Note: Descriptions are shown in the official language in which they were submitted.
83~
-- 1 --
5-1498g/~
Pesticidal compositions
The present inventlon relates to novel
N-(2 nitrophenyl)-2-aminopyrimidine derivatives of formula I below.
The invention further relates to the preparation of thesP compounds
and to agrochemical compositions which contain at least one of these
compounds as active ingredient. The invention also relates ~o the
preparation of such compositions and to the use of the novel
compounds or compositions for controlling harmful microorganisms,
preferably phytopathogenic fungl and bacteria.
Specifically, the prssent invention relates to compounds of the
genersl formula I
~N02 ,R7
~1 R4 ~5
wherein
Rl and R2 are hydrogen, N02 or CF3, with the proviso that only R
or R2 can be N02;
R4 is hydrogen or the -C(O)R' group, in which R' is C1-C4alkyl which
is unsubstituted or 3ubstituted by halogen, C1-C3alkoxy or
Cl-C3alkylthio;
~23~837;~
Rs, R6 and R7 are each independently halogen, nitro, cyano,
thiocyano, C1-Cl2alkyl, C3-C8cycloalkyl, C1-C8alkylthio,
Cl-C6alkylsulfonyl, Cl-C6alkylsulfoxyl, C3-C6alkenyl,
C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl,
C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkenylthio,
C3-C6alkynyloxy, C3-C6haloalkynyloxy, Cl-C8alkyl which is
substituted by halogen, cyano and/or Cl-C4alkoxy, or are
unsubstituted Cl-C8alkoxy or halogen-substituted Cl-Cgalkoxy, the
alkyl moiety of which may be interrupted by one or more single
oxygen atoms, or are the Q-(E) -(X) group, in which n is 0
or 1, m ls 0 or 1, Q is phenyl which is unsubstituted or
substituted by halogen, nitro, C1-C3alkyl, CF3 and/or
Cl-C3alkoxy, or i9 a ~aturated or unsaturated heterocyclic
radical containing one or more hetero atom3, E is a Cl-C3alkylene
bridge, and X is oxygen or sulfur, and ~6 and/or one of the
radicals Rs or R7 can al~o be hydrogen~
Depending on the number of indicated carbon atoms, alkyl by itself
or a8 moiety of another sub3tituent, e.g. alkoxy, haloalkyl,
haloalkoxy etc., denotes for example the following straight chain or
branched groups: ~ethyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl etc. and the isomers
thereof/ e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc.
Throughout this specification, a substituent prefixed by "halo"
indicates that said substituent may be mono- to perhalogenated.
Halogen and halo 3ignify fluorine, chlorlne, bromine or iodine.
Hence haloalkyl i8 a mono- to perhalogenated alkyl radical, e.g.
CHCl2, CHzF, CCl3, CHzC1, CHFz, CHzCH2Br, CZCls~ CHzBr, CHBrCl etc.,
and i8 preferably CF3. Alkenyl i9 for example l-propenyl, allyl,
l-butenyl, 2-butenyl or 3-butenyl, and chains containing several
double bond~s. Depending on the number of lndicated carbon atoms,
cycloalkyl i8 for example cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl etc. Alkynyl i8 for example
2-propynyl, propargyl, l-butynyl, 2-butynyl etc., with propargyl
bein8 preferred.
12~
Throughout this specification, a saturated or unsaturated hetero-
cyclic radical containing one or more hetero atoms will be under-
stood as meaning a saturated or unsaturated 5- or 6-membered
heterocyclic ring system containing 1 to 3 identicsl or different
hetero atoms, e.g. oxygen, nitrogen or sulfur atoms. Typical
representatives of such heterocyclic ring systems are: tetrahydro-
furanl furan, tetrahydrothiophene, thiophene, pyrrolidine, pyrrole,
pyrroline, pyrazole, imidazole, pyrazoline, oxazole, thiazole,
isoxazole, isothiazole, pyran, dihydropyran, tetrahydropyranl
thiopyranl dihydrothiopyran, tetrahydrothiopyran, pyridazine,
dihydropyridazine, tetrahydropyrida~ine, pyrimidine, dihydropyr-
imidine, tetrahydropyrimldine, pyrazine, dihydropyrazine, tetra-
hydropyrazine, morpholine, thiazine, dihydrothiazine, tetrahydro-
thiazine, piperazine and triazine. Cl-C3Alkylene is for example the
following groups: -CH2-, -CH2C~2-, -CHzCH2CH2-, -CH(CH3)-CH2-,
-CH2CH(CH3)-, -CH(C2H5)-, -C(CH3)2-. Alkylsulfoxyl is the alkyl-
S(O)-group. Phenyl is C6H5.
At room temperature the compounds of formula I sre oils, resins or
mainly crystalline solids which have extremely valuable biocidal
properties. They can be used for example in agriculture or related
fields preventively and curatively for controlling phytopathogenic
pests, e.g. fungi or bacteria. The compounds of formula I have an
excellent biocidal activity aDd a broad activity spectrum when
applied in wide ranges of concentration and their use poses no
problems.
The following groups of compounds are preferred on account uf their
pronounced biocidal, especially phytofungicidal, properties:
Group Ia: Compounds of formula I, wherein Rl, Rz and R4 are as
defined for formula I and Rs, R6 and R7 are each independently
halogen, nitro, cyano, C1-C6alkyl, cyclopentyl, cyclohexyl, C1-C3-
alkylthio, C1-C3alkylsulfonyl, C1-C3alkylsulfoxyl, C3-C4alkenyl,
propargyl, C1-C3alkyl which is substituted by halogen, cyanu and/or
C1-C3alkoxy, or are C1-C6alkoxy, the alkyl moiety of which is
37~
4 -
interrupted by 1 or 2 single oxygen atoms, or are the Q-(E) -(X)
group, in which n is O or 1, m is O or 1, Q i8 phenyl which is
unsubstituted or substituted by halogen, nitro, methyl, CF3 or
methoxy, or is a pyridyl group, E is a methylene bridge, and X i9
oxygen or sulfur, and R6 and/or one of the radicals Rs or R7 can
also be hydrogen.
