CA1248964A - 2,2-difluoro-4-amino-1,3-benzodioxole and a process for its preparation - Google Patents

Abstract

ABSTRACT
This invention relates to a compound of formula II

Description

This application is a divisional application for application no. 505,550 filed on April 1, 1986. This divisional application relates to 2,2-difluoro-4-amino-1,3-benzodioxole and to a process for its preparation.
The invention of the parent application relates to the novel anilinobenzodioxole compound of the ,formula I helow.
The invention further relates to the preparation of this compound and to compositions which contain said compound as active ingredient, as well as to the use of the novel compound or said compositions for controlling pests, in particular phytopathogenic fungi or bacteria, and also insects and acarids.
The compound of the parent invention has the formula I.

~N02 2N ~ ~ - NH ~
~ ~ \ (I) In accordance with this invention, said compound is prepared by reacting the compound of formula II

:: ' , -la- 21489-6921D

H2N \ ~ (II) ~ F

with the compound of formula III

02N - ~ CF3 (III) in the presence of an acid acceptor in an inert solvent or diluent.

-2- 21~89-6921~

Examples of suitable inert solvents or diluents are:
aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloro~orm, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), dioxane, tetrahydrofurane;
nitriles such as acetonitrile, propionitrile; N,N-diaikylated amides such as dimethylEormamide; dimethyl sulfoxide; ketonessuch as acetone, diethyl ketone, methyl e-thyl ke-tone; and mixtures of such solvents with each other. Dimethylformamide, tetrahydro-furan and dioxane are preferred. In some cases it is advantageous to carry out the reaction in aqueous suspension.
Examples of suitable acid acceptors are inorganic bases, e.g. oxides, hydroxides, carbona-tes or bicarbonates of alkali metals or alkaline earth metals, as well as alkali metal hydrides or alkali metal acetates, and also or~anic bases, e.g.
tertiary amines such as trialkylamines (trimethylamine, triethylamine etc.), pyridine or pyridine bases (~-dimethylamino-pyridine, ~-pyrrolidylaminopyridine). Preferred acid acceptors are alkali metal hydroxides, alkali metal bicarbonates and alkali metal hydrides.
The xeaction temperature iq variable depending on the reaction conditions. It is in general in the range ~rom -25 to 150C, preferably from ~10 to 120C.
The reac-tion partners are normally employed in equimolar amoun-ts,.

J~

-2a- 21489-6921D

The compound of formula ~I employed for the preparation of the compound of formula I of this invention is novel. Said novel compound of formula II is a valuable intermediate for the synthesis of biocidal compounds and constitutes a subject of the divisional application. It is prepared e.g. by Hofmann degradation, i.e. by reacting 2,2-difluoro-4-carbamoyl-1,3-benzodioxole with bromine, in the presence of aqueous alkali metal hydroxide, which is also the subject of the divisional application.

~ONH2 ~H2 ~ / \O X allall m~ta~ ~ \1/ X (II) This process i6 carried out in accordance wlth the method of L.M.
Yagupol6kil ~t al., Zhur. Obshch. Khym. 31, 628 (1981).

The precursors for the preparation of the compound of formula II are syntheslsed as follows starting from 4-carboxy~1,3-benzodioxole (in accordance with W.H. Perkin ~nd V.M. Triko~us, J. Chem. Soc. 1926, 2925): -1~
~00~2 ~OCl ~ \ PCl,s __~ T~,~X

~OCl ~OF

oXc~ X

3~
~OF ICONH2 ~-~ /O\ /F ~ O
~ \o~ ~ N~3 ~

Diaryla~ine~ are known which have been proposed for u~e as fungi-cides, insectlcides and acaricides (q.v. German Offenlegungsschrift 28 23 168). Howev~r, the activity of ~ald diarylsmlnes ls not entirely satisfgctory to the dssired degree. The followlng com-pound A for example is known from the aforHmentloned German OfEen-legungsschrift:

~NO2 02N~ -N~ (A).
~CF3 \~ ~ F

Surprislngly, it has been found that th~ compound of formula I of this lnvention has a very useful biocidal activity spsctrum against fungi, bacteria, ln6ects and representatives of tho order Acarina, in particular against phytopathogenic fun~l and bacteria, which activity spectrum satisfies practical requirements well. The compound of formula I has very advantageous curative, systemic and, in partlcular, preventive properties, and can be used for protecting numerous cultivated plants. With the compound of formula I it ls possible to inhlbit or destroy the pests which occur in plant6 or parts of plants (fruit, blossoms, leaves, stems, tubers, roots~ in different crops of useful plants, while at the same tlme the part6 of plants which grow later are also protected from attack by phytopathogenic microorganisms and lnsects. Acarina can also be succQssfully controlled with the compouna of fo~mula I.

