GB2255557A - Fungicidal compounds, fungicidal compositions, their production and use - Google Patents

Fungicidal compounds, fungicidal compositions, their production and use Download PDF

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GB2255557A
GB2255557A GB9109415A GB9109415A GB2255557A GB 2255557 A GB2255557 A GB 2255557A GB 9109415 A GB9109415 A GB 9109415A GB 9109415 A GB9109415 A GB 9109415A GB 2255557 A GB2255557 A GB 2255557A
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group
alkyl
formula
hydrogen
phenyl
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GB9109415D0 (en
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John Walter Liebeschuetz
Ruth Bernice Katz
Hak-Fun Chow
Neil Vincent Kirby
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Dow Chemical Co Ltd
Dow Chemical Co
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Dow Chemical Co Ltd
Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
    • C07D223/12—Nitrogen atoms not forming part of a nitro radical

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The use as a fungicide of a compound of the formula: <IMAGE> wherein R<1> is H, CN, NO2, NH<2>, OH, or SiR<10>R<11>R<12>, or a group of the formula <IMAGE> R<2> is hydrogen or C1-C6 alkyl, R3, R4 and R5 are hydrogen or C1-C4 alkyl, R<6> is a cyclohexyl group or a monocyclic or bicyclic aromatic group substituted with from 1 to 5 groups of the formula R<7>, wherein R<7> is halogen, a C1-C10 alkyl group, a C1-C10 alkoxy group, a trialkylsilyl group, or a phenyl, phenoxy, phenyl C1-C2 alkylene, or phenyl alkenylene group, optionally substituted on the phenyl or phenoxy group with from 1 to 5 halogen atoms, C1-C6 alkyl or C1-C6 alkoxy groups, trihalomethyl groups, phenyl groups or phenoxy groups, p is 0, 1 or 2 Y is a group of the formula -(CR<8>R<8>)n-, wherein n is 3, 4 or 5 each R<8> is hydrogen or C1-C4 alkyl, R<9> is a cyclohexyl group or a monocyclic aromatic group optionally substituted with from 1 to 5 groups of the formula R<7>, or is a straight or branched C1-C20 alkyl or C2-C20 alkenyl group, optionally substituted with one or more of F, Br, Cl, I, cyclohexyl or a monocyclic aromatic ring, R<10>, R<11>, and R<12> are C1-C4 alkyl, or phenyl, and

Description

FUNGICIDAL COMPOUNDS, FUNGICIDAL COMPOSITIONS, THEIR PRODUCTION AND USE This invention relates in one aspect to the use as fungicides, particularly for use against fungal pathogens of cereal crops, of compounds containing a cyclic amidine grouping. In a second aspect, the invention relates to novel chemical compounds having fungicidal activity, which contain a cyclic amidine grouping.
Many substituted amidines are known to have activity in a variety of pharmaceutical applications, for example as anticoagulants, diuretics, hypoglycemics, hypotensives and cardiac stimulants, as disclosed, for example in BE 783271, GB 1412726, GB 1328934, and CA 850116.
Certain amidine-type compounds are also known to have fungicidal activity, for example as disclosed in Czechoslovakian Patent 197976, US 3132151, and US 3378438.
We have discovered that certain amidine-type compounds structurally dissimilar from amidines known previously to have fungicidal activity are active as fungicides.
The present invention provides the use as a fungicide of compounds of the formula:
wherein R1 is H, CN, N02, NH2, OH, or SiR10RR, or a group of the formula
R2 is hydrogen or C1-C6 alkyl, R3 and R4 independently and each R5 independently are hydrogen or C1-C4 alkyl, R6 is a cyclohexyl group or a monocyclic or bicyclic aromatic group (for example phenyl or naphthenyl) substituted with from 1 to 5 groups of the formula R7 wherein R7 is halogen, a Cl-Clo alkyl group, preferably C3-C4 alkyl, more preferably t-butyl, a C1-C10 alkoxy group, a trialkylsilyl group, or a phenyl, phenoxy, phenyl Cl-C2 alkylene,or phenyl alkenylene group, optionally substituted on the phenyl or phenoxy group with from 1 to 5 halogen atoms, C1-C6 alkyl or C1-C6 alkoxy groups, trihalomethyl groups, phenyl groups or phenoxy groups, p is 0, 1 or 2 Y is a group of the formula -(CR8R8)n~, wherein n is 3, 4 or 5 each R8 independently is hydrogen or C1-C4 alkyl, R9 is a cyclohexyl group or a monocyclic aromatic group (for example phenyl) optionally substituted with from 1 to 5 groups of the formula R7, wherein R7 is as defined above, or is a straight or branched C1-C20 alkyl or C2-C20 alkenyl group, optionally substituted with one or more of F, Br, Cl, I, cyclohexyl or a monocyclic aromatic ring (for example phenyl), and R1O, R1l, and R12 are each independently C1-C4 straight or branched alkyl, or phenyl, X is a suitable counter-ion, for example the anion of a mineral acid, an alkyl or aryl carboxylic acid, or alkyl or aryl or alkaryl sulphonic acid, provided that, when R1 is hydrogen or alkyl, R3 is C1- C4 alkyl.
