Note: Descriptions are shown in the official language in which they were submitted.
~209152
Case 5-1422.'/+
1-Azolyl-2-aryl-3-fluoroalkan-2-ols as microbicides
The present invent;on relates to novel, substituted
1-azolyl-2-aryl-3-fluoroalkan-2-ols and ethers thereof, of
the formula I below, and to acid addition salts, quaternary
azolium salts and metal complexes thereof. The ;nvention
furthermore relates to the preparation of these substances
and microbicidal compositions containing at least one of
these compounds as the active substance. The invention also
relates to the preparation of the above compositions and to
the use of the active substances or of the compositions
for the control of harmful microorganisms, preferably fungi
wh;ch are harmful to plants.
The compounds according to the invention are those
of the general formula I
Ar R3
in which Az is 1H-1,2,4-triazole, 4H-1,2,4-triazole or 1H-
imidazole; Ar is an unsubstituted or substituted aromatic
radical from the series comprising phenyl, biphenyl, phenoxy-
phenyl and naphthyl; R1 is hydrogen, C1-C4-alkyl, C3-C5-
alkenyl or benzyl; R2 is hydrogen, fluorine or C1-C6-
alkyl and R3 is hydrogen, fluorine, C1-C6-alkyl, C1-C6-
haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, phenyl,
phenoxy, phenylthio or C3-C7-cYcloalkyl, and each aromatic
substituent or aromatic moiety of a substituent is unsubstituted
, ,
~20gi52
- 2 -
or mono- or poly-substituted by haLogen, C1-C4-alkyl, C1-C4-
alkoxy, C1-C4-haloalkYl~ nitro and/or cyano; including
the acid add;tion salts, quaternary azolium salts and metal
complexes.
The term alkyl by itself or as a constituent of ano-
ther substituent is to be understood as meaning, for example,
one of the following groups, depending on the number of car-
bon atoms stated: methyl, ethyl, propyl, butyl, pentyl,
hexyl and the like and their isomers, for example isopropyl,
isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is
a monohalogenated to perhalogenated alkyl substituent, for
example CHCl2~ CHF2~ C~2Cl~ CCl3, CH2F, CH2CH2Cl
CH2Br and the like, in particular CF3. Here and in the fol-
lowing text, halogen is to be understood as meaning fluorine,
chlorine, bromine or iodine, preferably fluorine, chlorine
or bromine. Alkenyl is, for example, prop-1-enyl, allyl,
but-1-enyl, but-2-enyl or but-3-enyl. Naphthyl is I- or I-
naphthyl.
The present invention thus relates to the free com-
pounds of the formula I and acid addition salts, quaternaryazolium salts and metal complexes thereof. The free com-
pounds, in particular the 1H-1,2,4-triazole derivatives, are
preferred in the context of formula I.
Examples of salt-forming acids are inorganic acids,
such as hydrogen halide acids, such as hydrofluoric acid,
hydrochloric acid, hydrobromic acid or hydriodic acid, as
well as sulfuric acid, phosphoric acid, phosphorous acid and
nitric acid, and organic acids, such as acetic acid, tri-
fluoroacetic acid, trichloroacetic acid, propionic acid, for-
mic acid, benzenesulfonic acid, p-toluenesulfonic acid or
methanesulfonic acid.
Metal complexes of the formula I consist of the ba-
sic organic molecule and an inorganic or organic metal salt,
for example the halides, nitrates, sulfates, phosphates, ace-
tates, trifluoroacetates, trichloroacetates, propionates,tartrates, sulfonates, salicylates, benzoates and the like
of the elements of the third and fourth main group, such as
~209~52
-- 3 --
alum;nium, t;n or lead, and of the f;rst to eighth sub-group,
such as chrom;um, manganese, ;ron, cobalt, nickel, zirconium,
copper, zinc, s;~ver, mercury and the like. The sub-~roup
elements of the 4th period are preferred. The metals can
be in the various valences with which they are associated.
The metal complexes of the formula I can be mononuclear or
polynuclear, i.e. they can contain one or more organic mole-
cule components as ligands. Complexes with the metals copper,
zinc, manganese, tin and zirconium are preferred.
The compounds of the formula I are oils, resins or,
chiefly solids, which are stable at room temperature and are
distinguished by very useful m;crobic;dal properties. They can
be used prevent;vely and curat;vely in the agricultural sector
or related fields for controlling micro-organisms which damage
plants, the triazolylmethyl derivatives in the context of the
formula I being preferred. The active substances of the
formula I according to the invention are distinguished by a
very good phytofung;cidal action and problem-free application
when used ;n low concentrations. Moreover, they also have a
growth-regulating action, in particular a growth-inhibiting
action, especially on tropical cover crops.
The following groups of substances are preferred, be-
cause of their marked microbicidal action, in particular
their phytofungicida~ action: compounds of the formula I
in which Az is 1H-1,2,4-triazole or 1H-im;dazole; Ar ;s an
unsubstituted or substituted aromatic radical from the se-
ries comprising phenyl, biphenyl and phenoxyphenyl, R1 is
hydrogen; R2 is hydrogen, fluorine or c1-c3-alkyl; and
R3 is hydrogen, fluorine, C1-C4-alkyl, C1-C3-haloalkyl,
C1-C3-alkoxy, C1-C3-alkylthio, phenyl, phenyloxy
ox phenylthio, each phenyl moiety being unsubstituted
or substituted by fluorine, chlorine, bromine, methyl, me-
thoxy, CF3, N02 and/or cyano; including the acid addition
salts, quaternary azolium salts and metal complexes.
Particularly preferred compounds of the formula I
within this group are those in which Az is 1H-1,Z,4-triazole;
Ar is phenyl or phenoxyphenyl which is unsubstituted or, pre-
~209152
- 4 -
ferably, substituted ;n the 2- and/or 4-pos;t;on by methyl or
halogen, preferably fluor;ne or chlor;ne; R1 ;s hydrogen;
R2 is hydrogen, fluorine or methyl; and R3 ;s hydrogen,
fluorine, c1-C4~alkyl or a radical from the series com-
prising phenyl, phenoxy and phenylthio which is substitutedby fluorine, chlorine and/or bromine.
