DE1542994A1 - New fungicidal preparations and methods for combating fungi and infections in humans, plants and animals - Google Patents

Description

U _{1 nF71966} DipLJng H. ZOEPKE te * 2 »9 4. ^^ '^ t" ^ltL

PIi

N. V. PHILIPS "GLOElLAMPEiSTABPJEKEN, ΕΙΝΏΚ0Υ1 & / H0M4ND

"lev · fungizid · Frlpara / w <s and Yerfahi«?} buI- Pi Ix- ühJ! »Foklions« in Μφκβοίιβη, Fflanssen and Ti. »r # n. ^rt

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ode? f1 # r «n MFid φ? freift fl ^^ witilnd · or Rto * f ^> « _t die ir. ffr da« liöftfes'l ^ Ä viii ·; Ptlwm gfef ^ igf *: · »· TcrhSltnifty ^ i V5rk; il ^r r, '., -

laa den ff !, 'dis «r« Sh.nt «r. Eatsßovt &r;"cr'^ li ^ l: - · ^ Hlaon

a .inf «« tsr.e _f celebration, ph ^ er = ³ «icu'i ■:? ■» ι? ·!

aini fe ^: · ¹ * · ^ " ^f fi" l "fun ^ liii * ^ itt-Λ κ.ϊ; ueh-i- or

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organic tin eels, antibiotics.

Despite the fairly large number of means, there are some can be chosen for fungus control, there is still one Need for smocks, ir.it improved application possibilities.

Ss a barley of substances was found that not only for common mushrooms, the important KiiJ lurpflarzer. threaten a good " have a fungicidal effect, but first look for the treated plants are jfihytotoxic.

According to the invention, it was found that compounds of the formula

in which form "1 X" inert possibly "represents ubatitvated phenyl residue ^ a" uag "a * iohnet # fungi" id # Viricuztg, namely against i "arable and horticultural occurring"? i1 * infections but also against in Menech ur.d Tier "uftT ^ tonde Hwutpil"". The invention consists * o "lt * ue fuftglgiden PripaWiten, v" loh "di * above feet" ir: Wn Terbindvmgen al "active"! Substances hold for 5 h% * _f dft «Terfahren for processing the g * -» «« inten Verbi.i «feng * n to f« ngi »i4« m PrtpArtten «

Sin «very gat% fungicidal Virk« amk <-: it was used for compounds of the commonwines

in &"rR." int ^ on ei "** · ed" y srsl

ffiit J «1-4 coals ·· in dar? L ei»

008S2S / 2027

^0RIGINAL

Chlorine atoms at positions 4 baw, 2, 4 and 5 or an alkoxy group 1-6 carbon atoms and a cyano or nitro group.

Pie test fungi »idea results were however achieved Bit the connections of the ioreel

-I - Cl

in which R. and IL represent a methyl or a thyroid group. In particular, the "", l-Sieethylaeinoverbindungen produces a high adhesion in a low concentration in a spore fungal association with the spores Pusarium culsroru, Venturi inaequalis and Phytophthora infeatana.

Veiter has found it out! 4a «s this connection against the mushrooms A. niger, C. albioana, Ipidereophyio, Flt ^ jooeum, micro sporun oe is, Trichyphyto BMntagrophjrtes and T. rubrun Wirkeae is«

The compound 4- (1, ¥ -Dieethylaijino) -benzoldiaaotyanld is therefore particularly important for controlling fungal infestation in fields , especially in fruit trees and potatoes. A nematocidal reaction has also been found of the invented compounds, this applies in particular to 4 ^< - (N _> ¥ -Pimethylaniirio5-benzcliazoayanide.

From their use in other habitats it can be expected to control Cercoapora beti-cula in HGben, Pirioularia orjcae in ReiHj Flanmopara vi ti cola in Wp h, grapes \ n \ ä Septoria apii in celery *

It is also necessary to save the connection in "ri'je'rcn PrSpar file; zv process, e.g. «B. be in color to combat multiple Fila, "di" ^one is able "In addition, the V" kBnnen rbindimgen as Se * * -üniterte \ Icher

009826/202?

