Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids

Definitions

• This invention relates to organic compounds, processes for preparing them and pesticidal compositions containing them. More particularly this invention relates to new substituted quinones and pesticidal compositions containing them.
• R represents an atom of hydrogen or a hydrocarbyl group
• R represents a hydrocarbyl group
• Q represents a naphthaquinonyl or anthraquinonyl radical.
• the invention provides a compound having the formula:
• R represents an atom of hydrogen or an alkyl group; and R represents an alkyl group; and Q represents either (i) a 1,4-naphthaquinon-2-yl radical optionally substituted with one or more alkyl groups of halogen atoms, or
• R and R represent alkyl groups
• Q represents a 1,4-naphthaquinon-2-yl radical bearing substituent alkyl groups
• the said alkyl groups are preferably lower alkyl groups comprising from 1 to 6 carbon atoms, for example, methyl, ethyl and n-butyl groups.
• the invention provides a compound having the formula:
• R represents an atom of hydrogen or an alkyl group comprising from 1 to 6 carbon atoms
• R represents an alkyl group comprising from 1 to 6 carbon atoms
• Q represents either (i) a 1,4naphthaquinon-2-yl radical optionally substituted with one or more alkyl groups comprising from 1 to 6 carbon atoms, or halogen atoms, or
• the invention provides a quinone derivative having either (i) the formula:
• R represents an atom of hydrogen or an alkyl group comprising from 1 to 6 carbon atoms
• R. represents an alkyl comprising from 1 to 6 carbon atoms
• X represents an alkyl group comprising from 1 to 6 carbon atoms, or a halogen atom: or
• R and R represent alkyl groups comprising from 1 to 6 carbon atoms.
• Specific compounds according to the present invention are those whose structure formulae are displayed in Table 1 hereinafter, together with the melting point (expressed in degrees centigrade) for each compound.
• the compounds of the invention may be prepared by a number of difierent methods.
• compounds of the invention having the structure:
• Hal-N R R wherein Hal represents an atom of chlorine, bromine or iodine, and R and R have any of the meanings recited above.
• the compounds of this invention may also be prepared by reacting a quinonyl chloroformate having the formula:
• the above reactions may be carried out in the presence of a solvent and optionally in the presence of a base.
• the quinonyl chloroformate used in the above reactions may be prepared by reacting the corresponding quinone, bearing an hydroxyl group, with phosgene, in a suitable solvent and optionally in the presence of a base.
• Suitable solvents for all the above reactions are nonhydroxylic solvents, such as ethers, e.g. diethyl ether, dioxan; ketones, e.g. acetone, cyclohexanone; esters, e.g. ethyl acetate; and hydrocarbons, e.g. benzene and cyclohex ane.
• ethers e.g. diethyl ether, dioxan
• ketones e.g. acetone, cyclohexanone
• esters e.g. ethyl acetate
• hydrocarbons e.g. benzene and cyclohex ane.
• aprotic nitrogen-containing solvents e.g. pyridine, dimethylformamide.
• methylmorpholine e.g. carbonic acid
• metals particularly the alkali and alkaline earth metals.
• Especially useful bases for the reactions are sodium and potassium carbonates.
• the reactions are conveniently carried out at temperatures in the range in which the solvent is in the liquid state, i.e. between its melting point and its boiling point under the ambient pressure.
• the compounds of this invention are usefully prepared at temperatures in the range C. to 150 C., and preferably in the range C. to 100 C.
• the invention provides a process for preparing a compound having the formula:
• Q represents a quinonyl radical
• R is a hydrocarbon group in which a quinone bearing a hydroxyl group at the appropriate position is reacted with an isocyanate of the formula:
• the invention provides a process for preparing a compound having the formula:
• Hal represents an atom of chlorine, bromine or iodine.
• the invention provides a process as described hereinabove carried out in the presence of a solvent or diluent, and a base.
• the invention compounds and compositions comprising them are very toxic to arachnid and insect pests, including for example, the following.
• Tetranychus telarius red spider mites
• Aedes aegypri yellow fever mosquitoes
• the invention compound No. 1 of Table 1 are very useful in the control of red spider mites, and gives outstanding control of strains which have become resistant to the toxicants normally used against them.
• This compound is also very advantageous in use because of its remarkably low toxicity to mammals, thus rendering it safer in use than many of the red spider controlling agents presently available.
• Table 2 below where the acute oral LD toxicity value for rats of compound No. l of Table is compared with those of several acaricides presently used in the control of red spider mites.
• the compounds are named with their British Standard common names, and the toxicity data was obtained from The Pesticide Manual (1st edition, 1968) edited by H. Martin, and published by the British Crop Protection Council.