Examples of specific particularly preferred substan-
ces from a fungicidal point of view are: 1-(1H-1,2,4-tri-
azol-1-yl)-2-(2,4-dichlorophenyl)-3-fluorobutan-2--ol, 1-(1H-
10 1,2,4-triazol-1-yl)-2-(2-chloro-4-fluorophenyl)-3--fluoro-
butan-2-ol, 1-(1H-1,2,4-triazol-1-y~)-2-(2,4-d;chlorophenyl)-
3-fluoropentan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-di-
chlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1-(1H-1,2,4-
triazol-1-yl)-2-(2-chloro-4-fluorophenyl)-3-fluoroopentan-
2-ol,1-(1H-1,2,4-triazol-1-yl)-2-t2,4-dichloropheny~)-33-
(4-chlorophenoxy)-3-fluoropropan-2-ol, 1-(1H-1,2,4-triazol-
1-yl)-2-Cp-(4-chlorophenoxy)phenyl]-3-fluoropropann-2-ol,
1-(1H-1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-3,3,33-trifluoro-
propan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-
3,3,3-trifluoropropan-2-ol, 1-(1H-1,2,4-tr;azol-1-yl)-2-(4-
chlorophenyl)-3-fluorohexan-2-ol, 1-(1H-1,2,4-triazol-1-yl)-
2-~2,4-dichlorophenyl)-3-fluorohexan-2-ol, 1-(1H-1,2,4-tri-
azol-1-yl)-2-(2,4-dichlorophenyl-3,3-difluoropentaan-2-ol,
1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-33-fluoro-4-
methylpentan-2-ol, 1-(1H-1,2,4-triazol-1~yl)-2-Cp-(4-bromo-
phenoxy)phenyl]-3,3-difluoropropan-2-ol, 1-(1H-1,2,4-tri-
azol-1-yl)-2-Cp-(4-fluorophenoxy)phenyl]-3,3-difluuoro-propan-
2-ol,1-(1H-1,2,4-triazol-1-yl)-2-Cp-(4-chlorophenoxy)phhenyl]-
3,3-difluoropropan-2-ol and 1-(1H-1,2,4-triazol-1-yl)-2-Cp-
30 (4-chlorophenoxy)-2-methylphenyl]-2-hydroxy-3-fluooropropane.
The compounds of the formula I are prepared by a pro-
cess which comprises first reacting an oxirane of the for-
mula II
Ar-c~cH2 (II)
R2-C-R3
F
~2Q9~52
with an azole of the formula III
M--Az (III)
to give a compound of the formula Ia
OH
Ar-C-C~ -Az (Ia)
2 3
F
and, if required, converting the alcohol Ia into an ether of
the formula I in the conventional manner, or example by re-
action with a compound of the formula IV
R1 W (IV)
in which formulae Ia, II, III and IV, the substituents R1,
R2, R3, Ar and Az are as defined under formula I, M is
hydrogen or, preferably, a metal atom, in particular an
alkali metal atom, such as Li, Na or K, and W is OH or a con-
ventional weaving group. Conventional leaving groups are
known from the literature.
If appropriate, the reaction of II with III to give
Ia is carried out in the presence of condensing agents or
acid-binding agents. Suitable agents are organic and inor-
ganic bases, for example tertiary amines, such as trialkyl-
amines (trimethylamine, triethylamine, tripropylamine and
the like), pyridine and pyridine bases (4-dimethylaminopyri-
dine, 4-pyrrolidylaminopyridine and the like), oxides, hyd-
rides and hydroxides, carbonates and bicarbonates of alkali
metals and alkaline earth metals (CaO, CaO, NaOH, KOH, NaH,
Ca~OH)2, KHC03, NaHC03, Ca(HC03)2, K2C03,
and Na2C03) and alkali metal acetates, such as CH3COONa
or CH3COOK. Moreover, alkali metal alcoholates, such as
C2H50Na, C3H7-nONa and the like, are also suitable.
In some cases, it may be advantageous if the free azole III
(M = hydrogen) is first converted into the corresponding salt,
for exampLe in situ with an alcoholate, and then to react the
salt with the oxirane of the formula II. In the preparation
of the 1,2,4-triazole derivatives, 1,3,4-triazolyl isomers
are generally also formed in a parallel reaction, and these
:
1209152
can be separated from one another in a conventional manner,
for example with different solvents.
The reaction (II with III to give Ia) is preferably
carried out in an organic solvent which is relatively polar
but inert ;n the react;on, for example N,N-d;methylformam;de,
N,N-dimethylacetam;de, dimethylsulfoxide, acetonitrile, benzo-
nitrile and the like. Such solvents can be used in combina-
tion with other solvents which are inert in the reaction,
for example benzene, toluene, xylene, hexane, petroieum
ether, chlorobenzene, nitrobenzene and the like. The reac-
tion temperatures are in a temperature range from 0 to
150C, preferably 20 to 100C.
This reaction (II with III to give Ia) can further-
more be carried out analogously to reactions which are al-
ready known for other oxiranes with azoles (cf. Berman Offen-
legungsschr;ft 2,912,288).
In the part react;ons mentioned, the intermed;ates
can be isolated from the reaction medium and, if desired,
purified by one of the generally convent;onal methods, for
example by washing, digestion, extraction, crystallisation,
chromatography, distillation and the like, before the further
reaction.
In cases where W in formula IV is a conventional
leaving group, the further reaction of Ia to give I is car-
ried out in the absence or, preferably, in the presence of asolvent which is inert in the reaction.
Examples of suitable solvents are the following:
N,N-dimethylformamide, N,N-dimethylacetam;de, hexamethyl-
phosphoric acid triamide, dimethylsulfoxide, Z-methyl-2-pen-
tanone and the like. Mixtures of these solvents with oneanother or with other conventional inert organic solvents,
for example with aromatic hydrocarbons, such as benzene,
toluene, the xylenes and the like, can also be used. In some
cases it may prove advantageous to carry out the reaction in
the presence of a base, for example an alkali metal hydride,
hydroxide or carbonate, in order to accelerate the rate of
reaction. However, it may also be advantageous first to
, .