Group Ib: Compounds of formuls I, wherein R1 and R2 are as defined
for formula I, R4 is hydrogen and Rs, R6 and R7 are each indepen-
dently halogen, nitro, cyano, Cl-C6alkyl, cyclopentyl, cyclohexyl,
Cl-C3alkylthio, Cl-C3alkylsulfonyl, C1-C3slkylsulfoxyl, C3-C4-
alkenyl, propargyl, Cl-C3alkyl which is substituted by halogen,
cyano and/or Cl-C3alkoxy, or are Cl-C6alkoxy, the alkyl moiety of
which is interrupted by 1 or 2 slngle oxygen atoms, or are the
Q-(E)n-(X) group, in which n is O or 1, m is O or 1, Q is phenyl
which is unsubstituted or substituted by halogen, nitro, methyl, CF3
or methoxy, or is a pyridyl group, E is a methylene bridge, and X is
oxygen or sulfur, and R6 and/or one of the radicals Rs or R7 can
also be hydrogen.
Group Ic: Compounds of formula I, wherein Rl is CF3; R2 is NO2; R4
is hydrogen, R6 is hydrogen and Rs and R7 are each independently
fluorine, chlorine, bromlne, Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3-
alkoxy, C1-C3haloalkoxy, unsubstituted phenoxy or halogen-substi-
tuted phenoxy, OCHzOCH3~ OC2H40CH3, OcH20c2Hs~ OC2H40C2Hs,
OC2H40C2H40C2Hs or -S-(2-pyridyl).
Further, the ~ollowing compounds of formula I, which are distin-
guished by special substitution characteristics, have particularly
advantageous fungicidal properties:
Group IIa: Compounds of formula I, wherein Rl is CF3 and R2 i9 N2~
R4 is hydrogen and Rs, R6 and R7 are as defined for formula I, with
the exception of hydrogen.
337~
-- 5 --
Group IIb: Compounds of formula I, wherein R1 i8 CF3 and Rz is NO2,
R4 is hydrogen and R57 R6 and R7 are halogen, C1-C6alkyl, cl-c4-
alkoxy, C1-C3alkylthio, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6-
alkynyl, C3-C6haloalkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy,
C~-C6alkyl which is ~ubstituted by halogen or C1-C4alkoxy, or are
alkoxy which is ~ubstituted by halogen or C1-C~alkoxy.
ExamplPs of particularly preferred indivldual compounds are:
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4-chloro-6-di-
fluoromethoxypyrimidine (1.1);
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4,6-dichloro-
pyrimidine (1.2~;
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4,5,6-trichloro-
pyrimidine (1.69);
N-(2'-trifluoromethyl-4',6'-dlnitrophenyl)-2-amino-4,5-dichloro-6-
methoxypyrimidine (1.136);
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4-chloro-5-bromo-
6-propin-2-yloxypyrimidine (~.133);
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4-chloro-5-bro~o-
6-propen-2-yloxypyrimidine (1.131);
N-(2'-trifluoromethyl-4',6'-dinitrophenyl)-2-amino-4,5-dichloro-6-
(2,2,2-trifluoroethoxypyrimidine (1..143).
In accordance with the pre~ent invention, the compounds of formula I
are prepared by reactlng a compound of formula II
~ 2
R2~ -Z (II)
with a pyrimidine derivative of formula III
Y ~ \ R (III)
~2~ 33'~
-- 6 --
in the presence of a base, to give a compound of formula I'
~NO2 ~R~
R2~ NH ~ ~ -R6 (I')
and to obtain an N-acylated derivative, N-acylating the compound of
formula I' with a reactive derivative of the carboxylic acid of
formula IV
R4COOH (IV)
in which formulae above the 6ubstituents R1 to R7 are as defined for
formula I and Z and Y are NH2 or halogen, with the proviso that, if
Z i9 halogen, Y ~8 NH2 and, lf Z is NH2, Y is halogen.
The followlng reaction condltions are advantageous for the prepara-
tlon of compounds of formula I and/or I':
The N-arylation of (II) with (III) to give (I') and the N-acylation
of (I') with (IY) to glve (I) take place with dehydrohalogenation.
The reaction temperature of the N-arylstion is in the range from
-20 to +150C, preferably from -20 to +30C, and that for the
N-acylation is in the range from 0 to +180C, prefer~bly from 0 to
~150C or at the boiling point of the ~olvent or solvent mixture. In
both reactions it is convenient to use an acid acceptor or a
condensing agent. Examples of suitable acid acceptor~ or condensing
agents are organic and ~norganic basas, e.g. tertlary amine~ such a~
trialkylamines (trimethylam1ne, triethylamine, tripropylamine etc.),
pyridine and pyridine base~ (4-dimethylaminopyridine, 4-pyrrolidyl-
aminopyridine etc.), alcoholates such as potassium tert-butylate,
oxldes, hydroxides, carbonates and bicarbonate~ of alkali ~etals and
alkaline earth metals, a~ well as alkali metal acetates.
lZ~L837;~
-- 7 --
Hydrogen halide evolved can in some cases be removed from the
reaction mixture by introducing an inert gas, e.g. nitrogen.
