CA1331385C - 3-substituted pyridines and fungicides containing them - Google Patents
3-substituted pyridines and fungicides containing themInfo
- Publication number
- CA1331385C CA1331385C CA000578570A CA578570A CA1331385C CA 1331385 C CA1331385 C CA 1331385C CA 000578570 A CA000578570 A CA 000578570A CA 578570 A CA578570 A CA 578570A CA 1331385 C CA1331385 C CA 1331385C
- Authority
- CA
- Canada
- Prior art keywords
- formula
- alkyl
- substituted
- hydrogen
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: 3-substituted pyridines of the formula (I) where R1 is hydrogen, alkyl, alkenyl, alkynyl, acyl, haloacyl, benzoyl or benzyl;
R2 is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, arylalkyl or aryloxyalkyl, R3 is the radical or
R2 is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, arylalkyl or aryloxyalkyl, R3 is the radical or
Description
.
133~ 38~ ~
- 1 - o.z. 0050/39507 3-substituted pyridlnes and fungicides containing them The present invention relates to nove~ 3-substituted pyridine derivatives and fungicides ~hich conta;n these compounds, and ~ethods for controlling fungi.
Structurally related 3-propenylpyridines, eg. 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridyl)-2-propen-1-ol, Z-n-butyl-3-(4-~ethylphenyl)-1-(3-pyridyl)-2-propen-1-one and 2-n-butyl-3-(4-fluorophenyl)~ 3-pyridyl)-2-propen-1-ol are disc~osed as fungicides in EP-214 566. Ho~ever, their action is not al~ays conpletely satisfactory for certain indications, particularly at lo~ application rates.
~e have found that 3-substituted pyrid;ne der;va- A~, tives of the fornula ~R: (I) 1~ R2 I~n ~here R1 is hydrogen, C1-Cg-alkyl~ C3-Cg-alkeny~ C3-Cg-alkynyl, C2-C12-acyl, C2-C12-haloacyl or unsaturated -; C3-acyl, or is benzoyl uhich is unsubstituted or ~onosub- ~ -stituted to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy, phenyl, acetoxy, C1-C4-haloalkyl, halogen or nitro, or is benzyl uhich is unsubst;tuted or subst;tuted by 1 to 3 radica~s of the tYPe C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, halogen, cyano or n;tro, R2 ;s hydrogen, ~;~ 25 C1-C12-alkyl, C3-C12-cycloalkyl, C4-C20-cycloalkyl-alkyl, C4-C20-alkylcycloalkyl, unsubst;tuted or subst;tu-ted C7-C20-arylal,ky~,~oir lun~subst;tuted or subst;tuted!C7-C20-aryloxyalkyl ~hose aryl radicals are unsubstituted or - ~onosubstituted to trisubstituted by C1-C4-alkyl, C1-C4-30 aikoxy, C1-C4-haloalkyl or halogen, R3 ;s a rad;cal ~
R~ R5 RS ~-- ~ :
~R O r ~R 5 ~? ~N~R~
: 133~.~8~
, - 2 - O.z. 0050/39507 where R4 to R~ independently of one another are each hydro-gen, C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkoxycarbonyl, C2-C4-dialkylamino, phenyl, hydro~-yl or halogen, and R4 and R5 or RS and R6 together may S furthermore be the group -CH=CH-CH=CH-, and n is 0 or 1, and their plant-tolerated salts surprisingly have a sub-stantially better fungicidal action than the unsaturated pyridine derivatives disslosed in EP-214 566.
R1 jS, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2,4,4-trimethylpent-2-yl, 2-ethylhexyl, allyl, 2-methyl-allyl, 3-methylallyl, 3,3-dimethylallyl, 3-buten-1-yl, 3-octen-1-yl, propargyl, 3-octyn-1-yl, acetyl, mono-, di-or trichloroacetyl, trifluoroacetyl, propionyl, 3-bromo-propionyl, butyryl, 4-bromobutyryl, 3-methylbutyryl, 3,3-dimethylbutyryl, pentanoyl, hexanoyl, heptanoyl, octan-oyL, 2-ethylhexanoyl, nonanoyl, decanoyl, lauroyl, dodecan-oyl, acryloyl, benzoyl, mono-, di- or trimethylbenzoyl, 4-tert-butylbenzoyl, 4-phenylbenzoyl, fluorobenzoyl, mono-, di- or trichlorobenzoyl, trifluoromethylbenzoyl, mono-, di- or trimethoxybenzoyl, 2-acetoxybenzoyl, mono- or di-~ nitrobenzoyl, benzyl, mono-, di- or trimethylben2yl, 4-- tert-butylbenzyl, mono-, di- or tr;methoxybenzyl, tri-fluoromethylbenzyl, trichloromethylbenzyl, mono-, di- or trichlorobenzyl, cyanobenzyl or mono- or dinitrobenzyl.
R2 j5, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexy~, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyc~ohexy~, cycloocty~, cyc~ododecy~, 2-cyclohexylethyl, 3-cyclohexyl-2-methylproPyl, 4-tert-butylcyclohexyl, benzyl, mono-, di- or trimethylbenzyl, 4-tert-butylbenzyl, mono-, di- or trimethoxybenzyl, tri-fluoromethylbenzyl, mono-, di- or trichlorobenzyl, fluorobenzyl, phenylethyl, (4-fluorophenyl)-ethyl, (chlorophenyl)-ethyl, (2,4-dichlorophenyl)-ethyl, .
133i3~
133~ 38~ ~
- 1 - o.z. 0050/39507 3-substituted pyridlnes and fungicides containing them The present invention relates to nove~ 3-substituted pyridine derivatives and fungicides ~hich conta;n these compounds, and ~ethods for controlling fungi.
Structurally related 3-propenylpyridines, eg. 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridyl)-2-propen-1-ol, Z-n-butyl-3-(4-~ethylphenyl)-1-(3-pyridyl)-2-propen-1-one and 2-n-butyl-3-(4-fluorophenyl)~ 3-pyridyl)-2-propen-1-ol are disc~osed as fungicides in EP-214 566. Ho~ever, their action is not al~ays conpletely satisfactory for certain indications, particularly at lo~ application rates.
~e have found that 3-substituted pyrid;ne der;va- A~, tives of the fornula ~R: (I) 1~ R2 I~n ~here R1 is hydrogen, C1-Cg-alkyl~ C3-Cg-alkeny~ C3-Cg-alkynyl, C2-C12-acyl, C2-C12-haloacyl or unsaturated -; C3-acyl, or is benzoyl uhich is unsubstituted or ~onosub- ~ -stituted to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy, phenyl, acetoxy, C1-C4-haloalkyl, halogen or nitro, or is benzyl uhich is unsubst;tuted or subst;tuted by 1 to 3 radica~s of the tYPe C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, halogen, cyano or n;tro, R2 ;s hydrogen, ~;~ 25 C1-C12-alkyl, C3-C12-cycloalkyl, C4-C20-cycloalkyl-alkyl, C4-C20-alkylcycloalkyl, unsubst;tuted or subst;tu-ted C7-C20-arylal,ky~,~oir lun~subst;tuted or subst;tuted!C7-C20-aryloxyalkyl ~hose aryl radicals are unsubstituted or - ~onosubstituted to trisubstituted by C1-C4-alkyl, C1-C4-30 aikoxy, C1-C4-haloalkyl or halogen, R3 ;s a rad;cal ~
R~ R5 RS ~-- ~ :
~R O r ~R 5 ~? ~N~R~
: 133~.~8~
, - 2 - O.z. 0050/39507 where R4 to R~ independently of one another are each hydro-gen, C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-haloalkyl, C2-C4-alkoxycarbonyl, C2-C4-dialkylamino, phenyl, hydro~-yl or halogen, and R4 and R5 or RS and R6 together may S furthermore be the group -CH=CH-CH=CH-, and n is 0 or 1, and their plant-tolerated salts surprisingly have a sub-stantially better fungicidal action than the unsaturated pyridine derivatives disslosed in EP-214 566.
