METHOD OF COMBATING HARMFUL FUNGI

PROCEDE POUR LUTTER CONTRE LES CHAMPIGNONS PARASITES

English Abstract

The invention concerns a method of combating harmful fungi which is
characterized in that the fungi, their biosphere or the materials,
plants, seeds, soils, surfaces or areas to be protected from fungal infection
are treated simultaneously together or separately or successively
with an active substance I which inhibits the respiration of cytochrome
complex III and a) with an active substance of formula IIA,
R1-CO--NR2-OR3, in which the substituents have the following meanings: R1 is
hydrogen, alkyl, alkenyl or alkynyl, cycloalkyl or cycloalkenyl,
optionally substituted aryl, hetaryl, heterocyclyl, arylcarbonyl or
hetarylcarbonyl, R2, R3 designate hydrogen, alkyl or aryl, or b) with an
active substance of formula IIB, R a-CO-NR b-R c, in which the substituents
have the following meanings: R a is optionally substituted phenyl,
furyl, dihydropyranyl, oxathi-inyl, oxathi-inyl dioxide, pyridyl or thiazolyl;
R b is hydrogen, alkyl or alkoxy; R c is optionally substituted
phenyl or cyclohexyl, and mixtures suitable therefor.

French Abstract

Procédé pour lutter contre les champigons parasites, caractérisé en ce que les champignons, leur biotope ou les matériaux, végétaux, graines, sols, surfaces ou espaces à protéger contre l'attaque sont traités simultanément, conjointement ou séparément, ou successivement, par une matière active (I) inhibant l'inhalation du complexe cytochrome (III) et a) par une matière active de formule (IIA): R<1>-CO-NR<2>-OR<3>, dans laquelle les substituants ont les significations suivantes: R<1>: hydrogène, alkyle, alcényle ou alcynyle, cycloalkyle, ou cycloalcényle; aryle, hétaryle, hétérocyclyle, arylcarbonyle, ou hétarylcarbonyle éventuellement substitué, R<2>, R<3>: hydrogène, alkyle ou aryle, ou b) par une matière active de formule (IIB): R<a>-CO-NR<b>-R<c>, dans laquelle les substituants ont les significations suivantes: R<a>: phényle, furyle, dihydropyranyle, oxathi-inyle, oxathi-inyle-dioxyde, pyridyle ou thiazolyl éventuellement substitué; R<b>: hyrdogène, alkyle ou alcoxy; R<c>: phényle ou cyclohexyle éventuellement substitué, ainsi que par des mélanges de ces composés appropriés pour lutter contre une telle attaque.

Claims

32


We claim:



1. A method for controlling harmful fungi, wherein the fungi,
their habitat or tho materials, plants, seed, soil, surfaces
or spaces to be protected from fungal attack are treated
jointly or separately at the same time or in succession with
an active ingredient I of the formula IA or IB

Image
used [sic] where

R' is -C[CO2CH3]=CHOCH3, -C[CO2CH3]=NOCH3, -C[CONHCH3]-NOCH3,
-C[CO2CH3]=CHCH3, -C[CO2CH3]=CHCH2CH3, -C[COCH3]=NOCH3,
-C[COCH2CH3]=NOCH3, -N(OCH3)-CO2CH3, -N(CH3)-CO2CH3 or
-N(CH2CH3)-CO2CH3,

R" is a C-organic radical, which is bonded directly or via
an oxy, marcapto [sic], amino or alkylamino group, or
together with a group X and the ring O or T to which they
are bonded, an unsubstituted or substituted bicyclic,
partially or completely unsaturated system which, in
addition to carbon ring members, may contain hetero atoms
selected from the group consisting of oxygen, sulfur and
nitrogen,

R x is -OC[CO2CH3]=CHOCH3, -OC[CO2CH3]=CHCH3,
-OC[CO2CH3]=CHCH2CH3, -SC[CO2CH3]=CHOCH3,
-SC[CO2CH3]=CHCH3, -SC[CO2CH3]=CHCH2CH3,
-N(CH3)C[CO2CH3]=CHOCH3, -N(CH3)C[CO2CH3]=NOCH3,
-CH2C[CO2CN3]=CHOCH3, -CH2C[CO2CH3]=NOCH3 or
-CH2C[CONHCH3]=NOCH3,

R Y is oxygen, sulfur, =CH- oder =N-,

n is 0, 1, 2 or 3, and the radicals X may be different when
n is > 1,



33


X is cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloylkyl
[sic], C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or,
where n is > 1, a C3-c5-alkylene, C3-C5-alkenylene.
oxy-C2-C4- alkylene, oxy-C1-C3-alkyleneoxy,
oxy-C2-C4-alkenylene, oxy-C2-C4-alkenyleneoxy or
butadienediyl group bonded to two adjacent carbon atoms
of the phenyl ring, where these chains in turn may carry
from one to three of the following radicals: haloger,
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy or C1-C4-alkylthio,

Y is =C- or -N-,

Q is phenyl, pyrrolyl, thienyl, furyl, pyrazolyl,
imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thia-
diazolyl, triazolyl, pyridinyl, 2-pyridonyl, pyrimidinyl
or triazinyl and

T is phenyl, oxazolyl, thiazolyl, thiadiazolyl, oxadi-
azolyl, pyridinyl, pyrimidinyl or triazinyl,

and a synergistic amount of

a) an active ingredient of the formula IIA

Image
where

R1 is hydrogen,
C1-C10-alkyl, C2-C10-alkenyl or C3-C10-alkynyl,
C3-C8-cycloalkyl or C4-C8-cycloalkenyl,
aryl, hetaryl, heterocyclyl, arylcarbonyl, het-
arylcarbonyl, where the radicals may be partially
or completely halogenated and/or may carry from
one to three of the following groups:

- cyano, nitro, hydroxyl, mercapto, amino,
carboxyl, aminocarbonyl, aminothiocarbonyl,
C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkyl-
sulfonyl, C1-C6-alkylsulfonyl, C1-C6-alkoxy,
C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl,
C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-
alkylamino, C1-C6-alkylaminocarbonyl,



34


di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-
aminothiocarbonyl, di-C1-C6-alkylaminothio-
carbonyl,
- C2-C6-alkenyl, C2-C6-alkenyloxy or C1-C6-
alkylcarbonyl, where these groups may be
partially or completely halogenated,
- C3-C6-cycloalkyl, benzyl, benzyloxy, aryl,
aryloxy, arylthio, hetaryl, hetaryloxy or
hetarylthio, where these groups may be par-
tially or completely halogenated and/or may
carry from one to three of the following
radicals: cyano, nitro, hydroxyl, C1-C4-
alkyl, C1-C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy or C1-C4-alkylthio,
- C(=NOR i)-A x-R ii where
R i,R ii independently of one another are each
hydrogen or C1-C6-alkyl,
A is oxygen, sulfur, amino or alkyl-
amino and
x is 0 or 1, and

R2 and R3 independently of one another are each hydrogen,
C1-C6-alkyl or aryl

or a synergistic amount of

b) an active ingredient of the formula IIB

Image
where
R a is phenyl, furyl, dihydropyranyl, oxathiinyl, oxathiinyl
dioxide, pyridyl, pyrazolyl or thiazolyl, where these
radicals may carry from one to three of the following
substituents: halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy or C1-C4-alkylthio,

R b is hydrogen, C1-C4-alkyl or C1-C4-alkoxy;

R c is phenyl or cyclohexyl, where these rings may be
partially or completely halogenated and/or may carry from
one to three of the following radicals: C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4- haloalkoxy or
C1-C4-alkylthio.



35


2. A synergistic mixture suitable for controlling harmful fungi
and containing a solid or liquid carrier, an active ingredi-
ent of the formula I as claimed in claim 1, and a synergistic
amount of an active ingredient of the formula IIA as claimed
in claim 1.

3. A synergistic mixture suitable for controlling harmful fungi
and containing a solid or liquid carrier, an active ingredi-
ent of the formula I as claimed in claim 1, and a synergistic
amount of an active ingredient of the formula IIB as claimed
in claim 1.

4. Use of a compound IA or IB as claimed in claim 1 for the
preparation of an agent suitable for controlling harmful
fungi, as claimed in claim 2 or 3.

5. Use of a compound IIA as claimed in claim 1 for the prepara-
tion of an agent suitable for controlling harmful fungi, as
claimed in claim 2.

6. Use of a compound IIB as claimed in claim 1 for the prepara-
tion of an agent suitable for controlling harmful fungi, as
claimed in claim 4.

7. A method as claimed in claim 1, wherein an active ingredient
of the formula IA as claimed in claim 1 is used for inhibit-
ing the respiration at the cytochrome complex III.

8. A method as claimed in claim 1, wherein an active ingredient
of the formula IB as claimed in claim 1 is used for inhibit-
ing the respiration at the cytochrome complex III.

9. An agent for carrying out the method as claimed in claim 1,
which is conditioned in two parts, one part containing a com-
pound of the formula Ia or Ib in a solid or liquid carrier
and the other part containing a compound of the formula IIa
or IIb as claimed in claim 1 in a solid or liquid carrier.