The invention also provides fungicidal compositions which contain such compounds, particularly together with an agriculturally acceptable carrier or diluent.
Certain of the compounds of Formula I and II are novel, and the invention also provides such novel compounds. In particular, the invention provides compounds of Formula I and II above, wherein R1 is other than hydrogen or alkyl. This group of compounds is particularly preferred, in view of their fungicidal activity.
It will of course be appreciated that although the compounds of formula II are illustrated as containing a simple double bond, in practice considerable delocalisation of the double bond structure will take place over the nitrogen atoms of the compound. The compounds of the invention contain two basic nitrogen atoms, and thus can exist either in the form of the free base formula I or a salt formula II, for example a quaternary salt or an acid addition salt. Where R1 is hydrogen in Formula I, the compound can exist in tautomeric forms, both of which are within the scope of the present invention.
R1 is preferably
and R is preferably hydrogen or methyl, more preferably hydrogen. Preferably when R is other than hydrogen or alkyl, R2 is hydrogen.
Y is preferably a group of the formula -(CR8R8)d-, wherein R8 is as defined above (preferably hydrogen or methyl), more preferably a group of the formula -(CH2)4-, or -CHMe(CH2)3 Each of groups R4 and R5 are preferably hydrogen, group R3 is preferably methyl, and p is preferably 1.
The group R6 is preferably a substituted phenyl group, more preferably a 4-t-butylphenyl, 4-trimethylsilylphenyl, or 4-ethyldimethylsilylphenyl group.
R9 is preferably a C1-C20 alkyl group, more preferably a C1-C4 alkyl group.
The terms alkyl, alkoxy, alkylene, alkenylene and the like, as used herein, are intended to include within their scope both straight and branched groups, and the terms alkenyl, alkenylene and the like are intended to include groups containing one or more than one double bonds. The term halogen and halo as used herein include chlorine, bromine, fluorine and iodine. It will be appreciated that certain combinations of substituent groups for compounds which fall within the definition of formula I and II given above will be impossible to prepare for steric and other chemical reasons. Such compounds are not included within the scope of the invention.
The anion X in formula II may be any suitable counter-ion, for example chloride, bromide, acetate, stearate, benzoate, trifluoromethane sulphonate or dodecylbenzenesulphonate, the chloride being preferred.
Certain of the compounds of formula I wherein R1 is other than hydrogen may be prepared by reacting a compound of the formula I wherein R1 is hydrogen, with a suitable alkyl trifluoromethyl sulphonate, acid chloride, chloroformate, or sulphonyl chloride. The reaction may be carried out in a polar aprotic solvent, for example tetrahydrofuran, diethyl ether, dimethyl formamide, or dimethyl sulphoxide, in the presence of a base, for example triethylamine.
Certain other compounds of formula I may be prepared by reacting a compound of the formula I wherein R1 is hydrogen with an isocyanate, or isothiocyanate, a trialkyl/aryl substituted chlorosilane, an oxidising agent, or nitric acid.
The compounds (salts) of Formula II wherein R1 and R2 are both hydrogen may be prepared from the corresponding compound of Formula I wherein R1 is hydrogen by reaction with the appropriate acid HX. The compounds of Formula II wherein R1 and R2 are identical, and are C1-C4 alkyl may be prepared by treating the corresponding compound of Formula I wherein R1 is hydrogen, with a suitable quaternising agent, for example an alkyl chloride, bromide, sulphate or sulphonate.
Compounds of formula I wherein R1 is hydrogen may be prepared by reacting a compound of the formula III or IV,
wherein L is a suitable leaving group such as, for example alkoxy, and Y is as defined above, with a compound of formula NH2-CR3R4(CR5R5)pR6 V wherein R3 R4 R5 and R6 are each as defined above, preferably at a temperature of from 50 to 2000C.
The reaction may be carried out in a suitable organic solvent for example an alkanol such as n-pentanol, or in the absence of solvent.
Compounds of the formula V may generally be prepared by the reaction of a compound of the formula Na+ R3R4CNo2 VI with a compound of the formula
followed by reduction of the nitro group, preferably employing a metal hydride such as LiAlH4.
Compound VII may be prepared according to Katrizky, de Ville and Patel (J.C.S. Chem.Comm. 1979, 602) from a compound of formula R6-(CR5R5)p NH2 and 2,4,6,-triphenylpyrilium tetrafluoroborate.