1209152
convert the alcohol of the formula Ia (R1 = OH) into a sui-
table metal salt in a manner which is known per se, for ex-
ample by reaction with a strong base.
Examples of suitable strong bases are alkali metal
hydrides and alkaline earth metal hydrides (NaH, KH, CaH2
and the like) and alkali metal-organic compounds, for ex-
ample butyl-lithium or an alkali metal tert.-butoxide, and
alkali metal hydroxides, such as NaOH or KOH, can moreover
also be used if the reaction is carr;ed out ;n an aqueous
two-phase system in the presence of a phase transfer cata-
cyst.
However, it is also possible first to convert the
alcohol of the formula Ia into an alkali metal alcoholate
;n a convent;onal manner before the further reaction, and
then to react the alcoholate with a compound of the formula
IV (;n wh;ch W ;s a Leaving group), the reaction advanta-
geously being carried out in the presence of a crown ether.
If M = K, 18-crown-6, in particular, is present; and if M =
Na, 15-crown-5, in particular, is present. The reaction is
advantageously carried out in a medium which is inert in
the reaction. Examples of suitable solvents are ethers and
ether-like compounds, for example di-lower alkyl ethers (di-
ethyl ether, diisopropyl ether, tert.-butyl methyl ether and
the like), tetrahydrofuran and dioxane, and aromatic hydro-
carbons, such as benzene, toluene or the xylenes.
The following solvents are examples of the organicwater-immiscible phase: aliphatic and aromatic hydrocarbons,
such as pentane, hexane, cyclohexane, petroleum ether, lig-
roin, benzene, toluene, the xylenes and the like, halogenated
hydrocarbons, such as methylene chloride, chloroform, carbon
tetrachloride, ethylene dichloride, 1,2-dichloroethane,
tetrachloroethylene and the like, or aliphatic ethers, such
as diethyl ether, diisopropyl ether, t-butyl methyl ether
and the like. Examples of suitable phase transfer catalysts
are: tetraalkylammonium hal;des, bisulfates or hydroxides,
such as tetrabutylammonium chloride, bromide or iodide; tri-
ethylbenzylammonium chloride or bromide; tetrapropylammonium
1209~52
chloride, bromide or iodide; and the like. Possible phase
transfer catalysts include phosphonium salts. The reaction
temperatures are ;n general between 30 and 13ûC, or
at the bo;l;ng po;nt of the solvent or solvent mixture.
S In cases where W ;n formula IV ;s a hydroxyl group,
a condensation reaction ;s advantageously carried out. The
two reactants are refluxed in a suitable solvent.
In principle, any solvent which is inert towards the
reactants and, advantageously, forms an azeotrope with water
1û can be used here. Examples of suitable solvents here are
aromatic hydrocarbons, such as benzene, toluene and the
xylenes, or halogenated hydrocarbons, such as methylene
chLoride, chloroform, carbon tetrachloride, 1,2-d;chloro-
ethane, tetra-chloroethylene and chlorobenzene, as well as
ether-L;ke compounds, such as tert.-butyl methyl ether,
dioxane and the Like. In some cases, the compound of the
formula III itself can be used as the solvent. This
condensat;on reaction is advantageously carried out in the
presence of a strong acid, for example paratoluenesulfonic
acid, at the boiling point of the azeotropic mixture.
To prepare the ethers of the formuLa I, it is also
possible first to replace the free OH group in the compounds
of the formula Ia by one of the above conventional leaving
groups W and then to react the product with a compound of
the formula IV (where W = OH).
The starting substances of the formula III are gene-
raLly known, or they can be prepared by methods which are
known per se.
The oxiranes of the formula II are novel, ar,d are
intermediates which have been developed particularly for the
preparation of the useful active substances of the formula I.
Because of their structural nature, they can be converted
into the compounds of the formula Ia in a simple manner, and,
moreover, some of the compounds of the formula II have a fun-
gicidal activity towards harmful fungi from the families ofAscomycetes, Basidiomycetes or Fungi ;mperfecti.
Epox;des of the formula II can be prepared from
1209152
ketones of the formula V
R2
Ar-C-C-F (V)
Il I
o R3
in a manner which is known per se by reaction with dimethyl-
sulfonium methylide or dimethyloxosulfonium methylide`(Corey
and Chaykovsky, JACS, 1962, 84, 3782).
The ketones of the formula V are accessible by me-
thods which are known per se from the literature of J. Le-
roy, J. Org. Chem. 46, 206 (1981) or Houben-Weyl, volume V/3,
page 211), from the corresponding known a-bromo-ketones
by conventional replacement of the bromine by fluorine, or
they can also be prepared by acylation of the aromatic on
which they are based with fluorinated carboxylic acid deri-
vatives, for example by a Friedel-Crafts reaction.
In principle, unless expressly specified in a parti-
cular case, one or more solvents or diluents which are inertin the reaction can be present in the preparation of all the
starting substances, intermediates and end products mentioned
here. Examples of suitable solvents or diluents are alipha-
tic and aromatic hydrocarbons, such as benzene, toluene,
the xylenes and petroleum ether; halogenated hydrocarbons,
such as chlorobenzene, methylene chloride, ethylene chloride,
chloroform, carbon tetrachloride and tetrachloroethylene;
ethers and ether-like compounds, such as dialkyl ethers (di-
ethyl ether, diisopropyl ether, tert.-butyl methyl ether and
the like), anisole, dioxane and tetrahydrofuran; nitriles,
such as acetonitrile and propionitrile; N,N-dialkylated
amides, such as dimethylformamide; dimethylsulfoxide; ke-
tones, such as acetone, diethyl ketone and methyl ethyl ke-
tone, and mixtures of these solvents with one another. In
some cases, it may also be advantageous to carry out the re-
action or part steps of a reaction under a protective gas at-
mosphere and/or in absolute solvents. Suitable protective
gases are inert gases, such as nitrogen, helium, argon or,
in certain cases, also carbon dioxide.
