Note: Descriptions are shown in the official language in which they were submitted.
27~;~
_ L 21489-6415D
Aromatic Oxiranes Case 5-14227/+/DIV
This Application is a divisional from Application 4~3,044, filed
December 12, 1983.
Application 443,044 relates to substituted 1-azolyl-2-aryl-3-
fluoroalkan-2-ols and ethers thereof, of the formula I below; to acid
addition salts, quaternary azolium salts and metal complexes thereof;
to the preparation of these substances; to microbicidal compositions
containing at l.east one o:E these compounds as the active substance;
to the preparation of the above compositions; and to the use of ~he active
substances or of the compositions for the control of harmful microorganisms,
preferably fungi which are harmful to plants.
The compounds according to Application 443,044 are those
of the general formula I
OR R
Az - CH2 - C - - C - F (I)
Ar R3
in which Az is lH-1,2,4-triazole, 4H-1,2,4-triazole or lH-imidazole; Ar
is an unsubstituted or substituted aromatic radical from the series
comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; Rl is hydrogen,
Cl-C4-alkyl, C3-C5-alkenyl or benzyl; R2 is hydrogen, fluorine or Cl-C6-
alkyl and R3 is hydrogen, fluorine,Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C6-
alkoxy, Cl-C6-alkylthio, phenyl, phenoxy, phenylthio or C3-C7-cycloalkyl, and
each aromatic substituent or aromatic moiety of a substituent is
unsubstituted or mono- or poly-substituted by halogen, Cl-C~-alkyl, Cl-C
~,
3L~2~7~;
alkoxy, Cl-C4-haloalkyl, nitro and/or cyano; including the acid addition salts,
quaternary azolium salts and metal complexes.
The term alkyl by itself or as a constituent of another substituent
is to be understood as meaning, for example, one of the following groups,
depending on the number of carbon 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 CHC12, CHF2CH2Cl, CC13, CH2F,
CH2CH2Cl CH2Br and the like, in particular CF3. Here and in the following text,
halogen is to be understood as meaning fluorine, chlorine, bromine or iodine,
preferably fluorine, chlorine or bromine. ~lkenyl is 9 for example, prop-l-enyl,
allyl, but-l-enyl, but-2-enyl or but-3-enyl. Naphthyl is ~- or ~- naphthyl.
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, trifluoroacetic acid,
trichloroacetic acid, propionic acid, formic acid, benzenesulfonic acid,
p-toluenesulfonic acid, or methanesulfonic acid.
Metal complexes of the formula I consist of the basic organic
molecule and an inorganic or organic metal salt, for example the halides,
nitrates, sulfates, phosphates, acetates~ trifluoroacetates, trichloroacetates,
propionates, tartrates, sulfonates, salicylates, benzoates and the like of the
elements of the third and fourth main group, such as aluminium, tin or lead,
and of the first to eighth sub-group, such as chromium, manganese, iron,
cobalt, nickel, zirconium, copper, zinc, silver, mercury and the like.
The sub-group elements of the ~th period are preferred. The metals can
be in the various valences with which they are associated. The metal
76~i
-- 3 --
complexes of the formula I can be mononuclear or polynuclear, i.e. they can
contain one or more organic molecule 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
microbicidal properties. They can be used preventively and curatively 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 phytofungicidal action and problem-
free application when used in low concentrations. Moreover, they also have a
growth-regulating action, in particular a growth-inhibiting action, especially
on tropical cover crops.
According to Application 443,044, the following groups of
substances are preferred, because of their marked microbicidal action, in
particular their phytofungicidal action: compounds of the formula I in which
Az is lH-1,2,4-triazole or lH-imidazole; Ar is an unsubstituted or substituted
aromatic radical from the series comprising phenyl, biphenyl and phenoxy-
phenyl, ~1 is hydrogen; R2 is hydrogen, fluorine or Cl-C3-alkyl; and
~3 is hydrogen, fluorine, Cl-C4-alkyl, Cl-C3-haloalkyl, Cl-C3-alkoxy, Cl-C3-
alkylthio, phenyl, phenyloxy or phenylthio, each phenyl moiety being
unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy,
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 lH-1,2,4-triazole; Ar is phenyl or phenoxyphenyl
which is unsubstituted or, preferably, substituted in the 2- and/or 4-position
~2~2t76~
- 4
by methyl or halogen, preferably fluorine or chlorine; Rl is hydrogen;
R2 is hydrogen, fluorine or methyl; and R3 is hydrogen, fluori.ne, Cl-C4-alkyl
or a radical from the series comprising phenyl, phenoxy and phenylthio which
is substituted by fluorine, ch.Lorine and/or bromine.
