3 .
PS/S- I 8()26/A
Nitroenamine derivatives
The present invention relates to novel nitroenamine derivatives, i.e. novel
1,1-diamino-2-nitro-3-hydroxybut-1-ene derivatives, to processes for their preparation, tO
pesticides comprising these compounds, and to their use in pest control.
The nitroenamine derivatives aceording to the invention are those of the formula I
1 1 l2
X~4 3 2 I N - CH A
Y C~H(OH)-C(NO2)=C~N_R3 (I)
R4
in which
Rl is hydrogen, Cl-C6alkyl or C3-C6cycloalkyl,
R2 is hydrogen or Cl-C6alkyl,
R3 is hydrogen, Cl-C6alkyl or C3-C6eyeloalkyl,
R4 is hydrogen, Cl-C6alkyl7 C3-C6eyeloalkyl or a ntclieal -Cl-12-B, or
R3 and R4 together are -(Cl~ or -(CI-I2)s-;
X is halogen or Cl-C6haloalkyl;
Y allLI Z ;lre l1al0g~n;
A is .ln unsubstituted or rnonosubstituted to tetrasubstituted arornatic or nall-aromatic,
monoeyelie or bieyelie, heterocyelic radieal in whieh one or two substituents belong to the
group comprising Cl-C3haloalkyl, eyclopropyl, halocyelopropyl, C2-C3alkenyl,
C2-C3alkynyl, C2-C3haloalkenyl, C2-(:3haloalkynyl, Cl-C3haloalkoxy, Cl-C3aLkylthio,
Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy,
haloallylthio, cyano and nitro and one to four substituents belong to the group comprising
C1-C3alkyl, Cl-C3alkoxy and halogen;
B is phenyl, cyanophenyl, nitrophenyl, halophenyl having I to 3 halogen atoms, 3-pyridyl,
5-thiazolyl, or 5-thi~zolyl which is substituted by one to two substituents from the group
comprising Cl-C3alkyl, Cl-C3haloalkyl, cyclopropyl, halocyelopropyl, C2-C3alkenyl,
,
,
3 7 ~ ~
C2-C3alkynyl, Cl-C3alkoxy, C2-C3haloalkenyl, C2-C3haloalkynyl, Cl-C3h~1ualkoxy,
Cl-C3alkylthio, C'l-C3haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio,
haloallyloxy, haloallylthio, halogen, cyano and nitro; or 3-pyridyl which is substitutecl by
one tO two radicals from the group comprising Cl-C3haloalkyl, cyclopropyl,
halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloal1kenyl, C2-C3haloalkynyl,
Cl-C3haloalkoxy, Cl-C3alkylthio, Cl-C3haloalkylthio, allyloxy, propargyloxy, allylthio,
propargylthio, haloallyloxy, haloallylthio, cyano and nitro or by one to four radicals from
the group comprising Cl-C3alkyl, Cl-C3alkoxy or halogen, and their salts with inorganic
acids; it only heing possible for one of the radicals Rl, R3 and R4 to be hydrogen.
Preferred compounds of the forrnula I according to the invention are those in which the
heterocyclic radical A is unsaturated and bonded to the radical of the compound of the
formula I via one of its ring carbon atoms; those in which the heterocyclic radical A
contains at least one nitrogen atom; and those in which the heterocyclic radical A contains
one to three hetero atoms from ~he series comprising oxygen, sulfur and nitrogen, of which
not more than one is an oxygen or sulfur atom.
The ring systems which come under the definition of the heterocyclic radical A therefore
contain, as a ring member, at least one hetero atom, i.e. at least one of the atoms which
form the basic ring-shaped skeleton is other than carbon. In principle, all atoms of the
periodic system of the elements are capable of acting as ring members if they can form at
least two covalent bonds. In this context, the heterocyclic radicall is pre~era~ly unsalturllted
and bonded to the skeleton of the nitroenamine of the formulal [ via al callbotl atolll rh1g
member. IJnsaturated ring systems of the ~lefinitiotl A therefore contairl ona or more
double bon~ls. RinL~ ~ysterns of this type alrc profcr.lbly polyunsatllr.lte(î alnd gcnerallly have
alromaltic chalracter. Preferred rin~ systems which come uncler the definition of A are those
in which the heterocyclic radical A contains one to three hetero atoms from theseries
comprising oxygcn, sulfur and nitrogen, of which one hetero atom is always nitrogen and
not more than one oxygen atom or sulfur atom is present. Examples of heterocyclic
radicals according to the invention, of the definition A, can be found in the group of
skeletons of the following structures:
p~ ~
N~ N~
0/~/ N~ N~ ~ N~N
O~N~J ~S 3 O~N~ s~oJI S~S } S~N~
E E
N~~N~ N~ N N~~N~.
o~ss~oJI s~s O~N
E
N~NN~ ~N~ N~NN~
o~ssd~sJI o~N 0~0S~N~I S
e E E
N~N N~ 3, ~ ~N ~ ~I N~; 3
s~oJ o~o o ~o o o~ o~ls
~N ' ~N3 O~NJ o~N
E E E
N~ 3 ~/ N ~, N N~ 3 ~ ~-- ~N
S O S oJ S 0~ S~S S sJ
3^~ 3
S ~ S ~ S S~ N } S ~N ~I S ~N ~ ~;3
E E E
N ~ N
Y
~3 r~3 r~3 r~
Y y
N N N N N
~ " ~ 11~ -11
N~o/ ' N~S ~ N~N/ ~ ~ ~N ~ ~ "N
I
Y
N ~ T~ ~ ~N . I I r
~N~'N ~o~ N~S~N ~N~ ~1`1J
Y Y Y
~1 N--N N l ~1l ~
N~N ~ N ~N ~N~ ~N ~ N~N .
