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US3673236A - Basically substituted 1-cyano-0-carbamoyl-formoximes - Google Patents

Basically substituted 1-cyano-0-carbamoyl-formoximes Download PDF

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US3673236A
US3673236A US844163A US3673236DA US3673236A US 3673236 A US3673236 A US 3673236A US 844163 A US844163 A US 844163A US 3673236D A US3673236D A US 3673236DA US 3673236 A US3673236 A US 3673236A
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cyano
formoxime
methylcarbamoyl
parts
carbamoyl
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US844163A
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Hans Ulrich Brechbuhler
Kurt Gubler
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Novartis Corp
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Ciba Geigy Corp
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    • 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)

Abstract

New basically substituted 1-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-diethylamino-O-(N''-methylcarbamoyl)-formoxime. Processes for the production of these compounds are described as well as pesticidal compositions containing these compounds as active substances.

Description

Elite tes atet Brechhuhler et a1.
[ 1 June 27, 1972 BASHCALLY SUBSTITUTED l-CYANO-O- I CARBAMOYL-FORMOXHM ES Hans Ulrich Brechbuhler, Basel; Kurt l r 339b b9!!! ffiwitzsfl n Assignee: Ciba fieigy Corporation, Ardsley, N.Y.
Filed: July 23, 1969 Appl.No.: 844,163
Foreign Application Priority Data Inventors:
[56] References Cited UNITED STATES PATENTS 3,466,316 9/1969 Payne, .11. et a1. ..260/465.4
Primary Examiner-Joseph P. Brust Attorney-Kar1 F. Jorda and Frederick H. Rabin [57] ABSTRACT New 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.
10 Claims, No Drawings BASICALLY SUBSTITUTED l-CYANO-OCARBAMOYL- FORMO DETAILED DESCRIPTION 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.
Examples of 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. Examples of 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.
The 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:
R NCO (Ill) b. with a carbamic acid halide of the Formula IV:
HalC[l-N\ wherein I-Ial represents chlorine or bromine,
c. with the components forming the carbamic acid halide of Formula IV, namely with phosgene and an amine of the Formula V:
preferably in the presence of an acid-binding agent and a solvent or diluent which is inert towards the reaction components. In the Formulas II to V, the symbols R to R have the meanings given for Formula I.
For the production of the novel l-cyano-O-carbamoyl-formoximes of Formula I in which R represents hydrogen, a mixture of an isocyanate of Formula 111- and an N-mono-alkyl-carbamic acid halide of the formula can also be used.
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. 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. The novel carbamoyl oximes are obtained according to the invention in good to very good yields. They are soluble in the usual organic solvents and water and are stable. Some of the starting materials of Formula II used for the reactions according to the invention are known. The compounds which have not previously been described can be obtained according to the method described by W. Steinkopf et al., [.I.pr.Chemie (2), 83, 453-470 (1911)], by reacting l-chloro-l-cyano-form-oxime with primary and secondary amines.
It is known that 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.
The following examples illustrate the process according to the invention. The temperatures are given in degrees centigrade and all parts and percentages are by weight unless otherwise specified.
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.
The solvents are removed by suction under vacuum, the residue is dissolved in a small volume of water, acidified (pH 3-4) with phosphoric acid and extracted with diethyl ether. The ethereal extracts are dried with anhydrous sodium sulfate,
and the ether is removed under vacuum. in this manner, 21.4 g of l-dimethylamino-l-cyano-formoxime are obtained as brownish crystals having a melting point of 1 12.
b. 5.3 g of l-dimethylamino-l-cyano-fonnoxime are dissolved in 50 ml of dioxane, treated with 0.25 ml of triethyl amine, and 7.5 ml of methylisocyanate are added thereto. This mixture is kept for 16 hours at 40-50. After cooling, the dioxane is re-moved under vacuum and the residue is recrystallized from ethanol. in this manner, 6.9 g of white crystals (m.p. l 141 17) of l-dimethylamino-l-cyano-O-(N- methylcarbamoyl)-formoxime are obtained. The mother liquor yields a further 4.5 g, m.p. l 12-1 15.
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.
The residue is washed with hexane in order to remove the paraffin oil and then recrystallized from a water/ethanol mixture. Thus l-morpholino- 1 -cyano-O-( N'-dimethyl-carbamoyl)-formoxirne melting at 120-121 is obtained.
