Note: Descriptions are shown in the official language in which they were submitted.
2~3~
PS/5-17920/=
Nematicidal and fun icidal compositions
The present invention relates to novel 2-(pyrimidyl or pyrazinyl)-imino-1,3-dithietanes, to
the preparation thereof, and to nematicidal compositions that contain at least one of those
compounds as active ingredient. The invention relates also to novel intermediates of the
process for the preparation of the compounds, to the use thereof, and to compositions for
controlling nematodes and fungi, especially plant-destructive nematodes and fungi.
(especially
The invention relates to 2-(pyrimidyl or pyrazinyl)-imino- 1,3-dithietanes of formula I
/S\ /XI
Ar--N=-\ /-\ (I),
S X2
wherein
Ar is one of the radicals
~N ~N N~ ~N3
R is unsubstitùted Cl-C3alkyl or Cl-C3alkyl which is substituted by halogen, Cl-C3alkyl,
Cl-C3aLkoxy, Cl-C3aLlcylthio or cyano, independenUy of one another, or is unsubstituted
or halo-substituted C3-C7aLI~enyl, unsubstituted or halo-substi~uted C3-C7aL~cynyl, or
C3-C5cycloalkyl, Cl-C3alkoxy, Cl~C3alkylthio, di-CI-C3aLIcylamino, nitro or halogen,
n is a number from 0 to 3,
Xl and X2 independently of each other are hydrogen or halogen, including ~e addition
salts formed with acids of the formula H~3X~3 in which the anion X/3 is Cl~, Br~HS04, H2P04, H2P03, N03-, CH3C00~, CH2ClCOO-, CF3C00-, HOCH2C00-,
~ .
- ~
.: . : .
2~3~
- 2-
CH3CH(OH)COO~), HOOCCOO~, HooCCH2Coo~3~ HooCCH=CHCoo~
S03H
CH3~ 50~
S03
AL~yl as an independent radical and as part of another group, such as alkoxy, aL~ylthio or
dialkylamino, shall be understood as includin~g the methyl and ethyl groups and also
normal propyl and isopropyl. Halo-substituted alkyl is a mono to per-halogenated aLIcyl
radical, for example CHCI2, CH2F, CC13, CH2Cl, CHFCH2, CH2CH2Br, CF2CF3, C2Cls,
CH2Br, CHBrCl, etc.. An example of alkylthio is ethylthio. Alkenyl is, for example,
propenyl-(l)t allyl, butenyl-(l), butenyl-(2) or butenyl-(3), and also chains having several
double bonds. Alkynyl is, for example, propynyl-(2), butynyl-(l), butynyl-(2),
pentynyl-(4), etc.. Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine.
Examples of salt-forming acids are, of the inorganic acids: hydrohalic acids, such as
hydrochlo~ic acid, hydrobromic acid or hydriodic acid, and also sulfurous acid, sulfuric
acid, phosphoric acid, phosphorous acid and nitric acid, and of the organic acids: acetic
acid, trifluoroacetic acid, monochloroacetic acid, glycolic acid, succinic acid, oxalic acid,
maleic acid, fumaric acid, p-toluenesulfonic acid and naphthalene-1,5-disulfonic acid.
Salts of 2-(2-pyridylimino)-1,3-thietane having nematicidal activity are already known
from FP-A-310540, but in the control of harmful nematodes they are unable fully to
satisfy the demands made of them.
With the provision of the compounds of formula I according to ~he invention, it is now
possible to make a valuable contribution to controlling plant nematodes and fungi which
cause considerable agricultural damage to plants. In this manner, losses in yield of
cultivated plants, for exarnple potatoes, cereals, beet crops, rape, cabbage, tobacco~
soybe~ms, cotton, maize, rice ~md vegetables, and also damage caused in tree nurseries and
to ornamentals can be inhibited over a prolonged period. The compounds according to the
invention are distinguished especially by the fact that ~hey effectively control soil
.
.