The reactions may be conducted in the presence of inert solvents or
diluent3. Examples of suitable solvents and diluents are: aliphatic
and aromatic hydrocarbons such as benzene, toluene, xylenes,
petroleum ether; halogenated hydrocarbons such as chlorobenzene,
methylene chloride, ethylene chloride, chloroform, carbon tetra-
chloride, tetrachloroethylene; ethers and ethereal compounds ~uch as
dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl
ether etc.), anisole, dioxane, tetrahydrofuran; nitriles such as
acetonitrile and propionitrile; N,N-dialkylated amides such as
dimethylformamide; d~methyl sulfoxide; ketones ~uch as acetone,
diethyl ketone, methyl ethyl ketone; and mixtures of such solvents.
In some cases the acylating or arylatlng agent ltself may be used as
solvent.
The reaction of (II) with (III) can also be carried out in an
aqueous two-phase system in accordance with the generally known
principle of phase transfer catalysis.
The following solvents for example are suitable for the organlc
water-immiscible phase: aliphatic and aromatic hydrocarbons such as
pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene,
toluene, xylenes etc.; halogenated hydrocarbons ~uch as dichloro-
methane, chloroform, carbon tetrachloride, ethylene dichloride,
1,2-dichloroethane, tetrachloroethylene etc.; or allphatic ethers
such as diethyl ether, diisopropyl ether, tert-butylmethyl ether
etc. Examples of suitable phases transfer catalysts are: tetra-
slkylammonium halides, hydrogen sulfates or hydroxides, e.g.
tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl-
ammonium iodide, triethylbenzylammonium chloride or triethylbenzyl-
smmonium bromide, tetrapropylammonium chloride, tetrapropylammonium
bromide or tetrapropylammonium iodide etc. Su~table phase transfer
lZ~837~
-- 8 --
catalysts are also phosphonlum salts. The reaction temperatures are
generally in the range from -30 to 130C or may also be at the
boillng point of the solvent or mixture of solvents.
llnless otherwise expressly specified, one or more inert solvents or
diluents may be present in the preparation of all starting
materials, intermediates and final products mentioned herein.
Examples of suitable inert solvents or diluents a~e: aliphatic and
aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum
ether; halogenated hydrocarbons such as chlorobenzene, methylene
chloride, ethylene chloride, chloroform, carbon tetrachloride,
tetrachloroethylene; ethers and ethereal compounds such as dialkyl
ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether
etc.), anisole, dioxane, tetrahydrofuran; nitriles such as aceto-
nitrile, propionitrile; N,N-dislkylated amldes such as dimethyl-
formamide; dimethyl sulfoxide; ketones such as acetone, diethyl
ketone, methyl ethyl ketone; and mixtures of such solvents with each
other. It can in some caAes be convenient to carry out the reac-
tlon, or partial steps of a reaction, under an inert gas atmosphere
and~or in absolute solvents. Suitable inert gases are nitrogen,
helium, argon or, in certain cases, also carbon dioxide.
The above described preparatory process, including all partial
steps, constitutes an important object of the present invention.
Phenyl-2-aminopyrimidine derivatives are already known as pesti-
cidally and fungicidally effectivs compounds. However, they can not
always fully meet the demands made of them in practice. Such
compounds are described for example in Japanese published patent
application 141 647. They are of the gener~l formula
~CF3
OzN~ NH--'~ --X
~NOz
1~1837;~
wherein X is hydrogen or halogen. In comparison, the compounds of
the present invention are distinctly superior ln their fungicldal
activity to these known compounds.
Surprisingly, it has been found that the compounds of formula I have
for practical purposes a very useful biocidal spectrum against fungi
and bacteria, especially against phytopathogenic fungi and bacteria.
They have very advantageous curative, systemic and, in particular,
preventive properties, and can be used for protecting numerous
cultivated plants. With the compounds of formula I it is possible to
inhibit or destroy the pests which occur in plants or parts of
plant~ (fruit, blossoms, leaves, stems, tubers, roots) in different
crops of useful plants, whlle at the same time the parts of plants
which grow later are also protected from attack by such phytopatho-
genic microorganisms and insects. Plant-destructive Acarina and
Nematoda as well as undesired species of plants can also be success-
fully controlled with compounds of formula I.
As microbicides, the compounds of formula I are effective against
the phytopathogenic fungi belonging to the following classes~ Fungi
imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria,
Cercospora and Alternaria); Bssidiomycetes (e.g. of the genera
Hemileia, Rhi~ocotonia, Puccinia); and, in particular, against the
class of the Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe,
Monilinia, Uncinula). They can also be used as dressing agents
for protecting seeds (fruit, tubers, grains) and plant cuttings
against fungus infections.
Accordingly, the invention also relates to pesticidal compositions,
especially phytofungicidal compositions, and to the use thereof in
agriculture or related fields.
The present invention further embraces the preparation of such
compositions which comprises homogeneously mixing the active
ingredient with one or more compounds or groups of compounds
12~L837~
-- 10 --
described herein. The invention furthermore relates to a method of
treating plants, which comprises applying thereto the compounds of
the formula I or the novel compositions.
Target crops to be protected within the scope of the present
invention comprise e.g. the following species of plants:
cereals (wheat, barley, rye, oats, rice, sorghum and related crops),
beet (sugar beet and fodder beet), pomes, drupes and soft fruit
(apples, pears, plums, peaches, almonds, cherries, strawberries,
rasberries and blackberries), leguminous plants (beans, lentils,
peas, soybeans), oil plants (raps, mustard, poppy, olives, sun-
flowers, coconuts, castor oil plants, cocoa beans, groundnuts),
cucumber plants (marrows, cucumber, melons) fibre plants (cotton,
flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit9
mandarins), vegetables (spinach, lettuce, asparagus, cabbages,
carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados,
c~nnamon, camphor), or plants such as maize, tobacco, nuts, coffee,
sugar cane, tea, vines, hops, bananas and natural rubber plants, as
well as ornamentals (composites).
