U.S. patent application number 12/101175 was filed with the patent office on 2008-09-11 for 4- piridinylmethylsulphonamide derivative as fungicidal plant protection agents.
Invention is credited to Carsten Blettner, Markus Gewehr, Norbert Gotz, Wassilios GRAMMENOS, Thomas Grote, Jordi Tormo i Blasco, Bernd Muller, Joachim Rheinheimer, Peter Schafer, Maria Scherer, Frank Schieweck, Ulrich Schofl, Anja Schwogler, Reinhard Stierl, Siegfried Strathmann, Oliver Wagner.
Application Number | 20080221177 12/101175 |
Document ID | / |
Family ID | 34400459 |
Filed Date | 2008-09-11 |
United States Patent
Application |
20080221177 |
Kind Code |
A1 |
GRAMMENOS; Wassilios ; et
al. |
September 11, 2008 |
4- PIRIDINYLMETHYLSULPHONAMIDE DERIVATIVE AS FUNGICIDAL PLANT
PROTECTION AGENTS
Abstract
Sulfonamides of the formula I ##STR00001## where the
substituents are as follows: R.sup.1 is hydrogen, alkyl, alkoxy,
alkenyl or alkynyl; and R.sup.2, R.sup.3, R.sup.4, R.sup.5 are
hydrogen, halogen, alkyl, alkoxy or halomethyl; R.sup.2 and R.sup.3
together may also form a phenyl, cyclopentyl or cyclohexyl ring, it
being possible for these rings to carry two groups R.sup.2' and
R.sup.3', R.sup.2', R.sup.3' are hydrogen, halogen, alkyl, alkoxy
or halomethyl; in case a), if R.sup.2, R.sup.3, R.sup.4 and R.sup.5
are hydrogen: X is phenyl substituted by a group
C(R.sup.6).dbd.NOR.sup.7, where R.sup.6 is alkyl and R.sup.7 is
alkyl, benzyl, alkenyl, haloalkyl, haloalkenyl, alkynyl or
haloalkynyl; and in case b), if at least one of the groups R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 is not hydrogen: X is phenyl, naphthyl
or a five- or six-membered saturated, or partially unsaturated or
aromatic heterocycle which is attached via a carbon atom and
contains one to four heteroatoms from the group consisting of O, N
and S, where X may be substituted according to the description;
Processes for preparing these compounds, compositions comprising
them and their use for controlling phytopathogenic harmful
fungi.
Inventors: |
GRAMMENOS; Wassilios;
(Ludwigshafen, DE) ; Blettner; Carsten; (Mannheim,
DE) ; Muller; Bernd; (Frankenthal, DE) ;
Gewehr; Markus; (Kastellaun, DE) ; i Blasco; Jordi
Tormo; (Laudenbach, DE) ; Grote; Thomas;
(Wachenheim, DE) ; Rheinheimer; Joachim;
(Ludwigshafen, DE) ; Schafer; Peter; (Ottersheim,
DE) ; Schieweck; Frank; (Hessheim, DE) ;
Schwogler; Anja; (Mannheim, DE) ; Wagner; Oliver;
(Neustadt, DE) ; Gotz; Norbert; (Worms, DE)
; Strathmann; Siegfried; (Limburgerhof, DE) ;
Schofl; Ulrich; (Bruhl, DE) ; Scherer; Maria;
(Godramstein, DE) ; Stierl; Reinhard; (Freinsheim,
DE) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
34400459 |
Appl. No.: |
12/101175 |
Filed: |
April 11, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10570893 |
Mar 7, 2006 |
7388018 |
|
|
PCT/EP2004/010124 |
Sep 10, 2004 |
|
|
|
12101175 |
|
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Current U.S.
Class: |
514/357 |
Current CPC
Class: |
C04B 35/632 20130101;
C07D 409/12 20130101; C07D 213/42 20130101; C07D 215/12 20130101;
C07D 401/12 20130101 |
Class at
Publication: |
514/357 |
International
Class: |
A01N 43/40 20060101
A01N043/40; A01P 3/00 20060101 A01P003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 18, 2003 |
EP |
03021098.3 |
Claims
1. A method for controlling harmful fungi in the protection of
material, comprising: treating the materials to be protected from
fungal attack with a fungicidally effective amount of a compound of
formula I ##STR00013## wherein R.sup.1 is hydrogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or benzyl;
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently of one
another hydrogen, halogen, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-alkoxy or halomethyl; R.sup.2 and R.sup.3 together
may also form a phenyl, cyclopentyl or cyclohexyl ring, it being
possible for these rings to carry two groups R.sup.2 and R.sup.3,
R.sup.2 and R.sup.3 independently of one another are hydrogen,
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
halomethyl; in case a), if R.sup.2, R.sup.3, R.sup.4 and R.sup.5
are hydrogen: X is phenyl substituted by a group
--C(R.sup.6).dbd.NOR.sup.7, wherein R.sup.6 is
C.sub.1-C.sub.4-alkyl and R.sup.7 is C.sub.1-C.sub.8-alkyl, benzyl,
C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl or
C.sub.2-C.sub.4-haloalkynyl; and in case b), if at least one of the
groups R.sup.2, R.sup.3, R.sup.4 and R.sup.5 is not hydrogen: X is
phenyl, naphthyl or a five- or six-membered saturated, partially
unsaturated or aromatic heterocycle which is attached via a carbon
atom and contains one to four heteroatoms selected from the group
consisting of O, N and S, where X may carry one to four groups
R.sup.a: R.sup.a is halogen, cyano, nitro, C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-haloalkoxy,
C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.4-alkoxycarbonyl,
--C(R.sup.6).dbd.NOR.sup.7, C.sub.1-C.sub.4-alkylaminocarbonyl,
di(C.sub.1-C.sub.4-alkyl)aminocarbonyl or phenyl or phenoxy, where
the rings may carry one to three groups R.sup.b: R.sup.b is
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-C.sub.4-haloalkyl or C.sub.1-C.sub.8-haloalkoxy; R.sup.a or
R.sup.b may also be a C.sub.3-C.sub.4-alkylene or a
C.sub.4-alkenylene group which, together with two adjacent ring
members of the phenyl ring to which it is attached, forms a ring
which may be substituted by one or more of the abovementioned
groups R.sup.a or R.sup.b.
2. The method according to claim 1, wherein the treating is
performed before the infection of the materials.
3. The method according to claim 1, wherein R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 of formula I are independently of one another
hydrogen, methyl, fluorine, chlorine, CF.sub.3, OCF.sub.3 or
OCHF.sub.2.
4. The method according to claim 1 or 3, wherein R.sup.1 of formula
I is hydrogen, methyl, methoxy, ethoxy, allyl or propargyl.
5. The method according to claim 1 or 3, wherein X of formula I is
a phenyl ring which is substituted in the para position.
6. The method according to claim 1 or 3, wherein X of formula I is
an aromatic heterocycle.
7. The method according to claim 4, wherein X of formula I is a
phenyl ring which is substituted in the para position.
8. The method according to claim 4, wherein X of formula I is an
aromatic heterocycle.
Description
[0001] This application is a Divisional of pending U.S. application
Ser. No. 10/570,893, filed on Mar. 7, 2006, which is the national
phase of PCT/EP2004/010124 filed on Sep. 10, 2004, which designated
the United States and which claims priority to European Application
No. 03021098.3 filed on Sep. 18, 2003. The entire contents of the
above applications are hereby incorporated by reference.