R1 jS, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2,4,4-trimethylpent-2-yl, 2-ethylhexyl, allyl, 2-methyl-allyl, 3-methylallyl, 3,3-dimethylallyl, 3-buten-1-yl, 3-octen-1-yl, propargyl, 3-octyn-1-yl, acetyl, mono-, di-or trichloroacetyl, trifluoroacetyl, propionyl, 3-bromo-propionyl, butyryl, 4-bromobutyryl, 3-methylbutyryl, 3,3-dimethylbutyryl, pentanoyl, hexanoyl, heptanoyl, octan-oyL, 2-ethylhexanoyl, nonanoyl, decanoyl, lauroyl, dodecan-oyl, acryloyl, benzoyl, mono-, di- or trimethylbenzoyl, 4-tert-butylbenzoyl, 4-phenylbenzoyl, fluorobenzoyl, mono-, di- or trichlorobenzoyl, trifluoromethylbenzoyl, mono-, di- or trimethoxybenzoyl, 2-acetoxybenzoyl, mono- or di-~ nitrobenzoyl, benzyl, mono-, di- or trimethylben2yl, 4-- tert-butylbenzyl, mono-, di- or tr;methoxybenzyl, tri-fluoromethylbenzyl, trichloromethylbenzyl, mono-, di- or trichlorobenzyl, cyanobenzyl or mono- or dinitrobenzyl.
R2 j5, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexy~, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyc~ohexy~, cycloocty~, cyc~ododecy~, 2-cyclohexylethyl, 3-cyclohexyl-2-methylproPyl, 4-tert-butylcyclohexyl, benzyl, mono-, di- or trimethylbenzyl, 4-tert-butylbenzyl, mono-, di- or trimethoxybenzyl, tri-fluoromethylbenzyl, mono-, di- or trichlorobenzyl, fluorobenzyl, phenylethyl, (4-fluorophenyl)-ethyl, (chlorophenyl)-ethyl, (2,4-dichlorophenyl)-ethyl, .
133i3~
- 3 - o.z. 0050/39507 phenylpropyl, 4-tert-butylphenylpropyl, 3-phenyl-2-propyl, 3-(4-tert-butylphenyl)-2-propyl, 3-(chloro-phenyl)-2-propyl, 3-(fluorophenyl)-2-propyl, 3-(2,4-di-chlorophenyl)-2-propyl, phenoxymethyl, mono-, di- or tri-chlorophenoxymethyl, fluorophenoxymethyl, phenoxyethyl, mono-, d;- or trichlorophenoxyethyl, fluoroPhenoxyethyl, ;
phenoxypropyl, mono-, di- or trichlorophenoxyproPyl, ,luorophenoxypropyl, phenoxybutyl, mono-, di- or tri-chlorophenoxybutyl, mono-, di- or trichlorophenoxybutyL
- 10 or fluorophenoxybutyl.
R3 ;s, for example, phenyl, mono-, di- or tri-~ethylphenyl, ethylphenyl, 4-tert-butylphenyl, ~ono-, di-or trimetho~yphenyl, trifluoromethylphenyl, trichloro-~ethylphenyl, N,N-dimethyl(ethyl)aminophenyl, methoxy-carbonylphenyl, hydroxyphenyl, biphenyl, mono-, di- or trichlorophenyl, fluorophenyl, naphthyl, pyridyl, methyl-pyridyl, chloropyridyl, quinolyl or iso~uinolyl.
Plant-tolerated salts are, for example, addition salts with inorganic mineral acids, such as hydrochlor-ides, hydrobromides, sulfates, phosphates or nitrates;
salts with formic acid or ~ith alkylcarboxylic acids, such as acetates, 2-ethylhexanoates or oxalates; and salts with arylsulfonic acids, such as benzenesulfonates, toluenesulfonates or dodecylbenzenesulfonates.
The compounds of the formula I may have two centers of asymmetry and therefore occur in two diastereomeric forms, which, if required, can be separated by known ~ethods. The present invention relates to the individual diastereom-rs as well as their mixtures. ~
The compounds of the formula I may be in the form ~r of the pyridines,or in the form of the pyridine N-oxides.
The novel 3-substituted pyridines of the formula I can be prepared, for example, by reacting a pyridyl atcohol of the formula I
OH
C~R3 t I ) , ~ ~33~ 3~5 - 4 - O.Z. 0050/39507 ~here R2 and R3 have the abovementioned meanings, ~ith an alkyLating or acylating agent of the formula II
R1-X (II) ~here R1 has the abovementioned meanings, excePt for hydrogen, and X is a nucleofugic group, eg. chlorine, bromine, iodine, methanesu~fonate, benzenesulfonate or p-toluenesulfonate.
This reaction is advantageously carried out by a procedure in which a mi~ture of pyridyl alcohol of the formula I, not less than an e~uimolar amount of an auxiliary base and an inert, organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dimethylformam-ide, Jimethyl sulfoxide, acetonitrile, toluene or xylene, is initially taken and the alkylating or acylating agent is metered in.
The reaction temperatures are from 0 to 120C, preferably from 20 to 80C.
Suitable auxiliary bases are inorganic and or-ganic acid acceptors.
Examples of inorganic bases are sodium hydride, sodium amide, sodium hydroxide, sodium carbonate, potas- ~ -sium carbonate and potassium hydroxid~.
Examples of organic bases are amines, in particu-lar tertiary amines, such as triethylamine, ethyldiiso-25 propy~amin- or pyridine, and alcoholates, such as sodium -;
methy~at-, sodium ethylate or potassium tert-butylate.
In an advantageous variant of this process, the reactions of the pyridyl alcohols of the formula I with alkylating agents,of the formula II are carried out in a tvo-phase system consisting of aqueous sodium hydroxide solution and an organic solvent, preferabLy ;~-toluene or dichloro~ethane, ~ith the addition of a phase--~` transfer cata~yst, eg. tetra-n-butylammoniu~ chLoride, ~- benzy~triethylammonium chloride or methyltrioctylammonium chloride.
r - , 133138~
The novel compounds I where R1 ;5 hydrogen are prepared, for example, by reducing a pyridyl ketone ot the formula III or a pyridyl alcohol of the formula IV
H
~R3 ( 111 ) G~R~ ~ IY?
S where RZ and R3 have the abovementioned meanings, with a reducing agent, for exampla a complex hydride or hydro-gen, in the presence of a catalyst (cf. for e~a~ple M
Hudlicky, Reductions in Organic Che~istry, page 119 et seq , Ellis Horwood Serie~, Chichester, 19a4) The pre-paration of the pyridy~ ketones of the for~ula III and ofthe pyridyl alcohol~ of the formula IV i~ kno~n ~EP-A-214 566) In another process for the preparation of th~
novel co~pounds I ~here R1 j5 hydrog~n, for ~xanple, an organometallic conpound of tht for~ula V
R~ ~ ~
2 :
where R2 and R3 have th~ abovt~entioned meanings and M
is lithiu~ or th- radical ~gCl or Mg~r, is react~d ~ith nicotinaldehyde ~3-tornylpyridine) For this purpose, the organo~etallic co~pound of th~ fornula V i~ advan--~ t~g~ou~ly initially taken in an inert solv~nt, prefer-ably diethyl eth~r or tetrahydrofuran, and th~ nicotin-ld~hyd~ ettred ;n ~ a ~ixture ~ith tht ~n~ solvent -~
at tro~ -30 to ~50C.
The organonetallic compound~ of the formula V are ~-obtainable fro~ th~ corresponding halidts ~chloride~ or bro~ides) by kno~n proces~t~ tcf. for exanple Houben-~eyl, Methoden der Organi~chen Chenie, Volumt 13/1, page 134 t ~eq., Georg Thie~e Vtr~ag~ Stuttgart 1970; ibid., Voluoe 13/2a, pagt 54 ~t se~., G~org Thie~ V~r~ag, Stutt-gart, 1973). Tht ~atttr ar~ ~ith~r kno~n or can be ~
,:
, . . ,, , .. , , , . .," ,., . . ;,. ..
.
- 6 - o.z. 0050/39507 prepared by known processes. The Pyridine N-oxides are ;
obtained from the pyridines by known processes, for e~a~-ple ~y oxidation with a peracid (cf. for exa~Ple Katrit-zky and Lagowski, Che~istry of Heterocyclic N-O~ides, pages 21-56, Acade~ic Press, Ne~ York, 1971).
