NZ207229A - Pyridine,pyrazine and pyrimidine derivatives and fungicidal compositions - Google Patents

Pyridine,pyrazine and pyrimidine derivatives and fungicidal compositions

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Publication number
NZ207229A
NZ207229A NZ207229A NZ20722984A NZ207229A NZ 207229 A NZ207229 A NZ 207229A NZ 207229 A NZ207229 A NZ 207229A NZ 20722984 A NZ20722984 A NZ 20722984A NZ 207229 A NZ207229 A NZ 207229A
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NZ
New Zealand
Prior art keywords
signifies
pyridyl
pyrazinyl
pyrimidinyl
oxide
Prior art date
Application number
NZ207229A
Inventor
F Dorn
Original Assignee
Hoffmann La Roche
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Publication date
Application filed by Hoffmann La Roche filed Critical Hoffmann La Roche
Publication of NZ207229A publication Critical patent/NZ207229A/en

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    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • 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
    • C07D213/32—Sulfur atoms
    • 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
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £07229 niority Date(s): J.
Q / - J Ll Complete Specification Filed: Class: . fSHP.m£<?.7P2.y.\.... . i.ftp.i PAZlkPs.
Publication Date: P.O. Journal, No: 'tii'OCf )98Sf |27 b NO DRAWINGS No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION HETEROCYCLIC COMPOUNDS y X/We, F. HOFFMANN-LA ROCHE & CO. AKTIENGESELLSCHAFT, 124-184 Grenzacherstrasse, Basle, Switzerland, a Swiss Company, hereby declare the invention for which % / we pray that a patent may be granted to ?&}§/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by la) - la - 207229 1 The invention is concerned with heterocyclic com pounds, namely pyridine, pyrazine and pyrimidine derivatives of the general formula R —CH —C — R 11 I2 R R wherein R and R R R signifies mono-, di- or tri-substituted phenyl, the substitu-ents being 1-3 halogen atoms and/or 1 or 2 C^_2~alkyl groups and/or 1 or 2 C-^^-alkoxy groups and/or 1 or 2 trifluoromethyl groups, signifies C^g-alkenyl, C3_g-alkynyl, C^.g-alkenyloxv, C3_g-alkynyloxy, C^.g-alkenylthio or C^.g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C^^-alkyl, aryloxy or arylthio optionally mono-, di- or tri-substituted in the aryl nucleus, the optionally present sub-stituents being 1 to 3 halogen atoms and/or 1 or 2 C^^-^^yl groups and/ or 1 or 2 Cj^-alkoxy groups and/or a nitro group, and aryl being as hereinafter defined, signifies hydroxy, chlorine or bromine, signifies hydrogen or C^_4~alkyl signifies 3-pyridyl, 3-pvridyl 1-oxice, 2-pyrazinyl, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl, 5-pvrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide, 207229 and acid addition salts of these compounds.
The compounds of formula I and their acid addition 5 salts have fungicidal properties and are suitable as fungicidal active substances, especially for use in agriculture and in horticulture.
The invention is also concerned with a process for 10 the manufacture of the compounds of formula I and their acid addition salts, compounds of formula I and acid addition salts thereof as fungicidal active substances, fungicidal compositions which contain the compounds of formula I or acid addition salts thereof as the active sub-15 stance as well as the use of said compounds, acid addition salts and compositions for the control of fungi in agriculture and in horticulture.
The term "halogen" in formula I above embraces 20 fluorine, chlorine, bromine and iodine. The alkyl, alkenyl and alkynyl groups can be straight-chain or branched-chain and this also applies to the alkyl, alkenyl or alkynyl part of the alkoxy, arylalkyl, alkenyloxy, alkenylthio, alkynyloxy and alkynylthio groups. The term "aryl" per se or as part 25 of "aryloxy" or "arylthio" preferably signifies phenyl, falthough heterocyclic groups having aromatic character^ such as pyridyl, furyl and thienyl also come into consideration. In di- or trisubstituted phenyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, arylalkyl, 30 aryloxy or arylthio groups the substituents can be the same or different.
In general, the alkenyl group is preferably allyl and the alkynyl group is preferably propargyl.
Independently of one another R preferably signifies mono-, di- or trihalophenyl, especially 2,4-dichlorophenyl; R^ preferably signifies optionally substituted alkenyl, alkynyl, alkenylthio, alkynylthio, arylalkyl or arylthio, 20722<l t — 0. especially optionally substituted alkenyl, alkynyl or arylthio, as more precisely defined above; preferably sig- 4 nifies hydrogen or methyl; and R preferably signifies 5 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl.
Especially preferred compounds of formula I are: cc- (a-Allyl-2,4-dichlorobenzyl)-3-pyridylmethanol, 10 a-[2,4-dichloro-a-(2-propynyl)-benzyl]-3-pyridy1- methanol, a-[a-(2,4-dichlorophenyl)-phenethyl]-3-pyridylmeth-anol and a-(2,4-dichloro-a-phenylthio-benzyl)-3-pyridylmeth- anol.
Other representative compounds of formula I are: a- [2 ,4-Dichloro-at-phenoxy-benzyl] -a-methyl-3-pyridyl-20 methanol, ct- [a-allyloxy-2, 4-dichlorobenzyl] -a-methyl-3-pyridyl-methanol, a- [2, 4-dichloro-cc-propargyloxy-benzyl] -a-methyl-3-pyridylmethanol, a-[a-allyloxy-2,4-dichlorobenzyl]-3-pyridylmethanol, a-[a-allyloxy-2,4-dichlorobenzyl]-3-pyridylmethyl chloride, a-[ a-allylthio-2,4-dichlorobenzyl]-3-pyridylmethanol and a-[a-allyloxy-2,4-dichlorobenzyl]-a-methyl-2-pyra- zinylmethanol.
Having regard to the presence of at least two asym-metric carbon atoms in the compounds of formula I it follows 35 that the compounds can occur in isomeric forms which stand in enantiomeric or diastereomeric relationship to one another. As a consequence of the possible presence of an 2 07 27^ - 4 . - aliphatic C=C double bond geometric isomerism can also occur. Formula I is intended to embrace all of these possible isomeric forms.
As acid addition salts of the compounds of formula I there come into consideration physiologically compatible salts. These salts are preferably salts of the compounds of formula I with inorganic and organic acids such as hydro-10 chloric acid, nitric acid, phosphoric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids (e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonic acids (e.g. 1,5-naphthalene-15 disulphonic acid). In the case of the'N-oxides, i.e. the compounds of formula I in which R4 signifies 3-pyridyl 1-oxide, 2-pyrazinyl 1-oxide, 4-oxide and 1,4-dioxide, and 5-pyrimidinyl 1-oxide and 1,3-dioxide, there come into consideration as acid addition salts especially phvsio-20 logically compatible salts with strong acids such as inorganic acids (e.g. hydrochloric acid, nitric acid and phosphoric acid) and sulphonic acids (e.g. 1,5-naphthalene-disulphonic acid).