[0002] The present invention relates to sulfonamides of the formula
I
##STR00002##
where the substituents are as follows: R.sup.1 is hydrogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl or benzyl;
R.sup.2, R.sup.3, R.sup.4, R.sup.5 independently of one another are
hydrogen, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-halomethyl; R.sup.2 and R.sup.3 together may also form a
phenyl, cyclopentyl or cyclohexyl ring, it being possible for these
rings to carry two groups R.sup.2' and R.sup.3', R.sup.2', R.sup.3'
independently of one another are hydrogen, halogen,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or
C.sub.1-halomethyl; in case a), if R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 are hydrogen: X is phenyl substituted by a group
--C(R.sup.6).dbd.NOR.sup.7, where R.sup.6 is C.sub.1-C.sub.4-alkyl
and R.sup.7 is C.sub.1-C.sub.8-alkyl, benzyl,
C.sub.2-C.sub.4-alkenyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl or
C.sub.2-C.sub.4-haloalkynyl; and in case b), if at least one of the
groups R.sup.2, R.sup.3, R.sup.4 and R.sup.5 is not hydrogen: X is
phenyl, naphthyl or a five- or six-membered saturated, partially
unsaturated or aromatic heterocycle which is attached via a carbon
atom and contains one to four heteroatoms selected from the group
consisting of O, N and S, where X may carry one to four groups
R.sup.a: R.sup.a is halogen, cyano, nitro, C.sub.1-C.sub.8-alkyl,
C.sub.1-C.sub.8-alkoxy, C.sub.1-C.sub.8-haloalkoxy,
C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.4-alkoxycarbonyl,
--C(R.sup.6).dbd.NOR.sup.7, C.sub.1-C.sub.4-alkylaminocarbonyl,
di(C.sub.1-C.sub.4-alkyl)aminocarbonyl or phenyl or phenoxy, where
the rings may carry one to three groups R.sup.b: R.sup.b is
halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.1-haloalkyl or C.sub.1-haloalkoxy; R.sup.a or R.sup.b may
also be a C.sub.3-C.sub.4-alkylene or a C.sub.4-alkenylene group
which, together with two adjacent ring members of the phenyl ring
to which it is attached, forms a ring which may be substituted by
one or more of the abovementioned groups R.sup.a or R.sup.b.
[0003] Moreover, the invention relates to processes for preparing
these compounds, to compositions comprising them and to their use
for controlling phytopathogenic harmful fungi.
[0004] In a general manner, DE-A 31 22 700 and WO 00/06083 disclose
pyridinosulfonamides as pharmaceuticals. The general disclosure of
these documents comprises 4-pyridinemethylsulfonamides.
[0005] Individual 4-pyridinemethylsulfonamides are known from EP-A
206 581 and Lieb. Ann. Chem. 641 (1990). The compounds described in
the publications mentioned are suitable for controlling harmful
fungi.
[0006] However, in many cases their action is unsatisfactory. Based
on this, it is an object of the present invention to provide
compounds having improved action and/or a broader activity
spectrum.
[0007] Accordingly we have found that this object is achieved by
the compounds defined at the outset. Furthermore, we have found
processes and intermediates for their preparation, compositions
comprising them and methods for controlling harmful fungi using the
compounds I.
[0008] The compounds according to the invention differ from those
described in EP-A 206 581, DE-A 31 22 700 and WO 00/06083 by the
4-pyridinomethyl group and from the compounds known from Lieb. Ann.
Chem. 641 (1990) by the substitution of the pyridine ring or group
X.
[0009] Compared to the known compounds, the compounds of the
formula I have increased activity against harmful fungi.
[0010] The compounds according to the invention can be obtained by
different routes. Advantageously, they are obtained from pyridine
derivatives of the formula II by reaction with sulfonic acids or
activated sulfonic acid derivatives of the formula III in which X
is as defined in claim 1, under basic conditions. In formula III, L
is hydroxyl or halogen, preferably chlorine.
##STR00003##
[0011] This reaction is usually carried out at temperatures from
-30.degree. C. to 120.degree. C., preferably from -10.degree. C. to
100.degree. C., in an inert organic solvent in the presence of a
base [cf. Lieb. Ann. Chem. 641 (1990)].
[0012] Suitable solvents are aliphatic hydrocarbons, such as
pentane, hexane, cyclohexane and petroleum ether, aromatic
hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated
hydrocarbons, such as methylene chloride, chloroform and
chlorobenzene, ethers, such as diethyl ether, diisopropyl ether,
tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran,
nitrites, such as acetonitrile and propionitrile, ketones, such as
acetone, methylethyl ketone, diethyl ketone and tert-butyl methyl
ketone, and also dimethyl sulfoxide, dimethylformamide and
dimethylacetamide, particularly preferably diisopropyl ether,
diethyl ether and tetrahydrofuran. It is also possible to use
mixtures of the solvents mentioned.
[0013] Suitable bases are, in general, inorganic compounds, such as
alkali metal and alkaline earth metal hydroxides, such as lithium
hydroxide, sodium hydroxide, potassium hydroxide and calcium
hydroxide, alkali metal and alkaline earth metal oxides, such as
lithium oxide, sodium oxide, calcium oxide, and magnesium oxide,
alkali metal and alkaline earth metal hydrides, such as lithium
hydride, sodium hydride, potassium hydride and calcium hydride,
alkali metal and alkaline earth metal carbonates, such as lithium
carbonate, potassium carbonate and calcium carbonate, and also
alkali metal bicarbonates, such as sodium bicarbonate, moreover
organic bases, for example tertiary amines, such as trimethylamine,
triethylamine, triisopropylethylamine and N-methylpiperidine,
pyridine, substituted pyridines, such as collidine, lutidine and
4-dimethylaminopyridine, and also bicyclic amines. Particular
preference is given to pyridine, triethylamine and potassium
carbonate. The bases are generally employed in catalytic amounts;
however, they can also be used in equimolar amounts, in excess or,
if appropriate, as solvent.
[0014] The starting materials are generally reacted with one
another in equimolar amounts. In terms of yield, it may be
advantageous to employ an excess of II, based on III.
[0015] The starting materials required for preparing the compounds
I are commercially available or known from the literature [J. fur
praktische Chemie, p. 695 (1994); Heterocycles, p. 675 (1995);
Tetrahedron, p. 12483 (1996); Chem. Pharm. Bull., p. 1927 (1973);
J. Chem. Soc., p. 426 (1942); EP-A 983 982; Synthesis, p. 852
(1986)] or can be prepared in accordance with the literature
cited.
[0016] The reaction mixtures are worked up in a customary manner,
for example by mixing with water, separating the phases and, if
appropriate, chromatographic purification of the crude products.
Some of the intermediates and end products are obtained in the form
of colorless or slightly brownish viscous oils which are purified
or freed from volatile components under reduced pressure and at
moderately elevated temperature. If the intermediates and end
products are obtained as solids, purification can also be carried
out by recrystallization or digestion.
[0017] If individual compounds I cannot be obtained by the routes
described above, they can be prepared by derivatization of other
compounds I.