BATH ORIGINAL '

be used. In general, it is used in agriculture The compound according to the invention is considered to be a dosage of 1-10 kg of active compound per ha.

For use in aoker and horticulture, the Usual forms of administration can be selected, e.g. rcischbare T'le, Wettable powder} dust or granules. Ea have become granules and Wettable powder proved to be particularly suitable.

JT-r the production of mixable CIe, the aVtive

^ binding in a suitable solvent that is poorly soluble in water

dissolved and an emulsifier is added to this solution. Suitable Solvents are, for example, xylene, toluene diol, petroleum distillates, which are rich in aromatic compounds, *, B. So lventn aphtha distilled · "TeerCl further tetralin _r Zyklohex n * or Ki" ohungen this Flt e "igk * ith _t Al · BeuLgatoren can be used inter alia, Alkylphenojqrglykoi |! Lth» r _f Pol / oiylthjrleneorbitaneeter od of · fatty acids " The polyoxyethylene orbitol esters of fatty acids, eggs of these types of emulsifiers are available under the trade name Triton ¹¹ ! "Tween", and "Atlox" known «

The concentration of the active compound in that in water

ψ Badly soluble fluids are not set up. she

can vary, for example, from 2 to 30% by weight. The Misohbaren oils are einulgiert in water before use and the Eaulaion obtained verepritet Xn · d "r ^ is the rule Koneentration of active compound in these wleerifsn BKulsionen iwieohen 0.01 and 0 _t 05 wt..

Wettable powders can be produced djiduroh, because ·· dl « active compound with an inert Trtgematerial is venoisoht and ground, in the Hegel in the presence of a dispersion and / or "Het * nittela. Before use, the wettable powders are in a liquid"

009826/2027 bad original

The ability to disperse in Yaeeer, uni this diapereion is allowed.

Possible carrier materials include, for example, clay, diatomaceous earth, kaolin, dolomite, talc, gypsum, chalk, bentonite, attapulgite, kieselguhr, time, wood flour, tobacco dust or ground coconut halves. Suitable Dispersants and lignosulfonates and saphthalene sulfonates. ale Letting agents can be used fatty alcohol sulfonates, alkyl aryl sulfonates or fatty acid condensation products, i.B. those under known by the trade name "Igepon".

Auoh in the Sprits powders are the concentration of the active ones Connections no strict limits set. In general, one becomes the Concentration »wipe 10 and 30 select Oew.ji *,

Stlut & ulvar can be produced by having a active «connection per se or in a» LSeuneaittel dissolved on a fixed support is brought at Oebrauoh this is done on the Preparations made in trooknea or finely powdered condition into the air * These powders can, if suitable lightweight carriers

t materials are chosen, also on the »primary division of fuel powders All carrier materials know the substances mentioned above in the description of the production of fuel powders into consideration. As a rule, the concentration of active compounds in the tube powder is lower than that in the syringe powder or oil that can be consumed. However, it is higher than the consensus of the active dilution in dispersions or emulsions which can be obtained through the use of fuel powders or "wherever possible". The compounds according to the invention can be used for skin fungus testing

BATH 009826/2027

Obliche width zv skin preparations such as skin wash, ointments, creams, "emulsions or Γ <1 solutions are processed,

Particularly wettable powders have proven to be very suitable for the implementation of the invention. The active substances of the preparations according to the invention can be prepared in a manner known for the preparation of analogous compounds. A suitable process is that according to which a compound of the formula X-EH ₂ , in which X represents an optionally substituted phenyl radical, is diasotized with an alkali metal nitrite and then the diasonium compound is reacted with an alkali metal cyanide.

In this way, inter alia, were accomplished in the making of the invention

2- (K, I-dimethylaraino) -benzenediazcxyanide.