The process in accordance with the invention for the manufacture of the compounds of formula I and of their acid addition salts comprises a) for the manufacture of the compounds of formula I in which R signifies optionally substituted C^_g-alkenyloxy, C.,g-alkynyloxy or aryloxy, as more precisely defined above, o 4 Rz signifies hydroxy and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reacting an epoxide of the general formula II R —CH—G—R \ / 0 3 wherein R and R have the significances given above 4 ' and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, or an alcohol of the general formula B3 I 4, lo R— CH—C —R III I I X OH 3 41 wherein R, R and R have the significances given above ^ and X signifies a halogen atom (e.g. chlorine or bromine), an alkylsulphonate group (e.g. the methanesulphonate group) or an arylsulphonate group (e.g. the benzenesulphonate or p-toluenesulphonate group), with a compound of the general formula R1'— H IV i » wherein R signifies g-alkenyloxy or C^g" alkynyloxy optionally substituted with 1 to 3 halogen atoms; or optionally mono-, di- or trisubstituted aryloxy, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^_2-alkyl groups and/or 1 or 2 alkoxy groups and/or a nitro group, fc>) for the manufacture of the compounds of formula I in which R^" signifies optionally substituted C^g-alkenyl, C^^g-alkynyl, C^g-alkenylthio, C3_g-alkynylthio, aryl- or arylthio, as more precisely defined above, R2 207229 3 4 signifies hydroxy, R signifies hydrogen and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reducing a ketone of the general formula 4' r—ch— c — r v :h—c r, If 4' wherein R and R have the significances given above 1" and R signifies C^g-alkenyl, C^g-alkynyl, C^g-alkenylthio or C^g-alkynylthio 15 optionally substituted with 1 to 3 halo gen atoms; or aryl-C^^-alkyl or arylthio optionally mono-, di- or trisub-stituted in the aryl nucleus, the optionally present substituents being 20 l.to 3 halogen atoms and/or 1 or 2 groups and/or 1 or 2 alkoxy groups and/or a nitro group, c) for the manufacture of the compounds of formula I in which R^" signifies optionally substituted C^g-alkenyl, C^.g-alkynyl, C^g-alkenylthio, C^_g-alkynylthio, aryl- C, ^-alkyl or arylthio, as more precisely defined above, 2 3 4 R signifies hydroxy, R signifies C^_^-alkyl and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reacting 30 a ketone of general formula V, as defined above, with a compound of the general formula 3' R — Y VI 3 » wherein R signifies C^_4~alkyl, Y signifies lithium or MgZ and Z signifies halogen, especially bromine or iodine, d) for the manufacture of the compounds cf formula I 2 4 in which R signifies chlorine or bromine and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, treating an alcohol of the general formula R3 1 4' R— CH— C—R I' ll 1 R OH 13 4' wherein R, R , R and R have the significances given above, with a chlorinating agent or a brominating agent, ^ e) for the manufacture of the compounds of formula I in which R^" signifies optionally substituted C -alkenyl- o — O thio, C3^6-alkynylthio or arylthio, as more precisely defined above, and R2 signifies hydroxy, reacting a thio- ether of the general formula Till r— ch2 —r vii wherein R has the significance given above Till and R signifies C. -alkenylthio or C - « r J — O 3-6 " alkynylthio optionally substituted with 1 to 3 halogen atoms; or optionally mono-, di- or tri-substituted arylthio, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^^-alkyl groups and/or 1 or 2 C^_3-alkoxy groups and/or a nitro group, with an aldehyde or ketone of the general formula R3— C—R4 VIII 3 4 wherein R and R have the significances given above, or f) for the manufacture of the compounds of formula I in 4 which R signifies 3-pyridyl 1-oxide, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide, N-oxidizing a pyridine, pyrazine or pyrimidine derivative of the general formula R3 I 4.
R—CH—C—R I" >1 l2 R R 1 2 3 4' wherein R, R , R , R and R have the significances given above, and, if desired, converting a compound of formula I obtained into the corresponding acid addition salt by reaction with an acid.
Process variant a) is conveniently carried out with an excess of the compound of formula IV and in a temperature range between 0°C and the reflux temperature of the reaction mixture. When the reaction is carried out using the epoxide of formula II the preferred temperature range is 0°C to 70°C and the preferred excess of the compound of formula IV is up to 200 weight percent. When the reaction is carried out using the alcohol of formula III the preferred temperature range is between room temperature and the reflux temperature of the reaction mixture. When the alcohol of formula III is reacted with the compound of formula IV the latter can also be used in the form of a metal salt, preferably an alkali metal salt or an alkaline earth metal salt.
Moreover, in both cases the reaction can be carried out in a diluent. If a diluent is used, then this is preferably the reagent of formula IV, which is used in 2072^9 excess, or an inert organic solvent such as an aromatic hydrocarbon (e.g. benzene or toluene), an aliphatic or cyclic ether (e.g. diethyl ether, dioxan or tetrahydrofuran), a 5 halogenated aliphatic hydrocarbon (e.g. methylene chloride, chloroform or carbon tetrachloride) or dimethy1formamide.
When the epoxide of formula II is used the addition of a mineral acid (e.g. sulphuric acid), a sulphonic acid 10 (e.g. p-toluenesulphonic acid) or a Lewis acid (e.g. aluminium chloride, zinc chloride or boron trifluoride) is often advantageous.
When the alcohol of formula III is used an inversion 15 at the carbon atom carrying groups R and X occurs and thus, for example, from an alcohol of formula III there can be manufactured a different enantiomeric form of the product of formula I than from the corresponding epoxide of formula H.
Examples of salts of the compound of formula IV which may be used in this process variant are alkali metal salts such as the sodium and potassium salts and alkaline earth metal salts such as the calcium and magnesium salts.
It has been found to be advantageous to produce the alcohol of formula III in situ by reacting the corresponding epoxide of formula II with an alkylsulphonic acid or arylsulphonic acid or with hydrogen chloride or hydrogen 30 bromide and subsequently to react the resulting alcohol of formula III without isolation with a compound of formula IV or a salt thereof to give the desired product of formula I.
The reduction in accordance with process variant b) 35 is preferably carried out by means of a complex metal hydride such as sodium borohydride, in which case the reduction is carried out in a protic diluent such as an alcohol (e.g. methanol or ethanol) at temperatures about room temperature, or lithium aluminium hydride, which is used in an aprotic 70717^ diluent, especially an aliphatic or cyclic ether (e.g. diethyl ether, tetrahydrofuran or dioxan) at temperatures between 0°C and room temperature. As complex metal hydrides 5 in suitable solvents there also come into consideration lithium borohydride in ethanol or tetrahydrofuran, sodium borohydride-aluminium chloride in an ether (e.g. diglyme) and lithium tri(tert.butoxy)aluminium hydride in tetrahydrofuran. The ketone of formula V can also be reduced to the 10 compound of formula I, for example, by means of diborane in tetrahydrofuran or by catalytic hydrogenation known per se. The reaction conditions are familiar to the person skilled in the art from analogous reductions.
Process variant c) is conveniently carried out by reacting the ketone of formula V with the compound of formula VI in an inert diluent, preferably an aprotic solvent such as an aliphatic or cyclic ether (e.g. diethyl ether, tetrahydrofuran or dioxan) and in a temperature range 20 between -70°C and the reflux temperature of the reaction mixture, preferably between -30°C and room temperature.
The reaction of the alcohol of formula 11 according to process variant d) is preferably carried out using 25 phosphorus pentachloride, thionyl chloride or phosphorus oxychloride as the chlorinating agent or phosphorus tri-bromide as the brominating agent. The reaction is conveniently carried out in the presence of an inert diluent, especially an aprotic organic solvent, and optionally also 3° in the presence of a base. The preferred diluents are aliphatic and aromatic hydrocarbons such as n-hexane, benzene, toluene and xylenes, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, halogenated aromatic hydrocarbons such as 35 chlorobenzene and tertiary amines such as triethylamine and pyridine. Triethylamine, pyridine and calcium carbonate are preferred bases. The reaction temperatures generally lie between 0°C and the reflux temperature of the reaction mixture, preferably between room temperature and the reflux 207229 - li - temperature. The chlorinating agent or brominating agent is preferably used in excess.