~. ' -
2 ~
- 3 -
nematodes that parasitise roots, for example nematodes of the genera Heterodera an(l
Globodera (cystogenic nematodes), Meloidogyne (root-knot nematodes) and also of ~he
genera Radopholus, Pratylenchus, Tylenchulus, Longidorus, Trichodorus and Xiphinema.
The nematode genera Ditylenchus (stem parasites~, Aphelenchoides (leaf nema~odes) and
Anguina (blossom nematodes) can also be effectively controlled with the compounds
according to the invention.
Preferably, the compounds of formula I are used for successfully controlling especially
harmful nematode species of the genus Meloidogyne, for example Meloidogyne incognita,
of the genus Heterodera, for example Heterodera glycines (soybean cyst nematode), and of
the genus Globodera, for example Globodera rostochiensis (potato cyst nematode), as well
as representatives of mi~rating endoparasites, for example Pratylenchus penetrans or
Radopholus similis, and representatives of ectoparasites, for example Trichodorus spp.
and Xiphinema spp..
Preferably, the compounds of formula I are likewise used for successfully controlling
especially harmful fungi, for example Ascomycetes, such as Erysiphe gramini, Fungi
imperfecti, such as Botrytis cinerea, and Cercospora beticola.
To control plant nematodes and soil fungi and for the preservation of plant health, the
novel compounds may be used curatively, preventively or systemically. They have a
broad spectrum of activity against the various nematode and soil fungus species and
therefore meet the requirements made of them in practice. The nematicidal and fungicidal
mode of action of the compounds of the invention is coupled in advantageous manner with
a low phytotoxicity, whereby the generally desirable reduction of harm to the environment
is especially accommodated.
A preferred sub-group comprises compounds of formula I wherein R is methyl, methoxy,
methylthio or chlorine, n is a number from O to 2, and Xl and ~2 independently of each
other are hydrogen or fluorine.
Of the above-mentioned compounds, special preference is given on account of their
nematicidal activity to those compounds wherein R is methyl, methoxy or methylthio, n is
O or 1, and Xl and X2 are hydrogen.
Of ~hose compounds~ special mention should be made of those of formulae Ia, Ib, Ic and Id
2~3~2~l~
N = / \ (Ia),
R,~ S (Ib),
N S
N~ S~ (Ic),
N S
~!LN= / \CU ad)
Of the compounds of formula Ia, special mention should be made of
2-~2-pyrimidyl)-imino-1,3-dithietane.
Of the compounds of formula Ib, mention should be made of
2-(4-pyrimidyl)-imino- 1 ,3-dithietane.
Similarly, of the compounds of formula Ic, special mention may be made of
2-(5-pynmidyl)-imino- 1,3-dithietane.
Finally, of the compounds of formula Id, 2-(2-pyrazinyl)-imino-1,3-dithietane is of
importance.
According to the invention, compounds of formula I are prepared by converting a
pyrimidyl- or pyrazinyl-amine of formula II into an adduct of fonnula III with carbon
disulfide and with a base B, with or without a solvent, at from -10 to 50C
''-'' ` 2 ~ 3
Ar - NH2 + CS2 + B Ar - NH--C
Il .
II Il[
converting that adduct into the reaction product of formula I with a dibromomethane
derivative of formula IV or with the corresponding diiodo derivative and with a base, with
or without a solvent, at from -10 to 100C
Br Xl
\ /
III +C\ +B _ I + 2Br~
Br X2
IV
and isolating that reaction product or converting it into the addition sait I.H~X~3 with an
acid of the formula HfflX~, the radicals Ar, Xl, X2 and X0 being as defined under
formula I and B being a hydroxide, a hydride or a carbonate of an alkali metal or an
aLIcaline earth metal, or a tertiary amine. The present invention also includes ~hat process.
The starting materials of forrnulae II and IV are generally known and can be prepared by
known processes.