The Examples ~hich follow illustrate the prepara-tion of the novel fungicidal pyridines.
2-n-butyl 3-(4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol 1û In a 0.3 l stirred autoclave, a mixture of 17.1 9 (0.6 mole) of 2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridyl)-2-propen-1-ol, 160 ml of tetrahydrofuran and 4.5 9 of a hydrogenation catalyst (O.SZ of Pd on Al203) is hydro-genated at 30C and under a hydrogen pressure of 50 bar until the pressure remains constant. The solution is then filtered under suction over silica gel, the filtrate is evaporated down under reduced pressure and the residue is purified by distillation. Yield: 7.9 9 of conpound No. 1, bp. 187C (0.3 mbar).
' 2-n-butyl-3-(4-fluorophenyl~-1-(3-pyridyl)-propan-1-ol 2,4-dichlorobenzoate 4.6 9 ~0.02Z ~ole) of 2,4-dichlorobenzoyl chlor- ;~
ide, dissolved in 10 nl of dichloromethane, are added dropuis~ to a ~olution of 5.74 9 (0.02 ~ole) of con-pound No. 1 in S0 ~l of dichloronethane and 10 ~l of tri-ethyla~ino at roon te~perature. The ~ixture is stirred overnight, aft~r which 30 ~l of 10X strength NaHC03 solution are add~d and st~ir~ring is continued for a further hour. The organic phase is washed with ~ater, - dried over ~gS~4 and evaporated down under reduced pressure. The residue is purified by chro~atograPhy over - silica gel using a 9 : 1 dichloronethane/acetone ~i~ture as the nobile phase. 6.7 9 (73~ of theory) of co~pound No. 2 are obtained as a yellow oil.
F' - : - . . ..
- 7 - O.Z. 0050/39507 ~XAMPLE 3 2-n-butyl-3-(4-fluoroPhenyl)-1-(3-pyridyl)-propan-1-ol 4-chlorobenzy! ether 0.72 9 (0.03 mole) of sodium hydride is added to a solution of 5.74 9 (0.02 mole) of compound 1 in 20 ml of dimethylformamide, and the mixture is stirred at 50C until the evolution of hydrogen has ended. The mixture is cooled to room temperature, after which 4.0 9 (0.025 mole) of 4-chlorobenzyl chloride in 10 ml of di- -methylformamide are added dropwise sufficiently slowly to prevent the internal temperature from exceeding 40C.
Stirring is continued for 1 hour at room temperature (20C), 50 l of water are carefully added drop~ise at 0C and 100 ml of ether are introduced. The aqueous phase is separated off and extracted by shaking with ether. The combined organic phases are dried over MgS04 and evaporated down under reduced pressure. The residue is purified by chromatography over silica gel using a 9 : 1 dichloromethane/acetone mixture as the mobile phase. 6.7 9 (81X of theory) of co~pound No. 3 are obtained as a yellow oil.
3-t4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol A solution of 10.7 9 (0.10 mole) of nicotinalde-hyde in 100 ml of diethyl ether i5 added dropwise, while stirring, to a solution prepared from 2.92 9 ~0.12 mole) of magn-sium and 24.4 9 ~0.12 mole) of 2-~4-fluoro-phenyl)-ethyl bromide in Z50 ~l of diethyl ether, and the mixture is then refluxed for 2 hours. Cooling is followed by hydrolysis ~ith water, and the pH is brought to 8 with saturat,ed,aqueous! NH4Cl solution. The phases are separated, the aqueous phase is extracted twice more with ether, and the combined organic phases are washed ~--with water and dried over MgS04. The solvent is 3S evaporated off and the residue is distilled under reduced ~;
pressure to give 10.2 9 ~44X of theory) of compound No. 4 of boiling point 190C ~2 mbar).
- 8 - O.Z. 0050/39507 The following compounds are obtained in a corre-sponding manner.
,' ` ''"' , ~, .
r . ~
' ~" ' . , ~ .:
, ' -~, - .
: ',,: , :', ~ , .
phenoxypropyl, mono-, di- or trichlorophenoxyproPyl, ,luorophenoxypropyl, phenoxybutyl, mono-, di- or tri-chlorophenoxybutyl, mono-, di- or trichlorophenoxybutyL
- 10 or fluorophenoxybutyl.
R3 ;s, for example, phenyl, mono-, di- or tri-~ethylphenyl, ethylphenyl, 4-tert-butylphenyl, ~ono-, di-or trimetho~yphenyl, trifluoromethylphenyl, trichloro-~ethylphenyl, N,N-dimethyl(ethyl)aminophenyl, methoxy-carbonylphenyl, hydroxyphenyl, biphenyl, mono-, di- or trichlorophenyl, fluorophenyl, naphthyl, pyridyl, methyl-pyridyl, chloropyridyl, quinolyl or iso~uinolyl.
Plant-tolerated salts are, for example, addition salts with inorganic mineral acids, such as hydrochlor-ides, hydrobromides, sulfates, phosphates or nitrates;
salts with formic acid or ~ith alkylcarboxylic acids, such as acetates, 2-ethylhexanoates or oxalates; and salts with arylsulfonic acids, such as benzenesulfonates, toluenesulfonates or dodecylbenzenesulfonates.
The compounds of the formula I may have two centers of asymmetry and therefore occur in two diastereomeric forms, which, if required, can be separated by known ~ethods. The present invention relates to the individual diastereom-rs as well as their mixtures. ~
The compounds of the formula I may be in the form ~r of the pyridines,or in the form of the pyridine N-oxides.
The novel 3-substituted pyridines of the formula I can be prepared, for example, by reacting a pyridyl atcohol of the formula I
OH
C~R3 t I ) , ~ ~33~ 3~5 - 4 - O.Z. 0050/39507 ~here R2 and R3 have the abovementioned meanings, ~ith an alkyLating or acylating agent of the formula II
R1-X (II) ~here R1 has the abovementioned meanings, excePt for hydrogen, and X is a nucleofugic group, eg. chlorine, bromine, iodine, methanesu~fonate, benzenesulfonate or p-toluenesulfonate.
This reaction is advantageously carried out by a procedure in which a mi~ture of pyridyl alcohol of the formula I, not less than an e~uimolar amount of an auxiliary base and an inert, organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dimethylformam-ide, Jimethyl sulfoxide, acetonitrile, toluene or xylene, is initially taken and the alkylating or acylating agent is metered in.
The reaction temperatures are from 0 to 120C, preferably from 20 to 80C.
Suitable auxiliary bases are inorganic and or-ganic acid acceptors.
Examples of inorganic bases are sodium hydride, sodium amide, sodium hydroxide, sodium carbonate, potas- ~ -sium carbonate and potassium hydroxid~.
Examples of organic bases are amines, in particu-lar tertiary amines, such as triethylamine, ethyldiiso-25 propy~amin- or pyridine, and alcoholates, such as sodium -;
methy~at-, sodium ethylate or potassium tert-butylate.
In an advantageous variant of this process, the reactions of the pyridyl alcohols of the formula I with alkylating agents,of the formula II are carried out in a tvo-phase system consisting of aqueous sodium hydroxide solution and an organic solvent, preferabLy ;~-toluene or dichloro~ethane, ~ith the addition of a phase--~` transfer cata~yst, eg. tetra-n-butylammoniu~ chLoride, ~- benzy~triethylammonium chloride or methyltrioctylammonium chloride.
r - , 133138~
The novel compounds I where R1 ;5 hydrogen are prepared, for example, by reducing a pyridyl ketone ot the formula III or a pyridyl alcohol of the formula IV
H
~R3 ( 111 ) G~R~ ~ IY?
S where RZ and R3 have the abovementioned meanings, with a reducing agent, for exampla a complex hydride or hydro-gen, in the presence of a catalyst (cf. for e~a~ple M
Hudlicky, Reductions in Organic Che~istry, page 119 et seq , Ellis Horwood Serie~, Chichester, 19a4) The pre-paration of the pyridy~ ketones of the for~ula III and ofthe pyridyl alcohol~ of the formula IV i~ kno~n ~EP-A-214 566) In another process for the preparation of th~
novel co~pounds I ~here R1 j5 hydrog~n, for ~xanple, an organometallic conpound of tht for~ula V
R~ ~ ~
2 :
where R2 and R3 have th~ abovt~entioned meanings and M
is lithiu~ or th- radical ~gCl or Mg~r, is react~d ~ith nicotinaldehyde ~3-tornylpyridine) For this purpose, the organo~etallic co~pound of th~ fornula V i~ advan--~ t~g~ou~ly initially taken in an inert solv~nt, prefer-ably diethyl eth~r or tetrahydrofuran, and th~ nicotin-ld~hyd~ ettred ;n ~ a ~ixture ~ith tht ~n~ solvent -~
at tro~ -30 to ~50C.
