Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
  • C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
  • C07D295/205—Radicals derived from carbonic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical

Definitions

• ABSTRACT basically substituted l-cyano-O-carbamoyl-formoximes are described as insecticides, acaricides and nematocides, which are distinguished from known carbamoyl-oximes by pronounced systemic insecticidal, acaricidal and nematocidal action.
• a typical compound is 1-diethy1amino-O-(N-methylcarbam0y1)-f0rmoxime. Processes for the production of these compounds are described as well as pesticidal compositions containing these compounds as active substances.
• the present invention concerns new carbamoyl-formoximes, namely l-cyano-O-carbamoyl-formoximes having a basic group in l-position, process for the production thereof, pesticidal agents containing these new compounds as active substance, as well as methods for the control of pests using the R represents hydrogen, a substituted or unsubstituted lower alkyl radical with one to five carbon atoms,
• R represents a lower alkyl radical with one to five carbon atoms, a cycloalkyl radical with three to six carbon atoms the phenyl radical, the tetrahydrofuryl radical, or
• R and R together with the adjacent nitrogen atom represent a fiveor six-membered heterocyclic radical
• R represents hydrogen or a lower alkyl radical with one to five carbon atoms and R represents a lower alkyl or alkenyl radical with one to five carbon atoms or two to four carbon atoms, respectively.
• lower alkyl radicals represented by R to R having one to five carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl and pentyl radicals.
• lower alkenyl radicals R are the allyl, methallyl or propenyl radical.
• Cycloalkyl radicals R are preferably monocyclic radicals such as cyclopropyl, l-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• Substituted alkyl radicals contain, for example, the following substituents: hydroxy, halogen, lower alkoxy, alkylthio, alkylarnino, dialltylamino, whereby alkyl always represents lower alkyl of from one to five carbon atoms.
• a fiveor six-membered heterocyclic radical formed by R and R, and the adjacent nitrogen atom is preferably saturated and can contain other hetero atoms such as another nitrogen atom or oxygen atom.
• These heterocyclic radicals can also contain substituents such as lower alkyl, lower alkoxycarbon yl, etc.
• Preferred heterocyclic radicals are: the piperidino, piperazino, 4-methylpiperazino, 4-alkoxycarbonyl-piperazino or the morpholino radical.
• novel l-cyano-O-carbamoyl-formoximes of the Formula 1 are produced according to the invention by reacting a lcyanoformoxime of the Formula II:
• NC NOH either a. with an isocyanate of the Formula III:
• the reactions according to the invention are performed in the presence of acid-binding agents such as inorganic bases, e.g., hydroxides, oxides and carbonates of alkali and alkaline earth metals, and organic nitrogen bases, for example tertiary amines such as pyridine, triethylamine, triethylene-diamine, etc., as well as organotin compounds.
• acid-binding agents such as inorganic bases, e.g., hydroxides, oxides and carbonates of alkali and alkaline earth metals, and organic nitrogen bases, for example tertiary amines such as pyridine, triethylamine, triethylene-diamine, etc., as well as organotin compounds.
• the reactions are carried out in the presence of solvents and diluents which are inert towards the reaction components, e.g., in ethers and ether-type compounds such as diethylether, propyl ethers, dioxane; ketones such as acetone, methylethyl ketone; amides such as N,N-alkylated carboxylic acid amides; in halogenated hydrocarbons or aliphatic and aromatic hydrocarbons.
• solvents and diluents which are inert towards the reaction components, e.g., in ethers and ether-type compounds such as diethylether, propyl ethers, dioxane; ketones such as acetone, methylethyl ketone; amides such as N,N-alkylated carboxylic acid amides; in halogenated hydrocarbons or aliphatic and aromatic hydrocarbons.
• the novel carbamoyl oximes are obtained according
• oximes can exist in two stereoisomeric forms, the synand the anti-form.
• the l-cyano-O-carbamoylforrnoximes of Formula I can also exist in these two forms. For this reason the term l-cyano-O-carbarnoyl-formoximes of Formula I should be understood to represent both of these stereoisomeric forms.
• EXAMPLE 1 a 200 ml of a 33 percent solution of dimethyl amine in ab solute ethanol are added to 500 ml of dioxane and then 24 g of 1-chloro-l-cyano-formoxime in ml of absolute dioxane are added dropwise with vigorous stirring under an atmosphere of nitrogen. The temperature rises to 40 and a precipitate of dimethylamine-hydrochloride is formed. Stirring is continued for 16 hours at room temperature and finally for 2 hours at 60.
• EXAMPLE 2 42.8 g of l-morpholino-l-cyano-formoxime [produced analogously to Example la) and 33.2 g of dimethyl-carbarnic acid chloride are dissolved in 700 ml of dioxane, and then treated with 44.2 g of anhydrous potassium carbonate. The mixture is allowed to react for 16 hours at 80 with vigorous stirring in an atmosphere of nitrogen. After cooling, the solid portion is removed by filtration and the dioxane is removed by distillation in vacuum. The residue is recrystallized from water. In this manner, 39.5 g of l-morpholino-1-cyanoO-(N- dimethyl-carbamoyl)-formoxime, m.p. 120-12l, are obtained.
• EXAMPLE 3 9.6 g of a 50 percent by weight of suspension of sodium hydride in paraifin oil are diluted under nitrogen atmosphere with 100 ml of dry tetrahydrofuran. A solution of 31 g of morpholino-l-cyano-formoxime in 200 ml of dry tetrahydrofuran is added dropwise at room temperature with Stirring vigorously to this suspension. Stirring is continued at 3540 for 30 minutes. This mixture is then added in small portions at 0-5 to a stirred solution of 39.6 g of phosgene in 400 ml of dry ether. Stirring is continued at room temperature for 30 minutes. The excess of phosgene is then removed in vacuo.