In the case of process variant e) the thioether of formula VII is conveniently firstly treated with a strong base such as an alkali metal amide (e.g. lithium diiso-propylamide) in an inert diluent such as a hydrocarbon or an aliphatic or cyclic ether (e.g. tetrahydrofuran) and at a 10 temperature of about -20°C. The addition of a complexing agent (e.g. hexamethylphosphoric acid triamide) to the reaction mixture has been found to be advantageous. The aldehyde or the ketone of formula VIII is subsequently added and the reaction mixture is brought to room temperature. 15 In this manner the reaction is normally completed within a short time.
Process variant f) comprises N-oxidizing those pro- 4 ducts of formula I in which R has the significance given 4 1 above for R . The reaction can conveniently be carried out by N-oxidizing the compound of formula I" by means of hydrogen peroxide or a peracid in the presence of an inert diluent.
When hydrogen peroxide is used as the oxidizing agent there come into consideration as diluents especially lower alkanols such as methanol, ethanol and isopropanol, and the N-oxidation is preferably carried out in a temperature range between 0°C and 60 °C, especially between 20°C 30 and 40 °C.
As peracids there come into consideration preferably peracetic acid, perbenzoic acid and m-chloroperbenzoic acid, the oxidation being preferably carried out in a halogenated 35 hydrocarbon (e.g. methylene chloride or chloroform) as the diluent. The N-oxidation with a peracid is preferably carried out in a temperature range between 0°C and the reflux temperature of the reaction mixture, especially between 0°C and room temperature. An especially preferred embodiment of this process variant comprises carrying out the N-oxidation with m-chloroperbenzoic acid in chloroform in a temperature range between 0°C and room temperature.
For the manufacture of the acid addition salts of the compounds of formula I, the compounds of formula I are reacted with the desired acids in the usual manner.
( The isolation and purification of the thus-manufact- I ured compounds of formula I or of the acid addition salts (_can be carried out according to methods known per se.
The epoxides of general formula II usable as starting 15 materials are for the most part novel. They can be produced by reacting a halide of the general formula r_CH2 —Hal ix wherein R has the significance given above and Hal signifies chlorine, bromine or iodine, with an aldehyde or ketone of general formula VIII given 4 41 above in which R has the significance given above for R and with dimethyl sulphide in an aqueous medium.
This reaction is conveniently carried out as a one-pot process in the presence of an inert organic solvent 30 and a base. It is therefore preferably carried out in an aqueous-organic system. Especially suitable organic solvents are aliphatic and aromatic hydrocarbons such as n-hexane, benzene and toluene, alcohols such as methanol, ethanol and isopropanol and aliphatic and cyclic ethers such as diethyl 35 ether, tetrahydrofuran and dioxan. Preferred bases are water-soluble alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The reaction is generally carried out at a temperature between room temperature and the reflux temperature of the reaction mixture. 207 The starting materials of general formula III can be produced for example, by reacting an epoxide of formula II with hydrochloric acid or hydrobromic acid or with an 5 alkanesulphonic acid or an aromatic sulphonic acid analogously to process variant a).
Those starting materials of general formula V in 1" which R signifies optionally substituted C^g-alkenyl, 10 C^g-alkynyl or aryl-Cj^-alkyl, as raore precisely defined above, are novel and can be produced by treating a ketone of the general formula R— CH2 — C—R X 4' wherein R and R have the significances given 20 above, with an alkylating agent of the general formula 1 II If R —U XI i ii n wherein R signifies C3_g-alkenyl or C^g-alkynyl optionally substituted with 1 to 3 halogen atoms; or aryl-C^^-alkyl optionally mono-, di- or trisubstituted 30 in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^_3-alkyl groups and/or 1 or 2 C^^-alkoxy groups and/or a nitro group, 35 and U signifies a leaving group, especially chlorine, bromine or iodine.
In the reaction the ketone of formula X is advantageously converted with a base such as sodium hydride or lithium diisopropylamide in a diluent, preferably an aprotic organic solvent such as tetrahydrofuran, dimethoxyethane or dimethylformamide,at reaction temperatures between -70°C and 50°C into an anion which is then treated with the alkylating agent of formula XI. The treatment of the ketone of formula X with the alkylating agent of formula XI can also be carried out in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, i.e. under the conditions of phase transfer catalysis [see, for example, J. Dockx, (Synthesis (1973) , 441] .
The remaining starting materials of general formula 1" V, i.e. those ketones of formula V in which R has the significance given above for R1'\ are novel. They can be produced by reacting a thioether of general formula VII with an ester of the general formula R4' — C — OR5 XII 0 4' wherein R has the significance given above and R signifies C1_4~alkyl or phenyl.
The reaction is conveniently carried out under the reaction conditions described above in connection with process variant e), the ester of formula XII being used in place of the ketone of formula VIII.
The starting materials of general formula V form a further object of the present invention.
The starting materials of general formula I1 are 2 those compounds of formula I in which R signifies hydroxy 4 and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl. These compounds can be produced, for example, in accordance with process varaints a) to c) and e). 207229 The starting materials of general formula I" also represent a sub-class of compounds of general formula I and can be produced, for example, in accordance with process 5 variants a) to e).
The starting materials of general formulae IV, VI to IX, XI and XII are either known or can be produced according to methods known per se.
The ketones of general formula X which are used as starting materials are either known or can be produced according to methods known per se [see, e.g., u.S. Patent Specification No. 3,929,807]. The following process is, 15 however, especially preferred: R— CH- — Hal + HC —R4' »• R—CH-,— C—R4 ' ►ketone X 2 I 2 1 CN CN IX XIII XIV 4 ' wherein R, R and Hal have the significances given above and Q signifies a disubstituted amino group (e.g. dimethylamino, diethyl-amino, piperidino or morpholino) or the trimethylsilyloxy group.
The reaction of the compound of formula IX with the compound of formula XIII can be carried out, for example, under the conditions of phase transfer catalysis [see, for example, J. Dockx, Synthesis (1973) , 441] or using a base such as, for example, sodium hydride or lithium diisopro-35 pvlamide in an inert solvent such as, for example, an aliphatic or cyclic ether (e.g. tetrahydrofuran or dimethoxy- preferably between -30°C and room temperature, and with the exclusion of water. The compound of formula XIII in which Q signifies the trimethylsilyloxy group is preferably reacted in the presence of a base. The thus-obtained compound of formula XIV can thereupon be converted into the ketone of formula X by hydrolysis (e.g. by conventional treatment with an aqueous acid). Acids which can be used for this purpose are especially strong inorganic acids such as sulphuric acid, hydrochloric acid and hydrobromic acid as well as sulphonic acids such as benzenesulphonic acid and p-toluenesulphonic acid. The hydrolysis is conveniently carried out in a temperature range between 20°C and the reflux temperature of the reaction mixture, preferably between 80°C and 100°G.
The starting materials of general formula VIII are either known or can be produced according to methods known per se; for example, from the corresponding aldehydes of the 4 • formula R -CHO [see, for example, E. Leete et al., J. Org.. Chem. _43, 2122 (1978) and W. Lidy et al., Chem. Ber. 106, 587 (1973)] .
The compounds in accordance with the invention, i.e. the compounds of formula I and their acid addition salts, have fungicidal activity and can accordingly be used for the control of fungi in agriculture and in horticulture.