The organonetallic compound~ of the formula V are ~-obtainable fro~ th~ corresponding halidts ~chloride~ or bro~ides) by kno~n proces~t~ tcf. for exanple Houben-~eyl, Methoden der Organi~chen Chenie, Volumt 13/1, page 134 t ~eq., Georg Thie~e Vtr~ag~ Stuttgart 1970; ibid., Voluoe 13/2a, pagt 54 ~t se~., G~org Thie~ V~r~ag, Stutt-gart, 1973). Tht ~atttr ar~ ~ith~r kno~n or can be ~
,:
, . . ,, , .. , , , . .," ,., . . ;,. ..
.
- 6 - o.z. 0050/39507 prepared by known processes. The Pyridine N-oxides are ;
obtained from the pyridines by known processes, for e~a~-ple ~y oxidation with a peracid (cf. for exa~Ple Katrit-zky and Lagowski, Che~istry of Heterocyclic N-O~ides, pages 21-56, Acade~ic Press, Ne~ York, 1971).
The Examples ~hich follow illustrate the prepara-tion of the novel fungicidal pyridines.
2-n-butyl 3-(4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol 1û In a 0.3 l stirred autoclave, a mixture of 17.1 9 (0.6 mole) of 2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridyl)-2-propen-1-ol, 160 ml of tetrahydrofuran and 4.5 9 of a hydrogenation catalyst (O.SZ of Pd on Al203) is hydro-genated at 30C and under a hydrogen pressure of 50 bar until the pressure remains constant. The solution is then filtered under suction over silica gel, the filtrate is evaporated down under reduced pressure and the residue is purified by distillation. Yield: 7.9 9 of conpound No. 1, bp. 187C (0.3 mbar).
' 2-n-butyl-3-(4-fluorophenyl~-1-(3-pyridyl)-propan-1-ol 2,4-dichlorobenzoate 4.6 9 ~0.02Z ~ole) of 2,4-dichlorobenzoyl chlor- ;~
ide, dissolved in 10 nl of dichloromethane, are added dropuis~ to a ~olution of 5.74 9 (0.02 ~ole) of con-pound No. 1 in S0 ~l of dichloronethane and 10 ~l of tri-ethyla~ino at roon te~perature. The ~ixture is stirred overnight, aft~r which 30 ~l of 10X strength NaHC03 solution are add~d and st~ir~ring is continued for a further hour. The organic phase is washed with ~ater, - dried over ~gS~4 and evaporated down under reduced pressure. The residue is purified by chro~atograPhy over - silica gel using a 9 : 1 dichloronethane/acetone ~i~ture as the nobile phase. 6.7 9 (73~ of theory) of co~pound No. 2 are obtained as a yellow oil.
F' - : - . . ..
- 7 - O.Z. 0050/39507 ~XAMPLE 3 2-n-butyl-3-(4-fluoroPhenyl)-1-(3-pyridyl)-propan-1-ol 4-chlorobenzy! ether 0.72 9 (0.03 mole) of sodium hydride is added to a solution of 5.74 9 (0.02 mole) of compound 1 in 20 ml of dimethylformamide, and the mixture is stirred at 50C until the evolution of hydrogen has ended. The mixture is cooled to room temperature, after which 4.0 9 (0.025 mole) of 4-chlorobenzyl chloride in 10 ml of di- -methylformamide are added dropwise sufficiently slowly to prevent the internal temperature from exceeding 40C.
Stirring is continued for 1 hour at room temperature (20C), 50 l of water are carefully added drop~ise at 0C and 100 ml of ether are introduced. The aqueous phase is separated off and extracted by shaking with ether. The combined organic phases are dried over MgS04 and evaporated down under reduced pressure. The residue is purified by chromatography over silica gel using a 9 : 1 dichloromethane/acetone mixture as the mobile phase. 6.7 9 (81X of theory) of co~pound No. 3 are obtained as a yellow oil.
3-t4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol A solution of 10.7 9 (0.10 mole) of nicotinalde-hyde in 100 ml of diethyl ether i5 added dropwise, while stirring, to a solution prepared from 2.92 9 ~0.12 mole) of magn-sium and 24.4 9 ~0.12 mole) of 2-~4-fluoro-phenyl)-ethyl bromide in Z50 ~l of diethyl ether, and the mixture is then refluxed for 2 hours. Cooling is followed by hydrolysis ~ith water, and the pH is brought to 8 with saturat,ed,aqueous! NH4Cl solution. The phases are separated, the aqueous phase is extracted twice more with ether, and the combined organic phases are washed ~--with water and dried over MgS04. The solvent is 3S evaporated off and the residue is distilled under reduced ~;
pressure to give 10.2 9 ~44X of theory) of compound No. 4 of boiling point 190C ~2 mbar).
- 8 - O.Z. 0050/39507 The following compounds are obtained in a corre-sponding manner.
,' ` ''"' , ~, .
r . ~
' ~" ' . , ~ .:
, ' -~, - .
: ',,: , :', ~ , .
5' ~' ' ~
j':" ';;
,'"~ .
' ~
,~
,~ , ,, ~ 133~38~ '' - g L L
,~ L n _ ~ E
E u~ _ n E
-- ~ o -- o - ~
E o o o o a~ -- ._ .o ~ a~
~ _ o o o o o ~ ~
~ :~, _ 'C _ _ _ _ ~:
O C C_ ~ e C O ~ C C C C O O ~ ~ C OL L
----Cc--~Co~L----__~,cccooCccoo O O O O -- I O S ~ ~ C O C C -- O O O C r o O O ' OOOOC~O--C~COCC--OOO~ OOO----~~ E ~ u ~ E ~ ~ ~ C c t:L ~ u u ~ ~ u u ~ ~ ~ ` ~
., , ~ i .
:~ :, C ' ~ ~ ~ ~ -- -- -- ~ o --~.', 8~ 8 ~ 8 8 8 8 8 8 8 8 8 8 8 0 ~ O O .~ ~ ~ C ~ ~ o ~, , ~ '`~'~ ,' ,:. :, _ ~:
O '"' ~
" ~ ' o C ~,. - '~:
~: -- 8 ' ~ :: _ o ~ !
,: ~ 1- 'UC
S I T I S T
~: :, : O
: C , ':
"-~ O ' ~ ~
,,, ~ ~ C :: :.
,,:' : : , ,' ' ~.".
, ~ , ",', ",, ",";",1~,~ '' ' j '' ," " "', ,",~ ,, ,",'~ ", ' ' ,''",,~ ,'," ,' 133~38~
L
L
~ E E 'a o o o o : i : ., ~, Q
O ' ~;' .
O
O
~ :~, ~, C :~ C C :-~
O ~ ~ S ~ S S ~ ~ ' S _ _ _ S _ _ ~ _ S _ CL ~L -- _ _ -- C
C C C~ ~ ~ ~ V ~ ~ ~ L ~ ~ ~ ~ ~ e C LO
C S O S S S O S S ~ S O S ~ ~ S _ S S - O
o O s o o O s o o ~ o s o I I o c -- o o C
L L ~ L L L ~ L L . L ~ L ~ ~ L ~ ~ . L L U
~_ _ _ _ _ _ O ~ _ ~ O ~ ~ _ S~ -- ~
S S I C S S I S _ ~ S I _ ~ ~ .C ~ C ~> C C S I
t.> v ~ ~ ~ ~ ~ E ~ u C C C C C N 1~ N 1~
a~ ~ ~ c ~ c e c c c S ~, _ C _ ~C~ _ $ g ~ ~ ~ ~
O -- O -- O ~ O ~`~ O ~ O O O O O O O _ _ -- --L :~, L ::~ o o o o~ o o o o o o o _ o " ,, ~ o o o o .