• a solution of 22.5 g of dimethylamine in 100 ml of dry tetrahydrofuran is then added dropwise at room temperature and the whole is stirred for 16 hours at room temperature.
• the reaction mixture is then heated to 60 for 1 hour, the solution is filtered after cooling and the solvent is removed in vacuo.
• solid preparations dusts, scattering agents, granulates
• liquid preparations solutions, aerosols.
• the concentration of active substance in these preparations is from 0.01 to percent.
• Other biocidally active substances or agents can be admixed with the agents described according to the invention.
• the new agents may contain, for example, other insecticides, fungicides, bactericides, fungistatic and bacteriostatic substances or other nematocides in order to broaden the range of action.
• the agents according to the invention may also contain plant fertilizers, trace elements, etc.
• novel active substances are used for soil disinfection in the form of solid or liquid agents.
• soil disinfection those agents which assure an even distribution of the active substance throughout a layer of soil 15 to 25 cm deep are especially favorable.
• the method and form of application are, in particular, dependent upon the type of soil pests to be controlled, the climate and the nature of the soil.
• novel active substances are not phytotoxic and do not adversely afiect seed germination they can be used before seeding without observing a waiting time and in crops which have already been planted.
• the active substances are mixed and ground with the carriers.
• the dusts obtained are used, e.g., for the control of cockroaches and ants, etc. in buildings, and also for plant protection.
• the active ingredients are intimately mixed with the additives in suitable mixers and ground in mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration. Such suspensions are used primarily in plant protection for the control of biting and sucking insects.
• PASTE The following ingredients are used to produce a percent paste:
• the active ingredient is intimately mixed and ground with the additives in apparatus suitable therefor.
• a paste is ob tained from which, by dilution with water, suspensions of any 5 concentration desired can be produced. These suspensions are suitable for the control of insects in plant protection.
• EMULSION To produce a 10 percent emulsion concentrate, 10 parts of l-morpholinol -cyano-O-( N -methylcar bamoyl)-formoxime, 55 parts of xylene, 32 parts of dirnethyl formamide and 3 parts of an emulsifying agent consisting of nonylphenyl decaethyleneglycol and calcium nonylphenylsulfonate (weight ratio about 1: l are mixed together.
• This concentrate can be diluted with water to form emulsions having concentrations suitable for the protection of plants and stored goods.
• SPRAY 1 part of l-methylamino-1-cyano-O-(N-rnethylcarbamoyl)-formoxime are dissolved in 99 parts of water;
• the solution (a) is advantageously used for the control of leaf aphids on fruit trees and other plants.
• the solutions (b) and (c) are used in particular for the control of flies and mosquitoes in buildings, storerooms and slaughter houses.
• insects of the families Muscidae, Stomoxidae and Culicidae e.g., with polyvalent resistant and normally sensitive house flies (Musca domestica), stable flies (Stomoxys calcitmns) and mosquitoes e.g., Aedes Aegypti, Culex fatigans, Anopheles stephensi); with insects of the families Curculionidae, Bruchididae, Dermestidae, Tenebrionidae and Chrysomelidae, e.g., granary weevils (Sitophilus granan'us), bean beetles (Bruchidus obtectus), larder beetles (Dermestes vulpinus), yellow meal worms (Tenebrio molitor), Colorado potato beetles (Leptinotarsa decemlineata) and their stages of development; with insects of the families Muscidae, Stom
• the active substances of the Formula I according to the invention have a good action on the larval and adult stages of spiders, e.g., of the families Acarinae, Ixodidae, Arachnidae and Argasidae.
• active substances of Formula I have excellent nematocidal and soil-fungicidal properties.
• the range of action of the 70 active substances according to the invention is broadened and,
• insecticidal and acaricidal action is improved.
• insecticidal action can be substantially broadened and adapted to the prevailing circumstances by the addition of other insecticides such as phosphoric, thiophosphoric and dithiophosphoric acid esters and amides, carbamic acid esters, halogenated hydrocarbons and analogues of DDT active substance, as well as pyrethrins and synergists thereof.
• R represents a lower alkyl radical with one to five carbon atoms or a cycloalkyl radical with three to six carbon atoms
• R represents hydrogen or a lower alkyl radical with one to five carbon atoms and R represents a lower alkyl or alkenyl radical with one to five carbon atoms or two to four carbon atoms, respectively.
• a compour'd as defined in claim 1 which is ldiethylaminol -cya.no-O-( N -methylcarbamoyl )-formoxime.
• a compound as defined in claim 1 which is lisopro pylaminol -cyano-O-( N -methylcarba.moyl )-formox- 12 ime.
• a compound as defined in claim 1 which is l-npropylaminol-cyano-O-( N'-methylcarbamoyl )-formoxime.
• a compound as defined in claim 1 which is l-n-butylaminol -cyano-O-( N -methylcarbamoyl )-formoxime.
• a compound as defined in claim 1 which is lmethylaminol-cyano-O-( N'-methylcarbamoyl )-formoxime.
• a compound as defined in claim 1 which is ldimethylamino-l-cyano-0-(N-methylcarbamoyl)-formoxime.
• a compound as defined in claim 1 which is ldimethylamino-l-cyano-O-(N'-dimethylcarbamoyl)-formoxlme.
• a compound as defined in claim 1 which is l-ethylaminol -cyano-O-( N -methylcarbamoyl )-formoxime.
• a compound as defined in claim 1 which is l-isobutylamino- 1 -cyano-( N-methylcarbamoyl )-formoxime.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (1)