As microbicide6, the compound of formula I ls effectlve e.g. again6t the phytopathogenic fungi balonging to the following cla6ses: Fungl imperfecti ~e.g. Botrytis, Helmintho6porium, Fu6arium, Septoria, Cerco~pora and Alternaria); ~asidiomycotes (e.g. of tho genera Hemileia, Rhizocotonia, Puccinia); as woll as a~ainst Oomycetes (Q . g. Plasmopar~ viticola) belonglng to tho class of the Phyco-mycetes; and, in partlcular, agalnst the class of the Ascomycet~6 (s.g. Venturla, Podospllaera, Erysipho, Monllinia, Uncinula). In addition, the compound of formula I ha a systemic action. It can also be usHd as drQsslng agent for protscting soeds (fruit, tuber6, gralns) and plant cuttlngs against fungus infections es wHll as against phytopsthogenic fungi which occur in th~ soil~

A6 insectlclde, the compound of formula I can also be used for controlling lnsects of the orders: Lepidoptera, Coleoptera, Homop-tera, Heteroptera, Diptora, Thysanoptera, Orthoptera, ~lattaria, Anoplura, Siphonaptera, Mallophaga, Thy6anura, Isoptera, Psocoptera and Hymenoptera.

The compound of formula I is also suitable for controlling represen-tatives uf the order Acarins, e.g. of the families Ioxididae, Argasidae, Tetranychidae and Dermanyssldae. The compound of for-mula I can be successfully used for controlllng phytopathogenic mites, e.g. of the famili06 Tetranychidae and Phytoptipalpidae (spider mite6), Tarsonemidae and Eriophydiae (gall mites).

In addition to its action against flies, e.g. Aëdes aegyti and Musca domestica, the compound of formula I is also suitable for controlling plant-destructive feeding insects in ornamentals and crops of useful plants, especially in cotton (e.g. against Spodop-tera littoralis and }leliothis virQficens~ and in crops of ceraals, fruit and vegetables (e.g. agains~ Laspeyresia pomonelia, Leptlno-tarsa decemllneata and Epilachna varivestis)~ The compound of formula I has a good actlon against larval developmant stages and nymphs, ~specially of noxious feeding insects.

The compound of for~ula I can also 'oe ussd for controlllng ecto-parasitic lnsects and acarids in domestic animals and productivs livestoc~, e.g. by treating animals, cowsheds, barns, stables etc., and pa6tures.

Ths actlvity of the compound of formula I and of the composlt~on6 containing it can be substantlally broad~ned and adapted to pre-vailing circumstances by addition of other insecticides andlor acaricides.

Accordlngly, ~he invention also relates to pestlcidal compositlons (microbicideL, insectlcidesl acarlcldes) and to the use th~reof ln agriculture or related fields .

The invention Eurther embraces the preparatlon of the6e co~po61-tlons, which comprises homogeneously mlxing the actlve lngredient with one or more compounds or groups of compounds described hereln.
The invention furthermore relates to a method of treating plants, which comprlses applying thereto the compound of formula I or the novel composltions.

Target crops to be protected withln the scope of the pre6ent inventlon comprlse e.g. the followlng specles of plant6:
cereals (wheat, barley, rye, oat6, rice, sorghum and ralated crop6), beet (sugar beet and fodder beet), pomes, drupes and soft frult (apples, pears, plums, peaches, almonds, cherri~s, strawberrles, rasberrl~s and blac~berrles), legumlnous plants (beans, 10ntll6, peas, ~oybeans), oll plant6 (rape, mu6tard~ poppy, ollves, sun-flowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons), fibre plants (cotton, flax, hemp, ~ute), cltrus frult (orange6, lemons, grapefrult, mandarins), vagetables (spinach, lettuce, asparagus, cabbages, carrots, onlons, tomatoe6, potatoes, paprika)j lauraceae (avocados, cinnamon, camphor), or plants 6uch as malze, tobacco, nut6, coffee, sugar cane, tea, vine6~ hops, banana~ and nntural rubber plants, as well a6 ornamental6 (composite6).