Description

2~95577=
D050/45055

Controll9.ng harmtul fungi

The presant invae:;tian r&latea to a method for controliing harmiul
fungi and to suitable syneryistik: mxxtures for this purpose
which, in addition to an 4ctive ingredient I which inhibits the
respiration at the cytur-,hrome complex 111, caxita.in
s) an aetive ingxedient of the for.mula ITA
R1-CC-Nfi2-9R3 lIA
wherf:

RI is hyd:rogen,
C1-C1a-alkyl, C2-Clo-al,kenyl or C3-C1¾--aikinyl,
Cg-C -cycloalkyl or C4-Cp--cyc7.oal.kenyl,
aryl, hetaryl, heterocyelyl, arylcarb=onyi or hetarvl-
carbonyl, where the radical.s may be pattially or
completely haloq nat d and/or ntay carry from one to
three oi: tha following groups:
- cyann, nitro, hydroxyl, mercttpto, amino,
carboxyl, aminocarbonyl, aIDinothiocarbonyJ.,
Cl-Ca--alkyl, Cl-=C6--haloalkyl, Cx-C6-alkyl-
aulfanyi., Cx-C6'alkylsulfoxyl, C1-C6-a.1-koxy,
C1 C;-haloalkoxy', C1-'Cy-alkoxycarbonyl,
C1-Cr,-alkylthi.o, Cx_C6-a].kylamino, d3 CZ-C6-
alkylamino, Gj-Gd-a.lkyLaminocarbonyl, di-C;,-C6-
alkyl amiciocarbor:yl, Cl-C6--alkyl.aminott:iocarboqyl,
di-C1 =-C6-alkyt am i.nothiocarbonyl ,
-C2-C6-al.kenyl., G2-C6-alkenyloxy or C1--C4-alkyl-
carbonyl, wher.e these group3 inay be partially or
completel.y halogenated,
- Cj-Cb--cycloalkyl, benzyl, benzyloxy, aryl, aryl-
oxy, arylthio, hetaryl, hetar.yloxy or het.aryl-
thio, where these groups may be partially or
completely halogcnated and/or may carry fro,none
to three of tho following radical.s: cyano,
nitro, hyrlroxyl, Cz-Ca-alkyl, C1-C4-haloa':.ky7..,
Cl-Cg--alkoxy, Cl=-Cy-hal.aalkoxy ox Cx-Cq-al.kyx-
th.io,
where
R1,RAx indppnndently of c+ne another are each hydrogen
or C1-Cfi-alkyl,
h is oxygen, sulLuz c,:- NH and.
x is 0 or 1, and


0050/45055 2195577
2
R2 and R3 independently of oncs ancther are each hycii-agen,
C1--C6-alkyL or. aryl

oY conL2tin
b) an acti-ve ingzeditint nf the formllla I.T-B
P.a-i.O-Rh-R* ITB
where
Ra is phenyl, fur.y.l, dihydropyranyl, oxat.hiAnll, oxathi--
inyl. dioxide, pyridyl or thiazolyl, where these
zadicals may carry Prom one to three of the following
substituenxs: halogen, C,-C4-alkyl, C1-Cq-- haloalkyl,
Cx-Cq- allCOxy, C,t-C4-haloalkoxy oz Cl-Cq- a.lkylthio;
Rb is hvdrogen, Ci Cq-a1Sy1 or C;-Cq-alkox, anci

flc is p3ienyl or oyclohexyl, whxre thcye rings may br.
pa.ctially or completely halogenated and/or may caLZy
from orie t.r.> three of Che following radicals:
CL Cq-alky.l, CL-Cq-ha.loalky:l, Ci--C4-alkor.y, C;-Cq-
haloallcoay or C1--04-alkyli,hio.

28 It is known Erom the literature tkrztt active i,ngzedienta which in-
hibit the cytochrome bc complex (cyt.ocltxome complex 141) can be
used as fungicides (a.f. U. Brandt, J. Haase, H. Schagger. and G.
von Jaqow: "Spealf.i.tat; und Wii;kmenhanismus der Str.obiluLi.na;",
Dechema Monograph Vo1..129, 27-38, Vr;H Verlaysgesel.1schKf.1:.
90 Wainheim, 1993; J.M. Clpugri: Nata:,al Product Reports, 1993,
565-574; F. Rohl and H. 5auter: Biochem. Soc. Trans. 22, 633
(1.993)]. 11
Examples of such active ingredie,nts are compounds ot the focmula
35 IA or TB

Y~R' RX
c
r.RY
40 xn ^ Q ~ kn CT
R\ Rtt
IA I B
wh6re


21 55 7 7
,

3
~,,_is a doul~le or single bond,

R' is -C[C029[:133wCHOCi33, -C[CO2CH}J=NUCHj, -C[CONHCH3l=NOCH3,
'"C(CDCH31"NOCH
-C[CO~CIi37~CHCH3, C CO CH CHCH CH,3,
-' [ 2 3l`~ 2 3r
-CjCOCH2CH3)=NOCH3' ti(OCH3) CDgCHg~ -N(CH3)-CO2C1i3 or
-N(CH2CH3)-CO2CH3,

R" is a c-organic radical wliich ia k~onded directly ox via an
oxy, raercapto, anutio or alkylanlino gxoup, or

togeLher witli a group X and the ring g or T to which they are
bonded, an unsubstituted or subst3t.ut d bicyclic, partially
or completely unsaturated system which, in addition to carbon
ring mcembera, may contain hetero atoma aelected from the
g p g ygktn, sul2ur ar.d nitrogen,
1H rou cor.sistin of ox

Rx is -OC[C02C113]=C11OCH3, -oC[C02CH3]-CIICI13, -OC[C02CH3]aCHCH3CH3,
-SC[C02Cf13]-CHOCH3, -8C[C02CH31-CHCH3, -SC(C02CH3]-C.HCH2CH~,
-N(CH3)C[CO~CH37~CHOCH~,, -N(CH~)C[CUzCH3]==NUCH3,
-CH2C[CO2CHJl' =CHOCH71 -C.y2 -^[CO,t=CH3a=NUCH! oc'
-CHzC [ CUNHCFI j ] =430C133 r

P.y is oxygen, sulfur, wr:H- odsr -N-,

n Is 0, 1., 2 or 3, aiid the radicals X may be diff4rc:nt- when n
is > 1,

i; :i.s cyano, nitro, haloqen, Cl--Cg-alkyl, Cl-C,y-heiloalkyl.,
Ci-Cq-alkoxy, C1-C,i-haloalkoxy, C1-Ca--alkyl.thio or, whKre
n is > 1, a C3-'CS-alkYl.ene, Ca-,C,-alkenYleuc, oxY-C ~
a--~a-
xlkylene, oxy.-C1--C3-alkyleneoxy, axy-Cz-Ca-alkenylene,
oxy-C2-C4-alkenyleneoxy or butadienediyl group bonded to two
adjacent carbon atoms of t'he phenyl x'iny', wtiere these chains
in Lurn may carry from one to three of the following
radicals; halo en, ^. C alk l C=-G ha:loalk l., C-C -alkox
9 I"a" Y, I a- Y i n Y.
Cl,-'C,q--haloalkoxy ar CI-.-C4-alkyl.tl:i..o,

Y is ==C-- or -N-,

¾a Q is phenyl, pyrrolyl thienyl, furyl, pyr.azolyl., imiciazcly7.,
oxaxolyl, isoxazol.v]., C.ltiazolyl, thiadiazolyl, triaznlyl,
pyr'_cdi.ny, , 2-p1x.idony-1, py''irnidinyl or triazinyl and

i is phanyl., oxaznlyl, thiaxolyl, L-n..a:3'iazolyl, oxradiazolyl,
95 pyridirLyl, pyrimidinyi or triazinyl.


