Note: Descriptions are shown in the official language in which they were submitted.
s~
-- 1 --
21~9-65
The present invention relates to novel N-(2-nitrophenyl)-
4-aminopyrimidlne deri~atives of the formula I below. rrhe invention
further relates -to the preparation of these compounds and -to ayro-
chemical compositions which con-tain at least one of said compounds
as active ingredient. The invention relates also to the prepara-tion
of said compositions and to the use of the novel compounds or com-
positions for controlling harmful micro-organisms, in particular
phytopathogenic fungi.
Specifically, the invention relates to compounds of the
general formula I
R3 NO2 R8~ / 6
_ O = --
// ~ / \
R -~ -- N (I)
2 \
=- R N-
~
Rl R5
wherein
1 2 3
2 2 3
R3 is hydrogen or halogen
R4 is hydrogen or the -C(O)R7 yroup, in which
R7 is Cl-C12alkyl which is unsubstituted or substituted by
halogen, Cl-C3alkoxy or Cl-C3alkylthio, or is C2-C6alkenyl which is
unsubstituted or substituted by halogen, or is C3-C7cycloalkyl,
phenyl or phenyl which is substituted by halogen, nitro or Cl-C3
alkyl, or is an unsaturated or saturated 5- or 6-membered hetero-
` ' 3 4~
. .~
i6~
2 214~g-65~3
cyclic ring which contains 1 to 3 identlcal or dlfferent hetero
atoms and ls unsubstltuted or substituted by halogen, Cl-C3 alkyl or
nltro,
R5, R6 and R8 are each lndependently halogen, cyano, thio-
cyano, nltro or a group selected from -N(Rg)(Rlo)~ -Rll, R12-O- or
R13-S(O) -, ln whlch Rg and Rlo are each lndependently haloyen,
Cl-C12alkyl which is unsubstltuted or substltuted by hydroxy or
Cl-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl whlch ls substl-
tuted by halogen, nltro, Cl-C4alkyl or Cl-C4alkoxy, or together wlth
the nitrogen atom form an unsaturated or saturated 5- or 6-membered
heterocycllc ring which can contain 1 or 2 additional hetero atoms
and is unsubstituted or substituted by halogen, Cl-C4alkyl or Cl-C4
alkoxy,
n is 0, 1 or 2
Rll, R12 and R13 are each independently Cl-C12alkyl which
is unsubstituted or substituted by halogen, nltro, cyano, phenyl,
phenoxy, phenylthlo or by a saturated or unsaturated 5- or 6-mem-
bered heterocyclic ring which contains 1 to 3 hetero atoms, each
cyclic radical being in turn unsubstituted by halogen, nitro, Cl-C4
alkyl, Cl-C4haloalkyl or Cl-C4alkoxy, or are C2-C6alkenyl which is
unsubstituted or substituted by halogen, or are C3-C6alkynyl which
is unsubstituted by halogen, or C3-C7cycloalkyl which is unsubsti-
tuted or substituted by halogen or Cl-C3alkyl, or are phenyl or
phenyl which is substituted by halogen, Cl-C4haloalkyl, Cl-C4alkyl
or Cl-C4alkoxy, or are an unsaturated or satura-ted 5- or 6-membered
heterocyclic ring which contains 1 to 3 hetero atoms and is unsub-
~ .' ~ 2 -
.,,~
~2~ 6~
- 2a - 2148g-6583
stituted or substituted by haloyen, nitro, Cl-C4alkyl, Cl-C4halo-
alkyl or Cl-C4alkoxy; and in addltion R5 can be hydroyen, R6 can be
hydrogen or two of R5, R6 and R8 can be hydroyen.
Depending on the indicated number of carbon atoms, alkyl
by itself or as moiety of another substitutent such as alkoxy,
alkylmercapto, haloalkyl etc., comprises e.g. the following straight
chain or branched groups: methyl, 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"
will be understood as meaning that said substituent may be monohalo-
genated or perhalogenated. Halogen and halo signify F, Cl, Br or I.
Hence haloalkyl denotes a monohalogenated to perhalogenated alkyl
radical, e.g. CHC12, CH2F, CC13, CH2Cl, CHF2, CH2CH2Br, C2C15,
CHBrCl etc., with CF3 being preferred. Alkenyl is e.g. l-propenyl,
allyl, l-butenyl, 2-butenyl or 3-butenyl, as well as chains contain-
ing several double bonds. Depending on the indicated number of car-
bon atoms, cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl etc. Alkynyl is e.g. 2-propynyl,
propargyl, l-butynyl, 2-butynyl etc, with propargyl being preferred.
Throughout this specification the term "heterocyclyl" or
"heterocyclic ring" shall be understood as meaning a ~aturated or a
unsaturated heterocyclic radical containing one or more hetero-
- 2a -
"' ,.'' .i
s~
-- 3 --
atoms, preferably a saturated or unsaturated 5- or 6~neMbered
heterocyclic ring system containing 1 to 3 identical or different
heteroatoms, e.g. oxygen, nitrogen or sulfur atoms. Typical
representatives of such heterocyclic ring systems are:
tetrahydrofuran, furan, tetrahydrothiophene, thiophene, pyrrolidine,
pyrrole, pyrroline, pyrazole, imidazole, pyrazoline, o~azole,
thiazole, isoxazole, isothiazole, pyran, dihydropyran,
tetrahydropyran, thiopyran, dihydrothiopyran, tetrahydrothiopyran,
pyridazine, dihydropyridazine, tetrahydropyridazine, pyrimidine,
dihydropyrimidine, tetrahydropyrimidine, pyrazine, dihydropyrazine,
tetrahyropyrazine, morpholine, thiazine, diyhdrothiazine, piperazine
and triazine.
The compounds of formula I are oils, resins or mainly crystalline
solids which are stable under normal conditions and have extremely
valuable pesticidal properties. They can be used for example in
agriculture or related fields preventively and curatively for
controlling phytopathogenic pests, e.g. phytopathogenic fungi. The
compounds of formula I have an excellent pesticidal activity and a
broad activity spectrum when applied in wide ranges of concentration
and their use poses no problems, especially in agriculture.