^" 1209152
- 10 -
The compounds of the formula I
ORl R2
l*
Az--CH2-- f C--F (I)
Ar R3
always have an asymmetric C atom C* in the position adjacent
to the substituents Ar and OR1 and can therefore exist in
two enantiomeric forms. In general, a mixture of the two
enantiomers is formed in the preparation of these substances,
and this can be split into the pure optical antipodes in a
conventional manner, for example by fractional crystallisa-
tion of salts with strong optically active acids. The enan-
tiomers can have d;fferent biological actions; thus, forexample, the fungicidal action can be in the foreground in
one form and the pLant growth-regulating action can be in the
foreground in the other form. A gradual difference in ac-
tivity may also occur in the same action spectrum. If the
radicals R2 and R3 are different, the molecule contains
a further centre of asymmetry (*), which leads to the exis-
tence of diastereomeric mixtures (threo- and erythro-forms),
which can be separated by means of physical methods.
The present invention relates to all the pure enan-
tiomers and diastereomers and mixtures thereof with one ano-
ther.
The preparation process described, including all the
part steps' is an important component of the present inven-
tion.
It has been found, surprisingly, that compounds of
the formula I have a microbicidal spectrum against phyto-
pathogenic fungi and bacteria which is very favourable for
practical requirements. They have very advantageous cura-
tive, systemic and, in particular, preventive properties and
can be used for protecting numerous crop plants. The micro-
organisms which occur on plants or parts of plants (fruit,
blossom, foliage, stems, tubers and roots) of various useful
crops can be checked or destroyed with the active substances
I,
- ~Z09152
- 11 -
of the formula I, the addit;onal future growth of parts of
plants also remaining protected from such m;croorgan;sms.
The active substances of the formula I are effec~;ve
against phytopathogenic fungi belonging to the following
classes: Fungi imperfecti (for example, sOtrytiS, Helmin-
thosporium, Fusarium, Septoria, Cercospora and Alternaria);
and Basidiomycetes (for example the genera Hemileia, Rhizoco-
tonia and Puccinia); and they are particularly active against
the class of Ascomycetes for example Venturia, Podosphaera,
1û Erysiphe, Mon;l;nia and Uncinula). Moreover, the compounds
of the formula I have a systemic action. They can further-
more be used as dressings for the treatment of seed (fru;t,
tubers and seed) and plant seedlings, for protection from
fungal infections and against phytopathogenic fungi which
occur in the soil.
The invention thus also relates to microbicidal com-
positions and to the use of the compounds of the formula I
for the control of phytopathogenic microorganisms, in parti-
cular fung; which are harmful to plants, and for preventive
prophylaxis of an attack on plants.
The present invention furthermore also includes the
preparation of agrochemical compositions which comprises
;ntimate m;x;ng of the active substance with one or more
substances or groups of substances described in this Appli-
cation. The present invention also includes a method oftreating plants which comprises application of the compounds
of the formula I or of the novel compositions.
The following plant species are examples of target
crops in the context of this invention for the fields of in-
dication disclosed herein: cereals: (wheat, barley, rye,oats, rice, sorghum and related species); beet (sugar-beet
and fodder beet); pomaceous fruit, stone fruit and berries:
(apple, pear, plum, peach, almond, cherry, strawberry, rasp-
berry and blackberry); pulse: (bean, lentil, pea, soya bean);
oil crops: (rape, mustard, poppy, olive, sunflower, coconut,
castor, cacao and groundnut); cucumber crops: (pumpkin, cu-
cumber, melon); fibre crops: (cotton, flax, hemp and jute);
1209~S2
- 12 -
c;trus fru;ts: (orange? lemon, grapefru;t and mandar;n)~
vegetable variet;es: (spinach, lettuce, asparagus, cabbage
var;eties, carrot, onion, tomato, potato and paprika); laurel
crops: (avocado, cinnamon and camphor); or pLants such as
maize, tobacco, nut, coffee, sugar cane, tea, vine, hop and
banana and natural rubber crops, and ornamental plants (com-
posites).
Active substances of the formula I are usually em-
ployed in the form of formulations and can be applied to the
area or plant to be treated at the same time as or after
other active substances. These other active substances can
be fertilisers, carriers of trace eLements or other products
which influence plant growth. They can also be, however,
selective herbicides, insecticides, fungicides, bactericides,
nematicides, molluscicides or mixtures of several of these
products, if necessary together with other carriers, surfac-
tants or other application-promoting adjuvants conventionally
used in the art of formulation.
Suitable carriers and adjuvants can be solid or li-
quid and correspond to the substances appropriate in the artof formulation, for example natural or regenerated mine-
ral substances, solvents, dispersants, wetting agents, tacki-
fiers, thickeners, binders or fertil;sers.
A preferred method of application of an active sub-
stance of the formula I or of an agrochemical compositioncontaining at least one of these active substances is appl;-
cation to the foliage leaf application). The number of
applications and the amount applied depend on the threat of
attack by the corresponding pathogen species of fungus).
However, the active substances of the formula I can also en-
ter the plants through the root via the soil systemic action)
by a method in which the location of the plant is soaked with
a liquid formulation or the substances are incorporated into
the soil in solid form, for example in the form of granules
soil application). The compounds of the formula I can, how-
ever, also be applied to seed coating), by a method in which
the seed is either soaked in a liquid formulation of the
- 120915Z
active substance or coated with a soLid formulation. More-
over, other types of application are possible in particular
cases, thus, for example, controlled treatment of the plant
stems or the buds.
The compounds of the formula I are used here in un-
modified form or, preferably, together with the assistants
conventionally used in the art of formulation, and are
thus processed in a known manner to, for example, emulsion
concentrates, brushable pastes, directly sprayable or dilu-
table solutions, dilute emulsions, wettable powders, soluble
powders, dusts or granules, by encapsulation in, for example,
polymeric substances. The methods of application, such as
spraying, misting, dusting, scattering, brushing or watering,
;s chosen according to the intended aims and the given cir-
cumstances, as is the type of composition. Favourable appli-
cation amounts are generally 50 9 to 5 kg of active substance
(AS) per hectare; preferably 100 9 to 2 kg of AS/hectare,
and in particular 200 9 to 600 9 of AS/hectare.