~ 21 5577
0050/45055

4
auch active ingreciients T(or IA and 28) are described, for
axample, in the EollUwing publications: EP-A 178 826, EP-A 203
606, EP-A 203_608, EP-A 206 523,
EP-A 212 859, 2P-A 226 917, EP-A 229 974, EP-A 242 070,
S EP-A 242 081, EF-A 243 012, EP-A 243 014, EP-A 251 082,
I:P-A 253 213, FSP-A 254 426, EP-A 256 667, EP-A 260 794,
EP-A 260 $32, EP-A 267 734, EP-k 273 572, EP-A 274 825,
EP-A 278 595, EP-A 280 185, FP-A 293 196, EP-=A 299 694,
EP--A 307 101, EP-A 307 103, EP-A 310 954, EP-A 312 221,
EP-A 312 243, EP-A 329 011, EP--A 331 966, EP-A 335 519,
EP-A 336 27.1, EP-A 337 211, EP-A 341 845, EP-A 350 691,
EP-A 354 571, EP-A 363 818, EF-A 370 629, EP-A 373 775,
EF-1 374 811, EP-A 378 308, EP-A 378 755, EP--A 379 098,
EP-P. 382 375, EP-A 383 117, EP-A 384 211, EP-A 385 224,
EP-A 385 357, EP-A 386 567., P;P-A 386 681, EP-A :389 901,
EP-A 391 451, EP-A 393 428, EP-A 393 861, EP-A 398 692,
EP=-'A 400 417, EP-A 402 246, EF--A 405 782, EP-A 407 873,
EP--A 409 369, EP-A 414 153, EP-A 416 746, E,P-A 420 091,
EP-A 422 597, EP-A 426 460, EP-A 429 968, EP-A 430 471,
EP-A 433 233, EP-A 433 899; EP-A 439 785, EP-A 459 285,
EP--A 466 575, .EP-A 463 3$8, EFA 463 513, FA-A 464 381,
EP-A.468 684, EP-A 468 695, EP-A 468 775, EP-A 471 261,
EP--A 472 224, EP--A 472 300, EP-A 474 042, EP-A 475 15$,
EE'--A 477 531, E,E+-A 480 795, EP-A 483 851, EP^-A 483 985,
EP--A 487 409, EP-A 493 711, EP-A 498 188, EP-A 498 396,
EP-A 499 823, LP-A 503 436, EP-A 508 901, EP-A 509 857,
EP-A 513 580, EP-A 515 901, EP-A. 517 301, EF-A 528 245,
EP-A 532 022, EP-A 532 126, EP-A b32 327, E',P--A 535 980,
EP-A 538 097, EP-A 544 581, EP-A 546 387, EP-A 548 650r
EP'-A 564 928, EP-A 566 455, EP-A 567 828, EP-A 571 326,
EP-A 579 071, EP-A S79 124r EP-A 579 908, EP-A 581 095,
EP-A 582 902+ EP-A 582 925, T4P--A 583 806, EP-A 584 625,
EP-A 585 751, EP-A $90 63,0, EP-A 596 254, W0-A 90/07,493,
WQ-A 92/13,830, WO-A 92/18,487, Wo-A 92/18,494, WO-A 92/21,693,
WO-A 93/07,116, Wp-A 93/08,180, WO-A 93/08,183, WU-A 93/15,046,
WO-A 93/16,986, WO--A 94/00,436, WQ-A 94/05,626, WO-A 94/08,948,
WO.-A 94/08,968, WO-A 94/10,159, W0-A 94/11,334, JP-A 02/121,970,
3P-A 04/182,461, TP-A 05/201,946, JP-A 05/201,980,
JP-A 05/255,01.2, TP--A 05/294,948, JP-A 06/025,133,
.7P-A 06/025,142, JP-A 06/056,756, FR-A 2 670 781, GB-A 2 210 041,
G8-A 2 218 702, GB-A 2 238 308, GB-A 2 249 092, GB-A 2 253 624,
GB-A 2 255 092, L7E-A :}9 05 911, Gersan Patunt Application 43 05
502.8,
Germen Petent ApYAicatinn 43 10 143.7, German Patent Appl..ia,ati<an
43 18 397,2,
Gezman Patent Application 43 34 709.6, Ge.nnan Putent ApplS.aa;:ion
44 03 446.6,


~ aa~a~~sas5 21 9 55 7 7

German Patent Applicai.ion 44 U3 447.4, German Patent. Application
44 03 448.2,
German Patent_Applicati,on 44 10 424.3, German Patent Application
44 21 180.5, German Patent Application 44 21 182.1, Geiutan Patenl.
S Application 4415 483.6, Gerinan Patent Application 44 23 615.8
and German Par.bnt Appl.ication 44 23 612.3.

When t-hzse active ingredier,ts are used, however, it is fouud that
their action Is only temporary, ie. further growth of the fungus
]0 occurs atte7r sqt4o time. I

P'urthermore, the literature discloses cotnpounda IIA (G.R. 5oh.cn-
baum at al.: Plant Physiol. 9,j,, (1971) 124-126J which inhibit ttre
cyanide-rasistant respiration in plarrts. However., a tungicidal
action of auclt compounds is not knouzr.

Gompounds ot the formula II8 are disclosed in tkre li'tereiture as
fungicides (o.f. Modern Selective Fungicides, Edit.o H. Lyr, VEB
Gustav 1'isahes Vw_rlqig, JÃina, L'nigaig, 1987, and ttre licerature
cited thers+]. However, these compoun4s do not have a br.oad and
satisfactory action spectrum.

It Is an obj ct of the present invQnti.on to remedy the disadva.n-
t.:ages in the use of the conrpourids IA cr If3.
We have found thaC this cbject is ach:ievpd and that harrnful i:ungi
ca.ri in principie be better controlled it, in addition ta an ao-
tive ingrediant S11 or IS which inhibits tha rraspiration at the
cytochrome compl.ex III, a tuzttier activa ].ngr4dient. of the formu-
la ITA or of Lhe formula IIB is used.

Thw novice.l mer.l:od Is presbably based on th* tact that, when the
respirat.ion at thc cytochromw complex III Is 3.nhibited, the fun-
gus uses a secondary route of alternative rAspiratl.on, so that
complete desr.ruction does nUt eccur. Tnis would mean that the ac-
tive ingredients of Lhe ormula ITA or IIH are auitable for j.n-
hibj.ting alternative reapiration. The oombination of inh.Lbi.t.ion
of both the respiratiõon via the cytochrorne complex III and that
of the alternative raspiration might be responsible for ensuring
that the Sungas is completely desCroyed.

By the novel com.bintation of aorresponding aotive ingreciierit:s,
more effective control of the hnr.mful tunaus is achieved since
lower application rates of the individual active ingredients are
reguired as a result of the combination of the active .in-qredients
Ih or IB and 1'IA or Iib (synerq.i.sCic effect).


;~r^ 7

0050/45055 2t l
~
6
In the novel method, In principle all active ingredients de-
scribed S.n the publications stated at the outset are suitable for
inhibiting ras,piration at thw cytochrome complex III, the corn-
pounds stated in the examples given there being particularly
suitable. Of particular importance are compounds IA and I5 where
g" is ane of the following groups:
unaubstituted or substituted aryloxy, unmubotituted or substi-
tuted hetaryloxy, unsubetituted or substitut.ed aryloxymethylene,
unsubstituted or substituted heturylvxymethylene, unsubstituted
or substituted arylethenylene, unsubstituted or substituted
hetarylettiaz'iylene or a group

RaRAC-NOCH2- or RyON=CR6CRBuN0CH2, where Ru, Rp, Ry, RS and Re in
general and in particular have the meaningas descri.bed in the
publi.caticna which followi EP-A 370 629, 8P-A 414 153, EP-A 426
460, EP-A 460 575, EP--A 463 488, EP-A 472 300, EP-A 498 188,
EF-A 498 396, EP-A 515 901, EP-A w85 751, WO-A 90/07,493,
WO-A 92/13,830, Wp-A 92/18,487, WO-A 92/18,494, WO-A 93/15,046,
WO-A 93/16,986, WO-A 94/08,948, Wo-A 94/08,968, JP-A 05/201,946,
JP-A 05/255,012, JP--A 05/294,948, JP-A 06/025,133,
JP-A 06/025,142, German Patiant Application 44 03 447.., German
Patent Application 44 03 448.., German Patent Application
44 21 180.5 and German Patent; Application 44 21 182.1.;

particularly preferred unsubstitut d or substituted ary.Loxy xnd
unsubstitutad or subs'tituted hetary2oxy radicals in general and
in particular have tha meanirigs described in the puDlications
which fol.lowa EP-A 178 826, EP-A 242 070, EP--A 242 081,
EP-A 253 213, EP-A 254 426, Ep-p, 256 667, EP-A 260 794,
EP-A 230 185, EP-A 30'7 103, EP-A 341 845, EP-A 382 375,
EP-A 393 861, EP-A 398 692, EP-A 405 782, EP-A 430 471j
EP-A 468 684, EP-A 468 695, EP--k1 477 631, ISP-A 483 985,
EP-A 498 188, EP-A 513 580, EE'-A 515 901, WO-A 93/15,046,
WO-A 94/10,159, GB-A 2 253 624, JP-A 04/182,461 and German Pzte.nY.
Application 44 23 612.3;

particularly pref4rred unsubstituted or substituted ax=yjaxymethy-
Ier~e and uzisubst,z.tuted or subat.ituted hetary.to.xymethylene radi-
aals in general and in particular have tha meanings stated in the
publications whict; followa EP-A 178 826, EP-A 226 917,
EP-A 253 213, EP-A 254 426, EP--A 278 595, EP-A 280 185,
EP-A 299 694, EP-A 335 519, EP-A 350 691, EP-A 363 818r
EP-A 373 775, EP-A 378 308, EP-A 385 224, EP-A 386 561.,
EP-A 3.98 692, EP-A 400 47.7, EP-A 407 87.9, EP-A 472 224,
EP-A 477 ~31, EP-A 498 188, EP--A 498 396, EP-A 513 580,
,..
EP-A 515 901, EP-A 579 124, Wn-2 93/08,180, WO-A 93/15,046,
W!7--A 94/00,436, JP-A 00182,461, German Applioation No.