4 - (*, I-T) ie «thjrlaBir.o) ~ benzoldlaEoayanid.

Z ₉ 4 _f ^ -Triohloro-betitoldi & zozyanid «

4-chloro-benioldiazoiyanide,

4 -Me thozgr-ben % oldi az ozy an i d.

4 ^a * Z / ano-ben2oldiftxozyanid »

2-chloro-benzene di-soayanide

4- * itro-benB0ldiaaoeymnid

3,4-Diohloro-ben "oldiazo * yanid

2,6-diohloro-beneoldiaaoiiyanide.

009828/2027 bad original

Execution examples i

1, ^ Zyariotaenzolt uazocyanide .

5ι9 £ 4-cyanoaniline are listed in 15 »6 c * concentrated HCl and diazotized at -5 ° C with oa 4» 5 £ s ^ CL, which is poured in 8 ccrt H ₂ 0, the solution is avf -18 C and wäeariges KCV (3 "4 S in 6 oom H _? 0) is added drop-white. The red lump formed is washed free with water and absorbed in three hours Room temperature the stench becomes lousy eir.gedvaiet «t. The cocatarid is crystallized from cyclohexane. Αυβ-prey 2 g _f SchmelziianV: +, 141-142 C under Z «rs« f-ZT * »£, 2, Sii-Ptchlcrbenzoldiagozjanid .

32.4 g of 3,4-dichloroilin are dissolved in 9 1/2 cc of concentrated HCl with 90 ocff water. Thereafter diausotiert at -5 ⁰ C with 13.8 g TIaIfOp in a little water,! Fold cooled to -1C ° C, a LSaung of 26 g of KCS in 50 ^co * Wa "8 * r drop far" eti ^ ESpecify. The formed liieder-3 chi ag is washed with Ciawaeger eSurefr'i and in PetrolStVier Ither 1 * 1 exactly, laughing nextBi stand at Ziitnifrteniperaiiur wire! cooled to -50 ° C and filtered off. About 10 g of red crystalline product are obtained that can be cleaned by recrystallization aua PetrolSther 4O-6O | Sohnelxpunkt ί4-ίί ° C with decomposition, 3i 2 ^ $ -

This connection is made in the same way as the 3,4-dichloro derivative. However, Ea is not followed by crystallization at "cooling to '50 C. The L8eunf is therefore eingedunstet and ROckBtand is purified by L8sunf in Idgroin and cooled to -5o C ^0. Yield approx. 5 g of roAe crystals, melting point 92-94 ° C with misting,

0 0 9 8 2 6/2027 & D

4th

17 g of 2-dimethyrlaminoaniline are dissolved in 250 co «HpO, to which 50 cob concentrated HCl have been added. At -5 ° C ait 8.7 g of WaIO ₃ , which is dissolved in a little water, is diazotized. 250 g of you and ¹ 3> 5 g of soda in 63 cca of water are added. A solution of 20.6 g of KCl in 45 ecm of water was added with stirring. Kaon two-door. Digea carrots, the plumage was sucked off. Yield 20 g, melting point 66 ° -θ ° C after uacrystallization from ligroin. 5 · 2-MethjrW- (ljT-l) iltbjrl «ino) -b« nzoldiazoayanld .

25.5 β 2-methyl-4-ditthjrlaainoanilin were diazotized in 100 coa. And 40 al concentrated hydrochloric acid at -5 ° to 0 ° C bit 7 g latriuenitrite. Approx. 15 Hin. After the Fitrit had been added, 200 g of bis were added, after which a solution of 11.1 g of soda in 50 ml of water was added dropwise. The reaction after that was still acidic. A weight of 16.5% Kaliunzjanld in 35 ml of water was added dropwise to Danaoh. After a three-hour listening session, a red, crystalline song base was formed, which was vacuumed off, washed with water and dried. Yields 15.8 g, melting point 114-115 ° C. below ψ Decomposition"

6. In a spore germination experiment ait spores from Pua * riua '.- \

oulacru · tm * Tenturia inaequalls were naoiuit * nde fabrics under the * eMt 4-Ofelor-BenzoldiMozjranid (i)

4 - (»laeth / laaino) -ben * oldiaeoiyaHid (£);", ..