The following groups of compounds are preferred on account of their
pronounced pesticidal, especially fungicidal, properties:
Group Ia: Compounds of the formula I, wherein Rl is N02 or CF3; R2
is NO~ or CF3; R3 is hydrogen or halogen; R~ is hydrogen or the
-C(O)R7 group, in which R7 i8 Cl-C4alkyl which is unsubstituted or
9ubstituted by halogen, Cl-C3alkoxy or Cl-C3alkylthio~ or is C2-C4-
alkenyl which is unsubstituted or substituted by halogen, or is
C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen,
nitro or Cl-C3alkyl, or is an unsaturated or saturated 5- or
6-membered heterocyclic ring which contains 1 to 3 identical or
different hetero atoms and is unsubstituted or substituted by
halogen, Cl-C3alkyl or nitro; R5, R6 and R8 are each independently
halogen, cyano, thiocyano, nitro, or a group selected from
~2~
-- 4 --
9 10 ~ R12 or R13-S(O)n-, in which E~g and R are
each independently hydrogen, Cl-C12alkyl which is unsubstituted or
substituted by hydroxy or Cl-C~alkoxy, or are C3-C6alkenyl, phenyl
or phenyl which is substituted by halogen, nitro, Cl-C4alkyl or
Cl-C4alkoxy~ or together with the nitrogen atom forrn an unsaturated
or saturated 5- or 6-membered heterocyclic ring which can contain 1
or 2 additional hetero atoms and is unsubstituted or substituted by
halogen, Cl-C4alkyl or Cl-C4alkoxy; n is 0, 1 or 2; Rll, R12 and R13
are each independently C2-C6alkenyl which is unsubstituted or
substituted by halogen, Cl-C12alkyl which is unsubstituted or
substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or
by a saturated or unsaturated 5- or 6-membered heterocyclic ring
which contains 1 to 3 hetero atoms, each cyclic radical being in
turn unsubstituted or substituted by halogen, nitro, Cl-C4alkyl,
Cl-C4haloalkyl or Cl-C4alkoxy~ or are C3-C6alkynyl which is unsub-
stituted or substituted by halogen, or C3-C7cycloalkyl which is
unsubstituted or substituted by halogen or Cl-C3alkyl~ or phenyl or
phenyl which is substituted by halogen, Cl-C4haloalkyl, Cl-C4alkyl
or Cl-C4alkoxy, or are an unsaturated or saturated 5- or 6-membered
heterocyclic ring which contains 1 to 3 hetero atoms and is unsub-
stituted or substituted by halogen, nitro, Cl-C4alkyl, Cl-C4halo-
alkyl or Cl-C4alkoxy; and in addition R5 can be hydrogen, R6 can be
hydrogen or two of R5, R6 and R8 can be hydrogen.
Group Ib: Compounds of the formula I, wherein Rl is N02 or CF3; R2
is N02 or CF3; R3 is hydrogen or halogen; R4 is hydrogen; R5, R6 and
R8 are each independently halogen, cyano, thiocyano, nitro, or a
9 10)' 11~ 12 or R13 S()n , in
which Rg and Rlo are each independently hydrogen, Cl-C12alkyl which
is unsubstituted or substituted by hydroxy or Cl-C4alkoxy, or are
C3-C6alkenyl, phenyl or phenyl which is substituted by halogen,
nitro, Cl-C4alkyl or Cl-C4alkoxy~ or together with the nitrogen atom
form an unsaturated or saturated 5- or 6-membered heterocyclic ring
which can contain 1 or 2 additional hetero atoms and is unsubsti-
tuted or substituted by halogen, Cl-C4alkyl or Cl-C4alkoxy; n is 0,
1 or 2; Rll, R12 and R13 are each independently C2-C6alkenyl which
3"Z~
is unsubstituted or substituted by halogen, Cl-Clzalkyl which is
unsubstituted or substituted by halogen, nitro, cyano, phenyl,
phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-member-
ed heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic
radical being in turn unsubstituted or substituted by halogen,
nitro~ Cl-C4alkyl, Cl-C4haloalkyl or Cl-C4alkoxy, or are C3-C6alkyn-
yl which is unsubstituted or substituted by halogen, or C3-C7cyclo-
alkyl which is unsubstituted or substituted by halogen or Cl-C3alk-
yl, or are phenyl or phenyl which is substituted by halogen, Cl-C4-
haloalkyl, Cl-C4alkyl or Cl-C4alkoxy~ or are an unsaturated or
saturated 5- or 6-membered heterocyclic ring which contains 1 to 3
hetero atoms and is unsubstituted or substituted by halogen, nitro,
Cl-C4alkyl, Cl-C4haloalkyl or Cl-C4alkoxy; and in addition R5 can be
hydrogen, R6 can be hydrogen or two of R5~ R6 and R8 can be
hydrogen.
Group Ic: Compounds of the formula Il wherein Rl is N02 or CF3; R2
is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is
halogen, cyano, thiocyano, nitro or a group selected from
9 10 ~ R12 or R13-S(O)n-, in which Rg and R are
each independently hydrogen, Cl-C4alkyl, C3-C4alkenyl, phenyl or
phenyl which is substituted by halogen, nitro, methyl or methoxy, or
taken together they form an unsubstituted or methyl-substituted
piperidine ring; n is 2; Rll, R12 and R13 are each independently
C3-C4alkenyl or Cl-Cl2alkyl which is unsubstituted or substituted by
halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an unsatu-
rated or saturated 5- or 6-membered heterocyclic ring which contains
1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur~ each
heterocyclic radical being in turn unsubstituted or substitute(l by
halogen, nitro~ methyl, CF3 or methoxy~ or are C3-C4alkynyl, C3-C6-
cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro,
Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R6 and R8 are hydrogen-
Group Id: Compounds of the formula I, wherein Rl is N02 or CF3; R2is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is
hydrogen; R6 is hydrogen, cyano, thiocyano, nitro or a group
5~
9 ( 10)' Rll' R12-- or R13-S~o) -, in whic~ R
and Rlo are each independently hydrogen, Cl-C3alkyl, or together
with the nitrogen atom are piperidine; n is 2; Rll, R12 and R13 are
each independently C3-C4alkenyl, Cl-C4alkyl which is unsubstituted
or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenyl-
thio, or C3-C6cycloalkyl, phenyl or phenyl which is substituted by
halogen~ CF3~ Cl-C2alkyl or Cl-C2alkoxy; and R8 is hydrogen.
Group Ie:compounds of the formula I, wherein Rl is N02 or CF3; R2
is N02 or CF3; R3 is hydrogen or chlorine; R4, R5 and R6 are
hydrogen; R8 is halogen, cyano, thiocyano, nitro or a group selected
9 10)' Rl1, R12 0 or R13-S(O)n-, in ~"hich Rg and R1o
are each independently hydrogen, Cl-C3alkyl, or together with the
nitrogen atom are piperidine; n is 2; Rll, R12 and R are each
independently C3-C4alkenyl~ Cl-C4alkyl which is unsubstituted or
substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio,
or are C3-C6cycloalkyl, phenyl or phenyl which is substituted by
halogen, CF3, Cl-C2alkyl or Cl-C2alkoxy.
Group If: Compounds of the formula I, wherein R1 is N02 or CF3; R2
is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 and R8
are each independently halogen, cyano, thiocyano, nitro or a group
selected from -N(Rg)(Rlo)~ -Rll, R12 or 13 n 9
and Rlo are each independently hydrogen, Cl-C4alkyl, C3-C4alkenyl,
phenyl or phenyl which is substituted by halogen, nitro, methyl or
methoxy, or taken together they form an unsubstituted or methyl-
substituted ring selected from piperidine, tetrahydrofuryl and
morpholine; n i8 2; Rl1, R12 and R13 are each independently C3-C4-
alkenyl or Cl-C12-alkyl which is unsubstituted or substituted by
halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an un-
saturated or saturated 5- or 6-membered heterocyclic ring which
contains 1 or 2 hetero atoms selected from nitrogen, oxygen and
sulfur, each heterocyclic radical being in turn unsubstituted or
substituted by halogen, nitro, methyl, CF3 or methoxy, or are C3-C4-
alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by
halogen, nitro, Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R6 is hydrogen.