According to a preferred form of the process according to the invention, the preparation of
the adduct of formula III is carried out in a solvent at from 0 to 40C, and the reaction of
that adduct with the dibromomethane derivative of formula IV is carried out in a solvent at
from 0 to 80~C
This forrn is preferred when B is a trialkylamine or a hydride, a hydroxide or a carbonate
of an alkali metal or an aLI~aline earth metal.
Solvents or diluents suitable for the preparation of the active ingredients according to the
invention are, for exarnple, alcohols, such as methanol, ethanol, isopropanol or butanol;
`
,
. ~ :
f~
- 6 -
N,N-diaL~ylated amides, such as dimethylforrnamide; dimethyl sulfoxide; ethers and
ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl
methyl ether, etc.), anisole, dioxane, tetrahydrofuran; aliphatic and aromatic hydrocarbons,
such as benzene, toluene, petroleum ether; halogenated hydrocarbons, such as
chlorobenzene, methylene chloride, chlorofo~m, ethylene chloride, carbon tetrachloride,
tetrachloroethylene; nitriles, such as acetonitrile, propionitrile; ketones, such as acetone,
diethyl ketone, methyl ethyl ketone; and also water and, very generally, mixtures of such
solvents with one another.
~uitable bases are organic and inorganic bases; for example preferably tertiary amines,
such as triaL~cylamines (trimethylamine, triethylamine, tripropylamine, etc.) as well as
oxides, hydroxides, carbonates and hydrogen carbonates of aLIcali metals and aL~aline earth
metals (e.g. CaO, BaO, NaOH, KOH, Ca(OH)2, KHCO3, NaHCO3, Ca(HCO3)2, K2CO3,
Na2CO3, etc.), and also acetates, such as CH3COONa or CH3COOK. Furthermore,
suitable bases are also aL~ali metal alcoholates, for example sodium ethanolate, sodium
propanolate, potassium tert.-butanolate or sodium ethanolate, and also aLIcali metal
hydrides, for example sodium hydride.
The invention relates also to compositions, for controlling plant-destructive nematodes
and for protecting plants from attack by nematodes, that contain the compounds of
formula I.
In addition, the present invention also includes the preparation of nematicidal and
fungicidal compositions, which comprises homogeneously mixing compounds of
forrnula I with one or more of the carliers and adjuvants described herein. Also included
is a method of treating plants, which comprises applying thereto the compounds of
formula I or the novel compositions.
A preferred method of applying a compound of formula I or a nematicidal composition
containing at least one of those compounds, is incorporation into the soil, which comprises
treating the locus of the plants with a liquid or solid formulation.
The compounds of formula I can, however, also be applied to seeds ~dressing/coating)
either by impregnating the seeds with a liquid formulation of the active ingredient or by
coating them with a solid formulation. In special cases, other methods of application are
also possible, ~or example selective treatment of the plant stems, buds or leaves.
2 ~
The compounds of formula I are normally applied in the form of compositions and can be
applied to the crop area or plant to be treated, simultaneously or in succession, with further
compounds. These further compounds can also include other substances applied in
agriculture which are used to increase production by promoting the growth of useful
plants, such as fertilisers, herbicides, insecticides, fungicides, molluscicides etc., or may
be mixtures of several of these preparations, if desired together with further carriers,
surfactants or other application-promoting adjuvants customarily employed in the art of
formulation.
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances
ordinarily employed in formulation technology, e.g. nalural or regenerated mineral
substances, solvents, dispersants, wetting agents, tacki~lers, thickeners, binders or
fertilisers.
The compounds of formula I are used in unmodified form or, preferably, together with at
least one adjuvant or the adjuvants conventionally employed in the art of formulation,
respectively. They are formulated in known manner e.g. into emulsifiable concentrates,
directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble
powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with
the nature of the compositions, the methods of application, such as spraying, dusting,
scattering or pouring, are chosen in accordance with the intended objectives and the
prevailing circumstances. Advantageous rates of application are normally from 300 g to
6 kg of active ingre~ient (a.i.) per hectare; preferably from 0.3 to 2 kg a.i./ha.