The formulations, i.e. the compositions, preparations
or mixtures, containing the active substance of the formula
I and, if appropriate, a solid or liquid adjuvant are pre-
pared in a known manner, for example by intimate mixing and/
or grinding of the active substances with extenders, for ex-
ample with solvents, solid carriers and, if necessary, sur-
face-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, pre-
ferably C8 to C12 fractions, for example xylene mixtures
or substituted naphthalenes, phthalic acid esters, such as
dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons,
such as cyclohexane or paraffins, alcohols and glycols and
ethers and esters thereof, such as ethanol, ethylene glycol,
ethylene glycol monomethyl or monoethyl ether, ketones, such
as cyclohexanone, strongly polar solvents, such as N-methyl-
2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and,
where relevant, epoxidised vegetable oils, such as epoxidised
coconut oil or soya bean oil; or water.
The solid carriers used, for example for dust and
- 1209~52
dispersible powders, are as a rule ground natural minerals,
such as calcite, talc, kaolin, montmorillonite or attapulgite.
Highly disperse silica or highly disperse absorbent polymers
may also be added to improve the physical properties. Sui-
table granular, adsorptive carriers for granules are poroustypes, for example pumice, broken brick, sepiolite or ben-
tonite, and suitable non-adsorptive carriers are, for example,
calcite or sand. A large number of pre-granulated materials
of inorganic or organic nature, such as, in particular, dolo-
mite or comminuted plant residues, can moreover be used.Further particularly advantageous adjuvants which promote
application and can lead to a large reduction in the amount
applied are natural tanimal or vegetable) or synthetic
phosphoLipids of the cephal;n and lecithin series, for example
phosphatidylethanolamine, phosphatidylserine, phosphatidyl-
choline, sphingomyelin, phosphatidylinositol, phosphatidyl-
glycerol, lysolecithin, plasmalogens or cardiolipin, which
can be isolated, for example, from animal or vegetable cells,
in particular from the bra;n, heart or liver or from egg yolks
or soya bean. Examples of commercial mixtures which can be
used are phosphatidylcholine mixtures. Examples of synthetic
phospholipids are dioctanoylphosphatidylcholine and
dipalmitoylphosphatidylcholine.
Suitable surface-active compounds, depending on the
nature of the active substance of the formula I to be formu-
lated, are non-ionic, cationic and/or anionic surfactants
with good emulsifying, dispersing and wetting properties.
Surfactants are also to be understood as meaning surfactant
mixtures.
Suitable anionic surfactants can be either so-called
water-soluble soaps or water-soluble synthetic surface-active
compounds.
Soaps are the alkali metal, alkaline earth metal or
unsubstituted or substituted ammonium salts of higher fatty
acids (C1û-C22), for example the Na or K salts of oleic
acid or stearic acid, or of naturally occurring fatty acid
mixtures, which can be obtained, for example, from coconut
~209152
- 15 -
oiL or taLlow oil. The fatty acid methyL-laurin saLts are
aLso suitable.
However, so-called synthetic surfactants, in parti-
cular fatty suLfonates, fatty sulfates, sulfonated benzimi-
dazole der;vatives or alkylsulfonates, are more frequentlyused.
The fatty suLfonates or suLfates are as a rule in the
form of alkaLi metal, alkal;ne earth metal or unsubstituted
or substituted ammonium saLts and contain an aLkyl radical
having 8 to 22 C atoms, alkyL aLso incLuding the aLkyl moiety
of acyL radicaLs, for exampLe the Na or Ca saLt of LigninsuL-
fonic acid, dodecyLsuLfuric acid ester or a fatty aLcohoL
sulfate mixture prepared from naturally occurring fatty acids.
These compounds also include the salts of sulfuric acid es-
ters and sulfonic acids of fatty alcohol/ethylene oxide ad-
ducts. The sulfonated benzimidazole derivatives preferably
contain 2-suLfonic acid groups and a fatty acid radicaL hav;ng
8-22 C atoms. Examples of alkyLarylsulfonates are the Na,
Ca or tr;ethanoLamine saLts of dodecyLbenzenesuLfonic ac;d,
d;butyLnaphthaLenesuLfonic ac;d or a naphthaLenesuLfonic
acid/formaLdehyde condensate.
Corresponding phosphates, for exampLe saLts of the
phosphoric acid ester of a p-nonyLphenol-(4-14)-ethyLene
oxide adduct, are aLso suitable.
Part;cularly su;table non-ion;c surfactants are poly-
glycol ether derivatives of aliphatic or cycloaliphatic al-
cohoLs, saturated or unsaturated fatty acids and aLkyLphenols,
wh;ch may conta;n 3 to 30 gLycol ether groups and 8 to 20
carbon atoms in the (aliphatic) hydrocarbon radicaL and 6 to
18 carbon atoms in the aLkyL radicaL of the aLkyLphenoLs.
Other suitable non-ionic surfactants are the water-
soluble adducts, conta;ning 20 to 250 ethylene glycol ether
groups and 10 to 100 propylene glycol ether groups, of poly-
ethylene oxide and polypropylene gLycol, ethylenediaminopoLy-
propylene glycol and an alkylpolypropylene gLycol having 1to 10 carbon atoms in the aLkyl chain. The compounds men-
tioned usuaLLy conta;n 1 to 5 ethyLene gLycoL un;ts per
, .
120915Z
- 16 -
propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpoly-
ethoxyethanols, castor oil polyglycol ethers, polypropylene
polyethylene ox;de adducts, tributylphenoxypolyethylene-
ethanol, polyethylene glycol and octylphenoxypolyethoxy-
ethanol.
Fatty acid esters of polyoxyethylene sorbitan, such
as polyoxyethylene sorbitan trioleate, are also suitable.
The cationic surfactants are, in particular, quater-
nary ammonium salts which contain at least one alkyl radicalhaving 8 to 22 C atoms as N-substituent and lower alkyl or
benzyl radicals, which may or may not be halogenated, or
lower hydroxyalkyl radicals, as further substituents. The
salts are preferably in the form of halides, methylsulfates
or ethylsulfates, and are, for example, stearyltrimethyl-
ammonium chloride or benzyldi(2-chloroethyl)ethylammonium
bromide.