0050/45055 21g 5577
7
43 05 502.., Gorman Appla.cation No. 44 10 424.. and German
Patent Application 44 15 483.61

parta.cularly preferred unsubstltuted or substituted arylatheny-
lene and unsubstxtuted or substituted hetdtry2ethenylene radicals
in general and in pat'ticular hav the meanings dbccribed 9,n the
publicatione wtiich Eol2owi F:P-A 178 826, EP-A 203 606,
EP--A 253 213, EP-A 254 426, EP-1% 280 185, EP-A 378 755,
BP-A 398 692, EP-A 402 246, E2-A 474 042, EP-A 475 158,
FP-A 477 631, EP-A 487 409, EP-A 498 188, EP-A 498 396,
EP-A 513 580, EP-A 515 901, EP-A 528 245, EP-A 544 587,
WO-A 93/15,046, WO-A 94/11,334, FR-A 2 670 781 and German Patent
App].9.cat.inn 44 23 615.8;

particularly preferrad active inyredienta of the Eormula lA where
R' is -C(COZCH33~CHOCHa corraspnn.d in general and in particular to
=the compourids dascr.i.bad in thb publications which follows
EP A. 178 826, EP-A 203 606, EP-A 226 917, EP-A 242 070,
EP--A 242 081, EP-A 256 667, EP-A 260 794, EP-A 278 595,
EP--;q, 299 694, EP-A 307 103r EP,-A 335 519, RB-A 341 845,
EP-A 350 691, EP-A 370 629, EP-A 373 775, EP-A 378 308,
EP-A 378 753, EP-A 362 7'75, EP-.8, 385 224, EP-A 386 561,
EP-A 393 861, EP-A 402 246, EP-A 405 782, EP-h 407 873,
EP-A 414 1.53, EP-A 426 460, EP-A 430 471, EP-A 463 488,
EP-A 468 695, EP-A 472 224, EP-A 474 042, EP-A 475 158,
EP-A 483 985, EP-A 487 409, EP-A 515 901, F-P-A 528 245,
EP-A 544 587, Wq-A 90/07,493, WO~A 92/18,487, W9-A 92/18,494,
WO-A 93/08,180, WO-A 93/16,986, WO-A 94/00,436, WO-A 94/08,948,
WO--A 94/00,968, W0-A 94/10,159, WO-A 94/11,334, FR-A 2 670 781,
,7P--A 06/025,133, German Application No. 44 03 447,., German
Application No. 44 10 424.. and German Patent Applipation

44 21. 180.5; particularlli preLe:rred active ingredients of the f4rmula 7
where
R' is --C[CO2GH31-NOCt33 correspond in general and in parti.culaT to
the cornpound.s desaribed in the publicati.ona which follow:
EP-=A 253 213, EP-A 254 426, EP-A 299 694, EP-A 363 818,
38P-A 378 308, EP-rA 385 224, EP-A 386 561., EP--A 400 41-7,
EP-A 407 873, EP-A 460 575, EP-A 463 488, EP-A 468 684,
EP--h 472 300, EP-A 515 901, Wo-A 94/00,436, W0-A 94/08,948,
W0-A 94/10,159, WO-A 94/11,334, .7P-A 05/201,946, JP-A 05/255,012j
.TP-A 05/294,948, German Appliaation No. 44 03 447,., German
ApFlicat.ion No. 44 10 424.. and 6erman Patent Ap4lic:ation
44 21 180.5;


= 0050/451755
2195577
s
particularly prRferred a^tiwe ing.redients of the formttla I whe-re
R' is -C[C9NHCH31-NQCH3 oarrespond in gwneral and in part i,;u..ar to
the+ compounds-dascribed in the publications which follow:
EP-A 398 692, EP-A 463 488, EP-A 477 631, EP-A 515 901,
EP--A 579 124, EP-P. 585 751, WO-,A 92/13,830, WO-A 93/08,180,
WO-A 94/08,948, WO-A 94/10,159, WO-A 94/11,334, GB-A 2 253 624,
JP-A 04/182,461, JP-A 05/201,946, 7P-A 05/255,012,
JP-A 05/294,948, German Appli.cation No. 43 05 502.., German
Application No. 44 03 448.., German Application No. 44 10 424..,
German Patent B.ppl.i.cation No. 44 23 615.8 and German Patent
}1pp1 i-cat-.ion 44 21 182.11

particularly preferrad active ingr dients of the formuln I where
R' is -C[C0=CH3y] CHCHa or -C[C02CH3]a-CHCH2CH3 correspond in gginerai
anci in particular to the aompounds described in the publications
which follow: EP-A 280 185, EP-A 463 488, EP--A 501 901,
EP-A 513 580, EP-A 515 901, German Application No. 44 03 447..,
German Application No. 44 10 424..,
German Patent Application No. 44 21 180.5 and German Patent
Application No. 44 15 493.6;

particularly preferred active. ingredients of the formula I where
R' ia -C[C0CH3)aN0CH3 or -C[COCH2CH3]=NOCH3 correspand in general
and in particular to the compounds described in EP-A 498 188;
partioularly preferred active i.ngrediente of the formula I wtiero
R' i -N(OCH3)-COZCfl3, -N(CH3)-CO2CH3 or -N(CH2CH3)-C07CH3
correspond Sn general and in pcrticular to the compounds
described in the publications which follow: EP-A 498 396,
WO--A 93/15,046, JP-A 06/025,142 and Gnr.man Patent Application
44 23 612.3;

parLicularly preferred'active ingredients of the fvrmula I where
R' is -OCjCO2CH3]=CHOCHgf -OC[CO2CH3]=CHCH3, flG[CQ2CH3]=CHCHyGH3,
95 -OC[COCH2CH3]RN0CH3, -6C[C02CH3)=CHOCH3, -BC[C02CH37KCHC1i3,
-5C[C01CH3]=CHCHZCfig, -N(CHj)C[C02CH3]=CH0CHJ,
-N(CH3)C[C02CH3] NOCEI3e -Cti2C[CO2CH3]=CH0CH3r -CHzC[COaCHg]~NCCHa or
-C:H;:=:[COhHCH3;=N0CH3 ccaYrespon.j in general and in pa.rtict>>e;r to
the compounds described in the publications which fo.llow:
EP-A 212 859, EP--A 331 966, EP-A 383 117, EP-A 384 211,
EP-A 389 901, EP-A 409 369, EP-A 464 381, EP-A 471 261,
EP-A 503 436, EV-A 546 387, EP-A 548 650, EP-A 579 908 and
EP-A 584 625.

Ex.amplec f pdrticularly suitab].e as;tive ingredients I are listed
1.n the tables below,


= 0050/45055 21 7 5577
9
Table 1.tA

Compounds ot trls formula IA where Q is phenyl, R' is
-C(CO2CH3)rCE4UCH3, n is 0 and R" is unsubstituled or substituted
5(het;)aryloxyraethylene, the unsuhst.itutecS or subst:ituted (het)aryl
group having the following meanings

Ho. unsubskitutad or suhstituted (het)aryl Raferenr;e
7,7R-t 2 UH3 CcH4 1P-A 226 917
I.1A-2 2,5-(Ci13)2--C6H3 EP--A 226 917
I.1A-3 2-CH3, 4-C[CHa1=N6CH3-C6Ha EP-A 386 561
I.1A-4 2-CHaCHaC1I3, 6--CF2-pyrimidir.-4-y3. EP--A 4Q7 873
11
I.lA-5 ~ 2,9-(CH3)2-C6H,~ EP-A 226 917

FTable 1.19

Compounds of the fozmula IA where R' is -C(CO;2CH33)@CHOCH33, Q,is
pllenyl, n is 0 and R" is unsubstituted or substituted (hec)aryl-
oxy, the unsubst.i.tuted or substituted (het)aryl groug having the
following meanings

-- -- ~_~~~= _- --- õ ~
tto. unsu'bstituted or subst.ituted Reference
(het)aryl

1.1B-1 C6H!i~- _- -~ -- EP-A 178 826 S.1i3-2 6--[2-CH-CbHy-o)-pyrimidin-4-=yl
EP-A. 382 375

Table 1.1C

Compounds c,f the formula IA where R' iS -C(CO2CH3) CEtOCH3, Q is
phenyl, n is 0 and R" is unsubstituted or substituted (het)aryl-
ethenylene, ttie unsubstituted or substituted (het)dryl group
having thE foll.owing meanings

[-I,. o. unaubt3.k.uked or substituted (het)ary], Ratoreuce
. 7.C-1 1- ( 2, -C12-C6H3 ), 5-CF;~-=pyrazol.-4-y7, EP -A 528 246 ---
1c-.2 1-(4-.C1..,Cd&~4)-pyra.zol-4-yl >wP-A 378 755
iC- 3 3-cF:3-'CoH4 EP-A 203 606
z.1c-4 3-C1.-C6$9 EP-A 203 G06
+dS _..-.. .-......-.
L 1C-5 9-C6H5'CSHy EP-A 203 06
s--..__ . - -=-*~:.....-...~..~r ~_.~ -


~ 0050/45055

TabJ,ta 1.1[5

Compounds of tho formula IA where Q is phonyl, R' is
-C(Cp2CH3)=CHCCH3, n is 0 and R" is CH2oN=CRaRP, Ra and RP havir,q
5 the following meani.ngs

Ho. R R Reference
1.10-1 CH3 4-C1-C6H4 8P-A 370 629 V Y
10 ~-.. _
I.1D-=2 CH3 3-CF,y-C6H4 EP-A 370 629
I.1D 3 Cfll 4-OCH2CH3-pyrimidin-2-yl WO-A 92/18,487
Table ] . ].E
Compounds of the formula IA where Q is phenyl, R' is
-C(CO2CI33)=CHOCH3, n is 0 and R" is CHaON=CRYCRB-NORE, RY, Rd and R.e
having the .fcai.lowing meanings

No. RY R RE Raference
I.IF,-1 CH3 CH3 CH3 German Application
44 03 447.4

I.1E-? CH3 ~ Cfi3 CHZCH3 German Application
44 03 447.4
1.1E-3 CH3 C4H5, CH3 Gexman Appl'icetian
44 03 447.4
I.Er:-4 cH, <.EH5 CFs2CH3 Gennan Application
44 03 447.4
I.lE-5 CH3 4-C1-C6H4 CH3 German ApplicaLion
44 21 180.5
I.1S-6 CH3 4-'Cl-C04 C142Ct3; German Application
44 ?1 180.5 35 Table 1.2A

Coxupounds oE the formula IA where Q is phenyl, R' is
-C(CO2CH3)=NOCH3, n is 0 and R" is unsubstituted or substituted
(hei:)azyloxymethylene, the unsubstituted or substituted (het)aryl
group having the fotlow5ng meanings

llNo. unaubstituted or eubsti.tuted Reference
(het)aryl
I.2A-1 2-CH3 C6Qa EF-A 253 213
1.2A-2 2,5-(Cti3)2-CeH3 EP-A 400 417


= 0050/45055 219557?