Alternatively and preferably, compounds of formula V, wherein certain of the R5 groups are restricted to hydrogen, may be prepared by the reaction of a compound of the formula R3CH2No2 with a compound of the formula R6-(CR5R5)p 1CR50 preferably in the presence of a mild base at a temperature of from 25 to 1500C, followed by reduction of the nitro group and the double bond. The reduction may be carried out, for example using a metal hydride such as LiAlH4, at a temperature of from -80 to 100 C.
The compounds of formula I and II may be used as fungicides in particular for agricultural use, against a wide range of pathogens, for example Ascomycetes, Eumycetes and Fungi Imperfecti, in a protectant or eradicant fashion, and exhibit low phytotoxicity to crops, in particular cereal and broadleaf crops. In particular, the compounds in accordance with the invention may be applied to the roots, seeds, or foliage of barley and'other plants, for the control of various fungi, without damaging their commercial value. In particular the compounds of the present invention effectively control a variety of undesirable fungi which infest useful plant crops.Many of the compounds are particularly effective against members of the i) Deuteromycotina such as Septorianodorunz (glume blotch of cereals), tyricularia oryzae (rice-blast), Botrytiscinerea (grey mould of grapes) and Fusariumoxysporunz (various wilt diseases), ii) Ascomycotina such as Pyrenophora feres (net-blotch) and Erysiphegranzii:is (powdery mildew), and iii) Basidiomycotina such as Pucciniarecondita (leaf rust).
The compounds can be applied to the seeds, roots or foliage of cereals or other plants and will kill or control the growth of various fungi without damaging the commercial value of the said plants. Where the acid addition salt is employed, the improved water solubility (especially of the chloride) also allows the preparation of solutions (in water or organic solvents) in which, at use rate, the addition salt is completely soluble in the spray dilution.
At least utilising the preferred embodiments of the invention a single application of the compounds can provide a residual control of powdery mildew diseases over an extended period. Also, the compounds can be effective in eliminating established barley powdery mildew infestation.
Furthermore, many compounds have been found to be translocated in plants and, thus, can provide a systemic protection against powdery mildew.
The compounds of the invention may also find application as non-agricultural fungicides for example in medicine as antimycotics against organisms such as Candida albicans, Candida spp, Trichophton spp, Aspergillus spp, Microsporum spp and Sporothrixspp, and also as agents against parasites such as Leishmania.
As indicated above, the invention includes within its scope fungicidal compositions comprising a fungicidally effective amount of a compound of formula I or II together with an inert carrier or diluent. Such compositions may be in the form of a liquid, powder, dust or granular composition containing one or more of the active compounds in and one or more inert, non-phytotoxic materials, known in the art as agricultural adjuvants and/or carriers, in solid or liquid form. Thus, for example, the active compound(s) can be admixed with one or more additives including water or other liquid carriers such as organic solvents, and petroleum distillates, surface active dispersing agents, and finely divided inert solids.
In such compositions, the active ingredients are generally present in a concentration of from 2 per cent to about 95 per cent by weight preferably from 10 per cent to 95 per cent by weight and most advantageously 10 per cent to 75 per cent by weight. The compound can be employed in the form of a solution, a diluted flowable composition or a wettable powder composition containing 2 to 10,000 ppm of active ingredient. Preferably 10 to 600 ppm are employed.
When the carrier contains a surface active agent, from about 0.1 to about 20 per cent by weight of the active ingredient is advantageously employed. Depending upon the concentration in the composition, such augmented compositions are adapted to be employed for the control of the undesirable fungi or employed as concentrates and subsequently diluted with additional inert carrier, e.g.
water, to produce the ultimate treating compositions.
In general, good results can be obtained with liquid compositions containing from about 0.0001 to about 2.0 per cent by weight of the active compound in the final diluted form. With dusts, good results can usually be obtained with compositions containing from about 0.1 to about 2.0 per cent or more by weight of active compound. Where the compositions are to be applied to foliage of plants, it is preferred that the toxicant be present in an amount not to exceed about 0.8 per cent in liquid compositions and about 1.0 per cent in dusts.
In terms of hectarage application, good controls of powdery mildews can be obtained when the active ingredients are applied to growing plants at a dosage of from about 0.004 to about 4 kg/hectare. When employed as fungicides for the treatment of seeds or non-living substrates, from about 0.1 to about 100 gram of active ingredient per kilogram of substrate is an effective dose.
In the preparation of dust, or wettable powder compositions, the toxicant products can be compounded with any of the finely divided solids, such as prophyllite, talc, chalk, gypsum, fuller's earth, bentonite, attapulgite, starch, casein, gluten, or the like. In such operations, the finely divided carrier is ground or mixed with the toxicant or wet with a solution of the toxicant in a volatile organic solvent. Also, such compositions when employed as concentrates can be dispersed in water, with or without the aid of dispersing agents to form spray mixtures. Dust compositions are advantageously employed when treating seeds.
