Note: Descriptions are shown in the official language in which they were submitted.
7~
Case 5-1371~
Microbicidal Compositions
The present invention relates to novel N-sulfenylated pyrrole
deriva~ives, to the preparation thereof, and to microbicidal
compositions which contain at least one of these novel com-
pounds. The invention relates ~urther to the preparation of
the said compositions and to the use o~ the novel compounds
and compositions for controlling harm~ul microorganisms, in
particular phytopathogenic ~ungi.
The novel compounds of this invention have the general
formula I
R ~
\N/ (I)
wherein
Rl is a fragment selected from the group consisting of
[X,Y,Z(phenyl)], [X,~,Z(biphenyl)], [U,V,W(pyridyl)],
[U,~,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and Z
are each independently selected :Erom the group consisting
oE hydrogen, halogen, Cl-C~alkyl, Cl-C3haloalkyl,
di(Cl-C4alkyl)amino, nitro, cyano, -COO(Cl-C~alkyl),
-CON(Cl-C~alkyl)2 and the group -E-R~, where E is -O-,
-S-, -SO- or -S02-, R~ is Cl-C6alkyl which is unsub-
stituted or substituted by Cl-C~alkox~?, C3-C5alkenyl
which is unsubstituted or substituted by halogen, C3-C5-
alkynyl which is unsubstituted or substituted by halogen
or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y?Z(phenyl)];
U, V and T~ are each independently selected ~rom the group
consisting of hydrogen, halogen and Cl-C4alkyl,
~L9~
-- 2 --
R2 ls -COO(Cl-C6alkyl), -CO(Cl-C6)alkyl), -CO-N(Cl-C6alkyl)2,
cyano, nitro, -S02-(Cl-C6alkyl), -P(O)-(Cl-C6alkoxy)2,
-SO-(Cl-C6alkyl) or -S02 N(Cl-C3alkyl)2; and
3 1 3 Y
Throughout this specification, the symbols [X,Y,Z~phenyl)~,
[X,Y,Z(biphenyl)]-, [U,V,W(pyridyl)l, [U,V,W(furyl)] and
[U,V,W(thienyl)~ are respectively the following groups:
x- ;~ v~ u
~.=.,- \.=./ \.=./ w o~ !
Z' Z~
V~ ! v
~o/ ' ~S/
Depending on the indicated number of carbon atoms, alkyl by
itsel~ or as moiety of another substituent will be ~mder-
stood as comprislng e.g. the Eollowing groups: methyl,
ethyl, propyl, butyl, pentyl, hexyl etc., and the isomers
thereo, e.g. isopropyl, isobutyl, tert-butyl, isopentyl
etc. Haloalkyl is a monohalogenated to perhalogenated alkyl
subskituent such as C~12Cl, C~LC12, CC13, C~12Br, CHBr2, CBr3,
CH2F, CHF2, ('F3, CC:L3F, CC:L2-CHC12, CH2CH2F, CI3 etc.
Throughout this speciEication, ha:l.ogen will be ~mderstood as
sign:lEying fLuorine, ch:Lorine, bromine or iodine, with
Eluorine, ch:lorine or bromine being pre~erred. C3-C5Alkenyl
denotes an unsaturated aliphatic radical containing one or
more double bonds and at most 5 carbon atoms, and is e.g.
propen-l-yl, allyl, buten-l-yl, buten-2-yl, buten-3-yl,
CH3CH-CHCH=CH- etc. Pyridyl is 2-pyridyl, 3-pyridyl and
4-pyridyl, and furyl is 2-furyl and 3-Euryl. Thienyl is
724~3
2-thienyl ancl 3-thienyl and biphenyl is biphenyl-~-yl,
biphenyl-3-yl and biphenyl-2-yl. Alkynyl is in parti.cular
propargyl.
The compounds o~ formula I are oils, resins or mainly solids
which are stable under normal conditions and have very
valuable microbicidal properties. They can be used in
agricuLture or related ~ields prevenLively and curatively
for controlling phytopathogenic microorganisms. The com-
pounds of the ~ormula I have excellent ~ungicidal activity
in broad concentration ranges and their use is unproblematical.
On account o~ their pronounced microbicidal activity,
pre~erred compounds o~ the formula I are those compounds
which contain the ~ollowing substituents or combinations
thereo~ with one another:
or Rl a) [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-~-yl)],
[X,Y,Z(biphenyl-3-yl)]. [X,Y,Z(biphenyl-2-yl)],
[U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)],
[U,V,W(~-pyridyl)], [U,V,W(2-~uryl)], [U,V,W(3-
furyl)], [U,V,W(2-thienyl)], [U,V,W(3-thienyl)]i
b) [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-~-yl)],
[U,V,Z(2-pyridyl)], [U,V,W(3-pyridyl)],
[U,V,W(2-f~lryl)], [U,VJW(2-thienyl)];
c) [X,Y,Z(phenyl)], [U,V,W(2-furyl)]i
d) [~,Y,Z(phenyl)]i
or X,Y,Z: a) H, halogen, Cl-C3alkyl, Cl-C3haloalkyl,
di(Cl-C3alkyl)amino, nitro, cyano, -COO(Cl-C3-
alkyl), -CON(Cl-C3alkyl)2, Cl-C~alkoxy,
Cl-C4alkylthio.^ C3-C5alkenyloxy, C3-C5halo-
alkenyloxy, phenoxy, benzyloxy;
b) H, F, Cl, Br, CH3, C2H5, CF3, -N(CH3)2,
-~(C2H5)2, -COOCH3, -COOC2H5, -CON(CH3)2,
Cl-C~alkoxy, cl-c~alkylthio, C3-C5alken~10xy,
C3-C5haloalkenyloxy, pheno~y, benzyloxyi
c~ H, Cl, Br, CH3, C2H5, CF3, N(CH3)2~ 3
-CON(CH3)2, Cl-C4alkoxy, Cl-C~,alkylthio,
C3alkenyloxy, phenoxy, benzyloxy;
d) H, Cl, Br, CH3, Cl-C~alkoxy, Cl--C4alkylthio,
C3alkenyloxy .
or U,V,W: a) H, halogen, Cl-C4alkyl;
b) H, Cl, Br, Cl-C2alkyl;
c) H, Cl, Br, CH3;
or R2: a) -COO(Cl-C3alkyl), -CO-(Cl-C3alkyl), -CO-N(Cl-
C3alkyl), cyano, nitro, -SO2(Cl-C3alkyl),
~P(o)(cl-c3alkoxy)2~ ~S2N(cl-c3alkyl)2;
b) -COOCH3~ ~COOc2Hs~ -COCH3~ -COC2H5~ -CON(C~I3)
-CON(C2H5)2, cyano, nitro, -SO2-CH3, -SO2C2H5,
-sO-cH3~ _p(o)(OCH3)2~ -P(O)(OC2H5)2'
-so2-N(cH3)2~ -S02-N(C2H5)2;
c) -COOCH3, -COCH3, -CON(CH3)2, cyano, nitro,
S2 CH3~ P(O)(OC2~Is)2, -SO2-N(CH3)2;
d) -COCH3, CNi
or R3: a) Cl-C3haloalkyl;
b~ cl-c2haloalkYli
c) CC13~ CC12F~ CC12H, CClH2, CF3, CF2H, C2C15,
CC12C~IC12;
d) CC13, CC12F, CC12CMC12.
The Eollowing combinations a) to g) o:E these types oE sub-
stituents result
a) (Rl-a), (X,Y,Z-a), (U,V,W-a), (R2-a), (R3-a)
b) (Rl-b), (X,Y,Z-b), (U,V,W-b), (R2-b), (R3-b)
c) (Rl-c), (X,Y,Z-c), (U,V,W-c), (R2-c), (R3-c)
d) (Rl-d), (X,Y,Z-d), (R2-d~, (R3-d)
1~7~
-- 5
e) (Rl-a), (X,Y,Z-c), (U,V,W-c), (R2-b), (R3-c)
f) (Rl-b), (X,Y,Z-c), (U,V,W-c), (R2-d), (R3-d)
g) (Rl-d), (X,Y ,Z-~), (R2-a~, (R3-a) .
Accordingly, preferred groups of compounds are:
a) compounds of the ~ormula I, ~he,-ein Rl is a fragment
selected from the group consisting of [X,Y,Z(phenyl)],
[X,Y,Z(biphenyl-4-yl)], ~X,Y,Z(biphenyl-3-yl)], [X,Y,Z(bi-
phenyl-2-yl)], [U,V,W(2-pyridyl)~, [U,V,W~3 pyridyl)],
[U,V,W(~-pyridyl)], [U,V,W(2-furyl)], [~,V,W(3-furyl)],
[U,V,W(2-thienyl)] or [U,V,W-3-thienyl], wherein .Y,Y and Z
are each independently selected from the group consisting
of hydrogen, Cl-C3alkyl, Cl-C3haloalkyl, di(Cl-C3alkyl)amino,
nitro, cyano, -coo(Cl-C3alkyl), -CON(Cl-C3alkyl)2, Cl-C4-
alkoxy, Cl-C4alkylthio, C3-C5alkenyloxy, C3-C5haloalkenyl.oxy,
phenoxy and benzyloxy; U,V and W are each independently
selected from the group consisting of hydrogen, halogen and
Cl-C4alkyli R2 is -COO(Cl-C3alkyl), -CO-(Cl-C3alkyl),
-CO-N(Cl-C3alkyl)2, cyano, nitro, -SO2-(Cl-C3alkyl),
-P(O)(Cl-C3alkoxy)2 or -SO2-N(Cl-C3alkyl)2; and R3 is
Cl-C3haloalkyl i
b) compo-mds of the formula I, wherein Rl is a fragment
selected from the group consisting of [X,Y,Z(phenyl)],
[X,Y,Z('biphenyl-~-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)],
[U,V,W(2-fury:L)] or [U,V,W(2-thienyl)], wherein X, Y and Z
are each independent'ly selected from the group consisting o:~
hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tri-
fluoromethyl, -N(CH3)2~ -N(C2~15)2' 3 2 5
-CON(C~I3)2, Cl-C4alkoxy, Cl-C~alkylthio, C3-C5alkenyloxy,
C3-C5haloalkenyloxy, phenoxy and benzyloxy; U, V and W are
each independently selected from the group consisting of
hydrogen, chlorine, bromine and Cl-C2alkyl; R2 is R2-COOCH3,
-Cooc2H5~ -COcH3~ -Coc2H5~ -CON(CH3)2, -CON(C2H5)2, cyano,
3 ~
2 3' 2 2 5~ ( )( 3)2' 3~
2 5 2 2 N(CH3)2 or -SO2-N(C2H5)2; and ~. is
Cl-C2haloalkyl .