They are especially suitable for the inhibition of the growth or for the eradication of phytopathogenic fungi on parts of plants (e.g. leaves, stems, roots, tubers, fruits or flowers) and on seeds as well as in the soil and are especially effective in the control of Botrytis cinerea (grey mould); of powdery mildew fungi such as, for example, Uncinula necator (powdery mildew of vines), Erysiphe cichoracearum (powdery mildew of curcubits), Podosphaera leucotricha (powdery mildew of apples) and Erysiphe graminis (powdery mildew of cereals); of Venturia inaequalis (apple scab); and of harmful fungi of the genera Puccinia, Uromyces Hemileia, Rhizoctonia, Penicillium, Septoria, Corticium, 2072^9 Cercospora, Helminthosporium and Alternaria.
Individual representatives of the compounds in 5 accordance with the invention have, moreover, a pronounced activity against wood-destroying fungi such as, for example, Coniophora puteana and Gloeophyllum trabeum.
The compounds in accordance with the invention are 10 distinguished by local and/or systemic activity.
The compounds in accordance with, the invention are active under greenhouse conditions even at a concentration of 1 mg to 500 mg of active substance per litre of spray 15 liquor. In the open, concentrations of 25 g to 1000 g of active substance of formula I per hectare and treatment are- V ^ advantageously used. For the control of seed-borne fungi in a disinfecting process there are advantageously used 0.05 g to 1.5 g of active substance of formula I per kg of 20 seeds.
The above-mentioned ketones of general formula V as well as their N-oxides are also valuable as fungicides, since they have a similar spectrum of activity as the 25 compounds of formula I. These compounds can accordingly also be used for the control of fungi in agriculture and in horticulture, namely in the same manner as the compounds of formula I. The N-oxides of the ketones of formula V can be produced by N-oxidizing the ketones of formula V analo-30 gously to process variant f). These N-oxides also form an object of the present invention.
The compounds in accordance with the invention can be formulated to give a wide variety of compositions (e.g. 35 solutions, suspensions, emulsions, emulsifiable concentrates and pulverous preparations). The fungicidal compositions in accordance with the invention contain an effective amount of at least one compound of general formula I, 2o~ri2q as defined above, or an acid addition salt of such a compound as well as formulation adjuvants. The compositions conveniently contain at least one of the following form-5 ulation adjuvants: Solid carrier substances; solvents or dispersion media; tensides (wetting and emulsifying agents); dispersing agents (without tenside action); and stabilizers.
As solid carrier substances there essentially come into consideration: natural mineral substances such as kaolin, aluminas, siliceous earth, talc, bentonite, chalk (e.g. whiting), magnesium carbonate, limestone, quartz, 15 dolomite, attapulgite, montmorillonite and diatomaceous earth; synthetic mineral substances such as highly dispersible silicic acid, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and 20 nitrates, whereby such carrier substances can be present, for example, in the form of granulates or powders.
As solvents or dispersion media there essentially come into consideration: aromatics such as toluene, 25 xylenes, benzene and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. petroleum fractions); alcohols such as butanol and 30 glycol as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and strongly polar solvents or dispersion media such as dimethylformamide, N-methylpyrrolidone and dimethyl sulphoxide, such solvents or dispersion media 35 preferably having flash points of at least 30°C and boiling points of at least 50°C, and water. Among the solvents or dispersion media there also come into consideration so-called liquified gaseous extenders or carrier substances, these being products which are gaseous at room temperature and under normal pressure. Examples of such products are especially aerosol propellants such as halogenated 5 hydrocarbons (e.g. dichlorodifluoromethane). When water is used as the solvent, organic solvents can, for example, also be used as auxilliary solvents.
The tensides (wetting and emulsifying agents) can be 10 non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide, fatty acid esters and ethers of sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation with ethylene 15 oxide? block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.
The tensides can also be anionic compounds such as soaps; fatty sulphate esters (e.g. dodecyl sodium sulphate, 20 octadecyl sodium sulphate and cetyl sodium sulphate); alkyl sulphonates, aryl sulphonates and fatty-aromatic sulphonates such as alkylbenzene sulphonates (e.g. calcium dodecyl-benzene sulphonate) and butylnaphthalene sulphonates; and more complex fatty sulphonates (e.g. the amide condensation 25 products of oleic acid and N-methy1taurine and the sodium sulphonate of dioctyl succinate).
Finally, the tensides can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethyl-30 ammonium chlorides, alkyltrimethylammonium chlorides and ethoxylated quaternary ammonium chlorides.
As dispersing agents (without tenside action) there essentially come into consideration: lignin, sodium and 35 ammonium salts of lignin sulphonic acids, sodium salts of maleic anhydride-diisobutylene copolymers, sodium and ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphit4 lyes.") As dispersing agents, which are especially suitable as thickening or anti-settling agents, there can be used, for example, raethylcellulose, carboxymethylcellulose, hydroxy-ethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.
Examples of suitable stabilizers are acid-binding agents (e.g. epichlorohydrin, phenyl glycidyl ether and soya epoxides); antioxidants (e.g. gallic acid esters and butyl-hydroxytoluene)} UV-absorbers (e.g. substituted benzophenones, diphenylacrylonitrile acid esters and cinnamic acid esters); and deactivators (e.g. salts of ethylenediaminetetraacetic acid and polyglycols).
The fungicidal compositions in accordance with the invention can contain, in addition to the active substances of formula I, other active substances (e.g. other fungicidal agents, insecticidal and acaricidal agents, bactericides, plant growth regulators and fertilizers). Such combination compositions are suitable for broadening the spectrum of activity or for specifically influencing the plant growth.
The fungicidal compositions in accordance with the invention generally contain, according to type, between 0.0001 and 9 5 weight percent of compound in accordance with the invention or compounds in accordance with the invention as the active substance(s). They can be present in a form which is suitable for storage and transport. In such forms (e.g. emulsifiable concentrates) the active substance concentration is normally in the higher region of the above concentration range. These forms can be diluted with the same or different formulation adjuvants to give active substance concentrations which are suitable for practical use and such concentrations normally lie in the lower region of the above concentration range. Emulsifiable concentrates generally contain 5 to 9 5 weight percent, preferably 25 to 75 weight percent, of the compound or compounds of formula 207229 I. As forms of use there come into consideration, inter alia, ready-for-use solutions, emulsions and suspensions which are suitable, for example, as spray liquors. In such 5 spray liquors there can be present, for example, concentrations between 0*0001 and 20 weight percent. In.the Ultra-Low-Volume process there can be formulated spray liquors in which the active substance concentration is preferably from 0.5 to 20 weight percent, while the spray liquors 10 formulated in the Low-Volume process and in the High-Volume process preferably have an active substance concentration of 0.02 to 1.0 weight percent or 0.002 to 0.1 weight percent, respectively.
The fungicidal compositions in accordance with the invention can be manufactured by mixing at least one compound of general formula I or an acid addition salt of such a compound with formulation adjuvants.
The manufacture of the compositions can be carried out in a known manner? for example, by mixing the active substance with solid carrier substances, by dissolution or suspension in suitable solvents or dispersion media, if necessary with the use of tensides as wetting or emulsifying 25 agents or of dispersing agents, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.
In the case of pulverous compositions the active 30 substance can be mixed with a solid carrier substance (e.g. by grinding them together) or the solid carrier substance can be impregnated with a solution or suspension of the active substance and then the solvent or dispersion medium can be removed by evaporation, heating or sucking-off under 35 reduced pressure. By adding tensides or dispersing agents such pulverous compositions can be made readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as spray compositions . 2.072.2? The compounds in accordance with the invention can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is dispersible in water 5 or they can be mixed with, a solid pre—granulated carrier substance to form a product in the form of a granulate.