O O O Y S
N--N N ~ O--_ 3 ~ 5 1~3 N ~
N N N N IN/~
S S Y
2. ~ 3 ~
N~ N ~ N~ ~N~
~NJ~N~OJ~NJI SJ~N~I NJ~N
--N ~3~ N ~3 ~r ~--~
N~\NN~\N N~N N~`N
o~\N1~3 O~N~1~3 O~N/1~3 5
N~NN~N
5~N~l~3 and ~ ,1~3 ~ where a r~dical according to the above
y
forrnulae is unsubstituted or can carry Up to four subs~ituents from those defined under
forrnula I, depencling on the scope of the ring system in questioll for xubstitutioll, and E is
Cl-C3.alkyl ancl Y is hydrogen, Cl-C3alkyl or cyclopropyl. Pref~r.lbly, these h~t~roeycles
A are unsubstitllted or ealry one to three substituGIlts trom the gl'Ollp COlllpl'iSin~ halogen,
C~-CInlkyl, (~ 3h;~ l1kyl, C'l-C3h~l10.llkoxy or Cl-C3alkoxy. Very parti~ lrly preferrc(l
hutcro~:ycl~ A arc pyridyl r.~di~llls or thi.azolyl radic;lls, for cx~atllple 3-pyriclyl,
2-halopyrkl~S-yl, 2,3-dih~lopylid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl,
1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.
Other compounds of the formula I according to the invention which must be emphasi~ed
are those in which the radical B is a phenyl, pyridyl or thiazolyl radical, each of which is
unsubstituted or subslituted by one to two radicals from the group comprising halogen,
Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3haloalkoxy or Cl-C3alkoxy.
Compounds of the formula I which are prefer~d because of their biological action are
those in which Rl and R3 are hydrogen, methyl, ethyl or cyclopropyl; in which R2 is
hydrogen; in which R4 is hydrogen or methyl; in which Rl and R3 independently of one
~.
, . ~ .
r~ r~
arlother are hydrogen, methyl, ethyl or cyclopropyl~ R2 iS hydrogen, R4 is hydrogen or
methyl, A is pyridyl, 1-oxopyridyl, thiazolyl, or is pyridyl, 1-oxopyridyl or thiazolyl, eacl
of which is substituted by one to three substituents from the group comprising halogen,
C~-C3alkyl, Cl-C3haloalkyl, C~-C3haloalkoxy or C1-C3alkoxy; in which X is fluorine,
chlorine, bromine or Cl-C3haloalkyl having I to 7 fluorine atoms, and Y and Z
inclependently of one another are fluorine, chlorine or bromine in which, in particular, X,
Y and Z independently of one another are fluorine, chlorine or bromine, and, especially,
X, Y and Z are chlorine; in which Rl and R3 are methyl, R2 and R" are hydrogen; and X,
Y and Z independently of one another are fluorine, chlorine or bromine; in which A is
pyridyl or pyridyl which is substituted by one or two chlorine atoms; or in which A is
thiazolyl or thiazolyl which is substituted by a chlorine atom, preferably 1,3-thiazol-5-yl.
Compounds of the formula I according tO the invention which are of special interest
because of their good pesticidal properties are those in which X is fluorine or bromine,
preferably fluorine, and Y and Z are halogen, preferably fluorine or chlorine; those in
which X is C1-C6haloalkyl having 4 to 13, preferably 2 to 13, halogen atoms; and those in
which X is trifluoromethyl or one of the radicals -C2Fs or -C3F7.
The individual generic terrns in the definition of the formula I according to the invention
are to be understood as meaning the following:
The halogen atoms which are suitable as substituents are fluorine ancl chlorine as well as
bromine alld iodine, fluor~ne, chlorine and brorninc beiIlg preferlecl. In this ~olltext,
hnlogen is to be unclerstoo(l as meaning ~ subs~itllent in its own right or part o~ a
sllbstituent, sllch as in halo.llkyl, haloalkylthio, halo.llkoxy, h~llo~ycloalkyl, h.lloalkenyl,
hal(ralkyllyl, h;lloallyloxy or haloallylthio. 'I'he alkyl, alkylthio1 alkenyl, alkynyl ancl
alkoxy radicals which are suitable as substituents can be straight-chain or branchecl.
Examples of such alkyls which may be mentioned are methyl, ethyl, propyl, isopropyl,
butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals which may be mentioned
are, inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.
Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the butylthio
isomers. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as
substituents are substituted by halogen, they can be only partially halogenated, or,
alternatively, perhalogenated. In this context, the definitions of halogen, alkyl and alkoxy
are those given above. Examples of the alkyl elements of these groups are methyl which is
monosubstituted to trisubstituted by fluorine, chlorine and/or bromine, for example CHF2
2~3¢3~77~
or CF3; ethyl which is monosubstituted to pentasubstituted by flllorine, chlorine and/or
bromine, for example CH2CF3, CF2CF3, CF2CCI3, CF2CE~C12, CF2CHF2, CF2CFCI2,
CF2CHBr2, CF2CHClF, CF2CHE3rF or CCIFCHCIF; propyl or isopropyl, each of which is
monosubstituted to heptasubstituted by fluorine, chlorine and/or bromine, for example
CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers,
each of which is monosubstituted to nonasubstituted by fluorine, chlorine and/or bromine,
for example CF(CF3)CHFCF3 or CH2(CF~)2CF3; 2-chlorocyclopropyl or
2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroallyl,
2,3-dichlorovinyl or 2,3-dibromovinyl.