Examples of specific particularly preferred substances from a
fllngicidal point of view are: l-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-
3-fluorobutan-2-ol, 1-(lH-1,2,4-triazo].-1-yl)-2-(2-chloro-4-fluorophenyl)-3-
fluorobutan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-
pentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-
methylpentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2-chloro-4-fluorophenyl)-3-
fluoropentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-(4-
chlorophenoxy)-3-fluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chloro-
phenoxy)phenyl]-3-fluoropropan-2-ol,l-(lH-1,2,4-triazol-1-yl)-2-(4-fluoro-
phenyl)-3,3,3-trifluoropropan-2-ol, :L-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichloro-
phenyl)-3,3,3-trifluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(4-chloro-
phenyl)-3-fluorohexan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-
3-fluorohexan-2-ol, 1-~lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl-3,3-
difluoropentan-2-ol,l-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-
4-methylpentan 2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-bromophenoxy)phenyl]-
3,3-difluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-4-fluorophenoxy)phenyl]-
3,3-difluoro-propan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chlorophenoxy)
phenyl]-3,3-difluoropropan-2-ol and 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chloro-
phenoxy)-2-methylphenyl]-2-hydroxy-3-fluoropropane.
According to Application 443,044, the compounds of the formula I are
prepared by a process which comprises first reacting an oxirane of theformulca II
Ar- ~ ~CH2 (II)
F
;27~
-- 5
with an azole of the formula III
~Az (III)
to give a compound of the formula Ia
OH
. Ar-C-CR -Az (Ia)
R2-C-R3
and, if required, converting the alcohol Ia into an ether of
the formula I ;n the conventional manner, for example by re-
act;on with a compound of the formula IV
R1 ~ W (IV)
in which formulae Ia, II, III and IV, the substituents R1,
R2, R~, 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 leaving 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 tCaO, BaO, NaOH, KOH, NaH,
CatOH)2, KHC03, NaHC03, CatHC03)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 advantaseous if the free azole III
tM = 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
~Z27~6
-- 6
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 in the reaction, for example N,N dimethylformamide,
N,N-dimethylacetamide, 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, petroleum
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. German Offen-
legungsschrift 2,912,288).
In the part reactions mentioned, the intermediates
can be isolated from the reaction medium and, if desired,
purified by one of the generally conventional 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,~-dimethylacetamide, hexamethyl-
phosphoric acid triamide, dimethylsulfoxide, 2-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 advantaseous 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
convert the alcohol of the Formula Ia (R1 = OH) into a sui-
table metal salt ;n a manner which is known per se, for ex-
ample by reaction w;th a strong base.
Examples of su;table strong bases are alkali metal
hydr;des and alkaline earth metal hydr;des (NaH, KH, CaH2
and the like) and alkali metal-organic compounds, for ex-
ample butyl-l;th;um or an alkali metal tert.-butoxide, and
alkali metal hydroxides, such as NaOH or KOH, can moreover
also be used if the reaction is carried out in an aqueous
two-phase system ;n the presence of a phase transfer cata-
lyst.
However, it is also possible first to convert the
alcohol of the formula Ia into an alkali metal alcoholate
in a conventional manner before the further reaction, and
then to react the alcoholate with a compound of the formula
IV (in wh;ch W is 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
ZO 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,Z-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: tetraaLkYlammon;um halides, bisulfates or hydroxides~
such as tetrabutylammonium chloride, bromide or iodide; tri-
ethylbenzylammon;um chloride or bromide; tetrapropylammonium
~2~766
-- 8 --
chloride, bromide or iodide; and the like. Possible phase transfer catalysts
include phosphonium salts. The reaction temperatures are in general between
30 and 130C, or at the boiling point of the solvent or solvent mixture.
In cases where W in formula IV is a hydroxyl group, a condensation
reaction is 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 can be used here. ~xamples 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-dichloroethane, tetra-chloroethylene and chloro-
benzene, as well as ether-like 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 condensation 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 twhere W = OH).
The starting substances of the formula III are generally known, or
they can be prepared by methods which are known per se.
The oxiranes of the formula II are novel, and 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 in-to the compounds of the formula Ia in a simple manner, and,
moreover, some of the compounds of the formula II have a fungicidal activity
towards harmful fungi from the families of Ascomycetes, Basidiomycetes or Fungi
27~6
- 8a -
imperfecti.