The compound of formula I is normally applied ln the form of composition6 contalning ad~uvants such as carriers ~nd diluent6 and can be applied to the crop area or plant to be treated, slmulta-neously or ln succ~6sion, with further compounds. These further compounds can be both fsrtlllsers or micronutrlent donor6 or other preparatlons that ~nfluence plant growth. They can also be selective herblcides, ins~cticldes, fungicides, bactericides, nematlcides, mollu6clcide6 or mixtures of several of the6e preparatlon6, lf de61red together with further carrlers, sur~actant6 or application ~$~

promoting adjuvants customarlly employed ln the art of forMulatlon.

Suitable carriers and ad~uvants can be solid or liquid and corres-pond to the substances ordlnarily employed in formulation tech-nology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying the compound of formula I or an agrochemical composition which contains said compound, ls foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding parasite (e.g. type of fungus). However~ the compound of formula I can also penotrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant wlth a llquld co~posltlon, or by applying the compound in solid orm to the soil, e.g. in granular form (soil appllcation). The compound of formula I may also be applied to seeds (coatlng) by impregnating the saeds either with a liquld formulatlon containlng sald compound, or coating them with a solid formulation. In special casas, further types of appllcation are also possible, e.g. seloctivo treatment of the plant stems or buds.

The compound of formula I is used ln unmodifled form or, preferably, together with ths ad~uvants conventionally employed in the art of formulation, and is therofore formulat0d in known manner e.g. to emulslflabla concentrates, coatable pastes, directly 6prayable or dilutable solutions, dilute emulsions, wettablo powders, soluble powders, dusts, granulates, and also encapsulations ln e.g. polymer substances. As with the nature of the compositions, tho methods of appllcatlon, such as 6praying, atomlsing, du~tlng, scatterlng, coatlng or pouring, are chosen in accordance with the lntonded ob~ectivos and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 ~g of active lngredient (a.i.) por hecta~e, preferably fro~ 100 g to 2 ~g a.l.lha~ most preferably from 200 g to 600 g a.i./ha.
: ' The formulations, l.e. the compositions or preparations containlng the compound (actlve ingredient) of formula I and, wher~
appropriate 7 a solid or liquid ad~uvant, are prepared in known manner, e.g. by homogeneously mixing and/or grindlng the active ingredient with extenders, e.g. solvents, solid carrier& and, where appropriate, surEace-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containlng 8 to 12 carbon atoms, e.g. ~ylene mixturss or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatlc hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketone6 such as cyclohexanone, strongly polar solvents such as ~-methyl-2-pyrrolldone, dimethyl sulfoxide or dimethylformamlde, as well as vegetable oils or epoxidised vegetable oils 6uch as epoxidised coconut oil or soybean oll; or water.

The 601id carrlers used e.g. for du6ts and dlsper61ble powders, are normally natural mlneral flller6 such as calcite, talcum, kaolin, ~ontmorillonite or attspulgite. In order to improve the physical properties it ls also posslble to add highly dispersed silicic acld or hlghly dl6persed absorbent polymers. Sultable granulated adsorp-tive carriers are porous types9 for example pumice, broken brick, sepiollte or bentonlte; and su~tabl0 nonsorbent carrlers are materlals such as calclte or sand. In addltlon, a great number of pregranulated materlals of inorganic or organic nature can be used, e.g. especially dolomlte or pulverisad plant residues. Particularly advantageous appllcatlon promotlng ad~uvants whlch are able to reduce ~ubstantially the rate of appllcatlon ara slso natural (anl~al or vagetable) or synthatlc phosphollplds of the serles of the cephalins and leclthin6, e.g. phosphatidyl ethanolamlne, pho6phatidyl serine, pho8phatidyl chollne, sphlngomyallne, phosphat-ldyl lnosltol, phosphatldyl glycerol~ lysolacithln, plasmalogenes or cardlolipln, wh:Lch can be obtained e.g. from animal or plant c0116, 36~

ln partlcular from the brain, heart, liver, egg yokes or soybeAns.
Examples of useful physlcal forms are phosphatldyl choline mixtures.
Examples of synthetic phospholipids are dioctanoylphosphatidyl chollne and dipalmitoylphosphatidyl choline.