If the alkyl, alkoxy or cycloalkyl groups which have been de~med are subs~ituted by other
substituents, they can be monosubstituted or polysubstituted by an identical substituent or
by different substituents of those mentioned. The substituted groups preferably contain
one or two further substituents. The cycloalkyl radicals which are suitable as substituents
are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Alkenyl and alkynyl
groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl,
methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy,
propargyloxy, allylthio or propargylthio are preferably separated from the site at which
these are linked to the hetero atom (O or S) by a saturated carbon atom.
Heterocyclic compounds containing a nitroenarnine structure have already been disclosed
as insecticides in EP-A-192 06(), EP-A-302 389 and EP-A-302 833; however, the
biological properties of these compounds are not entiraly satisfactory when used in pest
control. In terrns of structure, the compounds of the fo mula I accorclin~g to th~ invelltion
are distinL~uished from the abovementioned, known nitroenamines in particular by the
presence of tha spccific 3,4-substitucnts in the n-but-l-one chain,
The compoun(ls of the formula I accorcling to the invention also encompass salts with
inorg,lnic acids which are agriculturally acceptable. Examples of such acids arehydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and nitric acid and
acids which have the same central atom and higher or lower levels of oxidation, such as
perchloric acid, nitrous acid or phosphorous acid.
The compounds of the formula I according to the invention can exist as double-bond
isomers, for example cis and trans isomers, or as stereoisomers at the carbon atom 3. The
compounds of the forrnula I are understood as meaning such isomeric fo rns and mixtures
;
of these.
The compounds of the forrnula I according to the invention can be prepared analogously to
known processes. For example, the compound of the forrnula I is obtained by reacting a
1,1-diamino-2-nitroethyl derivative of the forrnula II
I I 1 2
N ~ CH--A
CH(N02)= C~ , R3
R4
with a compound of the forrnula III
x\ ~o
Y ~c~c\ (III),
Z H
in which Rl to R4, A, X, Y and Z are as de~lned above.
The above process according to the invention is advantageously can~ed out in an inert
solvent at temperatures between 0C and ~120C, in particular between -~2(:)C and
-~80C. The following are particularly suitable as solvents: example~ of suitable solventx
are aromatic hyclrocarbons such ns benzene, toluene and xylene; ethr,rs such a~
tetrahydrofllran, clioxane and diethyl ether; halogenatecl hy(lrocarbolls sllch a~ methylene
chlorkle, chloroform, c.lrbon tctrachloride ancl chlorobcnzene; alcohols such as metharlol,
ethanol un~l propanol; esters of aliphatic acids, such as ethyl acetate; aliphatic amides,
such as dimethylformamide and dimethylacetamide; acetonitrile, and other solvents which
do not interfere with the reaction These solvents can also be used as rnixtures. The
reaction can be carried out with the addition of a dehydrating agent, for example
molecular sieves, or by azeotropic removal of the reaction water forrned, in particular
when the aldehyde starting cornpound of the fonnula III is present in the hydrate forrn.
Basic conditions, i.e. pH values of > 8, and high ternperatures above approx. 100C should
advantageously be avoided when carrying out the reaction, since the desired products of
the forrnula I are unstable under these reaction conditions.
The interrnediates of the forrnulae II (1,1-diamino-2-nitroethylene derivatives) and III
3 ~ ~7 ~ ~
()
(haloacetal(lehydes) are known or can be prepared in analogy to known pracesses (cf.
European Patent Application Nos. 302 389 and 302 833).
It has now been found that the compounds of the forrnula I according to the invention are
valuable active substances in pest control while their toxicity properties as regards
warm-blooded species, fish and plants are favourable. In par~icular, the use of the active
substances according to the invention relates to insects and arachnids which occur in
usefu} plants and ornamentals in agriculture, in particular in cotton plantations, vegetable
plantations and fruit plantations, in forests, in the protection of stored products and
materials, and in the hygiene field, in particular on domestic animals and productive
livestock. The compounds of the forrnula I are also suitable for seed treatment
(compositions for seed-dressing) for controlling, in particular, aphids, Ihe fact that the
compounds have a low toxicity to birds being highly important. They are effecùve ag~inst
all or individual development stages of nonnally sensitive, but also of resistant, species. In
this context, their action can become apparent by immediate destruction of the pests or
only after some time, for example during moulting, or by reduced oviposition and/or
hatching rate. The abovementioned pests include:
from the order of the Lepidoptera, for example
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois
spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa syp., Busseol.
fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia
ambiguella, Cnaphalocr~cis spp., Cnephasia spp., Cochylis spp., (:oleophol;l spp,t
Crociclolomia binotalis, Cryptophlebia leucotreta, Cyclia spp., Diatrae;l spp., Diparopsis
cast.lllea, Earias spp., E~phesti.a spp., Ellcosma spp., Lllpoecilia ambigllella, E~uproctis spp.,
I~ XO;l xpp., Grapholita spp., ~le(lya nubi~cran.l, ~leliothis spp., llellula un~lalis, ~lyphnntria
cune;l, Keiferia Iycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrarla,
Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,
Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella
xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp.,
Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta
spp.;
from the order of the Coleoptera, for example
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites
spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,
Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,
~?J ~
Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and
Trogoderma spp.; from the order of the Orthoptera, for example Blatta spp" Blattella spp.,
Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca
spp.;
from the order of the Isoptera, for example
Reticulitermes spp.; from the order of the Psocoptera, for éxample Liposcelis spp.; from
the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus
spp., Pemphigus spp. and Phylloxera spp; from the order of the Mallophaga, for example
Damalinea spp. and Trichodectes spp.;
from the order of the Thysanoptera, for example
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and
Scirtothrips aurantii;
from the order of the Heteroptera, for example
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.,
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
Scotinophara spp. and Triatoma spp.;
from the order of the Homoptera, for example
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
Chrysomphalus dictyospermi, Coccus hesperidurll, Empo,lsca spp., Eriosoma lariL~erurrl,
Elythronellra spp, Cascardka spp, L,ao(lelph/lx spp" Lecanillnl corni, LepillosLIp}l~ spp,
Maclosiphus spp" Myz~s spp, Nephotetti,Y spp" Nih~ lvatll sl~p, Par.ltorkl spp,
PCll~ pp. ~ ()C~CCll~ s~ Px~ c;l.~pis s~ Ps~ cocclls spp., Psyll~l ~;pp.,
I'ulvinarkl actlliopica, Qua~lraspicliotlls spp., Rhopalosiphum spp., Saissetia spp.,
Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Troiz~
erytreae and Unaspis citri;
frorn the order of the Hymenoptera, for example
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,
Hoplo~ampa spp., Lasius spp., Monomoliurn pharaonis, Neodiprion spp., Solenopsis spp.
and ~/espa spp.;
from the order of the Diptera, for exarnple
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis
spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
Fannia spp, Gastrophilus spp., Glossina spp.~ Hypoderrna spp., Hyppobosca spp.,
Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,
(:~rseolia spp., Oscinella frit, Pegomyi,l hyoscy,lmi, Phorbi.l spp, Rhagoletis pomonella,
Sci.ua spp., Stoms~xys spp., Tabanus spp., T.lnnia spp. and Tipula spp.;
from the order of the Siphonaptera, for example
Ceratophyllus spp., Xenopsylla cheopis,
from the order of the Acarina, for example
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosLI, Calipitrimerus spp., Chorioptes spp.,
Vermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes
spp., Olygonyehus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.,
Sareoptes spp., Tarsonemus spp., and Tetranyehus spp.; and
from the order of the Thysanura, for example
Lepisma saccharina.
The good pesticidal action of the compounds of tlle formula I according to lhe invention
corresponds to a destmction rate ~mortality) of at least 50-60 % of the pests mentioned.
The action of the compounds according to the invention and of the compositions which
comprise them ean be broadened substantially by adding other insecticides and/oracaricides and can be adapted to suit prevailing cireumstanees. E~xamples of suitable
additives are representatives of the following elasses of aetive substances:
organophosphorus eompour1ds, nitrophenols and derivatives, formamidines, ureas,
carbam.ltes, pyre~hroi(ls, chlorin;lte(l hydlocarbons arlcl F~acilllls thuringiell~is prepa~ iorls.
'I`he colllpollll(ls of the formulLl I are ellll)loyed in ul~altere(l form")r prefer~lbly to~e~her
with the allxiliaries eonverltionally used hl formul.ltioll teehnology, and they can therefore
be processed in a known manner to give, for exa,Tlple, emulsion coneentrates, directly
sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders,
dusts, granules, and also encapsulations in polymerie substanees. The application
methods, such as spraying, atomising, dusting, scattering or pouring, as well as the
compositions are selected to suit the intended aims and the prevailing cireumstances.
The formulation, i.e. the compositions, preparations or combinations comprising the active
substance of the formula I, or blends of these active substanees with other insecticides or
acaricides, and, if desired, a solid or liquid additive, are prepared in a known manner, for
example by intimately mixing andlor glinding the aetive substanees with extenders, for
example with solvents, solid carners and, if desired, surface-ac~ve compounds
(surfactants).
The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8
to Cl2, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as
dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, sueh as cyclohexane,
paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene
glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones,
such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl
sulfoxide or dimethylformarnide, and also epoxiclized or unepoxidized vegetable oils, such
as epoxidized coconut oil or soya oil, or water.
Solid carriers used as a rule, for example for dusts and dispersible powders, are ground
natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve
the physical properties, it is also possible to add highly-disperse silicas or highly-disperse
absorptive polymers. Possible particulate, adsorptive carriers for granules a~e either
porous types, for example pumice, brick grit, sepiolite or bentonite, or non-sorptive carner
materials, such as calcite or sand. Moreover, a large number of ~ranulated materials of
inorganic or organic nature can be used, such as, in particular, dolornite or comminuted
plant residues.
Suitable surface~clctive compollrlds arc non-ionic, cationic an(l/or anionic surfclct.lnts
h(lvin6 good emulsifyinL~, dispersillg and wottin~ propertie/., deperlding on the nature of
the active xubst.lrlce of the formula ~ to b~ formlllatecl or ot' the blcn~ls of thcse active
subst,lllces with other insectici-les or acaricicles. Surfactants are also to be understoocl as
meaning mixtures of surfactants
Anionic surfactants which are suitable can be either so-called ~ater-soluble soaps or
water-soluble synthetic surface-active compounds.
Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal
salts or substituted or unsubstituted ammonium salts of higher fatty acids (C1O-C22), such
as the sodium salts or potassium salts of oleic or ste~ric acid, or of natural mixtures of
~fatty acids which can be obtained, for exarnple, from coconut or tall oil. Mention must
also be made of the fatty acid methyltaurinates aml of modified and unmoclified
phospholipids as surfactants.
r~ r~ 3
- 13-
However, so-called synthetic surf.lctants are used more frequently, in particular fatty
sulfonates, fatty sulfates, sulfonated benzimidazole deriYatives or alkylarylsulfonates.
The fatty sulfonates or fatty sulfates are, as a rule, in the form of alkali metal salts,
alkaline earth met~l salts or substituted or unsubstituted ammonium salts, an~l generally
have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl
radicals, for example the sodium or calcium salt of ligninsul~onic acid, of the
dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty
acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty
alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably
contain 2 sulfonyl groups and one fatty acid radical having 8 to 22 C atoms. Examples of
alkylarylsulfonates are the sodium, calcium or triethanolamine salts of
dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a
naphthalenesulfonic acid/forrnaldehyde condensation product. Other suitable compounds
are the corresponding phosphates, such as the salts of the phosphoric ester of ap-nonylphenol-(~-14)-ethylene oxide adduct, or phospholipids.
Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or
cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can
contain 3 to 30 glycol ether groups and 8 to ~0 carbon atoms in the (aliphatic)
hyclrocarbon radical and 6 to 18 carbon atoms in the alkyl rallical of the alkylptlenols.
Other non-ionic surfact~lnts which are suitable are the water-soluble polyethylene oxi~le
ad(lllcts with polypropylf~l1e ~Iycol, ethylet1edi.~ opolypropylene L~lycol and
;Itlcylpolypropylene glycol WtliCtl h.tve I to 1() calborl atoms irl the alkyl chain alld which
contain 20 to 250 ethylene glycol ether groups an(l 10 to 100 propylene glycol ether
groups. Ttle abovementioned compounds customarily contain 1 to 5 ethylene glycol units
per propylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are
nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate,
polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are
fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts, which contain at least one
.
- 14 -
alkyl radical having 8 to 22 C atoms as N-substituents and which have lower halogenated
or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are
preferably in the form of halides, methylsulfates or ethylsulfates, for example
stear,vltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customary in forrnulation technology are described, inter alia, in the
following publications:
"1885 International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985",
H. Stache, "Tensid-Taschenbuch [Surfactant Guide]", 2nd edition, C. Hanser Verlag,
Munich, Vienna, 1981;
M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New
York, 1980-1981.
As a rule, the pesticidal preparations contain 0.1 to 99 %, in particular 0.1 to 95 %, of the
active subs~ance of the formula I or of blends of this active substance with other
insecticides or acaricides, 1 to 99.9 % of a solid or liquid additive and 0 to 25 %, in
particular 0.1 to 20 %, of a surfactant. While concentrated compositions are more
preferred as commercial goods, the end user uses, as a rule, dilute preparations which have
substantially lower concentrations of active substance. Typical use concentrations are
between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per
hectare are generally 1 to 1000 g of active substance per hectare, preferably 25 to
500 g/l~
In p.lrtic~ prcfcrrc~l formul~ltiolls c()nsist of thc followin~ (C/o ~ perc~nt by w~ ht)~ thc
active sLlbstance comprise(l being a compourld of the formula I, for example thecompoundsNos. 1.0()1, 1.008, 1.009, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085,
1.101, 1.102, 1.157, 1.105, 1.1()9, 1.010, 1.028, 1.022:
Emulsi~lable concentrates:
Active substance: 1 to 20 %, 5 to 10 % being preferred
Surfactant: S to 30 %, preferably 10 to 20 %
Liquid carrier: 50 to 94 %, preferably 70 to 85 %
Dusts:
Active substance: 0.1 to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
- 15- ,
Suspension concentrates:
Active substance: 5 to 75 %, preferably 10 to 50 %
Water. 94 to 24 %, preferably 88 to 30 %
Surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
Active substance: 0.5 to 90 %, preferably 1 to 80 %
Surfactant: 0.5 to 20 %, preferably l to 15 %
Solid carrier: 5 to 95 %, preferably 15 to 90 %.
Granules:
Active substance: 0.5 to 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, preferably 97 to 85 5to.
The compositions can also contain other additives such as stabilisers, antifoams,
preservatives, viscosity regulators, binders, adhesives and fertilisers or other active
substances for achieving specific effects.
The examples which follow are intended to illustrate the invention. They do not impose
any restriction on the invention.
_x m~Preparltis1n oP l m t.byl~ ~(6-chloropyrld-3 ylme~ ne~
2-ni~o~ . xy-4 4,4-trichlorobllt- I-ene.
L~
'I'o a mixture of 2.56 g (10 mmol) of 1-methylamino-1-[N-(6-cllloropyrid-3-ylmethyl)-
N-methyll-amino-2-nitroethylene in 30 ml of methylene chloride there are added 1.06 ml
(10.8 mmol) of chloral. After the reaction mixture has been stirred at room temperature for
2 1/2 hours~ it is filtered, and the crystals obtained are washed with a large amount of
methylene chloride. 3.81 g (94 %) of the title compound of the formula
C~13
CC13-CH(OH)-C(N02)=C~ ~L Cl
of melting point 1 30C ~re obtained (Cornpound No 1.0()8).