- -------------._...._, _ ---~ -..._..._
No. uusubstitutud or suubstituted Reference
(bat.) aryl
I.2A-? 2i 4-- (CHa ),1--Cy,ij EP-A 400 417
--~-
yr I.2A-4 2,3,5"'(CHS)1-CBH2 EP-A 400 417

I.2A'-5 2-Ci, S-CH3-C6H3 EP-A 400 417
1.2A--6 2-CH3, 4--C[CH3j=NOCi13--C03 EP-A 386 56l
Tabla 1.2B
Compounds of the formula IA where Q is phenyl, R' is
-C(C02CH3) NOCH3, n is 0 and R" is unaubstitutecl or substituted
(het)aryl.oxy, tho unsubstituted or substituted (het)aryl gro+.i>:,
having the fo].lowing meanings

No. unFubetituted or substituted Reference
(het)aryl
-- - ~-_- _-~~
T.28-1 C6Hg EP-A 253 213
I.28--2 '6-[2-CN-C6Ha Oj-pyrimidin--4-y1 EP-A 468 684
Table 1.2C

Compounds of the formula IA where Q is pheriyl, R' is
-C(CO2CH3)=NQCH3, n.i.s 0 and R" is CH2ON-CR"RP, Ro' and RPhavin5 the
following m*anings

No. Ru Ra ReferwncA
- - ' o-xs- - - ~==
T.20-E CH3 4-C1-C6H4 EP-A 463 488
1.2C-2 CHi 3-Cl-C6H4 EP-A 463 488
1.2C-3 CH3 4-C.F3-C6Ha EP-A 463 488
Z.2C-4 CH3 3-CF3-C6H4 EP-A 463 486
2.2C-5 CHS 4-CH3-C6H4 EP-A 463 488
I12C~6 C.HS 4-OCH2C51-pyrimidi.n-2-y1 EP-A 472 300
1.2C-7 CH3 3,5-C1Z-C6H3 HP-2 463 488
TaLile I.1D

Compounds of the formula IA where Q is phenyl., R' is
-C(C02CH3)=NOCH3, n is 0 and R" zs CH24N=CRYCR6aNORI, RY, Rd and R
having the following m.4anings


~ ao~o~~5ass 2195577

12
- ~ -- --- - ---
No. R Re Refereace
I.21Y-Y CH3 CH3 CH3 German Application
44 03 447.4
~_-
S I.2D--2 CH3 CH3 CHZCH; German Application
44 03 447.4
I.2n-3 CHi C6H5 CHy German AppLicntl.on
44 03 447.4
t.2A-4 CHj CgHS -'~- CY32cH3 German Application
lq 44 03 447.4
1.2A=S CHg 4-C1-C6H4 CH3 German Application
44 21 180.5
I.2A-6 CHy 4-C1-C6H4 CH2CH3 1 German Application
44 21 180.5
x5 ~__ _ __.~ ..............._. _.___ ~.,
Tabie 1.3A

Conpounds of the :formu34 IA where Q is phenyl, R' is
-C(CONHCH3)mNOCH3, n is 0 and R^ is unsubstituted or substituted
20 (het')aryloxymethylene, ttie unsubstituted or subatiCutad (het)aryl
group having ttie following meanings

No. 'unaubat3tuted or aubat.ituted Raference
25 (het)aryl
1.3A-1 2=-CHs-CcH4 EP-A 477 631
I.3A--2 2,5-(CH3)2-CCH3 EP-A 477 631
I.3A-3 2,4-(CH3)1-C6H3 EP-A 477 631
30 I.3A-4 -2,3,5-(CH3)3-C6H2 EP-A 477 631
1.3A-5 2--CH3, 4-C[CH3]=NOCH3--C6H3 EP--A 587 124
1.3A-6 1-[4--C1-CbHy]-pyrazol-3-y1 Gelman Application 43 05 502.8

35 1.3A-7 1-[2,4-Ciz-CyH3]-pyrazo].-3-y1 Gsrman Application
43 05 502.8
Table 1.38

40 Compounds of Che formula TA where Q is phenyl, R' is
-C(CQNHCHj)=NOCftI, n is 0 and R" is unsubstituted or substituted
(hQt)aryloxy, tha im subatituted or substituted (het)ar.yl group
having the following meanings



0050/45055
2155577
13
9t0. uncuhstit:uLed ur substituted Refereace
(het)axy].
~_ _ .. ._. ._._ . :~.a -----
~~
i,38-1 c~HS EP--A 398 692
g I.3i4-2 6-(2-CN--C6H4-0]-pyrimidin--4-y'L Ga-A 2 253 624
Table 1.3C -

Compounds of t:he formula IA. where Q is phenyl, R' is
-C(CONHCHj)=210CH3, n is 0 and R" is unsuhst,f.tuted or siibstituted
(het)arylethenylene, the unsubstituted or substituted (het)aryl
group having the following mean.ings

Na. uasubetituted or aubstitute+i ReFatence 1
(hat)aryl L.3C-3 1 j2,4-C1~-C~H~I, German Appllcat.icon
5-CF3-pyrazol-4--.y7. 44 23 615.8
Tak)le 1.3D
Compounds ox the formrila IA where Q is phenyl, R' is
-C(CONHCH3)=NOCH3r n i.s 0 and R" is CHZON,CR"R@, Ra and RO having
the following meanings


[1.3D-2 R9ference 3D-1 CII3 4-C1-C6H4 E8 A 463 A88

CHa 3-C1-CSH3 EP-A 465 488
.i 3St-.i CH5 4=CD ~-C6H4 EP-A 585 751
Y.3n-4 C113 3-CF3-C6114 EP-A 585 751
I.3D-5 CBJ 4--CH3-CSH; EP-A 463 488
1.3D-6 CH} 3,S Clz-C6Hy EP-A 463 488
7.3D-7 CH3 Z-CrCH1CFia-pyrimidin-2-y1 Wo-A 92/13,8?0
Tahle 1.3E

Compounds of the farmul.a T8 whele Q is phenyl, R' is
-C(CQNHCH3)mN0CH3, n is 0 and R" is CH20N=CRYCR6~11GR , RY, R6 and Re
having the following meanings

F--f RE mranc9 4S CH3 CH,q - cH3 German Pat.ent Applica-
tion 44 21 182.1


0050/45055 2195577
.~,

14
lio. RY Re Rl;f6reclce
=.31=-,2 CH3 i:H, CH2CH3 German Patent Applica--

tion 44 21 182.1 5 I,32b--3 CH1 C6Hg CH3 German PatenC Appii.qa-tion 44 21
182.i

I.3E-4 Cf13 C05 CH2CH3 German Patent Applica-
tion 44 21 182.1
I.3E-5 CH3 4-C1-C6H4 CHg German Patent Applicn-
tion 44 21 132,1
I.3E-6 CH3 4-C1--C6Hq CH2CHa German Patent Appli,aa-
tion 44 21 3.82.1

Z.3E--7 CH3 4-E-CEH4 CHa German Patent Applica-
t.ion 44 21 182.1
Table 1.4A

Compounds of the formula IA where Q is phenyl., R' is
-C(C02CHy)-CHCH3r n is 0 and R" is unsubstituted or substituted
(heft)aryloxymethylene, the unsubstituted or substituted (het)aryl
group having the following meanings
._, m~_...~..__ .
No, unaubatituted or aubatituted Reference
(het)aryi
1.4A-1 2-CH3-C6H4 F.P-A 280 185
2.4A-2 2, 5- (CEi;,) 2-C6113 EP-A 513 580
Y,4A-3 2,4-(CHj)2-CbH3 EP-A 513 580
1.4A-4 2,3r5"(CH3)3-C02 ZP-A 513 580
I.4A-5 2=-C1, 5-CH3-CSH3 >p-A 513 580
I.QA-6 2-C43, 4-C[Cf13J=NOC:H3-C5H3 EP-A 513 580
I.4A-7 1-(4-C1--CIR4]-,pyzatol-3--y1 Gacman Pate:lt Appli.ca-
tion 44 15 483.6
Table. 1.4B

Compounds of tie formula IA where Q is phenyl, R' is
-C(CO2CH;)-CHCH3, n is 0;and R" is unsubstituted or substituted
(hzt) aryi.oxy, ~.he un cabstitated or substituted (het) aryl g>:o(:F
l.avi.ng the following meanirigs

No. nxiaub9tituted or substituted Reterenee
(hat)aryl
z.4H-1 C5f;5 EP-A 513 580


~ 0050/45055 G 19J 57/
'fa.ble 1.4C

Compounds of the forniula IA where Q i.s phanyl, R' Ss
-C(CC]2CHj)-CHCH3, n is 0 and R" is CH2ON=CRYCRb=NURe, Ry, Rb and Re
5 hav.4ng the fol7owinU meanings

No. RY R RE Refer nca
I.4C-I CHa C43 CH9 Gexnian Patent Application
18 44 21 180.5

4r,-2 CH3 CH3 CHzCH; German Patent Applicatian
44 21 180.5

1.4C-3 CH; C6H5 CH3 German Patent Applioation
44 21 180.5
I.4C-9 Cfly C6HS CH2CH3 German Patent Application
44 21 180.5
r.4C-5 CHy 4-CI-=C4H4 CH3 German Patent Application
44 21 180.5