Granular formulations are usually prepared by impregnating a solution of the toxicant in a volatile organic solvent onto a bed of coarsely divided attapulgite, bentonite, diatomite, or the like.
Similarly, the toxicant products can be compounded with a suitable water-immiscible inert organic liquid and a surface active dispersing agent to produce an emulsifiable concentrate which can be further diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions which may optionally contain water miscible organic co-solvents to improve the physical properties of the formulation. In such compositions, the carrier comprises an aqueous emulsion, i.e., a mixture of inert water-immiscible solvent and optional water miscible organic co-solvent,emulsifying agent, and water.
Emulsifiers which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxide or mixtures of ethylene and propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amines.
Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil soluble salts or sulphated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
Representative organic liquids which can be employed in preparing the emulsifiable concentrates of the present invention are the aromatic liquids such as xylene; propyl benzene fractions; or mixed naphthalene fractions; mineral oils substituted aromatic organic liquids such as dioctyl phthalate; kerosene; butene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, and the methyl ether of triethylene glycol. Mixtures of two or more organic liquids are also often suitably employed in the preparation of the emulsifiable concentrate. The preferred organic liquids are xylene, and propyl benzene fractions, with xylene being most preferred.The surface active dispersing agents are usually employed in liquid compositions and in the amount of from 0.1 to 20 per cent by weight of the combined weight of the dispersing agent and active compound. The active compositions can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
In particular, the active compositions may contain adjuvant surfactants to enhance the deposition, wetting and penetration of the composition onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will vary from 0.01 per cent to 1.0 per cent v/v based on a spray-volume of water, preferably 0.05 to 0.5 per cent. Suitable adjuvant surfactants include ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines and blends of surfactants with mineral or vegetable oils.
In such embodiments, the compounds of the present invention or compositions containing the same, can be advantageously employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, miticides, arthropodicides, or bactericides that are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use or as an additive. The compounds in combination can generally be present in a ratio of from 1:100 to 100:1.
The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled and the stage of growth thereof as well as the part of the plant to be contacted with the toxic active ingredient. Thus, all of the active ingredients of the present invention and compositions containing the same may not be equally effective at similar concentrations or against the same fungal species.
The compounds in accordance with the invention may be applied in the form of any of the generally used formulation types, for example as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates.
The invention includes within its scope a method for the control or prevention of fungal attack, which method comprises applying to the locus of the fungus, or to a locus in which the infestation is to prevented,(for example applying to cereal grain plants), a fungicidal amount of one or more of the compounds. A number of preferred embodiments of the invention are illustrated in the following Examples.
Example 1 a) Preparation of 1-(4-t-butylphenyl) -2-nitroprop-l-ene 12.4g of 4-t butylbenzaldehyde, 30 ml of nitroethane and 2.9g of ammonium acetate were refluxed together under nitrogen for 4 hours. The nitroethane was distilled off and the residue taken up in ethylacetate. This was washed twice with water, dried, filtered and the solvent evaporated off. The residue was distilled at 900C (t'.5 torr) to afford a lemon yellow oil.
Elemental analysis indicated the following: C = 71.2%; H = 7.80%; N = 6.4%.
(calculated, C = 71.3t; H = 7.85%; N = 6.5%) vmaX(neat) 2965,1655,1608,1522,1324 cm 1 6 8.07(1H,s),7.43(4H,ABq J=8Hz),2.47(3H,s), 1.33(9H,s) b) Preparation of 1-(4-t-butylphensl)propan-2-amine 7.6g of the nitroolefin prepared in (a) above was dissolved in 150 ml dry diethylether and added dropwise to lOg of lithium aluminium hydride in 300 ml diethylether under nitrogen with stirring. On completion of addition the mixture was refluxed for 24 hours. 35 ml of triethanolamine was added over 2 hrs with cooling and then 9 ml water added dropwise. The mixture was stirred for 2 hrs and the resulting suspension of sandy consistency filtered. The solids collected were washed with diethylether and the washings combined with the organic solution. This was washed, dried with MgS04, filtered, the solvent evaporated under reduced pressure and the residue distilled at 650C, (0.44 torr) to afford 5.4 g of an oil.