When desired, a compound in accordance with the invention can be dissolved in a water-immiscible solvent 10 such as, for example, an alicyclic ketone, which conveniently contains dissolved emulsifying agent, so that the solution becomes self-emulsifying upon addition to water. Alternatively, the active substance can be mixed with, an emulsifying agent and the mixture can then be diluted with water to give the desired concentration. Moreover, the active substance can be dissolved in a solvent and thereafter the solution can be mixed with an emulsifying agent. Such a mixture can likewise be diluted with water to give the desired concentration. In this manner there are obtained 20 emulsifiable concentrates or ready-for-use emulsions.
The use of the compositions in accordance with the invention can be carried out according to the application methods which are usual in plant protection or in a^ricul-25 ture. The method in accordance with the invention for the control of fungi comprises treating the locus to be protected (e.g. plants, parts of plants or seeds) with an effective amount of a compound in accordance with the invention or of a composition in accordance with the 30 invention. 207219 The following Examples illustrate the invention: I. Manufacture of the active substance of formula I: Example 1 3 g of 2-(2,4-dichlorophenyl)-1-(3-pyridyl)-4-penten-l-one are dissolved in 20 ml of methanol and treated with 1° 0.5 g of sodium borohydride. After 1 hour at room temperature the mixture is concentrated somewhat, poured on to ice-water and extracted with diethyl ether. The organic phase is washed, dried over anhydrous sodium sulphate and the solvent is removed under reduced pressure. There is obtained cc- (a-allyl-2,4-dichlorobenzyl)-3-pyridylmethanol as a light brownish oil.
In an analogous manner, from 2-(2,4-dichlorophenyl)-1,3-di-(3-pyridyl)-1- propanone there is obtained by reduction with sodium borohydride 2-(2,4-dichlorophenyl)-1,3-di-(3-pyridyl)-1-pro-panol, m.p. 65-67°C; from 2-(2,4-dichlorophenyl)-4-methy1-1-(3-pyridyl)- 4-penten-l-one there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-(2-methallyl)-benzyl]-3-pyri-dylmethanol as a yellowish oil; from 2-(2,4-dichlorophenyl)-1-(3-pyridyl)-4-pentyn- 1-one there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-(2-propynyl)-benzyl]-3-pyridylmethanol as a yellowish oil; from 2-(2,4-dichlorophenyl)-3-pheny1-1-(3-pyridyl)- 1-propanone there is obtained by reduction with sodium borohydride a-[a~(2,4-dichlorophenyl)-phenethyl]-3-pyridyl-methanol, m.p. 120-122°C; 201229 from 2-(2,4-dichlorophenyl)-1-(2-pyrazinyl)-4-penten-l-one there is obtained by reduction with sodium borohydride a-(a-ally1-2,4-dichlorobenzyl)-2-pyrazinylmethanol as a yellowish oil.? from 2-(2,4-dichlorophenyl)-1-(5-pyrimidinyl)-4-pentyn-l-one there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-(2-propynyl)-benzyl]-5-pyri-midinylmethanol, m.p. 138-140°C; from 2-(2,4-dichlorophenyl)-2-phenylthio-l-(3-pyridyl)-ethanone there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-phenylthio-benzyl]-3-pyridylmethanol, m.p. 119-121°C; from 4,5-dibromo-2-(2,4-dichlorophenyl)-1-(3-pyridyl)-4-penten-l-one there is obtained by reduction with sodium borohydride cc- [ a- (2, 3-dibromoallyl) - 2, 4-dichlorobenzylJ-3-pyridylmethanol, m.p. 108-114°C? from 2-(2,4-dichlorophenyl)-5-methy1-1-(3-pyridyl)-4-hexen-l-one there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-(3-methyl-2-butenyl)-benzyl]-3-pyridylmethanol, m.p. 97-100°C; from 2-(2,4-dichlorophenyl)-3-(p-nitrophenyl)-1-(3-pyridyl)-1-propanone there is obtained by reduction with sodium borohydride a-[a-(2,4-dichlorophenyl)-p-nitro-phenethyl]-3-pyridylmethanol, m.p. 164-165°C; from 2-(2,4-dichlorophenyl)-3-(2-thienyl)-1-(3-pyridyl)-1-propanone there is obtained by reduction with sodium borohydride 2-(2,4-dichlorophenyl)-3-(2-thienyl)-1-(3-pyridyl)-1-propanol, m.p. 112-114°C? from 2-(2,4-dichlorophenyl)-3-(2-furyl)-1-(3-pyridyl)-1-propanone there is obtained by reduction with sodium borohydride a-[2,4-dichloro-a-(2-furfuryl)-benzyl]-3-pyri- 207129 dylmethanol, m.p. 132-133°C; and from a 4:1 mixture of 4- and 5-chloro-2-(2,4-dichloro-5 phenyl)-1-(3-pyridyl)-4-penten-l-one there is obtained by reduction with sodium borohydride a 4:1 mixture of a-[l-(2,4-dichlorophenyl)-3- and 4-chloro-3-butenyl]-3-pyridy1-methanol as a yellowish amorphous substance.
Example 2 8 g of 2,4-dichloro-a-(4-chlorophenylthio)-toluene dissolved in a small amount of tetrahydrofuran are slowly added dropwise at -20°C to a solution of lithium diisopro-15 pylamide (prepared from 3.2 g of diisopropylamine and an equivalent amount of n-butyl lithium) in 7.1 g of hexa-methylphosphoric acid triamide and 350 ml of tetrahydrofuran and the mixture is stirred at -20°C for 1 hour. 2.54 g of 3-pyridinecarbaldehyde diluted with a small amount of 20 tetrahydrofuran are then added dropwise and the temperature of the mixture is allowed to rise slowly to room temperature. The mixture is treated with a small amount of water and concentrated somewhat. The mixture is subsequently poured on to ice-water and extracted with ethyl acetate, the 25 organic phase is dried over anhydrous sodium sulphate and the solvent is removed. The crude product is purified by chromatography on silica gel with n-hexane/ethyl acetate (1:1). There are obtained pale yellow crystals of a-[2,4-dichloro-a-(4-chlorophenylthio)-benzyl]-3-pyridylmethanol, 30 m.p. 140-141°C.
In an analogous manner, from 2,4-dichloro-a-(2-pyridylthio)-toluene and 3-pyridinecarbaldehyde there are obtained brownish crystals of a-[2,4-dichloro-a-(2-pyridyl-35 thio)-benzyl]-3-pyridylmethanol, m.p. 121-123°C. 207 ) Example 3 6.0 g of 2-(2,4-dichlorophenyl)-1-(3-pyridyl)-4-5 penten-l-one diluted with 20 ml of diethyl ether are added dropwise to a solution of methylmagnesium iodide (prepared from 0.62 g of magnesium shavings and 3.8 g of methyl iodide) in 70 ml of diethyl ether. After 45 minutes at room temperature the mixture is treated with saturated aqueous ammonium 10 chloride solution, diluted with water and subsequently extracted with diethyl ether. After drying the organic phase over anhydrous sodium sulphate the solvent is removed under reduced pressure, a-(a-Ally1-2,4-dichlorobenzyl)-ct-methyl-3-pyridylmethanol is obtained as a red-brown 15 amorphous substance.