C133 4-C1- CeH4 CH2CII3 ; German Patent Application
I.4C-6
44 21 180.5
~:-~ - . -
2abla I.SA

Compounds of the formula IA where Q is phenyl, R' is
--C(Cd2CH3)=CHCHaC1I3, ra is 0 and R" .i.e unsubstituted or substituted
(het)aryloxymethylene, the unsubstit.uted or subs'titutnd (het)aryl
group liaving the following ttteanir,g's

No. uasubatiLut:ad or substituted RefGrence
(hut)axyl
I.5A 1 2-CH3-CGH4
>P-A 513 580
L.5A-2 2,5-(CH3)2-C6H3 EP-A 513 580
L.5A-3_ 2,4-(CH3)7-CfiFi3 - EP-A 513 580

2.5A4 2,3,5-(CH;)Y' C6H2 EP-A 513 580
I.5A-S 2-C1, 5-CH;=-Cre; EP-A 523 580
s_SA-6 2-CH31 4-C[CH3l=NOCH3-CaH,3 EP-A 513 580
Tab1e 1.5B

Compourlds of the formula IA where Q is phenyl? R' is
-C(C02CH3)=CHCH1CH3r n is 0 and R" ie unsubsti'tuted or substituced
(het.)a.ryloxy, the unyubstituted or suiistituted (het)aryl group
having the following meaning


= 0050/45055 2 Y 7557 7
16
ft Nn, ~ uasubstituted or substituted Refe ea ec
(bet)aryl
-~ -~ -~ ^-.-
I.5H^1 C6H5 P-A 513 580
- ---_ -- ^= -
Table 1.5<:.

compounds of the formula IA where Q is phenyl, R' is
-C(CO2CH3)=CHCR2CH3, n is 0 and R" is CH2ON=CRYCRa=NOR`, RY, R8 and
R¾ havirig the following meanings

_- c:EiCHa 3 G eTmari Pat.ent Appl-ication
44 21 180.5
n5c-4CS3 ~ R -- RE RefereaCa
CH; CHZC.H3 German Patent App7ica,Y.in
44 21 180.5

CgBg CH3 Gexzsian Patent Applio&Lion
44 21 180.5

24 CgHS CH2CR3 German Patent Appliqation
44 21 180.5

õ'TiC-4 CHg 4-C1--C4H4 CH; German Patent Appl3cat.i.on
44 21 180.5

7.5C-6 CHI 4-C1-C6H4 C.R2CH3 German Patent Applicat.ion
25 44 21 180.5

Table 1.6A

compaunds of the formula IA where Q is phenyl, R' is
30 -C(COCH3)=NOCH3r n is 0 and R" unsubstituted or substituted
(het)aryloxymethylenej the unsubstitute,d or oubstituted (het)aryl
group having the following meanings

--_~
35 Ho, unsubstituted or substituted RefQreace
(het)aryl
I.6A-1 2-CEi3-C6PIa EP-A 498 188
Z.6A-2 2,5-(CH3)2-C6Hj EP-A 498 188
40 I.6A--3 - 2,4-(CHx)r-C6ti3 EP-A 498 188
T.6A-~~4 2,3,5-(CH3)j-CgH2 EP-=A 498 188
Y.6A-S 2-CBI, 4-C[CH;l=NOCEi3-C6p3 EP-A 498 188


= 0050/45055 2 p 955?-7
1
17
Table 1.69

Compounds of the formula IA where Q is phenyl, R' is
-=C(COCH3);;NOCH3r n is O and R" is unsubstituted or substituted
S(het)aryloxy, the urtsubstituted or 9ub9ti.tuted (het)erya rroup
hav'-ng L-he folJowing tnc'anings

~= -- ~
No. Attsubst.ituted or substituted Reference
(het)ery].
T.68^i~~ Cbf3g_ -~ G+H-A 498 188
1.6a-2 6-[2-Ct1-CfiH4-Oj--pyrimidin-4-yl E2-A 488 188
------'---
Table 1.'7A
Compaunds of the forcnula IA where Q is phenyl, R' is
-C(COCH2C133)aNOCFi3, n is 0 and R" is unsubstituted or substituted
chet)aryloxymethylene, the unsubst.ituted or substituted (heL)aryl
group having the following meanings

xe. ^ uasnbstituted or substituted Referaace
(hat)aryl
S.7A-1 2-CH3-C6%q EP-A 498 188
Z."IA-2 2,5-(CH3)Z-C6H3 EP-A 498 188
I.7A-3 2,4'-(CH3).,-C6H, EP-A 498 188
T.7A-9 CH~)3-C6A1 EP-A 498 188
.7A-5 2-CH3, 4-'C(eH3)=NCCx3-GSEfl 5P-A 498 188
~---
Tabl.a 1.78

Conipounds of the formula TA where Q is phenyl, R' is
-C(CpCF32CH3) NOCH3, n is 0 and R" is unsubstituted or u.nsubsti-
tuted (het)aryloxy, the unsubstituted or substituted (het)aryl
clzoup having ttle fu3.lowing meanings

n, unsubstitnted or substituted (het)aryl RQferenca ~
':= -- -
1.7a-1i CeHS EP-A 498 388
1.'78-2 6-( 2-C17-C684-o)-pyrimidin-4-y1 B2'-A 498 168


= 0050/45055
2195577
Table 1.8A

Compounds of the formula IA where Q is phenyl, R' is
-CT(7CH3)-C62CfJ3, n is 0 and R" is unsubstituted or substituted
5(het)nry7.oxylnethylene, the unsubstituted or substitutad (het)eryl
grcup having the following meanings

tI4. unsubstituted or substituted Reference
(het)aryl
I.SA-d 2-C$3-C6H6 WO-A 93/15,046
I.BA-2 2,S-SCH~)2 c6H~ WO-A 93/15,046
I.8A--3 2,4-(CHI)z-C6H3 WO-A 93/15,046

z5 I.aA-4 2,3,5-(CH3)I-C6H2 WO-A 93/15,046
I.SA-5 2-Cl, 5-Ctd3-C6a3 WO-A 93/15,046
I,8A-=6 2-CH3, 4-C[CH3]=NOCHJ-C6H3 WQ-A 93/15,046
I.BA-7 2-CHI, 4-C[CH3]=NOCH=CH3-CcHI WO-A 93/15,046
I.BA- ~ 2-CHI, 4-C(CH1CH3J-NOCHI-C6E13 WO-A 93/15,046
I-SA-9 2-CH3. 4-C[CH2C1i33 NOCHxCH3-C6H, WO--A 93/15,U46
I,$A- 10 L-[4-C1-CEH4j-pyyaxa1-3--!rl German Patent App].(aa--
tion 44 23 612.3
.~... _ -- d
Table 1.8B

Compounds of the formula TA where Q is phenyl, R' is
-P7(oCH3)-CO2CH3, n is 0 and R" 9.s CH2ON=CRV, where R" and R~ have
'Chc fallowing meaning

.--- No. ReT'ereace

2.L-1 WO-A 93/15,046

43


~
! aa~a/~aass 21 9557 !
i~
l;xaniples vf particularly suitable active ingredients of the for-
mtala IA are listua in the table below

No. R1 ft~ R3 ~ Reference
ITA i 2 OH-C6H5H J. Am. Chem T-
SOC. I_U
(1989),
114-120

IfA.2 C6E35 H H Org. Synth.
Col. Vol. II,
(1943). 67

ISA.3 3,5-C12-C6H3 CH3 B Similar to J.
Org. Cham. 2A
(1959), 802
~.~
ITA.4 4-CH3-Cy14 H H J. Itidian
Chem. Sac.
(1974), 437

xYA.S 2-C1-C6H9 B Cli3 Tetrahedron
9.~ (1987),
5375

IIA.B 2,6-C12-C6H,f A H EP-A 133 155
TIA.7 :3,5-C12-C6H3 H Ei J. Med. Che.m.
13,(1970),
571
IIA.g 2-0H, 3,5-Br2-C6fi2 H ;7 Gazz. Chim.
Ital. 78
(1948), 5:3fi
IzA.9 3-I-CEH9 fi s Bull. Acad.
Pol. Sci.
Ser. sci.
Chim. i2
(1964), 733

IIA.10 3-C1-C6A4 H H Sull. Acad.
Pol.. Sci.
S'. Ser. Sci.
Chim. ,1,,'y'.,
(1964), 733
- - --- - - - -~'



,~ -
= 0050/45055 2195577
Examples of partic.ular.'?.y suitable active ingradients of the for-
mula IIB are listed in the table below

~r- -- r ~ -~ -
5 No. Ra Rb RQ JI+eference
11B.1 2-CH3-1,4-0xa- H C6E5 Carboxin
thiin-3-yl US-A 3,249,499
US-A 3,393,202
US-A 3,454,391
10 i1&.2 2--CH3--1,4-oxa- H C6H5 Oxycarbaxin
thiiu-3-yl- US.-A 3,399,214
4,4--diox_ide US-A 3,402,241
US-A 3,454,391
2I15.3 2,4,5-(CH;)j-, [i C6Hy Methflurox un
furan-3-yl DE-A 20 06 471
15 _ _ _
II9. G 2-CIr3'-4, 5-di.- H CõHS Fyracazbol.i.d
hydro- DE-A 16 6$ 790
pyran-=3-yl