Dependlng on the nature of th0 compound of formula I to be formu-lated, 3uitable surface-active compound6 are nonlonlc, cationic and/or anionic sllEactants havlng good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anlonic 6urfactants can be both water-601uble soaps and water-soluble synthetic surface-actlve compounds.

Suitable soaps are the alkali metal salts, alkallne earth metal saltB or unsubstituted or substituted ammonium salts of higher fatty acid6 (C1O-C22), e.g. the sodium or potassium salts of olelc or stearlc acld, or of natural fatty acid mlxtures which can oe obtalned e.g. from coconut oil or tallow oil. Mention may also ba made of fatty acid methyllaurin salts~

More frequeDtly, however, so-called synthotic surfactants are used, especially fatty sulEonates, fatty sulfates, sulfonated benzlmid-azole derivatives or alkylarylsulfonates.

ThP fatty sulfonates or sulfates are usually in the form of alkall metal salts, alkaline earth metal salt6 or un~ubstltuted or sub-stituted a~monium salts and contain a C8-C22alkyl radical which also lncludes the alkyl moiety of acyl radlcal~, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and 6ulEonic acids of fatty alcohol/ethylene oxide adduct6. The sulfona-ted benzimidazole derivatlves preferably contain 2 sulfonic acid groups and one fatty acld radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamlne salts of dodecylbenzenesulfonic acid, dibutylnsphtha-lenesulfonic acid, or of a naphthalenesulfonlc acid~formaldehyde condensation product. Also suitable are corre~ponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol wi~h 4 to 14 moles of othylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatlc or cycloaliphatic alcohols, or saturated or unsaturated ~atty acids and alkylphenols, said derivative6 containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms ln the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms ln the alkyl molety of the alkylphenols.

Further suitable non-ionic surfactant6 are the water-601uble adducts of polyethylene oxlde wlth polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol contalning 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds u6ually contaln 1 to 5 ethyl~ne glycol units per propylene glycol unit.

Representative axamples of non-lonlc surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropyleneJ
polyethylene oxide adducts, trlbutylphenoxypolyethoxy~thanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters o~ polyoxyethylene sorbitan, e~g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are pre~erably quaternary a~nonium salts which contaln, as N-substituent, at 18a6t one C8-C22alkyl radical and, a~
f~rther substituents, unsubstituted or haloganated lower alkyl, benzyl or hydro~y-lower alkyl radicals. The salts are prefsrably in the form of halide6, methylfiulfates o~ ethylsulfates, e.g. stearyl-trimethylammonium chlorlde or benzyldi(2-chloroethyl)ethylammonium bromida.

.:

f~

The 6urfactants customarily amployed ln the art of formulatlon are described e.G. ln "McCutcheon's Detergents and Emulsifier6 Annual", MC Publishing Corp., Ridgewood, New Jersey, 1~81;
Slsley and ~ood, "Encyclopedia of Surface Active Agent6", Chemical Publishing Co. Inc., New York, 1980;
Helmut Stache, "Tensld-Taschenbuch" (Handbook of Sur-factants~, Carl Hanser Verlag, Munich/Vienna, 1981.

The agrochemical compo6itions usually contain 0.1 tD 99 %, prefer-ably 0.1 to 95 Y0, of the compound of formula I, 99.9 to 1 %, preferably 99.8 to 5 %, of 8 solid or liquid ad~uvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.

Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ dilute formulations.

The compofiitions may also contaln further ingredients such a6 stabilisers, antifoams, vlscosity regulators, binders, tackifiers a6 well as fertiliser6 or other actlve ingredient6 in order to obtain special effects.

Such agrochemical compositions also constitute an ob~ect of the present lnvention.

The invention is illu~trated in more detall by the followlng Examples, without implying any restrlction to what is described therein.

, , : : , .