-- 7 --
Group Ig: Compounds of the forrnula I, wherein Rl is N02 or CF3; R2
is N02 or CF3 ; R3 is hydrogen or chlorine; R4 is hydrogen; R6 and
R8 are each independently halogen, cyano, thiocyano, nitro or a
group selected from -N(R9)(Rlo)l Rll, R12 13 n
which Rg and Rlo are each independently hydrogen, Cl-C4alkyl, C3-C4-
alkenyl, phenyl or phenyl which is substituted by halogen, nitro,
methyl or methoxy, or taken together they form an unsubstituted or
methyl-substituted piperidine ring; n is 2; Rll, R12 and R13 are
each independently C3-C4alkenyl or Cl-C4alky1 which is unsubsti-
tuted or substituted by halogen, nitro, cyano, phenyl, phenoxy, or
by an unsaturated or saturated 5- or 6-membered heterocyclic ring
which contains 1 or 2 hetero atoms selected from nitrogen, oxygen
and sulfur, each heterocyclic radical being in turn unsubstituted or
substituted by halogen, nitro, methyl, CF3 or methoxy, or are C3~C4-
alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by
halogen, nitro, Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R5 is hydrogen.
Examples of particularly preferred individual compounds are:
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-
chloropyrimidine (compound 2.2);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-
methylmercaptopyrimidine (compound 2.5);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-
methoxypyrimidine (compound 2.4);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-
(2,2,2-trifluorethoxy)pyrimidine (compound 2.6);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-
methoxy-5-chloropyrimidine (compound 5.1);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2,5-
dichloropyrimidine (compound 5.3);
N-(3'-chloro--2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-
chloro-5-fluoropyrimidine (compound 5.4);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-arnino-2-
methoxy-5-fluoropyrimidine (compound 5.6);
N-(3'-chloro-2',6'-dinitro-4'-tr;fluoromethylphenyl)-4-amino-5-
nitro-6-methoxypyrimidine (coMpound 6.1);
N-~3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-arnino-5-
nitro-6-aminopyrimidine (compound 6.2);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-
methylmercapto-5-nitro-6-methoxypyriMidine (compound 7.1);
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-
methyl-5-ethyl-6-chloropyrimidine (compound 7.3);
The compounds of formula I are prepared by reacting a compound of
the formula II
~o
// ~
2 \ / ~Z (II)
\
Rl
with a pyrimidine derivative of the formula III
R R
8\ / 6
/ \
Y-- N (III)
~ //
N--
R5
in the presence of a base, to give a compound of the formula I'
=. =-
/ \ / \
R -- ~---N~---- N (I')
2 ~ // ~ //
o_- N--
Rl R5
_ 9 _
and, to obtain an N-acylated derivative, N-acylating the compound of
the formula I' with a reactive derivative of the carbo~ylic acid of
the formula IV
R4COOH (IV)
in which formulae above the substituents Rl to R8 are as defined for
formula I and Z and Y are NH2 or halogen, with the proviso that, if
Z is halogen, Y is NH2 and, if Z is NH2, Y is halogen.
The following reaction conditions are advantageous for the prepara-
tion of the compounds of formula I and/or I':
The N-alkylation of (II) with (III) to give (I') and the N-acylation
of (I') with (IV) to give (I) take place with dehydrohalogenation.
The reaction temperature of the N-alkylation 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, preferably from 0 to
+150C or at the boiling point of the solvent or solvent mixture. In
both reactions it is convenient to use an acid acceptor or a
condensing agent. ~xamples of suitable acid acceptors or condensing
agents are organic and inorganic bases, e.g. tertiary amines such as
trialkylamines (trimethylamine, triethylamine, tripropylamine etc.),
pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidyl-
aminopyridine etc.), oxides, hydroxides, carbonates and bicarbonates
of alkali metals and alkaline earth metals, as well as alkali metal
acetates.
The reactions may be conducted in the presence of inert solvents or
diluents. ~xamples of suitable solvents and diluent3 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 compoullds such as
dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl
ether etc.), anisole, dioxan, tetrahydrofuran; nitriles such as
acetonitrile and propionitrile; N,N-dialkylated amides such as
dimethylformamide; dimethylsulfoxide; ketones such as acetone,
-- 10 --
diethyl ketone, methyl ethyl ketone; and mixtures of such solvents.
In some cases the acylating or alkylat;ng agent itself 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 catalysisO
The following solvents fGr example are suitable for the organic
water-immiscible phase: aliphatic and aromatic hydrocarbons such as
pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene,
toluene, xylenes etc.; halogenated hydrocarbons such as dichloro-
methane, chloroform, carbon tetrachloride, ethylene dichloride,
1~2-dichloroethane~ tetrachloroethylene and the like, or aliphatic
ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl
ether etc. Examples of suitable phases transfer catalysts are:
tetraalkylammonium halides, hydrogen sulfates or hydroxides, e.g.
tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl-
ammonium iodide, triethylbenzylammonium chloride or triethylbenzyl-
ammonium bromide, tetrapropylammonium chloride, tetrapropylammonium
bromide or tetrapropylammonium iodide etc. Suitable phase transfer
catalysts are also phosphonium salts. The reaction temperatures are
generally in the range from -30 to ~130C or may also be at the
boiling point of the solvent or mixture of solvents.
Unless 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 are: alipllatic and
aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum
ether; halogenated hydrocarbons such as chlorobenzene, methylene
chloride, ethylene chloride, chloroform, carbon tetrachloride,
tetrachloroethylenel ethers and ethereal compounds such as dialkyl
ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether
etc.), anisole, dioxane, tetrahydrofurane; nitriles such as aceto-
nitrile, propionitrile; N,N-dialkylated amides such as dimethyl
formamide; dimethylsulfoxide; ketones such as acetone, diethyl
ketone~ methyl ethyl ketone; and rnixtures o~ such solvents with each
other. It can often be convenier-t to carry out the reaction, or
partial steps of a reaction, under an inert gas atmosphere and/or in
absolute solvents. Suitable inert gases are nitrogen, helium, argon
etc.
The above described preparatory process, including all partial
steps, constitutes an irtlportant object of the present invention.
Surprisingly, it has been found that the compounds of formula I have
for practical purposes a very useful biocidal spectrum against
harmful micro-organisms, especially against phytopathogenic fungi.
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 microorganisms which occur in plants or parts
of plants (fruit, blossoms, leaves, stems, tubers, roots) in
different crops of useful plants, while at the same time the parts
of plants which grow later are also protected from attack by
phytopathogenic microorganisms.
As microbiocides, 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); Basidiomycetes (e.g. of the genera
Hemileia, Rhizocotonia, Puccinia); and, in particular, against the
class of the Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe,
Monilinia, Uncinula). In addition, the compounds of formula I have a
systemic action. They can also be used as seed dressing agents for
protecting seeds (fruit, tubers, grains) and plant cuttings against
fungus infections as well as against phytopathogenic microorganisms
which occur in the soil.
s~
- 12 -
Accordingly, the invention also relates to microbicidal compositions
and to the use thereof in agriculture or related fields for control-
ling phytophatogenic microorganisms, for exarnple fungi.