Within the subgroup b), particularly pre:~erred compounds of
the formula I are those wherein Rl is a fragment selected
from the group consisting of [X,Y,Z(phenyl)], [U,V,W(2-
pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)] or [U,V,W(2-
thienyl)], wherein X, Y and Z are each independently selected
from the group consisting of fluorine, chlorine, bromine,
methyl, ethyl, trifluoromethyl, Cl-C3alkoxy and Cl-C3alkyl-
~hlo; U, V and W are each independently selected from the
gro up consisting of hydrogen, chlorine, bromine, methyl and
ethyl; R2 is -COOCH3, COC~I3, NO2 or CN; and R3 is CFCl2 or
CCl3.
c) Compounds of the formula I, wherein Rl is a fragment
selected from the group consisting o:E [X,Y,Z(phenyl)] and
[U,V,W(2-furyl)], wherein X, Y and Z are each independently
selected from the group conslsting of hydrogen, chlorine,
l~romine, methyl, ethyl, trifluoromethyl, N(C~13)2, -COOCH3,
-CON(CH3)2, Cl-C~alkoxy, Cl-C4alkylthio, C3alkenyloxy,
phenoxy and benzyloxyi U, V and W are each independently
selected :Erom the group consisting of hydrogen, chlorine,
bromine and Cl-C2a:lkyli ~2 is -COOC~13, -COC~13, -CON(CH3)2,
S2 C~13~ P(O)(OC2H5)2 or -SO2-N(C~13)2; and
R3 is CC13, CCl2F, CCl2H, CCl~l2, CF3, CF2H, C2Cl5 or
CC12C~IC12 i
d) compounds of the formula I, wherein Rl is the ragment
[X,Y,Z(phenyl)], wherein X, Y and Z are each independently
selected from the group consisting of llydrogen, chlorine,
bromine, methyl, Cl-C4alkoxy, Cl-C~+alkylthio and C3alkenyloxy;
R2 is -COCH3 or cyano; and R3 is CCl3, CCl3F or CCl2CHCl2.
~g~z'~
-- 7 --
Within the scope o:E the present invention, the Eollowing
individual compounds are especially preferred:
a) intermediates of the formula II', in particular on account
of their advantageous properties in storage and plant
protection:
3-(2-methylthiophenyl)-4-cyanopyrrole,
3-(2-methoxyphenyl)-4-cyanopyrrole;
b) final products of the formula I, in particular on account
o~ their pronounced fungicidal properties:
N-fluorodichloromethylsulfenyl-3-(2-allyloxyphenyl)-4-cyano-
pyrrole,
N-~luorodichloromethylsul~enyl-3-(2-chlorophenyl)-4-cyano-
pyrrole,
N-fluorodichloromethylsul:~enyl-3-phenyl-4-acetylpyrrole,
N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetyl-
pyrrole,
N-Eluorodichloromethylsulfenyl-3-(4-methylphenyl)-4-acetyl-
pyrrole,
N-fluorodichloromethylsulEenyl-3-(3-chlorophenyl)-4-acetyl-
pyrrole,
N-1uorodichloromethylsulenyl-3-(3-methylphenyl)-4-acetyl-
pyrrole,
N-Eluorodichloromethylsul:Eenyl-3-(3-chlorophenyl)-4-methoxy-
carbonylpyrrole,
N-~luorodichloromethylsulEenyl-3-(2-ch:Lorophenyl)-4-methoxy-
carbonylpyrrole,
N-fl-torodichloromethylsulEenyl-3-(2-chlorophenyl)-4-nitro-
pyrrole,
N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole,
N-trichloromethylsulEenyl-3-(2-pyridyl)-4-cyanopyrrole,
N-~luorodichloromethylsulfenyl-3-(2,3-dichlorophenyl)-4-
cyanopyrrole.
~9~7~
In the practice of this invention, the compounds o~ formula I
are prepared by sulfenylating a free pyrrole of the ~ormula IL
R ~ -R ( I I )
\N/
H
at the pyrrole nitrogen~ with a reactive acid derivative
o~ a sul~enic acid o:~ the ~ormula III-
R3-S-OH (III)
in the presence o~ a base. In the above formulae, Rl, R2 and
R3 are as de~ined ~or formula I.
Suitable reactive sul~enic acid derivatives for this
sulfenylation reaction are e.g. the lower alkyl esters and,
pre~erably, the sulfenic acid halides, in particular the
chlorides and bromides, with the chlorides being especially
preferred. Lower alkyl will here be understood as meaning
Cl-C6alkyl .
Both organic and inorganic bases may be successfully
employed in the above reaction. Examples o~ suitable
inorganic bases are alkali metal carbonates and alkaline
earth metal carbonates such as sodium carbonate, potassium
carbonate, calcium carbonate etc. Examples o~ suitable
organic bases are ter~iary amines such as trialkylamines
(triethylamine, methyl diethylamine), N,N-dimethoxycyclo-
hexylamine, N-methylpiperidine, N,N-dimethylaniline or
pyridines. Trialkylamines are preferred. It is advantageous
to use the base in stoichiometric proportion or in excess
thereo~, e.g. in up to 100% excess oE stoichiometric
proportion, based on the pyrrole o~ the ~ormula II. The
reactive derivative o~ the sul~enic acid of the formula III
is also used in stoichiometric proportion or in excess thereo~.
The sul~enylation reaction may be carried out in the presence
or absence, preferably in the presence, o~ an inert solvent
2~8
_ 9 _
or mixture of inert solvents. In principle, the c~tstomary
organic solvents are suitable for this reaction, provided
they contain no reactive hydrogen atoms. Examples oE
suitable solvents are: aliphatic and aromatic hydrocarbons
such as benzene, toluene, xylenes, petroleum ethers,
halogenated hydrocarbons such as chlorobenzene, methylene
chloride, ethylene chloride, chloroform, carbon tetrachloride,
tetrachloroethylene; e~hers and ethereal compounds such as
dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl-
methyl ether etc.), ethylene glycol di- and monoether and
diethylene glycol di- and monoether, containing 1 to ~
carbon atoms in each of the alkyl moieties, for example
ethylene glycol dimethyl, diethyl and di-n-butyl ether,
diethylene glycol diethyl and di-n-butyl ether, ethylene
glycol monoethyl ether and diethylene glycol monomethyl
ether; furan, dimethoxyethane, dioxan, tetrahydrofuran,
anisole; sulfones such as dimethylsulfoxidei ketones such
as acetone, methyl ethyl ketone; esters such as ethyl acetate,
propyl acetate, butyl acetate; and mixtures of such solvents
with one another. In some cases the sulEenylating reagent
of the formula III may itsel act as solvent.
To hasten khe reaction rate, a catalyst such as ~-dimethyl-
aminopyridine may be added, if appropriate.
The sulEenylation reaction is normally carried out in the
temperature range from -30 to -~100C, preferably from -10
to -~ 20C, The reaction time is then generally Erom about
~ hour to 20 hours. However, addition o~ a reaction
catalyst will on occasion often reduce the reaction time to
less than ~ hour.
At normal temperatures, the free sulfenic acids of :Eormula III
are generally relatively unstable substances which have a
tendency to self-oxidation. The known sulfenic acid halldes,
~7~4~3
- 10 -
howe-ver, which can be obtained e.g. by halogenation ~rom the
corresponding mercaptans or dialkyl disulfides. are stable.
Also known are lower alkylsul~enic acid esters, which can
be obtained e.g. hy reacting sul~enic acid chlorides with
alkali alcoholates. At elevated temperature they undergo
rearrangement to form the corresponding sulfoxides, but can
be handled at lower temperatures.
Some o~ the pyrroles of the ormula II are known ~rom the
literature. For example, the method o~ preparing and the
chemical properties of 4-cyano-3-phenylpyrrole are described
in Tetrahedron Letters No. 52, pp. 5337-53~0 (1972). Nothing
is reported on the biological properties o~ the compoun~.
DifEerently substituted 3-phenyl-~-cyanopyrrole derivatives
are known from the literature. For example, pyrroles o~ the
~ormula IV
. _ .
-CW (IV),
~n \N/
wherein X is a halogen atom, a lower alkyl group or a lower
haloalkyl group, and n is 0, 1 or 2, are described in German
O~fenlegungsschri~t 29 27 ~80 as in~ermediates having
insigni~icant ~ungicidal activity.
Novel pyrro:le derivatives are those o~ the ~ormula II'
R - o---.o . 1~ ( I I ' )
\N/' '
Il
wherein Rl is a ~ragment selected ~rom the group consisting
of [X~Y,Ztphenyl)], l~,Y,Z(biphenyl)], [U,V,W(pyridyl)],
[U,V,W(Euryl)] and [U,V,W(thienyl)], wherein X, Y and Z are
each independently selected ~rom the group consisting of
~9~2~1~
hydrogen, halogen, Cl-C~alkyl, Cl-C3haloalkyl, di(Cl-C4alkyl)-
amino, nitro, cyano, -COO(Cl-C~alkyl), -CON(Cl-C~alkyl)2 and
the group -E-R~, wherein E is -O , -S-, -SO- or -S02-, R4
is Cl-C6alkyl which is unsubstituted or substituted by
Cl-C4alkoxy, C3-C5alkenyl which is insubstituted or sub-
stituted by halogen, C3-C5alkynyl which is unsubstituted or
substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or
-CH2-[~,Y,Z(phenyl)], and U, V and W are each independently
selected ~rom the group consisting of hydrogen, halogen or
Cl-C4alkyl; R2 is -COO(Cl-C~,alkyl), -CO-(Cl-C6alkyl),
-CO-N(Cl-C4alkyl)2, nitro~ S02-(Cl-C6alkyl), -P(O)(Cl-C6-
alkoxy)~, -SO-(Cl-C6alkyl) and -S02-N(Cl-C3alkyl)2, and,
where Rl is a fragment [X,Y,Z(biphenyl)], [IJ,V,W(pyridyl)],
[U,V,W(furyl)] or [U,V,W(thienyl)], R2 is additionally cyano.