[0018] However, if the synthesis yields mixtures of isomers, a
separation is generally not necessarily required since in some
cases the individual isomers can be interconverted during work-up
for use or during application (for example under the action of
light, acids or bases). Such conversions may also take place after
use, for example in the treatment of plants in the treated plant,
or in the harmful fungus to be controlled.
[0019] In the definitions of the symbols given in the formulae
above, collective terms were used which are generally
representative of the following substituents:
halogen: fluorine, chlorine, bromine and iodine; alkyl: saturated
straight-chain or branched hydrocarbon radicals having 1 to 4, 6 or
8 carbon atoms, for example C.sub.1-C.sub.6-alkyl such as methyl,
ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,
2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,
hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl:
straight-chain or branched alkyl groups having 1 to 2 or 4 carbon
atoms (as mentioned above), where in these groups some or all of
the hydrogen atoms may be replaced by halogen atoms as mentioned
above; in particular, C.sub.1-C.sub.2-haloalkyl, such as
chloromethyl, bromomethyl, dichloromethyl, trichloromethyl,
fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,
1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
2,2,2-trichloroethyl, pentafluoroethyl or 1,1,1-trifluoroprop-2-yl;
alkenyl: unsaturated straight-chain or branched hydrocarbon
radicals having 2 to 4, 6 or 8 carbon atoms and one or two double
bonds in any position, for example C.sub.2-C.sub.6-alkenyl, such as
ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl,
2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,
1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and
1-ethyl-2-methyl-2-propenyl; haloalkenyl: unsaturated
straight-chain or branched hydrocarbon radicals having 2 to 6
carbon atoms and one or two double bonds in any position (as
mentioned above), where in these groups some or all of the hydrogen
atoms may be replaced by halogen atoms as mentioned above, in
particular by fluorine, chlorine and bromine; alkynyl:
straight-chain or branched hydrocarbon groups having 2 to 4, 6 or 8
carbon atoms and one or two triple bonds in any position, for
example C.sub.2-C.sub.6-alkynyl, such as ethynyl, 1-propynyl,
2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl,
1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,
1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,
1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,
3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,
1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,
2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,
4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,
1-ethyl-3-butynyl, 2-ethyl-3-butynyl and
1-ethyl-1-methyl-2-propynyl; cycloalkyl: mono- or bicyclic
saturated hydrocarbon groups having 3 to 6 or 8 carbon ring
members, for example C.sub.3-C.sub.8-cycloalkyl such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and
cyclooctyl; five- to ten-membered saturated, partially unsaturated
or aromatic heterocycle which contains one to four heteroatoms from
the group consisting of O, N and S: [0020] 5- or 6-membered
heterocyclyl which contains one to three nitrogen atoms and/or one
oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for
example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl,
3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,
5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl,
5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl,
2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,
2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl,
2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl,
3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,
4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl,
4-hexahydropyridazinyl, 2-hexahydropyrimidinyl,
4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl and 2-piperazinyl;
[0021] 5-membered heteroaryl which contains one to four nitrogen
atoms or one to three nitrogen atoms and one sulfur or oxygen atom:
5-membered heteroaryl groups which, in addition to carbon atoms,
may contain one to four nitrogen atoms or one to three nitrogen
atoms and one sulfur or oxygen atom as ring members, for example,
2-thienyl, 3-thienyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,
2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl,
5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3,4-triazol-2-yl;
[0022] 6-membered heteroaryl which contains one to three or one to
four nitrogen atoms: 6-membered heteroaryl groups which, in
addition to carbon atoms, may contain one to three or one to four
nitrogen atoms as ring members, for example 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,
2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
alkylene: divalent unbranched chains of 3 to 5 CH.sub.2 groups, for
example CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2,
CH.sub.2CH.sub.2CH.sub.2CH.sub.2 and
CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2; oxyalkylene: divalent
unbranched chains of 2 to 4 CH.sub.2 groups, where one valency is
attached to the skeleton via an oxygen atom, for example
OCH.sub.2CH.sub.2, OCH.sub.2CH.sub.2CH.sub.2 and
OCH.sub.2CH.sub.2CH.sub.2CH.sub.2; oxyalkyleneoxy: divalent
unbranched chains of 1 to 3 CH.sub.2 groups, where both valencies
are attached to the skeleton via an oxygen atom, for example
OCH.sub.2O, OCH.sub.2CH.sub.2O and OCH.sub.2CH.sub.2CH.sub.2O;
Alkenylene: divalent unbranched chains of 4 or 6 CH groups which
are linked by conjugated C.dbd.C double bonds, for example
CH.dbd.CH or CH.dbd.CH--CH.dbd.CH.
[0023] The scope of the present invention includes the (R)- and
(S)-isomers and the racemates of compounds of the formula I having
chiral centers.
[0024] With a view to the intended use of the sulfonamides of the
formula I, particular preference is given to the following meanings
of the substituents, in each case on their own or in
combination:
[0025] The invention preferably provides compounds of the formula
I, in which R.sup.1 is hydrogen, methyl, methoxy, ethoxy, allyl or
propargyl, in particular hydrogen or methyl.
[0026] Preference is likewise given to compounds of the formula I,
in which R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently of one
another are hydrogen, methyl, ethyl, fluorine, chlorine, CF.sub.3,
OCF.sub.3 or OCHF.sub.2.
[0027] In addition, preference is also given to compounds of the
formula I in which at least one, in particular one or two, groups
selected from the group consisting of R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 are not hydrogen.
[0028] Preference is likewise also given to compounds of the
formula I which are substituted by two identical groups selected
from the group consisting of R.sup.2, R.sup.3, R.sup.4 and
R.sup.5.
[0029] Further preferred embodiments of the formula I are in each
case per se compounds of the formulae I.1 to I.6 where the
variables are as defined for formula I:
##STR00004##
[0030] Preference is given to compounds of the formula I.4 in which
the groups R.sup.2' and R.sup.3' are located in the
6,7-position.
[0031] Particular preference is given to compounds of the formula I
in which X is a phenyl ring which carries a group R.sup.a in the
para-position; these compounds correspond to the formula IA:
##STR00005##
[0032] Particular preference is given to compounds of the formula I
in which R.sup.a has the following meanings:
C(R.sup.6).dbd.NOR.sup.7, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,
tert-butoxy, chloromethyl, dichloromethyl, trichloromethyl,
fluoromethyl, difluoromethyl, trifluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
2,2,2-trichloroethyl, pentafluoroethyl, trichloromethoxy,
fluoromethoxy, difluoromethoxy, trifluoromethoxy,
chlorodifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,
2,2,2-trichloroethoxy and pentafluoroethoxy.
[0033] A particularly preferred embodiment of R.sup.6 is methyl;
R.sup.7 is preferably methyl, ethyl, allyl or propargyl, it being
possible for the groups R.sup.7 to be halogenated.
[0034] In particular with a view to their use, preference is given
to the compounds I compiled in the tables below. Moreover, the
groups mentioned for a substituent in the tables are per se,
independently of the combination in which they are mentioned, a
particularly preferred embodiment of the substituent in
question.