Publications (1)

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ID=4370100

Family Applications (2)

Family Applications After (1)

Country Status (12)

Cited By (3)

Citations (1)

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• 1968
  • 1968-07-24 CH CH1110568A patent/CH496395A/de not_active IP Right Cessation
• 1969
  • 1969-07-21 SE SE10253/69A patent/SE356295B/xx unknown
  • 1969-07-21 DK DK391369AA patent/DK125392B/da unknown
  • 1969-07-23 ES ES369815A patent/ES369815A1/es not_active Expired
  • 1969-07-23 BE BE736476D patent/BE736476A/xx unknown
  • 1969-07-23 ES ES369816A patent/ES369816A1/es not_active Expired
  • 1969-07-23 IL IL32684A patent/IL32684A/xx unknown
  • 1969-07-23 AT AT426170A patent/AT289463B/de not_active IP Right Cessation
  • 1969-07-23 FR FR6925075A patent/FR2013603A1/fr not_active Withdrawn
  • 1969-07-23 US US844163A patent/US3673236A/en not_active Expired - Lifetime
  • 1969-07-23 NL NL6911319A patent/NL6911319A/xx unknown
  • 1969-07-23 AT AT708669A patent/AT292013B/de not_active IP Right Cessation
  • 1969-07-23 GB GB36917/69A patent/GB1282583A/en not_active Expired
  • 1969-07-23 ES ES369814A patent/ES369814A1/es not_active Expired
  • 1969-07-24 RO RO60617A patent/RO56687A/ro unknown
• 1972
  • 1972-04-13 US US00243847A patent/US3725418A/en not_active Expired - Lifetime

Patent Citations (1)

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