:~ _ ~ _ ~ _ ~ _ ~ _ CL _ -- _ _ C S S ~ ~ ~ L L L L '-v v ~ ~ n ~ c~
o I o I ~O~ i 0~. 1 OX ~ ~ ~ I ,~. ~ c c c I ~ I C C C C .
- - :
~:
~, ` _ ~
L :
-- S ---- I S -- -- I I -- -- ~ ~ ~ I S -- ~
~, -, -'"~ O ,, ,::
C
o_ ~ ~ ~ u~ O O ~ ~ ~ ~ O --" :, ~
~: .. -~, .
i33138~ ~
C~
E ~ :
~ :
o o~
~ : ~, .;
; ~ .
O ~ :
O ~ ~ ~ '' C C ~ C _ a~ ~ ~ ~ ~ L O ~ ~U ~ L ~ ~ O ~ ~ L ~ ~ ~ ~
C .C ~ ' C O ' ~ C -- O ' ~ .C C C O -- ~ C- ~ :
C~ ~ 8 ~ CL-- 1~ n ~ ~ 8 0 ~ ` E
L ~, . 2 L U L 2 ~ I _ o o s o I L X ' ~
O S ~1 ~ O O _ O ~ _ O O _ O ~ ,C O o ~_ o _ ~ ~ C
L ~ _ _ ~ ~ L ~ _ _ ~ ~ L ~ _ _ ~ ~ ~ L O ~ : : ~ ~`
E ~ ~ u 'u ~ ~ ~ u ~u ~ ~ E ~ c ~ -- c : . ~
~ ~ __ _ _ _ _ ~. . :
CL L ~ L L L L
L LL II I I I I ~, ~, ~ , ~ C C C C ~C C ~ C
O O O O O O C C ,C C ,C C C ~ ~> ~ ~ ~ ~ ~ ~>
c c c ~ -- ~ o 0 0 ~ 0 0 E E E E E E E E .::
. ~, :~ : ~ ,::
i. ~,~.
.`" , .
,,-: :
~ ~,: : . . :' :: ' ~, .
133i385 - ~:
a E _.
o ~ ::
U~
a-o o _ _ :
C ~ C C C ~ ~
-- -- ~L -- -- , _ _ _ _ C _ _ C _ C -- -- _ C _ _ _ C
CC~CoC C~C~oCCoCoCCCoCCCo c C ~ ` o c _ c ~ C c o c ~ O c o C c c o C c c O
O -- I o ~ o c o o o o c o o c o s o o O C O O O C
L ~ ~ ~ L ~ ~ L ~ ~ L ~
O ~ ~ _ ~-- O C O _ O _ ~-- O ~ _ O _ ~-- _ O O -- - ' ~ ~;
~: -- ~ ~ ,C I ,C 1~ _ ,c _ ,c I _ ,c ~ C ~ C _ C ~ C _ C ~ .. ..
~ E ~ ~J -t v C q~
.~,,:
~ C = ~ ~ C C ~ C C ~ L L
-? ~ -. : ~ ~ ~ ' - ' :
, . .
S S I S S I S: S S S S S S S S S ~: S T S T T I S . . ~ ~;
C
.,,, ~. .
.", ~ o " D % ,~ ~ ~ ~ ~ ~ ~' P~'. ~ .
?.~: :
, ':
':"'~
: ~
.~ , , '/', , ,,, ' . ', . ,, ., ' . .,, . . ' ' ' , " ' ' I : . ' .. , . ,.. ' ' -133~ 385 ~
~, .
~ ~,, o .
~ .
,~ ," ,,~,.
O !, ` . ~ ~:
O V
___,C__ ~ .
C O ~ -~ L
O O O ' O O `~
L L V L L
O O O ~_ O O :
~t U ~
; ` ' `., -:
" C ~ C C
E E E E
S S S S S S "`' '~'~ , "''` ~'''':"
.''~ ' ., ', :
,~,~ , ' ' , :
.~ ~ O '' ~ :
~": ~ ~S O _ ~ ~ ' O O O O O O
X _ ~
~, W ' :: :
G
, _ 14 O.Z. 0050/3~ ~ 3 ~. 3 8 ~
In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomy~etes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, PodoSphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, 20 Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea ~gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 30 Fusarium and Verticillium species in various plants, PlaSmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such 40 as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water 133~.38~
O.z 0050/39507 is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., 5 methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyl-10 ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from G.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The application rates are from 0.02 to 3 15 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, e.g., on Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as 20 solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
30 II. 20 parts by weight of compound no. 5 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene 35 oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 6 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-40 butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxideand 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
16 o z 0050/39507 IV. 20 parts by weight of compound no. 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
15 Vl. 3 parts by weight of compound no. 5 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 6 is intimately mixed with a 20 mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
25 VIII. 40 parts by weight of compound no. 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stabte - aqueous dispersion. Dilution in water gives an aqueous dispersion.
30 IX. 20 parts by weight of compound no. 1 is intimatety mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by - weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodiùm salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is 35 obtained. ; ~ , ! ' ' ."
In these apptication forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be 40 mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in a greater fungicidal action spectrum.
~ 133~ 385 17 O.Z. 0050/39507 The following list of fungicides with which the novel compounds may be combined is intended.to illustrate possible combinations but not to impose any restrictions.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, ::
dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, 10 zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, : .
tetramethylthiuram disulfides, 15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithioccarbamate and N,N'-polypropylenebis(thiocirbamyl) disulfide;
20 nitro derivatives, such as dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and ~` diisopropyl 5-nitroisophthalate;
.~ 25 heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, ~: 2,4-dichloro-6-(o-chloroanilino)-s-triazine, ~: a, 0-diethyl phthalimidophosphonothioate, 30 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio[4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 35 2-(fur-2-ylj-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, , '~
N-trichloromethylthiotetrahydrophthalimide, -~ N-trichloromethylthiophthalimide, ~.
: ~- 40 N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, ~ -5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, - 2-thiocyanatomethylthiobenzothiazole, ;~ 1,4-dichloro-2,5-dimethoxybenzene, ~ , , , ., ., , ~ , ~ ~ , .. . .
18 0 z. 0050/39507 1 33~. 385 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, 15 piperazine-1,4-diylbis-(1-(2,2,2-trichtoroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-t3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, 20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N -imidazolyl-urea, :
1-(4-chlorophenoxy)-3~3-dimethyl-1-(lH-1~2~4-triazol-1-yl)-butan-2-one~
1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol, 1-(4-phenylphenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanol, ~-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 30 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyr~dinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as 35 dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, ~:
hexachlorobenzene, . -:
DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, ~
methyl DL-N-(2,6-dimethylphenyl)-N-(2 -methoxyacetyl)-alanate, :
40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, `
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, ~,. . .... . . ........ ... .... ..... .
,---\
19 O.Z. 0050/39507 N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-aCetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-lH-1,2,4-triazole, 2,4-difluoro-a-(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, 5 N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
Use examples The agents used for comparison purposes were 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-one (C), 2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridinyl)-2-propen-1-ol (A), and 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-ol (B) 15 disclosed in EP-214,566.
Use Exampte 1 Action on wheat mildew 20 Leaves of pot-grown wheat seedlings of the "FrUhgold" variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier, and dusted, 24 hours after the sprayed-on layer had dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants were then set up in the greenhouse at from 20 to 22C and a rela-25 tive humidity of from 75 to 80%. The extent of mildew spread was assessedafter 7 days.
The results show that active ingredients 1 and 5, when employed as 0.025 and 0.006wt~ spray liquors, had a better fungicidal action (97%) than ;
30 prior art active ingredients A, B and C (70%).
use Example 2 Action on cucumber mildew 35 Leaves of pot-grown cucumber seédlings of the i'Chinesische Schlange"
variety were sprayed at the two-leaf stage with an aqueous conidial suspension of cucumber mildew. After about 20 hours, these plants were sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After ~he sprayed-on layer had 40 dried, the plants were set up in the greenhouse at 20 to 22C and a - relative humidity of 70 to 80%. The extent of fungus spread was determined 21 days after inoculation.