The formulations, i.e. the compositions, preparations or mixtures containing the compound
(active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are
prepared in known manner, e.g. by homogeneously mixing and/or grinding the active
ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-
active compounds (sur~actants).
Suit~ble solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12
carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibu~l
phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins,
alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene
glycol monometnyl or monoethyl ether, ketones such as cyclohexanone, strongly polar
,
~ .
-"' ' . ' ~ `
solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as
well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or
soybean oil; or water.
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural
mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgi~e. In order to
improve the physical properties it is also possible to add highly dispersed silicic acid or
highly dispersed absorbent polymers. Suitable granulated adsorpdve carriers are po~ous
types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent
carriers are, for example, calcite or sand. In addition, a great number of pregranulated
materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised
plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable
surface-active compounds are non-ionic, cationic an~Vor anionic surfactants having good
emulsifying, dispersing and wettin~ properties. The term "surfactants" will also be
understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active
compounds are suitable anionic surfactants.
Suitable soaps are the aL~ali metal salts, alkaline earth metal salts or unsubstituted or
substituted ammonium salts of higher fatty acids (C1O-C22), e.g. the sodium or potassium
salts of oleic or stearic acid, or of natural fatty acid mixtures which c~m be obtained e.g.
from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts
and modifled and unmodified phospholipids.
More frequently, however, so-called synthetic surfactants are used, especially fatty
sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.
The fatty alcohol sulfonates or sulfates are usually in the form of aL~ali metal salts,
aL~aline earth metal salts or unsubstituted or substituted ammonium salts and contain a
C8-C22aL~yl radical, which also includes ~he alkyl moiety of acyl radicals, e.g. the sodium
or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol
sulfates obtained from natural fatty acids. These compounds also comprise the salts of
sulfated and sulfonated fatty alcohollethylene oxide adducts. The sulfonated benz-
2~3~?~c~
imidazole derivatives preferably con~ain 2 sulfonic acid groups and one fatty acid radicalcontaining g to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium
or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid,
or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an
adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or
cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said
derivatives containing 3 to 30 ~lycol ether groups and 8 to 20 carbon atoms in the
(aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl Moiety of the
aL~cylphenols.
Further suitable non-ionic surfactants are the water soluble adducts of polyethylene oxide
with polypropylene glycol, ethylenediaminopolypropylene glycol and aL~ylpolypropylene
glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250
ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These
com~ounds usually contain 1 to S ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols,
castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-
polyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are
also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as
N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or
halogenated lower aLlcyl, benzyl or hydroxy-lower al}~yl radicals. The salts are preferably
in the form of halides, methyl sulfates or ethyl sulfates, e.g. ste~ryltrimethylammonium
chloride or benzyldi(2-chloroethyl)ethylammoniurm bromide.
The surfactants customarily employed in the art of formulation are described inter alia in
the following publications:
.
' '
2 ~
- 10-
"McCutcheon7s De~ergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood,
New Jersey, 1979; Dr. Helmut Stache, "Tensid Taschenbuch", Carl Hanser Verlag,
Munich/Vienna.
The agrochemical compositions usually contain 0.1 to 99 % by weight, preferably 0.1 to
95 % by weight, of a compound of forrnula I, 99.9 to l % by weight, preferably 99.8 to 5
% by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 %
by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user
will normally employ dilute formulations.
The compositions may also contain further auxiliaries such as stabilisers, antifoams,
viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for
obtaining special effects.
The present invention relates also to such agrochemical compositions.
The following Examples illustrate the invention in greater detail but do not limit the
invention.
1. Preparation Examples:
2-(5-Pyrimidylimino)-1,3-dithietane (compound 1.1)
23.4 g (0.232 mol) of triethylamine are added dropwise to a ready-prepared solution of
20 g (0.211 mol) of 5-aminopyrimidine and 12.7 ml (0.211 mol) of carbon disulfide in
50 ml of ethyl alcohol. The reaction mixture is then stirred for 15 hours at 70C and the
resulting suspension is filtered off. Drying yields 10 g of carbon disulfide adduct. The
filtrate is concentrated by evaporation, yielding a further 27 g of the intermediate as the
residue.