NMR and IR spectra were consistent with the title compound vmax(neat)3360,3290,2965,1601(br),1515,1461,1366 cm 1 6 7.35(2H,d J=8Hz),7.2(2H,d J=8HZ), 3.2(1H,m),2.6(2H,m),1.5(2H,s,disappears on D20 shake), 1.28(9H,s), 1.15(3H,d J=6Hz) c) Preparation of 2-91-(4-t-butylphenyl)prop-2-ylimino) l-piperidine 2.4g of 2-ethoxy-3,4,5,6-tetrahydropyridine and l.lg of 1-(4-t butylphenyl)propan-2-amine (prepared as in b) were refluxed together for sixteen hours. The mixture was then heated under reduced pressure to remove volatile components leaving a gummy residue. NMR and IR spectra were consistent with the expected structure.
v'nax(KBr)3419,3212,3O6O,2965,1658,1l26 cm 1 6 7.30(s,CHCl3,proton exchange), 7.23(2H,ABq,J=8Hz), 4.6(1H,quin,J=7Hz),3.43(2H,m), 2.88(2H,d,J=7Hz),1.98(2H,m),1.6(4H,m),1.30(9H,s)),1.13(3H,d ,J=7Hz) Example 2 Preparation of hydrochloride salt The gummy residue of Example 1 was dissolved in dry diethylether. HCL gas was bubbled through the solution until an oil began to separate. The mixture was seeded and, after leaving for three hours, a colourless solid could be collected. This was recrystallised from ethylmethyl ketone to afford a crystalline solid in 60% yield, m.pt. 190.30C.
Elemental analysis indicated the following C = 69.78; H = 9.30t; N = 9.15%.
(calculated, C = 70.0%; H = 9.45%; N = 9.1t) vmax(KBr) 3400,3212,3052,2965,1658 cm 1 Examples 3 to 22 The following compounds were prepared in a similar fashion 3 2-(1-(4-t-butylphenyl)prop-2-ylimino)pyrrolidine 4 2-(1-(4-t-butylphenyl)prop-2-ylimino)pyrrolidine hydrochloride 5 2-( 1-( 4-t-butylphenyl )prop-2-ylimino )perhydroazepine 6 2-(1-(4-t-butylphenyl)prop-2-ylimino)-6-methyl piperidine 7 2-(1-(4-t-butylphenyl)prop-2-ylimino)-6-methyl piperidine hydrochloride 8 2-(1-(4-t-butylphenyl)eth-1-ylimino)piperidine 9 2-(1-(4-t-butylphenyl)eth-1-ylimino)piperidine hydrochloride 10 2-(1-(4-ethylphenyl)prop-2-ylimino)piperidine 11 2-(1-(4-ethylphenyl)prop-2-ylimino)piperidine hydrochloride 12 2- (1- ( 4-i-propylphenyl )prop-2-ylimino )piperidine hydrochloride 13 2-( 1-( 4-trimethylsilylphenyl )prop-2-ylimino )piperidine 14 2-( 1-( 4-trimethylsilylphenyl )prop-2-ylimino )piperidine hydrochloride 15 2-(1-(4-ethyldimethylsilylphenyl)prop-2-ylimino) piperidine 16 2-(1-(4-ethyldimethylsilylphenyl)prop-2-ylimino) piperidine hydrochloride 17 2-(l-(4-phenylphenyl)prop-2-ylimino)piperidine 18 2-(1-(3-phenoxyphenyl)prop-2-ylimino)piperidine 19 2-(1-(4-hexylphenyl)prop-2-ylimino)piperidine 20 2-( l-(4-hexylphenyl )prop-2-ylimino)perhydroazepine 21 2-(1-(4-butoxyphenyl)prop-2-ylimino)piperidine hydrochloride 22 (1-napth-2-ylprop-2-ylimino )piperidine hydrochloride Example 23 Preparation of l-methyl-2-(l-(4-t-butylphenyl)prop-2ylimino)piperidine 2-( l-( 4-t-butylphenyl )prop-2-ylimino piperidine (2g) was dissolved in benzene (10ml). Triethylamine (1.05ml) was added and the mixture cooled to OOC, with stirring, under nitrogen. Methyl trifluoromethanesulphonate (1.38g) in benzene (5ml) was added dropwise. The mixture was then refluxed for 30 minutes, allowed to cool, washed with 3N sodium hydroxide, three times with water and dried over sodium sulphate. The solution was filtered and the solvent removed under reduced pressure to afford 2g of an oil.
Elemental analysis indicated the following C = 79.4%; H = 10.70%; N = 10.2% (calculated, C = 79.7%; H = 10.55t; N = 9.8%).
Vmax 2964(s),2865,1619(s),1513,1446,1321 cm 1 NMR(CDC13) 6 7.30 (2H,d,J=8Hz), 7.14 (2H,d,J=8Hz), 3.63 (lH,sext,J=7Hz), 3.10 (2H,t,J=5Hz), 2.89 (3H,s), 2.73 (2H,d,J=7Hz), 2.0 (2H,m), 1.6 (4H,m), 1.33 (9H,s), 1.17 (3H,d,J=7Hz) Example 24 1-methyl-2-(N-methyl,1-(4-t-butylphenyl)prop-2ylimino)piperidinium trifluoromethanesulphonate was prepared in a similar fashion Example 25 Preparation of 1-acetyl-2-( (l-(4-t-butylphenyl )prop-2-yl- imino)piperidine 2-(1-(4-t-butylphenyl)prop-2-ylimino)piperidine preared as in Example 1 (0.5g) was dissolved in dry THF (15ml), diisopropylethylamine (0.53g) was added and the mixture cooled to OOC. Acetyl chloride (0.16g) in THF (40ml) was added dropwise.The mixture was allowed to warm to room temperature over 2 hrs. The solvent was removed under reduced pressure and the residue taken up in diethylether and washed with sodium bicarbonate solution and twice with water. The organic layer was dried (Na2SO4), filtered and the solvent evaporated off under reduced pressure to afford a yellow gum (0.55g, 95%).