- 12 - 2148~-6921D

1. rr~paratory Examples (Example 1.2 is the ~ject o~ the divisional applicatlon) xa~el~ 1.1 Prcparatlon of 2,2-dlfluoro-4-¦2'14'~dlnltro-6'~(trl-fluorometllYl~anll~

/Dx~ I O~N~ Cl L1011~11,0 _ ~2 02N~ Nll ~ /
CF ~ of ~0 \/
- F/~F
20.8 g of Ll0ll~ll20 are addud at O~C to a 601utlon of 24.5 g of 2,2-dlfluoro-4-amlno-1,3-banzodloxolo in 70 ml of dlmathyl sulf-oxlde. Tha mixture ls thon stlrrud for 20 minutus. Subsuguantly, ~
6nlutlon of 38.3 ~ of 2,4-dlnltro-6-trlfluoromethylchlorobenzona in 70 ml of dlmethyl 6ulfoxldu i5 addud, and the ruGultant resctlon mlxturu i8 stlrred at O~C for 20 minutafi and thun heatad to room temperatur~. After 5 hours~ thu mixturu 1~ pourod into 350 ml o~
uatar, acldlflud ulth dilute hydrochlorlc acid and extracted saveral tlmes wlth die~hyl ather. Ths comblnud etllor pha6e6 ara washud tll~0a tlmes ulth a 5 X solution of sodlum carbonate and tllen wltll 5 X
hydrochlor c acld and drlud oYa~ sodlum fiulEata, an~ tha Gol~ont 16 uYaporated off ln vacuo. Tho resldue comprlse6 51.6 e of oranga-brown crystals which ara rocry6talll6ud ln toluenu.
Ylel~: 41.6 g; meltlng polni: 14b-146C.

Exampla 1.2: Preparntlon of 2,2-difluo~n-4-fimlno-l,3-benzodloxolu ~ONI12 ~i~l2 .SSS \,f \~ Dr2lKOII ,;~
~ !\o~ o/~F

52.5 g of bromlne are added dropwl6e at 0C to a solutlon of 120 g of pota~slum hydro~ide ln 780 ml of water. Sub6equently, so.a g of 2,2-difluoro-4-carbamoyl-1,3-benzodioxole are added, and the reactlon mi~ture is stir~ed for 30 minute6 at room temperature and then heated for 45 mlnutes to 80C. The reaction solution ls then diluted ln 400 ml of water and distilled with steam. Thc distlllate is e~tracted with diethyl ether and dried over sodium sulfate. The solvent ls evaporated off, affording 38.1 g of the title co~pound as a yellowish oil with a refrac~ive lndex nDlof 1.4955.
xample 1.3: Preparation of 2,2-dichloro-4-carbonyl chloride 1,3-benæodioxole ICOOH ICOCl E~ \ PCls~ D~oXcl 40 g of 4-carboxy-1,3-benzodioxole are mixed with 150 g of phos-phorus pentachloride, and the mixture is heated to 70C. After 3.5 hours, the temperature i8 incrsased to 90C and then held at thls level for 12 hour6. Sub6equently, the volatile components are dlstilled off at 110C and 2000 Pa, and the re6idue i6 di~tilled off under high va~uum, affordlng 45 g of the tltle compound as a sllghtly yellowish solld.

Example 1.4: Preparatlon of 2,2-difluoro-4-carkonyl fluoride 1,3-benzodioxole ICOCl ICOF
i~ \ti~ X SbF3 ~ O Cl ~- ~

In a dlstillation apparatus, 5S.7 g of SbE3 are added to 59.4 g of 2,2-dichloro-4-carbonyl chloride 1,3-benzodioxole, whereupon a reactlon take6 place immediately. In order to maintain the reaction, ~L2~

~ 14 -the tempera~ure ls 610wly increased, while simul~aneously gradually evacuating. 59.5 g of a red oil distill over at 105-117~C and 66S6 Pa. The distillate is taken up in 100 ml of dlethyl ether and washed with two 150 ml portlons of semiconcentrated hydrochloric acld and then with water. The ether solution is dried over sodium sulfate and the solvent i6 evaporated off, affording 42.0 g of the title compound.
xample_1.5: Preparation of 2,2-difluoro-4~carbamoyl-1,3-b~nzo-dioxole ~OF ~ONh~
E~ ~i' X ~ NH3 ~ X

With ice cooling and stirrlng, 63,6 g of 2,2-difluoro-4-carbonyl fluoride 1,3-benzodioxole are added dropwi6e to 120 ml of a concen-trated 25 % solution of ammonia. In the coUrsQ of several hours a cry6talline slurry i6 formed which is then i601ated by filtration and ~ashed in 6ucces610n with a dilute solution of am~onia and then with water, affording Sl g of 2,2-difluoro-4-carbamoyl-1,3-benzo-dioxole with a melting point of 129.5-131C.