The surfactants conventionally used in the art of
formulation are descr;bed, inter alia, in the following
publications:
"Mc Cutcheon's Detergents and Emulsifiers Annual"
BC Publishing Corp., Ridgewood New Jersey, 1981
and Helmut Stache "Tensid-Taschenbuch" ("Surfactant
Handbook"), Carl Hauser-Verlag Munich/Vienna 1981.
The agrochemical formuLations as a rule contain 0.1
to 99Z, in particular 0.1 to 95%, of active substance of the
formula I, 99.9 to 1X, in particular 99.8 to 5%, of a solid
or liquid adjuvant and 0 to 25%, in particular 0.1 to 25X,
of a surfactant.
Whilst concentrated compositions are rather prefer-
red as commercial products, the final user as a rule employs
dilute compositions.
The compositions can also contain other adjuvants,
such as stabilisers, antifoams, viscosity regulators, binders,
tackifiers and fertilisers, or other active substances, in
order to achieve speciaL effects.
Such agrochemical compositions are a component of
1209152
- 17 -
the present invention.
The examples which foLlow serve to illustrate the
invention in more detail without restricting it. Tempera-
tures are in degrees centigrade. Percentages and parts are
by weight. In addition, the following symbols are used: h =
hour; d = day; min. = minute; RT = room temperature; N = nor-
maLity; abs = absolute, anhydrous; DMS0 = dimethylsulfoxide,
and DMF = dimethylformam;de. Pressures are given in milli-
bar mb or bar b.
Preparat;on examples
Example H1: Preparat;on of
/C1 OH
C1 \ / 2 5
CIN2
Il I
N
1-(1H-1,2,4-Tr;azol-1-yl)-2-(2,4 dichlorophenyl)-3-fluoro-
pentan-2-ol
a) Preparation of the intermed;ate
/Cl
Cl \ / 11 2 5
1-(Z,4-Dichlorophenyl)-2-fLuorobutanone
31 9 of dry potassium fluoride were added to a mix-
ture of 77 9 of 1-(2,4-dichlorophenyl)-2-bromobutanone and
500 mg of 18-crown-6 in 750 ml of absolute acetonitrile and
the mixture was slowly heated to 100 to 110C, while
stirring. After about 48 hours, the reaction had ended
(checked by gas chromatography or by NMR). The reaction solu-
tion was then poured onto 2 litres of ice-water and extracted
several times with diethyl ether. The combined extracts were
washed with water, dried over sodium sulfate and evaporated.
Yield: 57 9 of the oily product. (H-F coupling constant 50 Hz)
Boiling point: 77-78/0.008 mbar.
b) Preparation of another intermediate
12091S2
- 18 -
C1~ HF-C2H5
2-(2,4-Dichlorophenyl)-2-(1-fluoropropyl)-oxirane
8 9 of 80% sodium hydride were suspended in 300 ml
of absolute DMS0. 68 9 of tri0ethyloxosuLfonium iodide were
introduced into this suspension in portions under a nitrogen
atmosphere, while stirring. When the evolution of hydrogen
had ended and the exothermic reaction had subsided, the
mixture was stirred at RT for a further 2 hours. A solution
of 57 g of 1-(2,4-dichlorophenyl)-2-fluorobutanone in 100 ml
of tetrahydrofuran was then added dropwise in the course
of 30 minutes, and the resulting mixture was stirred for 3
hours and then diluted to five times its volume with ice-
water and extracted several times with diethyl ether. The
combined extracts were washed with water, dried over sodium
sulfate and freed from the solvent in vacuo. Yield: 55 g
in the form of a brown oil.
c) Preparation of the end product:
A mixture of 55 9 of 2-(2,4-dichlorophenyl)-2-(1-
fluoropropyl)-oxirane, 3û 9 of 1,2,4-triazole and 3.5 9 of
potassium tert.-butylate in 500 ml of DMF was stirred at
80C for 20 hours. The reaction solution was then cooled
to RT, poured onto 2 litres of ice-water and extracted seve-
ral t;mes w;th diethyl ether. The combined extracts were
washed with water, dried over sodium sulfate and concentra-
ted. Yield of 1-~1H-1,2,4-triazol-1-yl)-2-(2,4-dichloro-
phenyl)-3-fluoropentan-2-ol: 26 9 in the form of colourless
crystals. Melting point: 204-206C.
Example H2: Preparation of
C1--~ f ;-Cl
I- .
Il 11
. , .
-- 1209152
- 19 -
1-(1H-1,2,4-Tr;azole-1-yl)-2-(2,4-dichlorophenyl)~~3~(4~chloro~
phenoxy)-3-fluoropropan-2-ol
a) Preparation of the intermediate:
/Cl
Cl--\ /--C- ca
0 Br
1-(2,4-Dichlorophenyl)-2 bromo-2-fluoroethanone
A solution of 16 9 of bromine in 100 ml of carbon
tetrachloride was added to a soLution of 20.7 g of ~-fluoro-
2,4-dichloroacetophenone in 100 ml of carbon tetrachloride
at 40 to 45C. After about 1 hour, the brown solution
had decolourised. Stirring was continued for another hour
and the mixture was then extracted by shaking with aqueous
sodium bicarbonate solution and evaporated in vacuo. The
oily residue was then distilled under a high vacuum. Yield:
17 9. Boiling point: 89-92C/0.02 mbar.
15 b) Preparation of another intermediate:
Cl
Of ~--C-CHF-O--~ Cl
. .
1-(2,4-Dichlorophenyl)-2-(4-chlorophenoxy)-2-fluorroethanone
12.8 g of chlorophenol and 13.8 g of potassium car-
bonate were stirred in 200 ml of acetone for 1 hour. 28 9
of 1-~2,4-dichlorophenyl)-2-bromo-2-fluoroethanone in 50 ml
of acetone were added dropwise to this suspension and the
mixture was refluxed for 3 hours. After cooling to RT, the
colourless salt precipitate was filtered off, the acetone
was removed in vacuo and diethyl ether was added. The ether
solution was washed with water, dried over sodium sulfate
and filtered and the filtrate was concentrated. The oily
crude product crystallises after digestion with n-hexane.