NMR, IR and mass spectroscopic evidence was in accordance with the proposed structure.
Elemental analysis indicated the following C = 76.4%; H = 9.55%; N = 9.1t (calculated, C = 76.4%; H = 9.60%; N = 8.9%).
Vmax3255,2965,2870,1657(s), 1555,1368,1270 cm-1 NMR(CDC13) 6 7.285 (2H,d,J=8Hz), 7.085 (2H,d,J=8Hz), 3.945 (lH,m), 3.83 (lH,m), 3.26 (lH,m), 2.85 (dd,J=13, 5Hz), 2.70 (1H,dd,J=13,9Hz), 2.07(1H,m), 2.04(3H,s), 1.50 (2H,m), 1.3 (5H,m), 1.29 (9H,s), 1.23 (3H,d,J=6Hz).
Examples 26 to 30 The following compounds were prepared in a similar fashion 26 1-propanoyl-2-(1-(4-t-butylphenyl)prop-2-ylimino)- piperidine 27 1-butanoyl-2-(1-(4-t-butylphenyl)prop-2-ylimino) piperidine 28 1-i-butanoyl-2-(1-(4-t-butylphenyl)prop-2-ylimino)- piperidine 29 1-hexanoyl-2-(1-(4-t-butylphenyl)prop-2-ylimino) piperidine 30 1-t-butanoyl-2-(1-(4-t-butylphenyl)prop-2-ylimino)- piperidine Example 31 Preparation of 1-benzoyl-2-(1-(4-t-butylphenyl)prop-2ylimino)piperidine 2-(1-(4-t-butylphenyl)prop-2-ylimino)piperidine (1.64g, 6mmols) and triethylamine (1.67ml, 2eq.) were dissolved in dry THF (30mls) and the mixture cooled to OOC.
Benzoylchloride (0.84ml, 1.2eq) in THF (20ml) were added dropwise with stirring, under nitrogen. The mixture was allowed to warm to room temperature during which time a white precipitate was formed.
Ethanol (2ml) was added and the mixture stirred for 10 minutes. The solvent was removed under reduced pressure, the residue taken up in diethyl ether and washed twice with water, once with NaHCO3 solution and once again with water.
The solution was dried (Na2S04), filtered and the solvent removed under vacuum to leave a solid (2.4g) that could be recrystallised from benzene/hexane.
NMR and IR spectroscopic analysis were consistent with the desired compound, present in both cis and trans amid conformations.
Elemental analysis indicated the following C = 79.4%; H = 8.55%; N = 7.4% (calculated, C = 79.7%; H = 8.60%; N = 7.3%).
vmax2967,2932,2861,1657(s),1447,1360,1348 cm 1 NMR (CDC13) 6 7.35 (7H,m), 7.0(2H,m), 4.08(1H,m), 3.42(1H,m), 2.55 (1H,m), 2.42 (1H,dd,J=13,5Hz), 2.30 (lH,dd,J=13,9Hz), 2.20 (1H,m), 2.0 (1H,m), 1.30 (3H,m) 1.25 (9H,s), 1.25 (2H,m), 0.85 (1H,m), 0.44 (2.0H,d=6Hz), 0.13 (lH,m).
Example 32 Preparation of l-(methoxycarbonyl)-2-(1-(4-t-butylphenyl)prop-2-ylimino)piperidine.
2-((1-(4-t-butylphenyl)prop-2-ylimino)piperidine (0.7g) was dissolved in diethyl ether (lOml).
Diisopropylethylamine (0.66g) was added and the mixture cooled to OOC, with stirring, under nitrogen. Methyl chloroformate (0.4g, 1.7eq) in diethyl ether (10ml) was added dropwise. The mixture was allowed to warm to room temperature. It was then washed three times with water, dried (over Na2S04), filtered and the solvent removed under reduced pressure to afford a gummy material (0.7g, 86w).
NMR, IR and Mass spectroscopic evidence was in accordance with the proposed structure.
Elemental analysis indicated the following C = 76.4%; H = 9.55t; N = 9.1% (calculated, C = 76.4%; H = 9.60%; N = 8.9%).