These compounds are specially developed intermediates for
obtaining the valuable compo~mds o~ the ~ormula I. Because
of their structure they can be readily converted by N-sulfen-
ylation into the compounds of the formula I. In addition,
the compounds of Eormula II' have ~ungicidal activity against
important harmful fungi in plant protection, as well as
e~cellent storage protection properties. The novel com-
pounds o~ ~ormula II', including the preparation thereof and
use thereof, therefore fall within the province o~ ~his
invention.
The compounds oE Eor~lula II, and thereEore also those o~
:Eormula II', can be prepared in alkaline medi~ by a Michael
cycloaddition reaction oE a compound o~ Eormula V with
tosylmethyl isocyanide, aecompanied by the elimination of
p-tol~lenesulfinic acid or the salt thereof:
1 R21 3 \ / So2-c~l2-Nc/base
(V) p R ~ -R
C113~ --SOZ(~) ~) I (II,II ') .
. .
12 -
In ~he above formulae, Rl and R2 have meanings assigned to~hem previously.
Both here and subsequently, the tosyl group s~ands for a
large number of groups which are able to activate the
methylene group in the methyl isocyanide radical for a
Michael addition reaction. Further preferred examples o~
such activating groups are benzenesul~onyl, p-chlorobenzene-
sul~onyl, lower alkylsul~ony-l such as mesyl.
The cycloaddition is carried out in the presence o a non-
nucleophilic base. Suitable bases are alkali metal hydrides
such as sodium hydride, or alkali metal carbonates or
alkaline earth metal carbonates such as ~a2C03, K2C03, or
alkali alcoholates such as (CH3)3C0 K and others. The
base is advantageously used in at least equimolar amount,
based on the starting materials.
As in all reactions, it is convenient also in this case to
conduct the reaction in an inert solvent. Examples oE
pre~erably anhydrous solvents suitable ~or the cycloaddition
are: aromatic and aliphatic hydrocarbons such as benzene,
toluene, xylenes, petroleum ethers, ligroin, cyclohexane;
ethers and ethereal compounds such as dialkyl ethers (di-
ethyl ether, cliisopropyl ether, tert-butyl methyl ether etc.)
dimethoxymethane, ~etrahydro~uran, aniso:Lei sulfones such as
dimethylsul~o~lde; climethylEormamidei and m-lxtures oE such
so:lvents w:lth one another.
The cycloaclclition is normally carried out in the temperature
range Erom -30 to -~120C, preEerably ~rom -30 to -~50C, or
at the boiling point oE the solvent o~ solvent mixture.
When choosing suitable bases, the cycloaddition can also
conveniently be carried out in aqueous medi~m. Suitable bases
~9~
- 13 -
are water-soluble inorganic and organic bases, in particular
alkali metal hydroxides such as LiO~I, NaOH or KOH, and
ammonium bases, e.g. tetraalkylammonium hydroxides such as
(CH3)~NOH. At least an equimolar amount o~ base is used,
based on the starting materials. When using aqueous bases, it
is advantageous to conduct the reaction in a heterogeneous
two-phase system.
Examples o~ suitable organic solvents for the organic water-
immiscible phase are: aliphatic and aromatic hydrocarbons
such as pentane, hexane, cyclohexane, petroleum ether,
ligroin, benzene, toluene, xylenes etc.,; halogenated hydro-
carbons such as dichloromethane, chloro~orm, carbon tetra-
chloride, ethylene dichloride, 1,2-dichloroethane, tetra-
chloroethylene etc.; or aliphatic ethers such as diethyl
ether, diisopropyl ether, tert-butylmethyl ether etc.
The presence o~ a phase trans~er catalyst can be o~
advantage in this mode of carrying out the reaction in
order to hasten the rate of reaction. Examples o~ such
catalys~s are: tetraalkylammonium halides, hydrogen sul~ates
or hydroxides such as tetrabutylammonium chloride, tetra-
butylammonium bromide or tetrabutylammonium iodide; tri-
ethylbenzylammonium chloride or bromide; tetrapropylammonium
chloride, bromicle or ioclicle etc. Phosphonium sa:lts are also
suitable Eor use as phase trans~er catalysts.
The phase trans~er catalysed cycloaddit:lon can be carried
out in the temperature range ~rom 0 to -~80C, pre~erably
~rom -10 to -~50C or at the boiling point oE the solvent
mixture. The cycloaddition can be carried out in the
described embodiment of the process under normal pressure.
The reaction time is in general ~rom 1 to 16 hours, and in
phase trans~er catalysis ~rom ~ hour to 10 hours.
~L97Z~3
- 14 -
Surprisingly, it has been found that the compounds of
form~lla I and the compositions containing them have for
practical purposes a very useEul microbicidal spectrum
against phytopathogenic fungi and bacteria. They can be
used bo~h in plant protection for controlling harmful
microorganisms on cultivated plants and in storage protection
for preserving perishable goods. The compounds of Eormula I
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 diferent crops oE useful
plants, while at the same time the parts of plants which
grow later are also protected Erom attack by such mlcro-
organisms. The intermediates oE Eormula II' also have a
corresponding activity.
The compounds of Eormula I are effective against the
phytopathogenic fungi belonging to the following classes:
Ascomycetes (e.g. Erysiphe, Sclerotinia, Fusarium, Monilinia,
Helminthosporium; Basidiomycetes, e.g. Puccinia, Tilletia,
Rhizoctonia; and the Oomycetes belonging to the class of the
Phycomycetes such as Phytophthora. As plant protective agents
the compounds of formula I can be used with particular success
against important harmEul fungi oE the family of the Fungi
imperEecti, e.g. against Cercospora, Piricularia and, in
particular, against ]30trytis. Botrytis spp. (B. Cinerea, B.
alli:i) and the grey mould on vines, strawberries, apples,
onions and other varieties oE fruit and vegetables, are a
source of significant economic damage. In addition, the
compounds oE formula I can be used successfully for protecting
perishable goods of vegetable or animal origin. They combat
mould fungi such as Penicillium, ~spergillus, Rhizopus,
Fusarium, Helminthosporium, Nigrospora and Alternaria as
7~
- 15 -
well as bacteria such as butyric acid bacteria and yeast
fungi such as Candida. Furthermore, these compounds have
excellent activity against fungi which occur on seeds or in
the soil.
As plant protective agents, the compounds of formula I have
for practical application in agriculture a very advan~ageous
activity spectrum for protecting cultivated plants without
adversely affecting said plants by unwanted side-effects.
They can therefore 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.
Accordingly, the invention also relates to microbicidal
compositions and to the use of compounds of the formula ~
for controlling phytopathogenic microorganisms, especially
harmful fungi, and for the preventive treatment o~ plants
and storable goods of vegetable or animal origin to protect
them from attack by such microorganisms.
The invention further embraces the preparation of aggro-
chemical compositions which comprises homogeneously mixing
an active ingredient with one or more substances or groups
of substances described herein. The invention Eurthermore
relates to a method o treating plants or storable goods,
which comprises applying to plants, parts o~ plants, the locws
thereof or the substrate, the compounds of the formula I or
the novel compositions.
Target crops to be protected within the scope of the present
invention comprise e.g. the following species of plants:
cereals (wheat, barley, rye, oats, rice, sorghum and related
crops), beet (sugar beet and fodder beet), drupes, pomes and
soft fruit (apples, pears, plums, peaches, almonds, cherries,
:1~97~
- 16 -
strawberries, rasberries and blackberries), leguminous
plants (beans,lentils, peas, soybeans), oil plants (rape,
mustard, poppy, olives, sunflowers, coconut, castor oil
plants, cocoa beans, groundnuts), cucumber plants (cucumber,
marrows, melons),fibre plants (cotton, ~lax, 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, nu-ts,
co~fee, sugar cane, tea, vines, hops, bananas and natural
rubber plants, as well as ornamentals (composites).
In storage protection, the compounds of formulae I and II' are
used in unmodified ~orm or, pre~erably, together with the
adjuvants conventionally employed in the art of ~ormulation,
and are therefore ~ormulated in known manner to e.g.
emulsifiable concentrates, brushable pastes, directly
sprayable or dilutable solutions, dilute emulsions, wettable
powders, soluble powders, dusts, granulates, and also
encapsulations in e.g. pol~ner substances. The methods of
application, 9uch as spra~ing, atomising, dusting, scattering
or pouring, and the ~ormulation o~ the composition, are
chosen in accordance with the intended objectives and the
prevailing circumstances. Suitable rates o~ application are
in general in the range Erom 0.01 to at most 2 kg o~ active
ingredient per 100 kg of substrate to be protected. However,
they depend very materially on the nature (surace area,
consistency, moisture content) o~ the substrate and its
environmental inEluences.
~i.thin the scope o~ this invention, s~orable goods will be
understood as meaning natural substances of vegetable and/or
animal origin and the prod~lcts obtained therefrom by further
processing, for example the plants listed below whose natural
life cycle llas been interrupted and the parts thereo~ (stalks,
~g7Z~8
17 -
leaves, tubers, seeds, fruit, grains) which are in Ereshly
harvested or further processed form (predri.ed, moistened,
crushed, ground, roasted). The following produce may be cited
by way oE example, without any restriction to tlle Eield of
use within tlle scope of this invention: cereals (wheat,
barley, rye, oats, rice, sorghum and related crops); beet
(carrots, sugar beet and fodder beet); drupes, pomes and soft
fruit (apples, pears, plums, peaches, almonds, cherrLes,
strawberries, rasberries and blackberries); leguminous plants
(beans, lentils, peas, soybeans)i oil plants (rape, mustard,
poppy, olives, sunflowers, coconuts, castor oil plants,
cocoa beans, groundnuts); cucumber plants (cucumber, marrows,
melons); fibre plants (cotton, flax, hemp, jute,ramie);
citrus fruit; vegetables (spinach, lettuce, asparagus,
cabbages, carrots, onions, tomatoes, potatoes, paprika);
lauraceae (avocados, cinnamon, camphor), or maize, tobacco,
nu~s, coffee, sugar cane, tea, vi.nes, chestnuts, hops,
bananas, grass and hay.
Examples of natural products of animal origin are, in
particular, dried meat and processecl Eish products such as
dry-cured meat, dry-cured fish, meat extracts, bone meal,
fish meal and animal dry feeds.
The treated storable goods are given lasting protection from
attacl~ by mould Eungi and other harmEul microorganis~s. The
Eormation of toxic and in some cases carcinogenic mould
:Eungi (aElato~ins and ochratox:Lns) ls :inhibited, the goocls
are preserved ~rom deteriorati.on, and their quality is main-
tained over a prolonged period of time. The method oE the
inven~i.on is susceptible of appLication to all forms oE dry
and moist storable goods~Llich are liable to attack by microorganisms
such as yeast Eungi, bacteria and, in particular, mould fungi.