Yield: 21.5 9 in the form of yellowish crystals. Melting
point: 85-87C.
.
-`` 1209~52
- 20 -
c) Preparat;on of another intermediate:
Of
Of ~CHF-O--~ Of
- '
2-(2,4-Dichlorophenyl)-2-(4-chlorophenoxyfluorometthyl)~
ox;rane
1 9 of 80X sodium hydride was stirred ;n 80 ml of
DMS0 under a nitrogen atmosphere and 10.3 9 of trimethyloxo-
sulfonium iodide were added in portions. After the exother-
mic reaction had subsided, the mixture was stirred at RT
for a further hour, a solution of 2-(2,4-dichlorophenyl)-2-
(4-chlorophenoxy)-2-fluoroethanone in 30 ml of tetrahydro-
furan was then added dropwise and the resulting mixture was
st;rred at 25 to 30C for a further 5 hours and then
poured onto 1 litre of water. The product was extracted with
diethyl ether, the extracts were washed with water, dried
over sodium sulfate and filtered and the filtrate was concçn-
trated. YieLd: 15 9 as a yellowish oil.
d) Preparation of the end product:
A solution of 13 9 of 2-(2~4-dichlorophenyl)-2-(4-
chlorophenoxyfluoromethyl)-oxirane, 4 9 of 1,2,4-triazole
and 0.5 9 of potassium tert.-butylate in 100 ml of DMF was
stirred at 80 to 100C for 15 hours. After cooling to
RT, the reaçtion solution was poured into 500 ml of water,
whereupon the crude product separated out as an oil. The
mixture was extracted with diethyl ether, the combined ex-
tracts were washed with water, dried over sodium sulfate and
filtered and the filtrate was concentrated. Yield: 11 9 of
an oily crude product, which crystallised on digestion with
n-hexane. Yield of the purified product: 7 9. Melting
point: 155-157C.
The substances shown below can also be prepared in
an analogous manner:
120~5Z
C
'U~'o'~ '
_ o
u) aJ Ql a,
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--' 1209152
-- 27 --
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ye
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-- 28 --
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~209152
- 29 -
Formulat;on examples for l;qu;d active substances of the
formula I (% = per_cent by we;ght)
F1. Emulsion concentrates a) b) c)
Active substance from the table 25% 4~% 50%
5 Ca Dodecylbenzenesu~fonate 5% 8% 6%
Castor oil polyethylene glycol ether
(36 mol of ethylene oxide)SX - -
Tributylphenol polyethylene glycol
ether (30 mol of ethylene oxide) - 12% 4%
10 Cyclohexanone - 15X Z0%
Xylene mixture 65X 25% 20X
Emulsions of any desired concentration can be pre-
pared from such concentrates by diLution with water.
F2. Solutions a) b) c) d)
15 Active substance from the table 80% 10% 5% 95X
Ethylene glycol monomethyl ether 20X
Polyethylene glycol MW 400 - 70X
N-Methyl-2-pyrrolidone - 20X
Epoxidised coconut oil - - 1X 5X
20 Benzine boiling range 160-190C) - - 94%
(MW = molecular weight)
The solut;ons are suitable for application in the
form of very small drops.
F3. GranuLes a) b)
25 Active substance from the table 5X 10X
Kaolin 94X
Highly disperse silica 1X
Attapulgite - 90%
The active substance is dissolved in methylene chlo-
ride the solution is sprayed onto the carrier and the sol-
vent is then evaporated off in vacuo.
F4 Dusts a) b)
Active substance from the table 2X 5X
Highly disperse silica 1X 5X
35 Talc 97X
Kaolin 90%
Ready-to-use dusts are obtained by intimate mixing
" ~2~)9152
- 30 -
of the carriers with the active substance.
Formulation examples for solid active substances of the
formula I (% = per cent by we;ght)
F5. Wettable powders a) b) c)
Active substance from the table 25% 50% 75%
Na Ligninsulfonate 5% 5%
Na Laurylsulfate 3% - 5%
Na Diisobutylnaphthalenesulfonate - 6X 10%
Octylphenol polyethylene glycol ether
(7-8 mol of ethylene oxide) - Z%
Highly disperse silica 5% 10% 10%
Kaolin 62% 27%
The active substance is mixed thoroughly with the
adjuvants and the mixtùre is ground thoroughly in a suitable
mill. Wettable powders are obtained, which can be diluted
with water to give suspensions of any desired concentration.
F6. Emulsion concentrate
_
Active substance from the table 10%
Octylphenol polyethylene glycol ether
(4-5 moL of ethylene oxide)3%
Ca Dodecylbenzenesulfonate 3%
Castor oil polyglycol ether
(35 mol of ethylene oxide
Cyclohexanone 30%
25 Xylene mixture 50%
Emulsions of any desired concentration can be pre-
pared from this concentrate by dilution with water.
F7. Dusts a) b)
Active substance from the table 5X 8%
30 Talc 95%
Kaolin - 92%
Ready-to-use dusts are obtained by mixing the active
substance with the carrier and grinding the mixture on a
suitable mill.
F8. Extruded granules
Active substance from the table 10X
Na Ligninsulfonate 2%
~209~52
- 31 -
Carboxymethylcellulose lX
Kaolin 1X
The act;ve substance ;s mixed with the adjuvants and
the mixture is ground and mo;stened with water. Th;s m;x-
ture ;s extruded and subsequently dr;ed ;n a stream of a;r.
F9. Coated granules
Active substance from the table 3X
Polyethylene glycol (MW 200)3%
Kaolin 94%
10 (MW = molecular weight)
The finely ground act;ve substance is uniformly ap-
plied, in a mixer, to the kaolin, which has been moistened
with polyethylene glycol. Dust-free coated granules are
obtained ;n this manner.
15 F10. Suspension concentrate
Active substance from the table 40X
Ethylene glycol 10%
Nonylphenol polyethylene glycol ether
(15 mol of ethylene oxide) 6
20 Na Ligninsulfonate 10%
Carboxymethylcellulose 1X
37% Aqueous formaldehyde solution 0.2%
Silicone oil in the form of a 75X
aqueous emuls;on 0.8X
25 Water 32X
The finely ground active substance is intimately
mixed with the adjuvants. A suspension concentrate is thus
obtained, from which suspensions of any desired concentra-
tion can be prepared by dilution with water.