In an analogous manner, from 2-(2,4-dichlorophenyl)-1-(3-^yridyl)-4-penten-20 1-one and ethylmagnesium bromide there is obtained a-(a-allyl-2,4-dichlorobenzyl)-a-ethyl-3-pyridylmethanol, m.p. 105-110°C ; from 2-(2,4-dichlorophenyl)-3-(2-furyl)-1-(3-pyridyl)-25 1-propanone and methylmagnesium iodide there is obtained a-[2,4-dichloro-a-(2-furfuryl)-benzyl]-a-methy1-3-pyridyl-methanol as an amorphous reddish substance; from 2-(2,4-dichlorophenyl)-3-(2-thienyl)-1-(3-30 pyridyl)-1-propanone and methylmagnesium iodide there is obtained 3-(2,4-dichlorophenyl)-4-(2-thienyl)-2-(3-pyridyl)-2-butanol as an amorphous orange substance; and from a 4:1 mixture of 4- and 5-chloro-2-(2,4-dichloro-35 phenyl)-1-(3-pyridyl)-4-penten-l-one and methylmagnesium iodide there is obtained a 4:1 mixture of a-[1-(2,4-dichloro-phenyl)-3- and 4-chloro-3-butenyl]-a-methyl-3-pyridyl-. methanol as an amorphous yellowish substance having a melting range of 123-152°C. 2 07 Example 4 4 g of oc- (a-allyl-2, 4-dichlorobenzyl)-3-pyridy 1-5 methanol are stirred with 20 ml of phosphorus oxychloride at 90°C for 1 hour. The mixture is then poured on to ice-water, made basic with sodium carbonate solution and extracted with diethyl ether. The organic phase is dried over anhydrous sodium sulphate, the solvent is removed under 10 reduced pressure and the product obtained is purified by chromatography on silica gel with n-hexane/ethyl acetate (3:1). 3-[1-Chloro-2-(2,4-dichlorophenyl)-4-pentenyl]-pyridine is obtained as a yellowish oil.
Example 5 1.5 g of 3-(2,4-dichlorophenyl)-4-(2-thienyl)-2-(3-pyridyl)-2-butanol.dissolved in 20 ml of chloroform are treated with 1.5 g of 3-chloroperbenzoic acid and held 20 at 4 °C for 18 hours. The mixture is treated with water and chloroform and the organic phase is washed with aqueous potassium carbonate solution, subsequently dried over anhydrous sodium sulphate and concentrated under reduced pressure. There is obtained a-[2,4-dichloro-a-(2-thenyl)-25 benzyl]-a-methy1-3-pyridylmethanol 1-oxide which is recrystallized from n-hexane/ethyl acetate. M.p. 95°C (with decomposition).
II. Preparation of the starting materials: Example 6 A solution of 25 g of 2,4-dichlorobenzyl (3-pyridyl) ketone in 120 ml of dimethylformamide is treated portion-35 wise at 0°C with 4 g of sodium hydride (60% dispersion in oil). After 2 hours at room temperature 13.6 g of allyl bromide are added and the mixture is stirred at room temperature for a further 3 hours. The mixture is then 1072 29 poured, into water and extracted with diethyl ether,and the organic phase is washed, dried over anhydrous sodium sulphate and subsequently concentrated. By chromatography on silica gel 5 with ethyl acetate there is obtained 2-(2,4-dichlorophenyl)-1-(3-pyridyl)-4-penten-l-one as an oil, In an analogous manner, from 2,4-dichlorobenzyl (3-pyridyl) ketone and 3- picolyl chloride there is obtained 2-(2,4-dichlorophenyl)-1,3 di-(3-pyridyl)-1-propanone as an oil; • from 2,4-dichlorobenzyl (3-pyridyl) ketone and 0-15 methallyl chloride there is obtained 2-(2,4-dichlorophenyl)-4-methyl-l-(3-pyridyl)-4-penten-l-one as a brownish oil; from 2,4-dichlorobenzyl (3.-pyridyl) ketone and pro-pargyl bromide there is obtained 2-(2,4-dichlorophenyl)-1-20 (3-pyridyl)-4-pentyn-l-one as a brownish oil; from 2,4-dichlorobenzyl (3-pyridyl) ketone and benzyl bromide there is obtained 2-(2,4-dichlorophenyl)-3-phenyl-l-(3-pyridyl)-1-propanone as a brownish oil; from 2,4-dichlorobenzyl (3-pyridyl) ketone and 2-bromomethylthiophene there is obtained 2-(2,4-dichlorophenyl) 3-(2-thienyl)-1-(3-pyridyl)-1-propanone as a reddish oil; from 2,4-dichlorobenzyl (3-pyridyl) ketone and p- nitrobenzyl chloride there is obtained 2-(2,4-dichlorophenyl) 3-(p-nitrophenyl)-1-(3-pyridyl)-1-propanone as a reddish oil; from 2,4-dichlorobenzyl (3-pyridyl) ketone and 1-35 bromo-3-methyl-2-butene there is obtained 2-(2,4-dichlorophenyl) -5-methy 1-1- ( 3-pyridyl) -4-hexen-l-one as an orange coloured oil; 207 2 29 from 2,4-dichlorobenzyl (3-pyridyl) ketone and 1,2,3-tribromo-propene there is obtained 4,5-dibromo-2-(2,4-dichlorophenyl) -1-(3-pyridyl)-4-penten-l-one, m.p. 76-83°C; from 2,4-dichlorobenzyl (3-pyridyl) ketone and 3-bromo-2-chloro-l-propene contaminated with about 20% of 3-bromo-l-chloro-l-propene there is obtained a 4:1 mixture of 4- and 5-chloro-2-(2,4-dichlorophenyl)-1-(3-pyridyl)-10 4-penten-l-one as an orange coloured oil; from 2,4-dichlorobenzyl (3-pyridyl) ketone and 2-furfuryl chloride there is obtained 2-(2,4-dichlorophenyl)-3-(2-furyl)-1-(3-pyridyl)-1-propanone as an oil; from 2,4-dichlorobenzyl (2-pyrazinyl) ketone and allyl bromide there is obtained 2-(2,4-dichlorophenyl)-1-(2-pyrazinyl)-4-penten-l-one as a brownish oil; and from 2,4-dichlorobenzyl (5-pyrimidinyl) ketone and pro-pargyl bromide there is obtained 2-(2,4-dichlorophenyl)-1-(5-pyrimidinyl)-4-pentyn-l-one as an oil.
The novel ketones which are used as the starting 25 materials in this Example can be prepared as follows: A solution of 10 g of a-(trimethylsilyloxy)-a-(2-pyrazinyl)-acetonitrile (prepared from 2-pyrazinecarbalde-hyde and trimethylsilyl cyanide) in 30 ml of tetrahydro-30 furan is added dropwise at -70°C to a solution of lithium diisopropylamide (prepared from 5.4 g of diisopropylamine and an equivalent amount of n-butyl lithium) in 50 ml of tetrahydrofuran. After 1 hour there are added at the same temperature 9.4 g of 2,4-dichlorobenzyl chloride diluted with 35 lo ml of tetrahydrofuran and the mixture is left to warm slowly to room temperature. 125 ml of 2N hydrochloric acid are subsequently added and the mixture is left to react at room temperature for 10 hours. The mixture is then made basic, extracted with ethyl acetate and concentrated, and T22<j the crude product is purified by chromatography on silica gel with n-hexane/ethyl acetate (2:1). There is obtained 2,4-dichlorobenzyl (2-pyrazinyl) ketone, m.p. 109-111°C.
In an analogous manner, from a- (trimethylsilyloxy)-a-(5-pyrimidinyl)-acetonitrile and 2,4-dichlorobenzyl chloride there is obtained 2,4-dichlorobenzyl (5-pyrimidinyl) ketone, m.p. 135-140°C.
