GB2190374A - Fungicdal, insecticidal, nematicidal and plant growth regulating pyridines - Google Patents

Fungicdal, insecticidal, nematicidal and plant growth regulating pyridines Download PDF

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GB2190374A
GB2190374A GB08707530A GB8707530A GB2190374A GB 2190374 A GB2190374 A GB 2190374A GB 08707530 A GB08707530 A GB 08707530A GB 8707530 A GB8707530 A GB 8707530A GB 2190374 A GB2190374 A GB 2190374A
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optionally substituted
formula
compound
och3
alkyl
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GB8707530D0 (en
GB2190374B (en
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Christopher Richard Ay Godfrey
Patrick Jelf Crowley
Kenneth Anderton
Vivienne Margaret Anthony
John Martin Clough
Paul Defraine
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Priority claimed from GB868609456A external-priority patent/GB8609456D0/en
Priority claimed from GB878701627A external-priority patent/GB8701627D0/en
Priority to GB8707530A priority Critical patent/GB2190374B/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to EG218/87A priority patent/EG18672A/en
Priority to MYPI87000509A priority patent/MY101727A/en
Priority to BR8701894A priority patent/BR8701894A/en
Publication of GB8707530D0 publication Critical patent/GB8707530D0/en
Publication of GB2190374A publication Critical patent/GB2190374A/en
Priority to GB8922230A priority patent/GB2222163B/en
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
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    • 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
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
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    • 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
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
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    • 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
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
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    • 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
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C07D213/66—One oxygen atom attached in position 3 or 5 having in position 3 an oxygen atom and in each of the positions 4 and 5 a carbon atom bound to an oxygen, sulphur, or nitrogen atom, e.g. pyridoxal
    • C07D213/67—2-Methyl-3-hydroxy-4,5-bis(hydroxy-methyl)pyridine, i.e. pyridoxine
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    • 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
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    • C07D213/69—Two or more oxygen atoms
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    • 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
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    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Description

GB2190374A 1
SPECIFICATION
Funglicides This invention relates to derivatives of acrylic acid useful in agriculture (especially as fungicides 5 but also as insecticices, nematicides and plant grown regulators), to processes for preparing them, to agricultural compositions containing them, and to methods of using them to combat fungi, especially fungal infections in plants, to kill or control insect and nematode pests and to regulate plant growth.
The invention provides a compound having the general formula (1): 10 D E B W (I) A, 15 and stereoisomers thereof, wherein W is 13102C-C=CH-ZR2, wherein R' and R2, which are the same or different, are alkyl or fluoroalkyl groups, and Z is either an oxygen or sulphur atom; A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally 20 substituted arylalkoxy, optionally substituted alkenyi, optionally substituted alkynyl, optionally substituted aryi, optionally substituted aryloxy, optionally substituted arylthio, optionally substi tuted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, - C02R 3, -CONR 3 R 4, -COR 3, -CR3=NR 4, -N=CR 3 R 4 or -SPnR3 groups; any two of the groups A, B, 25 D and E, when they are in adjacent positions on the ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R 3 and R4, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylal ky], alkenyl, alkynyi, optionally substituted aryl or optionally substituted aralkyl groups; and metal complexes thereof. 30 The compounds of the invention contain at least one carbon-carbon double bond, and are sometimes obtained in the form of mixtures of geometric isomers. However, these mixtures can be separated into individual isomers, and this invention embraces such isomers, and mixtures thereof in all proportions including those which consist substantially of the (2)-isomer and those which consist substantially of the (E)-isomer. 35 The individual isomers which result from the unsymmetrically substituted double bond of the substituent W are identified by the commonly used terms "E' and "Z'. These terms are defined according to the Cahn-Ingold-Prelog syste which is fully described in the literature (see, for example, J March, -Advanced Organic Chemistry-, 3rd edition, Wiley- Interscience, page 109 et seq). 40 Usually one isomer is more fungicidally active than the other, the more active isomer being the one in which the group -ZR2 on the W substituent (W02C-C=CH-ZR2) is on the same side of the double bond as the pyridine ring. In the case of the compounds of the present invention this is the (E)-isomer. These isomers form a preferred embodiment of the invention.
In the compounds of formula (1), alkyl groups and the alkyl moiety of alkoxy groups can be in 45 the form of straight or branched chains, and preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
Examples are methyl, ethyl, propyl (n-and iso-propyl) and butyl (n-, sec-, iso- and tert-butyl).
Cycloalkyl groups, which are preferably C3-6 Cycloalkyl groups, include cyclohexyl and cycloalky Jalkyl groups, which are preferably C3-6 CYCloalkyl (Cl-4) alkyl groups, include cyciopropylethyl. 50 Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4, carbon atoms in the form of straight or branched chains. Examples are ethenyl, allyl and propargyl. Aryl is preferably phenyl and aralkyl is preferably benzyl, phenylethyl or phenyl- n-propyl. Optionally substituted alkyl includes, in particular, haloalkyl, hydroxyalkyl, alkoxyalkyl and optionally substi- tuted aryloxyalkyl (especially optionally substituted phenoxyalkyl) and optionally substituted heter- 55 oaryl-oxyalkyl (especially pyridinyl- and pyrimidinyloxyalkyl); optionally substituted alkenyl includes optionally substituted phenylaikenyl, especially optionally substituted phenylethenyl; and optionally substituted arylalkoxy includes optionally substituted benzy[oxy.
Substituents which may be present in any optionaly substituted aryl or heteroaryl moiety include one or more of the following; halogen (especially fluorine, chlorine and bromine), hydroxy, 60 Cl4 alkyl (especially methyl and ethyl), (Cl-4) alkoxy (especially methoxy), halo (Cl-J alkyl (espe cially trifluoromethyl), halo Cl-4 alkoxy (especially trifluoromethoxy), C,-4 alkylthio (especially me thylthio) Cl-4) alkoxy (C,J alky], C3-, cycloalkyl, C,-, cycloalkyl-(ClJ alky], aryl (especially phenyl), aryloxy (especially phenyloxy), aryl(ClJ alkyl (especially benzyi, phenylethyl and phenyl n-propyl), aryl (Cl-Jalkoxy (especially benzyloxy), aryloxy (Cl-Jalkyl (especially phenyloxymethyl), acyloxy 65 2 GB2190374A 2 (especially acetyloxy and benzoyloxy), cyano, thiocyanato, nitro, -NRW, - NHCOR', -NHCONR'R", CONRW', -COOR', -OSO,R', -S02R', -COR', -CR'=NW or - N=CR'R" in which R' and W are independently hydrogen, C,-, alkyl, C,-, alkoxy, C,-, alkylthio, C3-6 cycloalkyl, C3-6 cycloalkyl (C,-Jalkyl, phenyl or benzyi, the phenyl and benzy] groups being optionally substituted with halogen, C,-, alkyl or Cl-4 alkoxy. 5 Optionally substituted amino, acylamino and acyloxy groups include the groups -NRW', NHCOR' and -OCOR' in which R' and W are as defined above.
Compounds of formula (1) which are of particular interest are those in which A, B, D and E are selected from the group consisting of hydrogen, halogen (especially fluorine, chlorine and brom- ine), C,-4 alkyl (especially methyl and ethyl), trifluoromethyl, C,4 alkoxy (especially methoxy), 10 trifluoromethoxy, aralkyl (especially phenyl (C,-Jalkyl including benzyi, phenylethyl and phenyl n propyl), aralkenyl (especially phenyletheny], which may be the (E)- or (2)-isomer), -COOR 3, in which R is C1-4 alkyl (especially methyl or ethyl), C3-4 alkenyl (especially ally]) or aryl (especially phenyl) aryloxy (especially phenoxy), arylthio (especially phenyloxy and phenylthio), heteroaryloxy, heteroarylthio (especially pyridinyl-, pyrimidinyl-, pyrazinyl- and benzoxazolyl-oxy and thio), benzy- 15 loxy, benzylthio and phenyloxymethyl, all of which may carry one or more ring substituents such as halogen (especially fluorine, chlorine and bromine), cyano, nitro, C1- 4 alkyl (especially methyl), C1-4 alkoxy (especially methoxy), trifluoromethyl and trifluoro-methoxy.
It is preferred that at least one of A, B, D and E is a group other than hydrogen and that it is in a position on the pyridine ring ortho to the substituent W. Thus when W is in the 2- or 4- 20 position of the pyridine ring, one of A to E is in the 3- position, and when W is in the 3 position, which is preferred, one of A to E is in the 2-(preferably) or 4position. When any two of A, B, D and E are in adjacent positions on the pyridine ring they may join to form a fused ring either aromatic or aliphatic, optionally containing one or more heteroatoms, such as a fused benzene ring. 25 It is further preferred that at least one of R' and R 2 is methyl, preferably R 2, and even more preferably, that both are methyl.
It is still further preferred that Z (in the substituent W) is oxygen.
Thus in a particular embodiment of the invention, there is included the compound (11) 30 COOCH C 'CH C C H30 N 35 preferably the ffl-isomer, wherein A, which is in a position ortho to the acrylate group, is phenoxy (optionally substituted with one or more of fluoro, chloro, bromo, methyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro), phenylthio, benzyi, phenylethyl, phenylethenyl (either the (E)- or (2)-isomer), benzyloxy, phenyloxymethyl, benzyithio, - COOR3 (in which R3 is 40 methyl, ethyl, ally] or phenyl), pyridinyi-, pyrimidinyl- or pyrazinyl- oxy or -thio (optionally substi tuted with chloro, bromo or trifluoromethyl), or benzoxazolyl-oxy or - thio.
Examples of the compounds of the invention are shown in Table 1. In this Table---Ph- stands for phenyl (ie C61-15).