4-aijrBno-beiizoldlazozjranid (4) '* /

4-iitro-benzene diazocyanide (5)

4- (DiIthyla «ino) -benzenediazozyanid

009826/2027 BAD o _{RIQ (NAL}

For all connections, (t) to (6), it was found that the KLD (Mean · Lethal Dosia) -itert, i.e. the mean concentration at which

Spores is killed, lay between 4 and 6.5 »(These numbers correspond to the negative logarithm of the single concentrations given in g / l). . 7. Fhytophthora-Blattverayoh i

She ia Example 6 mentioned substances 1 his <were in

an OlasaOhl «with the addition of a surface-active substance, finely distributed in water. Cut toeat sheets were sprayed with various consantrations of these suspensions. For this purpose, 9 flowers, the underside facing up, were spread horizontally on a piece of filter paper of 1000 °, and 3 ml of the suspension was uniformly distributed over this area with the help of a spray syringe. The leaves were then divided into a bottle with water and the stems were old. When the fuel was dried out, the animals were infused with a suspension containing 100,000 zoospores of the Pilate Fh / tophthora infeetane per ooa. The bottles of old leaves were kept in a dark place, in a relative humidity of 9% -100 % and a temperature of 15 ° C. For 24 hours the laj »» 1t Leuehtsioffröhren voe Ta «» »High type on a Beleuofatunga thickness of 34KXMkXX) Ix. "Ur Hia · der Fflansan» illuminates the temperature to 10 ° C », Vaob had 3-4 days on the lZatto ^ rfllok · Pl »oiwn develop, AIa i» HJtUl for all «concerningta

Terbjüfidungen raiehHo »vnt« jr 4er Hilft · dar fssaaten llattob * rflltJh # stayed. In addition, the "de * infestation voe" went further ahead

Fhjrtophthora-FilB as strong »t * n old connection (?) Can be encountered.

BATH 009826/2027

-10- PHN. 1315

8. Phytophthora effects aiauerversuoh .

The substances 1-6 mentioned in Example 6 were finely distributed in a QleMBQhle with the addition of a surface-active substance in Waeeer. The top of the butter from potted tomato plants 15-20 ca high was sprayed with this suspension, concentration ρ 3.5. The plants were placed in a house. Three days later another group of plants was sprayed with the same substances in the same way. Once the spray liquid of these plants was dry, both groups were infected with a suspeneLon containing 100,000 zoo apores of the fungus Phytophthora infestans per ml, with 1.5 »1 suspension being sprayed per plant. The plants were stored under a plastic cap for 36 hours and kept moist. The cap was then removed and the plants stood in the greenhouse for 48 hours , 9 » Apple aohorf . ,

Yereuohe an Unterstjaaen In a Tersuohsgarton , a) PrKvintiv · Sprinting.

The fabric 2 gea & as example ί was in an OlasaChle under Tojr »b · a surface-active substance ·· finely distributed in water. Braus sen, la Tersuchsgarten, were under "tlMM von AjpfelbluÄen (Pray »• Hing Nil) ait this suspension In various accounts tr ations bwspritstj per concentration were 10 shoots, each with 1 ^ B suspension, splattered. When the liquid was dry, all the shoots were dead 1 ^ al of a suspension in front of spores of Van Türla inaequalis, the 180000 Sportfh per ml contained, infected. ■ In order to keep the flowers free during the incubation period, the shoots poured into a cunate cloth bag

009828/2027 ^8AD ° R'GfNAL "

light, which remained open on the underside, and in order to keep the temperature in these bags below reasonable limits, water was first stubbed for a while during the serene periods and during the daytime from time to time water over the plants. After 48 hours the Xunetoff bags were removed and the sprinkling stopped. When the temperature rises to 25 C, it was rained again. Three weeks after vaccination * The infestation is assessed · b) Wi rkxmgadauerve reuoh .