• Compounds of the present invention and compositions comprising them are also toxic to nematode pests, including for example, Meloidogyne incognila (root knot nematodes) and possess activity against a wide variety of fungal diseases including, for example, the following specific diseases:
• the invention further consists in pesticidal compositions comprising as an active ingredient a compound having the formula:
• R represents an atom of hydrogen or an alkyl grolup; R represents an alkyl group; and Q represents cit er (1) a l,4- naphthaquinony-2-yl radical optionally substituted with one or more alkyl groups or halogen atoms, or
• the invention consists in pesticidal compositions comprising as an active ingredient a compound having the formula:
• R represents an atom of hydrogen or an alkyl group comprising from 1 to 6 carbon atoms
• R represents an alkyl group comprising from 1 to 6 carbon atoms
• Q represents either (i) a 1,4-naphthaquinon-2-yl radical optionally substituted with one or more alkyl groups, comprising from 1 to 6 carbon atoms, or halogen atoms, or
• the invention consists in pesticidal compositions comprising as an active ingredient a quinone derivative having either (i) the formula:
• R represents an atom of hydrogen or an alkyl group comprising from 1 to 6 carbon atoms
• R represents an alkyl comprising from 1 to 6 carbon atoms
• X represents an alkyl group comprising from 1 to 6 carbon atoms, or a halogen atom
• R and R represent alkyl groups comprising from 1 to 6 carbon atoms.
• a particularly useful pesticidal composition is one which comprises as an active ingredient compound No. 1 of Table 1 hereinbefore.
• this invention provides a pesticidal composition
• a pesticidal composition comprising as an active ingredient the compound having the formula:
• the invention compounds, or compositions containing them may be applied in a variety of ways.
• their application can suitably be directed onto the foliage of the plane or to infected and/or infested areas thereof, alternatively the soil surrounding the plant can be treated with the invention compounds or compositions containing them.
• the seeds themselves can be similarly treated.
• the invention provides a method of combating pests on plants which comprises applying to the plants or to seeds thereof a compound or composition as hereinbefore defined.
• the invention further includes a method of treating agricultural soil which comprises applying to the soil a compound or a composition as hereinbefore defined.
• the invention includes a method of combating pests which comprises applying to the pests or to a pest habitat a compound or composition as hereinbefore defined.
• compositions of the invention may be used for agricultural or horticultural purposes and the compound or type of composition used in any instance will depend upon the particular purpose for which it is to be used.
• compositions comprising the invention compounds may be in the form of dusting powders or granules wherein the active ingredient is mixed with a solid diluent or carrier.
• Suitable solid diluents or carriers may be, for example, kaolinite (china clay), montmorillonite, attapulgite, talc, pumice, silica, calcium carbonate, gypsum, powdered magnesia, fullers earth, Hewitts earth and diatomaceous earth.
• Compositions for dressing seed may comprise an agent assisting the adhesion of the composition to the seed, for example, a mineral oil.
• composition may also be in the form of dispersible powders or grains comprising, in addition to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in liquids.
• powders or grains may include fillers, suspending agents and the like.
• compositions may also be in the form of liquid preparations to be used as clips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more wetting agents, dispersing agents, emulsifying agents or suspending agents.
• 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, cetyltrimethylammonium 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, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyland triisopropylnaphthalene sulphonic acids.
• 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 octylphenol, nonylphenol and octylcresol.
• 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, the lecithins, and block copolymers of ethylene oxide and propylene oxide.
• Suitable suspending agents are, for example, bentonite, pyrogenic silica, and hydrophilic colloids, for example polyvinylpyrrolidone and sodium carboxymethyl-cellulose, and the vegetable gums, for example gum acacia and gum tragacanth.
• aqueous solutions dispersions or emulsions may be prepared by dissolving the active ingredient or ingredients in an organic solvent which may contain one or more wetting, dispersing or emulsifying agents and then adding the mixture so obtained to water which may likewise con tain one or more wetting, dispersing or emulsifying agents.
• organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.
• compositions comprising capsules or microcapsules containing either the active ingredients itself, or a composition containing the active ingredent, and prepared by any of the known encapsulation or microencapsulation techniques.
• compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlordifluoromethane.
• a propellant such as fluorotrichloromethane or dichlordifluoromethane.
• the different compositions can be better adapted for the various uses for which they are intended.
• the compounds of this invention may also be conveniently formulated by admixing them with fertilizers.
• a preferred composition of this type comprises granules of fertilizer material incorporating, for example coated with, a compound of the invention.