Example 7 17 g of 2,4-dichloro-a-phenylthio-toluene dissolved in a small amount of tetrahydrofuran are added dropwise at 15 -10°C to a solution of lithium diisopropylamide (prepared from 7.6 7 g of diisopropylamine and an equivalent amount of n-butyl lithium) in 61.9 g of hexamethylphosphoric acid triamide and 400 ml of tetrahydrofuran. The mixture is stirred for 1 hour, 4.33 g of methyl nicot±nate are added and the mixture is then 20 stirred at rocsn temperature for 1 hour. After the addition of a small amount of water the mixture is concentrated under reduced pressure, the residue is poured on to ice-water and extracted with ethyl acetate. The organic phase is dried over anhydrous sodium sulphate and concentrated. The crude product 25 is purified by chromatography on silica gel with n-hexane/ ethyl acetate (1:1). There is obtained 2-(2,4-dichlorophenyl)-2-phenylthio-l-(3-pyridyl)-ethanone as a brownish oil.
III. Formulation Examples: Example 8 1. Spray powder (for active substances which are liquid or which melt below 75°C).
Parts by weight Active substance of formula I or V 50 Hydrated silicic acid 37 Kaolin 5 Alkylphenol ethoxylate 4 Sodium polynaphthalenesulphonate 4 100 The liquid or molten active substance is taken up on the silicic acid, the remaining components are admixed and the mixture is finely ground in a suitable mill. 2. Spray powder (for active substances which melt above 75°C) .
Parts by weight Active substance of formula I or V 50 Hydrated silicic acid 5 Kaolin 42 Sodium lauryl sulphate 1 Sodium lignosulphonate 2 100 The components are mixed with one another and the mixture is then finely ground in a suitable mill.
Example 9 Emulsifiable concentrate (for active substances which are liquid at 20-25°C).
Parts by weight Active substance of formula I or V 500 Castor oil ethoxylate 100 Calcium dodecylbenzenesulphonate 25 207229 Mixture of C^-alkylbenzenes ad .1000 parts by volume The components are mixed with one another until a 5 clear solution is obtained. 207229 •/2 6

Claims (22)

WHAT WE CLAIM IS:
1. Compounds of the general formula R— CH- C 1 12 R R wherein R signifies mono-, di- or trisubstituted phenyl, the substituents being 1-3 halogen atoms and/or 1 or 2 C^^-alkyl groups and/or 1 or 2 C^^-alkoxy groups and/or 1 or 2 trifluoromethyl groups, R"*" signifies C^_g-alkenyl, C^.g-alkynyl, C^g-alkenyloxy, C^_g-alkynyloxy, C^_g-alkenylthio or C^g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C-^^-alkyl, aryloxy or arylthio optionally mono-, di- or trisubstituted in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^_2~alkyl groups and/or 1 or 2 ^2.-3" alkoxy groups and/or a nitro group, and aryl being as hereinbefore defined, 2 R signifies hydroxy, chlorine or bromine, 3 R signifies hydrogen or C^_4~alkyl and R4 signifies 3-pyridyl, 3-pyridyl 1-oxide, 2-pyrazinyl, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl, 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide, and their acid addition salts.
2. Compounds according to claim 1, wherein R sig- nifies 2, 4-dichlorophenyl. . ' - 34 - 3 G103/2 0
3. Compounds according to claim 1 or 2, wherein R^" signifies C^g-alkenyl or C3_g-alkynyl optionally substituted with 1 to 3 halogen atoms, or optionally mono-, 5 di- or trisubstituted arylthio, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 alkyl groups and/or 1 or 2 C^_3-alkoxy groups and/or a nitro group. 10 i-
4. Compounds according to any one of claims 1 to 3, wherein R3 signifies hydrogen or methyl. j
5. Compounds according to any one of claims 1 to 4, 4 wherein R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl 15
6. a-(a-Ally1-2,4-dichlorobenzyl)-3-pyridylmethanol.
7. ct- [ 2,4-Dichloro-a- (2-propynyl) -benzyl] -3-pyri dyl-methanol. 20
8. a- [or(2,4-Dichlorophenyl)-phenethyl]-3-pyridy1-methanol.
9. a-(2,4-Dichloro-a-phenylthio-benzyl)-3-pyridy1-25 methanol.
10. A compound according to claim 1, selected from: 2-(2,4-Dichlorophenyl)-1,3-di-(3-pyridyl)-1-propanol, 30 a-[2,4-dichloro-a- (2-methallyl)-benzyl]-3-pyridyl- methanol, a-(a-allyl-2,4-dichlorobenzyl)-2-pyrazinylmethanol, a-[2,4-dichloro-a-(2-propynyl)-benzyl]-5-pyrimidinyl-methanol, 35 a-[2,4-dichloro-a-(4-chlorophenylthio)-benzyl]-3- -pyridylmethanol, a-[2,4-dichloro-a-(2-pyridylthio)-benzyl]-3-pyridy1-methanol, a-[a-(2,3-dibromoallyl)-2,4-dichlorobenzyl]-3-pyridyl methanol, 2-(2,4-dichlorophenyl)-3-(2-thienyl)-1-(3-pyridyl)-1-propanol, cc— [2,4-dichloro-a- (2-furfuryl) -benzyl] -3-pyridyl-methanol and 3-[l-chloro-2-(2,4-dichlorophenyl)-4-pentenyl]-pyridine.
11. A compound according to claim 1, selected from: a-[2,4-Dichloro-a-(3-methyl-2-butenyl)-benzyl]-3-pyridylmethanol, a-[a-(2,4-dichlorophenyl)-p-nitrophenylethyl]-3-pyridylmethanol, a-[1-(2,4-dichlorophenyl)-3-chloro-3-butenyl]-3-pyridylmethanol, a-[1-(2,4-dichlorophenyl)-4-chloro-3-butenyl]-3-pyridylmethanol, a-(a-allyl-2,4-dichlorobenzyl)-a-methyl-3-pyridyl-methanol, a-(a-allyl-2,4-dichlorobenzyl)- a-ethy1-3-pyridy1-methanol, a-[2,4-dichloro-a-(2-furfUryl)-benzyl]-a-methyl-3-pyridylmethanol, 3-(2,4-dichlorophenyl)-4-(2-thienyl)-2-(3-pyridyl)-2 butanol, a-[1-(2,4-dichlorophenyl)-3-chloro-3-butenyl]-a-methy1-3-pyridylmethanol, a-[1-(2,4-dichlorophenyl)-4-chloro-3-butenyl]-a-methy1-3-pyridylmethanol and a-[2,4-dichloro-a-(2-thenyl)-benzyl]-a-methyl-3-pyridylmethanol 1-oxide.
12. Compounds according to claim 1 as fungicidal active substances.
13. Compounds of the general formula - 36 - 207229 R— CH —C—R4 I !» II R 0 wherein R signifies mono-, di- or trisubstituted phenyl, the substituents being 1-3 halogen atoms and/or 1 or 2 C^_3~ alkyl groups and/or 1 or 2 C^_3~ alkoxy groups and/or 1 or 2 trifluoro-methyl groups, 1" R signifies C^g-alkenyl, C3_g-alkynyl, C-^g-alkenylthio or C3_g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C^_3~alkyl or arylthio optionally mono-, di- or tri-substituted in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2" C^_3~alkyl groups and/or 1 or 2 C^_3~ alkoxy groups and/or a nitro group, and aryl being as hereinbefore defined, 4 and R signifies 3-pyridyl, 3-pyridyl 1-oxide, 2-pyrazinyl, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl, 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide.