TABLE I
4 D E B W AON Cond W A B D E Melting olefinic NO 1 Point (C) 1 2-((E)-CH302.C=:CH.OCH3) 3-Pho- H H H Oil 7.56 2 2-((E)-CH302C.C=CH.OCH3) 3(4'-chlorophenoxy)- H H H 3 2-((E)-CH392.C=CH.OCH3) 3-(4'-fluorophenoxy)H H H 4 2-((E)--CH302C.C=CH.OCH3) 3-(4'-brcmophenoxy)- H H H 2-((E)-CH302.C=CH.OCH3) 3-(4'-mthylpherioxy)- H H H 6 2-((E)-CH302C.C=CH.OCH3) 3-(4'methoxyphenoxy)- H H H 7 2- ( (E)--M302. C=CH.OCH3) 3-(4-trifluorcmthyl phenoxy)- H H H 8 2-((E)-CH302C.C=CH.OCH3) 3-(4'trifluorcei--thoxy phenoxy)- H H H 9 2-((E)-CH 302C.C=CH.OCH3) 3-(3'-chlorophenoxy)- H H H 2-((E)-CH302C.C=CH.OCH3) 3-PhS- 11 H H 11 2-((E)-CH302C.C=CH.OCH3) 3-phCH2- H H H 12 2-((E)-CH302C.C=CH.OCH3) 3-PhCH2C112- 11 H H G) W r-i (D 0 W j PS W P.
TABLE I CONTINUED CCMd W A B D E Melting olefinic No Point ('C) 13 2-((-E)-CH302C.C=CH.OCH3) 3-(E-CH=CHPh)- H H H 14 2-((E)-M302C.C=CH.OCH3) 3-(Z-CH=CHPh)- H H H is 3-((!)-CH302C.C=:CH.OCH3) 2-pho- H H H 121-3 7.6 16 3-((E)-CH302C.C=CH.OCH3) 2-(4'--c'hlorophenoxy)- H H H 113-115.6 7.58 17 3-((E)-CH302C.C=.CH.OCH3) 2-(4'-fluorophenoxy)- H H H 116-118 7.60 is 3-((!)-M302C.C=CH.OCH3) 2-(4'-brenoxy)- H H H 89.8-90.5 7.44 19 3-((E)-CH302C.C=CH.OCH3) 2-(4'-mthylphenoxy)- H H H 105.2-106.8 7.59 3-((E)-CH302C.C=CH.OCH3) 2-(4'-mthoxyphenoxy)- H H H 105.6-106.6 7.60 21 3-((E)-CH302C.C=CH.OCH3) 2-(4'-trifluorcmethyl phenoxy)- H H H Oil 7.50 22 3-((E)-CH302--.C=CH.OCH3) 2-(4'-trifluorcmthoW phenoxy)- H H H 23 3-((E)-CH302C.C=CH.OCH3) 2-(3'-chlorophenoxy)- H H H Oil 7.58 24 3-((E)-M302C.C=CH.OCH3) 2-PhS- H H H 3-((E)-CH302C.C=CH.OCH3) 2-PhCH2- H H H 26 3-((E)-.CH302C.C=CH-OCH3) 2-PhCH2CH2- H H H NJ Cl TABLE I =INUED CnW_cund W A B D E Melting olefinic No Point CC) 27 3- ( (E) -CH302C. C=:CH. OCH3) 2-((E)-CH==CHPh)- H H H 28 3-((E)-CH 302C.C=CH.OCH3) 2- ( (Z) --C) - H 11 H 29 3-((E)-CH302C.C=CH.OCH3) 4-PhO- H H H Gum 7.64 3-((E)-CH 302C.C=CH.OCH3) 4-(4'-chlorephenoxy)- H H H 31 3-((E)-CH10,)C 'C=CH-OCH3) 4- (4'-fluorophenoxy) - H 11 H 32 3-((E)-CHIO9C C=CH.OCH3) 4(4'-brcwophenoxy) - H H H 33 3-((E)-.CHIOIC.C=CH.OCH3) 4(4'-mthylphenoxy) - H H H 34 3-((E)-CH-10,)C.C=CH.OCH3) 4(4'-mthoxyphenoxy) - H H H 3-((E)-,CHIO9C.C=CH.OCH3) 4-(4'-trifluorcn-ethyl phenoxy) - 11 H H 36 3-((E)-ICHiOiC.C=CH.OCH3) 4-(4'-trifluorcmethoxy phenoxy)- H H H 37 3- (E) -M 302C.C=CH.OCH3) 4W-chlorophenoxy) - H H H 38 3- (E)---CHIO,C. C=.CH. OCH3) 4-PhS- H H H M TABLE 1 COMINUED Caqxund Melting No W A B D E Point (OC) olefinic 39 3-((E)-,CH302C.C=:CH.OCH3) 4-PhCH2- H H H 3-((E)--CH302C.C=CH.OCH3) 4-PhCH2CH2- H H H 41 3-((E)--CH302C.C=CH.OCH3) 4-((E)-CH=CHPh)- H H H 42 3-((E)-CH302C.C=CH.OCH3) 4-((Z)-CH=CHPh)- H 11 H 43 4-((E)-'CH302C.C=CH.OCH3) 3-Pho- H H H Oil 7.50 44 4-((E)-CH302C.C=CH.OCH3) 3-(4'-chlorephenoxy)- H H H 4-((E)-'CH302C.C=CH.OCH3) 3-(4'-fluorop'henoxy)- H H H 46 4-((E)-CH302C.C=CH.OCH3) 3-(4'-brhenoxy)- 11 H 11 47 4-((E)-'CH302C.C=CH.OCH3) 3-(4'thylphenoxy)- H H H 48 4-((E)-CH302C.C=CH.OCH3) 3-(4'-iTk--thoxyphenoxy)- H H H 49 4-((E)-CH302C.C=CH.OCH3) 3-(4'-trifluorcmthyl phenoxy)- H H H 4-((E)-.CH3o2c.c=cH.OCH3) 3-(4'-trifluorcmthow phenoxy)- H H H G) W 0 W 1.4 4-1 1 1 TABLE I =INUED Cmd W A B D Melting olefinic NO Point (OC) 51 4-((E)--CH302C.C=:CH.OCH3) 3-(3'-chlorapbenoxy)- II H H 52 4-((E)-ICH3P2C.C=CH.OCH3) 3-PhS- 11 H H 53 4- (E) -CH302C. C=CH. OCH3) 3-2- H H H 54 4- (E) -CH302C - C=CH. OCH3) 3-phCH2CH2- H H H 4-((E)-CH302C.C=CH.OCH3) 3-NE)-CH=CHPh)- H H H 56 4- ( (E) -CH302C. C=CH. OCH3) 3-((Z)-<M=:QM)- H H H 57 3-((E)-CH302C.C=CH.OCH3) 2-(3'-fluoraphenoxy)- H H H Oil 7.59 58 3-((E)-CH302C.C=CH-OCH3) 2-(3-mthylphenoxy)- H H H 113-5 7.55 59 3- ( (E) __M302C. C=CH - OCH3) 2-(2'-fluorophenoxy)- H H H 3-((E)-CH302C.C=CH-OCH3) 2-W,5'-dichloro- H H H 99-102 7.60 phenoxy) 61 3-((E)-CH302C.C=CH.OCH3) 2-(3-mthoxypbenoxy)- H H H 81-83 7.59 62 3-((E)-CH302C.C=CH.OCH3) 2-(3'-chlorc>-5'- H H H niethoxyphenoxy) 63 3-((E)-CH302C.C=.CH.OCH3) 2-WX-dichloro- H H H Oil 7.61 phenoxy) - G) 0 OD TABLE I =INUED Melting No W A B D E Point (OC) olefinic 64 3-((E)-CH3o2C.c=,cH.OcH3) 2-(4'cyariaphenoxy)- H H H 3-((E)-CH302C.C=CH.OCH3) 2-(4'-nitraphenoxy)- H H H 66 3-((E)-CH302C.C=CH.OCH3) 2-PhCH20- H H H 76.77 7.51 67 3-((E)-CH302C.C=CH.OCH3) 2-PhOCH2- H H H Oil 7.53 68 3-((E)-.CH302C.C=CH.OCH3) 2-PhCH2S- 11 H H 69 3-((E)-CH302C.C=CH.OCH3) 2-CH302C- H H H 3-((E)--a1302C.C=CH.OCH3) 2-C2H502C- H H H 71 3-((E)--(M302C.C=CH.OCH3) 2-CH2=CH.CH202C- H H H 72 3-((E)-CH302C.C=CH.OCH3) 2-PhO2C- H 11 H 73 3-((E)-CH302C.C=CH.OCH3) 2- GN 0 H H 11 74 3-((E)__CH302C.C=CH.OCH3) 2- (1 n', H H 11 CD 0 W j OD TABLE I XWINUED Cúrrpmnd Melting No W A B D E Point CC) olefinic 3-( (-E)-CH-1,0'-.'C.C=CH.OCH3) 2- H H H N 0."