1 ~ 7
- 18 -
preferred mettlod of applying active ingredient comprises
spraying or wetting the substrate with a liquid formulation,
or mixing the substrate with a solid formulation, of the
active ingredient. The invention also relates to the described
method of preserving storable goods.
The compounds of ~ormula I are normally applied in the Eorm
of compositions and can be applied to the crop area, plant
or substrate 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, bactericides,
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 of formulation. Suitable carriers and
adjuvants can be solid or liquid and correspond to the
substances ordinarily employed in ~ormulation technology,
e.g. natural or regenerated mineral substances, solvents,
dispersants, wetting agents, tackiEiers, binders or
fertilisers. Phospholipids are particularly useful adjuvants.
pre~erred m~thod oE applying a compound of the formula I
or an agrochemical composition which contains at least one
of said compounds, is Eoliar (leaf) application The
number oE applications and the rate o:E application depcnd
on the intensity oE inEestation by the corresponding
pathogen (type of fungus). ~lowever, the compounds of
formula I can also penetrate the plant through the roots
via the soil (systemic action) by impregnating the locus
oE 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
- 19 -
be applied to seeds (coating), by impregnatlng the seeds
either with a liquid ~ormulation containin~ a compo~lnd o~
the Eormula I, or coating them with a solid formulation.
In special cases, further types o~ application are also
possible, e.g. selective treatment o~ the plant stems
or budso
The compounds o~ the ~ormula I are used in unmodified form
or, pre~erably, together with the adjuvants conventionally
employed in the art o~ ~ormulation, and are therefore
~ormula-ted in known manner to emulsi~iable concentrates,
coatable pastes, direc-tly sprayable or dilutable solutions,
dilute emulsions, wettable powders, soluble powders, dusts,
granulates, and also encapsulations in e.g. polymer
substances. As with the na~ure o:E the compositions, the
methods of application, such as spraying, atomising,
dusting, scattering or pouring, are chosed in accordance
with the intended objectives and the prevailing circumstances.
Advantageous rates o~ applicati.on are normally ~rom 50 g to
5 kg o~ active ingredient (a.i.) per hectare, preferably
from 100 g to 2 kg a.i./ha, most pre~erably ~rom 200 g to
600 g a.i./ha.
The form-~lations, i.e. the compositions containing the com-
pound (active ingredient) o~ the formula I and, where
appropriate, a solid or liq~licl adjuvant, are prepared in
known manner, e g. by homoger~eo~lsly mixing and/or grinding
the active ingredients with extenders, e.g. solvents, solid
carriers and, where appropriate, surface-active compo~mds
( s ~Ir:Eac tanl:s ) .
Suitable solvents are: aromatic hydrocarbons, pre~erably
the ~ractions containing 8 to 12 carbon atoms, e.g. xylene
mixtures or substituted naphthalenes, phthalates such as
dibutyl phthalates or dioctyl phthalate, aliphatic hydro-
z~
- 20 -
carbons such as cycloheY~ane or parafEins, 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-pyrrolidone, dimethyl sulfoxide or dimethyl
formamide, as well as epoxidised vegetable oils such as
epo~idised 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
adsorptive carriers are poxous types, for exa~ple pumice,
broken brick, sepoli-te or bentonite; and suitable nonsorbent
earriers are materials such as ealcite or sand. In addition,
a great number of preganulated materials oE inorganic or
organic nature can be used, e.g. especially dolomite or
pulverised plant residues, e.g. cork powder or sawdust.
Depending on the nature of the compound of the formula I
to be formulated, suitable surface-active eompounds are
nonionic, cationic and/or anion:ic surfactants having good
emulsi:Eying, dispersing and wetting properties. The term
"surEaetants" will also be understood as comprising
mixtures of swrfactants,
Suitable anionie sur~aetants ean be both water-soluble
soaps and water-soluble synthetie surfaee-active eompounds.
Suitable soaps are the alkali metal salts, alkaline earth
metal salts or unsubstituted or substituted ammonium salts
7;2 ~
- 21 -
o~ higher fatty acids (C10-C22), e.g. the sodium or
potassium salts o~ oleic or stearic acid, or oE natural
fatty acid mixtures which can be o~tained e.g. ~rom
coconut oil or tallow oil. Mention may also be made of
fatty acid methyl ~urin salts.
More ~requently, however, so called synthetic surfactants
are used, especially fatty sul~onates, fa~ty sul~ates,
sulfonated benzimidazole derivatives or alkylarylsul~onates.
The ~atty sulfonates or sulfates are usually in -the ~orm
of alkali metal sal~s, alkaline earth metal salts or
unsubstituted or substituted ammonium salts and contain
a C8-C22alkyl radical which also includes the alkyl
moiety o~ acyl radicals, e.g. the sodium or calcium salt
o~ lignosul~onic acid, o~ dodecylsulfate or of a mixture
of fatty alcohol sul~ates obtained ~rom natural ~atty
acids. These compounds also comprise the salts of sulfuric
acid esters and sulfonic acids o~ ~atty alcohol/ethylene
oxide adducts. The sulfonated benzimidazole derivatives
pre~erably contain 2 sulfonic acid groups and one ~atty
acid radical containing 8 to 22 carbon atoms Examples
o~ alkylarylsulfonates are the sodium, calcium or
triethanolamine salts o~ dodecylbenzenesul~onic acid,
dibutylrlaphthalenesul~onic acid, or o~ a naphthalene-
sulfonic acid/~ormaldehyde condensation product. ~lso
suitable are corresponding phosphates, e,g. salts o~ the
phosphoric acicl ester o~ an add~ct o~ p-nonylphenol with
~ to 1~ moles o~ ethylene oxicle.
Non-ionic sur~actants are preferably polyglycol ether
derivatives o~ aliphatic or cycloaliphatic alcohols, or
saturated or unsaturated ~atty acids and alkylphenols,
said derivatives containing 3 to 30 glycol`ether groups
7Z4~3
- 22 -
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 glycolg
ethylenediamine propylene glycol and ~lkylpolypropylene
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 groupsO These
compounds usually contain 1 to 5 ethylene glycol ~InitS
per propylene glycol unit.
Representative examples of non-ionic surfactants are
nonylphenolpolyethoxyethanols, castor oil polyglycol
ethers, polypropylene/polyethylene oxide adducts, tributyl-
phenoxypolyethoxyethanol, polyethylene glycol and octyl-
phenoxyethoxyethanol. Fatty acid esters of polyoxyethylene
sorbitan and polyoxyethylene sorbitan trioleate are also
suitable non-ionic suractants.
Cationic surfactants are preferably quaternary ammonium
salts which contain, as N-substituent, at least one C8-C22-
alkyl radical and, as further substituents, lower
unsubstituted or halogenated alkyl, benæyl or lower hydroxy-
alkyl radicals. The salts are preferably in the form of
halides, methylsulfates or ethylsulfates, e,g. stearyl-
tr:imethylammonium chloricle or benæy:ldi(2-chloroethyl)-
ethylammonium bromide.
The surfactants customarily employed in the art of
formulation are described e.g. in "McCutcheon's Detergents
and Emulsi~iers Annual", MC Publishing Corp. Ringwood,
New Jersey, 1979, and Sisely and Wood, "Encyclopedia of
- 23 -
Surface Active Agents", Chemical Publishing Co , Inc.
New York, ]980.
The agrochemical compositionsusually contain 0.1 to 99%,
preferably 0.1 to 95%, o-f a compound of the formula I, 1 to
99 9% to 1%, preferably 99.8 to 5%~ of a solid or liquid
adjuvant, and 0 to 25%~ preferably 0.1 to 25% of a surfactant.
Whereas commercial products are preferably ~ormulated as
concentrates, the end user will normally employ dilute
formulations.
The compositions may also contain further ingredients, such
as stabilisers, anti~oams, viscosi-ty 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
Eollowing Examples, without implying any restriction to
what is described therein. Parts and percentages are by
weight.
Preparatory Examples
a) Startin~ materials
Example a: Preparation of
~SCH3 ~SCH3
CII=CH-CN ~ ~ ~--1; il-CN (compound 2~)
, .
~7;~
- 24 -
3-(2-Methylthiophenyl)-4-cyanopyrrole
A solution of 123 g (0.7 mole) oE E/Z-3-(2-thiomethylphenyl)-
acrylonitrile and 192 g (0.98 mole) of tosylmethyl isocyanide
in 800 ml of tetrahydroEuran is added slowly dropwise at
-13 to ~8C to a solution of 158 g (1.4 moles) of potassium
tert-butylate in 400 ml of tetrahydrof~lran. The mixture is
then stirred for 2 1/4 hours at room temperature, poured
into 3 litres of ice/water and extracted twice with ethyl
acetate. The combined extracts are washed 4 times with semi-
saturated sodium chloride solution, dried over sodium
sulfate, decolorised with silica gel and activated carbon,
Eiltered and the filtrate is concentrated. The residue is
crystallised from dichloromethane/petroleum ether to give
95 g of beige-coloured crystals with a melting point of
121-124C. The mother liquor is worked up to give another
21 g of substance. Repeated recrystallisation from dichloro-
methane/petroleum ether yields an almost colourless product
with a melting point o~ 128-134C.
Example b: Preparation of
~Cl ` ~Cl
CH=CH-COCH3 D ~ COCH
~ (compound 49)
3-(2-Chlorophenyl)-4-acetylpyrrole
A solution of 60 g (0.33 mole) of E/Z-4-(2-chlorophenyl)-3-
buten-2-one and 75 g (0.38 mole) of tosylmethyl isocyanide
in ~00 ml of tetrahyclrofuran is slowly added dropwise at
-10 to -~30C to a solution of 48 g (o,L~3 mole) of potassium
tert-butylate in 100 ml o~ tetrahydrofuran. The reaction
mixture is stirred Eor 2~ hours at 5-10C, then warmed to
room temperature, poured into 2 litres of ice/water and
extracted twice with ethyl acetate. The combined extracts
are washed 4 times with semi-saturated sodium chloride
solution, dried over sodium sulfate, decolorised with silica
~7~
- ~5 -
gel and fuller's earth, filtered and the filtrate is con-
centrated. The residue is digested in dichloromethane under
reflux, cooled and :Eiltered. Yield: 40 g of beige-coLoured
crystals with a melting point of 198-201C.