The compounds of formula I are normally applied in the form of
compositions and can be applied to the crop area or plants to be
treated, simultaneously or in succession, with further compounds.
These compounds can be both fertilisers or micronutrient donors or
other preparations that influence plant growth. They can also be
selective herbicides, insecticides, fungicides, bactericides,
nematicides, molluslcides or mixtures of several of these prepara-
tions, if desired, together with further carriers, surfactant~ or
appllcation promoting adjuvants customarily employed in the art of
formulation. Suitable carriers and adjuvants can be solid or liquid
and correspond to the substsnces ordinarily employed in formulation
technology, e.g. natural or regenerated mineral substances,
solvents, dispersants, wetting agents, tackifiers, binders or
fertilisers.
1~1kl37~
-- 11 --
A preferred method of applying a compound of the formula I or an
agrochemlcal composition which contains at least o~e of said
compounds, is foliar application. The number of applications and the
rate of application depend on the risk of infestation by the
correspGnding pathogen ~type of fungus). The compounds of formula I
may also be applied to seeds (coating) by impregnating the seeda
either with a liquid formulation containing a compound of the
formula I, or coating them with a solid formulation. ln speclal
cases, further types of application are also possible, e.g. selec-
tive treatment of the plant stems or buds.
The compounds of the formula I are used in unmodified form or,
preferably, together with the adjuvants conventionally employed in
the art of formulation, and are therefore formulated in known manner
to emulsifiable concentrates, coatable pastes, directly sprayable or
dilutable solutions, dilute emulsions, wettable powders, soluble
powders, dusts, granulates, and al~o encapsulations in e.g. polymer
substances. As with the nature of the compositions, the methods of
application, such as spraying, atomising, dusting, scattering or
pouring, are chosen in accordance with the intended ob~ectives and
the prevailing circumstances. Advantageous rates of application are
normally from 50 g to 5 kg of actlve ingredient (a.i.) per hectare,
preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to
600 g a.i./ha.
The formulations, i.e. the compositions, preparations or mixtures
containing the compound (active ingredient) of the formula I and,
where appropriate, a solid or liquid ad~uvant, 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 (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the
fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or
substituted naphthalenes, phthalates such as dibutyl phthalate or
dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or
12:~837~
- 12 -
paraffins, alcohols and glycols and their Pthers and esters, such as
ethaDol, ethylene glycol monomethyl or monoethyl ether, ketones such
as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro-
lidone, dimethyl sulfoxide or dimethylformamide, as well as
vegetable oil3~ epoxidised vegetable oils such a8 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, kaolln,
montmorillonite or attapulgite. In order to improve the phy~ical
properties it is also possible to add highly dlspersed 6ilicic acid
or highly dispersed absorbent polymers. Suitable granulated ad~orp-
tive carriers are porous types, for example pumice, broken brick,
sepiolite or bentonite; and suitable nonsorbent carriers are
materials such as cslcite or sand. In addition, a 8reat number of
pregranulated materials of inorganic or organic nature can be used,
e.g. especially dolomite or pulverised plant residues. Particularly
advantageous application promoting ad~uvants which arP able to
reduce substantially the rate of applicstion are also natural
(animal or vegetable) or synthetic phospholipids of the series of
the cephalinY and lecithin~, e.g. phosphatidyl ethanolamine,
phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphat-
idyl inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or
cardiolipin, which can be obtained e.g. from animal or plant cells.
Examples of useful physical forms are phosphatidyl chollne mixtures.
Examples of synthetic phospholipids are dioctanoylphosphatidyl
choline and dipalmitoylphosphatidyl choline.
Depending on the nature of the compound of the formula I to be
formulated, suitable surface-active compounds are nonionic, catlonic
and/or anionic sufactants having good emulsifying, dispersing and
wetting properties. The term "surfactant~" will also be understood
as comprising mixtures of surfactants.
Suitable anionic ~urfactants can be both water-soluble soaps and
water-soluble synthetic surface-active compounds.
lZ~8~
- 13 -
Suitable soaps are the alkall metal salts, alkalin~ earth metal
salts or unsubstituted or substituted ammonium salts of hlgher fatty
acids (Clo-C2z)~ e.g. the sodium or potassium salt3 of oleic or
stearic acid, or of natural fatty acid mixtures which can be
obtained e.g. from coconut oil or tallow oll. Mention may also be
made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used,
especially fatty sulfonates, fatty sulfates, sulfonated benzlmid-
a~ole derivatives or alkylarylsulfonates.
The fatty sulfonate~ or sulfates are usually in the form of alkali
metal salts, alkaline earth metal salts or unsubstituted or sub-
stltuted ammonium salts and contain a Cg-C2zalkyl radicsl which also
includes the 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 compri3e the 6alts of sulfuric acid esters and
sulfonic acids of fatty alcohol~ethylene oxide adducts. The sulfona-
ted benzlmidazole derivatives prefersbly contain 2 sulfonic acid
groups and one fatty acid radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri-
ethanolamine salts of dodecylben~enesulfonic acid, dibutylnaphtha-
lenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde
condensation product. Also suitable are corresponding phosphates,
e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-
phenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of
aliphatic or cyclosliphatic alcohols, or saturated or unsaturated
fatty acids and alkylphenols, sald derivatives containing 3 to
30 glycol 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~ylphenols.