Example 2: Preparation of l-methvlamino-l-~N-(6-chloropYrid-3-YlmethYl)-N-meth~-2-nitro-3-hYdroxy-4,4-difluoro-4-chlorobut- 1 -ene.
To a mixture of 14.4 g of 1-methylamino-1-[N-(6-chloropyrid-3-ylmethyl)-N-methyl]-
amino-2-nitroethylene in 150 ml of methylene chloride there are adcled 7.42 g ofchlorodifluoroacetaldehyde H20. After the reaction mixture has been sti-rred at room
temperature for 2 days, it is filtered, and the crystals obtained are washed with methylene
chloride. The title compound of the forrnula below
CH3
~N--CH2~
CF2CI-CH(OH)-C(N02)= \NH--CH3 ~NJI--Cl
is obtained in an arnount of 17.2 g, melting point 142-143C (Compound No. 1.011).
Example 3: Preparation of 1-methylamino-1-fN~(6-chloropyrid-3-~lmethyl)-N_e ~-
2-nitro-3-hydroxY-4.4,5~5 ,6~6 6 heptafluorohex- 1 -ene.
To a Inixture of 2.56 ~ o~ 1-methylamino-1-[N-(6-chloropyrid-3-ylmettlyl)-N-lllethylJ-
amino-2-nitroethylene an~l 3.24 g of hopt.lflllorobutyr~Lldehyde hydr.lte in 5() ml of
mcthylcne chlori(lt~ therc slre s~ le~i S L~ Of molecLllslr siove 4 A. ~ftcr tlle reactioll mixtLIre
hLIS bccn stirrc~l at room ternperature for 2 ~lays, it is filterc(l an(l the filtratc is evaporate(l
'rhe resulting cr~stals are washed with hexsme/isopropsmol (1:1) 4.02 g of the title
compound of the formula
CF3cF2cF2-cH(vH)-c(No2)= C~ l~L Cl
of melting point 93-98C are obtained (Compoun~l No. 1.012).
ç.;,~
- 17 -
The compounds of the formula Ia which are listed in Table I below can be prcpared in an
analogous manner to the above procedure.
Table 1
R~
~N--CH2---A
R5-CH(OH)-C(Nt)2)= C ~N ~ R3 (Ia)
R4
- 18 -
V~ ~ V~ ~ ~
D~
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- 19-
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- 26
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- 27 -
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- 32 -
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- 35 -
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- 51
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- 57 -
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- 61 -
<IMG>
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Example 4: (Formulations - % = percent bY weigh~2
E:~ample4.1: Emulsion concen~ates a) b) c)
Active substance of Table 1 25 % 40 % 50 %
Cadodecylbenzenesulfonate 5 % 8 %6 ~/~
Castor oil polyethylene glycol
ether (36 mol of EO) 5 %
Tributylphenol polyethylene
glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - 15 % 20 %
Xylenemixture 65 % 25 % 20 %
Emulsions of any desired concentration can be prepared from such concentrates bydilution with water.
Example4.2: Solutions a) b) c) d)
Active substance of Table 180 %10 % 5 % 95 %
Ethylene glycol monomethyl
ether 20 %
Polyethylene glycol
MW 400 70 %
N-methyl 2-pyrroliclons~ -2() ~/o ~ -
E~poxitlised eoconut oil - - I % 5 %
Petroleum ether
(boiling range 160-19ûC) - - 94 %
The solutions are suitable for use in the form of microdrops.
Example 4.3: Granules a) b)
Active substance of Table 15 % 10 %
Kaolin 94 %
Highly-clisperse silica 1 %
Attapulgite - 90 %
~3 ~ ~ ~ 7 ~ ~ ~
- 63 -
The active substance is dissolved in methylene chloride, the solution is sprayed onto the
carrier, and the solvent is subsequently evaporated in vacuo.
Example4.4: Dusts a) b)
Active substance of Table 1 2 %5 %
I-lighly-disperse silica 1 %5 %
Talc 97 %
Kaolin - 9() %
Ready-for-use dusts are obtained by intimately mixing the carriers with the active
substance~
Example 4.5: Wettable powders a)b) c)
Active substance of Table 1 25 %sn %75 %
Naligninsulfonate 5 ~/O5 %
Na lauryl sulfate 3 % - S %
Na diisobutylnaphthalenesulfonate - 6 % 10 %
Octylphenol polyethylene glycol
ether (7-8 mol of EO) - 2 %
Highly-disperse silica S %1()% 10 %
Kaolin 62 %27 ~/o
'ï he active subxtance or the active substance combination is mixed with the additives and
thoroughly ground in a suitable mill. This gives wettable powders which can be diluted
with water to give suspensions of any desired concentration.
Example 4.6: Emulsion concentrate
Active substance of Table 1 10 %
Octylphenol polyethylene glycol ether
(4-5 molofEO) 3 %
Ca dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether
(36 mol of EO) 4 %
J,~j 3,~
.,
- 64-
Cyclohexanone 30 %
Xylene mixture 50 %
Emulsions of any desired concentration can be prepared from this concentrate by dilution
wilh water.
Example 4.7: Dusts a)b)
Active substance of Table I 5 %8 %
Talc 95 %
Kaolin - 92 %
Ready-for-use dusts are obtained by mixing the active substance with the carrier and
grinding the mixture on a suitable mill.