Thus this invention provides aromatic oxiranes of the formula II
Ar-C - CH2 II
R2-C-R3
in which
Ar is an unsubstituted or substituted aromatic radical chosen from
phenyl, biphenyl, phenoxy-phenyl and naphthyl;
R2 is hydrogen, fluorine or Cl-C6 alkyl; and R3 is hydrogen,
fluorine, Cl-C6 alkyl, Cl-C6 haloalkyl, Cl-C6 alkoxy, Cl-C~ alkylthio~ phenyl~
phenoxy, phenylthio or C3-C7 cycloalkyl, wherein each aromatic radical or
moiety is unsubstituted or mono- or poly-substituted by halcgen, Cl-C4 alkyl,
Cl-C4 alkoxy, Cl-CL haloalkyl, nitro and/or cyano.
Epoxides of the formula II can be prepared Erom
~L~2Z~766
ketones o-f the formula V
R2
~r~C-C-F (V)
Il I
o ~3
in a manner which is known per se by reaction with dimethyl-
sul-Fonium 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 (cf. J. Le-
roy, J. Org. Chem. 46, 2û6 (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-
vat;ves, 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-
t;c 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.
~ 2766
- 10 ~
The compounds of the formula I
ORl R2
I* I'
Az- C~2 f _ c ~
Ar R3
always have an asymmetric C atom C* in the pos;tion 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 crystall;sa-
t;on of salts with strong optically active acids. The enan-
tiomers can have different 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 ;n the other form. A gradual difference in ac-
tiv;ty 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 diastereomer;c m;xtures (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 ;mportant component of the present ;nven-
tion.
Application 443,044 discloses that compounds of the formula I
have a microbicidal spectrum against phytopathogenic fungi and bacteria
which is very favourable for practical requirements. They have very
advantageous curative, systemic and, in particular, preventive properties
and can be used for protecting numerous crop plants. The microorganisms
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
766
of the formula I, the additional future growth of parts of
plants also remaining protected from such microorganisms~
The active substar~Ps of the formula I are effective
against phytopathogenic tungi belonging to the following
classes: Fungi imperfecti (for examp-le, Botrytis, 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,
Erysiphe, Monilinia 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 (fruit,
tubers and seed) and plant seedlings, for protection from
fungal infections and against phytopathogenic fungi which
occur in the soil.
~22Z~7~6 - -
- 12 -
The examplrs which follow serve to illustrate the
invention in more detail without restricting it. Tempera-
tures are in degrees centigrade. Percentages and parts are
S by weight. In addition, the following symbols are used: h =
hour; d = day; ,nin. = minute; RT = room temperature; N = nor-
mality; abs = absolute, anhydrous; D~lS0 = dimethylsulfoxide;
and DllF = dimethylformamide. Pressures are given in milli-
bar mb or bar b.
1û Preparation examDles
Example H1: Preparation of
~C 1 o
Cl~ rJ--C.ir-C H
'=' C~
Il 11
1-(1H-1r2r4-Triazol-1-yl) 2-~2,4-dichloroDhenyl)-3-fluoro-
pentan-2-ol
a) Preparation of 1-(2.4-dichlorophenyl?-2-fluorobutanone
/C1
Cl--~ ~--C-CX~-C ~
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 N~1R). 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 S0 Hz)
Boiling point: 77-78/0.008 mbar.
I
Preparation of 2-(2~4=diclllorophenyl)-2~ f1~lorop
/C1
C1~ IF-C21l5
8 9 of 80% sodium hydride were suspended in 300 ml
of absolute D~lS0. 68 9 of trimethyloxosulfonium iodide were
introduced ;nto 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 9 of 1-t2,4-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 9
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, 30 9 of 1,2,4-triazole and 3.5 9 of
potassium tert.-butylate in 500 ml of DilF was stirred at
80C for 20 hours. The reaction solut;on was then cooled
to RT, poured onto 2 litres of ice-water and extracted seve-
ral times with 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-Z-ol: 26 9 in the form of colourless
crystals. Melting point: 204-206C.
Example HZ: Preparation of l-(lH-1,2,4-triazole-1-yl~-2-(2,4-
dichlorophenyl)-3-(4-chlorophenoxy-3-fluoropropan-2-ol
Cl
Cl-~ ~o- I-CHF-O--\ ~--Cl
=- CH2 --
~-
a) Preoaration of l-(2,4-cllcllloro~ ellyl?-2-bromo-2-
fluoroetl1anone
--- --- F
Cl-~ C--CE'
O ~r
A solution of 16 9 of bromine in 100 ml f carbon
tetrachloride was added to a solution of 20.7 9 of a-fluor
2,4-dichloroacetophenone in 1ûO 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. ~oiling point: 89-92C/0.02 mbar.