1~:3L83~
- 14 -
Further suitable non-ionic surfactants are the water-soluble adducts
of polyethylene oxide with polypropylene glycol, ethylenediamino-
polypropylene glycol and alkylpolypropylene 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 compounds usually contain 1 to 5 ethylene glycol
unlts per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-
polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adduct~, tributylphenoxypolyethylene ethanol,
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 quaternsry ammonium salts which
contain, a~ N-substituent, at least one Cg-C22alkyl radical and, as
further substituents, unsubstituted or halogenated lower alkyl,
ben~yl or hydroxy-lower alkyl radicals. The salts are preferably in
the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-
trimethylammonium chloride or benzyldi~2-chloroethyl)ethylammonium
bromide.
The surfactants customarily emplayed in the art of formulation are
described e.g. in "McCutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp. Ringwood, New Jersey, 1981; Helmut Stache
"Tensid-Taschenbuch" (Handbook of Surfactsnts), Carl Hanser-Verlag,
MunichtVienna, 1981.
The agrochemical compositions usually contain 0.1 to 99 %, prefer-
ably 0.1 to 95 %, of a compound of the formula I, 99.9 to 1 %,
preferably 99.8 to 5 %, of a solid or liquid adjuvant, and 0 to
25 %, preferably 0.1 to 25 %, of a surfactant.
Whereas commercial products are preferably formulated as concen-
trates, the end u~er will normally employ dilute formulations.
~z~
The compositions may also contain further ingredients such a!3
6tabilisers, antifoams, viscosity regulators, binders, tackifiers as
well as fertilisers or other active ingredients in order to obtain
special effects.
Such agrochemical compositions also constitute an ob~ec~ of the
present invention.
The invention is illustrated in more detail by the following
Examples, without implying any restriction to what is described
therein. Parts and percentages are by weight.
l.Preparatory Examples:
Exampla 1.1: Preparation of
~ 2 /Cl
02N~ NH - ~ ~ (Compound 1.2)
~CF3 \Cl
N-(2'-Trifluoromethyl-4',6'-d~nitrophenyl)-2-amino-4,6-dichloro-
pyrimidine
With stirring, 13.2 parts of 85 % powdered potasslum hydroxide are
added, in portions, at room temperature to a solution of 15 parts of
4,6-dichloro-2-aminopyrimidine in 400 ml of tetrahydrofuran. During
this addition, the temperature rises to 23C in the course of half
an hour. The reaction mixture is cooled to 5C and 28 parts of
2-chloro-3,5-dinitrobenzotrifluoride in 80 ml of tetrahydrofuran are
ad~ed dropwise in the course of l hour to the suspension, which
turns red. The reaction mixture is stirred for 15 hours at room
temperature, poured into ice-water, acidified with 10 ml of concen-
37,'~
- 16
trated hydrochloric acid and extracted with two 200 ml portions of
ethyl acetate. The combined extracts are washed with two 100 ml
portions of water, dried over sodium sulfate, filtered and con-
centrated by evaporation. The crystalline residue ls recrystallised
from 400 ml of lsopropanol. The yellow crystals 50 obtained have a
melting point of 170-173C.
The following compounds of formula I are prepared by procedures
analogous to those described above.
lZ~837;~
- 17 -
Table 1: Compounds of the formula
~ 2 ~7
02N-~ NH ~ R6
CF3 Rs
. . _ _ _ _
Comp. Rs R6 R7 Phy~3ical data
. _ . _
1.1 Cl H OCHzF m.p. 159-161
1.2 Cl H Cl m.p. 170-173
1.3 SCH3 CN H
1.4 OCH3 CN H
1.5 CH3 CH3 H
1.6 OCH3 Br 8
1.7 OC3H7-i H OC3H7-i
1.8 CH3 CN H
1.9 OCzOCzHs H CH3
1.10 SC2Hs H CH3
1.11 OCZHs H F
1.12 OCH3 OC2Hs H
1.13 CH3 I CH3 resin
1.14 CH3 CN S(O~CH3
1.15 OCzHs H CH3
1.16 C4Hg-l H H
1.17 Cl CH3 H
1.18 Cl H H
1.19 C6Hs CN H
1.20 H CH2-C6Hs H
1.21 CH3 CN SO2CH3
1.22 C3H7-n H H
1.23 Cl OCH3 H
1.24 CHzOCH3 H CH3
1.25 CHBrz Br H
1.26 OCH3 OCH3 H
1.27 Cl H SC2Hs semi-
. . crystalline
~2:18~
- 18 -
Tabl~ Continuatlon)
Co~p. = = =~ 0~
1.28 CH3 NOz SO2CH3
1.29 SC3H7-i H CH3
1.30 Cl F H
1.31 OC2Hs OCH3 H
1.32 CH3 H SC3H7-n
1.33 OCH3 H H
1.34 CH3 C2H40C2Hs H
1.35 Cl H SO2CH3 resin
1.36 OCZHs NO2 H
1.37 OCH3 .~ H
1.38 CH3 . H SCH3
1.39 C4Hg-n H CH3
1.40 SCzHs H H
1.41 Cl H OC2Hs resln
1.42 Cl SO2CH3 H
1.43 C3H7-l H H
1.44 H C4Hg-n H
1.45 CH20CH3 OCH3 H
1.46 H CN H
1.47 Cl OC2Hs H
1.48 SO2C2Hs H H
1.49 CH3 H O-C6Hs
1.50 OcH2-c6H5 H F
1.51 Cl H SCH3 resin
1.52 F H F
1.53 Cl CH2-C6Hs C6Hs
1.54 Br H H
1.55 Cl SCH3 H
1.56 CCl3 H CCl3
1.57 _ . C3H7-l H
:~Z18~7'~
- 19 -
Table 1: (Continuation)
Corp. Rs R6 R7 Fhysical d,ta
1.58 CH3 H CF3
1.59 Cl S-C6Hs H
1.60 OC3H7-i H CH3
1.61 Cl H SCN ~emi-
cry~3talline
1.62 CH2-C6Hs H CH3
1.63 Cl CH2-C6H5 Cl
1.64 SCH2-C6Hs H CH3
1.65 Cl Br Cl m.p. 206-208
1.66 Cl CH2-C6Hs CH3
1.67 Cl H OCH2F re~in
1.68 Cl C6Hs Cl
1.69 Cl Cl Cl m.p. 177-178
1.70 H CH3 H
1.71 SCH2-C6Hs H SCHz-C6Hs
1.72 Cl Br Cl
1.73 Cl CH3 Cl
1.74 H OC4Hg H
1.75 Cl OC2Hs Cl
1.76 Cl Cl CH3
1.77 Cl CsHg-n CH3
1.78 SCH3 H SCH3
1.79 Cl C4H9-n Cl
1.80 H OC4Hg-sec. H
1.81 H NO2 H
1.82 CH3 C6Hs CH3
1.83 CH3 CH3 CH3
1.84 H O-cyclohexyl H
1.85 SC3H7-n H SC3H7-n
1.86 H OC2Hs H
I . a 7 Br Cl Cl
~Z~8~3'7~
-- 20 --
Table 1: (Continuation)
~ .. _ _ . . ..