The invention further embraces the preparation of these cornposi-
tions, which comprises homogeneously mixing the active ingredient
with one or more compounds or groups of compounds described herein.
The invention furthermore relates to a method of treating plants,
which comprises applying thereto the compounds of the forrnula 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) 7
beet (sugar beet and fodder beet), drupes, pomes and soft fruit
(apples, pears~ plums, peaches, almonds, cherries, strawberries,
rasberries and blackberries), leguminous plants (beans, lentils,
peas, soybeans), oil plants (rape, mustard, poppy, olives, sun-
flowers, coconuts, castor oil plants, cocoa beans, groundnuts),
cucumber plants (cucumber, marrows, melons) fibre plants (cotton,
flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit,
mandarins), vegetables (spinach, lettuce, asparagus, cabbages,
carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados,
cinnamon, 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 plant to be
treated, simultaneously or in succession, with further compounds.
These further compounds can be both fertilisers or micronutrient
donors or other preparations that influence plant growth. They can
also be selective herbicides, insecticides, fungicides, bacterici-
des, nematicides, mollusicides or mixtures of several of these
preparations, if desired together with further carriers, surfactants
or application promoting adjuvants customarily employed in the art
5~
.~
- 13 -
of formulation. Suitable carriers and adjuvants can be solid or
liquid and correspond to the substances ordinarily employed in
formulation technology, e.g. natural or regenerated Mineral sub-
stances, solvents, dispersants, wetting agents, tackifiers, thick-
eners binders or fertilisers.
A preferred method of applying a compound of the formula I or an
agrochemical composition which contains at least one of said
compounds, is foliar application. The number of applications and the
rate of application depend on the risk of infestation by the
corresponding pathogen (type of fungus). However, the compound of
formula I can also penetrate the plan~ through the roots via the
soil (systemic action) by drenching the locus of the plant with a
liquid composition, or by applying the compounds in solid form to
the soil, e.g. in granular form (soil application). The compounds of
formula I may also be applied to seeds (coating) by impregnating the
seeds either with a liquid formulation containing a compound of the
formula I, or coating them with a solid formulation. In special
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 also 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 objectives and
the prevailing circumstances. Advantageous rates of application are
normally from 50 g to 5 kg of active ingredient (a.i.) per hectare,
preferably from lO0 g to 2 kg a.i./ha~ most preferably from 200 g to
600 g a.i./ha.
.
- 14 -
The formulations, i.e. the compositions or preparations containing
the compound (active ingredient) of the ~ormula ~ and, where
appropriate, a solid or liquid adjuvQnt, are prepared in kno~r1
mannerl e.g. by homogeneously mixing and/or grinding the active
ingredients with extenders, e.g. solvents, solid carriers andl where
appropriatel surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbonsl 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
paraffins, alcohols and glycols and their ethers and esters, such as
ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such
as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro-
lidone, dimethylsulfoxide or dimethylformamide, as well as epoxid-
ised 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 attapulgite. In order to improve the physical
properties it is also possible to add highly dispersed silicic acid
or highly dispersed absorbent polymers. Suitable granulated adsorp-
tive carriers are porous types, for example pumice, broken brick,
sepiolite or bentonite; and suitable nonsorbent carriers are
materials such as 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. Particularly
advantageous application promoting adjuvants which are able to
reduce substantially the rate of application are also natural
(animal or vegetable~ or synthetic phospholipids of the series of
the cephalins and lecithins, e.g. phosphatidyl ethanolamine,
phosphatidyl serine, phosphatidyl choline, sphingomyelinel phosphat-
idyl inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or
cardiolipin, which can be obtained e.g. from animal or plant cells,
in particular from the brain, heart, liver, egg yokes or soya
56~
beans. Examples of useful physical forrns are phosphatidyl choline
mixtures. Examples of synthetic phospholipids are dioctanoylphos-
phatidyl choline and dipalmitoylphosphatidyl choline.
Depending on the nature of the compound of the fo~nula I to be
formulated, suitable surface-active compounds are nonionic, cationic
and/or anionic sufactants having good emulsifying, dispersing and
wetting properties. The term "surfactants" will also be understood
as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and
water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal
salts or unsubstituted or substituted ammonium salts of higher fatty
acids (C10-C22), e.g. the sodium or potassium salts of oleic or
stearic acid, or of natural fatty acid mixtures which can be
obtained e.g. from coconut oil or tallow oil. 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 benzimid-
azole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali
metal salts, alkaline earth metal salts or unsubstituted or sub-
stituted ammonium salts and contain a C8-C22alkyl radical 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 comprise the salts of sulfuric acid esters and
sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-
ted benzimidazole derivatives preferably 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 dodecylbenzenesulfonic acid, dibutylnaphtha-
- 16 -
lenesulfonic acid, or of a naphthalenesulfonic acid/forrnaldehyde
condensation product. Also suitable are correspondillg pho~phates~
e.g. salts of the phosphoric acid ester of an adduct of p-norlyl-
phenol with 4 to 1~ moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated
fatty acids and alkylphenols, said 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 alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts
of polyethylene oxide with polypropylene glycol, ethylenediamine
propylene 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 units
per propylene glycol ~mit.
Representative examples of non-ionic surfactants are nonylphenol-
polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol,
polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters
of polyoxyethylene sorbitan and 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, lower unsubstituted or halogenated alkyl,
benzyl or lower hydroxyalkyl radicals. rhe salts are preferably in
the forrn of halides, methylsulfates or ethylsulfates, e.g. stearyl-
trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium
bromide.
5~i~
The surfactants custornarily emp10ye~l in the art of formulation are
described e.g. in "McCutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp. Ringwood, New Jersey, 1981; ~lelMut Stache,
"Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, lg81.
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 O to
25 ~, preferably 0.1 to 25 ~, of a surfactant.
Whereas commercial products are preferably formulated as concen-
trates, the end user will normally employ dilute formulations.
The compositions may also contain further ingredients such as
stabilisers, 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 object 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.
Preparatory Example
Example Pl: Preparation of
C\ No2 No2 oc~3
0 = ~
/ \ / \
F C~ N - . N (6.1)
-- H N--
N02
- 18 -
N-(3'-Chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-(5-
nitro-6-methoxy)pyrimidine
With stirring, 3.2 parts of 4-amino-5-nitro-6-methoxypyriMidine are
added, in portions and at room temperature, to a solution of 6.1
parts of 2,4-dichloro-3,5-dichloro-3,5-dinitrobenzotrifluoride in 50
ml of dimethylsulfoxide. With cooling, a solution of 4.5 parts of
potassium tert-butylate in 25 ml of dimethylsulfoxide is added
dropwise at room temperature to the suspension over 1/2 hour and
stirring is continued for 12 hours at room temperature. The red
reaction mixture is then poured into 700 ml of water, acidified with
3 ml of hydrochloric acid, and extracted with 3 x 200 ml of chloro-
form. The combined extracts are washed with 2 x 100 ml of water,
dried over sodium sulfate, filtered and dried. The brown crystalline
residue is purified by column chromatography through silica gel
eluted with a 3:2 mixture of petroleum ether/ethyl acetate. The
eluant is evaporated off and the product is recrystallised from
toluene/cyclohexane, affording the title compound with m.p.