76 3- ( (E) -CH 302C.C=CH.OCH3) 2 nI-, H H H N S" 77 3-( (-E)-CH-IO-IC.C=CH.Oa'3) 2 H H H 78 3-((E)-CHnOiC.C=CH.OCH 2 H H H 3) N S" (0 TAELE I =INUED Cond Melting NO W A B D E Point ('C)olefinic 3 ', Q.:1.1 " - 79 3-((E)-CH302C.C=CH.OCH3) 2- 1 H H H N 0 3-((E)-CH302C.C=CH.OCH3) 2- C3n__ H H H N 2-C CI 81 3-((-E)-CH302C.C=CH.OCH3) 1 IN H H H N 0 82 H H H - -M302C.C=CH.OCf'3) 3-((E) N N S 0 W j 1 TABLE I CONTINUED Caffd Melting No W A B D E Point PC) olefinic 0 83 3-((E)-CHIO.)C.C=CH.OCH3) 2- /\,I- 0 H H H 84 3-((E)-CH10.3C.C=.CH.OCH3) 2 /\/)--S - H H H N N 3-((E)-CHIC)C.C=CH.OCH3) 2- Clf' N'I 0," H H H N 86 3-((E)-CH-10,C.C=CH.OCH3) 2- H H H C1r' N S hi T I CONTINUED Ckirpound W A B D E Melting olefinic No Point (C) 87 3-((-E)-'(M302C.C=CH.OCH3) 2-(2',4'-difluoro- H 11 H 105-7 7.60 phenoxy) 88 3-((E)-M302C.C=CH.OCH3) 2-W,5'-difluoro- H H H 88-89 7.60 pbenoxy) 89 3-((E)-'(M302C.C=CH.OCH3) 2-Pho- 6-F H H 3-((E)-M302C.C=CH.OCH3) 2-PhO6-Cl H H 91 3-((E)-CH302C.C=CH.OCH3) 2-PhO- 4-F 5-P 6-F 92 3-((E)-<:H302C.C=CH.OCH3) 2- 6-CH3 H H 93 3-((E)-CH302C.C=CH.OCH3) 2-PhO4-F 6-F H 94 3-((E)-CH302C.C=CH.OCH3) 2-PhO- 6-Br H H 0 W TABLE I CONTINUED Ccnd W A B D E MPoitting(OC) olefinic NO 3-( (E)-CH10,)C. C=CH.OCH3) 2-Pho- H 96 3 -((E) -CH-iOgC. C=CH.OCH3) 2-Pho-- 6---CH31H H H 4_F 97 3-((E)-CH 2-Pho. 5-F H H - 302;C-C=CH.OCH3) _p 98 3-((E)-CHIO,3C.C=CH.OCH3) 2-Pho- 4-F 6---CH3H 99 3-((E)-CH302C.C=CH.OCH3) 2-PhS- 6-F H H 3-((E)-CHIO,)C.C=CH.OCH3) 2-CH3 H H H Oil 7.59 101 3-((E)-CH302C.C=CH.OCH3) 2-(V,5- H H H difluorephenoxy) 102 3-((E)-ICHnOiC.C=CH.OCH3) 2-(Y,4'- H H H difluorophenoxy) 103 3-((E)-CH-40.)C.C=CH.XH3) 2-(Y-phenoxy)- H H H phenoxy 104 3-((E)-CH302C.C=CH.SCH3) 2-PhO H H H 3-((Z)-CH 302C.C=CH.OCH3) 2-PhO H H H 106 2-((E)-,CH302C.C=CH.OCH3) H H H H Oil 8.02 "1:yh" means phenyl ChEmical sbift of singlet frem olefinic proton on betathoxyacrylate group (ppm frcm tetramethylsilane) Solvent CDC13 14 GB2190374A 14 Table 11 shows selected proton rimr data for certain compounds described in Table 1. Chemical shifts are measured in ppm for tetramethylsilane, and deuterochloroform was used as solvent throughout. The following abbreviations are used:
br = broad t =triplet 5 s =singlet q =quartet d =doublet m =multiplet J =coupling constant Hz = Hertz TABLE II: SELECTED PROTON NMR DATA 10 15 Compound Proton nmr data No 20 1 3.60 M,s); 3.76 (3H,s); 6.85-7.40 MM; 7.56 (1H,s); 8.44 (1H,t). 25 21 3.55 (3H,s); 3.69 (3H,s); 6.94 (1H,d); 7.06 (2H,d); 7.45-7.60 (3H,m); 7.50 (1H,s); 30 8.0 (1H,m).
23 3.68 (3H,s); 3.86 (3H,s); 6.98-7.18 (4H,m); 7.20-7.32 (1H,m); 7.58 (1H,s); 7.62-7.66 35 (1H,m); 8.10-8.14(1H,m).
29 3.71 (3H,s); 3.88 (3H,s); 6.70 (1H,d); 7.06 40 (2H,d); 7.23 (1H,t); 7.40 (2H,m); 7.64 (1H,s); 8.35 (1H,d); 8.43 (1H,s).
45 GB2190374A 15 TABLE II CONTINUED: SELECTED PROTON NMR DATA 5 Compound Proton nmr data 10 No 43 3.62 (3H,s); 3.80 (3H,s); 6.95 (2H,m); 7.08 15 (1HM; 7.28 (1H,m); 7.50 (1H,s); 8.28 (1H,m); 8.35 (1H,m).
20 57 3.69 (3H,s); 3.86 (3H,s); 6.80-6.90 (3H); 7.05 (1H); 7.25-7.35 (1H) 7.59 (1H,s); 7.65 (1H); 8.13 (1H) 25 63 3.70 (3H,s); 3.87 (3H,s); 6.9-7.4 (3H,m); 7.46 (1H,d); 7.61 (1H,s); 7.68 (1H,q); 8.16 30 (1H,q).
100 2.41 (3H,s); 3.71 (3H,s); 3.85 (3H,s); 7.12 35 (1H,d); 7.59 (1H,s); 8.44 (1H,d).
106 3.74 (3H,s); 3.99 (3H,s); 6.98 (1H,m); 7.12 40 (1HM; 7.48 (1HM; 8.02 (1H,s); 8.38 (1H,m).
1 45 The compounds of the invention having the general formula (1) can be prepared by the chemical processes outlined in Scheme 1, Scheme 11 Scheme ffi. Throughout Scheme 1, Scheme 11 and Scheme fil the terms W, R2, Z, A, B, D and E are as defined above, G is hydrogen or a 50 metal atom (such as a sodium atom), M is a metal atom (such as lithium atom) or a metal atom plus an associated halogen atom (such as M91, MgBr, or M9C1) and L is a halogen atom or other good leaving group. The compounds of general formula (1) may exist as mixtures of geometric isomers which can be separated by chromatography, distillation or fractional crystallisation. The use of the formula 55 16 GB2190374A 16 C02R1 CH 2 ZR 10 is intended to signify a separable mixture of both geometric isomers about the acrylate double bond, ie.
15 C02R1 C02R1 1 20 C-H and c - ZR2 1 2 1 ZR H 25 Referring to Scheme 1, compounds of general formula (1), in which Z is 0 but not S, can be prepared by treatment of compounds of general formula (IV) with a base (such as sodium hydride or a sodium alkoxide) and a formic ester of the formula HC02R1 (such as methyl formate) 30 in a suitable solvent (step (b) of Scheme 4. If a species of general formula R2L, wherein L is a leaving group (such as a halide or R2S04 anion), is then added to the reaction mixture, com pounds of general formula (1) may be obtained (step (a) of Scheme 4. If a protic acid is added to the reaction mixture, compounds of general formula (111) wherein G is hydrogen are obtained.
Alternatively, the species of general formula (111) wherein G is a metal (usually an alkali metal 35 such as sodium) may itself be isolated from the reaction mixture.
Compounds of general formula (111) wherein G is a metal atom can be converted into com pounds of general formula (1) by treatment with a species of general formula R2L, wherein L is as defined above, in a suitable solvent. Compounds of general formula (111) wherein G is hydrogen can be converted into compounds of general formula (1) by successive treatments with a base 40 (such as potassium carbonate or sodium hydride) and a species of general formula R2L, in a suitable solvent.
Alternatively, compounds of general formula (1), wherein Z is oxygen, can be prepared from acetals of general formula (XII) by elimination of the appropriate alkanol under either acidic or basic conditions, at a suitable temperature and often in a suitable solvent (step (c) of Scheme 1). 45 Examples of reagents or reagent mixtures which can be used for this transformation are lithium di-isopropylamide; potassium hydrogen sulphate (see, for example, T Yamada, H Hagiwara and H Uda, J. Chern. Soc., Chemical Communications, 1980, 838, and references therein); and triethy lamine, often in the presence of a Lewis acid such as titanium tetrachloride (see, for example, K Nsunda and L Heresi, J. Chem. Soc., Chemical Communications, 1985, 1000). 50 Acetals of general formula (XII) can be prepared by treatment of alkyl silyl ketene acetals of general formula (Xlil), wherein R is an alkyl group, with a trialkyl orthoformate of formula (R2 0)3CH in the presence of a Lewis acid such as titanium tetrachloride, at a suitable temperature and in a suitable solvent (see, for example, K Saigo, M Osaki and T Mukaiyarna, Chemistry Letters, 1976, 769) (step (f) of Scheme 4. 55 Alkyl sily] ketene acetals of general formula (XIII) can be prepared from esters of general formula (IV) by treatment with a base and a trialkylsilyl halide of general formula R3SiCI or R,SiBr, such as trimethylsilyl chloride, or a base and a trialkylsilyl triflate of general formula R3Si 0S02C17, in a suitable solvent and at a suitable temperature (see, for example, C Ainsworth, F Chen and Y Kuo, J. Organometallic Chemistry, 1972, 46, 59) (step (9) of Scheme 4. 60 It is not always necessary to isolate the intermediates (X11) and (Xlil); under appropriate conditions, compounds of general formula (1) may be prepared from esters of general formula (N) in a---onepot- sequence by the successive addition of suitable reagents listed above.
Alternatively, compounds of general formula (Xli), wherein Z is oxygen, can be prepared from compounds of general formula (IV) by treatment with an orthoformate HC(ZR2), in the presence 65 17 GB2190374A 17 of a carboxylic acid anhydride (such as acetic anhydride) and a Lewis acid catalyst (such as zinc chloride) at a suitable temperature. In this way, under appropriate conditions, such as elevated temperatures or extended reaction times, compounds of general formula (1) may be obtained directly (see, for example, R. Huisgen, H. Seidl and J. Wuiff, Chem. Ber, 1969, 102, 915; and A. Marchesini, J. Org. C-hem., 1984, 49, 4287) (step (h) of Scheme 4. 5 Compounds of general formula (IV) can be prepared by methods described in the chemical literature. For example, they can be prepared from compounds of general formula (V) by treatment with an a[c6hol R10H in the presence of an acid (such as hydrogen chloride) (Step (d) of Scheme 4.
18 GB2190374A 18 Scheme 1 C02R1 C02R 1 D E step (c) D E 1 C ZR2 cil ZR2 C. (1) A ZR2 R2_L Step (a) step (f) ZR2 (Xli) 10 C02R1 OR1 D E 1 step D E H B CH 0SiR3 a C C 0 2R 1 step C (h) B APN A OG (Xlii) step (9) F02R1 Step (b) E CH2 20 A (IV) CH3S 0 E 1 11 25 11 C SCH3 Step (d) B CH A; gN 30 (V) Step (e) D E B - A;FN- CHO 35 (VI) 19 GB2190374A 19 Compounds of general formula (V) can be prepared from aldehydes of general formula (V1) by treatment with methyl methyisulphinyimethyisulphide (CH3SOCH2SCH3) in the presence of a base (such as Triton-13) in a suitable solvent (such as tetrahydrofuran) (see K. Ogura and G. Tsuchi hashi, Tetrahedron Letters, 1972, 1383-6) (Step (e) of Scheme 4.
Compounds of general formula (V() can be prepared by standard methods described in the 5 chemical literature.