CODP. - ---~-- R7 Phyj3ical data
1 . 88 Br C1 Br
1. 89 OCH3 OCH3 OCH3
1.90 Cl H OC(CH3~2C-CH
1.91 CN H CH3
1. 92 Cl NO2 OCH3
1.93 H OC2H40CH3 H
1.94 Cl H C6Hs
1.95 CH3 CH2-CH=CH2 CH3
1 . 96 CsHs H C6Hs
1.97 SC4Hg-n H CH3
1. 98 CH3 H C6Hs
1. 99 Br H Br
1.100 OC2Hs H OC2Hs
1.101 H CH20CH3 H
1.102 Cl OCH 3 Cl
1.103 OCH3 H SCH3
1.104 Cl OCH3 CH3
1.105 Cl C3H7-n C6H5
1.106 Cl C6H3Cl2(2,4) Cl
1.107 Cl H SC3H7-n resin
1.108 Cl C6H4(CH3)(4) Cl
1.109 Cl Br CH3
1.110 Cl CZHs Cl
1.111 Cl C6H4(0CH3)(4) Cl
1.112 Cl CH3 C6Hs
1.113 C6H4(CF3)(4) CN H
1.114 Cl C6H4(No2)(4) Cl
1.115 Cl H SCH3 resin
1 .116 C1 H OCH2-phenyl
1.117 c6Hl3-n U H ..
- 21 -
Table 1: (Continuation)
_
Comp. Rs R6 R7 [C]
