts by weight of compound no. 5,2 parts by weight ofthe calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyslycol ether, parts by weight of the sodium salt of a phenolsulfonie acid-urea- formaldehyde condensate and 68 parts by weight of a paraffinic min- eral oil. XA hammer-milled mixture of 10 parts by weight of ‘compound no. 1,4 parts by weight ofthe sodium salt of iisobutyinaphthalene-a-sulfonic acid, 20 parts. by ‘weight of the sodium salt of a lignin-sulfonic acid ob- tained from a sulfite waste liquor, 38 parts by weight of silica gel, and 38 parts by weight of kaolin. By finely ispersing the mixture in 10,000 parts by weight of ‘water, a spray liquor containing 0.1 wt % of the active ingredient is obtained. ‘Used alone, the active ingredients act as low-foaming biocides. A significant increase in the action of biocidal formulations containing these compounds is achieved if tri-Ce- to Ciz-alkylmethylammonium salts, preferably in amounts of from 20 to 40 wt %, based on the weight of compounds of the general formula I, are added. The active ingredients may also be mixed with other, prior art, mierobicides. In many instances, a synergistic effect is achieved, ic, the microbicidal action of the ‘mixture is greater than the added actions of its individ- ual components. Prior art microbicides may be added to the novel substances in a weight ratio of from 1:100 to 100-1 ‘Examples of such active ingredients are as follows: 2-{thiocyanomethylthio)-benzothiazole 1-[2-(,4-dichlorophenyl)-2-(-propenyloxy)-thyl]-1H- ‘imidazole 2,4,5,6-ttrachloroisophthalodiniteile mcthylene bisthiocyanate tributyltin oxide, naphthenate, benzoate, salicylate mercaptobenzothiazole 1,2-benzisothiazolone and its alkali metal salts alkali metal compounds of N'-hydroxy-N-cyclohexyl- diazenium oxide 2-{methoxycarbonylamino)-benzimidazole 2-methyl-3-oxo-5-chlorothiazolin-3-one trihydroxymethyinitromethane slutardialdehyde chloroacetamide polyhexamethylene bisguanide S-chloro-2-methyl--isothiazoli salts 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione hnexahydrotriazine N.N-methylolchloroacetamide 2en-octyl-tisothiazolin-3-one ‘oxazolidines bisoxazolidines 2,5-dihydro-2,5-dialkony-2,5-dialkylfurans iethyldodecyTbenzylammonium chloride ‘dimethyloctadecyidimethylbenzylammonium chloride

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