A mixture of 41.9 g (0.241 mol) of dibromomethane and 3.7 g (0.037 mol) of
triethylarnine in 20 ml of dimethylformamide is added dropwise at 25C with stirring to
10 g (0.037 mol) of the intermediate in 40 ml of dimethylforrnamide. The reaction
mixture is stirred at 25C for 20 hours and then poured onto ice-water and extracted with
diethyl e~her. The comhined diethyl ether extracts are extracted three times with 100 ml
2 3~ 3 ~ ~J ~
of water each time, dried over sodium sulfate, filtered and concentrated by evaporation.
The crude product is purified over a silica gel flash column with ethyl acetate/hexane
(2/1), yielding 2.7 g (40 % of the theoretical yield) of product having a melting point of
97-99C.
2-(5-Pyrimidylimino)-1,3-dithietane hydrochloride (compound 1.2)
Dry HCl gas is introduced at 0-10C over a period of half an hour into a solution of 0.5 g
(2.732 mmol) of 2-(5-pyrimidylimino)-1,3-dithietane in 50 ml of diethyl ether. The resul-
ting product is filtered off, washed with diethyl ether and dried, yielding 0.5 g (83.4 % of
the theoretical yield) of product having a melting point (decomp.) of 150C and above.
The compounds listed in the following Tables 1 to 4 can be prepared analogously to the
above Examples.
Table 1 2-(5-Pyrimidyl)-imino-1 3-di~hietatles
R2
N~ S Xl
Rl~/ ~ c~s /
R3
,
.
.
2 0 3 ~
- 12-
__
NomP Rl R2 R3 Xl X2 HXPhysical data
1.1 H H H H H m.p. 97-99C
1.2 H H H H H HClm.p. >150C (decomp.)
1.3 H H H H H H2~4m.p.>ll0C (decomp.)
1.4 H H H H H HBR
1.5 H H H H H HI
1.6 H H H H H HNO3
1.7 H H H H H H2SO3
1.8 H H H H H H3PO4
1.9 H H H H H CH3COOH
1.10 H H H H H (COOH)2
1.11 H H H H H ClCH2COOH
1.12 H H H H H EIOCH2COOH
1.13 H H H H H CH2(COoH)2
1.14 H H H H H CH-COOH
CH-COOH
1.15 H H H H H CH3~ SO3H
SO3H
.16 ¦H l ¦ ~1 ~ H ¦ s )3H
1.17 CH3- H H H H
1.18 CH3 H H H H HCl
1.19 CH3 H H H H H2SO4
1.20 H H H F F
1.21 H H H Cl Cl
1.22 CH3 H H P F _ . _ .
- 13-
Table 2- 2-(4-PyAmidyl)-imino-1,3-dithietanes
.
R2 R3
N~N=C~ ~C ~ (Ib).HX
Rl
Comp R~ R2 R3 Xl X2 HX Physical data
_
2.1 H H H H H m.p. 153-155C
2.2 H H H H H HCI
2.3 H H H H H H2SO4
2.4 H H H H H CH3COOH
2.5 H H H H H CH3--~ S03H
2.6 CH3 CH3 H H H
2.7 CH3 CH3 H H H HCI
2.8 CH3 CH3 H H H H2SO4
2.9 CH3S Cl H H H
2.10 CH3S Cl H H H HCl
2.11 CH3S Cl H H H H2SO4
2.12 H H H F F
2.13 H H H CI CI
2.14 CH3S H CI F F
:Z. 15 CH3C H CH3C F F
. ,.
... .. . . . ..
: . . . ~ , .