1.118 Cl H OCH2CH-CH2 semi~
~rystalline
1.119 Cl H OCH2C=CH m.p. 130
1.120 Cl Br oCH3
1.121 Cl Br OC2Hs
1.122 Cl Br OC3H7-i
1.123 Cl Br OC4Hg-sec.
1.124 Cl Br OCH2CF3
1.125 Cl Br OCH2CH2Cl
1.126 Cl Br OCHzCH2Br
1.127 Cl Br oCHF2
1.128 Cl . Br OCH2CH20CH3
1.129 Cl Br SC2Hs
1.130 Cl Br SC3H7-i
1.131 Cl Br OCHzCH3CH2 m.p. 105-110
1.132 Cl Br OC(CH3)2C~CH
1.133 Cl Br OCHzCGCH m.p. 141-143
1.134 Cl Br OCH2-phenyl
1.135 Cl Br SCN
1.136 Cl Cl OCH3 m.p. 168-169
1.137 Cl H OCH3 m.p. 169-170
1.138 Cl Cl OcH2cH'cH2 m.p. 115-116
1.139 Cl H OCH2CF3 m.p. 139-140
1.140 Cl Cl SC3H7-i m.p. 146-148
1.141 Cl Cl OCH2C-CH m.p. 134-135
1.142 Cl Cl OCH2CHzOCH3 m.p. 102-105
1.143 Cl Cl OCH2CF3 m.p. 138-141
1.144 H CF3 H
lZ~
- 22 -
Table 2: Compoun~s of the formula
~ Oz /R7
F3C~ NH ~ ~--R6
\NOz ~ S
__ _ . _ _ _
Comp. Rs R6 R7 Physical data
_
2.1 Cl H Cl m.p. 144-145
2.2 CH3 Cl H
203 C6Hl3-n H Cl
2.4 Br H Br
2.5 CH3 Cl Cl
2.6 Cl CHz-G6Hs Cl
2.7 Cl Br Cl m.p. 193-195
2.8 Cl OCzHs Cl
2.9 CN H CH3
2.10 Cl C4Hg-n Cl
2.11 F H F
2.12 H CN H
2.13 CH3 CH3 H
2.14 Cl C6H4Cl(4) Cl
2.15 CH3 Br H
2.16 Cl CzHs Cl
2.17 Cl C6Hs Cl
2.18 Cl C3H7-n C6Hs
2.19 Br C6Hs Br
2.20 Cl CH3 Cl
2.21 CH3 CN H
2.22 Cl SC~3 Cl
2.23 Cl CHz-C6Hs H
2.24 Br C3H7-n Br
2.25 SCH3 CN H
2.26 OCH3 CN H
2.27 CH3 CH3 D . p . 200-202
~2~8~
- 23 -
Table 2: (Continua~ion~
Co:p. = R7 ~
2.28 Cl H OCHzcH-cH2 m.p. 124
2.29 Cl H OCH2CsCH m.p. 170 172
2.30 Cl H OC(CH3)2C9CH
2.31 Cl H SCH3 m.p. 153
2.32 Cl Cl OCH3 m.p. 141-142
2.33 Cl Cl OCzHs
2.34 Cl Cl OC3H7-i
2.35 Cl Cl OC4Hg-se~.
2.36 Cl Cl OC(CH3)3
2.37 C1 Cl OCHzCF3 m.p. 110-111
2.38 Cl Cl OCHFz
2.39 Cl Cl OCH2CHzCl
2.40 Cl Cl OCH2CH20C2Hs
2.41 Cl Cl OCH2CHsCHz m.p. 140-141
2.42 Cl Cl OCHzC=CH m.p. 129-131
2.43 Cl Cl OC(CH3)z~=CH
2.44 Cl Cl OCH2-phenyl
2.45 Cl Cl SCN
2.46 Cl Cl SCzHs
2.47 Cl Cl SC3H7-i nD 1.6188
2.48 Cl H OCH3 m.p. 129-131
2.49 Cl Cl Cl m.p. 156-157
2.50 Cl Cl OCH2CHzOCH3 m.p. 116-117
2.51 Cl Br OCHzcH3cH2 m.p. 120-122
2.52 Cl H OCHzCF3 m.p. 125-126
2.53 Cl Br OCHzC_CH m.p. 143-144
2.54 Cl H CH2Cl m.p. 40-48
2.55 Cl H CHzF m.p. 108-112
~8~7'~
- 24 -
Table 3: Compounds of the formula
~ 2 ~7
R2~ -R6
~1 " \Rs
_
Comp. R1 R2 R~ Rs R6 R7 Physical data
3.1 NO2 CF3 C(O)CH3 Cl H Cl m.p. 92-94
3.2 CF3 NO2 C(O)CH3 Cl H Cl
3.3 NO2 CF3 C(O)CH2Cl Cl C4Hg-n Cl
3.4 NO2 CF3 C~O)CH20CH3 Cl CH3 Cl
3.5 NO2 CF3 C(O)CH3 Cl OC2Hs Cl
3.6 CF3 NO2 C(O)CH20C2Hs Cl CH3 Cl
3.7 CF3 NO2 C(O)CH2OCH3 Cl CN CH3
3.8 No2 CF3 C(O)CH3 SCH3 CN H
3 9 NO2 CF3 C(O)CH3 OCH3 CN H
2. Formulation Examples
Formulation Exa~ples for llquid active ingredients of formula I
(throughout, percentages are by weight)
2.1. Emulsifiable concentrates a) b) ~)
a compound of the Tables 25 % 40 % 50 %
calcium dodscylbenzenesulfonate 5 % 8 % 6 ~0
castor oil polyethylene glycol ether
(36 mole~ of ethylene oxide) 5 % - -
trlbutylphenol polyethylene glycol ether
(30 moles of ethylene oxide) 12 % 4 %
cyclohexanone - 15 % 20 %
xylene mixture 65 % 25 % ,20 %
12~837;~
- 25 -
Emulsions of any required concentration can be produced from such
concentrates by dilution with water.
2.2. Solutions a) b~ c) d)
n compound of the Tables 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether 20 %
polyethylene glycol 400 - 70 % - -
N-methyl-2-pyrrolidone - 20 %
epoxidised coconut oil - - 1 % 5 %
petroleum distillate (boillng range
160-190) - - 94 %
These solutions are suitable for application in the form of micro-
drops.
2.3. Granulates a) b)
a compound of the Tables 5 % 10 %
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %
The active ingredient i8 dissolved in methylene chloride, the
solution i5 sprayed onto the carrier, and the solvent is subsequent-
ly evaporated off in vacuo.
2.4. Du~t~ a) b)
a compound of the Tables 2 % 5 %
highly dispersed 8ilicic acid 1 % 5 %
talcum 97 %
kaolin - 90 %
Ready-for-use dusts ars obtained by intimately mixing the carriers
with the acitve ingredient.
lZ18~37~
- 26 -
Formulation sxamples for solid active ingredients of formula I
(throughout, percentages are by weight)
2.5. Uettable powders a3 b) c)
a compound of the Tables 25 % 50 % 75 %
sodium lignosulfonate 5 % S %
sodium lauryl sulfate 3 % - 5 %
sodium diisobutylnaphthalenesulfonate - 6 % 10 %
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
~aolin 62 % 27 %
The active ingredient is thoroughly mixed wlth 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 the Tables 10 %
octylpher.ol polyethlene glycol ether
(4-5 moles of ethylene oxide) 3 %
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether
(36 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture S0 %
Emulsions of any required concentration can be obtained from this
concentrate by dilution with water~
2.7. Dusts a) b)
a compound of the Tables 5 % 8 %
talcum 95 %
kaolin - 92 %
~8~37~
- 27 -
Ready-for-use dusts are obtained by mixing the active ingredient
with the carrier, and grinding the mixture in a suitable mill.
2.8. Extruder granulate
a compound of the Tables10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient i8 mixed and ground with the adjuvants, and
the mixture i5 subsequently moistened with water. The mixture is
extruded and then dried in a stream of air.
2.9. Coated granulate
a compound of the Tables 3 %
polyethylene glycol 200 3 %
kaolin 94 %
The finely ground actlve ingredient is uniformly applied, in a
mixer, to the kaolin moistened with polyethlene glycol. Non-dusty
coated granulates are obtained in this manner.
2.10. Suspension concentrate
a compound of the Tables 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol
(15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 %
water 32 %
- 28 -
The finely ground active ingredlent is lntimately mixed with the
aduvants, giving a ~uspension concentrate from which suspensions of
any desired concentration can be obtained by dilution with water.