- -~ 1331385 O.Z. 0050/39507 The results show that active ingredients 1, 5 and 6, when emplayed as 0.0125 and 0.006wt% spray liquors, had a better fungicidal action (90%) than prior art active ingredients A and B (10~o).
5 Use Example 3 Action on Plasmopara viticola Leaves of potted vines of the M~ller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) ôO% of active ingredient and 10 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse.
Then the leaves were infected with a zoospore suspensio~ of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24C and then in a greenhouse for 5 days at from 20 15 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1, 5 and 6, when applied as 20 0.05wt% spray liquors, had a better fungicidal action (97%) than prior art comparative agents A, B and C (S0%).
use Example 4 Action on Pyrenophora teres Barley seedlings of the "Igri" variety were sprayed to runoff at the 2-leaf stage with aqueous suspensions containing (dry basis) 8~ of active ingredient and 20~ emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 30 hours in a high-hum1dity climatic cabinet kept at 18C. The plants were then cultivated for a further 5 days in the greenhouse at 20-22C and a -~
relative humidity of 70%. The extent of fungus spread was then determined.
The results show that active ingredients 1, 5 and 6, when applied as 0.05%
35 spray liquors, had a better fungiicidal action (97%) than~prior art active ingredients A, B and C (50%).
' ' ~, ~ `
j':" ';;
,'"~ .
' ~
,~
,~ , ,, ~ 133~38~ '' - g L L
,~ L n _ ~ E
E u~ _ n E
-- ~ o -- o - ~
E o o o o a~ -- ._ .o ~ a~
~ _ o o o o o ~ ~
~ :~, _ 'C _ _ _ _ ~:
O C C_ ~ e C O ~ C C C C O O ~ ~ C OL L
----Cc--~Co~L----__~,cccooCccoo O O O O -- I O S ~ ~ C O C C -- O O O C r o O O ' OOOOC~O--C~COCC--OOO~ OOO----~~ E ~ u ~ E ~ ~ ~ C c t:L ~ u u ~ ~ u u ~ ~ ~ ` ~
., , ~ i .
:~ :, C ' ~ ~ ~ ~ -- -- -- ~ o --~.', 8~ 8 ~ 8 8 8 8 8 8 8 8 8 8 8 0 ~ O O .~ ~ ~ C ~ ~ o ~, , ~ '`~'~ ,' ,:. :, _ ~:
O '"' ~
" ~ ' o C ~,. - '~:
~: -- 8 ' ~ :: _ o ~ !
,: ~ 1- 'UC
S I T I S T
~: :, : O
: C , ':
"-~ O ' ~ ~
,,, ~ ~ C :: :.
,,:' : : , ,' ' ~.".
, ~ , ",', ",, ",";",1~,~ '' ' j '' ," " "', ,",~ ,, ,",'~ ", ' ' ,''",,~ ,'," ,' 133~38~
L
L
~ E E 'a o o o o : i : ., ~, Q
O ' ~;' .
O
O
~ :~, ~, C :~ C C :-~
O ~ ~ S ~ S S ~ ~ ' S _ _ _ S _ _ ~ _ S _ CL ~L -- _ _ -- C
C C C~ ~ ~ ~ V ~ ~ ~ L ~ ~ ~ ~ ~ e C LO
C S O S S S O S S ~ S O S ~ ~ S _ S S - O
o O s o o O s o o ~ o s o I I o c -- o o C
L L ~ L L L ~ L L . L ~ L ~ ~ L ~ ~ . L L U
~_ _ _ _ _ _ O ~ _ ~ O ~ ~ _ S~ -- ~
S S I C S S I S _ ~ S I _ ~ ~ .C ~ C ~> C C S I
t.> v ~ ~ ~ ~ ~ E ~ u C C C C C N 1~ N 1~
a~ ~ ~ c ~ c e c c c S ~, _ C _ ~C~ _ $ g ~ ~ ~ ~
O -- O -- O ~ O ~`~ O ~ O O O O O O O _ _ -- --L :~, L ::~ o o o o~ o o o o o o o _ o " ,, ~ o o o o .
:~ _ ~ _ ~ _ ~ _ ~ _ CL _ -- _ _ C S S ~ ~ ~ L L L L '-v v ~ ~ n ~ c~
o I o I ~O~ i 0~. 1 OX ~ ~ ~ I ,~. ~ c c c I ~ I C C C C .
- - :
~:
~, ` _ ~
L :
-- S ---- I S -- -- I I -- -- ~ ~ ~ I S -- ~
~, -, -'"~ O ,, ,::
C
o_ ~ ~ ~ u~ O O ~ ~ ~ ~ O --" :, ~
~: .. -~, .
i33138~ ~
C~
E ~ :
~ :
o o~
~ : ~, .;
; ~ .
O ~ :
O ~ ~ ~ '' C C ~ C _ a~ ~ ~ ~ ~ L O ~ ~U ~ L ~ ~ O ~ ~ L ~ ~ ~ ~
C .C ~ ' C O ' ~ C -- O ' ~ .C C C O -- ~ C- ~ :
C~ ~ 8 ~ CL-- 1~ n ~ ~ 8 0 ~ ` E
L ~, . 2 L U L 2 ~ I _ o o s o I L X ' ~
O S ~1 ~ O O _ O ~ _ O O _ O ~ ,C O o ~_ o _ ~ ~ C
L ~ _ _ ~ ~ L ~ _ _ ~ ~ L ~ _ _ ~ ~ ~ L O ~ : : ~ ~`
E ~ ~ u 'u ~ ~ ~ u ~u ~ ~ E ~ c ~ -- c : . ~
~ ~ __ _ _ _ _ ~. . :
CL L ~ L L L L
L LL II I I I I ~, ~, ~ , ~ C C C C ~C C ~ C
O O O O O O C C ,C C ,C C C ~ ~> ~ ~ ~ ~ ~ ~>
c c c ~ -- ~ o 0 0 ~ 0 0 E E E E E E E E .::
. ~, :~ : ~ ,::
i. ~,~.
.`" , .
,,-: :
~ ~,: : . . :' :: ' ~, .
133i385 - ~:
a E _.
o ~ ::
U~
a-o o _ _ :
C ~ C C C ~ ~
-- -- ~L -- -- , _ _ _ _ C _ _ C _ C -- -- _ C _ _ _ C
CC~CoC C~C~oCCoCoCCCoCCCo c C ~ ` o c _ c ~ C c o c ~ O c o C c c o C c c O
O -- I o ~ o c o o o o c o o c o s o o O C O O O C
L ~ ~ ~ L ~ ~ L ~ ~ L ~
O ~ ~ _ ~-- O C O _ O _ ~-- O ~ _ O _ ~-- _ O O -- - ' ~ ~;
~: -- ~ ~ ,C I ,C 1~ _ ,c _ ,c I _ ,c ~ C ~ C _ C ~ C _ C ~ .. ..
~ E ~ ~J -t v C q~
.~,,:
~ C = ~ ~ C C ~ C C ~ L L
-? ~ -. : ~ ~ ~ ' - ' :
, . .
S S I S S I S: S S S S S S S S S ~: S T S T T I S . . ~ ~;
C
.,,, ~. .
.", ~ o " D % ,~ ~ ~ ~ ~ ~ ~' P~'. ~ .
?.~: :
, ':
':"'~
: ~
.~ , , '/', , ,,, ' . ', . ,, ., ' . .,, . . ' ' ' , " ' ' I : . ' .. , . ,.. ' ' -133~ 385 ~
~, .
~ ~,, o .
~ .
,~ ," ,,~,.