Biological examples:
Example B1: Action against Puccinia graminis on wheat
a) Residual-protective action
6 days after sowing, wheat plants were sprayed with
a spray liquor (0.02% of active substance) prepared from a
wettable powder of the active substance. After 24 hours,
the treated plants were infected with a uredospore suspension
of the fungus. After incubation at 95-100X relative atmos-
1209~5Z
-- 32 --pheric humidlty and about 20C for 48 hours, the infected
plants were placed ;n a greenhouse at about 22C. The
development of rust pustules was evaluated 12 days after the
;nfect;on.
5 b) Systemic act;on
S days after sow;ng, wheat plants were watered w;th
a spray l;quor (0.006% of act;ve substance, based on the
volume of soil) prepared from a wettable powder of the active
substance. After 48 hours, the treated plants were in'ected
1û with a uredospore suspension of the fungus. After incuba-
t;on at 95-100% relative atmospheric hum;dity at about 20C
for 48 hours, the infected plants were placed ;n a green-
house at about 22C. The development of rust pustules was
evaluated 12 days after the ;nfect;on.
Compounds from the table had a very good action
aga;nst Puccinia fungi. Untreated but infected control
plants displayed a Pucc;nia attack of 100%. Inter alia, the
compounds 1 to 10, 14, 15, 17, 19, 20, 25, 33 - 35, 45 - 51
and 53 - 57 inhibited the Puccinia attack to 0 to 5X.
20 Example G2: Action against Cercospora arachidicola on ground-
nut plants
Residual-protective act;on
Groundnut plants 10 - 15 cm h;gh were sprayed with
a spray liquor (0.006% of active substance) prepared from
25 a wettable powder of the active substance, and 48 hours later
were infected with a conidia suspension of the fungus. The
infected plants were incubated at about 21C at a high
atmospheric humidity for 72 hours and were then placed in a
greenhouse until the typical leaf spots appeared. The fun-
30 gicidal action was evaluated, on the basis of the number andsize of the spots which had appeared, 12 days after the in-
fection.
In comparison with untreated but infected control
plants tnumber and size of spots = 100%), groundnut plants
35 which had been treated with active substances from the table
showed a greatly reduced Cercospora attack. Thus, compounds
1 to 9, 14, 19, 20, 25, 33, 38, 45-51 and 54-58 almost
lZ09152
-- 33 --
completely prevented the occurrence of spots in ihe above
experiments (0-10%).
Example B3: Action against Erysiphe graminis on barley
a) Residual-protective action
Barley plants about 8 cm high were sprayed with a
spray liquor (0.002X of active substance) prepared from a
wettable powder of the active substance. After 3-4 hours,
the treated plants were dusted with conidia of the fungus.
The ;nfected barley plants were placed ;n a greenhouse at
about 22C and the fungal attack was evaluated after 10
days.
b) Systemic action
Barley plants about 8 cm high were watered with a
spray liquor ~0.006X of active substance, based on the volume
of soil) prepared from a wettable powder of the active sub-
stance. Care was thereby taken that the spray liquor did
not come ;nto contact with the above-ground parts of the
plants. After 48 hours, the treated plants were dusted
w;th conidia of the fungus. The infected barley plants were
placed in a greenhouse at about 22C and the fungal attack
was evaluated after 10 days.
Compounds of the formula showed a good action
against Erysiphe fung;. Untreated but infected control
plants displayed an Erysiphe attack of 1ûOX. Amongst other
compounds from the table, compounds 1 to 10, 14, 15, 17, 19,
20, 25, 33, 35, 38, 45 - 51 and 53 - 58 inhibited the fungal
attack on barley to 0 to 5%, and, ;n particular, compound
No. 2 effected complete reduction of attack.
Example B4: Residual-protective action against Venturia
inaequalis on apple shoots
Apple seedlings with fresh shoots 10 - 20 cm long
were sprayed with a spray liquor (0.006% of active substance)
prepared from a wettable powder of the active substance.
After 24 hours, the treated plants were infected with a
con;d;a suspens;on of the fungus. The plants were then incu-
bated at 90 - 100% relative atmospheric humidity for 5 days
and placed in a greenhouse at 20-24C for a further 10 days.
1209152
- 34 -
The scab attack was evaluated 15 days after the infection.
Compounds 1 to 6, 8, 9, 14, 17, 19, 20, 33, 45, 47, 49 - 51
and 53 - 57 inh;b;ted the d;sease ;nfestat;on to less than
10~. In contrast, untreated but ;nfected control shoots
showed 100% attack.
Example B5: Action against Botrytis cinerea on beans
Residual-protective action
Bean plants about 10 cm high were sprayed with a
spray liquor (0.02% of active substance) prepared from a
wettable powder of the active substance. After 48 hours,
the treated plants were infected with a conidia suspension
of the fungus. After incubation of the infected plants at
95-100% relat;ve atmospheric humidity at 21C for 3 days,
the fungal attack was evaluated. The compounds from the
table in many cases very greatly inhibited the fungal infec-
tion. At a concentration of 0.02X, compounds 1 to 6, 8, 9,
14, 15, 20, 25, 33, 35, 45, 47, 49, 50, 51 and 53-57, for
example, proved to be completely effective. The disease in-
festation was O to 8%.
The Botrytis attack of untreated but infected bean
plants was 100%.
ExampLe B6: Action against Piricularia oryzae on rice plants
Residual-protective action
After being grown for two weeks, rice plants were
sprayed with a spray liquor ~0.002% of active substance)
prepared from a wettable powder of the active substance.
After 48 hours, the treated plants were infected with a
conidia suspension of the fungus. After incubation at 95-
100% relative atmospheric humidity at 24C for 5 days, the
fungal attack was evaluated.
Rice plants which had been treated with a spray li-
quor containing one of the compounds from Table 1, such as,
for example, No. 14 or 33, as the active substance, showed a
fungal attack of less than 10X, in comparison with the
untreated control plants (lOOX attack).