Example c: Preparation of
Cl~ Cl~
-CH=C~I-N02 ~ j -NO
~ ~ (compound 41)
3-(3-Chlorophenyl)-~-nitropyrrole
1.6 g (0.036 mole) of an approx. 55% dispersion of sodium
hydride in mineral oil are digested under nitrogen twice
with petroleum ether and then 50 ml of diethyl ether are
added. With e:Eficient stirring, a solution of 5.5 g (0.03
mole) of 2-(3-chloxophenyl)-1-nitroethene and 5.9 g (0.03
mole) of tosylmethyl isocyanide in 20 ml oE dimethylsulEox-
ide and 40 ml of diethyl ether is added dropwise to the
above mixture such that the reaction mixture constantly
boils under reflux. After the exothermic reaction has sub-
sided, stirring is continued for 15 minutes at room
temperature. First ice/water is cautiously added to the
mixture, followed by the addition of saturated sodium
chloride solution. The batch is extracted twice with ethyl
acetate and the combined extracts are washed ~ times with
semi-saturated sodium chloride solution, dried over sodium
sulfate, Eiltered and the :Eiltrate is concentrated. The
residue is recrystallised from dichloromethane/petroleum
ether to give yellow crystals with a melting point of 133-
135C.
~xample d: Preparation o:E
C~ C~
~ ~--C~I=C~I-CN ~ CN ( compound 10)
.= . .= . . --
~:~g~2~
- 26 -
3-(3-Methylphenyl)-~-cyanopyrrole
6.1 g of a 55% dispersion of sodium hydride in mineral oil
are washed with petroleun- ether and then 60 ml o~ dimethoxy-
ethane and 10 ml o~ dimethylsulEoxide are added. With
stirring, a sol.ution o~ .3 g o~ 3-methylcinnamonitrile and
21.5 g of tosylmethyl isocyanide in 60 ml o~ dimethoxyethane
and 10 ml o~ dime-thylsulEoxide are added slowly dropwise at
-25 to -20C. The mixture is stirred for 1~ hours in a
thawing ice bath, then poured onto ice and extracted twice
with ethyl acetate. The organic phase is washed with aqueous
sodium chloride solution, dried over sodium sulfate, ~iltered
and the filtrate is concentrated, to give 19 g oE a viscous
oil which, after recrystallisation from di~hloromethane/
petroleum ether~ yields crystalline 3-(3-methylphenyl)-4-
cyanopyrrole with a melting point o 109-111C.
Example e: Preparation oE
c~ ~
-C~I=CH-CN ~ J~ -CN
~ (compound 1
3-(3-Chlorophenyl)-~-cyanopyrrole
a) 10.5 g of a 55% dispersion o sodium hydride in mineral
oil are washed with petroleum ether and then 120 ml oE
tetrahydrofuran are added. A solution oE 30.7 g o:E 3-chloro-
cinnamonitrile and ~1 g oE tosylmethyl isocyanide in 180 ml
oE tetrahydrofuran and 20 ml oE dimethylsul~oxide is then
added dropwise at-25 to -20C, and the mixture is stirred
~or 2 hours in a thawed ice bath. The mixture is then
poured onto ice and extracted twice with ethyl acetate. The
organic phase is washed repeatedly with aqueous sodium
chloride solution, dried over sodium sulEate and ~iltered.
The ~iltrate is concentrated and the residue is recrystallised
Erom dichloromethane, a~Eording crystalline 3-(3-chloro-
phenyl~-4-cyanopyrrole with a melting point o~ 138-130C.
- 27 -
Example f: Preparation of
Cl ~/ \C~I=CH-COOC~13 C~ COOCH3
(compo~md ~0) ~/
3-(3-Chlorophenyl)-~-methyloxycarbonylpyrrole
With stirring, a solution of 136 g of methyl E/Z-3-(3-chloro-
phenyl)-acrylate and 155 g of tosylmethyl isocyanide in
500 ml of tetrahydrofuran and a solution of 109 g of
potassium tert-butylate in 700 ml of tetrahydrofuran are
each added dropwise simultaneously at 0-10C from two drip
unnels to 400 ml of tetrahydrofuran. The mixture is stirred
for 1~ hours at 0-5C and for % hour at 25C, then poured
onto ice and extracted twice with ethyl acetate. The extracts
are washed 4 times with semi-saturated sodium chloride
solution, dried over sodium sulfate, decolorised with silica
gel and activated carbon, filtered and the filtrate is
concentrated. The residue is digested with dichloromethane
~mder reflux and the mixture is left to stand overnight at
-18C and filtered, yielding 13]. g of colourless product
with a melting point of 187-189C.
Example ~: Preparation o~
.~'\. .~-\.
~N CH=CH-CN ~ CN
(compound 63) ~
With stirring, a solut-Lon o;E 12$.8 g oE 3-(2-pyridyl)-prop-
2-ene nitrile and 200 g oE tosylmethyl isocyanide in 1500 ml
oE tetrahydrofuran and a solution oE 140 g o~ potassium
tert-butylate in 1500 ml of tetrahydrofurane are each added
dropwise simultaneously from two drip funnels at -10 to
0C to 200 ml o~ tetrahydro~uran. The mixture is stirred
for 1 hour at 0-5C and for 1 hour at 25C, then poured
onto ice and extracted twice with ethyl acetate. The organic
~l~9~48
28 -
phase is washed twice with aqueous sodium chloride solution,
dried over sodi~ sulfate, stirred with silica gel and
activated carbon, filtered and the filtrate is concentrated.
The dark residue is crystallised from dichloromethane at
-20C, afEording 75.5 g of brown crystals with a melting
point of 148-151C.
All intermediates, also those listed in the table, can be
prepared in corresponding manner. The compounds 8, 9, 11,
13 to 76 marked with an asterisk (*) are novel and some have
fungicidal properties. Compounds 16 and 24 in particular are
very active against Deuteromycetes, especially Botrytis
fungi, as well as against harmful microorganisms in storage
protection. These novel compounds constitute an important
embodiment of the present invention.
_ ~9 _
Table of intermediates o~ the formula
~ -R
Com- R R m.p- [ c]
pound
3-C1 CN 138-140
2 2,4-C12 CN 150-152
3 4-Cl CN 153-155
4 2-C1 . CN 136-138
4-F CN 137-138
6 3-F CN 138-139
7 3-Br CN 132-134
8* 4-NtCH3)2 CN 180-182
9* 3-N (CH3) 2 CN 144-146
3-CH3 CN 109-111
11* 3-N02 CN 232-234
12 3-CF3 CN 87-89
13* 3-OC6H5 CN 124-126
14* 3-OC113 CN 125-128
15* 3-OCUF2 CN 95_97
lG* 2-OCll3 CN 'l35-136
17''~ 2-OC'IIF2 CN 105-:lO7
18''~ 2-OC2H5 CN 134-135
l9* 2-OCII(C~1 ) CN 80-81
20* 2-OCH2CH=CH2 CN 83-86
21* 2 6 5 CN 91-93
22* 2-OH CN 130-132
23* 3-SCH3 CN 115-117
72~8
Com~ R R m-p [ C]
pound n
24 * 2-SCil3 CN 128-134
25 * 2-SO-C113 CN 168-171
26 * 2 H3 CN 150-152
27 ~; 2-SC2H5 CN 121-123
28 * 2-SO-C H CN 144-145
29 * 2 2 5 CN 141-143
30 * 2-S-CII(CH ) CN 121-123
31 * 2-S02-CH(CH3)2 CN 139-141
32 * 2-S-C~Hg-n CN 61-65
33 * 2-SO-C4Hg-n CN 120-123
34 * 2-S2C~SH9-n CN 151-152
35 * 2-COOC2H5 CN 130-132
36 * 3-C~C-C(OH) (CH3)2 CN oil
37 * 3-C-C-H CN 132-134
38 * 2-C--C-C(OH) (CH3)2 CN 140-143
39 * 2-C-C-H CN 109-115
40 * 3-C1 CO-OC~13 187-189
4l * 3-Cl N02 133-135
42 ~: 2-Cl N02 137-139
~3 * 3-Cl P(O) (OC2115)2 102-10~
* 3-C1 P(O) (OC~13)2 120-122
~5 * 2-C1 P(O) (OC2~15)2 129-131
~6 * 2-C1 P(O) (OC113)2 1~6 148
47 * 2,~l-CI2 r(o) (C2ll5)2 ~9~90
48 * 3-C1 CO-CH3 193-195
49 * 2-Cl CO-CH3 198-201
50* 2,4-Cl2 CO-C~13 184-186
51'~ H CO-CH3 156-158
52 * 3-CH3 CO-CH3 120-123
~L97~
- 31 -
Com- Rn R m.p. [ C]
pound
53* 4-Cl C0-C~13 170-174
5~* 3,4-C12 C0-C~3 162-164
55* 4-OCIl C0-CH3 179-182
56*. 4-C~13 C0-CII 181-184
57* 3-Cl S0 -CH 125-127
58* 4-Cl S0 -CH 154-156
59* 2,4-C12 S0 -CH 174-177
6C* 3-N02 2 3 133-135~
61* 2-C1~ 4-~2 S0 -C~l 197-200
62* 2-Cl S0 -CH 178-180
63* 6 5 CN 249-254
64* 1I CN 120-123
65* 2 3
Table of intermediates of the formula
R- j i-CN
Com- R m.p. ~c]
pound
66* 2-pyriclyl lll8-151
67* 3-pyridy:l . 160-l62
68* 4-pyridyl 200-203
69* 2-(5-chloropyridyl) 20~-206
70* 3-(2-chloropyrldyl) 217-220
71* 2-(3,5-dichloropyrLcyl) 176-179
72* 2-khienyl l22-124
73* 2-:E~tryl 98-100
74* 2-(N-methylpyrrole) 174-175
75* 2-(6-methylthienyl) 108-110
76* 2-(3-methylthienyl) 132-137
. .