184-186~C.
The following compounds of formula I are prepared in analogous
manner:
Table 1: Compounds of the forrnula
// ~ / \
R -~ ~-iN--- N
2 \ /
o=~ H N--
Rl R5
.__ _ .. __ _ _ _
. Compound Rl R2 ~ R3 R5 Physlcal data ~C] .
1.1NO2 CF3 Cl H m.p. 156
1.2NO2 CF3 H C3H7~n
1.3 NO2 CF3 Cl CH3
1.4CF3 NO2 H C6H5
1.5 NO2 CF3 Cl C3H7~n
1.6NO2 CF3 Cl Cl viscous substance
1.7CF3 No2 H Cl viscous substance
1.8CF3 No2 H OC2H5
1.9 NO2 CF3 Cl OC2H5
1.10CF3 NO2 H SCH3
1.11 No2 CF3 Cl OCH3
1.12 No2 CF3 Cl SCH3
1.13No2 CF3 H Cl
1.142 CF3 Cl 2 5
- 20
Table 1 (Continuation)
~ _ _ ~ ,_ _____ _
Compound RlR2 R3 R5 Physical data
_ _ _ .
1.15 No2 CF3 Cl CF3 resin
1.16 CF3 N02 H H resin
1.17 No2 CF3 Cl OC3H7-i
1.18 No2 CF3 H C2H5
1.19 No2 CF3 Cl CH20CH3
1.20 No2 CF3 Cl SCH2-C6H5
1.21 No2 CF3 H CF3 re~in
1.22 N02 CF3 Cl _
Table 2: Compounds of the formula
~R6
._. ~=.
// ~ / \
R ~ N-- N
2 \
~=- H N-~
Rl
1 1 . _ ._ .
Compound Rl R2 - 3 - 6 _ _ _ Physical data
2.1N02 CF3 H H
2.2N02 CF3 Cl Cl m.p. 97-99
2.3CF3 No2 H C6H5
2.42 3 1 1 ¦ OCH3 m.p. 128-129
2.5No2 CF3 Cl SCH3 m P~ 135-137
iL~5~
- 21 -
Table 2 (Continuation)
Compound L R2 n3 6 ~ Physlcal data
.
2.6 N02 CF3 Cl 2 3 m.p. 98-100
2.7 CF3 No2 H CF3
2.8 N02 CF3 Cl -C(CH3)3
2.9 CF3 No2 H Cl resin
2.10 No2 CF3 Cl -N(C2H5)2
2.11 No2 CF3 Cl C2H5
2.12 No2 CF3 Cl -N(CH3)2
2.13 No2 CF3 Cl C6H5
/~
2.14 No2 CF3 Cl -N\. ! -
2.15 No2 CF3 H -N(C3H7-n)2
2.16 No2 CF3 Cl CF3 viscous substance
2.17 No2 CF3 Cl CH3
2.18 No2 CF3 H OC4Hg-n
2.19 No2 CF3 Cl OC3H7-i
2.20 No2 CF3 Cl OCH3
2.21 CF3 30z 3 2 5 _ _
- 22 -
Table 3: Compound of the formula
R3 M2 R8
. . ~ .= ~
// ~ / \
R ~ N - N
2 \ / I ~ D
=- H N--
Rl
Co~po~nd d~ ~ 3 8 _ Physical data
3.1 CF3 No2 H H semicrystalline
3.2 NO2 CF3 Cl CN
3.3 NO2 CF3 H Cl resin
3.4 NO2 CF3 Cl Br
3'5 CF3 NO2 H CN
3.6 NO2 CF3 Cl Cl
3'7 NO2 CF3 Cl Cl resin
3.8 CF3 No2 H Br
3~9 NO2 CF3 Cl C3H7-i
3.10 NO2 CF3 Cl CH20C2H5
3.11 NO2 CF3 Cl CH20C6H5
3.12 NO2 CF3 Cl C2N5
3.13 CF3 No2 H CH3
3.14 NO2 CF3 Cl OCH3
3.15 NO2 CF3 Cl CH3
3.16 CF3 No2 H CH20CII3
3.17 ~O~ CP3 Cl C6~l5 _ _ _
- 23 -
Table 3: (Continuation)
CDmpo~md R~R2 R3 8
3.18 N02 CF3 Cl CH2C6H4Cl(4)
3.19 N02 CF3 Cl C6H13-n
3.20 N02 CF3 Cl C5H4Cl(4)
3.21 N02 CF3 Cl CH2Cl
3.22 mo CF3 Cl OC6H3C12(3 ,4)
Table 4: Compounds of the formula
\ / 2 8\ / 1
=~, ._0
/ \ // ~
CF -~ N~-~ N
3 ~ // I \ /
G_- R4 N-~
N02 R5
_ .................. .... _ l .
Compound R4 R8 R5
4.1 C(O)CH=CH2 F SCH3
4.2 C(O)CH=CH2 C1 CN
4.3 C(o)ccl=ccl2 F SCH3
4.4 C(O)Cyclopropyl F SCH3
4.5 C(O)CH=CH2 CN CF3
4.6 C(O)C6H4Cl(4) F SCH3
~.
4.7 C(0)-- OCH3 CN
5i6~
- 24 -
Table 4: (Continuation)
.. __ . . ,_. _. __ ,
Compound R4 R8 R5
. ~ ......... __ .
//~~
4.8 C(O)~- N F SCH3
,,_, Cl,_ _
Table 5: Compounds of the formula
R3 N2 R8
// ~ / \
R ~ N-- N
2 \ /
.=. H N-
Rl R5
I __ _ _ _ . _ __
Compound Rl R2 R3 R5 R8 data [C]
. . _ _ . .. __ . .
5.1 NO2 CF3 Cl OCH3 Cl m.p. 157-158
5.2 NO2 CF3 Cl CH3 C4H9-n
5.3 NO2 CF3 Cl Cl Cl m.p. 176-177
5'4 NO2 CF3 Cl Cl F m.p. 167-168
5.5 NO2 CF3 Cl CH3 CH2N(CH3)2
5.6 NO2 CF3 Cl OC113 F m.p. 158-159
~ ~2 CF3 Cl SCH3 _
- 25 -
Table 5: (Continuation)
_ __ __
Compound Rl R2 R3 R5 8dPhysical
. __ _ _ ___ . . _ .
5.8 CF3 No2 H CH3 C6H13-n
5 9 N02 CF3 Cl 3 7 CH2Br
5.10 N02 CF3 Cl CH2C6H5 CH2~r
5.11 N02 CF3 Cl CH3 CHzSCN
5.12 CF3 No2 H -N(CH3)2 CN
5.13 N02 CF3 Cl C1 CH2Cl
5.14 CF3 No2 H CH3 CH2CN
5.15 N02 CF3 Cl C2F5 CN
5.16 N02 CF3 C1 S02C2H5 CH3
5.17 CF3 No2 H SCH3 CH3
5.18 N02 CF3 C1 CF3 CN resin
5.19 N02 CF3 Cl OCH3 CN
5.20 N02 CF3 Cl 2 5 C6H5
5.21 CF3 No2 H CF3 CN
5.22 N02 CF3 C1 C1 OCH3
5.23 N02 CF3 C1 CF3 CH20C2H5
5.24 CF3 No2 H 3 7 CN
5.25 N02 CF3 C1 CH20CH3 CH20C2H5
5.26 N02 CF3 Cl S2CH3 CN
/'~-\
l 5 27 ~02 ~ L ~
- 26 -
Table 5: (Continuation)
_ _ __ .. _
Compound Rl R2 R3 K5 R8 dPhyical
, __ _ . _ .. __ .