Vmax3255,2695,2870,1657(s), 1555,1368,1270 cm-1 NMR(CDC13)6 7.285(2H,d,J=8Hz), 7.085(2H,d,J=8Hz), 3.945(1H,m), 3.83(1H,m), 3.26(1H,m), 2.85(dd,J=13,5Hz), 2.70(1H,dd,J=13,9Hz), 2.07(1H,m), 2.04(3H,s), 1.50(2H,m), 1.3(5H,m), 1.29(9H,-s), 1.23(3H,d,J=6Hz) Examples 33 to 38 The following compounds were prepared in a similar fashion 33 1-(ethoxycarbonyl)-2-(1-(4-t-butylphenyl)prop-2 ylimino)piperidine 34 1-(propoxycarbonyl)-2-(1-(4-t-butylphenyl)prop-2- ylimino)piperidine 35 1-(butoxycarbonyl)-2-(1-t-butylphenyl)prop-2 ylimino)piperidine 36 1-(but-2-oxycarbonyl)-2-(1-(4-t-butylphenyl)prop-2 ylimino)piperidine 37 1-(hexylcarbonyl)-2-(1-(4-t-butylphenyl)prop-2 ylimino)piperidine 38 1-(2,2,2-trichloroethoxycarbonyl)-2-(1-(4-t-butyl phenyl)prop-2-ylimino)piperidine Example 39 Preparation of l-(t-butoxycarbonyl)-2-(1-(4-t-butylphenyl)prop-2-ylimino)piperidine 2-(1-(4-t-butylphenyl)prop-2-ylimino)piperidine hydrochloride (2g) and triethylamine (1.89ml, 2.leq.) were dissolved in dichloromethane.A solution of di t-butylcarbonate in dichloromethane was added with stirring. After 16hrs the mixture was washed twice with water, dried (Na2S04) filtered and the solvent removed under reduced pressure. NMR and IR spectroscopic analysis of the residue was consistent with the assigned structure, existing in both cis and trans carbamate conformations.
Vmax2969(s), 2869,1713(s), 1670(s),1517,1368,1280,1165 cm-1 1H NMR (CDC13) 6 7.30 (2H,d,J=8Hz), 7.08(2H,d,J=8Hz), 3.7C(2H,m), 2.70(2H,m), 2.50(2H,m), 1.82(1H,m) 1.53(4H,s), 1.40(5H,s), 1.25(9H,s), l.3(9H,m) 13C NMR (CDC13) 6 153.3, 152.3, 149.8, 137.0, 129.5, 125, 85.2, 56.4, 45.7, 44.1, 35.9, 34,3, 31.8, 28.3, 25.9, 24.6.
In Vivo Bioloqical Test Procedures The compounds of Examples 1 to 39 were tested in accordance with the following test method.
Compounds are dissolved in acetone or water (as required) and made up with distilled water to give a final concentration of compound of 400 ppm (and 10% acetone where acetone is used).
For each compound 3 replicate plants per pathogen (at the 1 leaf stage for cereals and at least the 2 leaf stage for vines) are sprayed to run off. The plants are allowed to dry at room temperature for 24 hours prior to inoculation.
Untreated control plants and plants sprayed with 10% acetone water or water (as required) are included for each pathogen.
Method for ErYsiphe praminis Hordei Barley cv. Golden Promise is used as the host plant.
Seeds are sown 8 per 3" pot (plants approximately 2 weeks old). Spores are blown onto the test plants from the stock plants, which are then incubated at 200C, relative humidity 70% for 7 days. After a week symptoms are recorded. % infection is scored from 3 replicate plants and exprszd as a % of acetone/water control plants. % control is then recorded.
Method for Puccinia recondita Wheat cv. Tonic. Seeds are sown 1 cm deep in 4 rows per plastic tray 60 cm x 30 cm. Seedlings are inoculated at 1-2 leaf stage. 0.05 g of uredospores are put into 100 ml distilled water with a melting agent. This solution is sprayed onto seedlings leaving a fine coverage on the leaves. The plants are then incubated with 100% relative humidity at 15-200C for 4 days.
% infection is scored from 3 replicate plants and expressed as a % of acetone/water control plants. % control is then recorded.
The results are shown in Table 1.