1I5.5 2-I-C04 H C4Hg IIenodanil
DE-A 16 42 224
II8.6 2-CH3-C6H4 H 3-OCH(CH3)2-C6H4 Meproni.l
GB-A i 421 112
IIBw7 2-CF3-C6-1I4 H 3-OCII(CH3),-C6H4 FlutolaClil
JP-A 01/104,514
IIFa.d 2-CH3-furan H C6Hg Fenfuram
-3-y1 GB-A 1 215 066

YIB.9 2-CH;-C6114 H C4H5 Mebenil
DE-A 16 42 224
11B,19 2,4- (C.H;)2- H CdH5 Metsulfovax
thiazol-5-yl US-A 3,547,912
US-A 3,505,055
Us-A 3,709,992
US-A 3,725,427
IlIi.1L 2,$-(CFI3)2^= oCHI Cyclohuxyl 1'urmecyclox
furan-3-yl DE-A 24 55 092
11 .12 2-Cl-pyriei.in H 2,3-- [CH(CH3)CH2C(C8j)Z] EP-A 256 503
3 yl -C6H3

IIB.13 2-CH3, 4--CF3- H 2,6-Br2, 4--OCF3-CyHa EP-A 371 950
thiazol-5--y1
- --~-
In providing the 1cL.ixtures, it is preferable to use the pure ac-
tive ingredients IA ar TB and IIA or :GIB, wittl which, depending
on requirementa, further active ingredients against pests (for
exantple insects, arachni.ds or nematodes) or harmful f-ungi or else
her)aici.dal or cJrc-,wth-regulating active ingredients ar fertilizers
tnay be mixed.


~ 0050/45055 2195577
21
^he mixtures of Lhe compounds IA or IB and IIA or IIB and simul-
tanQous Joint or separate use af the compounds IA or IB and xIA
or IA or IH and IIB are distinguishad by an excellent action
against a broad spectrum of, in partiqular, phytopathogeni.c fun-
S gi. Some of them have systemio activity (ie. w11en used for plant
protection, they can Yie absorbed by the treated plant without
loss og activity and may be transported in the pl.ant) and can
t}.erefore also be used as foliage fungicides and sai.l. ftingicidea.

1.9 They are particularly i,mportant for oontroll5.ng a large nttmber of
fungi .fn various crops, suoh as cotton, vegetable plants (for ex-
ample oucumbers, beans and our.urbitaceae), barl.ey, grass, oats,
coffee, corn, fruit plants, rice, rye, soybean, grapevines,
rrheat, ornament,ala and eucfar cane, and a large numbcr of seeds.
They are particularly suitable for controlling the followind nhy-
topathagenic fungi: Erysiphe graminia (powdery mildew) on
cereals, Erysiphe cichoracearum and Sphxerotheca fuliginea on
cucurbitaceae, Podosphaera leucotsicha on apples, Puccinia
species on cereals, Rhi.zoetonia speciias an cotton and lawns,
Ustilago spacies on cer6ala and sugar cane, venturia inaequa].is
(scab) on apples, HelrniriLhosporium spec.ies on cereals, septori,a
nodorum on wheat, Botrytis cinera (gray mold) on strawberries and
arapevineu, cercoapora nraohidicola on peanuts, Paeudocereo-
spoLel.La herpotrichoides on wheat and barley, Pyricularia oryzae
on rice, Pttytophthora infestans on potatoes and tomatoes,
P145Topara viticola on 'y-`rapevines, Alterna.r!s species on
vegeL-ables and fruit and Fusarium and verticillium species.

They can also be u.sad in mater.ial protection (for example wood
preservatioti), for example againyt Paeciaomyces vari.otii.

Tha: campounds FA or TH and IIA or IA or SB aild 1T8 can be applied
simultaneous1y together or sGparately or iri succession, the order
in t:he case of separate application generally having no effect on
the succeas of conl:rol.

The compounds IA or IB and ITA are usually used in a weight ratio
of from 5:10 to 1:50, preferably from 2:1 to 1:20P in parL.i.c'ular
from 1;1 to 1:10 (I:IlA).

:'he compounds IA or IB and S.IB are usually used in a weight rat.io
of frorn 10:1 t:c 1:10, preferably from 5z1 tc 1:5, in particular
from 2;1 to 1;2 (I:IIB).
4S


~ d05G/45455 2195577

22
The application rates a= C.ha novel mixzures are from 0.015 to 10,
preferably frum 0.1 to 7, in particular fram 0.2 to 3, kg/ha, dz-
pending on the.type of effec:t desired.

The application .rates of ttte compcunds IA and IB are from 0.005
to 3, greferab].y from 2.02 to 2, in parti.cular from 0.05 to 1,
kg/ha.

The application rates of the compounds IIA are in general from
0.05 to 10, preferably from 0.1 to 5, in particular from 0.2 to
2, kq/ha.

The application rates of the compoutids IIB are in general from
0.01 to 5, preferably from 0.1 to 2, in particular from 0.2 to
1, k.g/ha.

In the seed tz4atment, thrs application rates of the mixture are
in general from 0.001 to 0.1, preferably from 0.002 to 0.05, in
particular from 0.005 to 0.05, g/kg of seed.
If phytopachogenic fungi are to be controllad, the joint or F;epa-
ratiad appli.catiori of the cotnpounds IA or IB and IIA or IA or IB
nnd IIB or of the mixtures of thm compounds IA or IS and IIA or
IA or IB and IIB is effected by spraying or dusting the seeds,
the pl.ants or the soils b4foz,e or after sowing of the plants or
befor.e or after germination of the plants.

The novel fungicidal synergistic mixtures or the compounds IR or
TB and IIA or IA or IB and TIB can be formu.lat.edi for example, in
the form of directly sprayable solutions, powders and auspensions
or in the form of highly concentrated aqueous, oily or other aus-
pensions, dispersions, Amulsions, oil diapersions, pastes, dust-
ing agents, broadcasting agents or granul¾s and can be applied by
spraying, nebulizing, dusting, broadcasting or pouring. The ap=-
p1.x,Ation form is depcndent on the intended use; it shou.lc? in any
case ensure very fine and uuiform distribution of the novel mix-
ture.

The formulations are prepazed in a manner known per sa, for exam-
ple by addittg solvents and/or carriers. Usually, inert additives,
such as emulsif.i.ers or dispersants, are mixed with ttte forrtula-
t.ions.

Suit.able surfactants are Lhe alkali metal, alkaline earth metal
and ammonium salts of aromatio sulfonic acids, for example li,g-
ninsul.fonic, phanolsulfonic, naphthalenesnitonic and dibutyl.naph-
thalenesulf'onic acid, and of fatLy acids, alkylsulfonates,


= 2195577
0050/45055

23
alky7.-arylsulEonatda, alkyl sulfates, lauryl ether aqlfatec and
fatty alaohol sulfatee, and salts at sulfated hexa-, hepta- and
octadecanols qV fatty alcohol glycol athwrs, condenaates of sul-
fonatad naphthalene and its derivatives with formaldehyde, con-
8 densates of naphthalene or of naphthalenesul#onic acids with phe-
nol and formaldehyde, polyoxyethylene octyiphenol ether, ethoxy-
lated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol
other, tributylphenyl polyglycol ethers alkylaryl polyether alco-
hols, isotridecyl alcohol, fatty alcohol athylene oxide conden-
lo sates, ethoxylated castor oil, polyoxyethylenw. alkyl ether or
polyoxypropylene, lauryl alkyl polyglycol nther acetal, sorbitol
asters, 1_igninsulfite waste liquors or methylcelluloae.

Powders, broadcasting and dusting agonta can be prepared by mix-
15 ing or m.U.ling compounds IA or Zs and IIA or IA or I$ and IIB or
the mixtures c,f the ccmpc=wnws ZP or. IH arid IIA or IA or IB and
IIB together with a solid carrier.

Granules (for example coated, impregnated or homogeneous aran-
7o ules) ara usually prepared by binding the tfative ingradienl: or
the active ingredients to a soli.d carrier.

The Pillers or solid carriers used are, ior example, mineral
Ãarths, such as silica gel, silicas, ailicatea, talc, kaolin,
25 limestone, lime, chalk, bola, ],oesc, clay, dolomi'te, kieselguhl:,
calcium sulfate, magaesium sultate, magnesitiun oxide, milled plas-
tics arid ferti7,i2ars, such a$ amznonium aulfa*_e, ammonium phos-
phate, ammonieuc nitrate and ureas, and vegetable products, such
as grain flour, bark meal, wood meal and nutahel.l. meal, cellulos-
30 ic pawders or other solid carr.iers.

The formulations contain in general from 0.1 to 95, preferably
S-.ron 0.5 to 90, t by weight of one of the compounds IA or IB, TIP.
or IIII or of the mixture of the compounda IA or IB and IIA or IA
35 or TB and IIB.

The active ingredirsnts are used in a purity of from 90 to 100%,
preferably from 95 to 100% (according to 1H-L72+IR or HPLC speotr.um).
40 Tha compounds IA or IB, TIA and IIH or the mi.xtures or the corre-
sponding formulations are applied by treating harmful fungi,
their habitat or the materials, plants, seeds, soils, surfaces or
spaces to be protected from ftu'i3a1 attack with aungicidal
amount of the mi.xture or of the compoands IA or I5 and IIA or IA
45 or lb and II13 in the case of separatu application. The t:re:attment
may be effected before or after infestation by thQ harmful fung.i..