2 ~ 3 ~ r ~
- 14-
Table 3. 2-~2-Pvrimidyl)-imino-1.3-dithieLanes
R
~N S X
R2~ N = C~ ~ C . HX (Ic) H~
~= N X2
R3
Comp Rl R2 R3 Xl ~2 HX Physical data
_ _
3.1 H H H H H m.p.: 173-17SC
3.2 H H H H H HCI
3.3 H H H H H H2SO4
3.4 H H H H H CH3COOH
3.5 H H H H H HNO3
3.6 H H H H H CH3~ SO3H-
3.7 H Br H H H
3.8 H Br H H H HCI
3.9 H Br H H H H2S~
3.10 H CH3 H H H m.p. lQ2-103C
3.11 H CH3 H H H HCl
3.12 CH3 H CH3 H H
3.13 CH3 H CH3 H H HCl
3.14 CH3 H CH3 H H H2SO4
- .
~'
- 15-
Table 3 (continuation)
Comp RlR2 R3 X1 X2 HX Physical data
__ _
3.15 CH3 H ~ H H
3.16 CH3 H D--H H HC1
3.17 CH3 H D--H H H2SO4
3.18 CH3 H H H EI
3.19 CH3 H H H H HC1
3.20 CH3 H H H H H2SO4
3.21 H No2 H H H
3.22 H No2 H H H HC1
3.23 H No2 H H H H2SO4
3.24 H H H F F .
3.25 H H H C1 C1
3.26 H Br H F F
3.27 H CH3 H F F
3.28 CH3 H CH3 F F
3.29 CH3 H C~ F F
3.30 H No2 H F F
3.31 C1 H CH3 H H
3.32 C1 H CH3 H H HCI
3.33 Cl H CH3 H H H2SO4
3.34 C1 H CH3 F F
3.35 Cl H Cl H H
3.36 CH3 H OCH3 H H .
3.37 CH3 H OCH3 H H HC1
3.38 CH3 H OCH3 H H H2SO4 _
'. ~' ~ ' . ,
~ ' - . ' ' ~
~ . . . . .
~ ~ 3 ~
- 16 -
Table 4: 2-(2-Pyrazinyl)-imino- 1 ,3-dithietanes
R2 ~ N R3
J~ ~CN =C~ \ /
X2
_ _
Comp RlR2 R3 Xl X2 HX Physical data
_ . .
4.1 H H H H H m.p. 154-156C
4.2 H H H H H HCl m.p. 162-165C
4.3 H H H H H H2SO4 m.p. 158-159C
4.4 H H H H H CH3 V S03H
4.5 H H H F F .
4.6 H H H F F HCI
4.7 H H H F F H2SO4
4.8 ~H3 H H H H
4 9 CH3 CH3 H H H
4.10 CH3 CH3 H F F
4.11 H H CH3 H H _ _
2. Formulation Examples for liquid active in~redients of formula I (throuohout,
percentages are by wei~ht)
2.1 Emulsifiable concentrates a) b) c)
a compound of Tables 1 to 4 25 % 40 % ~0 %
calcium dodecyl benzenesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether
. .
'
~ ~ 3 ~
- 17-
(36 moles of ethylene oxide) 5 % - -
tributylphenol polyethylene glycol
ether (30 rnoles of ethylene oxide) - - 12 %
cyclohexanone - 15 % 20 %
xylene mixture 65 % ~5 % 20 %
Emulsions of any desired concentration can be produced from such concentrates bydilution with water.
2.2 Solutions a) b) c) d)
-
a compound of Tables 1 to 4 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether 20 %
polyethylene glycol (mol. wt. 400) - 70 %
N-methyl-2-pyrrolidone - 20 % -
epoxidised coconut oil - - 1 % 5 %
petroleum fraction (boiling
range 160-190C) - - 94 % - `
These solutions are suitable for application in the form of microdrops.
2.3 Granulates a) b)
a compound of Tables 1 to 4 5 % 10 %
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the
carrier, and the solvent is subsequently evaporated off in vacuo.