Table 1
[0035] Compounds of the formula IA, in which R.sup.2, R.sup.3,
R.sup.4 and R.sup.5 are hydrogen and the combination of R.sup.1 and
R.sup.a corresponds for each compound to one row A-1 to A-14 of
Table A
Table 2
[0036] Compounds of the formula IA.1, in which R.sup.1 and R.sup.3
are methyl and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
##STR00006##
Table 3
[0037] Compounds of the formula IA.1, in which R.sup.2 and R.sup.3
are fluorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 4
[0038] Compounds of the formula IA.1, in which R.sup.2 and R.sup.3
are chlorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 5
[0039] Compounds of the formula IA.1, in which R.sup.2 and R.sup.3
are methoxy and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 6
[0040] Compounds of the formula IA.1, in which R.sup.2 and R.sup.3
are trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
Table 7
[0041] Compounds of the formula IA.2, in which R.sup.3 and R.sup.5
are methyl and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
##STR00007##
Table 8
[0042] Compounds of the formula IA.2, in which R.sup.3 and R.sup.5
are fluorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 9
[0043] Compounds of the formula IA.2, in which R.sup.3 and R.sup.5
are chlorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 10
[0044] Compounds of the formula IA.2, in which R.sup.3 and R.sup.5
are methoxy and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 11
[0045] Compounds of the formula IA.2, in which R.sup.3 and R.sup.5
are trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
Table 12
[0046] Compounds of the formula IA.3, in which R.sup.2 and R.sup.4
are methyl and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
##STR00008##
Table 13
[0047] Compounds of the formula IA.3, in which R.sup.2 and R.sup.4
are fluorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 14
[0048] Compounds of the formula IA.3, in which R.sup.2 and R.sup.4
are chlorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 15
[0049] Compounds of the formula IA.3, in which R.sup.2 and R.sup.4
are methoxy and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 16
[0050] Compounds of the formula IA.3, in which R.sup.2 and R.sup.4
are trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
Table 17
[0051] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are hydrogen and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
##STR00009##
Table 18
[0052] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are methyl and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 19
[0053] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are fluorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 20
[0054] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are chlorine and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 21
[0055] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are methoxy and the combination of R.sup.1 and R.sup.a corresponds
for each compound to one row of Table A
Table 22
[0056] Compounds of the formula IA.4', in which R.sup.2 and R.sup.3
are trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
Table 23
[0057] Compounds of the formula IA.5, in which R.sup.2 is methyl
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
##STR00010##
Table 24
[0058] Compounds of the formula IA.5, in which R.sup.2 is fluorine
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 25
[0059] Compounds of the formula IA.5, in which R.sup.2 is chlorine
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 26
[0060] Compounds of the formula IA.5, in which R.sup.2 is methoxy
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 27
[0061] Compounds of the formula IA.5, in which R.sup.2 is
trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
Table 28
[0062] Compounds of the formula IA.6, in which R.sup.3 is methyl
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
##STR00011##
Table 29
[0063] Compounds of the formula IA.6, in which R.sup.3 is fluorine
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 30
[0064] Compounds of the formula IA.6, in which R.sup.3 is chlorine
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 31
[0065] Compounds of the formula IA.6, in which R.sup.3 is methoxy
and the combination of R.sup.1 and R.sup.a corresponds for each
compound to one row of Table A
Table 32
[0066] Compounds of the formula IA.6, in which R.sup.3 is
trifluoromethoxy and the combination of R.sup.1 and R.sup.a
corresponds for each compound to one row of Table A
TABLE-US-00001 TABLE A No. R.sup.1 R.sup.a A-1 H
C(CH.sub.3).dbd.NOCH.sub.3 A-2 CH.sub.3 C(CH.sub.3).dbd.NOCH.sub.3
A-3 H C(CH.sub.3).dbd.NOCH.sub.2CH.sub.3 A-4 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.2CH.sub.3 A-5 H
C(CH.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.2 A-6 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.2CH.dbd.CH.sub.2 A-7 H
C(CH.sub.3).dbd.NOCH.sub.2C.ident.CH A-8 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.2C.ident.CH A-9 H
C(CH.sub.3).dbd.NOCH.sub.2CCl.dbd.CH.sub.2 A-10 CH.sub.3
C(CH.sub.3).dbd.NOCH.sub.2CCl.dbd.CH.sub.2 A-11 H H A-12 CH.sub.3 H
A-13 H CH.sub.3 A-14 CH.sub.3 CH.sub.3 A-15 H CH.sub.2CH.sub.3 A-16
CH.sub.3 CH.sub.2CH.sub.3 A-17 H CH.sub.2CH.sub.2CH.sub.3 A-18
CH.sub.3 CH.sub.2CH.sub.2CH.sub.3 A-19 H CH(CH.sub.3).sub.2 A-20
CH.sub.3 CH(CH.sub.3).sub.2 A-21 H CH.sub.2CH.sub.2CH.sub.2CH.sub.3
A-22 CH.sub.3 CH.sub.2CH.sub.2CH.sub.2CH.sub.3 A-23 H
CH(CH.sub.3)CH.sub.2CH.sub.3 A-24 CH.sub.3
CH(CH.sub.3)CH.sub.2CH.sub.3 A-25 H CH.sub.2CH(CH.sub.3).sub.2 A-26
CH.sub.3 CH.sub.2CH(CH.sub.3).sub.2 A-27 H C(CH.sub.3).sub.3 A-28
CH.sub.3 C(CH.sub.3).sub.3 A-29 H OCH.sub.3 A-30 CH.sub.3 OCH.sub.3
A-31 H OCH.sub.2CH.sub.3 A-32 CH.sub.3 OCH.sub.2CH.sub.3 A-33 H
OCH.sub.2CH.sub.2CH.sub.3 A-34 CH.sub.3 OCH.sub.2CH.sub.2CH.sub.3
A-35 H OCH(CH.sub.3).sub.2 A-36 CH.sub.3 OCH(CH.sub.3).sub.2 A-37 H
OCH.sub.2CH.sub.2CH.sub.2CH.sub.3 A-38 CH.sub.3
OCH.sub.2CH.sub.2CH.sub.2CH.sub.3 A-39 H
OCH(CH.sub.3)CH.sub.2CH.sub.3 A-40 CH.sub.3
OCH(CH.sub.3)CH.sub.2CH.sub.3 A-41 H OCH.sub.2CH(CH.sub.3).sub.2
A-42 CH.sub.3 OCH.sub.2CH(CH.sub.3).sub.2 A-43 H OC(CH.sub.3).sub.3
A-44 CH.sub.3 OC(CH.sub.3).sub.3 A-45 H CCl.sub.3 A-46 CH.sub.3
CCl.sub.3 A-47 H CHF.sub.2 A-48 CH.sub.3 CHF.sub.2 A-49 H CF.sub.3
A-50 CH.sub.3 CF.sub.3 A-51 H CHClF A-52 CH.sub.3 CHClF A-53 H
CH.sub.2CHF.sub.2 A-54 CH.sub.3 CH.sub.2CHF.sub.2 A-55 H
CH.sub.2CF.sub.3 A-56 CH.sub.3 CH.sub.2CF.sub.3 A-57 H
CF.sub.2CF.sub.3 A-58 CH.sub.3 CF.sub.2CF.sub.3 A-59 H OCHCl.sub.2
A-60 CH.sub.3 OCHCl.sub.2 A-61 H OCCl.sub.3 A-62 CH.sub.3
OCCl.sub.3 A-63 H OCH.sub.2F A-64 CH.sub.3 OCH.sub.2F A-65 H
OCHF.sub.2 A-66 CH.sub.3 OCHF.sub.2 A-67 H OCF.sub.3 A-68 CH.sub.3
OCF.sub.3 A-69 H OCH.sub.2CHF.sub.2 A-70 CH.sub.3
OCH.sub.2CHF.sub.2 A-71 H OCH.sub.2CF.sub.3 A-72 CH.sub.3
OCH.sub.2CF.sub.3 A-73 H OCH.sub.2CHClF A-74 CH.sub.3
OCH.sub.2CHClF A-75 H OCH.sub.2CCl.sub.3 A-76 CH.sub.3
OCH.sub.2CCl.sub.3 A-77 H OCF.sub.2CF.sub.3 A-78 CH.sub.3
OCF.sub.2CF.sub.3 A-79 H C.sub.6H.sub.5 A-80 CH.sub.3
C.sub.6H.sub.5 A-81 H OC.sub.6H.sub.5 A-82 CH.sub.3
OC.sub.6H.sub.5
[0067] The compounds I are suitable as fungicides. They are
distinguished by an outstanding effectiveness against a broad
spectrum of phytopathogenic fungi, especially from the classes of
the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some
are systemically effective and can be used in plant protection as
foliar and soil fungicides.