Referring to Scheme 11, compounds of general formula (1) can alternatively be prepared from alpha-ketoesters of general formula (V11) by treatment with phosphorus ylides of general formula (V111) in a suitable solvent (such as diethyl ether or tetrahydrofuran) (see, for example, EP-A 0044448 and EP-A-0178826) (Step (a) of Scheme 11. 10 Alpha-ketoesters of general formula (V11) can be prepared by standard methods described in the chemical literature. For example, alpha-ketoesters of general formula (V11) can be prepared by reaction of metallated pyridines of general formula (]X) with an oxalate (X) in a suitable solvent (such as diethyl ether or tetrahydrofuran) (Step (b) of Scheme 14. (For related reactions, see L.
M. Weinstock, R. B. Currie and A. V. Lovell, Syn. Commun., 1981, 11, 943 and references 15 therein).
Metallated pyridines of general formula (IX) can be prepared by standard methods described in the chemical literature.
Alternatively, alpha-ketoesters of general formula (V11) can be prepared from nitriles of general formula (Xl) using the procedure of K. Ogura, N. Katoh, 1. Yoshimura, G. Tsuchihashi, Tetrahe- 20 dron Letters, 1978, 375 (Step (c) of Scheme In.
GB2190374A 20 Scheme II C02R1 D E 1 5 -:W c B CH k ZR2 10 Step (a) \ Ph 3P--CHZR2 (VIII) 15 C02R1 D E 1 B c l 0 (Vii) A N 20 AL step (c) C02R1 25 C' 1 02R (X) Step (b) D E D E 30 B C.-N B m kON (XI) (IX) 35 21 GB2190374A 21 Certain of the compounds of general formula (1) can be prepared by an alternative route as shown in Scheme Ill.
When A is an optionally substituted phenoxymethy], phenylthiomethyl, alkoxymethyl, alkylthiomethyl or a hydroxymethyl group, compounds of formula (1) can be prepared by reaction of a compound of general formula (XV), with an optionally substituted phenol or thiophenol in the 5 presence of a base (such as sodium alkoxides, or sodium hydride) in a suitable solvent (such as dimethylformamide), or with an alkoxide, alkylthiolate, or hydroxide ion (step (a) of Scheme fil.
Compounds of formula (XV) wherein L is a halogen can be prepared by halogenation of compounds of formula (XIV), for example by Nbromosuccinimide, in a suitable solvent such as carbon tetrachloride (step (b) of Scheme fin. 10 Compounds of general formula (M) can be prepared by the route shown in Scheme L Compounds of general formula (1), where A is an optionally substituted alkenyl or optionally substituted phenylalkenyl group of the formula - CHR5=CR6137 can be prepared by reaction of compounds of general formula (XVI) with compounds of general formula (XVII), under the conditions of the well known Wadsworth-Emmons reaction (where Y is the group -P(O)(OR")2) or 15 under the conditions of the well known Wittig reaction (where Y is PAr3 and Ar is an optionally substituted phenyl group). Thus, compounds of general formula (XVI) are treated with a suitable base (such as sodium hydride or potassium t-butoxide) in a suitable dry solvent (such as N, N-dimethylformarnide or tetrahydrofuran) and then treated with the compounds of general formula (XVII) (step (c) of Scheme 114. 20 Compounds of general formula (XVI) can be prepared by reaction of compounds of general formula (XV) with a trialkyl phosphite, P(OR116 or with a triarylphosphine in a suitable solvent such as toluene or diethyl ether (step (d) of Scheme Iffi.
Throughout Scheme Ill R5 is preferably hydrogen, but may also be C,-, alkyl, or optionally substituted phenyl; R6 and R7 are hydrogen, C,-, alkyl, haloalkyl, optionally substituted phenyl or 25 the group -C02R 3. Preferably one of R6 and R7 is hydrogen and R8 is C,-, alkyl, usually methyl or ethyl. L is as defined for Scheme 1, but is preferably a halogen atom such as chlorine or bromine.
22 GB2190374A 22 Scheme III 0 Cn D1 D E R6 R7 B CH st p c) N A (Xvil) ZR C02R 1 C=CH i 2 D E ZR 10 step (a) p.' CHY B N R5 D C02R1 15 E c, (XVI) CH step (d) Bl'Q N ZR2 CHL 20 R step (b) (XV) 25 C02R1 1 c D CH B ON ZR2 30 CH2RS (XIV) 35 23 GB2190374A 23 In further aspects, the invention provides processes as herein described for preparing the compounds of the invention and the intermediate chemicals of formulae (111), (IV), (V), (VII) and (X11)-(XVI) used therein.
The compounds and metal complexes of the invention are active fungicides, and may be used to control one or more of the pathogens: 5 Pyricularia oryzae on rice Puccinia recondita, Puccinia stfliformis and other rusts on wheat, Pucciffia hordei, Pucciffia stfliformis and other rusts on barley, and rusts on other hosts eg, coffee, pears, apples, peanuts, vegetables and ornamental plants. Erysiphe grarninis (powdery mildew) on barley and wheat and other powdery mildews of various hosts such as Sphaerotheca macularis on hops Sphaerotheca fuliginea on cucurbits (eg. cucumber), Podosphaera leucotricha 10 on apples and Uncinula necator on vines.
Helminthosphorium spp., Rhynchosporium spp., Septoria spp. and Pseudocercosporelia herpo trichoides on cereals. Cercospora arachidicola and Cercosporidium personata on peanuts and other Cercospora species on other hosts for example sugar beet, bananas, soya beans and rice.
Altemaria species on vegetables (eg, cucumber), oil seed rape, apples, tomatoes and other 15 hosts. Venturia inaequalis (scab) on apples Plasmopara viticola on vines Other downy mildews such as Brernia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts and Pseudoperonospora humuli on hops and Pseudoperonos pora cubensis on cucurbits Phytophthora infestans on potatoes and tomatoes and other Phyto phthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and 20 other hosts.
Some of the compounds have shown a broad range of activities against fungi in vitro Some of the compounds may also have activity against various post-harvest diseases of fruit (eg, Penicillium digitatum and italicum and Trichoderma viride on oranges and Gloesporium musarum on bananas). 25 Further some of the compounds may be active as seed dressings against Fusarium spp., Septoria spp., Tilletia spp. (bunt, a seed borne disease of wheat), Ustilago spp., Helminthospo rium spp. on cereals, and Pyricularia oryzae on rice.
Therefore, in another aspect of the invention there is provided a methodof combating fungi, which comprises applying to a plant, to a seed of a plant, or to the locus of the plant or seed, 30 an effective amount of a fungicidal compounds of formula (1).
Some of the compounds can move acropetally in the plant tissue. Moreover, the compounds may be volatile enough to be active in the vapour phase against fungi on the plant.
The compounds may also be useful as industrial (as opposed to agricultural) fungicides, eq, in the prevention of fungal attack on wood, hides, leather and especially paint films. 35 The compounds of the invention have useful insecticidal activity against a range of insect species, and nematodes. Therefore in a further aspect of the invention there is provided a method of killing or controlling insect or nematode pests which comprises administering to the insect or nematode or to a locus thereof an effective amount of an insecticidal compound of formula (1). 40 A preferred group of compounds for use in this aspect of the invention are compounds of formula (1) where A is optionally substituted aryloxy (in particular at the 2-position) B, D and E are hydrogen and W is at the 3-position in the ring.
Particularly preferred compounds for use in this aspect of the invention are compund 15 in Table 1 which has been found to be active against Meloidogyne incognita (tomato root-knot 45 eelworm larvae) and compound 23 in Table 1 which has been found to be active against Diabrotica balteata (root worm larvae).
Similarly, some compounds may exhibit plant growth regulating activity and may be deployed for this purpose at appropriate rates of application. Therefore in yet a further aspect of the invention there is provided a method of regulating plant or seed, or to a locus thereof, growth 50 which comprises applying to a plant an effective amount of a plant growth regulating compound of formula (1).
The compounds may be used directly for fungicidal, insecticidal, nematocidal or plant growth regulating purposes but are more conveniently formulated into compositions using a carrier or diluent. The invention thus provides a fungicidal composition comprising a compound of general 55 formula (1) as hereinbefore defined, and a fungicidal acceptable carrier or diluent.
In addition the invention provides an insecticidal/ nematocidal composition which comprises an insecticidal or nematocidal compound of formula (1) in combination with a carrier or diluent and a plant growth regulating composition which comprises a plant growth regulating compound of formula (1) with a carrier or diluent. 60 As fungicides, the compounds can be applied in a number of ways. For example they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to the medium in which plants are growing or are to be planted. They can be sprayed on, dusted on or applied as a cream or paste formulation; or they can be applied as a vapour or as slow release granules. Application can be to any part of the plant including the foliage, stems, branches or 65 24 GB2190374A 24 roots, or to soil surrounding the roots, or to the seed before it is planted; or to the soil generally, to paddy water or to hydroponic culture systems. The invention compounds may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods.
The term---plant-as used herein includes seedlings, bushes and trees. Furthermore, the 5 fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged. 10 The compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gyp sum, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impreg 15 nating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for dressing seed may include an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methyl pyrrolidone, propylene glycol or dimethyiformamide). The compositions may also be in the form 20 of wettable powders or water dispersible granules comprising wetting or dispersing agents to facilitate their dispersion in liquids. The powders and granules may also contain fillers and suspending agents.
Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the 25 mixture to water which may also contain a wetting or emulsifying agent. Suitable organic solvents are aromatic solvents such as alkylbenzenes and alkyInaphthalenes, ketones such as isophorone, cyclohexanone and methylcyclohexa none, chlorinated hydrocarbons such as chloro benzene and trichlorethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers. 30 Suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent and including a suspending agent to stop the solid settling.
Compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, eg, fluorotrichloromethane or dichlorodifluoromethane. 35 The invention compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.
Alternatively, the compounds may be used in a microencapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance. 40 By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The invention compounds can be used as mixtures with fertilisers (eg, nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporat- 45 ing, for example coated with, the compound are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of general formula (1) or a salt or metal complex thereof.
Wettable powders, emulsifiable concentrates and suspension concentrates will normally contain 50 surfactants eg, a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.
Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylam monium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for 55 example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, bu tyinaphthalene sulphonate, and a mixture of sodium diisopropy]- and triisopropyl-naphthalene sulphonates).