2.4 Dusts a) b)
a compound of Tables 1 to 4 ~ % 5 %
highlydispersedsilicicacid 1 % 5 %
talcum 97 %
kaolin - 90 %
Ready-for-use dusts are obtained by intimately mixing the carriers with the active
.
2 ~ L~r ;~
- 18-
ingredient.
Formulation Examples for solid active inl redients of formula I ~throughout, percen~ages
are bY weight)
2.5 Wettable powders a) b) c)
acompoundofTables 1 to4 25 % 50 % 75 %
sodiumlignosulfonate 5 % 5 %
sodiumlaurylsulfate 3 % - 5 %
sodium diisobutyl naphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is
thoroughly ground in a suitable mill, affording wettable powders which can be diluted
with water to ,give suspensions of the desired concentration.
2.6 Emulsifiable concentrate
a compound of Tables 1 to 4 10 %
octylphenol polyethylene glycol ether
(4-5 moles of ethylene oxide) 3 %
calcium dodecyl ben7enesulfonate 3 %
castor oil polyglycol ether
(35 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture 50 %
Emulsions of any required concentration can be obtained from this concentrate by dilution
with water.
2.7Dus~s a) b)
acompound of Tables 1 to4 5 % 8 %
talcum 95 %
kaolin - 92 %
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Ready-for-use dusts are obtained ~y mixing the active ingredien~ with the carriers and
grinding the mixture in a suitable mill.
2.8 Extruder ~ranulate
a compound of Tables 1 to 4 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient is mixed and ground with the adjuvants, and the mixture ismoistened with water. The mixture is extruded and then dried in a strearn of air.
2.~ Coated ~ranulate
a compound of Tables 1 to 4 3 %
polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin
mois~ened with polyethylene glycol. Non-dusty coated granulates are obtained in this
manner.
2.10 SusPension concentrate
a compound of Tables 1 to 4 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether
(15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the forrn of a 75 %
aqueous emulsion 0.8 %
water 32 %
The finely ground active ingredient ls intimately mixed with the adjuvants, giving a
suspension concentrate from which suspensions of any desired concentration can be
2 ~ 3 l~
- 20-
obtained by dilution with water.
2. Biolo~ical Examples
2.1 Action against MeloidogYne inco~nita on tomato plants
Eggs of Meloidogyne incognita are mixed into sand. This mixture is then put into 200 ml
clay pots (5000 eggs per pot~. On the same day a three-week-old tomato plant is planted
in each pot and the formulated test compound is introduced into the pots by drench
application (0.0006 % of active ingredient, based on the volume of the soil). The potted
plants are then placed in a greenhouse at a temperature of 26+1C and a relative humidity
of 60 %. After 4 weeks, eval~lation is made by examining the plants for root-knot
for~ation in accordance with the so-called Root-Knot Index.
Compounds of Tables 1-4 exhibit activity against Meloidogyne incognita by reducing
root-knot formation. On the other hand, untreated and infected control plants exhibit
severe root-knot formation (= 100 %). Compounds nos. 1.1, 1.2, 1.3, 3.1 and 4.1, f~r
example, exhibit good activity with less than 20 % residual attack, the compounds even
inhibit root-knot formation almost comple~ely (0-10 % residual attack) in this test.
2.2 Action against Heterodera glycines on soybeans
Sandy soil is infested with eggs of the soybean cyst nematode H. glycines, approximately
6000 eggs per pot. The test compounds are then mixed in at the appropAate concentra-
tions. The treated and infested soil is then put into lc pots (180 ccm) and three soybeans
(cv. Maple Arrow) are sown in each pot. Each treatment is repeated three times. The pots
are incubated in a greenhouse at about 27C for four to five weeks. The plants are then
carefully removed from the pots, the roots are washed, and the number of cysts is
determined. The activity is rated in accordance with a scale of 1-9 (1 = full activity, 9 =
no activity).
The compounds of Tables 1-4 exhibit good activity against Heterode~a glycines, which is
shown by the almost complete reduction of cyst formation.
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