[0068] They are particularly important in the control of a
multitude of fungi on various cultivated plants, such as wheat,
rye, barley, oats, rice, maize, grass, bananas, cotton, soya,
coffee, sugar cane, vines, fruits and ornamental plants, and
vegetables, such as cucumbers, beans, tomatoes, potatoes and
cucurbits, and on the seeds of these plants.
[0069] They are especially suitable for controlling the following
plant diseases:
Alternaria species on fruit and vegetables, Bipolaris and
Drechslera species on cereals, rice and lawns, Blumeria graminis
(powdery mildew) on cereals, Botrytis cinerea (gray mold) on
strawberries, vegetables, ornamental plants and grapevines,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Fusarium and Verticillium species on various plants, Mycosphaerella
species on cereals, bananas and peanuts, Phytophthora infestans on
potatoes and tomatoes, Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples, Pseudocercosporella
herpotrichoides on wheat and barley, Pseudoperonospora species on
hops and cucumbers, Puccinia species on cereals, Pyricularia oryzae
on rice, Rhizoctonia species on cotton, rice and lawns, Septoria
tritici and Stagonospora nodorum on wheat, Uncinula necator on
grapevines, Ustilago species on cereals and sugar cane, and
Venturia species (scab) on apples and pears.
[0070] The compounds I are also suitable for controlling harmful
fungi, such as Paecilomyces variotii, in the protection of
materials (e.g. wood, paper, paint dispersions, fibers or fabrics)
and in the protection of stored products.
[0071] The compounds I are employed by treating the fungi or the
plants, seeds, materials or soil to be protected from fungal attack
with a fungicidally effective amount of the active compounds. The
application can be carried out both before and after the infection
of the materials, plants or seeds by the fungi.
[0072] The fungicidal compositions generally comprise between 0.1
and 95%, preferably between 0.5 and 90%, by weight of active
compound.
[0073] When employed in plant protection, the amounts applied are,
depending on the kind of effect desired, between 0.01 and 2.0 kg of
active compound per ha.
[0074] In seed treatment, amounts of active compound of 0.001 to 1
g, preferably 0.01 to 0.05 g, per kilogram of seed are generally
required.
[0075] When used in the protection of materials or stored products,
the amount of active compound applied depends on the kind of
application area and on the desired effect. Amounts customarily
applied in the protection of materials are, for example, 0.001 g to
2 kg, preferably 0.005 g to 1 kg, of active compound per cubic
meter of treated material.
[0076] The compounds I can be converted into the customary
formulations, for example solutions, emulsions, suspensions, dusts,
powders, pastes and granules. The application form depends on the
particular purpose; in each case, it should ensure a fine and
uniform distribution of the compound according to the
invention.
[0077] The formulations are prepared in a known manner, for example
by extending the active compound with solvents and/or carriers, if
desired using emulsifiers and dispersants. Solvents/auxiliaries
which are suitable are essentially: [0078] water, aromatic solvents
(for example Solvesso products, xylene), paraffins (for example
mineral oil fractions), alcohols (for example methanol, butanol,
pentanol, benzyl alcohol), ketones (for example cyclohexanone,
gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol
diacetate), glycols, fatty acid dimethylamides, fatty acids and
fatty acid esters. In principle, solvent mixtures may also be used,
[0079] carriers such as ground natural minerals (for example
kaolins, clays, talc, chalk) and ground synthetic minerals (for
example highly disperse silica, silicates); emulsifiers such as
nonionic and anionic emulsifiers (for example polyoxyethylene fatty
alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants
such as lignosulfite waste liquors and methylcellulose.
[0080] Suitable surfactants are alkali metal, alkaline earth metal
and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,
phenolsulfonic acid, dibutylnaphthalenesulfonic acid,
alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol
sulfates, fatty acids and sulfated fatty alcohol glycol ethers,
furthermore condensates of sulfonated naphthalene and naphthalene
derivatives with formaldehyde, condensates of naphthalene or of
naphthalenesulfonic acid with phenol and formaldehyde,
polyoxyethylene octylphenol ether, ethoxylated isooctylphenol,
octylphenol, nonylphenol, alkylphenol polyglycol ethers,
tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether,
alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol
ether acetal, sorbitol esters, lignosulfite waste liquors and
methylcellulose.
[0081] Suitable for the preparation of directly sprayable
solutions, emulsions, pastes or oil dispersions are mineral oil
fractions of medium to high boiling point, such as kerosene or
diesel oil, furthermore coal tar oils and oils of vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons, for
example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated
naphthalenes or their derivatives, methanol, ethanol, propanol,
butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar
solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or
water.
[0082] Powders, materials for spreading and dustable products can
be prepared by mixing or concomitantly grinding the active
substances with a solid carrier.
[0083] Granules, for example coated granules, impregnated granules
and homogeneous granules, can be prepared by binding the active
compounds to solid carriers. Examples of solid carriers are mineral
earths such as silica gels, silicates, talc, kaolin, attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers, such as, for example, ammonium
sulfate, ammonium phosphate, ammonium nitrate, ureas, and products
of vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders and other solid carriers.
[0084] In general, the formulations comprise between 0.01 and 95%
by weight, preferably between 0.1 and 90% by weight, of the active
compound. The active compounds are employed in a purity of from 90%
to 100%, preferably 95% to 100% (according to NMR spectrum).
[0085] The following are examples of formulations: 1. Products for
dilution with water
A Water-Soluble Concentrates (SL)
[0086] 10 parts by weight of a compound according to the invention
are dissolved in water or in a water-soluble solvent. As an
alternative, wetters or other auxiliaries are added. The active
compound dissolves upon dilution with water.
B Dispersible Concentrates (DC)
[0087] 20 parts by weight of a compound according to the invention
are dissolved in cyclohexanone with addition of a dispersant, for
example polyvinylpyrrolidone. Dilution with water gives a
dispersion.