Example 4.8: Extruder ~ranules
Active substance of Table 1 10 %
Na ligninsulfonate 2 %
Gurboxyrmethylcellulose 1 %
Kaolin 87 %
Tllc ,Ictive subst,lncc or the corllbitl.ltion of active xubst.lnce~ is mixed with the ad(litives7
and th~ mixture is groulld and moistcned with water. This mixture is extruded, gr"nul,lted
alld subscquently dried in a stream of air.
Exarnple 4.9: Coated ~ranules
Active substance of Table 1 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
In a mixer, the finely-ground active substance or combination of active substances is
applied uniforrnly to the kaolin which has been moistened with polyethylene glycol. In
this manner, dust-free coated granules are obtained.
t ~ r~
- 65 -
Example 4.10: _spension concentrate
Active substance of Table 1 40 %
Ethyleneglycol 10 %
Nonylphenol polyethylene glycol ether .
(lSmolofEO) 6 %
Na ligninsulfonate 10 %
Carboxymethylcellulose 1 %
37 % aqueous formaldehyde solu~ion ().2%
Silicone oil in the folm of a
75 % aqueous emulsion 0.8%
Water 32 %
The finely-ground active substance or the combination of active substances is mixed
intimately with the additives. In this manner, a suspension concentrate is obtainecl from
which suspensions of any desired concen~ation can be prepared by dilution with water.
Example 5: Effectiveness agains~ Nilaparvata lu~ens
Rice plants are treated with an aqucous ernulsion spray mixture which contains 400 ppm
of the active substance. After the spray coating has clried on, the rice plants are pop~llated
with cicada larvae of the ~nd .md 3rd stage. The test is evalu.lted after 21 (lays. 'l he
percentage reduction of the populatiorl (% efÇectivcness) i9 determirled by cornparirl~ the
nllmbor of .suIviving cica~ s on thl~ treated plants witll those Oll the untreated plants.
In this test, the compounc!s of Table I are very effective against Nilaparvata lugens. In
particular, cvmpounds 1.001, 1.008, 1.~9, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025,
1.028, 1.039, 1.081, 1.0~5, 1.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.169, 1.183
and 1.189 have an effectiveness of more than 80 %.
Example 6: Effectiveness aga-i-nst Nephotettix cincticeps
Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm
of the active substance. After the spray coating has dried on, the rice plants are populated
with cicada larvae of the 2nd and 3rd stage. The test is evaluated after 21 days. The
percentage reduction of the popula~ion (% effectiveness) is determined by comparing the
66 -
number of survivin~ cicadas on the treated plants with those Oll the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In
particular, compounds 1.001, 1.008, 1.009, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025,
1.028, 1.039, 1.081, 1.085, 1.101, 1.102, 1.103, 1.1~g, 1.153, 1.157, 1.165, 1.169, 1.183
and 1.184 have an effectiveness of more than 80 %.
Example 7: Effectiveness a~ainst Spodoptera littoralis caterpillars
Young soya plants are sprayed with an aqueous emulsion spray mixture which contains
400 ppm of the active substance. After the spray coating has dried on, the soya plants are
populated with 10 Spodoptera littoralis caterpillars of the third stage and placed in a
plastic container. The test is evaluated after 3 days. The percentage reduction of the
population, or the percentage reduction of feeding darnage, (% effectiveness) isdetermined by comparing the number of dead caterpillars and the feeding damage on the
treated plants with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Spodoptera littoralis. In
particular, compound 1.015 has an effectiveness of more than 80 %.
Ex,l~e 8: Effectlveness a~ainst Aphis cracci a
Pea seedlin~s are infec,ted with ~phis craecivor.l, then sprayed with a sprily mixtule wllich
cont;lirls 4()0 pprn of the netiv~ ~ubstnrlee, an~l incub.ltc,cl at 2()C. 'l'he tost is ev.~ .lte(l
.llt~r 3 iln(l 6 d;lys. Th~ percent.l~e redueti(ln of the population ~/o effectiv~lIes~) is
cletc,Imined by comparing the number oP dead aphids on the treated plants with tl-ose on
the untreated plants.
In this test, the compounds of Table 1 are very effective against Aphis craccivora. In
particular,compounds 1.008,1.010,1.()11,1.012,1.015,1.022,1.028,1.081,1.084, 1.085,
1.101, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
Example 9. Ef~ectiYeness a~ainst Nilaparvata lu~ens, sYstemic
Pots containing rice plants are placed in m aqueous emulsion solution which contains 400
ppm of the active substance. The rice plants are then populatecl with larvae of the 2nd and
- (17
3rd stage. The test is ev"luated .Ifter 6 days. The percentage recluction of the population
(% effectiveness) is deterrnine:l by comparing the number of cicadas on the treated plants
with those on the untreated plants.
In this test, the compounds of Table 1 ~ure very effective against Nilaparvata lugens. In
particular, compounds 1.001, 1.008, l.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028,
1.039, 1.081, 1.084,1.085, l.101, 1.102, 1.103, 1.149, 1.153, 1.157, 1.165, 1.16~), 1.183
and 1.184 have an effectiveness of more than 80 %, even when the concentration is 12.5
ppm.
Example 10: Effectiveness a~ainst Nepho~ettix cincticeps, sYstemic
Pots containing rice plants are placed in an aqueous emulsion solution which contains 400
ppm of the active substance. The rice plants are then populated with larvae of the 2nd and
3rd stage. The test is evaluated after 6 days. The percentage reduction of the population
(% effectiveness) is determined by comparing the number of cicadas on the treated plants
with those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Nephotettix cincticeps. In
particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.024, 1.025, 1.028, 1.039,
1.081, 1.084, 1 085,1.101, 1.102~ 1.10~, 1.1~9, 1.153, 1.157, l.l65, l.lt~, 1.183
I .184 have an effectiveness of more than 80 crto.