5.28 NO2 CF3 Cl C2F5 Br
5.29 NO2 CF3 Cl CF3 CH2Br
5.30 NO2 CF3 Cl SCH3 CH2Cl
5.31 NO2 CF3 Cl 2 5 CN
5.32 CF3 No2 H CF3 CH2Cl
5.33 NO2 CF3 Cl 2 5 F
5.34 NO2 CF3 Cl C5Hg-n CN
5.35 NO2 CF3 Cl -N(CH3)2 Br
5.36 NO2 CF3 Cl SCH3 NO2
5.37 CF3 NO2 H C4Hg-n CN
5.38 CF3 No2 H Cl NO2
5 39 NO2 CF3 H C6H4Cl(4) CN
5.40 CF3 NO2 H SCH2C6H5 CN
5.41 NO2 CF3 Cl -CH=CH2 CN
5.42 NO2 CF3 Cl SCH3 CH2Br
5.43 CF3 NO2 H Cl ~H ~r
5.44 NO2 CF3 H SCH2C6~5 I Ct~CH 2
5.45 NO2 CF3 Cl CH2F CH3
5.46 NO2 CF3 Cl OCH3 NO2 ~n.p. 178-179
5 47 NO2 CF3 Cl OC2~15 Cl m.p. 149-151
5.48 NO2 CF3 ¦ Cl 2CF3 Cl m.p. 146-147
5.49 ~ N2 CF3 Cl j (CH2)2cl~3 No2 m.p, 125 126
- 27 -
Table 5: (Continuation)
_ ~ _
Compound ~ Rl R2 R3 R5 8 data ~C]
. .. _ _ .. _ .
5.50 N02 CF3 Cl 2 3 N02 m.p. 138-140
5.51 N02 CF3 Cl 2 3 F m.p. 135-138
5.52 N02 CF3 Cl SCH3 CH3
5'53 N02 CF3 H SCH3 CH3
5'54 N02 CF3 H SCH3 Cl
5'55 N02 CF3 Cl OCH3 CH3
5.56 CF3 No2 H OCH3 CH3
5.57 CF3 N02 H Cl CH3
5.58 N02 CF3 H OCH3 CH3
5.59 CF3 N02 H OCH2-CH=CH2 Cl
5.60 N02 CF3 Cl Cl CH3
5.61 N02 CF3 H Cl CH3
5.62 CF3 No2 H SCH3 Cl
5.63 N02 CF3 H OCH2CH=CH2 Cl
5.64 N02 CF3 Cl SCH3 Cl
. 5.65 N02_ CF3 Cl OCH2CH=CH2 Cl
~ ~5 4~
- Z8 -
Table 6: Compounds of the formula
R3 N2 R8\ / 6
_O - ~
// ~ / \
R2~ N~-- N
\ / I ~ //
=o H N--
Rl
_ _______ Rl R2 R3 R6 R3 data [C]
6.1 NO2 CF3 Cl OCH3 NO2 m.p. 184-186
6.2 NO2 CF3 Cl -NH2 NO2 m.p. 184-189
6.3 CF3 No2 H CH20C2H5 CH3
6.4 NO2 CF3 Cl Cl No2
6.5 NO2 CF3 Cl CH3 CN
6.6 NO2 CF3 Cl -N(C3H7-n)2 No2
6.7 CF3 No2 H 2 4 2 5C6H5
6.8 NO2 CF3 Cl Cl OC4Hg-n
6.9 NO2 CF3 Cl F NO2
6.10 NO2 CF3 Cl Cl CH3
6.11 NO2 CF3 Cl Cl OCH3
6.12 CF3 No2 H 2 5 No2
6.13 NO2 CF3 Cl Cl C2H5
6.14 N~2 CF3 Cl CH3 Br
6.15 CF3 No2 H CH3 Cl
6.16 NO2 CF3 Cl Cl C6H5
6.17 NO2 CF3 Cl C21l40C2H5 OC4Hg-n
6.18 NO2 CF3 Cl Cl OC3H7-i
6.19 CF3 NO2 H CH3 CN
- 2g -
Table 6: (Continuation)
_ _ _~ ,
Compound Rl R2 R3 6 8 dPhtyai[al,]
. ._ _ _ _ ,
6.20 CF3 No2 H C1 OC3H7-i
6.21 CF3 No2 H CH3
6.22 N02 CF3 HCl C2H5
6.23 N02 CF3 Cl SCH3 N02 m.p. 185
6.24 N02 CF3 Cl 2 3 N02 m.p. 164-167
6.25 N02 CF3 Cl OCH3 Cl
6.26 CF3 No2 H2 3 C1
6.27 N02 CF3 C1 OCH2-CH=CH2 C1
6.28 N02 CF3 Cl SCH3 Cl
6.2930~ CF3 U Cl Cl . . _ _ _
Table 7: Compounds of the formula
3\ / 2 8\ / 6
// ~ / \
R ~ N--- N
=- H N--
Rl R5
C]
. ... _ .
7.1 No2 CF3 Cl SCH3 OCH3 No2 m.p. 181-183
7.2N02¦ CF31 C1 ¦ C1 ¦ C1 ¦ N02
7.3 ~ __ _ __ m.p. 134-136
D
-- 30 --
Table 7: (Continua~ion)
pound ~1 R2 R3 R5 d6 8 Ph~si[al dat~
.. _ _ _ . _ .
7.4 N02 CF3 C1 Cl C113 No2
7.5 N02 CF3 Cl CH2CN CH2CN CN
7.6 No2 CF3 Cl F F F
7.7 CF3 N02 H ClCl No2
7.8 CF3 N02 H ClCl Br
7 9 N02 CF3 Cl CH3 CH3 S2CH3
7.10 No2 CF3 Cl Cl Cl Br
7.11 No2 CF3 Cl SCH3 C1 Br
7.12 No2 CF3 Cl Cl Cl CH3 m.p. 184-187
7.13 CF3 N02 H SCH3 Cl C8H17-n
7.14 CF3 N02 H Br Br CH3
7.15 No2 CF3 Cl Cl Cl CH2C6H5
7.16 No2 CF3 Cl Cl CH3 CH3
7.17 CF3 N02 H CF3 CF3 CN
7.18 No2 CF3 Cl Cl Cl Cl
7.19 CF3 N02 H Cl Cl CH3 m.p. Z07-208
7.20 No2 CF3 Cl B~ Br CH3
7.21 No2 CF3 Cl CH3 Cl CH2N(CH3)2
7.22 CF3 N02 H Cl Cl Cl
7.23 CF3 N02 H Cl Cl C2H5
7.24 CF3¦ N02¦ H SCH3CH3 No2
7.25 ~ ~ CF3 H ~ Cl Cl ¦ Cl
- 31 -
Table 7: (Continuation)
Cum-Rl R~ 3 ~ 5 ~ R8 Physical data
. . ._ _ __ _ _ .