C Emulsifiable Concentrates (EC)
[0088] 15 parts by weight of a compound according to the invention
are dissolved in xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case
5%). Dilution with water gives an emulsion.
D Emulsions (EW, EO)
[0089] 40 parts by weight of a compound according to the invention
are dissolved in xylene with addition of calcium
dodecylbenzenesulfonate and castor oil ethoxylate (in each case
5%). This mixture is introduced into water by means of an
emulsifying machine (Ultraturrax) and made into a homogeneous
emulsion. Dilution with water gives an emulsion.
E Suspensions (SC, OD)
[0090] In an agitated ball mill, 20 parts by weight of a compound
according to the invention are comminuted with addition of
dispersants, wetters and water or an organic solvent to give a fine
active compound suspension. Dilution with water gives a stable
suspension of the active compound.
F Water-Dispersible Granules and Water-Soluble Granules (WG,
SG)
[0091] 50 parts by weight of a compound according to the invention
are ground finely with addition of dispersants and wetters and made
into water-dispersible or water-soluble granules by means of
technical appliances (for example extrusion, spray tower, fluidized
bed). Dilution with water gives a stable dispersion or solution of
the active compound.
G Water-Dispersible Powders and Water-Soluble Powders (WP, SP)
[0092] 75 parts by weight of a compound according to the invention
are ground in a rotor-stator mill with addition of dispersants,
wetters and silica gel. Dilution with water gives a stable
dispersion or solution of the active compound.
Products to be Applied Undiluted
H Dustable Powders (DP)
[0093] 5 parts by weight of a compound according to the invention
are ground finely and mixed intimately with 95% of finely divided
kaolin. This gives a dustable product.
I Granules (GR, FG, GG, MG)
[0094] 0.5 part by weight of a compound according to the invention
is ground finely and associated with 95.5% carriers. Current
methods are extrusion, spray-drying or the fluidized bed. This
gives granules to be applied undiluted.
J ULV Solutions (UL)
[0095] 10 parts by weight of a compound according to the invention
are dissolved in an organic solvent, for example xylene. This gives
a product to be applied undiluted.
[0096] The active compounds can be used as such, in the form of
their formulations or the use forms prepared therefrom, for example
in the form of directly sprayable solutions, powders, suspensions
or dispersions, emulsions, oil dispersions, pastes, dustable
products, materials for spreading, or granules, by means of
spraying, atomizing, dusting, spreading or pouring. The use forms
depend entirely on the intended purposes; the intention is to
ensure in each case the finest possible distribution of the active
compounds according to the invention.
[0097] Aqueous use forms can be prepared from emulsion
concentrates, pastes or wettable powders (sprayable powders, oil
dispersions) by adding water. To prepare emulsions, pastes or oil
dispersions, the substances, as such or dissolved in an oil or
solvent, can be homogenized in water by means of a wetter,
tackifier, dispersant or emulsifier. Alternatively, it is possible
to prepare concentrates composed of active substance, wetter,
tackifier, dispersant or emulsifier and, if appropriate, solvent or
oil, and such concentrates are suitable for dilution with
water.
[0098] The active compound concentrations in the ready-to-use
preparations can be varied within relatively wide ranges. In
general, they are between 0.0001 and 10%, preferably between 0.01
and 1%.
[0099] The active compounds may also be used successfully in the
ultra-low-volume process (ULV), by which it is possible to apply
formulations comprising over 95% by weight of active compound, or
even to apply the active compound without additives.
[0100] Various types of oils, wetters, adjuvants, herbicides,
fungicides, other pesticides, or bactericides may be added to the
active compounds, if appropriate not until immediately prior to use
(tank mix). These agents can be admixed with the agents according
to the invention in a weight ratio of 1:10 to 10:1.
[0101] The compositions according to the invention can, in the use
form as fungicides, also be present together with other active
compounds, e.g. with herbicides, insecticides, growth regulators,
fungicides or else with fertilizers. Mixing the compounds I or the
compositions comprising them in the use form as fungicides with
other fungicides results in many cases in an expansion of the
fungicidal spectrum of activity being obtained.
[0102] The following list of fungicides, in conjunction with which
the compounds according to the invention can be used, is intended
to illustrate the possible combinations but does not limit
them:
acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,
amine derivatives, such as aldimorph, dodine, dodemorph,
fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or
tridemorph, anilinopyrimidines, such as pyrimethanil, mepanipyrim
or cyprodinyl, antibiotics, such as cycloheximide, griseofulvin,
kasugamycin, natamycin, polyoxin or streptomycin, azoles, such as
bitertanol, bromoconazole, cyproconazole, difenoconazole,
dinitroconazole, epoxiconazole, fenbuconazole, fluquinconazole,
flusilazole, hexaconazole, imazalil, metconazole, myclobutanil,
penconazole, propiconazole, prochloraz, prothioconazole,
tebuconazole, triadimefon, triadimenol, triflumizole or
triticonazole, dicarboximides, such as iprodione, myclozolin,
procymidone or vinclozolin, dithiocarbamates, such as ferbam,
nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate,
thiram, ziram or zineb, heterocyclic compounds, such as anilazine,
benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid,
dazomet, dithianon, famoxadone, fenamidone, fenarimol,
fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil,
nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon,
quinoxyfen, silthiofam, thiabendazole, thifluzamide,
thiophanate-methyl, tiadinil, tricyclazole or triforine, copper
fungicides, such as Bordeaux mixture, copper acetate, copper
oxychloride or basic copper sulfate, nitrophenyl derivatives, such
as binapacryl, dinocap, dinobuton or nitrophthal-isopropyl,
phenylpyrroles, such as fenpiclonil or fludioxonil, sulfur, other
fungicides, such as acibenzolar-S-methyl, benthiavalicarb,
carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet,
diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam,
fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam,
fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,
metrafenone, pencycuron, propamocarb, phthalide, tolclofos-methyl,
quintozene or zoxamide, strobilurins, such as azoxystrobin,
dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin,
orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,
sulfenic acid derivatives, such as captafol, captan, dichlofluanid,
folpet or tolylfluanid, cinnamides and analogous compounds, such as
dimethomorph, flumetover or flumorph.
SYNTHESIS EXAMPLES
[0103] The procedures described in the synthesis examples below
were used to prepare further compounds I by appropriate
modification of the starting compounds. The compounds thus obtained
are listed in the tables below, together with physical data.
Example 1
Preparation of 4-acetyl-N-pyridin-4-ylmethylphenylsulfonamide
[0104] At -10.degree. C., a solution of 4.95 g (45.7 mmol) of
4-(aminomethyl)pyridine (4-picolylamine) in 10 ml of diethyl ether
was added dropwise to a solution of 10 g (45.7 mmol) of
4-acetylsulfonyl chloride in 150 ml of diethyl ether, and the
solution was then stirred at 20-25.degree. C. for about 18 hours.
The product was filtered off with suction and the residue was
washed with dilute NaHCO.sub.3 solution and water and then dried.
This gave 5.2 g of the title compound of m.p.: 162-167.degree.
C.