3. Biolo~lcal Examples
xample 3.1: Residual-protective action a~ainst
Puccinia graminis on wheat
Wheat plants are treated 6 days after sowing with a spray mixture
(0.02 %) prepared from a wettable powder formulation of the test
compound. After 24 hours the treated plants are infected with a
uredospore suspension of the fungu~. The infected planta are
incubated for 48 hours at 95-100 % relative humidity and about 20C
and then stood in a greenhouse at about 22C. Evaluation of rust
pustule development is made 12 days after infection.
Compounds of the Tables have a very good action against Puccinia
fungi. Puccinia attack on untreated and infected control plants was
100 %. Compounds 1.1, 1.2, 1.137, 1.139, 1,143 and others inhibited
Puccinia attacX to 0 to 5 %.
xample 3.2: Residual protective action against Cercospora
arachidicola on groundnut plants
Groundnut plants 10-15 cm in height are sprayed with a spray mixture
(0.02 %) prepared from a wettable powder formulation of the test
compound snd infected 48 hnurs later with a conidla suspension of
the fungus. The infected plants are incubated for 72 hours at about
21C and high humidity and then stood in a greenhouse until the
typicsl leaf specks occur. Evaluation of the fungicidal action is
made 12 days after infection and is based on the number and size of
the specks.
~;~i8.~37~
- 29 -
Compared with untreated and infected controls (number and size of
the ~pecks = 100 %), Cercospora attack on groundnut plants treated
with compounds of the Tables is subgtantially reduced. In the above
tests, compounds 1.1, 1.2, 1.69, 1.133, 1.136, 1.141 and 1.143
inhibited the occurrence of specks almost completely (0-10 %).
xample 3.3: Residual protective action against
Erysiphe graminis on barley
Barley plants abou~ 8 cm in height are sprayed with a spray mixture
(0.002 %) prepared from a wettable powder formulation of the test
compound. The treated plants are dusted with conidia of the fungus
after 3-4 hours. The infected barley plants are then stood in a
greenhouss at about 22C. The extent of the infestation is evaluated
after 10 days.
Compounds of formula I have a good action against Erysiphe fungi.
Erysiphe attack was 100 % on untreated and infected control plants.
Compounds of Tables 1 and 2 inhibited fungus attack on barley to
less than 30 %.
xample 3.4: Residual-protective action against Venturia inaequalls
on apPle shoots
Apple cutting~ with 10-20 cm long fresh shoots are sprayed with a
spray mixture (0.02 %) prepared from a wettable powder formulation
of the test compound. The plants are infected 24 hours later with a
conidia suspension of the fungus. The plants are then incubated for
5 days at 90-100 % relative humidlty and stood in a grsenhouse for a
further 10 days at 20-24C. Scab infestation is evaluated 15 days
after infection. Compounds 1.1, 1.2, 1.69, 1.131, 1.133, 1.139,
1.141, 1.142 and 1.143 inhibited attack to 0-10 %. On the other
hand, attack on untreated and infected control shoots was 100 %.
î~18~7~
- 30 -
Example 3.5: Residual protective action again~t
Botrytis clnerea on beans
Bean plants about 10 cm in height are sprayed with a spray mlxture
(0.02 %) prepared from a wettable powder formulation of the test
compound. After 48 hours, ~he treated plants are infected with a
conidia suspension of the fungus. The infected plants are incubated
for 3 days at 95-100 % relative humidity and 21C, and evaluation of
fungus attack is then made. Numerous compounds of Table 1 very
strongly inhibit the fungus infection. At a concentration of 0.02 %,
e.g. compounds 1.1, 1.2, 1.69, 1.131, 1.133, 1.136, 1.138, 1.139
and 1.143 were fully effective (0 to 10 % attack). ~otrytis attack
on untreated and infected bean plants was 100 %.
xample 3.6: Residual protective action against Phytophthora
infestans on tomato plants
After a cultivation period of 3 weeks, tomato plants are sprayed
with a spray mixture ~0.02 %) prepared from a wettable powder
formulation of the test compound. After 24 hours the treated plants
are infected with a sporangia suspension of the fungus. Evaluation
of fungus attack is made i9 made after the plants have been incu-
bated for 5 days at 95-100 % relative humidity and 20C.
In the above test~, compounds 1.1, 1.2, 1.65, 1.69, 1.119, 1.131,
1.133, 1.136, 1.138, 1.140, 1.141, 1.142 and 1.143 have a very good
action. These compounds inhibited fungus attack almost completely
(0 to 10 % attack) as against 100 % attack on untreated control
plants.
xample 3. ?: Residual protective action against
Plasmapora viticola on vines
Vine seedlings in the 4-5 leaf stage are sprayed with a spray
mixture (0.02 %) prepared from a wettable powder formulation of the
test compound. After 24 hours the treated plants are infected with a
sporangia suspension of the fungus. Fungus attack is evaluated after
incubation for 6 days at 95-100 % relative humidity and 20C.
~Z1~37~
- 31 ~
Compounds of the Tables have a very good fungicidal action against
Plasmopara viticola on vines. In partlcular, compounds 1.1, 1.2,
1.69, 1.131, 1.133, 1.136, 1.138, 1.139, 1.141, 1.142, 1.143, 2.S2
and 2.53 inhiblted fungus attack completely (0 to 5 %).
xample 3.8: Residual protective action against
Pyricularia oryzae on rice plants
After a cultlvatlon perlod of 2 weeks, ric8 plants are sprayed with
a spray mixture (0.02 %) prepared from a wettable powder formulation
of the test compound. After 48 hours the treated plants are
lnfected wlth 8 conidia ~uspenslon of the fungus. Evaluation of
fungus attack i9 made after incubation for 5 days at 95-100 %
relative humidity and 24C.
Compared with 100 % attack on untreated controls, fungus attack was
less than 10 % on rice plants whlch have been treated with one of
compounds 1.143 or 2.54.