• the fertilizer material may, for example, comprise nitrogen or phosphate-containing substances.
• a pesticidal composition comprising a compound of the invention as hereinbefore defined, in admixture with a fertilizer material.
• compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use.
• concentrates are often required to withstand storage for prolonged periods and after such storage, to 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 from 10-85 by weight of the active ingredient or ingredients and generally from 2560% by weight of the active ingredient or ingredients.
• diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient or ingredients depending upon the purpose for which they are to be used, but an aqueous preparation containing between 0.001% and 1.0% by weight of active ingredient or ingredients may be used.
• pesticidal compositions of this invention may comprise, in addition to a compound of the invention, one or more other compounds having biological activity.
• the invention provides a composition comprising in addition to a compound of the invention, the compound 0,0-dimethyl-O- 4(2-diethylamino 6 methylpyrimidinyl) thiophosphate, also known by the British Standards common name pirimiphos-methyl.
• the precipitated solid was collected by filtration, washed with cold water, and finally air dried to yield 3-methyl-l,4-naphthaquinon-3-yl n-butylcarbamate, as a yellow microcrystalline solid, having a melting point of 120-2" C.
• EXAMPLE 5 This example illustrates an atomisable fluid comprising a mixture consisting of 25% by weight of compound No. 1 of Table 1 and by weight of xylene.
• EXAMPLE 6 This example illustrates a dusting powder which may be applied directly to plants or other surfaces and comprises 1% by weight of compound No. 1 of Table 1 and 99% by weight of talc.
• EXAMPLE 7 25 parts by weight of the product described in Example 1, 65 parts by weight of xylene, and 10 parts of an alkyl aryl polyether alcohol (Triton X-lOO; Triton is a trademark) were mixed in a suitable mixer. There was thus obtained an emulsion concentrate which can be mixed with water to produce an emulsion suitable for use in agricultural applications.
• Triton X-lOO alkyl aryl polyether alcohol
• EXAMPLE 8 5 parts by weight of the product described in Example 1 were thoroughly mixed in a suitable mixer with 95 parts by weight of talc. There was thus obtained a dusting powder.
• EXAMPLE 9 10 parts by weight of the product described in Example 1, 10 parts of an ethylene oxide-octylphenol condensate (Lissapol NX; Lissapol is a trademark) and parts by weight of diacetone alcohol were thoroughly mixed. There was thus obtained a concentrate which, on mixing with water, gave an aqueous dispersion suitable for application as a spray in the control of pests.
• Lisapol NX ethylene oxide-octylphenol condensate
• diacetone alcohol diacetone alcohol
• EXAMPLE 10 This example illustrates a concentrated liquid formulation in the form of an emulsion. The ingredients listed below were mixed together in the stated proportions and the whole stirred until the constitutents were dispersed.
• EXAMPLE 13 A composition suitable for use as a seed dressing was prepared by mixing all three of the ingredients set out below in the proportions stated.
• Percent wt. Compound No. 1 (Table 1) 80 Mineral oil 2 China clay 18 EXAMPLE 14 A granular composition was prepared by dissolving the active ingredient in a solvent, spraying the solution obtained onto the granules of pumice and allowing the solvent to evaporate.
• Lubrol L is a condensate of 1 mole of nonyl phenol with 13 molar proportions of ethylene oxide.
• Aromasol H is a solvent mixture of alkylbenzenes.
• Dispersol T is a mixture of sodium sulphate and a condensate of formaldehyde with the sodium salt of naphthalene sulphonic acid.
• Lubrol APN 5 is a condensate of 1 mole of nonyl phenol with 5 /2 moles of naphthalene oxide.
• Lissapol NX is a condensate of 1 mole of nonyl phenol wth 8 moles of ethylene oxide.
• Triton X-100 is an alkyl aryl polyether alcohol.
• EXAMPLE 16 The toxicity of a number of the compounds of this invention towards a variety of insect and other invertebrate pests was investigated and the tests conducted and results obtained are set out below.
• the compounds of the invention were in each case used in the form of a liquid preparation containing 0.1 (1000 parts per million (p.p.m.)) by weight of the compound.
• the preparations were made by dissolving each of the compounds in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol.
• the solutions were then diluted with water containing 0.01% by weight of a wetting agents sold under the trade name of Lissapol NX until the liquid preparations contained the required concentrations of the compound (LissapoP is a trademark).
• these were further diluted until they contained 100 p.p.m. of the compound under test.
• test procedure adopted with regard to each test species basically the same and comprised supporting a number of the insects on some medium which may be a host plant or some foodstuff on which the insect feeds, and treating either or both the insect and the medium with the preparations.