~724~3
- 32 -
~) Final products
Example ~ Preparation of
~Cl ~Cl
COCH3 ~ . - . -COCH
~ (compound 1- 24) ~CFC12
N-Fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-
acetylpyrrole
A solution o~ 6 ml (0.0575 mole) o~ fluorodichloromethyl-
sulfenyl chloride in 20 ml of tetrahydrofuran is initially
added dropwise at 3-5C to a solution of 11 g (0.05 mole)
o~ 3-(2-chlorophenyl)-4-acetylpyrrole in 100 ml of tetra-
hydrofuran, followed by the dropwise addition of 8 ml
(0.0575 mole) of triethylamine in 20 ml of tetrahydrofuran
at 5-8C. The mix-ture is then stirred for 16 hours in a
thawing ice bath and filtered. The filtrate is concentrated
and the residue is recrystallised from diethyl ether/petroleum
ether. Yield: 9.4 g of beige crystals with a melting point
oE 85-87C. A ~urther crop of beige crystals (4.5 g) with
a melting point of 8~-86C is obtained after purification
by chromatography over silica gel with dichloromethane/
petroleum ether (~:1) as eluant, concentration oE the mother
liquor and recr~stallisation Erom cliethyl ether/petroleum
ether.
Example ~1~: Preparation oE
C113~, CE13~
j-COCH3 ) ~ COCE13
E~ (compound 1.31) ~-CC13
~-TrichloromethylsulEenyl-3-(3-methylphenyl)-4 acetylpyrrole
3.9 ml (0.036 mole) of trichlorometh~lmercaptan in 30 ml of
tetrahydrofuran are initially added dropwise at 0-5C to a
solution of 6 g (0.03 mole) of 3-(3-methylphenyl)-4-acetyl-
pyrrole in 100 ml of tetrahydrofuran, followea by the drop-
wise addition at 5-8C of 5 ml (0.036 mole) of triethylamine
in 30 ml of tetrahydrofuran. The reaction mixture is then
stirred for 16 hours in a thawing ice bath and filtered. The
filtrate is concentrated and the residue is puri~ied by
column chromatography over silica gel with dichlorome~hane/
petroleum ether (2:1) as el~lant. Recrystallisation from
petroleum ether yields 5 g of colourless crystals with a
melting point of 58-59C.
Example H3: Preparation of
~OC2115 ~OC2~15
\ ~~ -CN \ / ~
~ (compound 1.15) ~-cFCl2
N-Fluorodichloromethylsulfenyl-3-(2-ethoxyphenyl)-4-cyano-
pyrrole
A solution of 4 ml (0.039 mole) oE :Eluorodichloromethyl-
sulfenyl chloride in 15 ml of ethyl acetate is initially
added dropwise at 3-7C to a solution of 7.2 g (0.034 mole)
o~ 3-(2-ethoxyphenyl)-4 cyanopyrrole in 100 ml oE ethyl
acetate, followed by the dropwise addition of 5.4 ml (0.039
mole) oE triethylamine in 15 ml oE ethyl acetate. The
reaction mixture is stirred ~or 16 hours in a thawing ice
bath and then Eiltered. The filtrate is concentrated and
the residue is recrystallised from petroleum ether, aEfording
9.9 g of beige crystals with a melting point o:E 80-83C.
Example H4: Preparation of
il--il - CN ~ CN
~ (compound 2-1) I-CFcl2
~g7~
N-Fluorodichloromethylsul~enyl-3-(2-furyl)-~-cyanopyrrole
3.9 ml (0.037 mole) o:E fluorodichloromethylsulfenyl chloride
in 10 ml of tetrahydro~lran are ini~ially added dropwise at
0-5C to a solution of 5.2 g (0.33 mole) oE 3-(2-furyl)-~-
cyanopyrrole in 100 ml of tetrahydro~uran, followed by the
dropwise addition of 5.2 ml (0.037 mole) o~ trlethylamine in
10 ml of tetrahydrofuran at 5-8C. The reac~ion mixture is
then stirred for 16 hours in a thawing ice bath and filtered.
The filtrate is concentrated and the residue is purified by
column chromatography over silica gel with dichloromethane/
petroleum ether (3:1) as eluant. Recrystalllsation from
petroleum ether yields 7 g of yellowish crystals with a
melting point of 7~-76C.
Example H5: Preparation of
,~ \O .~ \
il li ~ \il--i1/
tCompound 2.3) ~
CC13
N-Trichloromethylsulfenyl-3-(2-pyridyl)-4-c~anopyrrole
A solution oE 13.7 g of perchloromethylmercaptan in 20 ml of
tetrahydrofuran is initially added dropwise at 0-10C to Q
solution of 16.9 g of 3-(2-pyridyl)-~-cyanopyrrole in 200 ml
of tetrahydrofuran, followed by the dropwise addition of
17.~ ml oE triethylamine in 20 ml of tetrahydroEuran. The
mixture is stirred Eor :l6 hours in a thawing ice bath and
then concentral:ed~ The residue is partitioned between ethyl
acetate and aqueous sodium carbonate solution. The aqueous
phase is separated and the organic phase is washed once with
saturated sodium bicarbonate solution and twice with semi-
saturated sodium chloride solution~ dried over sodium
sulfate, decolorised with silica gel and activated carbon,
filtered and the filtrate is concentrated until the onset
of crystallisation at a bath temperature oE 30C. The
~ ~ 7
- 35 -
residue is diluted with the same volume of petroleum ether
and allowed to crystallise completely in a crystallisation
cabinet. Yield: 27.5 g of colourless crystals which decompose
between 131 and 140C.
Example H6: Preparat~on of
C~ COOC~3 ~ COOCH3
~ (compound 1.34~ ~/
~-CFC12
H
N-Fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-methoxy-
carbonylpyrrole
A solution of 20.4 g of fluorodichloromethylsulfenyl chloride
in 15 ml of tetrahydrofuran is initially added dropwise at
0-5C to a suspension of 23.6 g of 3-(3-chlorophenyl)-4-
methoxycarbonylpyrrole in 150 ml of tetrahydrofuran, followed
by the dropwise addition of 12.2 g of triethylamine in 15 ml
of tetrahydro~uran. The mixture is stirred for 16 ho-lrs in a
thawing ice bath and then filtered. The ~iltrate is con-
centrated and the residue is crystallised from ethyl acetate/
petroleum ether, afEording 28 g oE colourless product with
a melting point of 77-79C.
The ~ollowing individual compounds of the Eormula I may be
prepared in corresponding manner.
7~8
Table 1: Compounds of the formula
R
~ 2
Rn \
~1~
Com- R R R ~ p [ C]
pound n 3 2 . .
1.1 3-OCH3 CC12F CN oil
1.2 2-S-C2H5 CC12F CN 59-60
1.3 2-S-C2~5 CC13 CN 90-92
1.4 2-S-CH(CH3)2 CC12F CN 64-66
1.5 2-S-CH(CH3)2 CC13 CN 100-102
1.6 2-SCH3 CC12F CN 86-87
1~7 2-SCH3 CC13 CN 125-127
1.8 4H9 CC12F CN 44-46
1.9 4 9 n CC13 CN 41-42
1.10 2-OCH(CH3)2 CC12F CN 95-98
1.11 2-OCH(CH3)2 CC13 CN 100-102
1.12 2-ben7.yloxy CC12F CN 127-129
1.13 2-ben7yloxy CC13 CN 111-113
lo 14 2-Br CC12F CN 69-71
1,15 2-OC2115 CC12F CN 80-83
1.16 2-OC2H5 CC13 CN 107-110
1,17 2 H2 CC12F CN 66-68
1.18 2-OCH2CII-CH2 CC13 CN 79-80
I.l9 3-Cl CC12F CN 87-89
L.20 3-Ct CC13 CN 81-84
1.21 2-Cl CC12F CN 59~61
1.22 H CC12F CO-CH3 43-45
1.23 H CCl~ CO-CH3 86-88
1.24 2-Cl CCl2F CO-CH3 86-88
1.25 2-Cl CC13 CO-CH3 104-109
:1 ~ $~2~3
37 -
Ta~le 1: (contin-lation)
pound Rn R3 R2 m.p [C]
1.26 ~,-C~l3 CC12F CO-CH3 82~84
1.27 4-CH3 CC13 CO-CH3 100-102
1.28 3-C1 CC12F CO-CH3 63-64
1.29 3-C1 CC13 CO-CH3 82-84
1.30 3-CH3 CC12F CO-CH3 nD : 1.5871
1.31 3-CH3 CC13 CO-CH3 58-59
1.32 4-OCH3 CC12F CO-CH3 n~ : 1.5927
1.33 4-OC113 CC13 CO-CH3 nD : 1.6098
1.34 3-Cl CC12F COOCH3 77-79
1.35 3-Cl CC13 COOCH3 89-90
1.36 3-Cl CC12F S2CH3 oil
1.37 3-Cl CC13 2 3 104-107
1.38 2 4-C1 CC12F' S2CH3 106-108
1.39 2,4-C1 CC13 S02C~13 111-113
1.40 2-C1 CC12F S2CH3 86-88
1.41 2-OC2H5 CC12CHC12 CN 103 decompos.