Exarl1~?le 11. E~f~ctiveness a~t MY~Ig ~ ;iCaC systerTlic
Pe~a scc(llings are infectecl with Myxus persicae, then placed with their roots in a spray
mixture which contains 400 ppm of the active substance, and incubated at 20C. The test
is evaluated after 3 and 6 days. The percentage reduction of the population
(% effectiveness) is deterrnined by comparing the number of dead aphids on the treated
plants with those on the untreated plants.
In this test, the compounds of 'I'able 1 are very effective against Myzus persicae. In
particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.028, 1.081, 1.084, 1.085, 1.101,
1.149, 1.153, 1.157, 1.165 and 1.169 have an effectiveness of more than 80%.
~ ~3 ~
- 6X -
Example 12: Effectiveness a~ainst Anthonomus grandis adults
Young cotton plants are sprayed with an aqueous emulsion spray mixture which contains
400 ppm of the active substance. When the spray coating has dried on, the cotton plants
are populated with 10 Anthonomus grandis adults and placed in a plastic container ~he
test is evaluated after 3 days. The percentage reduction of the population, or the
percentage reduction of the feeding damage ~% effectiveness), is determined by
comparing the number of dead beetles and the feeding damage on the treated plants with
those on the untreated plants.
In this test, the compounds of Table 1 are very effective against Anthonomus grandis. In
particular, compounds 1.008, 1.010, 1.011, 1.012, 1.015, 1.022, 1.028, 1.101, 1.149 and
1.153 have an effectiveness of more than 80 %.
~xample 13: Effectiveness a~ainst Bemisia tabaci
Dwarf bean plants are placed in gauze cages and populated with Bemisia tabaci adults
(whitefly). When oviposition has taken place, all adults are removed, and, after 10 days,
the plants together with the nymphs which live on them are treated with an aqueous
emulsion spray mixture of the active substances to be tested (concentration 400 ppm). 14
days after the active substance has been applied, the h.ltching rate is evalu.ltecl as a
percentage in cornparison with the untreated control batchex.
~n this test, the eompolln(ls in accor(l.lnce with l'able 1 are very efl~ective a~.lins~ Bemisia
tabaci. In partieular, compouncls 1.011, 1.()12, 1.015, 1.081, 1.084, 1.085, 1.101 and 1.1~)2
have an effectiveness of more than 80 %.
Example 1~: Effectiveness against Diabrotica balteata larvae
Maize seedlings are sprayed with an aqueous emulsion spray mixture which contains 400
ppm of the active substance. When the spray coating has dried on, the rnaize seedlings are
populated with 10 Diabrotica balteata larvae of the second stage and placed in a plastic
container. The test is evaluated after 6 days. The percentage reduction of the population
(/0 effectiveness) is determined by comparing the number of dead larvae on the treated
plants with those on the untreated plants.
~J ~ ~,
In this test, the compounds of Table 1 are very effective against Diabrotica balteata. In
particular, compounds 1.010, 1.012 and 1.015 have an effectiveness of more than 80 %.
Exam~le 15: Effectiveness against Heliothis virescens caterpillars
Young soya plants are sprayed with all aqueous emulsion spray mixture which contains
400 ppm of the active substance. After the spray coating has dried on, the soya plants are
populated with 10 caterpillars of the first sta~e of Heliothis virescens and placed in a
plastic container. The test is evaluated after 6 days. Ihe percentage reduction of the
population, or the percentage reduction of the feeding damage, (% effectiveness) is
determined by comparing the number of dead caterpillars and the feeding darnage on the
treated plants with those on the untreated plants.
'
In this test, the compounds of Table 1 are very effective against Heliothis virescens. In
particular, compounds 1.010, 1.011 and 1.015 have an effectiveness of more than 80 %.
Example 16: Effectiveness a~ainst Crocidolomia binotalis caterpillars
Young cabbage plants are sprayed with an aqueous esnulsion spray mixture which
contains 400 ppm of the active substance. After the spray coating has dr~ed orl, the
cabbage plants are populated with 10 caterpillars of the thircl ~tage of Crvci(:Lolvmia
binotalis and placed in a plastic container. The test is evaluated aftcl 3 d;lys. The
percenta~e reduction of the poplllation, or the pcrcenta~e redllctiorl of ~he fee(ling d;lmage,
(% effectivencss) ix determined by comparin~ the numbcr of ~lea(l caterpillars and the
Peeding darnage on the treated plants with those on the untreated plants.
In this test, the cornpounds of Table 1 are very effective against Crocidolomia binotalis. In
particular, compound 1.015 has an effectiveness of more than 80 %.
Effectiveness a~ainst MYZUS persicae
Pea seedlings are infected with Myzus persicae, th~n sprayed with a spray liquor which
contains 400 ppm of the active substance, and incubated at 20C The test is evaluated
after 3 and 6 days The percentage reduction of the popula~ion (% effectiveness) is
deterrnined by comparing the number of dead aphids on the treated plants with those on
the untreated plants.
r~ r~ ~3
- 7() -
In this test, the compounds of Table I are very effec~ive against Myzus persicae. In
particular, compounds 1.008, 1.010, 1.012, 1.015, 1.022 and 1.157 have an effectiveness
of more than 80 %.