Suitable non ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcre- 60 sol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clays such as bentonite or attapulgite.
Compositions for use as aqueous dispersons or emulsions are generally supplied in the form of 65 GB2190374A 25 a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, 5 suitably 10-85%, for example 25-60%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredi ent depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient may be used.
The compositions of this invention may contain other compounds having biological activity, eg, 10 compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.
A fungicidal compound which may be present in the composition of the invention may be one which is capable of combating ear diseases of cereals (eg, wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on 15 grapes and powdery mildew and scab on apple etc. By including another fungicide the compo sition can have a broader spectrum of activity than the compound of general formula (1) alone.
Further the other fungicide can have a synergistic effect on the fungicidal activity of the com pound of general formula (1). Examples of fungicidal compounds which may be included in the composition of the invention are carbendazim, benomyi, thiophanate-methyl, thiabendazole, fuber- 20 idazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxy], 4-chloro-(l cyano-l-ethoxymethyi)benzamide, benalaxyl, fosetyl-aluminium, fenarimol, iprodione, prothiocarb, procymidone, vinclozolin, penconazole, myclobutanil, propamocarb, diniconazole, pyrazophos, eth irimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, triacetate salt of 'IX iminodi (octamethylene)-diguanidine, buthiobate, propiconazole, prochloraz, flutriafol, hexacona- 25 zole, (2RS, 3RS)-2-(4-chlorophenyi)-3-cyclopropyi-l-(1H-1,2,4-triazol-lyi)butan-2-ol, (RS)-1-(4 chlorophenyi)-4,4-dimethyi-3-(1H-1,2,4-triazol-l-yimethyl)pentan-3-ol, fiusil azole, triadimefon, triad imenol, diclobutrazol, fenpropimorph, pyrifenox, fenpropidin, chlorozolinate, imazilil, fenfuram, car boxin, oxycarboxin, methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos, Kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane, tricyclazole, pyroquilon, chlor- 30 benzthiazone, neoasozin, polyoxin D, validamycin A, mepronil, flutolanil, pencycuron, diclomezine, phenazin oxide, nickel dimethyidithiocarbamate, techlofthalam, bitertanol, bupirimate, etaconazole, hydroxyisoxazole, streptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, 1-(2-cyano 2-methoxyiminoacetyi)-3-ethyl urea, fenapanil, tolclofos-methyl, pyroxyfur, polyram, maneb, man cozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, 35 dichlone, chloroneb, binapacryl, nitrothal-isopropy], dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dicloran, copper containing compounds such as copper oxychlo ride, copper sulphate and Bordeaux mixture, and organomercury compounds.
The compounds of general formula (1) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases. 40 Suitable insecticides which may be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XIVIC, 13PMC, carbofu ran, carbosulfan, diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion, propaphos, monocrotophas, buprofezin, ethroproxyfen and cycloprothrin.
Plant growth regulating compounds are compounds which control weeds or seedhead forma- 45 tion, or selectively control the growth of less desirable plants (eg, grasses).
Examples of suitable plant growth regulating compounds for use with the invention compounds are the gibberellins (eg, GA, GA, or GA7), the auxins (eg, indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (eg, kinetin, diphenylurea, benzimida- zole, benzyladenine or benzyiaminopurine), phenoxyacetic acids (eg, 2,4-D or IVICPA), substituted 50 benzoic acids (eg, triiodobenzoic acid), morphactins (eg, chlorfluoroecol), maleic hydrazide, gly phosate, glyphosine, long chain fatty alcohols and acids, dikegulac, paclobutrazol, flurprimidol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg, chloromequat chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl-3,6-dichloroani sate, daminozide, asulam, abscisic acid, isopyrimol, 1-(4-chlorophenyi)-4, 6-dimethyl-2-oxo-1,2dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (eg, bromoxynil), difenzoquat, benzoylprop ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide, triaphenthenoi and teenazene.
The following Examples illustrates the invention. Throughout these examples, the term "ether" refers to diethyl ether, magnesium sulphate was used to dry solutions, and reactions involving water-sensitive intermediates were performed under nitrogen and in dried solvents. Unless other- 60 wise stated, chromatography was performed using silica gel as the stationary phase. Where shown, infrared and NIVIR data are selective; no attempt is made to list every absorption. The following abbreviations are used throughout:
26 GB2190374A 26 THF =tetrahydrofuran delta =chemical shift DIVIF =NN-dimethyiformamide CDC13 =deuterochloroform S =singlet d =doublet 5 GC =Gas chromatography t =triplet MS Mass spectrum m =multiplet mmHg =millimetres pressure j =coupling constant of mercury Hz = Hertz mg =milligramme(s) NMR =Nuclear Magnetic 10 9 =gramme(s) Resonance EXAMPLE 1
This Example illustrates the preparation of (E)-methyl 2-(2'-phenoxypyrid3'-yi)-3-methoxyacry- 15 late (Compound No 15 of Table 1).
2-Phenoxy-3-cyanopyridine (209) and Raney-nickel alloy (20g) were stirred at reflux in 75% formic acid (200mi) for 1 hour. The reaction mixture was cooled and filtered and the resultant green solution was poured into water (150mi). After standing for several hours, needles of 2 phenoxy-3-pyridinecarboxaldehyde were deposited which were collected by filtration, washed 20 with water and air-dried (10g); m.p. 88-90'C; infrared max (nujol) 1675 cm-l; H NMR delta (CDCI,) 7.0-7.6 (m), 8.15-8.4 (2H,m), 11.05 (1H,s).
To a stirred solution of 2-phenoxy-3-pyridinecarboxaldehyde (9.959, 0. 05mol) and methyl methyisulphinyimethyl sulphide (6.2g, 0.05mol) in dry THF (20mi) was added dropwise Triton B (7.5mi, 40% solution in methanol). The reaction mixture was then heated to reflux for 1 hour. 25 GC analysis indicated that the reaction had gone to completion. The reaction mixture was allowed to cool and the solvent removed under reduced pressure. The brown oily residue was extracted repeatedly with ether and the combined ether extracts evaporated to give a white crystalline solid which was washed with a little ether and air- dried (7g); m.p. 123-6'C; infrared 30 max (nujol) 1565, 1400, 1235, 1200, 1060 cm -1; 'H NMR delta (CIDC1,) 2.33(3H,s), 2.8 (3H,s), 30 6.87-7.7 (m), 8.07 (1H,s), 8.1-8.6 (m). The product (6.8g) was dissolved in methanolic hydrogen chloride (150mi) (formed by adding acetyl chloride to methanol (1:5) at O'C) stirred for 1 hour at O'C and then left overnight. The reaction mixture was poured into water, neutralised with bicarbonate solution and then extracted with ether. The combined ether extracts were dried, filtered and evaporated to give a pale yellow liquid. Bulb-to-bulb distillation 35 (150'C/0.1mmHg) afforded methyl 2-phenoxypyrid-3-yl acetate (4.5g) infrared max (film) 1735, 1580, 1485, 1430, 1245 cm - 1; 'H NMR delta (CIDC13) 3.71 (3H,s), 3.80 (2H,s), 6.90-8.2 (m).
To a stirred solution of petrol-washed sodium hydride (1.8g, 0.037mol, 48% dispersion in oil) in dry DIVIF (30mi) at -15'C was added drop-wise a solution of methyl 2- phenoxypyrid-3-yi acetate (4.5g, 0.0185mol) and methyl formate (24g, 0.4mol) in dry DIVIF (20mi). A yellow colour 40 formed, accompanied by effervescene. After 30 minutes, the temperature was allowed to rise slowly. After stirring at room temperature for 30 minutes, the reaction mixture was poured into water (250mi) and extracted twice with ether. The combined ether extracts were then washed with potasium carbonate solution. The aqueous layers were combined, acidified to pH4 with conc. hydrochloric acid and then thoroughtly re-extracted with ether. The resultant ether extracts 45 were dried, filtered and evaporated to give an oil (5.4g). The oil (5.4g) and potassium carbonate (2.55g) were added to dry DMF (20mi) at O'C. Dimethyisulphate (1.75m]) was added in one portion and the temperature allowed to rise to room temperature. GC analysis indicated that the reaction had gone to completion. The reaction mixture was poured into water (150mi) and ether (10mi) added. White crystals were deposited which were collected by filtration. Recrystallisation 50 from ethyl acetate/60-80'C petroleum ether gave (E)-methyl 2-(2'- phenoxypyrid-3'-yi)-3-methoxy- acrylate (3.4g); m.p. 121-123'C; infrared max (nujol) inter alia 1710, 1635, 1575 cm-l; H NMR delta (CIDC13) 3.7 (3H,s), 3.85 (3H,s), 6.9-7.45 (m), 7.60 (1H,s), 7.5-7. 75 (m), 8.1 (m) ppm.
EXAMPLE 2 55
This Example illustrates the preparation of (E)-methy]-2-(3'-phenoxypyrid4'-yi)-3-methoxyacry- late (Compound No 43 of Table I).
To a solution of 3-phenoxypyridine (10.269, 0.06 mol) in dry THF (500 mi) under nitrogen was added copper (1) iodide and methyl sulphide (30 mi). The mixture was stirred at room temperature for 15 minutes and then cooled to -25'C. Phenyl chloroformate (8.0 m], 0.066 60 mol) was then added dropwise to produce a dark-brown solution. After 10 minutes methyimag nesium bromide (20 mls of 3M solution, 0.066 mol) was added dropwise at 25'C. After stirring at -25'C for 15 minutes the solution was warmed to room temperature over 1 hour, during which time the solution had become a clear light yellow colour. The reaction was quenched with 20% aqueous ammonium chloride solution (150 mi) and then partitioned with 65 27 GB2190374A 27 ether (250 mi). The organic layer was washed with 20 mi portions of 20% aqueous ammonium chloride-ammonium hydroxide (1:1) solution, 10% hydrochloric acid, water and brine. After drying the ether was evaporated to give a yellow oil which was redissolved in dry toluene (250 m]). A suspension of o-chloranil (159) in toluene (100 mi) was added portionwise at room temperature. The resulting dark solution was stirred overnight and then 10% aqueous sodium 5 hydroxide solution (200 mi) was added and stirring continued for 10 minutes at room tempera ture. The reaction mixture was partitioned with ether (200 mi) and the organic layer washed with mi portions of 10% aqueous sodium hydroxide solution and water and then 10% hydro chloric acid (4x250 mi). The acidic extracts were basified with 25% aqueous sodium hydroxide solution and then extracted with methylene chloride (x4). The combined methylene chloride 10 extracts were dried and evaporated to give a yellow oil. Bulb-to-bulb distillation (1OWC at 0.05 mBar) afforded 3-phenoxy-4-methylpyridine (6.59) as a clear liquid, 1H NIVIR delta (C13CIj 2.25 (3H,s); 6.9-7.4 (6H,m); 8.2 (1H,s); 8.3 (1H,d).
n-Butyllithium (6.1 mi of 2.6M solution in hexane, 0.0157 mol) was added dropwise to a stirred solution of 3-phenoxy-4-methylpyridine (2.99, 0.0157 mol) in dry THF (20 mi) at -78'C 15 under an atmosphere of nitrogen. The resulting brown suspension was stirred for 30 minutes and then a steady stream of carbon dioxide was bubbled through. After 30 minutes, the reaction mixture was poured into water (100 mi) and extracted (X2) with ether. The aqueous layer was evaporated to dryness under vacuum at WC. The resulting white solid was then treated with 150 mi of methanol saturated with hydrogen chloride and the resulting yellow solution left 20 overnight. The solvent was removed under reduced pressure and the residue partitioned between methylene chloride (100 mi) and saturated aqueous bicarbonate solution (100 mi). The organic layer was separated and the aqueous layer re-extracted (x2) with more methylene chloride. The combined organic extracts were dried and evaporated to give a brown liquid (2.59). Bulb-to-bulb distillation (1 4WC at 0. 1 mBar) afforded methyl 3-phenoxypyrid-4-yl acetate (2.15g) as a pale 25 yellow liquid; infrared maximum 1735 cm-1, 'H NIVIR delta (CIDC13) inter alia 3.60 (3H,s); 3.72 (2H,s).
Trimethylsilytrif late (2.22g, 0.01 mol) was added dropwise to a solution of triethylamine (1.019, 0.01 mol) in ether (10 mi) at room temperature. The resulting clear solution was added dropwise to a stirred solution of methyl 3-phenoxypyrid-4-yl acetate (2. 0g, 0.00823 mol) in 30 ether (10 mi) at O'C. The two-phase mixture was stirred for 1 hour at room temperature and then stood overnight at room temperature under nitrogen. The resulting brown oil was diluted with methylene chloride (5 mi) and transferred to a dropping funnel. In a separate flask, titanium tetrachloride (1.99, 0.01 mol) was dissolved in methylene chloride (10 mi) and then added dropwise to a solution of trimethyl orthoformate (1.1g, 0.01 mol) in methylene chloride (15 mi) 35 at -70T. The resulting yellow suspension was stirred at -700C whilst the preformed solution of the silyl enol ether was added dropwise. The internal temperature rose to -50'C. The reaction mixture was stirred rapidly, allowed to rise slowly to room temperature and then stood overnight. The resulting reaction mixture was poured into 5% potassium carbonate solution (200 mi) and then extracted with ether (x3). The dried ether extracts were evaporated to give a 40 brown oil. Chromatography on silica (eluent ether) afforded the title compound (0.89g) as a clear liquid; infrared maxima 1700, 1630 cm-l; 'H NMR delta (C13CIj 3.62 (3H,s); 3.80 (3H,s); 6.95 (2H,m); 7.08 (1H,m); 7.28 (3H,m); 7.50 (1H,s); 8.28 (1H,m); 8.35 (1H,m).
EXAMPLE 3 45
This example illustrates the preparation of (E)-methyl 2-(4'-phenoxypyrid3'-yi)-3-methoxycrylate (Compound No 29 of Table 1).
A solution of 4-chloropyridine (2.89 9, 25.5 mmol) in THF (15 mi) at 78'C was added to a stirred solution of lithium di-isopropylamide prepared by addition of n- butyl lithium (10.2 mi of 2.5 M, 25.5 mmol) to a solution of di-isopropylamine (2.58 9, 25.5 mmol) in dry tetrahydrofuran 50 at -78'C. After 2 hours a solution of DMF (2.05 g, 28.1 mmol) in THF (25 mi) at -78'C was added. After a further 1 hour at -78'C the reaction mixture was allowed to warm slowly to room temperature (16 hours). The resulting solution was poured into saturated brine (200 mi) and extracted with ether (3 x 100 mi). The combined ether extracts were washed with saturated brine and then the solvent was evaporated. Flash chromatography (eluent petrol-ether) of the 55 resulting residue gave 4-chloro-3-pyridine carboxaldehyde (2.86 g) as a solid; melting point 53-54'C; infrared max (nujol) 1580, 1695 cm-l; 'H NMR delta (CDCL,) 7.45 (1H,d), 8.70 (1H, d), 9.07 (1H, s), 10.50 (1H,s).
A solution of phenol (1.34 g, 14.3 mmol) in DMF (25 mi) was stirred with anhydrous potassium carbonate (0.99 9, 7.2 mmol) at 70-80'C for 40 minutes. 4- Chloro-3-pyridinecarbox- 60 aldehyde (2.02 g, 14.3 mmol) and copper bronze powder (0.10 g) were added and the resulting suspension stirred at 100-1 WC for 2 hours. The reaction mixture was cooled, filtered and the residues washed with ether. The combined ether washings were diluted to 400 mi with more ether, washed with saturated brine (4x) and the solvent removed to give 4- phenoxy-3-pyridine carboxaldehyde as a pale yellow crystalline solid (2.62 g); melting point 74-75'C; infrared max 65 28 GB2190374A 28 (nujol) 1590, 1695, 2760 em-'; 'H NMR delta (CDC13) 6.75 (1H broad), 7.15 (2H,d), 7.35 (1H,t), 7.50 (2H,t), 8.5-9.7 (2H, broad), 10.7 (1H,s).
To a stirred solution of 4-phenoxy-3-pyridinecarboxaldehyde (0.687 g, 3. 45 mmol) and methyl methyisulphinyimethyl sulphide (0.429 9, 3.45 mmol) in THF was added dropwise Triton B (0.53 mi, 40% solution in methanol). The mixture was heated at reflux for 2 hours, allowed to cool 5 and then diluted with dichioromethane (150 mi). The solution was washed with saturated brine (2x) and the solvent was evaporated. Flash chromatography (eluent ether- ethyl acetate) of the resulting residue gave 3-(2'-methylsulphinyi-2-methyithiovinyl)-4- phenoxypyridine as a pale yellow gum (0.128 g); 'H NMR delta (CDCI,) 2.32 (3H,s), 2.77 (3H,s), 6.60 (1H,d), 6.9-7.5 (5H, m), 7.93 (1H,s), 8.32 (1H,d), 9.10 (1H,s). 10 3-(2'-Methyisulphinyl-2'-methyithiovinyi)-4-phenoxy pyridine (0.128 g, 0. 42 mmol) was dissolved in methanolic hydrogen chloride [formed by adding acetyl chloride (1.2 mi) to dry metha nol (12 ml)l, and the solution was stirred overnight at ambient temperature. The reaction mixture was evaporated to dryness, stirred with aqueous sodium bicarbonate solution (25 mi) and then extracted with dichloromethane (2x). The combined extracts were washed with saturated brine 15 and the solvent was evaporated. Flash chromatography (eluent ether) gave methyl (4-phenoxypyrid-Y-y1) acetate as a pale brown oil (0.066 g); infrared max (film) 1580, 1740 em-'; H NMR delta (CDC[3) 3.68 (3H,s), 3. 74 (2H,s), 6.58 (1H,d), 7.0-7.5 (5H,m), 8.3-8.6 (2H,m).
To a stirred suspension of petrol-washed sodium hydride (0.026 9, 0.54 mmol, 50% disper- sion in oil) in DIVIF (4 ml) was added a solution of methyl (4'- phenoxypyrid-3'-yi) acetate (0.066 20 g, 0.27 mmol) and methyl formate (0.39 9, 6.5 mmol) in DIVIF. The mixture was stirred for 3.5 hours at ambient temperature. To the resulting almost clear pale yellow brown solution was added dropwise a solution of dimethyl sulphate (0.068 g, 0.54 mmol) in DMF (1.5 m[) and stirring continued for a further 2.5 hours at ambient temperature. The reaction mixture was then poured into saturated brine (50 mi) and extracted with ether (2x). The combined ether extracts 25 were washed with saturated brine and then the solvent removed. Flash chromatography (eluent ether) of the resulting residue afforded (E)-methyl 2-(4'-phenoxy-pyrid- 3'-yi)-3-methoxyacrylate as a pale yellow gum (0.032 g); 'H NMR (CDCI,) as in Table 11.
EXAMPLE 4 30
This example illustrates the preparation of (E)-methyl 2-(3'-phenoxypyrid2'-yi)-3-methoxyacry- late (compound No 1 of Table 1).
To a stirred solution of 2-methyl-3-hydroxypyridine (20 g, 0.1834 mol) in DIVIF (40 m]) was added sodium hydroxide (7.4 g), copper bronze (1 g) and bromobenzene (38. 7 mi, 0.367 mol).
The reaction mixture was heated to 153'C overnight. During this time, 40 mi of a volatile 35 component distilled out of the reaction mixture, which was replaced with more bromobenzene.
The reaction mixture was partitioned between ether and water, and the ether layer washed with water, dried and evaporated to give a brown oil (13 g). Bulb-to-bulb distillation (0.5 mmHg, 15WC) gave 2-methy]-3-phenoxypyridine as a colourless oil (5 g) contaminated with traces of DIVIF ('H NMR evidence). The oil was redissolved in ether, washed with water, dried and 40 evaporated to give 2-methyi-3-phenoxypyridine (3.6 g) as a clear colourless oil; 'H NMR delta (CDCI,) 2.52 (3H,s); 6.84-7.44 (7H,m); 8.78 (1H,m).
To a stirred solution of 2-methy]-3-phenoxypyridine (3.2 g, 0.017 mol) in THF (25 m]) at -60'C was added n-butyllithium (7 mi of a 2.5 M solution inhexane) via syringe over 15 minutes. A deep red colour formed immediately and there was a slight exotherm. After stirring 45 for a further 20 minutes, carbon dioxide gas was passed over the reaction mixture. A mildly exothermic reaction took place and a cream precipitate formed. The reaction mixture was allowed to warm to room temperature over 2 hours, diluted with water (100 mi), and then extracted with dichloromethane (x2) and ether (x 1). The aqueous phase was evaporated in vacuo at WC, and the resulting cream-coloured residue redissolved in methanolic hydrogen 50 chloride [formed from acetyl chloride (10 mi) and methanol (100 m])] and left overnight at room temperature. The solvent was removed in vacuo and the residue redissolved in dichloromethane and washed with dilute sodium hydrogen carbonate. The organic phase was dried and evapo rated to give an oily residue. Chromatography (eluent dichloromethane- ether) afforded methyl (3- phenoxypyrid-2-y1) acetate (1.5 g) as a brown oil; infrared max (film) 1735, 1400, 1250 em-,. 55 Methyl (3phenoxypyrid-2-yi) acetate (1.0g) was dissolved in a mixture of trimethylorthoformate (25 mi) and acetic anhydride and a catalytic amount of anhydrous zinc chloride added. The resulting reaction mixture was stirred at reflux for 3 hours. GC analysis of an aliquot indicated the loss of the starting material with the formation of two new products. The dark brown reaction mixture was cooled and evaporated to dryness in vacuo. The residue was partitioned 60 between ether and dilute aqueous sodium hydrogen carbonate solution. The ether layer was dried and evaporated to give a brown oily residue (1.26 g). Chromatography (eluent ether dichloromethane, 1:1) afforded both methyl 3,3-dimethoxy-2-(3'- phenoxypyrid-2'-yl) propanoate as a yellow oil (730 mg); infrared max (film) 1735, 1440, 1245, 1070, 750 em-'; H NMR delta (CDOJ 3.24 (3H,s); 3.45 (3H,s); 3.60 (3H,s); 4.65 (1H,d); 5.38 (1H,d); and (E)-methyl 2-(3'- 65 29 GB2190374A 29 phenoxypyrid-2'-yi)3-methoxyacrylate as a yellow oil (210 mg); infrared max (film) 1710, 1635, 1435, 1260, 1130 cm-l; 'H NMR delta (CIDC13) 3.60 (3H,s); 3.76 (3H,s); 6.85-7.40 (7H,m); 7.56 (1H,s); 8.44 (1H,t); m/e 285 (M+), 270, 254, 226.
EXAMPLE 5 5
This example illustrates the preparation of (E)-methyl 2-(2'phenoxymethylpyridin-3'-y])-3-me- thoxyacrylate (Compound No 67 of Table 1).
To a stirred suspension of sodium hydride (0.62 9, 60% dispersion in oil) in DIVIF (15 mi) at O'C was added dropwise a solution of methyl (2-methylpyridin-3-yi) acetate (1.968 9) and methyl formate (3.6 9) in DIVIF (5 m]). The solution was stirred at room temperature for 30 10 minutes and then allowed to stand overnight. The reaction mixture was poured into water (250 m]) and extracted with ether (100 mi). The aqueous layer was adjusted to pH 7 with dilute hydrochloric acid and then extracted with ethyl acetate (3 x 100 mi). The organic extracts were combined, dried and then evaporated under reduced pressure to give methyl 2-(2'-methylpyridin 3'-yi)-3-hydroxyacrylate as a brown oil (2.83 g, containing 58% DMF by NIVIR). The crude oil 15 (2.83 9) was stirred in DIVIF (40 mi) with dimethyl sulphate (1.59 9) and potassium carbonate (3.31 g) at room temperature for 30 minutes, then allowed to stand overnight. The reaction mixture was poured into water (300 m[), the solution adjusted to pH 8 with dilute hydrochloric acid and then extracted with ethyl acetate (3x200 mi). The combinated organic layers were washed with water (3x50 m]), then dried and evaporated under reduced pressure to give (E)- 20 methyl 2-(2'methylpyridin-3'-yi)-3-methoxyacrylate as a yellow liquid (0. 72 g). Infrared max (1717, 1640, 1260 cm-l; 'H NMR delta (CDCI,) 2.41 (3H,s), 3.71 (3H,s), 3.85 (3H, s), 7.12 (1H,m), 7.41 (1H,d), 7.59 (1H,s), 8.44 (1H,d) ppm.
(E)-methyl 2-(2'-methylpyridin-3'-yi)-3-methoxyacrylate (0.72 9) was stirred in carbon tetrachlo ride (25 mi) with N-bromosuccinimide (0.84 g) and azoisobutyronitrile (0. 025 g, catalyst) and 25 then heated to reflux for 3.5 hours. The reaction mixture was partitioned between saturated sodium bicarbonate solution (100 mi) and ethyl acetate (120 m]). The aqueous layer was further extracted with ethyl acetate (20x30 m]). The combined organic layer were washed with water (20 mi), and then dried and evaporated under reduced pressure to give (E)- methyl 2-(2'-bromo methyl pyridin-3'-yi)-3-methoxyacrylate as a brown oil (1.14 g), which was used without further 30 purification. The oil in DMF (5 mi) was added to a stirred solution of sodium phenoxide (0.41 g) in DMF (5 m]), then stirred at room temperature for 30 minutes and allowed to stand for 64 hours. The reaction mixture was poured into water (200 mi) and extracted with ethyl acetate (3 x 100 m[). The combined organic extracts were washed with water, (2 x 30 mi), dried and evaporated under reduced pressure to give a brown oil (0.97 g) which was purified by HPLC 35 (eluent ethyl acetate) to give (E)-methyl 2-(2'-phenoxymethylpyridin-3'- yi)-3-methoxyacrylate as a light brown oil, (0.194 g), infrared max (film) 1715, 1640, 1260, 1135 cml; H NIVIR delta (CIDC13) 3.66 (3H,s), 3.76 (3H,s), 5.12 (2H,s), 6.82-6.98 (3H,m), 7.16-7. 32 (3H,m), 7.51 (1H,d), 7.53 (1H,d), 7.53 (1H,s), 8.6 (1H,d) ppm.
The following are examples of compositions suitable for agricultural and horticultural purposes 40 which can be formulated from the compounds of the invention. Percentages are by weight.
EXAMPLE 6
An emulsifiable concentrate is made up by mixing and stirring the ingredients until all are dissolved. 45 Compound No 15 10% Benzyl alcohol 30% Calcium dodecylbenzenesulphonate 5% Nonylphenolethoxylate (13 moles 50 ethylene oxide) 10% Alkyl benzenes 45% EXAMPLE 7
The active ingredient is dissolved in methylene dichloride and the resultant liquid sprayed onto 55 the granules of attapulgite clay. The solvent is then allowed to evaporate to produce a granular composition.
Compound No 15 5% Attapulgite granules 95% 60 EXAMPLE 8
A composition suitable for use as a seed dressing is prepared by grinding and mixing the three ingredients. 65 GB2190374A 30 Compound No 15 50% Mineral oil 2% China clay 48% 5 EXAMPLE 9
A dustable powder is prepared by grinding and mixing the active ingredient with talc.
Compound No 15 5% 10 Tale 95% EXAMPLE 10
A suspension concentration is prepared by ball milling the ingredients to form an aqueous 15 suspension.
Compound No 15 40% Sodium lignosulphonate 10% Bentonite clay 1% 20 Water 49% This formulation can be used as a spray by diluting with water or applied directly to seed.
EXAMPLE 11 25
A wettable powder formulation is made by mixing and grinding the ingredients until all are thoroughly mixed.
Compound No 15 25% 30 Sodium lauryisulphate 2% Sodium lignosulphonate 5% Silica 25% China clay 43% 35 EXAMPLE 12 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows. 40 The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. 40 The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, the formulations (100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to 45 approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the disease. An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment. 50 Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants.
After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment. 55 The disease control was recorded by the following grading:
4=no disease 3=trace-5% of disease on untreated plants 2=6-25% of disease on untreated plants 1 =26-59% of disease on untreated plants 60 0=60-100% of disease on untreated plants The results are shown in Table Ill.
1 1 1 CA) T1 iii CCMPOUND PUCCINIA EMIPHE VENTURIA PYRICULARA CERODSPORA PLASMOPARA PHY7OPHTHORA NO RECONDITA GRAMINIS I1JAMUALIS ORYME ARACHIDICOLA VITICOLA INFESTANS (WHEAT) (RMUEY) (APPLE) (RICE) (PE (VINE) (TICMA10) 1 0 3 3 0 4 0 0 4 4 4 4 4 4 4 16 4 4 4 4 4 4 3 18 1 4 4 0 4 4 0 19 4 4 4 4 4 4 0 4 4 4 4 4 4 0 21 4 4 4 0 4 4 3 23 4 4 4 4 4 4 4 57 4 4 4 4 4 4 3 58 4 4 4 4 4 4 3 4 4 4 4 4 4 4 66 0 4 4 0 1 2 0 87 3 4 4 4 4 0 0 88 4 4 4 2 3 4 4 106 0 4 0 0 0 0 - co 0 ppm root drench only > W 32 GB2190374A 32 EXAMPLE 13
This example illustrates the plant growth regulating properties of compounds 15, 16, 19, 20, 23 and 43 of Table 1.
These compounds were tested on a whole plant screen for plant growth regulating activity against six species of plant. The plant species used in this screen are presented in Table]V with 5 the leaf stage at which they were sprayed.
A formulation of each chemical was applied at 4000 ppm (4 kg/ha in a 1000 1/ha field volume) using a tracksprayer and a SS8004E (Teejet) nozzle. Additional tests were done on tomatoes at 2000 and 500 ppm.
After spraying, the plants were grown in a glasshouse with 25'C day (22'C night tempera- 10 tures. The exceptions to this were the temperate cereals wheat and barley, which were grown in 13-16'C day/ 11- 1 3'WC night temperatures. Supplementary lighting was supplied when necessary to provide an average photoperiod of 16 hours (14 hours minimum).
After 2-6 weeks in the glasshouse, depending on species and time of year, the plants were visually assessed for morphological characteristics against a control plant sprayed with a blank 15 formulation. The results are presented in Table V.
TABLE IV
20 PLANT MATERIAL USED FOR WHOLE PLANT SCREEN 25 Species Code Variety Growth Stage No plants Compost 30 at Treatment per 3#1 pot Type 35 Barley BR Atem 1 - 1.5 leaves 4 JIP Wheat WW Tinvo 1 - 1.5 leaves 4 JIP Maize MZ Earliking 214 - 2 leaves 1 PEAT 40 Apple AP Red Delicious 4 - 5 leaves 1 JIP Rice Re Ishikari 2 - 2 leaves 4 JIP Thmato TO Ailsa Craig 2 2 leaves 1 PEAT 45 John Innes Potting Cst. 50 33 GB2190374A 33 TABLE V
5 Compound Table BR WW RC AP MZ TO TO TO+ No 10 NT NT NT 16 1 NT NT NT NT NT NT 15 19 1 NT NT NT 2GAT NT I 1 NT NT NT NT NT NT I 23 1 NT IG NT NT I I 2G 20 43 1 2T T T I G NT I 25 KEY 2000 ppm+50Oppm 30 Retardation 1-3 where 1 = 10-30% 2=21-60% 3=61-100% Green effect=G 35 Apical damage=A Tillering or side shooting=T Blank means less than 10% effect NT indicates that the compound was not tested against this species.
40

Claims (4)

1. A compound having the general formula (I):
D E B 45 A and stereoisomers thereof, wherein W is R102C-C=Cl-11-ZR 2, wherein R' and R2, which are the same or different, are alkyl or fluoroalkyl groups, and Z is either an oxygen or sulphur atom; A, 50 B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkyny], optionally substituted ary], optionally substituted aryloxy, optionally substituted arylthio, optionally substi tuted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally 55 substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, - CO,R3, -CONR3R4, -COR3, -CR3NR4, N=CR 3R4 or -S(O).R3 groups; any two of the groups A, B, D and E when they are in adjacent positions on the ring, optionally join to form fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R3 and R4, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, 60 alkenyl ' alkynyl, optionally substituted aryl, or optionally substituted aralkyl groups; and metal complexes thereof.
2. A compound according to claim 1 in which A, B, D and E are selected from the group consisting of hydrogen, halogen, C,-4 alkyl, trifluoromethy], C,-, alkoxy, trifluoromethoxy, aralkyl, aralkenyl, -COOR3, (in which R3 'S C1-4 alkyl or aryl), aryloxy, arylthio, heteroaryloxy, heteroaryl- 65 34 GB2190374A 34 thio, benzyloxy, benzylthio and phenyloxymethyl, all ofwhich may carry one or more ring substituents selected from the group consisting of halogen, cyano, nitro, 12, alkyl, C, alkoxy, trifluoromethyi and trifluoromethoxy.
3. A compounds according to claim 1 or 2 in which at least one of A, B, D and E is a group other than hydrogen and that it is in a position on the pyridine ring ortho to the substituent W. 5 4. A compound according to any one of the preceding claims in which R and R- are both methyl.
5. A compound according to any one of the preceding claims in which Z is oxygen.
6. A compound having the formula (ii):
10 wherein A, which is in a position ortho to the acrylate group, is phenoxy (optionally substituted with one or more of fluoro, chloro, bromo, methyl, methoxy, trifl uoro methyl, trifluoromethoxy, cyano or nitro), phenyithio, benzyl, phenylethyl, phenylethenyl (either the (E)- or (2)-isomer), benzyloxy, phenyl oxym ethyl, benzylthio, -COOR3 (in which R3 is methyl, ethyl, allyl or phenyl), 20 pyridinyi-, pyrimidinyl- or pyrazinyl-oxy or-thio (optionally substituted with chloro, bromo or trifluoromethyl), or benzoxazoiyi-oxy or-thio.
7. A process for preparing a compound according to claim 1 which comprises, (i) treating a compound of formula (ill):
25 Z 30 35 35 when G is a metal atom, with a species of the formula R2L in a suitable solvent, or, when G is hydrogen, successively with a base and a species WL in a suitable solvent; or (ii) eliminating from a compound of formula (Xli):
40 ew C=_ZR2 45 ZR2 (Xil) 50 the elements of the alkanol R-71-1 under acidic or basic conditions; or (5) treating an alpha-ketoester of formula (V11) - E 55 60 with a phosphorus ylide of formula Ph,,P=CHZW in a suitable solvent; or, when A is an optionally substituted phenoxymethyl, pheny[thiomethyl, alkoxymethyl, alkylthiom- ethyl or a hydroxymethyl group, 65 GB2190374A 35 (iv) reacting a compound of formula (XV) C02R1 1 5 E c 11 g2 ZR N XCHL 1 10 RS (xv) with an optionally substituted phenol or thiophenol in the presence of a base in a suitable 15 solvent or with an alkoxide, alkylthiolate or hydroxide ion; or, when A is an optionally substituted alkenyl or phenylalkenyl group of the formula -CHR5=CR6137, (v) treating a compound of formula (XVI) C02R1 20 1 E C=CH ZR2 i:., 25 B CHY 1 R5 (XVI) 30 with a base in a suitable solvent followed by treatment with a compound of formula (XVII) 0 35 11 c (XVI I R6 R 7 40 wherein A, B, D, E, R', R2, R3 and Z have the meanings given in claim 1 unless otherwise 45 stated, G is hydrogen or a metal atom, L is a leaving group, Ph is phenyl, R5 is hydrogen, C1-4 alkyl or optionally substituted phenyl, R6 and R7 are hydrogen, C,,,alkyl, haloalky], optionally substituted phenyl or C0,1R3, Y is -P(O)(OR8)2 or -P-1-Ar3, R8 'S C,-4 alkyl and Ar is optionally substituted phenyl.
8. Intermediate chemicals of the formula (111)-(V), (VII) and (X11) to (XVI) as herein defined. 50 9. A fungicidal composition comprising, as an active ingredient, a compound according to claim 1 and a fungicidally acceptable carrier or diluent therefor.
10. A method of combating fungi which comprises applying to a plant or seed to a locus thereof, a compound according to claim 1 or a composition according to claim 9.
11. An insecticidal/nematocidal composition comprising an insecticidal/nematocidal compound 55 of formula (1) as defined in claim 1 in combination with a carrier or diluent.
12. A method for killing or controlling insect and nematode pests which comprises administ ering to the insect or nematode or to a locus thereof an effective amount of an insecticidal/ne matocidal compound of formula (1) as defined in claim 1 or a composition according to claim 11.
13. A plant growth regulator composition of formula (1) comprising a plant growth regulating 60 compound of formula (1) according to claim 1 and a carrier or diluent therefor.
14. A method of regulating plant growth which comprises applying to a plant or seed of a plant or a locus thereof a plant growth regulating compound of formula (1) according to claim 1 or a composition according to claim 13.
36 GB2190374A 36 Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd, Dd 8991685, 1987. Published at The Patent Office, 25 Southampton Buildings, London, WC2A l AY, from which copies may be obtained.
4.
GB8707530A 1986-04-17 1987-03-30 Fungicidal ,insecticidal,nematocidal and plant growth regulating pyridines Expired - Lifetime GB2190374B (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB8707530A GB2190374B (en) 1986-04-17 1987-03-30 Fungicidal ,insecticidal,nematocidal and plant growth regulating pyridines
EG218/87A EG18672A (en) 1986-04-17 1987-04-15 Derivatives of acrylic acid useful in agriculture especially as fungicides but also as insecticides, nematicides and plant growth regulators
MYPI87000509A MY101727A (en) 1986-04-17 1987-04-20 Fungicides
BR8701894A BR8701894A (en) 1986-04-17 1987-04-21 COMPOUND, PROCESS FOR THE PREPARATION OF A COMPOUND, CHEMICAL INTERMEDIARIES, FUNGICIDE COMPOSITION, PROCEDURE TO COMBAT FUNGI, INSECTICIDE / NEMATICIDE COMPOSITION, PROCESS TO EXTERMINE OR CONTROL INSECTS AND NEMATODES, REGULAR PROCESSING UNDER THE REGULAR REGULATORY PLANT.
GB8922230A GB2222163B (en) 1986-04-17 1989-10-03 Pyridine intermediates

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB868609456A GB8609456D0 (en) 1986-04-17 1986-04-17 Fungicides
GB878701627A GB8701627D0 (en) 1987-01-26 1987-01-26 Fungicides
GB8707530A GB2190374B (en) 1986-04-17 1987-03-30 Fungicidal ,insecticidal,nematocidal and plant growth regulating pyridines

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2222163A (en) * 1986-04-17 1990-02-28 Ici Plc Pyridine intermediates
GB2228480A (en) * 1986-08-06 1990-08-29 Ici Plc Alpha-dimethoxymethyl-phenylacetic acid intermediates for fungicides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5061716A (en) * 1990-09-13 1991-10-29 Uniroyal Chemical Company, Inc. Fungicidal 3,3-bisthioalkyl-2-pyridylacrylic acid compounds

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Publication number Priority date Publication date Assignee Title
GB243012A (en) * 1924-11-17 1926-04-15 Skf Svenska Kullagerfab Ab Improvements in or relating to bogies for railway cars and the like
GB2190374B (en) * 1986-04-17 1990-07-04 Ici Plc Fungicidal ,insecticidal,nematocidal and plant growth regulating pyridines

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Title
CHEMICAL ABSTRACTS 101 (21): 191812C *
CHEMICAL ABSTRACTS 55: 24740A *
CHEMICAL ABSTRACTS 70 (21): 96597U *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2222163A (en) * 1986-04-17 1990-02-28 Ici Plc Pyridine intermediates
GB2222163B (en) * 1986-04-17 1990-06-20 Ici Plc Pyridine intermediates
GB2228480A (en) * 1986-08-06 1990-08-29 Ici Plc Alpha-dimethoxymethyl-phenylacetic acid intermediates for fungicides
GB2228480B (en) * 1986-08-06 1990-12-05 Ici Plc Heterocyclic intermediates

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GB8707530D0 (en) 1987-05-07
BR8701894A (en) 1988-02-09
GB2222163B (en) 1990-06-20
MY101727A (en) 1992-01-17
GB2222163A (en) 1990-02-28
GB2190374B (en) 1990-07-04
GB8922230D0 (en) 1989-11-15
EG18672A (en) 1993-10-30

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