Example 2
Preparation of
4-(1-ethoxyiminoethyl)-N-pyridin-4-ylmethylphenylsulfonamide
[0105] 0.42 g of a 40% strength aqueous O-ethylhydroxylamine
solution was added to a solution of 0.4 g (1.3 mmol) of the
compound from Example 1 in 20 ml of methanol. Using 10% strength
hydrochloric acid, the mixture was acidified to pH 4, and the
solution was then stirred at 20-25.degree. C. for about 18 hours.
The reaction solution was poured into water and adjusted to pH 8
using NaHCO.sub.3. The mixture was then extracted with methyl
tert-butyl ether (MtBE), and the combined organic phases were
washed with water and dried. Removal of the solvent gave 0.4 g of
the title compound as a viscous oil.
[0106] .sup.1H-NMR (.delta., CDCl.sub.3,): 8.5 (d, 2H); 7.5 (m,
4H); 7.1 (d, 2H); 5.0 (t, 1H); 4.25 (q, 2H); 4.1 (d, 2H); 2.25 (s,
3H); 1.3 (t, 3H).
Example 3
Preparation of
4-(1-ethoxyimino-ethyl)-N-methyl-N-pyridin-4-ylmethylphenylsulfonamide
[0107] 0.4 g (1.2 mmol) of the compound from Example 2 was added to
a slurry of 0.04 g (1.32 mmol) of NaH (95% pure) in 50 ml of
dimethylformamide (DMF), and the mixture was then stirred at
20-25.degree. C. for 10 min. A solution of 0.17 g (1.2 mmol) of
iodomethane in 10 ml of DMF was then added dropwise, and the
combined reaction solution was stirred at 20-25.degree. C. for
about 18 hours, poured into water and then extracted with MtBE. The
organic phases were washed with water and then dried. Removal of
the solvent gave 0.3 g of the title compound as a viscous oil.
[0108] .sup.1H-NMR (.delta., CDCl.sub.3,): 8.6 (d, 2H); 7.8 (m,
4H); 7.25 (d, 2H); 4.25 (q, 2H); 4.1 (d, 2H); 2.6 (s, 3H); 2.25 (s,
3H); 1.25 (t, 3H).
TABLE-US-00002 TABLE I I ##STR00012## phys. data (mp.[.degree. C.];
.sup.1H-NMR .delta. [ppm]; No. X R.sup.1 R.sup.2 R.sup.3 R.sup.4
R.sup.5 MS m/e [M + H.sup.+]) I-1
4-(C[CH.sub.3].dbd.NOCH.sub.3)--C.sub.6H.sub.4 H H H H H 4.2 (2H);
4.0 (3H); 2.25 (3H) I-2
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4 H H H H H
4.25 (2H); 4.2 (2H); 2.25 (3H); 1.3 (3H) I-3
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.dbd.CH.sub.2)--C.sub.6H.sub.4 H H H
H H 5.2 (2H); 4.7 (2H); 4.05 (2H); 2.25 (3H) I-4
4-(C[CH.sub.3].dbd.NOCH(CH.sub.3).sub.2)--C.sub.6H.sub.4 H H H H H
4.45 (1H); 4.2 (2H); 2.25 (3H); 1.3 (6H) I-5
4-(C[CH.sub.3].dbd.NOCH.sub.2C.ident.CH)--C.sub.6H.sub.4 H H H H H
4.8 (2H); 4.2 (2H); 2.5 (1H); 2.3 (3H) I-6
4-(C[CH.sub.3].dbd.NO(CH.sub.2).sub.5CH.sub.3)--C.sub.6H.sub.4 H H
H H H 4.2 (2H); 4.1 (2H); 2.25 (3H); 0.9 (3H) I-7
4-(C[CH.sub.3].dbd.NOCH.sub.2C.sub.6H.sub.5)--C.sub.6H.sub.5 H H H
H H 5.3 (2H); 4.25 (2H); 2.25 (3H) I-8
4-(C[CH.sub.3].dbd.NOCH.sub.3)--C.sub.6H.sub.4 CH.sub.3 H H H H 4.2
(2H); 4.05 (3H); 2.65 (3H): 2.25 (3H) I-9
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4 CH.sub.3 H H
H H 4.25 (2H); 4.2 (2H); 2.7 (3H); 1.35 (3H) I-10
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4
CH.sub.2CH.sub.3 H H H H 4.3 (2H); 4.2 (2H); 3.2 (2H); 2.2 (3H);
1.3 (3H); 0.9 (3H) I-11
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4
CH.sub.2C.ident.CH H H H H 4.35 (2H); 4.25 (2H); 4.0 (2H); 2.25
(1H) I-12 4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4
C.sub.6H.sub.5CH.sub.2 H H H H 4.3 (2H); 4.25 (2H); 4.2 (2H); 2.25
(3H) I-13 4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4
CH.sub.2CH.dbd.CH.sub.2 H H H H 5.5 (1H); 5.0 (2H); 4.3 (2H); 3.75
(2H) I-14 4-COOCH.sub.3--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH--
H H 8.45 (1H); 8.0 (1H); 7.4 (1H); 4.5 (2H) I-15
4-CH.sub.3--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH-- H H 8.1 (1H);
7.3 (1H); 4.65 (2H); 1.3 (9H) I-16 4-OCH.sub.3--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 8.1 (1H); 4.6 (1H); 3.0 (1H); 1.3 (6H)
I-17 4-Cl--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH-- H H m/e 333
I-18 2,5-Cl.sub.2--C.sub.6H.sub.3 H --CH.dbd.CH--CH.dbd.CH-- H H
m/e 367 I-19 1-naphthyl H --CH.dbd.CH--CH.dbd.CH-- H H m/e 349 I-20
2-CH.sub.3-6-CF.sub.3--C.sub.6H.sub.3 H --CH.dbd.CH--CH.dbd.CH-- H
H m/e 381 I-21 2-Cl-5-OCH.sub.3--C.sub.6H.sub.3 H
--CH.dbd.CH--CH.dbd.CH-- H H m/e 363 I-22
2,4-Cl.sub.2--C.sub.6H.sub.3 H --CH.dbd.CH--CH.dbd.CH-- H H m/e 367
I-23 4-CN--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH-- H H m/e 324
I-24 2,6-Cl.sub.2--C.sub.6H.sub.3 H --CH.dbd.CH--CH.dbd.CH-- H H
m/e 367 I-25 2-Br--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH-- H H
m/e 379 I-26 2,3-Cl.sub.2--C.sub.6H.sub.3 H
--CH.dbd.CH--CH.dbd.CH-- H H m/e 367 I-27
3,4-(OCH.sub.3).sub.2--C.sub.6H.sub.3 H --CH.dbd.CH--CH.dbd.CH-- H
H m/e 358 I-28 2-CH.sub.3-6-Cl--C.sub.6H.sub.3 H
--CH.dbd.CH--CH.dbd.CH-- H H m/e 347 I-29 2-Cl--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H m/e 333 I-30 C.sub.6H.sub.5 H
--CH.dbd.CH--CH.dbd.CH-- H H 8.45 (1H); 8.0 (1H); 7.4 (1H); 4.5
(2H) I-31 4-C(CH.sub.3).sub.3--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 8.1 (1H); 7.3 (1H); 4.65 (2H); 1.3
(9H) I-32 4-CH(CH.sub.3).sub.2--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 8.1 (1H); 4.6 (1H); 3.0 (1H); 1.3 (6H)
I-33 4-OCF.sub.3--C.sub.6H.sub.4 H --CH.dbd.CH--CH.dbd.CH-- H H
8.75 (1H); 8.0 (1H); 5.8 (1H); 4.7 (2H) I-34
4-OCF.sub.2CHF.sub.2--C.sub.6H.sub.4 H --CFWCH--CH.dbd.CH-- H H 8.8