2. Formulation Example~ for the active in~redisnt of formula I
(throughout, percentages are by weight) 2.1. Emulsiflable concentrates a) b) c) the compound of formul~ I2S % 40 % 50 %
calcium dodecylbQnzene6ulfonats 5 % 8 ~0 6 %
castor oll polyethylene glycol ether (36 moles of ethylene oxide)5 % - -tributylphenol polyethylena glycol ether (30 mole6 of ethylene oxide)12 % 4 %
cyclohexanone - 15 % 20 %
xylene mlxture 65 % 25 % 20 %

' ~ .

36~

Emulslons of any required concentration can be produced from such concentrates by dilutlon wlth watsr.

2.2. Solutlons a) b) c) d) the compound of formula I 80 % 10 % 5 % 9S %
ethylene glycol monomethyl etber 20 % - - -polyethylene glycol (mol.wt.400) - 70 %
N-methyl-2-pyrrolidone - 20 % - -epoxldised coconut oll - - 1 % 5 %
petroleum distlllate (bolling range 160-190C) ~ ~ 94 %

These solutlons are sultable for application in the form of mlcro-drops.
2.3. Cranulates a) b) the compound of formula I 5 % 10 %
kaolln 94 %
highly dlspersed silicic acld 1 %
attapulgite - 90 %

The active lngredient i8 dissolved in methylene chloride, the solution i5 sprayed onto the carrler, and the solvent is subse-quently evaporated off in vacuo.

2.4. Dusts a) b) .. ..
the compound of formula I 2 % 5 %
highly dispers2d silicic acld 1 % 5 %
talcum 97 %
kaolin 90 %

Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingrsdient.

~L2~ 4 2.5. Wettable powders a) b) c) the compound of formula 1 25 % 50 % 75 %
sodlum llgnosulfonate 5 % 5 %
sodium lauryl sulfate 3 % - 5 %
sodlum dllsobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
hlghly dlspersed &iliclc acid S % 10 % 10 %
kaolin 62 % 27 %

The actlve ingredlent is thoroughly mlxed wlth the ad~uvants and the mixture 1B thoroughly ground ln a suitable mill, affordinK wettable powders which can be diluted with water to give 6u6pensions of the desired concentration.

2.6. Emulsifiable concentrate the compound of formula I 10 %
octylphenol polyethlene glycol ether (4-5 moles of ethylene oxlde) 3 %
calcium dodecylbenzenesulfonate 3 %
castor oll polyglycol ether (35 moles of ethylene oxlde) 4 %
cyclohexanone 30 %
xylene mixture 50 %

Emulsions of any required concentration can be obtained from this concentrate by dilutio~ with water.

2.7. Dusts a) b) the compound of formula I 5 % 8 %
talcum 95 %
kaolin - 92 %

Ready-for-use dusts are obtalned by mixing the actl~e ingredient with the carriar, and grinding the mixture in a 6uitable ~111.

'~ .

~;241~
- ~7 -2.8. Extruder ~ranulata the compound of formula I10 %
sodlum llgnosulfonate 2 %
carboxymethylcellulo6e 1 %
kaolln 87 %

The active ingredient is mixed and grclund with the adjuvants, and the m1xture ls subsequently moistened wlth water. The mlxture 1 extruded and then dried in a stream of air.

2.9. Coated granulate the compound of formula I 3 %
polyethylene glycol (mol.wt.200) 3 %
kaolln 94 %

The finely ground active ingredient ls unlformly applled, in a mlxer, to the kaolin moistened with polyethlene glycol. Non-dusty coated granulates are obtalned in thls manner.

2.10. Su6pension conce trate the compound of formula I 40 %
ethylens glycol 10 %
nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6 %
sodium llgnosulfonate 10 %
carboxymethylcallulose 1 %
37 % aqueous formaldahyde 601utlon0.2 %
silicone oil in the fcrm of a 75 %
aqueous emulsion 0.8 %
water 32 %

The finely ground active ingredient is intlmately mixed with tha adJuvant6, givlng a ~uspension concentrate from which suspensions of any desired concentration can be obtained by dilutlon with wat~r.