O !, ` . ~ ~:
O V
___,C__ ~ .
C O ~ -~ L
O O O ' O O `~
L L V L L
O O O ~_ O O :
~t U ~
; ` ' `., -:
" C ~ C C
E E E E
S S S S S S "`' '~'~ , "''` ~'''':"
.''~ ' ., ', :
,~,~ , ' ' , :
.~ ~ O '' ~ :
~": ~ ~S O _ ~ ~ ' O O O O O O
X _ ~
~, W ' :: :
G
, _ 14 O.Z. 0050/3~ ~ 3 ~. 3 8 ~
In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomy~etes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, PodoSphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, 20 Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea ~gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 30 Fusarium and Verticillium species in various plants, PlaSmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the 35 active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such 40 as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water 133~.38~
O.z 0050/39507 is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., 5 methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyl-10 ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from G.1 to 95, and preferably from 0.5 to 90, wt% of active ingredient. The application rates are from 0.02 to 3 15 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, e.g., on Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as 20 solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
30 II. 20 parts by weight of compound no. 5 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene 35 oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 6 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-40 butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxideand 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
16 o z 0050/39507 IV. 20 parts by weight of compound no. 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
15 Vl. 3 parts by weight of compound no. 5 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 6 is intimately mixed with a 20 mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
25 VIII. 40 parts by weight of compound no. 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stabte - aqueous dispersion. Dilution in water gives an aqueous dispersion.
30 IX. 20 parts by weight of compound no. 1 is intimatety mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by - weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodiùm salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is 35 obtained. ; ~ , ! ' ' ."
In these apptication forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be 40 mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in a greater fungicidal action spectrum.
~ 133~ 385 17 O.Z. 0050/39507 The following list of fungicides with which the novel compounds may be combined is intended.to illustrate possible combinations but not to impose any restrictions.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, ::
dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, 10 zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, : .
tetramethylthiuram disulfides, 15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithioccarbamate and N,N'-polypropylenebis(thiocirbamyl) disulfide;
20 nitro derivatives, such as dinitro(1-methylheptyl)-phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and ~` diisopropyl 5-nitroisophthalate;
.~ 25 heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, ~: 2,4-dichloro-6-(o-chloroanilino)-s-triazine, ~: a, 0-diethyl phthalimidophosphonothioate, 30 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio[4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 35 2-(fur-2-ylj-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, , '~
N-trichloromethylthiotetrahydrophthalimide, -~ N-trichloromethylthiophthalimide, ~.
: ~- 40 N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, ~ -5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, - 2-thiocyanatomethylthiobenzothiazole, ;~ 1,4-dichloro-2,5-dimethoxybenzene, ~ , , , ., ., , ~ , ~ ~ , .. . .
18 0 z. 0050/39507 1 33~. 385 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, 15 piperazine-1,4-diylbis-(1-(2,2,2-trichtoroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-t3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, 20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N -imidazolyl-urea, :
1-(4-chlorophenoxy)-3~3-dimethyl-1-(lH-1~2~4-triazol-1-yl)-butan-2-one~
1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol, 1-(4-phenylphenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanol, ~-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 30 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyr~dinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as 35 dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, ~:
hexachlorobenzene, . -:
DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, ~
methyl DL-N-(2,6-dimethylphenyl)-N-(2 -methoxyacetyl)-alanate, :
40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, `
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, ~,. . .... . . ........ ... .... ..... .
,---\
19 O.Z. 0050/39507 N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-aCetamide, 1-[2-(2,4-dichlorophenyl)-pentyl]-lH-1,2,4-triazole, 2,4-difluoro-a-(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, 5 N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and 1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
Use examples The agents used for comparison purposes were 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-one (C), 2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridinyl)-2-propen-1-ol (A), and 2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-ol (B) 15 disclosed in EP-214,566.
Use Exampte 1 Action on wheat mildew 20 Leaves of pot-grown wheat seedlings of the "FrUhgold" variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier, and dusted, 24 hours after the sprayed-on layer had dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants were then set up in the greenhouse at from 20 to 22C and a rela-25 tive humidity of from 75 to 80%. The extent of mildew spread was assessedafter 7 days.
The results show that active ingredients 1 and 5, when employed as 0.025 and 0.006wt~ spray liquors, had a better fungicidal action (97%) than ;
30 prior art active ingredients A, B and C (70%).
use Example 2 Action on cucumber mildew 35 Leaves of pot-grown cucumber seédlings of the i'Chinesische Schlange"
variety were sprayed at the two-leaf stage with an aqueous conidial suspension of cucumber mildew. After about 20 hours, these plants were sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After ~he sprayed-on layer had 40 dried, the plants were set up in the greenhouse at 20 to 22C and a - relative humidity of 70 to 80%. The extent of fungus spread was determined 21 days after inoculation.
- -~ 1331385 O.Z. 0050/39507 The results show that active ingredients 1, 5 and 6, when emplayed as 0.0125 and 0.006wt% spray liquors, had a better fungicidal action (90%) than prior art active ingredients A and B (10~o).
5 Use Example 3 Action on Plasmopara viticola Leaves of potted vines of the M~ller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) ôO% of active ingredient and 10 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse.
Then the leaves were infected with a zoospore suspensio~ of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24C and then in a greenhouse for 5 days at from 20 15 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1, 5 and 6, when applied as 20 0.05wt% spray liquors, had a better fungicidal action (97%) than prior art comparative agents A, B and C (S0%).
use Example 4 Action on Pyrenophora teres Barley seedlings of the "Igri" variety were sprayed to runoff at the 2-leaf stage with aqueous suspensions containing (dry basis) 8~ of active ingredient and 20~ emulsifier. After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora teres and placed for 48 30 hours in a high-hum1dity climatic cabinet kept at 18C. The plants were then cultivated for a further 5 days in the greenhouse at 20-22C and a -~
relative humidity of 70%. The extent of fungus spread was then determined.
The results show that active ingredients 1, 5 and 6, when applied as 0.05%
35 spray liquors, had a better fungiicidal action (97%) than~prior art active ingredients A, B and C (50%).
' ' ~, ~ `
Claims (7)
1. A 3-substituted pyridine of the formula (I) where R1 is hydrogen, C1-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C2-C12-acyl, C2-C12-haloacyl, acryloyl, benzoyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-atkoxy, phenyl, acetoxy, C1-C4-haloalkyl, halogen or nitro, or is benzyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, halogen, cyano or nitro;
R2 is hydrogen, C1-C12-alkyl, C3-C12-cycloalkyl, C4-C20-cycloalkyl-alkyl, C4-C20-alkylcycloalkyl, substituted or unsubstituted C7-C20-arylalkyl, substituted or unsubstituted C7-C20-aryloxy-alkyl, whose aryl radicals are unsubstituted or substituted by C1-C4-alkgl, C1-C4-a1koxy, C1-C4-haloalkyl or halogen, R3 is the radical or R4 to R8 being identical or different and each denoting hydrogen, C1-C4-alkyl, C1-C4-alkoxy,C1-C4-haloalkyl, C2-C4-alkoxycarbonyl, C2-C4-dialkylamino, phenyl, hydroxy or halogen, and R4 and R5, or R5 and R6, additionally denoting the group -CH=CH-CH=CH-, n is 0 or 1, and its plant-tolerated salts.
R2 is hydrogen, C1-C12-alkyl, C3-C12-cycloalkyl, C4-C20-cycloalkyl-alkyl, C4-C20-alkylcycloalkyl, substituted or unsubstituted C7-C20-arylalkyl, substituted or unsubstituted C7-C20-aryloxy-alkyl, whose aryl radicals are unsubstituted or substituted by C1-C4-alkgl, C1-C4-a1koxy, C1-C4-haloalkyl or halogen, R3 is the radical or R4 to R8 being identical or different and each denoting hydrogen, C1-C4-alkyl, C1-C4-alkoxy,C1-C4-haloalkyl, C2-C4-alkoxycarbonyl, C2-C4-dialkylamino, phenyl, hydroxy or halogen, and R4 and R5, or R5 and R6, additionally denoting the group -CH=CH-CH=CH-, n is 0 or 1, and its plant-tolerated salts.