Table 1
Example * control No Erysip}ze graminis Puccinia recondita 1 100 100 2 100 100 3 95 94 4 100 94 5 80 40 6 100 100 7 100 50 8 98 100 9 100 100 10 40 90 11 98 89 12 100 84 13 90 100 14 100 100 15 98 98 16 98 98 17 96 72 18 72 50 19 32 50 20 80 62 21 96 89 22 46 94 23 100 75 24 98 80 25 100 93 26 85 93 27 85 93 28 85 85 29 93 93 30 98 70 31 93 98 32 100 100 33 70 85 34 40 70 35 98 98 36 98 93 37 98 80 38 98 80 39 93 93

Claims (18)

CLAIMS 1. The use as a fungicide of a compound of the formula: wherein R1 is H, CN, N02, NH2, OH, or SiRl0RllRl2, or a group of the formula R2 is hydrogen or C1-C6 alkyl, R3 and R4 independently and each R5 independently are hydrogen or C1-C4 alkyl, R6 is a cyclohexyl group or a monocyclic or bicyclic aromatic group substituted with from 1 to 5 groups of the formula R7, wherein R7 is halogen, a C1-C10 alkyl group, a C1-C10 alkoxy group, a trialkylsilyl group, or a phenyl, phenoxy, phenyl C1-C2 alkylene,or phenyl alkenylene group, optionally substituted on the phenyl or phenoxy group with from 1 to 5 halogen atoms, C1-C6 alkyl or C1-C6 alkoxy groups, trihalomethyl groups, phenyl groups or phenoxy groups, p is 0,
1 or 2 Y is a group of the formula -(CR8R81 - wherein n is 3, 4 or 5 each R8 independently is hydrogen or C1-C4 alkyl, R9 is a cyclohexyl group or a monocyclic aromatic group optionally substituted with from 1 to 5 groups of the formula R7, wherein R7 is as defined above, or is a straight or branched C1-C20 alkyl or C2-C20 alkenyl group, optionally substituted with one or more of F, Br, Cl, I, cyclohexyl or a monocyclic aromatic ring, R10, R1l, and R12 are each independently C1-C4 straight or branched alkyl, or phenyl, and X is a suitable counter-ion, provided that, when R1 is hydrogen or alkyl, R3 is C1 C4 alkyl.
2. The use as claimed in claim 1, wherein R1 is
3. The use as claimed in claim 1 or claim 2, wherein R2 is hydrogen or methyl.
4. The use as claimed in any one of claims 1 to 3, wherein the compound is a compound of formula II, R1 is other than hydrogen or alkyl, and R2 is hydrogen.
5. The use as claimed in any one of the preceding claims, wherein Y is a group of the formula -(CR8R8)4-, wherein R8 is as defined above.
6. The use as claimed in any one of the preceding claims, wherein Y is a group of the formula -(CH2)4-, or -CHMe(CH2 )3-.
7. The use as claimed in any one of the preceding claims, wherein p is 1.
8. The use as claimed in any one of the preceding claims, wherein each of groups R4 and R5 is hydrogen.
9. The use as claimed in any one of the preceding claims, wherein R3 is methyl.
10. The use as claimed in any one of the preceding claims, wherein R6 is a substituted phenyl group.
11. The use as claimed in any one of the preceding claims, wherein R6 is a 4-t-butylphenyl group, a 4-trimethylsilylphenyl, or a 4-ethyldimethylsilylphenyl group.
12. The use as claimed in any one of the preceding claims, wherein R1 is
and R9 is a C1-C20 alkyl group.
13. The use as claimed in Claim 12, wherein R9 is a C1-C4 alkyl group.
14. The use as claimed in any one of the preceding claims, wherein x in formula II is chloride, bromide, acetate, stearate, benzoate or dodecylbenzenesulphonate or trifluoromethane sulphonate.
15. An agricultural fungicidal composition comprising a compound as defined in any one of Claims 1 to 14, together with an agriculturally acceptable carrier or diluent.
16. A compound of the formula I or II as defined in any one of Claims 1 to 14, wherein R1 is as defined in Claim 1, but is not hydrogen, benzyl, or alkyl.
17. A method of preparing a compound as defined in Claim 16, which method comprises reacting a compound of the formula I as defined in claim 1, wherein R1 is hydrogen, with a suitable acid chloride, chloroformate, sulphonyl chloride, isocyanate, isothiocyanate, a trialkyl/aryl substituted chlorosilane, an oxidising agent, or nitric acid.
18. A method for the control or prevention of fungal infestation, which method comprises applying to the locus of the fungus, or in which the infestation is to be prevented, a compound as defined in any one of Claims 1 to 14 or a composition as claimed in Claim 15.
GB9109415A 1991-05-01 1991-05-01 Fungicidal compounds, fungicidal compositions, their production and use Withdrawn GB2255557A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6482840B2 (en) * 2000-05-22 2002-11-19 Merck & Co., Inc. Substituted cyclic amidine derivatives as inhibitors of cell adhesion

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB913937A (en) * 1958-03-03 1962-12-28 Rohm & Haas Substituted iminopyrrolidines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB913937A (en) * 1958-03-03 1962-12-28 Rohm & Haas Substituted iminopyrrolidines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6482840B2 (en) * 2000-05-22 2002-11-19 Merck & Co., Inc. Substituted cyclic amidine derivatives as inhibitors of cell adhesion

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