= 0050/45055 2195577
24
The synerglstic action of the novel mixtures can be demon3t.rated
by the following experimenLs:

Labo.xatory experiments:
Fffect of t.ha novel mix'turea on myce7.ium growttis

Agar platas which contained the a,Gkive ingredient were inoculated
with mycelia oL the fungi. The gxowtta of the fungi was deGermined
after from 1 to 4 weeks, depending on tli= type of fungusr by cotn-
parison of the fungal colonies of an untreated control and the
tteaCed plates [diameter (cm) of thu fungal colony i.s stated3.
xazznful fungus Control 1.$A-7 IrA.I T.BA-7
[200 ppLn] [100 ppm] [200 ppm]
IIA.1
[100 ppm]
Alternaria solarii 8.5 7 8.5 3.6
Botrytis cinerea 8.5 8.5 8.5 6
Chcanephora cuaurb9tazum 8.5 8.5 8.5 6,7
cladosporium herbarum 4.5 0.7 3.1 0
cylinclrocarpon mali 4.2 1 3.7 0.6
Drechalsra sigmni.duiu 815 1.5 8.5 2.1
Drechalera trsres 8.5 6.5 8.5 5.4
Fusarium oxyaporum B 4 6.7 2.6
GlaA-ocpor.ium fructigenun 3.4 7.8 a.7
cui.gnardia citricarpa 6 0.9 6.3 0
Monilinia spec. 6.3 5.2 5.7 0
Penicillium digitatum 5.7 3.1 5.4 0
Panicillicun expansutn 515 3.8 S 3.7 ~
Bhomcpsis lorgicola 8.5 3.5 7.1 2
Pk:ytophthora cactorum 7.7 4.5 4.3 2.6
$seudocercosporalla 4.4 1.8 4 0,3 -
hetpotrichoides
Pyricularia oryzae 7.5 2.6 6.8 2.1
Phythium ultimun 8.5 8.5 6.3 5.8
8hizopus stolonifer 8.5 7.7 8.5 5.5
'15 Sclerotinia sci rotiorum 8.5 8.5 8.5 4.2
Sclerotium rolfsii 8.5 2.7 5.8 2.1


_ .r

~ 005()/45055 2195577
= ~5
HarmEui tlnque Oontrol 7C.9A-7 STA.1 T.SA-7
[200 ppm] [100 ppp) [200 ppm]
YsH.i
[:00 pPm)
Septoria nodor uc 5.6 3.5 4.8 2.7
Thieleiapsis basicola 6.8 3.5 2.5 0.9
vantui.ia i.naequalis 2.9 1.5 1.5 0
Vertic7,].ium dahliaa 3.2 0.4 2.2 0
1q `~ -- - .
Spore germination test:

Suspensions of fungal sporas (Botrytis cinerea, 106 spores/mZ) in
mioratiter plates were incubated for 24 hours at 18*C atter the
addition of test solution. Therea.ft.er, the gerinination was eva-
luatad urider a microscope hy estimating the gxowth in com.parison
with Untreated control5. The evaluation was based on the follow-
ing rating;

0 plurality of spores not germinated (very good action)
(+) spores germinated for the most part ( S 58 myce.liuLr,
growth)
+ > ?t to 5 50% myceli.um growth
i+ > 50% to 80t mycelium growth
f-i > 80% to S 1008 mycelium growth (rio action)

40


= AA50/45p55 L I 1 557`
26
I.2A-I [ppml Ii8,5 [ppml &v~luatioa
- ~
+++

lv +++
25 +++
50 - ++-
100 ++
iQ 5 +++
10 10 iF
10 25 ++

I5 7U 50 ~ +
10 100 +
'P+}
i.2A-l jppm) 114.1 [ppm, Evaluatiob
to - -~ -- +
10 ++
50 +++
lan +
-~~
10 10 (+)
1G v 50 (+~ ~
10 ~ 100 0
- +++
I.2.A-1 [ppm] TIA.2 [ppm] Evaluation
-
10 - +
- 50 ++-}.
100 ++
..
10 10 (4)
iJ 50 (+)
lU 100 (+)
~~--- -- __ - --------
-- - +++


~ aas~iasoss 21 9b57 7

27
I.2A-1 [ppm] IIA.3[ppmj Evaluakion
+
10 +++
-
s 50 +++
100 +++
.~:. -- - - - -
10 +
3.0 5G (+) ~f
10 --
1a ]p0 0
~~~' - -- +++
~rss~vrr--
15 I.2A-1 [ppm] 1IA.4 ippmj Evsluatioa
10 - +
I0 ~ ++t
++.f.
24 ~ 100 ~ i-t
- *
10 10
ia 50 (+)
10 100 T (~)
--._,. - ---- ,. ---- ++t

T.2A- i [ppmp 1IA.5 (ppmj .Evaluatian
10 ~ +
m---~~ ~--
10' - +++ ~
---- +++
++
100
lu za +
10 5a
10 100 (+)
+ta
- -



4 `

= 0050/45055 2195577
28
T.2A-1 jPpmj TIA.6 (ppmj Evaluation
_-_ .- ~-:s-- -
J.0 } -

++-F
5 - 50 ~ +++
]Oo -- -- - itt ~ -
t
10 10
10 50 +
10 100 +
+++
- ~ -

~vnluation ~
I.2A-1 IPPmj I2A,7 IPPm]
.-.r------ ~~. - -- -
1n
10 +++
50 **+
100 +r
10 10 ~+j
10 50 0
l0 100 - 0

72A-1 [ppml YIA.9 GPpmj Evaluation
10 - -- - -- -+ -
- - - - anrc~- - . ---
10 +++
+++

100 ++
...
10 10 (+)

10 5o 0
10-- ---- - 100 0
GreEnhouse expe~ximents:

The active ingradientu were fUrmulated as a 20 $ s'trengt.h emul-
sion in a mixtur of '70 % by weight of cyclGhexanone, 20 t by
45 weight of Nekani;l(ALN (I,uti;n:aol(V AP6, wetting agent having an
emuisifying aud dispersirig action and based an etlroxylated
aakylphenols) and 10 % by we.ight cf Elnulphor=(l EL (Etau.latiO Et,,


2195577
= 0050/45055

29
emulsifier baeed on ethoxylated fatty aloohol;, ) and werc: d.Uuted
with water to give ttie desired concentration.

Action against Bot:.rytis cinerea (gray nold)
Capsicum seedlings (p7eusiedier ideal lite vaxiety) hav2ng 4-5
leaves were sprayed 1:o run-off with rhe active ingredient _ ar--
mulation. After the formulaT.i.on hacl dried off, the plants wc:r.e
snrayed with a oona.dia auapeneion of the fungus Botrytts ciaerea
and kept for S days at 22-24`C ard high humidity. The evaluation
was carried out visually.

..~--_- --- - - ~~c-~s - - ----_
I.2A-1 [ppm] IIIA.1 [p,gm] Infestation [9]
~~~
250
125 ~ ----^---'-'--~- ~ - -
63 10
250 95
250250 6
125 250 2
o? ~ ~ 256 7
------ - ` 45

Anti.cn against Botrytas c.inerea (gray mold)

3>3sks of green peppers were sprayed to run-oZf with the active
ingredient formulation. After the formulation had dried off, the
disks were sprayed with a spore auapension of Botryti.s c.inerea
(1.7 xl4E spores per ml of a 2 8 strerigth biomalt solution) and
kept for 4 dAys at 18*C and high ]'iumidi.Ly. The evaluati:ion was car-
ried out visually.

1.2A-1 [ppmj IIA.1 [ppmf Snf.eatation [%)
250 - 4
125 55
~
63 - so
..,.,,r..~~ . _._.....-... -_ .-_.. _.:.z,azr .. .. .~..____ .~.._-- -
- 250 90
250 250 6
125 250 10


~ aoso~~sass 2195577
I.2A-1 [ppml IIA.1 (ppm]~ Tnfeatation jt]
- 63 250 ].2
- 95
~

172A-1 [ppm]^ I18.5 (ppm] Znfestation (11
30 254~ _ . - ._ 4

125 55
63 -
---- - 125
15 - --- -
63 90
31 9D
250 250 6

20 125 2!50 10
63 250 12
250 --- 63 _^ . 3
125 63 3
25 63 63 3
.~...~ -..... ~5 ---_. .
Action against Pucci.nia recondita (wlleat brown rust)

30 Leaves of whaat seedlings (Kanzler variety) werw dusted wit:P,
spores of brown rusC (Puccinia recondita). The plants thus
l;reated were incubated for 24 hours at 2U-?2*G and 90-95 +L rela-
tive humidity and then treated with ttiea aqueous active ingLedi.ent
Eormulation. Aftar a furthsr 8 days at 20-22*C and 65--70 % x=ela-
tiva humi.dity, the extet:t ot fungal ds=ve7.opment: was dn.t:ermined-
Thr: evalnat-ion was carried out visually.

45


0050/45055 2195577
x_

~z
~. _
I,2A-1 [ppm] IIt.S [ppm} infestation [%}
- .~-~:,r-=-- - - - -------~-- --~.-250 - 15
125 -- 20
63 25
- 125 30

63 40
31 30
_ _ _ -._._-~ . .,~- ._..._.-...~.~. .._.. _....
- '-~
250 250 1
125 250 3
63 250 5
250 63 5
125 63 5
63 63 1S
60 ...-

r.2A-1 [ppm} lIA.1 [lipnm} Infestation [$]
250 4
125 55
63 50
~ _ - -- -- ~-' - -
250 90
250---- -- ----- 250 -- -- 4-- -- -
A25 250 7.0
63 2S0 12

- __- - - ~-.._

.