7.26 No2 CF3 Cl -N(CH3)2 Cl CN
7.27 No2 CF3 Cl CF3 CF3CN
7.28 CF3 N02 H Cl CH3C2H5
7.29 No2 CF3 Cl SCH3 OCH3 Br
7.30 N02 CF3 Cl SCH3 Cl C4Hg-n
7.31 No2 CF3 Cl Cl Cl C2H5
7.32 No2 CF3 Cl SCH3 CH3 CN
7.33 N02 CF3 Cl SCH3 Cl CH3 m.p. 169-172
7.34 N02 CF3 Cl CH20CH3 Cl C2H5
7.35 N02 CF3 Cl SCH3 NH2 N02 m.p. 250 (dec.)
7.36 No2 CF3 Cl OCH3 OCH3 N02 m.p. 164-166
7.37 N02 CF3 H SCH3 Cl CH3 m.p. 213-216
7.38 CF3 N02 H SCH3 Cl CH3 m.p. 150-160
7 39 N02 CF3 Cl CH3 CH3
7.40 N02 CF3 Br CH3 CH3
7.41 CF3 N02 H CH3 CH3
7.42 No2 CF3 Cl SCH3 Cl Cl
7.43 CF3 N02 H C2H5 OCH3 Cl
7.44 N02 CF3 Cl OCH3 Cl Cl
7.45 N02 CF3 Cl C2H5 SCH3 Cl
7.46 N02 CF3¦ Cl 2CF3 Cl Cl
j 7.47 ~ 3 H OcH2-cH-cH2 Cl Cl
- 32 -
Table 7: (Continuatiorl)
C m- ~1 R2 R3 R5 n6 8
. 7.48 N02 CF3 Cl C2H5Cl Cl .
7 49 N02 CF3 Cl OCH~CH Cl Cl
7.50 N02 CF3 Cl ClCF3 Cl
7.51 No2 CF3 Cl OCH3CF3 Cl
N02 CF3 Cl ~ _ CF3 Cl
Formulation Examples_
Formulation Examples for liquid active ingredients of_the formula I
(throughout, percentages are by weight)
Fl. Emulsifiable concentrates a) b) c)
~ .. . . _ .
a compound of tables 1 to 7 25 ~ 40 ~ 50
calcium dodecylbenzenesulfonate 5 ~ 8 ~ 6
castor oil polyethylene glycol ether
(36 moles of ethylene oxide) 5 ~ - -
tributylphenol polyethylene glycol ether
(30 moles of ethylene oxide) 12 ~ 4
cyclohexanone - 15 ~ 20
xylene mixture 65 ~ 25 ~ ZO ~
Emulsions of any required concentration can be produced from such
concentrates by dilution with water.
F2. Solutions a) b) c) d)
_
a compound of tables 1 to 7 80 ~ 10 ~ 5 ~ 95
ethylene glycol monomethyl ether 20 ~
polyethylene glycol 400 - 70 ~ - -
N-methyl-2-pyrrolidone - 20 ~ - -
s~
epoxidised coconut oil ~ 5
petroleum distillate (boiling range
160-190~ 94 ~ -
These solutions are suitable for application in the form of micro-
drops.
F3. Granulates a) b)
a compound of tables I to 7 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 i6 subsequent-
ly evaporated off in vacuo.
F4. Dusts a) b)
a compound of tables 1 to 7 2 ~ 5
highly dispersed silicic acid 1 ~ 5
talcum 97 ~ ~
kaolin - 90 ~
Ready-for-use dusts are obtained by intimately mixing the carriers
with the acitve ingredient.
Formulation examples for solid active ingredients of the formula I
(throughout, percentages are by weight)
F5. Wettable powders a) b) c)
... . _ _
a compound of tables 1 to 7 25 ~ 50 ~ 75
sodium lignosulfonate 5 % 5 ~ -
sodium lauryl sulfate 3 ~ - 5
sodium diisobutylnaphthalenesulfonate - 6 ~ 10
5~
- 34 -
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide) - Z ~ -
highly dispersed silicic acid 5 ~ 10 % 10
kaolin 62 ~ 27 ~ -
The active ingredient is thoroughly mixed with the adjuvants and the
mixtures is thoroughly ground in a suitable mill, affording wettable
powders which can be diluted with water to give suspensions of the
desired concentration.
F6. Emulsifiab e concentrate
a compound of tables 1 to 7 10
octylphenol 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 50 ~
Emulsions of any required concentration can be obtained from this
concentrate by dilution with water.
F7. Dusts a) b)
a compound of tables 1 to 7 5 ~ 8
talcum 95 ~ -
kaolin - 92 ~
Ready-for-use dusts are obtained by mixing the active ingredient
with the carriers, and grinding the mixture in a suitable mill.
F8. Extruder granulate
a compound of tables 1 to 7 10
sodium lignosulfonate 2
carboxymethylcellulose 1
kaolin 87
5~
- 35 -
The active ingredient is mixed and ground with the adjuvants, and
the mixture is subse4uently moistened with water. The rni~ture is
extruded and then dried in a streTn of air.
F9. Coated granulate
a compound of tables 1 to 7 3
polyethylene glycol 200 3
kaolin 94 ~
The finely ground acTtive ingredient is uniformly applied, in a
mixer, to the kaolin moistened with polyethlene glycol. Non-dusty
coated granulates are obtained in this manner.
F10. Suspension concentrate
.
a compound of tables 1 to 7 40
ethylene glycol 10
nonylphenol polyethylene glycol
(15 moles of ethylene oxide) 6
sodium lignosulfonate 10
carboxymethylcellulose 1
37 ~ aqueous formaldehyde solution 0.2
silicone oil in the form of a 75
aqueous emulsion 0.8
water 32 ~
The finely ground active ingredient is intimately mixed with the
aduvants, giving a suspension concentrate from which suspensions of
any desired concentration can be obtained by dilution with water.
~25~
- 36 -
Biological Examples
Example Bl: Action apainst Puccinia graminia on wheat
a) Residual-protective action
..
Wheat plants were treated 6 days after sowing with a spray mixture
prepared from a wettable powder formulation of the active ingredient
(0.02 ~). After 24 hours the treated plants were infected with a
uredospore suspension of the fungus. The infected plants were
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 was made 12 days after infection.
b) Systemic action
Wheat plants were treated 5 days after sowing with a spray mixture
prepared from a wettable powder formulation of the active ingredient
(0.006 ~ based on the volume of the soil). After 48 hours the
treated plants were infected with a uredospore suspension of the
fungus. The plants were then incubated for 48 hours at 95-100 ~
relative humidity and about 20C and then stood in a greenhouse at
about 22C. Evaluation or rust pustule development was made 12 days
after infection.
Compounds of the tables were very effective against Puccinia fungi.