Aue the substance 2 aue example 6 a spray powder was produced, because 20 $ C active component, 6% inagesamt contained surface-active substances and 74 ^ kaolin Infection periods of different lengths were chosen, during which the substance sprayed on the plants was exposed to the usual climatic conditions. Aue this attempt he ^ ab eich the udf> backatSbidige WirV.mig, difl beeeer was alß that of a well-known fungicide, Sonnte rve izen _f breed Pe co, was kneadable with opyr «n of Tille tia oariee, the exciter of Stelnbrand , infected | Part of the contaminated seed was treated with a seed decontamination agent whose substance 2 content in Example 4 was 25%.

The dosage was 4 g of the formulated substance per kg of seed. This 3e * tg * V was filled out in small beds in a Tereuohsgarten ^.

harvested, vmm bein vnbehanAelt "*, nioht-dehaeuohten seed was not the case.Utallohe pre-genoawnene Yereuohe with oats, breed KaXiIe ₁ veroeuoht 'with spores of Uetilago Avenae and wheat, contaminated with Tusarium nivale averaging that with the ^ urrind Fabric 2 ai: s den

009826/2027 BAD

-12- FHN. 1315

Example 6) "ine considerable reduction dee Pils Infestations in comparison with a control sample, can be achieved Vcann.

009826/2027 BAD or _1G1N al

Claims (3)

If you have a single copy May vvircen mrlii neandort -13- PATBT TABSPHÜECHE ι " , Pr5paraU», di>? Zv.r killing.of mushrooms (Fur. ^ I) bei Humans, plants, animals and seeds suitable air, d, dadv.rch Zt * ichn ι that the PrSparut as an active substance t \ infi quoted effect one Compound of the general formula X-W - N - Ca V in the X a gtff. fuabdtituierten Benzolr ^ st daruteilt, and further n \ n odor more solid or PlHHsi £ *> TrSgermaterialien, wetting agents, Eir.ulgierun ^ SRII ttel ud ^ l. contains » 2. Preparations no change 1, thereby indicating that a din aKtivö Verbindun _t · a substance of formula . H . N - Ca! is, in which R is one or more halogen atoms, especially chlorine, one substituted by 1 or 2 alicyl groups with 1-6 carbon atoms each Araino group, oiler in the R, an Alkoiygruppe, a Zyangrvppe or a nitro group can leg. 3. Preparations according to Claim 2, characterized in that the active compound is a substance of the formula - N. N - G «Ϊ j in the R, one of one or two alkyl groups, each with 1-6 carbon atoms / or one »or three chlorine atoms at Ίβη positions 4 or 2, jppe Jiet, and 5 (9 ^l; bHtituierte Amitiognippejiet, or an alkoxy group with 1-o carbon atoms or a cyan or nitro group. BATH ORIGINAL 009626/2027 4t. Preparations according to claim 3, characterized in that the active compound a substance of · Porael - CJiH ι iet _t in which R. and R.sup.- are alkyl groups with 1 or 2 carbon atoms and are similar to methoxy groups. . 5 »Method for PilsbetcXapfung, especially Fuiariu» ouleorua ,! Venturia inaequalie or Phytophthora infoetans, in JLcker- tind Oartenbaugevtoheen, characterized in that “the skin which protects against felt infestation is treated with a preparation according to one of claims 1-5. «Tlubt, sprinkled, beepritst or foggy murders» 6, Procedure naoh Anapruoh 5 »characterized by the fact that * · the formulas reveals a connection for FrSparat X -IT - Ci 00S32S / 2027 BATH ORIGINAL