(1H); 4.7 (2H) I-35 4-COCH.sub.3--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 8.8 (1H); 7.3 (1H); 4.6 (2H); 2.6 (3H)
I-36 4-(C[CH.sub.3].dbd.NOCH.sub.3)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.2 (NH); 4.6 (2H); 4.0 (3H); 2.2 (3H)
I-37 4-(C[CH.sub.3].dbd.NOCH.sub.2CH.sub.3)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.0 (NH); 4.6 (2H); 4.3 (3H); 2.3
(3H); 1.35 (3H) I-38
4-(C[CH.sub.3].dbd.NOCH(CH.sub.3).sub.2)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.1 (NH); 4.6 (2H); 4.5 (3H); 2.25
(3H); 1.3 (6H) I-39
4-(C[CH.sub.3].dbd.NOCH.sub.2CH.dbd.CH.sub.2)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.3 (NH); 5.2 (2H); 4.75 (2H); 4.6
(2H); 2.35 (3H) I-40
4-(C[CH.sub.3].dbd.NOCH.sub.2C.ident.CH)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.1 (NH); 4.8 (2H); 4.6 (2H); 2.5
(2H); 2.3 (3H) I-41
4-(C[CH.sub.3].dbd.NO(CH.sub.2).sub.5CH.sub.3)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.2 (NH); 4.6 (2H); 4.2 (2H); 2.25
(2H); 0.9 (3H) I-42
4-(C[CH.sub.3].dbd.NOCH.sub.2C.sub.6H.sub.5)--C.sub.6H.sub.4 H
--CH.dbd.CH--CH.dbd.CH-- H H 5.3 (2H); 5.2 (NH); 4.8 (2H); 2.3 (3H)
I-43 C.sub.6H.sub.5 CH.sub.3 --CH.dbd.CH--CH.dbd.CH-- H H 4.6 (2H);
2.7 (3H) I-44 5-Cl-thiophen-2-yl H H H H H m/e 339 I-45
thiophen-2-yl H H H H H m/e 305 I-46
5-([4-C(CH.sub.3).sub.3]--C.sub.6H.sub.4)-thiophen-2-yl H H H H H
166 I-47 5-Br-thiophen-2-yl H H H H H 148 I-48
4-NO.sub.2-5-Cl-thiophen-2-yl H H H H H 182 I-49
5-Cl-1,3-(CH.sub.3).sub.2-1H-pyrazol-4-yl H H H H H 147 I-50
3-Br-2,5-Cl.sub.2-thiophen-4-yl H H H H H 106 I-51
1-CH.sub.3-1H-imidazol-4-yl H H H H H 125 I-52
5-(4-tert-butylphenyl)thiophen-2-yl H H H H H 166 I-53
5-chloro-1,3-dimethyl-1H-pyrazol-4-yl H H H H H 147 I-54
5-bromothiophen-2-yl H H H H H 148 I-55
5-chloro-4-nitrothiophen-2-yl H H H H H 182 I-56
1-methyl-1H-imidazol-4-yl H H H H H 125 I-57
4-bromo-2,5-dichlorothiophen-3-yl H H H H H 106 I-58
5-biphenyl-4-ylthiophen-2-yl H H H H H 204 I-59
5-(4-trifluoromethoxyphenyl)thio- H H H H H 138 phen-2-yl I-60
5-(4-propylphenyl)thiophen-2-yl H H H H H 144 I-61
5-(4-ethylphenyl)thiophen-2-yl H H H H H 144 I-62
5-(3-trifluoromethylphenyl)thio- H H H H H 130 phen-yl I-63
5-(4-chlorophenyl)thiophen-2-yl H H H H H 176 I-64
5-(4-trifluoromethylphenyl)thio- H H H H H 165 phenyl I-65
5-(4-methoxyphenyl)thiophen-2-yl H H H H H 175 I-66
5-(4-trifluoromethylphenyl)thio- propargyl H H H H 116 phen-2-yl
I-67 5-(4-trifluoromethylphenyl)thio- n-propyl H H H H 97 phen-2-yl
I-68 5-(4-trifluoromethylphenyl)thio- methyl H H H H 101 phen-2-yl
I-69 5-(4-isopropylphenyl)thiophen-2-yl H H H H H 125 I-70
5-bromothiophen-2-yl H --CH.dbd.CH--CH.dbd.CH-- H H 137 I-71
5-(4-trifluoromethylphenyl)thio- H --CH.dbd.CH--CH.dbd.CH-- H H 180
phen-2-yl I-72 4-tert-butylphenyl methyl --CH.dbd.CH--CH.dbd.CH-- H
H 145-148
EXAMPLES OF THE ACTIVITY AGAINST HARMFUL FUNGI
[0109] The fungicidal action of the compounds of the formula I was
demonstrated by the following experiments:
[0110] The active compounds were prepared separately or together as
a stock solution using 0.25% by weight of active compound in
acetone or DMSO. 1% by weight of the emulsifier Uniperol.RTM. EL
(wetting agent having emulsifying and dispersing action based on
ethoxylated alkylphenols) was added to this solution, and the
mixture was diluted with water to the desired concentration.
Use Example 1
Activity Against Early Blight of Tomatoes Caused by Alternaria
solani
[0111] Leaves of potted plants of the cultivar "Goldene Prinzessin"
were sprayed to runoff point with an aqueous suspension having the
concentration of active compounds stated below. The next day, the
leaves were infected with an aqueous spore suspension of Alternaria
solani in a 2% biomalt solution having a density of
0.17.times.10.sup.6 spores/ml. The plants were then placed in a
water-vapor-saturated chamber at 20-22.degree. C. After 5 days, the
early blight on the untreated, but infected control plants had
developed to such an extent that the infection could be determined
visually in %.
[0112] In this test, the plants which had been treated with 250 ppm
of active compounds I-2 to I-6, I-14, I-15, I-17, I-30 to I-34,
I-36 to I-42 or I-45 had no more than 30% infection, whereas the
untreated plants were 100% infected.
Use Example 2
Activity Against Mildew on Cucumber Leaves Caused by Sphaerotheca
fuliginea, Protective Application
[0113] Leaves of potted cucumber seedlings of the cultivar "Chinese
Snake" were, at the cotyledon stage, sprayed to runoff point with
an aqueous suspension having the concentration of active compounds
stated below. 20 hours after the spray coating had dried on, the
plants were inoculated with an aqueous spore suspension of mildew
of cucumber (Sphaerotheca fuliginea). The plants were then
cultivated in a greenhouse at 20-24.degree. C. and 60-80% relative
atmospheric humidity for 7 days. The extent of the mildew
development was then determined visually in % infection of the
cotyledon area.
[0114] In this test, the plants which had been treated with 250 ppm
of the active compounds I-1 to I-5, I-15, I-18, I-30, I-32, I-33,
I-34, I-37 to I-40, I-42 or I-45 showed no more than 30% infection,
whereas the untreated plants were 100% infected.
* * * * *