2. A process for the manufacture of a pyridine of the formula (I) as set forth in claim 1, comprising the steps of:
either treating a pyridyl ketone of the formula (III) or a pyridyl alcohol of the formula (IV):
(III) (IV) where R2 and R3 have the meanings given in claim 1, with a reducing agent;
or reacting an organometallic compound of the formula (V):
(V) where R2 and R3 have the meanings given in claim 1 and M is lithium or one of the radicals MgCl or MgBr, with nicotinaldehyde, to obtain the compound of the formula (I) where R1 denotes hydrogen; and then reacting or not the compound that was so obtained with an alkylating or acylating agent of the formula (II):
R1-X (II) where R1 has the meanings given in claim 1, with the exception of hydrogen, and X is a nucleofugic group, to obtain another compound of the formula (I).
either treating a pyridyl ketone of the formula (III) or a pyridyl alcohol of the formula (IV):
(III) (IV) where R2 and R3 have the meanings given in claim 1, with a reducing agent;
or reacting an organometallic compound of the formula (V):
(V) where R2 and R3 have the meanings given in claim 1 and M is lithium or one of the radicals MgCl or MgBr, with nicotinaldehyde, to obtain the compound of the formula (I) where R1 denotes hydrogen; and then reacting or not the compound that was so obtained with an alkylating or acylating agent of the formula (II):
R1-X (II) where R1 has the meanings given in claim 1, with the exception of hydrogen, and X is a nucleofugic group, to obtain another compound of the formula (I).
3. A fungicidal composition containing at least one inert carrier and a fungicidal amount of a 3-substituted pyridine of the formula (I) as set forth in claim 1 or a plant-tolerated salt thereof.
4. A process for combating fungi, wherein the fungi, or the materials, plants soils or seed are treated with a fungicidally effective amount of a 3-substituted pyridine of the formula (I) as sert forth in claim 1 or a plant-tolerated salt thereof.
5. 2-n-Butyl-3-(4-fluorophenyl)-1-(3-pyridinyl)-propan-1-ol.
6. A fungicidal composition containing at least one inert carrier and a fungicidal amount of the compound of claim 5.
7. A process for combating fungi, wherein the fungi, or the materials, plants soils or seed are treated with a fungicidally effective amount of the compound of claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873734750 DE3734750A1 (en) | 1987-10-14 | 1987-10-14 | 3-SUBSTITUTED PYRIDINS AND FUNGICIDES CONTAINING THEM |
| DEP3734750.0 | 1987-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331385C true CA1331385C (en) | 1994-08-09 |
Family
ID=6338298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000578570A Expired - Fee Related CA1331385C (en) | 1987-10-14 | 1988-09-27 | 3-substituted pyridines and fungicides containing them |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0311907B1 (en) |
| JP (1) | JPH01132563A (en) |
| AT (1) | ATE91683T1 (en) |
| AU (1) | AU611209B2 (en) |
| CA (1) | CA1331385C (en) |
| DE (2) | DE3734750A1 (en) |
| ES (1) | ES2058204T3 (en) |
| HU (1) | HU203643B (en) |
| IL (1) | IL87798A (en) |
| NZ (1) | NZ226365A (en) |
| ZA (1) | ZA887642B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3744620A1 (en) * | 1987-12-31 | 1989-07-13 | Basf Ag | PYRIDINE N-OXIDES AND FUNGICIDES CONTAINING THEREOF |
| DE3914820A1 (en) * | 1989-05-05 | 1990-11-08 | Basf Ag | NEW PYRIDE DERIVATIVES AND THEIR USE AS FUNGICIDES |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3397273A (en) * | 1966-02-18 | 1968-08-13 | Lilly Co Eli | Controlling phytopathogenic fungi on plants with 3-pyridyl methane derivatives |
| DE3126819A1 (en) * | 1981-07-08 | 1983-01-27 | Basf Ag, 6700 Ludwigshafen | PYRIDINE CARBINOLS, PROCESS FOR PRODUCING THE SAME AND FUNGICIDES CONTAINING THEM |
| EP0117485A3 (en) * | 1983-02-28 | 1985-01-23 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Pyridine, pyrazine and pyrimidine derivatives and their use as fungicides |
| DE3531659A1 (en) * | 1985-09-05 | 1987-03-12 | Basf Ag | 3-PROPENYLPYRIDINE AND THEIR USE AS A FUNGICIDE |
| US4710508A (en) * | 1986-12-08 | 1987-12-01 | Warner-Lambert Company | O-substituted tetrahydropyridine oxime cholinergic agents |
| DE3744620A1 (en) * | 1987-12-31 | 1989-07-13 | Basf Ag | PYRIDINE N-OXIDES AND FUNGICIDES CONTAINING THEREOF |
-
1987
- 1987-10-14 DE DE19873734750 patent/DE3734750A1/en not_active Withdrawn
-
1988
- 1988-09-19 IL IL87798A patent/IL87798A/en not_active IP Right Cessation
- 1988-09-27 CA CA000578570A patent/CA1331385C/en not_active Expired - Fee Related
- 1988-09-28 NZ NZ226365A patent/NZ226365A/en unknown
- 1988-10-06 ES ES88116553T patent/ES2058204T3/en not_active Expired - Lifetime
- 1988-10-06 DE DE8888116553T patent/DE3882479D1/en not_active Expired - Lifetime
- 1988-10-06 AT AT88116553T patent/ATE91683T1/en active
- 1988-10-06 EP EP88116553A patent/EP0311907B1/en not_active Expired - Lifetime
- 1988-10-12 JP JP63255056A patent/JPH01132563A/en active Pending
- 1988-10-13 HU HU885286A patent/HU203643B/en not_active IP Right Cessation
- 1988-10-13 ZA ZA887642A patent/ZA887642B/en unknown
- 1988-10-13 AU AU23712/88A patent/AU611209B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| ES2058204T3 (en) | 1994-11-01 |
| DE3734750A1 (en) | 1989-04-27 |
| EP0311907A3 (en) | 1990-11-07 |
| EP0311907B1 (en) | 1993-07-21 |
| DE3882479D1 (en) | 1993-08-26 |
| HUT49454A (en) | 1989-10-30 |
| NZ226365A (en) | 1990-06-26 |
| IL87798A (en) | 1992-09-06 |
| HU203643B (en) | 1991-09-30 |
| AU2371288A (en) | 1989-04-20 |
| ATE91683T1 (en) | 1993-08-15 |
| JPH01132563A (en) | 1989-05-25 |
| ZA887642B (en) | 1990-06-27 |
| IL87798A0 (en) | 1989-03-31 |
| AU611209B2 (en) | 1991-06-06 |
| EP0311907A2 (en) | 1989-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4914128A (en) | Acrylates and fungicides which contain these compounds | |
| US5468717A (en) | Oxime ether derivatives, their preparation and fungicides containing these derivatives | |
| US4822908A (en) | Substituted acrylates and fungicides containing same | |
| US5157037A (en) | α-arylacrylates substituted by a heterocyclic radical, and fungicides which contain these compounds | |
| US5175167A (en) | Hetarylalkenes, their preparation and intermediates for their preparation and their use | |
| CA1289969C (en) | Substituted crotonates and fungicides containing them | |
| CA1276180C (en) | Propylamines, their preparation and their use as fungicides | |
| US4782177A (en) | Acrylic acid derivatives and fungicides which contain these compounds | |
| US5194438A (en) | α-arylacrylates substituted by a trifluoromethylpyrimidinyloxy radical, fungicidal compositions and methods | |
| US5081133A (en) | 2-anilinocyanopyridines having fungicidal properties | |
| KR0152517B1 (en) | Oximether, method for their preparation and fungicides containing them | |
| US4952720A (en) | Ortho-substituted benzyl carboxylates and fungicides which contain these compounds | |
| US5095021A (en) | Phenylalkylamines and fungicides containing these | |
| US4945112A (en) | Guanidinium compounds and fungicides containing them | |
| US4639447A (en) | Azolylnitriles, and fungicides containing these compounds | |
| CA1334594C (en) | 1-halo-1-azolylpropenes and -methyloxiranes and fungicides containing these compounds | |
| US5017595A (en) | Azolylmethylallyl alcohols and fungicides containing these compounds | |
| CA2003056C (en) | Sulfur-containing oxime ethers and fungicides containing them | |
| CA1331385C (en) | 3-substituted pyridines and fungicides containing them | |
| US4897425A (en) | Fungicidal cyclohexylamines | |
| US5039815A (en) | 1-halo-azolylethane derivatives and fungicides containing them | |
| US4678504A (en) | O-substituted 3-oxypridinium salts, their preparation and their use as fungicides for crop protection | |
| US5008438A (en) | Ortho-substituted phenol ethers and fungicides which contain these compounds | |
| US5118710A (en) | Sulfur-containing acrylic esters and fungicides containing them | |
| US5192767A (en) | 3-substituted pyridines and fungicides containing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |