GB2281295A - (2-Fluoroethyl) thio-substituted pyrimidines as nematicides - Google Patents

(2-Fluoroethyl) thio-substituted pyrimidines as nematicides Download PDF

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GB2281295A
GB2281295A GB9317761A GB9317761A GB2281295A GB 2281295 A GB2281295 A GB 2281295A GB 9317761 A GB9317761 A GB 9317761A GB 9317761 A GB9317761 A GB 9317761A GB 2281295 A GB2281295 A GB 2281295A
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alkyl
formula
sch2ch2f
hydrogen
phenyl
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Steven Fitzjohn
Michael Peter Robinson
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Syngenta Ltd
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Zeneca Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/58—Two sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/78—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4

Abstract

Compounds of formula (I) are useful as nematicides: <IMAGE> wherein R<1>, R<2>, R<3> and R<4> are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, haloalkenyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR<5>R<6>, CONR<6>R<7>, hydroxy, acylamino, -CO2R<7>, -O(CH2)mCO2R<7>, -S(O)nCH2CH2F, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R<2> and R<3> when taken together from a 5- or 6-membered ring; m is 1 or 2; n is 0, 1 or 2; R<6> and R<7> are hydrogen or C1-4alkyl; R<5> is C1-4alkyl; provided that at least one of R<1> to R<4> is -S(O)nCH2CH2F. Nematicidal compositions and methods of killing or controlling nematodes are also described.

Description

HETEROCYCLIC COMPOUNDS The present invention relates to novel pyrimidine derivatives having nematicidal activity, to processes for their preparation, to compositions containing them, and to methods for killing or controlling nematode pests using them.
According to the present invention there is provided a compound of formula (I) wherein R1, R2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, haloalkenyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, CONR6R7. hydroxy, acylamino, -C02R7, O(CH2)mCO2R7 -S(O)nCH2CH2F, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2; n is 0, 1 or 2; R6 and R7 are hydrogen or C1-4 alkyl;R5 is C1-4 alkyl; provided that at least one of R1 to R4 is -S(O)CH2CH2F; further provided that when R is -SCH2CH2F, either R, R and R are not all hydrogen, or R and R are not both methyl when R2 is hydrogen.
The compounds of formula (I) in which R4 is -SCH2CH2F and either R1, R2 and R3 are all hydrogen, or 1 and 3 22 both Id 2 are all R3 are all hydrogen, or R1 and R3 are both methyl and R2 is hydrogen are known (Khim. Geterotsikl. Soedin 1967 (6), 1087-8). However, their use as nematicides was previously unknown.
When any of R1 to R4 is an alkyl group it can be straight or branched chain and is preferably C14 alkyl, in particular ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tertiary butyl.
When any of R1 to R4 is an alkenyl or alkynyl group it can be straight or branched chain and preferably contains up to 6 carbon atoms, for example, allyl or propargyl.
When any of R1 to R4 is a phenyl, phenoxy, benzyl or benzyloxy group, the phenyl moiety may be optionally substituted with halogen, (for example, chlorine, bromine or fluorine), cyano, alkyl, haloalkyl, alkoxy or haloalkoxy, the alkyl group being preferably C1-4 alkyl and the alkoxy group being preferably C1-6 alkyl. Examples of such groups are 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6- difluorophenyl, 2,4or 2,6- dichlorophenyl, 2-chloro-4-fluorophenyl, 2-chloro-6-fluorophenyl, 2-fluoro-4-chlorophenyl, 2-fluoro-6-chlorophenyl, 2-,3- or 4-methoxyphenyl, 2, 4-dimethoxyphenyl, 2-, 3-, or 4-ethoxyphenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-trifluoromethylphenyl, and the corresponding ring substituted benzyl, phenoxy and benzyloxy groups.
1 any of R1 to II 4 when any of R to R is a cycloalkyl or alkylcycloalkyl group, it preferably contains from 3 to 7 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclopropyl.
When any of R1 to R is halogen, it is preferably fluorine, chlorine or bromine.
When any of R1 to R4 is haloalkyl or haloalkenyl, the halogen is preferably chlorine, fluorine or bromine, the alkyl moiety is preferably C1-4 alkyl, for example trifluoromethyl, trifluoroethyl or pentafluoroethyl, and the alkenyl moiety is preferably C1-6 alkenyl.
When any of R1 to R4 is an alkoxy, alkenoxy or alkoxyalkyl group, it can be straight or branched chain and preferably contains up to 6 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, butenoxy, methoxymethyl, methoxyethyl or ethoxymethyl.
When any of R1 to R4 is a haloalkoxy group, it can be straight or branched chain and preferably contains up to 6 carbon atoms. The halogen is preferably chlorine, fluorine or bromine. Particular examples are trifluoromethoxy, trifluoroethoxy or pentafluoroethoxy.
When any of R1 to R4 is a haloalkenoxy group, it can be straight or branched chain and preferably contains up to 6 carbon atoms. The halogen is preferably chlorine, fluorine or bromine. Particular examples are OCH2CH2CH=CF2 and OCH2CH2CH=CHF.
When any of R1 to R4 is an alkylthio group, the alkyl preferably contains up to 4 carbon atoms. For example, -S-methyl, -S-ethyl, -S-propyl, S-butyl.
When any of R1 to R4 is a haloalkylthio group, the alkyl preferably contains up to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl.
The halogen is preferably chlorine, fluorine or bromine. Particular examples are SCF3, -S(CH2)2CH2F, SCH2CH2F, SCB1F2, SCC1F2 and SCH2CF3.
When any of R1 to R is -S(O)nCH2CH2F, is is preferably a substituent in the R1 or R4 position, or alternatively, in both the R1 and R4 positions or in both the R1 and R3 positions.
When any of R1 to R4 is NR5R6, it is preferably NHCH3, N(CH3)2 or N(C2H5)2.
When any of R1 to R is acylamino, it is preferably NHCOCH3 or NCOC2H5.
When any of R1 to R4 is Co2R7, R7 is preferably hydrogen, methyl or ethyl.
When any of R1 to R4 is O(CH2) CO R7, m is preferably 2 and R7is preferably hydrogen, methyl or ethyl.
When any of R1 to R4 is CONR6R7, R6 and R7 are preferably hydrogen, methyl or ethyl. Especially preferred is CONH2.
When R2 and R3 are taken together to form a 5- or 6-membered ring, it is preferably a carbocylic ring, for example, -(CH2)3-, -(CH2)4- or -CH=CH-CH=CH-.
Of particular interest are the compounds of formula (I) where R1 is selected from C14 alkyl, C1-4 haloalkyl, halogen, C1-6 alkoxy or hydroxy, R2 is selected from hydrogen or C1-4 alkyl, R3 is selected from hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-6 alkoxy, hydroxy or halogen and R4 is S(O)nCH2CH2F where n is 0. Or alternately, the compounds of formula (I) where RI is phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted, R2 is hydrogen or C14 alkyl, R3 is selected from hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-6 alkoxy, hydroxy or halogen and R4 is S(O) nCH2CH2F where n is 0.
Also of particular interest are the compounds of formula (I) where K1 is S(O)nCH2CH2F where n is 0, R2 is selected from hydrogen and C1-4 alkyl, R13 is selected from hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, hydroxy or halogen and R4 is selected from hydrogen, C1-4 alkyl, C1-4 haloalkyl, halogen, C1-6 alkoxy or hydroxy. Or alternately, the compounds of formula (I) where R1 is S(O)nCH2CH2F, R2 is hydrogen or C1-4 alkyl, R3 is selected from hydrogen, C1-4 alkyl, C1-4 haloalkyl, C1-6 alkoxy, hydroxy or halogen and R4 is selected from phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted.
Examples of the compounds of formula (I) are set out in Table I.
TABLE I COMPOUND NO. R1 R2 R3 R4 1 H H H SCH2CH2F 2 CH3 H H SCH2CH2F 3 SCH2CH2F H H H 4 SCH2CH2F H H SCH2CH2F 5 OCH2CF H H SCH2CH2F 6 SCH2CH2F H SCH2CH2F H 7 OCH3 H n-C3H7 SCH2CH2F 8 C5H11 H H SCH2CH2F 9 OC H H H SCH2CH2F 10 OCH2CH=CHCH3 H H SCH2CH2F 11 OH H n-C3H7 SCH2CH2F 12 CF3 H H SUCH2CH2F 13 SCH2CH2F H O(CH2)2C2F5 H 14 SCH2CH2F H OCH2CF3 H 15 Cl H n-C3H7 SCH2CH2F 16 OCH2C6H5 H H SCH2CH2F 17 OCH2CO2CH3 H H SCH2CH2F 18 n-C3H7 H H SCH2CH2F 19 OCH2(4-Cl-C6H4) H H SCH2CH2F 20 C6H5 H OCH2CH3 SCH2CH2F 21 OH H CH(CH3)2 SCH2CH2F 22 CI H CH(CH3)2 SCH2CH2F 23 O(CH2)2CO2CH3 H H SCH2CH2F 24 OCH3 H CH(CH3)2 SCH2CH2F 25 CH(CH3)2 H H SCH2CH2F 26 OH -(CH2)4- SCH2CH2F 27 OCH3 -(CH2)4- SCH2CH2F 28 Cl -(CH2)4- SCH2CH2F 29 CH3 H H SCH2CH2F 30 H C(CH3)3 H SCH2CH2F 31 H C2H5 H SCH2CH2F 32 H CF3 H SCH2CH2F 33 H CH(CH3)2 H SCH2CH2F TABLE I continued COMPOUND NO. R1 R2 R3 R4 34 H Cl H SUCH2CH2F 35 H C6H5 H SCH2CH2F 36 H -(CH2)3- SCH2CH2F 37 H -(CH2)3- SCH2CH2F 38 H -(CH2)3- SCH2CH2F 39 CH3 CH3 CH3 SCH2CH2F 40 CH3 CH3 CH3 SCH2CH2F 41 -CsCH H H SCH2CH2F 42 CN H H SCH2CHzF 43 4-F-C6H4 H H H SCH2CH2F 44 4-F-C6H4 H H H SCH2CH2F 45 4-CF3-C6H4CH2 H H SCH2CH2F 46 CC3H5 H H H SCH2CH2F 47 1-CH3-C3H5 H H H SCH2CH2F 48 CH2CF3 H H SCH2CH2F 49 OCH2CF3 H Cl SCH2CH2F 50 CH2OCH3 H H SCH2CH2F 51 Cl H Cl SCH2CH2F 52 F H F SCH2CH2 F 53 F H H SCH2CH2F 54 SCH3 H F SCH2CH2F 55 C(CH3)3 H H S(O)CH2CH2F 56 C(CH3)3 H OCH2CH3 SCH2CH2F 57 H -CH=CH-CH=CH- SCH2CH2F 58 H -CH=CH-CH=CH- SCH2CH2F 59 H -CH=CH-CH=CH- SCH2CH2F 60 OCH2CF3 -CH=CH-CH=CH- SCH2CH2F 61 OCH2CF3 H H S(O)2CH2CH2F indicates the substituent is cyclic The compounds of formula (I) where R1 to R4 have the meanings defined above and n is 0 are prepared by reacting a correspondingly substituted mercaptopyrimidine of formula (I) where one or both of R1 and R4 is SH, with l-bromo-2-fluoroethane in the presence of a base such as a carbonate, for example, potassium carbonate, and an inert solvent, for example acetone. Both the mercaptopyrimidine and l-bromo-2-fluoroethane can be obtained by conventional methods or from commercial sources.
Thus, according to a further aspect of the present invention there is provided a process for the preparation of compounds of formula (I) where R to R4 have the meanings defined above which comprises reacting a correspondingly substituted compound of formula (I) where one or both of * and R4 is SH, with l-bromo-2-fluoroethane in the presence of a base.
A particularly useful method of preparing the 4-mercaptopyrimdine comprises reacting the corresponding 4-hydroxypyrimidine in a solvent containing a tertiary amine, (e.g. pyridine) with phosphorous pentasulphide under a nitrogen atmosphere.
The compounds of formula (I) where any one or more of R1 to R4 is alkoxy can alternatively be prepared by reacting the corresponding hydroxy derivative of formula (I) with an alkylating agent, for example, dimethyl sulphate.
Thus, according to a further aspect of the present invention there is provided a process for the preparation of compounds of formula (I) where R1 to R4 have the meanings defined above provided that at least one of K1 to R4 is alkoxy, which comprises reacting a corresponding hydroxy derivative of formula (I) with an alkylating agent.
The compounds of formula (I) where R1 to R4 have the meanings defined above and n is 1, are prepared by oxidising the correspondingly substituted compound of formula (I) when n is 0, using conventional methods, for example by treatment with a peroxide in an inert organic solvent. The compounds of formula (I) where R1 to R have the meanings defined above and n is 2, are prepared by oxidising the correspondingly substituted compound of formula (I) where n is 0 or 1 using conventional method, for example, by treatment with a peroxide in an inert organic solvent.
Suitable peroxides include organic peroxides such as peroxy carboxylic acids, or their salts, for example, magnesium monoperoxy-phthalic acid.
Suitable inorganic peroxides include potassium peroxymono-sulphate.
Thus, according to a further aspect of the present invention there is provided a process for the preparation of compounds of formula (I) where n is 1 and R1 to R4 have the meanings defined above, which comprises reacting a correspondingly substituted compound of formula (I) when n is 0 with an oxidising agent; and a process for the preparation of compounds of formula (I) where n is 2 and R1 to R4 have the meanings defined above, which comprises reacting a correspondingly substituted compound of formula (I) when n is 0 or 1 with an oxidising agent.
The compounds of formula (I) are nematicidal and can be used to control nematodes in crop plants. Therefore, in a further aspect of the invention, there is provided a method for killing or controlling nematodes which comprises applying to the locus of the pests or to a plant susceptible to attack by the pest an effective amount of a compound of formula (I) wherein R1, K2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, haloalkenyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, CONR6R7, hydroxy, acylamino, -Co2R7, -O(CH2)mCO2R7, , -5(O)nCH2CH2F, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2; n is 0, 1 or 2; R6 and R7 are hydrogen or C1-4 alkyl; R5 is C1-4 alkyl; provided that at least one of R1 to R4 is S(O)nCH2CH2F The term "controlling" extends to non-lethal effects which result in the prevention of damage to the host plant and the limitation of nematode population increase. These effects may be the result of chemical induced disorientation, immobilisation, or hatch prevention or induction. The chemical treatment may also have deleterious effects on nematode development or reproduction.
The compounds of the invention can be used against both plantparasitic nematodes and nematodes living freely in the soil. Examples of plant-parasitic nematodes are: ectoparasites, for example Xiphinema spp., Longidorus spp. and Trichodorous spp. semi-endoparasites, for example, Tylenchulus spp. migratory endoparasites, for example, Pratylenchus spp., Radopholus spp. and Scutellonema spp. sedentary endoparasites, for example, Heterodera spp., Globodera spp. and Meloidogyne spp.; and stem and leaf endoparasites, for example, Ditylenchus spp., Aphelenchoides spp . and Hirshmaniella spp..
The compounds of the invention can also be used in combating a range of insects and acarids. Examples include Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms).
In order to apply the compound to the locus of the nematode or to a plant susceptible to attack by the nematode, the compound is usually formulated into a composition which includes in addition to the compound of formula (I) suitable inert diluent or carrier materials, andlor surface active agents.Thus in a further aspect of the invention there is provided a nematicidal composition comprising an effective amount of a compound of formula (I) wherein R1, R2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, haloalkenyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, CONR6R7, hydroxy, acylamino, -Co2R7, -O(CH2)mCO2K7 -S(O)nCH2CH2F, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2; n is 0, 1 or 2; R6 and R7 are hydrogen 5 C1,4 alkyl;R5 is C1-4 alkyl; provided that at least one of 1 to 4 or C14 alkyl; K is C14 alkyl; provided that at least one of K to R4 is -S(O)nCH2CH2F; and an inert diluent or carrier material and optionally a surface active agent.
The amount of composition generally applied gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.
The compositions can be applied to the soil, plant or seed, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsion or suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions.
Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers andlor diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths, ground corn cobs, and the like, or on to hard core materials such as sands, silicates, mineral carbonates, sulphates, phosphates, or the like. Agents which are commonly used to aid in impregnation, binding or coating the solid carriers include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils.
with the active ingredient. Other additives may also be included, such as emulsifying agents, wetting agents or dispersing agents.
Microencapsulated formulations (microcapsule suspensions CS) or other controlled release formulations may also be used, particularly for slow release over a period of time, and for seed treatment.
Alternatively the compositions may be in the form of liquid preparations to be used as dips, irrigation additives or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents). The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients. An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent. An SC is a fine particle size dispersion of solid active ingredient in water.To apply the concentrates they are diluted in water and are usually applied by means of a spray to the area to be treated.
Suitable liquid solvents for ECs include methyl ketone, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, or butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulphonates.
Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. 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.
These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 10-85X by weight of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
The compounds of formula (I) may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or microcapsule suspension CS) for use in seed treatments. In use the compositions are applied to the nematodes, to the locus of the nematodes, to the habitat of the nematodes, or to growing plants liable to infestation by the nematodes, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying, or incorporation of granules.
The compounds of the invention may be the sole active ingredient of the composition or they may be admixed with one or more additional active ingredients such as nematicides or agents which modify the behaviour of nematodes such as hatching factors, insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate.
Suitable additional active ingredients for inclusion in admixture with the compounds of the invention may be compounds which will broaden the spectrum of activity of the compounds of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of the invention or complement the activity for example by increasing the speed of effect or overcoming repellency. Additionally multi-component mixtures of this type may help to overcome or prevent the development of resistance to individual components.
The particular additional active ingredient included will depend upon the intended utility of the mixture and the type of complementary action required. Examples of suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3- (2-oxothiolan-3-ylidenemethyl) cyclopropane carboxylate;; b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenophos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chloropyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pyrimiphos-methyl, pyrimiphos-ethyl, fenitrothion or diazinon; c) Carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl; d) Benzoyl ureas such as triflumuron, or chlorofluazuron; e) Organic tin compounds such as cyhexatin, fenbutatin oxide, azocyclotin; f) Macrolides such as avermectins or milbemycins, for example such as abamectin, avermectin, and milbemycin; g) Hormones and pheromones; h) Organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin; i) Amidines, such as chlordimeform or amitraz; j) Fumigant agents.
In addition to the major chemical classes of insecticide listed above, other insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture. For instance selective insecticides for particular crops, for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed.
Alternatively insecticides specific for particular insect species (stages for example ovo-larvicides such as chlofentezine, flubenzimine, hexythiazox and tetradifon, moltilicides such as dicofol or propargite, acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylon, cyromazin, methoprene, chlorofluazuron and diflubenzuron may also be included in the compositions.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan and dodecyl imidazole.
Suitable herbicides, fungicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicides which can be included is propanil, an example of a plant growth regulator for use in cotton is 'Pix", and examples of fungicides for use in rice include blasticides such as blasticidin-S. The ratio of the compound of the invention to the other active ingredient in the composition will depend upon a number of factors including type of target, effect required from the mixture etc. However in general, the additional active ingredient of the composition will be applied at about the rate as it is usually employed, or at a slightly lower rate if synergism occurs.
The following Examples illustrate the invention. The compounds were identified and characterised by means of the melting points, nuclear magnetic resonance spectroscopy (1H NMR 8 (CDCl3)), infra red (IR) or mass spectroscopy (M+).
EXAMPLE 1 This example illustrates the preparation of Compound No. 1 of Table I.
l-Bromo-2-fluoroethane (1.135g) was added dropwise to a stirred mixture of 2-mercaptopyrimidine (0.987g) and potassium carbonate (1.246g) in acetone (20ml) at room temperature. The mixture was heated under reflux for 2 hours and then left to stand overnight at room temperature.
The reaction mixture was quenched with water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried with magnesium sulphate and evaporated under reduced presure to give 2-(2-fluoroethylthio)-pyrimidine as a yellow liquid Compound No. 1 NMR :8.55 (2H,d); 7.01 (1H,t); 4.75, 4.59 (2H,2xt); 3.52, 3.45 (2H,2xt) M+ :158, 112 EXAMPLE 2 This example illustrates the preparation of Compound No. 2 of Table I.
l-Bromo-2-fluoroethane (0.561g) was added dropwise to a stirred mixture of 2-mercapto-4-pyrimidine hydrochloride (0.653g) and potassium carbonate (1.089g) in acetone (15ml) at room temperature. The mixture was heated under reflux for 2 hours and then left to cool to room temperature.
The reaction mixture was quenched with water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried with magnesium sulphate and evaporated under reduced presure to give 2-(2-fluoroethylthio)-4-methylpyrimidine as a brown liquid Compound No. 2 NMR :8.37 (1H,d); 6.86 (lH,d); 4.76, 4.58 (2H,2xt); 3.51, 3.45 (2H,2xt); 2.46 (3H,s) :172, 151 EXAMPLE 3 This example illustrates the preparation of Compound No. 3 of Table I.
(a) Preparation of 4-mercaptopyrimidine To a stirred suspension of 4-hydroxypyrimidine (lOOg) in dry pyridine (500ml) at room temperature under nitrogen was added phosphorus pentasulphide (100g) in a single portion. An exotherm to 540C was noted.
The mixture was allowed to cool to room temperature and stirred at that temperature for 30 minutes prior to heating at 960C (steam bath) for 1 hour.
The mixture was cooled to room temperature and poured into water (1000ml) and concentrated to dryness. The residue was triturated with water (200ml) and the brown solid collected by filtration and washed with water (200ml).
Recrystallisation from water and drying under vacuum over P205 gave 4-mercaptopyrimidine (84.34g, 72Z) as orange needles. The product was used without further purification.
(b) Preparation of Compound No. 3 of Table 1.
l-Bromo-2-fluoroethane (0.548g) was added dropwise to a stirred mixture of 4-mercaptopyrimidine (0.442g) and potassium carbonate (0.567g) in acetone (10ml) at room temperature. The mixture was heated under reflux for 2 hours and then left to stand overnight at room temperature.
The reaction mixture was quenched with water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried with magnesium sulphate and evaporated under reduced presure to give 4-(2-fluoroethylthio)-pyrimidine as a brown liquid Compound No. 3 NMR :8.94 (lH,s); 8.35 (lH,d); 7.20 (lH,d); 4.75, 4.57 (2H,2xt); 3.68, 3.49 (2H,2xt) :158, 137 EXAMPLE 4 This Example illustrates the preparation of Compound No. 4 of Table I.
l-Bromo-2-fluoroethane (1.15g) was added dropwise to a stirred suspension of dithiouracil (0.569g) and potassium carbonate (1.14g) in acetone (15ml) at room temperature. The mixture was heated under reflux for 2.5 hours and then allowed to stand at room temperature overnight.
The reaction mixture was quenched with water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried using magnesium carbonate and evaporated under reduced pressure to give 2,4,-bis(2-fluoroethylthio)-pyrimidine as a brown liquid.
NMR :8.15 (lH,d); 6.89 (lH,d); 4.74 (2H,m); 4.57 (2H,m); 3.58-3.37 (4H,m) M :236, 28 IR : 1545s, 1410s (film).
EXAMPLE 5 In order to illustrate the nematicidal properties of the compounds of formula (I), compounds from Table I were tested on root knot nematodes and cyst nematodes.
Methodology Cucumber plants (9 days old, variety 'Telegraph') were soil drenched with a composition of a compound of formula (I) (obtained by diluting 1 part of a solution of the compound in a 1:1 mixture of acetone and ethanol with 99 parts of water containing 0.05Z of a wetting agent) at a rate of 40ppm in a drench volume of 10ml/45g of soil. The plants were infested with second stage juveniles of the root knot nematode Meloidogyne incognita after the solution of the compound had been absorbed by the soil.
Nematodes were applied to the roots in a solution of water. The roots of the plants were examined after 9 days to determine the percentage reduction in the number of root knots compated with a control treatment omitting the compound. There were 3 replicates per treatment.
TABLE II
COMPOUND NO. Z ROOT KNOT REDUCTION AT 40 PPM 1 51 2 62 3 68 4 99 The compounds of the invention not only display nematicidal activity, a further advantage is that the compounds are not phytotoxic to the target plant. Very little phytotoxicity was observed in the above tests. This is a particularly desirable feature when treating young plants and seeds.
The following examples demonstrate formulations suitable for applying the compounds of the present invention. The amount of ingredient is expressed in parts by weight or grams per litre as indicated. A * indicates a trademark.
EXAMPLE 5 This example demonstrates granules suitable for soil application. The granules can be made be standard techniques such as impregnation, coating, extrusion or agglomeration.
Zwlw Impregnated granule : Active ingredient 5 Wood Rosin 2.5 Gypsum granules 92.5 (20-40 mesh) Coated granule : Active ingredient 0.5 'Solvesso' 200 0.4 Calcium carbonate granules 99.1 (30-60 mesh) Slow release granule : Active ingredient 10 Polyvinylacetatelvinyl 5 chloride copolymer latex Attapulgus granules 85 EXAMPLE 6 This example demonstrates formulations for use as a spray. The compounds can be formulated as wettable powders, water dispersible granules, suspension concentrates, emulsifiable concentrates, emulsions or microcapsule suspensions for application diluted in water.
gil Emulsifiable concentrate: Active ingredient 250 Calcium dodecyl- 50 benzene sulphonate Nonyl phenol ethoxylate 50 Alkylbenzene solvent to 1 litre Xwlw Wettable powder : Liquid active ingredient 40 lignosulphonate dispersant 5 silica 25 sodium lauryl sulphate 3 china clay (kaolin) 27 Microcapsule suspension : Liquid active ingredient 250 toluene diisocyanate 10 polymethylene polyphenyl isocyanate 20 nonyl phenol ethoxylate 6 lignosulphonate dispersant 15 xanthan gum 1 bentonite 10 biocide 'Proxel' 0.1 sodium carbonate 5 water to 1 litre The microcapsule suspensions can be used as a spray, soil drench or as an intermediate to prepare slow release granules for application to the soil.
gil Suspension concentrate : Solid active ingredient 400 lignosulphonate dispersant 50 sodium lauryl sulphate 30 xanthan gum 1 * biocide 'Proxel' 0.1 bentonite 10 water to 1 litre EXAMPLE 7 This example demonstrates formulations suitable for use as seed treatments in conventional application machinery.
xwlw Dry seed treatment : Active ingredient 20 dodecyl benzene 3 Rubine Toner (dyestuff) 2.7 Talc 53.3 Silica to 100Z The suspension concentrate and microcapsule suspension of Example 6 can be used as flowable concentrates for seed treatment.
EXAMPLE 8 This example demonstrates the formulation of the compounds for electrostatic spraying.
gil Active ingredient 200 N-methylpyrollidone 50 Soyabean oil 120 * 'Solvesso' 200 to 1 litre CHEMICAL FORMULAE (corresponding to formulae numbers in description)

Claims (5)

  1. CLAIMS 1. A compound of formula (I)
    wherein R1, R2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, haloalkenyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, CONR6R7, hydroxy, acylamino, -Co2R7, -o(CH2)mCo2R7, -S(O)nCH2CH2F, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2; n is 0, 1 or 2; R6 and R7 are hydrogen or C1,4 alkyl;R5 is C14 alkyl; provided that at least one of R1 to R4 is -S(O)nCHgCH2F; further provided that when R4 is -SCH2CH2F, either R1, R2 and R3 are not all hydrogen, or R and R3 are not both methyl when R2 is hydrogen.
  2. 2. A nematicidal composition comprising an effective amount of a compound of formula (I)
    wherein R1, R2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, hydroxy, acylamino, -CO2R7, O(CH2)mCO2K7' phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2; R6 and R7 are hydrogen or C1 4 alkyl;R5 is C1-4 alkyl; provided that one or both of R1 and R4 is -S(O)nCH2CH2F wherein n is 0, 1 or 2; and an inert diluent or carrier material and optionally a surface active agent.
  3. 3. A method for killing or controlling nematode pests which comprises applying to the locus of the pests or to a plant susceptible to attack by the pest an effective amount of a compound of formula (I)
    wherein R1, R2, R3 and R4 are independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, halogen, haloalkyl, alkoxy, alkenoxy, alkoxyalkyl, haloalkoxy, haloalkenoxy, alkylthio, haloalkylthio, cyano, nitro, amino, NR5R6, hydroxy, acylamino, -C02R7, -O(CH2)mCO2R7, phenyl, phenoxy, benzyl or benzyloxy, the phenyl group or phenyl moiety of the benzyl group being optionally substituted in the ring; or R2 and R3 when taken together form a 5- or 6-membered ring; m is 1 or 2;R6 and R7 are hydrogen or4C1-4 alkyl; R is C1,4 alkyl; provided that one or both of R and R is -S(O)nCH2CH2F where n is 0, 1 or 2.
  4. 4. Process for the preparation of the compounds of formula (I) as defined in any of claims 1 to 3 which comprises reacting a corresponding substituted compound of formula (I) where one or both of R1 and R4 is SH with l-bromo-2-fluoroethane in the presence of a base.
  5. 5. Process for the preparation of compounds of formula (I) according to claim 4 in which R1 is -SCH2CH2F which comprises reacting the correspondingly substituted 4-mercaptopyrimidine with phosphorous pentasulphide in a tertiary amine solvent and under a nitrogen atmosphere.
GB9317761A 1993-08-26 1993-08-26 (2-Fluoroethyl) thio-substituted pyrimidines as nematicides Withdrawn GB2281295A (en)

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Publication number Priority date Publication date Assignee Title
WO2006063848A1 (en) 2004-12-17 2006-06-22 Devgen N.V. Nematicidal compositions
US7229993B2 (en) * 2002-03-13 2007-06-12 Euro-Celtique S.A. Aryl substituted pyrimidines and the use thereof
US7517900B2 (en) 2003-10-10 2009-04-14 Bristol-Myers Squibb Company Pyrazole derivatives as cannabinoid receptor modulators
US7863220B2 (en) 2003-12-19 2011-01-04 David Alan Clark Herbicidal pyrimidines
US8101625B2 (en) 2005-10-21 2012-01-24 Exelixis, Inc. Pyrimidinones as Casein Kinase II (CK2) modulators

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Title
Chem. Abstr., Vol. 55, no 21386c *
Chem. Abstr., Vol. 69, no 67316 & Khim. Geterotsikl. Soedin., 1967, Vol.(6), pages 1087-1088 *
Chem. Abstr., Vol. 70, no 4015 & Izv. Akad. Nauk SSSR, Ser. Khim., 1968, Vol. (8), pages 1841-1846 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7229993B2 (en) * 2002-03-13 2007-06-12 Euro-Celtique S.A. Aryl substituted pyrimidines and the use thereof
US7517900B2 (en) 2003-10-10 2009-04-14 Bristol-Myers Squibb Company Pyrazole derivatives as cannabinoid receptor modulators
US7863220B2 (en) 2003-12-19 2011-01-04 David Alan Clark Herbicidal pyrimidines
US8802597B2 (en) 2003-12-19 2014-08-12 E I Du Pont De Nemours And Company Herbicidal pyrimidines
WO2006063848A1 (en) 2004-12-17 2006-06-22 Devgen N.V. Nematicidal compositions
US8101625B2 (en) 2005-10-21 2012-01-24 Exelixis, Inc. Pyrimidinones as Casein Kinase II (CK2) modulators

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