Puccinia attack on untreated and infected control plants was 100~.
Compounds of Tables 1, 2, 5 and 7 and others inhibited Puccinia
attack to 0 to 5~.
xample B2: Action against Cercospora arachidicola in groundnut
plants
Residual protective action
Groundnut plants 10-15 cm in height were sprayed with a spray
mixture (0.006 ~) prepared from a wettable powder formulation of the
test compound, and infected 48 hours later with a conidia suspension
of the fungus. The infected plants were incubated for 72 hours at
about 21C and high humidity and then stood in a greenhouse until
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the typical leaf specks occurred. Evaluation of the fungicidal
action was made 12 days after infection an(l was based on the number
and size of the specks.
Compared with untreated and infected controls (number and size of
the specks = 100~), Cercospora attack on groundnut plants treated
with compounds of the tables was substantially reduced. In the above
tests, compounds 1.1, 1.6, 1.7, 1.16, 1.21, 2.2, 2.5, 2.6, 2.9,
2.16, 3.1, 3.3, 3.7, 5.1, 5.3, 5.6, 5.18, 5.46, 5.48, 5.50, 5.51,
6.1, 6.2, 6.23, 6.24, 7.1, 7.3, 7.12, 7.36, 7.37 and 7.38 inhibited
the occurrence of specks almost completely (0-10~).
Example B3: Action against Erysiphe graminis on barley
a) Residual protective action
Barley plants about 8 cm in height were sprayed with a spray mixture
(0.002 ~) prepared from a wettable powder formulation of the test
compound. The treated plants were dusted with conidia of the fungus
after 3-4 hours. The infected barley plants were then stood in a
greenhouse at about 22C. The extent of the infestation was
evaluated after 10 days.
b) Systemic action
Barley plants about 8 cm in height were treated with a spray mixture
(0.006 ~), based on the volume of the soil) prepared from a wettable
powder formulation of compound. Care was taken that the spray
mixture did not come in contact with the growing parts of the
plants. The treated plants were infected 48 hours later with a
conidia suspension of the fungus. The infected barley plants were
then stood in a greenhouse at about 22C and evaluation of infesta-
tion was made after 10 days.
Compounds of formula I were very effective against Erysiphe fungi.
Erysiphe attack was 100~ on untreated and iunfected control plants.
Compounds 1.1, 1.6, 1.7, 1.16, 1.21, 2.2, 2.5, 2.6, 2.9, 2.16, 3.1,
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3.3, 3.7, 5.1, 5.3, 5.6, 5.18, 5.~6, 5.~8, 5.5U, 5.51, ~.1, 6.2,
6.23, 6.24, 7.1, 7.3, 7.12, 7.36, 7.37, 7.38 aad others, inhibited
fungus attack on barley to less than 30~.
xample B4: Residual-protective action against Venturia inaequalis
on apple shoots
Apple cuttings with 10-20 cm long fresh shoots were sprayed with a
spray mixture (0.006 ~) prepared from a wettable powder formulation
of the test compound. The plants were infected 24 hours later with a
conidia suspension of the fungus. The plants were then incubated for
5 days at 90-100 ~ relative humidity and stood in a greenhouse for a
further 10 days at 20-24C. Scab infestation was evaluated 15 days
after infection. Compounds of the tables inhibited attack to less
than 25~. On the other hand, attack on untreated and infected
control shoots was 100~.
xample B5: Action against Botrytis cinerea on beans
~ . _ . . _ . .
Residual protective action
Bean plants about 10 cm in height were sprayed with a spray mixture
(0.02~ concentration) prepared from a wettable powder formulation of
the test compound. After 48 hours, the treated plants were infected
with a conidia suspension of the fungus. The infected plants were
incubated for 3 days at 95-100~ relative humidity and 21C, and
evaluation of fungus attack was then made. Numerous compounds of the
tables very strongly inhibited fungal infection. At a concentration
of 0.02~, compounds 1.1., 1.6, 1.7, 1.15, 2.4, 2.6, 2.16, 3.3, 3.7,
5.3, 5.6, 5.18, 5.46, 5.49, 6.2, 7.1, 7.12 and 7.33 were fully
effective (O to 8~ attack). Botrytis attack on untreated and
infected bean plants was 100~.
Example B6:Action against Ph to hthora infestans on tomato plants
Y P
a) Residual protective action
After a cultivation period of 3 weeks, tomato plants were sprayed
with a spray mixture (0.06~) prepared from a wettable powder
formulation of the test compound. After 24 hours the treated plants
~25~
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were infected with a sporangia suspension of the fungus. ~valuation
of fungus attack wa~s made after the plants had been incubated for 5
days at 90-100~ relative humidity and 20~C.
b) Systemic action
A spray mixture (0.06~, based on the volume of the soil) prepared
from a wettable powder formulation of the test compound was poured
on tomato plants after a cultivation period of 3 weeks. Care was
taken that the spray mixture did not come in contact with the
growing parts of the plants. After 48 hours the plants were infected
with a sporangia suspension of the fungus. Evaluation of fungus
attack was made after the plants had been incubated for 5 days at
90-100% relative humidity and 20C.
In the above tests, compounds 1.1, 1.6, 1.21, 2.Z, 2.5, 2.9, 2.16,
3.1, 3.3, 3.7, 5.1, 5.3, 5.46, 5.48, 6.1, 7.1, 7.3 and 7.12 had a
very good systemic action. These compounds inhibited fungus attack
almost completely (0 to 5~ attack) as against 100~ attack on
untreated control plants.
Example B7: Action against Plasmapora viticola on vines
a) Residual protective action
Vine cuttings in the 4-5 leaf stage were sprayed with a spray
mixture to.o6~) prepared from a wettable powder formulation of the
test compound. After 24 hours the treated plants were infected with
a sporangia suspension of the fungus. Fungus attack was evaluated
after incubation for 6 days at 95-100~ relative humidity and 20C.
b) Residual curative action
Vine cuttings in the 4-5 leaf stage were infected with a sporangia
suspension of the fungus. After incubation for 24 hours in a humid
chamber at 9S-100~ relative humidity and 20C, the infected plants
were dried and sprayed with a spray mixture (0.06~) prepared from a
wettable powder formulation of the test compound. After the spray
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coating had dried, the treated plants were re~urned to the humid
chamber. Evaluation of fungus attack was made 6 days after
infection.
Compounds of the tables exhibited a very good fungicidal action
against Plasmopara viticola on vines. In particular, compounds 1.1,
1.6, 1.7, 1.21, 2.2, 2.5, 2.9, 2.16, 3.1, 3.3, 5.1, 5.3, 5.4, 6.1,
6.2, 7.1, 7.12 and 7.19 inhibited fungus attack completely (0 to
5~).
Example B8: Action against Piricularia on rice plants
Residual protective action
After a cultivation period of 2 weeks, rice plants were sprayed with
a spray mixture (0.02~) prepared from a wettable powder formulation
of the test compound. After 48 hours the treated plants were
infected with a conidia suspension of the fungus. Evaluation of
fungus attack was 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 which were treated with a spray
formulation containing a compound of tables 2 or 7, e.g. compounds
7.1 and 7.19.