1.42 2-Cl CC13 CN 93-95
1.43 2-OCH3 CC12F CN 39-42
1.44 2-OCH3 CC13 CN resill
3 7 CC12F CN 122-127
1.46 2 OC3~17 n CC13 CN
7 2-OC~I119-n CC12F CN
l.48 4 9 CCI3 CN
1.49 2-SC3117-n CC12F CN
1.50 2-SC3117-n CC13 CN
1.51 2-CN CC12F CN 112-115
1.52 2-CN CC13 CN resin
1.53 2,3-C~2 CC12F CO-CH3
1.54 2,3-C12 CC13 CO-CH3
1.55 4-C1 CC12F CO-C~3
~9~7;~
- 38 -
Table 1: (continuation)
Com- R R R2 m.P.[oc]
pound n 3
1.56 ~-Cl CC13 CO-CH3
1.57 2-SCH3 CC12F CO-CH3
1.58 2-SCH3 CC13 CO-CH3
1.59 2-OCH3 CC12F CO-CH3
1.60 2-OCH3 CC13 CO-CH3
1.61 2-CN CC12F CO-CH3
1.62 2 CN CC13 CO-CH3
1.63 ~I-N(CH3)2 CC12F CO-CH3
1.6~ -N(CH3)2 CC13 CO-OE13
1.65 3-CF3 CC12F CO-CH3
1.66 3-cr~'3 CC13 CO-CH3
lo 67 2-Cl CC12F COOCH3 oil
1.68 2-Cl CC13 COOCH3 83-86
1.69 ~-Cl CC12F COOCH3
1.70 ~-Cl CC13 COOCH3
1.71 3,~l-C1 CC12F COOC~13 92-9~D
1.72 3,~-C12 CC13 COOC~13 89-90
1.73 ~-C~13 CC12F COOCH3
1.7~ -C~13 CC13 COOC113
1~75 ~-OCH3 CC12F COOCH3 97~99
1.76 4-OCH3 CC13 COOC113
1.77 2-OC~13 CC12F COOCH3
1.78 2-OCH3 CC13 COOCll3
1.79 2-CN CC12F COOC~13
1.80 2-CN CC13 COOC1l3
1.81 2-C1 CC12F CON(CH3)2
1.82 2-C1 CC13 CON(CH3)2
1.83 3-C1 CC12F CON(CH3)2
1.8~ 3-C1 CC13 CON(CH3)2
1.85 ~-C1 CC12F CON(CH3)2
~7Z~
Table 1: (continuation)
Com- Rn R3 R2 m.p.[ C~
1~86 4-C1 CC13 CON(CH3)2
1.87 ~-CH3 CC12F CON(CH3)2
1.89 ~,-CH3 CC13 CON(CH3)2
1.90 4-OCH3 CC12F CON(CH3)2
1.91 4-ocH3 CC13 CON(CH3)2
1.92 2-OC~3 CC12F CON(CH3)2
1.93 Z-OCH3 CC13 CON(CH3)2
1.94 2-OC2H5 CC12F CON(CH3)2
1.95 2-OC2H5 CC13 CON(CH3)2
1.96 2 CN CC12F CON(CH3)2
1.97 2-CN CCl3 CON(CH3)2
1.98 2-C1 CC13 S2CH3 118-121
1.99 4-C1 CC12F S2CH3
1.100 4-C1 CC13 S2CH3
1.101 4-CH3 CC12F S2CH3
1.102 4~CH3 CC13 S2CH3
1.103 4-OCH3 CC12F S2CH3
1.104 4-oCH3 CC13 S2CH3
1.105 3,4-C12 CC12F S2CH3
1.106 3,~l-C12 CC13 S02C~13
1.107 2-OCII~ CC12F S02C113
1.]08 2-OCH3 CC13 S2CH3
1.lO9 2-SC4ll9-n CC12F S2C~13
l.llO 2-SC~1l9-ll C~13 S02C~13
1.111 2-CN CC12F S2CH3
1.L12 2-CN CC13 S2CH3
1.113 2-C1 CC12F S02N(CH3)2 103-105
1.114 2-C1 CC13 S02M(CH3)2
1.115 3-C1 CC12F S02N(CH3)2
72~1 3
- ~o -
Table 1: (continuation)
Com- R R R2 m .p.r C]
pound ll 3
1.1163-C1 CC13 SO,N(CH3)2
1.117 4-CH3 CC12FSO2N(CH3)2
1.118 4-CH3 CC13SO2N(CH3)2
1.119 4_0CH3 CC12FSO2N(CH3)2
1.120 4-OCH3 CC13SO2N(CH3)2
1.121 4-C1 CC12FSO2N(CH3)2
1.122 4-Cl CC13SO2N(CH3)2
1.123 2-C1 CC12F( )( 2 5)2
1.124 2-C1 CC13-P(O)(OC2H5)2 oil
1.125 3-C1 CC12FP(O)(OC2H5)2
1.126 3-C1 CC13_P(O)(OC2H5)2
1.127 4-C1 CC12F-P(O)tOC2H5)2
1.128 4-C1 CC13 -P(O)(OC2~l5)2
1.129 2-C1 -CC12F 2 85-87
1.130 2-C1 -CC 13 -N2
1.131 3-C1 -CC12F _NO2
1.132 3-C1 ' -CC13 -NO2
1.133 2-C1 -CC12F -~-CH3
l.134 2-C1 -CC13 -~-CH3
1.135 2-C1 -CC12F
1.136 2-Cl CC12-CHC:L2 CN 123-125
1.137 4-C6HS CC13 CN 168-175
1.138 4-C6H5 CFC12 CN 173-177
1.139 H CC12F CN 96-98
1.140 H CC13 CN 102~103
1.141 H CFC12 SO2CH3
1.142 3-C1 CCI2CHC12 COOCH3
J~
- 41 -
Table 1: (continuation)
Com- Rn R3 R2 m-p ~C]
1.143 2-Br CC13 CN 114-115
1.144 2-CH3 CC12F COCH3 85-89
1.145 2-CH3 CC13 COCH3 94-99
1.146 2,3-C12 CC12F CN 105-107
1.147 H CC12F S02N(CH3)2 124-126
1.148 H CC12F CON(CH3)2 oil
1.149 H CC13 CON(CH3)2 75-79
1.150 2,3-C12 CC12F COOCH3 56-61
- ~2 -
Table 2: Compounds of the formula
R -i -R
~Rq
Com- R R R m.p. [~C]
pound 1 2 3
2.1 2-furyl CN CCl2F 74_76D
2.2. 2 pyridyl CN CCl2F 92-1oodeccmp
2.3 2-pyridyl CN CC13 131-140d~cllp.
2.4 2-pyridyl COOCH3 CC12F
2.5 2-pyridyl COOCH3 CC13
2.6 2-pyridyl CON(CH3)2 CCl2F
2.7 2-pyridyl CON(C~13)2 CC13
2.8 3-(2~1~opyridyl) CN CC12F
2.9 3-(2~ ~ropyridyl) CN CC13 142-144
2.10 3-(2-~loropyridyl) CO-CFI3 CC12F
2.11 3-(2~hloropyridyl) CO-CH3 CC13
2.12 2~6-chloropyridyl) CN CCl2F
2.13 2-(6-chloropyridYl) CN CC13
2.14 2-(6~loropyridyl) COOCH3 CC12F
2.15 2-(6-c~loropyridyl) COOCH3 CC13
2.16 2-thienyl CN CCl2F 72-77
2.17 2-thienyl CN CC13 85-89
2.18 2-thienyl CON(C1l3)2 CCl2F
2.~9 2-thienyl CON(C~13)2 CCl3
2.20 2-pyridyl CN CCl -CHCl 103-106
2. 21 3-pyridyl CN CC12F 123-126d~comp.
2.22 3-pyridyl CN CC13 dec~np.from 156
2.23 '~-pyridyl CN CC12F deccmp.frcm145
2.24 ~-pyridyl CN CC13 d~corr,p,fiom 154
I ~
~g~
- 43 -
~ormulation Exlm~)les for liq-lid active in~redien~s o~ the
formu].a ~ (throughout, percentages are by weight)
Fl Emulsiflable concentrates a) ~) c)
a compound of the tables 25 % 40 % 50 %
calcium dodecylben~enesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol
ether (36 moles of ethylene
oxide) 5 % _ _
tributylphenol polyethylene
glycol ether (30 moles o~
ethylene oxide) - 12 % 4 %
cycl.ohexanone ~ 15 % 20 %
xylene mixture 65 % 25 V/o 20 %
Emulsions of any required concentration can be produced
from such concentrates by clilution with water.
F2 Solutions a) b)l c) d)
a compound of the tables ~0 % :L0 % 5 % 95 %
ethylene gLycol monomethyl ether ~0 % - ~ -
polye~hylene glycol MG 400 , 70 % - -
N-methyl-2-pyrrolidone - 20 %
epoxidlsed coconut oil - - 1 % 5 ~/0
ligroin (boi].lng ran~e 160-1')0) - - 9~ %
These solutions are suitable for appl:lcation in the ~orm
oE microcrops.
F3 Granulates a) b)
a compound of the tables 5 % 10 %
kaol.in 94 %
highly dispersed silicic acid1 %
attapulgite - 90 %
The active ingredient is dissolved in methylene chloride,
the solution is sprayed onto the carrier, and the solvent
is subsequently evaporated off in vacuoA
F4 Dusts a) b)
a compound of the tables 2 % 5 %
highly dispersed silicic acid 1 % 5
talcum 97 %
kaolin - 90 %
Ready Eor use dusts are obtained by intimately mixing the
carriers with the active ingredient.
Formula~ion examples for solid active in~redients oE the
formula I (thro-lghout, percentages are by weight)
F5 Wet~able powders a) b) c)
a compound oE the tables 25 % 50 % 75 %
sodium lignosul:EonaLe 5 % 5 %
sod:ium lauryl.sulEate 3 % - 5 %
sodlum cllis0l~uty:1.naph~llalene-
sul~onate - 6 % 10 %
octylphenol polyethyl.ene glycol
ether (7-8 moles oE ethylene o~ide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %
~7;2~8
- 45 -
Tlle active ingredient is thorougllly mixed ~ith the adjuvants
and the mi~ture is thoro~lghly ground in a s~litable mill,
af~orcling ~ettable po~Jclers ~hich can be diluted with water
to give suspensions of the desired concentration.
F6 Emulsi:~;able concentrate
a compound o~ the tables 10 %
octylphenol polyethylene glycol ether
(4-5 moles o~ ethylene oxide) 3
calcium cdodecylben~enesul~onate 3 %
castor oil polyglycol ether
(36 moles o~ ethylene oxide) 4
cyclohexanone 30 ~/o
xylene mixture 50 %
~mulsions of any required concentration can be obtained rom
this concentrate by dilution ~ith water.
F7 Dusts, a) b)
a compound of the tables 5 % 8 %
talc~m 95 %
kaol:in - 92 %
~eady fôr use dusts are obtained by rn:ix:ing the active
ingredl.ent witll the .carr:lers~ ancl grlndl.ng the mlxture in
a su:itable mil:l.
F8 E.xtrucler ~ranulate
a compound o~ the tables 10 %
sodi~l lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %.
- 46 -
The active ingredient is mi~ed ~nd ~round ~ith ~he adjuvants,
and the mi~ture is subscquently nloistened with wa~er. The
mi~ture is e~truded and then dried in a stream oE air.
F9 Coated ~,ranulate
a compound of the tables 3 %
polyethylene gylcoL MG 200 3 %
kaolin 94 %
The ~inely ground active ingredient is uniformly appliedg
in a mixer, to the kaolin moistened w;th polyethylene glycol.
Non dusty coated granulates are obtained in this manner.
F10 Suspension concentrate
a compound of the tables 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether
(15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil ln ~he form oE a 75 %
aqueous emulsion 0.8 %
water 32 %.
The finely ground active ingredient is intimately mixed
with the adjuvants, giving a suspension concentrate Erom
which suspensioTIs o~ any desired concentration can be
obtained by dilution with water.
Both the final products of the ~ormula I and the intermediates
o~ the formulae I and II' can be formulated in accor-Jance
with Examples Fl to F10.