• the mortality of the insects was then assessed at periods varying from one to three days after the treatment.
• Table 3A the columns indicate, from left to right, the specific name and the common name of the species under test, the host plant or medium on which it was supported and the number of days which elapsed after treatment before assessing the mortality of the pest, or other efiects, for example, if feeding had been discouraged (time interval T).
• the culture or apple plants is obtained by adding water to a solution was transferred to soil cornmeals, which consisted of 400 of the compound (200 mg.) in acetone (1 ml.) until the g ms f 5% iz a in h Innes seed compost total volume of the mixture is 400 ml, An aqueous solucontained in a /2 pint bottle.
• the cornmeals were plugged tion or suspension suitable for spraying onto the leaves with cotton wool and sterilized in an autoclave for 2 of wheat, barley, or rice plants is prepared similarly, but hours, before inoculation.
• the soil of the polyoxyethylenesorbitan monolaurate wetting was prepared by mixing the cornmeals with John Innes agent, Tween 20, is used (Tween is a trademark). 40 seed compost at the rate of 2 cornmeals to 3 buckets of compost (2 gallon capacity buckets). The seeds were presprayapphed Nursing Test pared by rolling 10 grams of wheat seeds in a 25% china A suspension or solution containing 500 ppm.
• EXIGIIt OfII lfCCtIOH was assessed compared with untreated Seeds and seeds treated with Visually after a Period of time Interval 3-566 table mercury (Agrosan) and calculations were made to obtain below) depending p the Plant and the fungusa grading for disease control, and the results given in (C) Spray-applied Eradicant Test (E.S.A.) Table 5 followmg- The plants were inoculated with the fungus under test, Test against Pythium ultimum-procedure and 24 hours later the liquid preparation containing 500 ppm. of the active compound was sprayed onto the leaves of the plants as described under A above. After a further period of time (time interval Csee table below), again depending upon the particular plant and fungus, the extent of infection was assessed visually.
• time interval C see table below
• the culture Pythium ultimum was maintained on 2% malt agar test tube slopes at 20 C. Thirteen to seventeen days prior to testing the chemical, the culture was transferred to soil cornmeals which consisted of 400 grams of 5% maize meal in John Innes seed compost contained in a /2 pint bottle. The cornmeals were plugged with cotton Timeinter- Timeinterwool and sterilized in an autoclave for 2 hours before valAand V81 0 inoculation. Two days prior to testing the chemical, the Disease and plant B (days) (days) seeds and the soil were prepared.
• the soil was prepared ga ing; by mixing the cornmeals with John Innes seed compost at (cucumbr'; the rate of 2 cornmeals to 3 /2 buckets of compost (2 Rodqsphaeraleucatricha (apple) gallon capacity buckets).
• the seeds were prepared by If" rolling 25 grams of peas in a 25% china clay formulation of the chemical (where the chemical was a powder) or a 12.5% china clay formulation (where the chemical was Piricularia oryzae (rice) 6 Venturia inaeqyalis (apple) 21 20 15 a liquid) at the rate of 500 p.p.m. weight/weight, e.g. 50 milligrams of 25% formulation on 25 grams seed.
• Rhizoctonia solam' was maintained on soil cornmeals which consisted of 400 grams of 5% maize meal in John Innes seed compost contained in a V2 pint bottle.
• the cornmeals were plugged with cotton wool and sterilized in an autoclave for 2 hours before inoculation.
• the soil was prepared by mixing the cornmeals with John Innes seed compost at the rate of l cornmeal to 1 /2 buckets of compost (2 gallon capacity buckets).
• Four days before testing the chemical it was mixed with 400 grams of soil in a quart bottle at the rate of 100 p.p.m. weight/weight. Approxi mately 100 grams of John Innes seed compost.
• VIVIAN GARNER Primary Examiner US. Cl. X.R.

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

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Cited By (2)

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• 1969
  • 1969-06-25 GB GB32069/69A patent/GB1263352A/en not_active Expired
• 1970
  • 1970-06-08 US US44643A patent/US3705914A/en not_active Expired - Lifetime
  • 1970-06-16 IL IL7034736A patent/IL34736A0/xx unknown
  • 1970-06-18 BE BE752196D patent/BE752196A/fr unknown
  • 1970-06-24 DE DE19702031311 patent/DE2031311A1/de active Pending
  • 1970-06-24 FR FR7023454A patent/FR2053942A5/fr not_active Expired
  • 1970-06-25 NL NL7009332A patent/NL7009332A/xx unknown

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