14. A fungicidal composition which contains an effective amount of at least one compound of the general formula R I , R— CH—C — R' In I i wherein R signifies mono-, di- or trisubstituted phenyl, the substituents being 1-3 halo - 37 - 207229 gen atoms and/or 1 or 2 C^_2~alkyl groups and/or 1 or 2 C^^-alkoxy groups and/or 1 or 2 trifluoromethyl groups, R^" signifies C^g-alkenyl, C^^-alkynyl, C3_g-alkenyloxy, C3_g-alkynyloxy, C^_g-alkenylthio or C^g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C^^-alkyl, aryloxy or arylthio optionally mono-, di- or tri-substituted in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^_2_alkyl groups and/or 1 or 2 alkoxy groups and/or a nitro group, and aryl being as hereinbefore defined, 2 R signifies hydroxy, chlorine or bromine, R3 signifies hydrogen or C^_4~alkyl and R4 signifies 3-pyridyl, 3-pyridyl 1-oxide, 2-pyrazihyl, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl, 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide, or an acid addition salt of such a compound as well as formulation adjuvants.
15. A fungicidal composition according to claim 14 which contains an effective amount of a-(c-ally1-2,4-dichlorobenzyl)-3-pyridy lmethanol or a-12,4-dichloro-a-(2-propynyl)-benzyl]-3-pyridylmethanol or a-[a-(2,4-dichlorophenyl) -phenethyl]-3-pyridylmethanol or a-(2,4-dichloro-a-phenyl-thio-benzyl)-3-pyridylmethanol as well as formulation adjuvants.
16. A process for the manufacture of compounds of the general formula - 38 - 207229 wherein R signifies mono-, di- or txisubstituted phenyl, the substituents being 1-3 halogen atoms and/or 1 or 2 C^_^-alkyl groups and/or 1 or 2 C^^-alkoxv groups and/or 1 or 2 trifluoromethyl groups, R^" signifies C^g-alkenyl, C^g-alkynyl, • C3_g-alkenyloxy, C^g-alkynyloxy, C^_g-alkenylthio or C.j_g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C^^-alkyl, aryloxy or arylthio optionally mono-/ di- or tri-substituted in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 alkyl groups and/or 1 or 2 C^^-alkoxy groups and/or a nitro group, and aryl being as hereinbefore defined , 2 R signifies hydroxy, chlorine or bromine, R3 signifies hydrogen or C^_4-alkyl . ana R4 signifies 3-pyridyl, 3-pyridyl 1-oxide, 2-pyrazinyl, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5-pyrimidinyl, 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide/ and of their acid addition salts, which process comprises a) for the manufacture of the compounds of formula I in which R signifies optionally substituted C^g-alkenyloxy, C, ..-alkynyloxy or aryloxy, as more precisely defined above, 5 4 R signifies hydroxy and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reacting an epoxide of the general formula 207 - 39 - ■ES 6103/2-6- wherein R and R3 have the significances given above 4' and R signifies 3-pyridyl, 2-pyrazinyl cr 5 5-pyrimidinyl, or an alcohol or the general formula R3 I 4' 10 R—CH— C —R III I I X OH 3 4' wherein R, R and R have the significances given 15 above and X signifies a halogen atom, an alkylsulph-onate. group or an arylsulphonate group, with a compound of the general formula 20 R1H IV wherein R signifies C3_g-alkenyloxy or C3_g-alkyn-yloxy optionally substituted with 1 to 25 3 halogen atoms; or optionally mono-, di- or trisubstituted aryloxy, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^_2~alkyl groups and/or 1 or 2 C]__3"" 30 alkoxy groups and/or a nitro group, b) for the manufacture of the compounds of formula I in which R^" signifies optionally substituted C3_g-alkenyl, C3_g-alkynyl, C3_g-alkenylthio, C3_g-alkynylthio, aryl-C^_3- 35 alkyl or arylthio, as more precisely defined above, R2 sig- 3 4 nifies hydroxy, R signifies hydrogen and R signifies 3- pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reducing a ketone of the general formula 2 0721c, 40 -ES 6103/26 R— CH—C —R4 ' V I r. II R 0 5 4' wherein R and R have the significances gxven above 1" and R signifies C^g-alkenyl, C^g-alkynyl, C-^g-alkenylthio or C3_g-alkynylthio optionally substituted with 1 to 3 halogen atoms; or aryl-C^_3-alkyl or arylthio optionally mono-, di- or tri-substituted in the aryl nucleus, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C^-j^lkyl groups and/or 1 or 2 alkoxy groups and/or a nitro group, c) for the manufacture of the compounds of formula I in 2° which R^ signifies optionally substituted C2_g-alkenyl, C^g-alkynyl, C^g-alkenylthio, C^g-alkynylthio, aryl-C, ,-alkyl or arylthio, as more precisely defined above, 2 3 4 R signifies hydroxy, R signifies C^^^-alkyl and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, reacting a 25 ketone of general formula V, as defined above, with a compound of the general formula R3'-Y VI 30 3 • wherein R signifies C^__4-alkyl, Y signifies lithium or MgZ and Z signifies halogen, d) for the manufacture of the compounds of formula I 35 2 4 in which R signifies chlorine or bromine and R signifies 3-pyridyl, 2-pyrazinyl or 5-pyrimidinyl, treating an alcohol of the general formula 1072. EG G 103/2-6- R3 I 4. R— CH —C—R I' U I Ra OH 13 4' wherein R, R , R and R have the significances given above, with a chlorinating agent or a brominating agent, e) for the manufacture of the compounds of formula I in which R^" signifies optionally substituted C 3_6-alkenyl-thio, C3_6-alkynylthio or arylthio, as more precisely defined above, and R2 signifies hydroxy, reacting a thio-ether of the general formula 11 • ' R— CH^—R VII wherein R has the significance given above r!''' signifies C3_6-alkenylthio or C3_6- -alkynylthio optionally substituted with 1 to 3 halogen atoms; or optionally mono-, di- or trisubstituted arylthio, the optionally present substituents being 1 to 3 halogen atoms and/or 1 or 2 C1-3~alkyl groups and/or 1 or 2 C^^-alkoxy groups and/or a nitro group, with an aldehyde or ketone of the general formula R3— C—R4 VIII II 3 4 wherein R and R have the significances given above, or 2072 ~ 42 ~ -Cg 6103/26 f) for the manufacture of the compounds of formula I 4 in which R signifies 3-pyridyl 1-oxide, 2-pyrazinyl 1-oxide, 2-pyrazinyl 4-oxide, 2-pyrazinyl 1,4-dioxide, 5 5-pyrimidinyl 1-oxide or 5-pyrimidinyl 1,3-dioxide, N-oxidizing a pyridine, pyrazine or pyriraidine derivative of the general formula 10 i < R—CH—C —R' ll »2 R R I" 1 2 3 41 15 wherein R, R , R , R and R have the significances given above, and, if desired, reacting a compound of formula I obtained with an acid in order to manufacture the corresponding acid addition salt. 20
17. A method for the control of fungi in agriculture and in horticulture, which method comprises treating, the locus to be protected with an effective amount of one of the compounds set forth in claims 1 to 11 or of a com- 25 position set forth in claim 14 or 15.
18. The use of one of the compounds set forth in claims 1 to 11 or of a composition set forth in claim 14 or 15 for the control of fungi in agriculture and in horticulture. 30 35 207229 - 43 -
19. A compound of the general formula I in claim 1, whenever produced by a process according to claim 16. 207229 - 44 - -£G 6103/26
20. A fungicidal composition according to claim 14, substantially as described herein with reference to Example 8 or 9. 5
21. A process according to claim 16, substantially as described herein with reference to any one of Examples 1 to 5.
22. A method according to claim 17, substantially as described herein 10 15 *-• 3 * tM - S. 20 / 30 25 35
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US5036074A (en) * 1989-03-01 1991-07-30 Ciba-Geigy Corporation Certain 2,4-dichloro-phenyl(loweralkylidene) pyridines having fungicidal activity
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