-- '~7 --
Biological Examples
Example Bl: Action a~alnst Puccinia graminia on wheat
a) Residual-protective action
Wheat pLants are treated 6 days after sowing with a spray
mixture prepared from a wettable powder formulation
of the active i~gredient (0.06 %). A~ter 24 hours the treated
plants are infected with a uredospore suspension of the
fungus. The infected plants are incubated for 48 hours at
95-100 % relative humidity and about 20 C and then stood
in a greenhouse at about 22 C. Evaluation of rust pustule
development is made 12 days after infection.
b) Systemic action
~leat plants are treated 5 days after sowing with a spray
mixture prepared from a wettable powder formulation of the
active ingredient (O.oO6% based on the volume of the soil).
~Eter ~8 hours the treated plants are infected with a uredos-
pore suspension oE the ungus. The plants are then
incubated Eor ~8 hours at 95-100 % relative humidity and
about 20C and then stood in a greenhouse at about 22C,
Evaluation oE rust pustule development is made 12 days
aEter inection. Compouncls oE tables 1 and 2 are very eEfective
against Puccinia Eungi. 100 % Puccinia attack is Eound on
untreated and inEected control plants. ~mong others,
compounds 16, 1.2~, 1.26, 1.3~, 1.75 and 1.1
inhibit f~mgus attack to 0-5 %.
xample B2: ~ction against Cercospora arachidicola in
groundnut plants
Residual-protective action
Groundnut plants 10-15 cm in height are sprayed with a spray
mi~ture prepared Erom a wettable powder Eormulation of the
active ingredient (concentration o.oo6%) and infected
~72~
- 48 -
48 hours later wlth a conidia suspension of the fungus, The
infected plants are incubatecl for 72 hours at about 21 C
and high humidity and then stood in a greenhouse until the
typical leaf specks occur. Evaluation of the fungicidal
action is made 12 days after infection~ and is based on the
number and size of the specks.
Compa~ed with un~reated and infected controls (number and
size of the speclcs = 100%), Cercospora attack on the ground-
nut plants ~reated with compounds of Tables 1 and 2 is
greatly reduced. For example, compounds 23, 1.11, 1.15, 1.17,
1~ 2~ 26 ~ 0 ~ 1.75 and 1~ inhibit speck development
almost completely (8%) in the above tests. Compound 24 has
this activity even when diluted to a concentration of 0~002~/o~
Example B3: Action against Erysiphe graminis on barley
a) Residual protective action
Barley plants about S cm in height are sprayed with a spray
mixture (0~02 %) prepared ~rom the active ingredient
Eormulated as a wettable powder. The treated plants are
dusted with conidia of the fungus after 3-~ hours. The
infected barley plants are then stood in a greenhouse at
about 22C~ The Eungus attack is evaluated after lO days.
b) Systemic act:lon
~arley plants about 8 cm in height are treated with a spray
mixture (0.006 %, basecl on the volume o~ the soil)
preprared ~rom the active ingredient Eor~nulated as
wettable powder. Care is talcen that the spray mixture does
not come irl contactwith the parts of the plants above the
soil. The treated plants are infected ~8 hours later with
a conidia suspension of the E~mgus. The infected barley
plants are then stood in a greenhouse at about 22C and
~7~8
- 49 -
evaluation of Eungus attack is made after 10 days. Compounds
of the formula I are very effective against Erysiphe fungi.
Erysiphe attack is 100% on untreated and infected controls.
Compounds of Tables 1 and 2 strongly inhibit fungus attack.
For example, compounds 2, 16, 1.15, 1.21, 1.24, 1.26, 1.36
and 2.2 inhi~it attack almost completely (0-5%). The most
active compounds are compounds 1.24 and 1.36.
xample B4: Residual-protective action a~ainst Venturia
inaequalis on apple shoots
Apple cuttings with 10-20 cm long Eresh shoots are sprayed
with a spray mixture (0.06%) prepared from a w~ettable powder
formulation of the active ingredient. The plants are infected
24 hours later with a conidia suspension of the fungus. The
plants are then incubated for 5 days at 90-100% relative
humidity and stood in a greenhouse for a further 10 days at
20-24C. Scab infestation is evaluated 15 days after
infection. Compounds 1, 4, 6, 7, 10, 24, 1.6, 1.8, 1.14,
1.17, 1.21, 1.2~, 1.26, 1.28, 1.3~, 1.36, l.~0, 1.52, 1.144,
2.3 and others inhibit attack to less than 10%. Venturia
attack is 100% on untreated and infected controls. Com-
pounds 1.24, 1.26, 1.40 and 2.3 are still fully effective
(0% attack) when diluted to a concentration oE 0.006%.
xample B5: ~esidual protective action a~ainst Botrytis
cinerea on beans
~ean plants about 10 cm in height are sprayed with a spray
mixture (0.02%) prepared from the active :Lngredient
~ormulat~d as wettable powder. ~ter 4~ hours, the treated
plants are infected with a conidia suspension oE the f~mgus.
The infected plants are incubated Eor 3 days at 95-100%
relative humidity and 21C, and evaluation of the fungus
attack is then made. The compounds of Ta~les 1 and 2 inhibit
fungus infection very strongly in many cases. For example,
compounds 1, 4, 6, 7, 10, 24, 1.1 to 1.8, 1.14, 1.15, 1.17,
~'7~
- 50 -
1.19, 1,20~ 1.34 and 2,1 are fully effective at a con-
centration of 0.02% (0 to 5% attack), Attack on untreated
and infected plants is 100%, The intermediates 16 and 24
are also equally effective,
Example B6: Action a~ainst Botrytis cinerea on apples
Ar-tificially damaged apples are treated by dropping a spray
mixture prepared from the respective active ingredient
formulated as wettable powder onto the injury sites, The
treated fruit is then inoculated with a spore suspension of
Botrytis cinerea and incubated for 1 week at high humidity
and abo~lt 20C.
Evaluation is made by counting the number of injury sites
attacked by rot and deducing the fungicidal action of the test
compound therefrom. Compared with untreated controls (100%
attack),compounds 1, 4, 6, 7, 10, 24, 1,1 to 1.8, 1.14 to
1.24, 1.26 to 1.34, 1,36 to 1.43, 1.51, 1.52, 1.67, 1.68,
1.71, 1,72, 1.75, 1.98, 1.113, 1.123, 1.129, 1.136 to 1.139,
1.144 -to 1.147, 1.150, 2.1, 2.2, 2.3, 2.9, 2.16, 2.17 and
2.21 to 2.24 and others inhibit f~mgus attack almost
completely. The intermediates 16 and 24 are also equally
effective.
Example B7: Action a~ainst Alternaria solani on tomato plants
Tomato plants are sprayed~ aEter 3 weeks' cultivation, with
a spray mixture prepared from the active ingredient
formulated as a wettable powder (0.06%). AEter 24 ho~lrs,
the treated plants are infested with a conidia suspension
o~ the Eungus. Evaluation oE the fungus attack is made after
incubation oE the inEested plants for 8 days at 18 to 22C
and high humidity. Compounds of Tablesl and 2 effect a
strong reduction of Alternaria attack. For example, com-
pounds 1.23, 1.24 and 1.26 inhibit attack completely (0.5%).
~7Z~3
- 51 -
Exam~le B8: Action a~ainst Piricularia oryzae on rice
Rice plants are sprayed, after 2 weeks' cultivation, with a
spray mixture prepared from the active ingredient formulated
as a wettable powder (0.02%). After 48 hours, the treated
plan-ts are infested with a conidia suspension of the fungus.
Evaluation of the fungus attack is made after incubation of
the infested plants for 5 days at 24C and 95-100C
relative humidity. Compounds o~ the formula I effect good
inhibition ofPiricularia attack. For example, compounds 1.23
1.24, 1.26, 1.75 and 1.1~4 inhibit attack to less than 10%.
Example B9: Grain preservative test
a) Short-term test a~ainst mould fun~i on moist maize
Dry maize kernels (80 g portions) intended for use as animal
feed are thoroughly mixed in sealable plastic beakers with
compounds of all Tables in the form o~ an aqueous suspension,
emulsion or solution. The application of active ingredient
is made so as to give a concentration oE 0.06%, based on the
dry weight of the maize. A moistened sheet of paper ensures
a saturated moist atmosphere in the beakers, which are
filled with the maize and then sealed. After incubation
Eor 2-3 weeks at about 20C, a mixed population of mould
fungi develops spontaneously on the maize samples treated
only with water. There is no need ko make an arti~icial
infection. The eEfectiveness oE the compounds of the Eormulfle
I and II' :is evaluated by determinin~ the e~tent of Eungus
clevelopment aEter 3 weeks.
~) Lon~-term test a~ainst moulcl fun~i on moist maize
I The mai~e samples exhibiting no f~mgus attack after 3
weelcs ar.e incubated for a further two months. A visual
assessment is made after each month, applying the same
criteria as in test a)
~7~
II The test procedure is in principle the same as in a) and
b), except that the text compo-md o~ the formula I or II'
is used in concentrations of 2000, 600 and 200 ppm a.i.
(based on the dry weight o~ the maize) over 6 months.
In all three tests a), bI) and bII), the Eormation of mould
fungi on moist maize is inhibited completely both short-term
(3 weeks) and long-term (6 months) by treatment with compounds
of the ~ormula I of all Tables.
For example~ compounds 16, 24, 1.14 and 1.15 in all three
tests a), bI) and bII) inhibit mould fungus attack almost
comp:Letely (0-5% attack) at a test concentration oE 600 ppm
a.i.
Treatment with compounds oE the ~ormulae I and II' in
similar tests using, alternatively, cereals (oats), hay,
carrot chips or broad beans instead of ~odder maize, give
similar results o~ long-term protection over several months.
Example B10: Action a~ainst Tilletia caries
Tilletia spores are suspended Eor 15 minutes in a spray
mixture containing 600 ppm o~ active ingredient. The spore/
compound mixture is pipetted dropwise onto the sur~ace oE
Einel.y sieved, moistened soil in Petri dishes. These
prepared dishes are then kept at high humidity (95-100%)
and 20C. Spore ~ormation is evaluated microscopically a;Eter
about 10 clays. The flction oE the test compouTIds is determined
in accordance with the number and length of the sporocysts.
Compounds oE the Eormulae I and II' are very eE~ective
against Tilletia caries Eungi. For example, compounds 1, 4,
6, 7, 10, 24, 1.6, 1.1~, 1.15, 1.17, 1.21, 1.2~, 1.26, 1.28,
1.36, 1.40, 1.52 and 2.3 inhibit the formation of sporocysts
completely.