15 b) Preparation of 1-(2,4-dichloropllenyl)-2-(4-ch1Orophenoxy)-
-2 -f luoroe thanone
/C1
~_ O
C1--.~ ~---C--C'.-~--O--~\ ~.--C1
. -- . . _ ~
12.8 9 of chlorophenol and 13.8 9 of potassium car-
bonate were stirred in 200 ml of acetone for 1 hour. 28 9
of 1-t2~4-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. ~lelting
point: 85-87C.
766
- 15 -
c) Preparation of 2-(2.4-dichl~ L~ =
phelloxyrluoromethy])-oxirane
/C1
Cl-~ iF-0 \ _ /
S 1 9 of 80% sodium hydride was stirred in 80 ml of
DMS0 under a n;trogen atmosphere and 10.3 9 of trimethyloxo-
sulfonium iodide were added in portions. After the exother-
mic reaction had subsided, the mixture was s-tirred 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
stirred 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 concen-
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 ~0 to 100C for 15 hours. After cooling to
RT, the reaction solution was poured into 500 ml of water,
whereupon the crude product separated out as an oil. The
m;xture 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 oxiranes required for the preparation of the compounds
shown below in Table 1 can also be prepared in an analogous manner.
~Z~66
-- 16 --
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l~iolo~ical e:;amr~les (taken from Application 443 ,044)
Example B1- Action aqainst Puccinia sraminiS 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 artive substance. After 24 hours,
the treated plants were infected with a uredospore suspension
of the fungus. After incubation at 95-100% relative atmos-
'7~6
-- 25 --pheric humidity and about 20C for 48 hours, the infected
plants were placed in a greenhouse at about 22C. The
development of rust pustules was evaluated 12 days after the
infection.
5 b) Systemjc action
5 days after sowing, wheat plants were watered with
a spray liquor (0.006% of active substance, based on the
volume of soil) prepared from a wettable powder of the active
substance After 48 hours, the treated plants were infected
10 with a uredospore suspension of the fungus~ After incuba-
tion at 95-100% relative atmospheric humidity at about 20C
for 48 hours, the infected plants were placed in a green-
house at about 22C. The development of rust pustules was
evaluated 12 days after the infection.
Compounds from the table had a very good action
against Puccinia fungi. Untreated but infected control
plants displayed a Puccinia 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 5%~
20 Examole s2: Action anainst Cercospora arac_idicola_on ground-
nut plants
Residual-protective action
Groundnut plants 10 - 15 cm high 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 (number 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
J~2~
-- 26 --
completely prevented the occurrence of spots in the above
experiments (0-10%).
Examole B3: Action aqainst ErysiDhe graminis on barley
a) Residual-protective action
Barley plants about 8 cm high were sprayed with a
spray liquor (0.002% 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 infected barley plants were placed in a greenhouse at
about 22C and the fungal attack was evaluated after 1û
days.
b) SYstemic action
. . .
Barley plants about 8 cm high were watered with a
spray liquor (0.006% 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 into contact with the above-ground parts of the
plants. After 48 hours, the treated plants were dusted
with 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.
Cornpounds of the formula I showed a good action
against Erysiphe fungi. Untreated but infected control
plants displayed an Erysiphe attack of 100%. Amongst other
compounds from the table, compounds 1 to 10, 14, 15, 17, 19,
20, 25, 33, 35, 38, 45 - 51 and 53 - 5a inhibited the fungal
attack on barley to 0 to 5%, and, in 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 subs-tance.
After 24 hours, the treated plants were infected with a
conidia suspension of the fungus. The plants were then incu-
bated at 90 - 100% relative atmospheric humidity for 5 days
and placed in a greenhouse at 23-24oc for a further 10 days.
-~LZ2'~766
- 27 -
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 inhibited the disease infestation to less than
10%. In contrast, untreated but infected control shoots
showed 100% attack.
Example B5: Action acJainst Botrytis cinerea on beans
Residual-protective action
Bean plants about 10 rm high were sprayed with a
spray liquor (0.02r~ 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% relative atmospheric humidity at 21C for 3 days,
the fungal attack was evaluated. The compounds frorn the
table in many cases very greatly inhibited the fungal infec-
tion. At a concentration of 0.02%, 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 0 to 8~o~
The Botrytis attack of untreated but infected bean
plants was 100%.
Example B6: Action a~ainst Piricularia oryzae on rice plants
Residual-~rotective 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% rela-tive 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 10%, in comparison w;th the
untreated control plants (100% attack).