96a~

3. niolo~ical Examples In the following tests (Examples 3.1 to 3.5) tha compound of formula I of the present invention 02N~ NH - ~
\C~3 O~ ~O

and the compound of Example 1 of Cerman OffenlegungsschriPt ~NOz 02N~ -NH-~ \ (A) C~3 ~ F

are subJected to a co~parison of thelr fungicidal actlvity.

Example 3.1: Actlon a~alnst Plasmopara vltlcola on vlnes Residual protective actlon Yine seedling6 in the 4-5 leaf stage are sprayed with a spray mixture (0.006 % a.i.) prepared from a wettable powdcr formulation of the test compound. After 24 hours the treated plants are infected with a sporangia suspension of the fungus. Fungus attac~ is evalua-ted after incubation for 6 days at 95-lOOX relative humidity and 20C.

Example 3.2: Action a~ainst Pyricularia oryzae on rice plants Residual protectlve action After a cultlvation period of 2 weaks, rlce plants are sprayed with a spray misture (0.006 % a.i.) prepared from a wettable powder for~ulatlon of the test compound. After 48 hour6 the treated plants .

are lnfectPd wlth 8 conldia suspen6ion of the fungu6. ~valuation oE
fungus sttack ls made after incubation for 5 days at ~5-100%
relatlve humldlty and 24C.

Example 3.3: Action a~ainst Cercos~ora arachidicola on ~oundnut plants Resldual protective actlo_ Groundnut plsnts 10-15 cm in height are sprayed wlth a spray mlxture (0.006 % a.l.) prepared from a wettab]Le powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus. The lnfected plants are incubated for 72 hours at abou~ 21C and high humidity and then stood ln a greenhouse until the typical leaf specks occur. Evaluation of the fungicldal actlon i6 made 12 days after infectlon and is based on the number and si~e of the 6peCkS.

Example 3.4: Actlon a~alnst Venturla in~g~ rple shoot6 Resldual protective action Apple cuttlngs wlth 10-20 cm long fresh shoot6 are sprayed with a spray mlxture (o.006 æ a.l.~ prepared from a wettable powder formulatlon of the test çompound. The plants are lnfected 74 hours later with a conldla suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relatlve humldity and stood in a greenhouse for a further 10 dayR st 20-24C. Scab infe6tation ls svaluated 15 day6 after lnfectlon.

Example 3.5: Action a~sinst ~otrrtls clnerea o~ ples Resldual protectlve action Artlficlally da~aged apples are treated by dropping a spray mixture (0.006 % a.i.) prepared from a wcttable powder formulatlon of the test compound onto the ln~ury sites. The treated frult6 are then infected wlth a conidia suspen6ion of the fungu& and lncubated for :' '`` .

::

~.248~6~

1 week at high humidity and about 20C. Evaluatlon i5 made by counting tlle number of in~ury sites attacked by rot and deducing the fungicidal actlon of the test compound therofrom.

Results:

Com- Test organisms (FUNGI) pound . . .
Plasmo- Pyricu- Cercospora Venturia ~otrytl~
para larla arachidlcola inae- clnerea I viticola oryzae quali A _ ~ _ Evaluation:
-The rating is bAsed on the percentage fungus attack in comparisonwith untreated and lnfected controls.
Rating % attack O O - S

3 ~ 50 (inactlve) Example 3.6: Action a~ainst OP-re61stant s~ider mites (Tetranychus clnnabarlnus) 24 hours before treatment~ bean plant6 ln the priMary leaf stage are populated with a mixed group of Tetranychus. The plants are then treated with the test solution containing 200 ppm of the test compound. Evaluation is made after 7 days to dstermine the mortality of the vsrious stages. In this test, the compound of the inventlon exhib~ts full activity (no llving indlvlduals).

Claims (2)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. The compound of formula II

(II)

2. A process for the preparation of the compound of formula II, according to claim 1 which process comprises subjecting the compound of the formula to Hofmann degradation with bromine, in the presence of aqueous alkali metal hydroxide.