The following compounds of Formula I were produced analogously to the processes described in the examples:
Melting Compounds point 1-methylamino-1-cyano-O-(N'- methy1carbamoyl)-formoxime 157-165 l-dimethylaminol -cyano-0-(N'-methylcarbamoyl)-formoxime 1 14-1 17 l-dimethylamino- 1 -cyano-0-( N-dimethyl carbamoyl)-formoxime 58-5 9 l-ethylaminol -cyano-0-(N'- methylcarbamoyl)-formoxime 132-142 l-diethylamino- 1 -cyano0-( N '-methyl- {60 carbamoyl )-formoxime 91 l-n-propylaminol -cyano-0-( N '-methyll-morpholino- 1 -cyano-0-( N '-methyl- {120 carbamoyU-formoxime 168 1-morpholino-1-cyano-0-(N dimethylcarbamoyl )-formoxime 1 20-12 1 l-diethylamino-1-cyano-0-(N'-diethylcarbamoyl )-formoxime oil 1 -di-n-propylarnin0- 1 -cyano-0-( N -methylcarbamoyl)-formoxime oil 1 -anilino- 1-cyano-0-( N -methylcarbamoyl )-formoxime l 72- 1 74 1 -piperidinol -cyano-0-( N '-methylcarbamoyl )-formoxime 1 54 1 -piperazino- 1-cyano-0-( N '-methylcarbarnoyl )-f0rrnoxirne 202 1-( 4-methyl-piperazino l-cyano-0-( N methylcarbamoyl )-formoxime 82 1-( 4-ethoxycarbonyl-piperazino)- 1 -cyano-( N methyl-carbamoyl )-formoxime 105 1-(4-ethoxycarbonyl-piperazino)-1-cyano-0- (N-di-methylcarbamoyl )-formoxime 13 7 1 -dimethylaminol -cyano-0-( N- ethylcarbamoyl )-forrnoxirne 8 1 l-dimethylamino' 1 -cyano-0-( N '-isopropylcarbamoyl )-formoxime 99 l-dirnethylaminol -cyano-0-( N 'allylcarbamoyl )-formoxime 86 l-dimethylamino- 1 -cya.no-0-( N '-npropylcarbamoy1)-fonnoxime 74 1 -morpholino- 1-cyano-0-( N -ethylcarbamoyl forrnoxime paste 1 -diethylaminol -cyano-0-( N-ethylcarbarnoyl)-formoxime oil l-tetrahydrofurfurylamino-0-( N methylcarbamoyl)-fonnoxime l2l-l22 The production of pesticidal agents according to the invention is performed in a known manner by intimate mixing and grinding of active substances of the general Formula I together with suitable carriers, optionally with the addition of dispersing agents, absorbents, or solvents, which are inert towards the active substances. The novel active substances can be prepared in the following forms:
solid preparations: dusts, scattering agents, granulates,
(coated granulates, impregnated granulates and homogeneous granulates);
water-dispersible concentrates of the active substance:
wettable powders, pastes, emulsions;
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. Thus, in addition to the said active substances of the general Formula I, 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.
The novel active substances are used for soil disinfection in the form of solid or liquid agents. For 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.
Since the 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 following forms for application of the pesticides according to the invention serve to illustrate the invention; where not expressly stated otherwise, parts and percentages" are by weight.
DUST
The following ingredients are used to produce a) a 10 percent and b) a 2 percent dust:
a. 10 parts of l-n-butylamino-1-cyano-0-(N'-methylcarbamoyl)-formoxime,
5 parts of highly dispersed silicic acid,
parts of talcum;
b. 2 parts of l-morpholino-l-cyano-0-(N-dimethylcarbamoyU-fonnoxime,
1 part of highly dispersed silicic acid,
97 parts of talcum.
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.
GRANULATE The following ingredients are used to produce a 5 percent granulate:
5 parts of isopropylamino-1-cyano-O-(N'-methylcarbamoyl)-formoxime,
0.25 part of epichlorohydrin,
0.25 part of octaethyleneglycol ether,
3.50 pans of polyethyleneglycol of a molecular weight of about 400,
91 parts of kaolin (particle size 0.3-0.8 mm). The active ingredient is mixed with epichlorohydrin and then dissolved in 6 parts of acetone, and the polyethyleneglycol and octaethyleneglycol ether are added thereto. The solution obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo. The granulate obtained is suitable for the protection of plants and stored goods.
WETTABLE POWDER For the production of a 50 percent [(a) and (b) a 25 percent [(c)], and a 10 percent [(d) wettable powder, the following components are used:
a. 50 parts of l-dimethylamino-l-cyano-O-(N'-methylcarbamoyl)-formoxime,
5 parts of naphthalene sulfonic acid/ benzene sulfonic acid/formaldehyde condensation product,
5 parts of nonylphenyl sulfonate,
5 parts of Champagne chalk,
20 parts of silicic acid,
parts of kaolin;
b. 50 parts of 1-diethylamino-l-cyano-O-(N'-dimethylcarba-moyl)-formoxime,
5 parts of nonylphenyl sulfonate,
10 parts of calcium lignin sulfonate,
1 part of Champagne chalk/hydroxyethyl cellulose mixture parts of silicic acid,
14 parts of kaolin;
c. parts of l-n-propylamino-l-cyano-O-(N-methylcarbamoyl)-formoxime,
5 parts of sodium oleyl methyl tauride,
2.5 parts of naphthalene sulfonic acid/formaldehyde condensation product,
0.5 part of carboxymethyl cellulose,
5 parts of neutral potassium-aluminum silicate,
62 parts of kaolin;
d. 10 parts of l-n-butylamino-l-cyano-O-(N'-methylcarbamoyl)-formoxime,
3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates,
5 parts of naphthalene sulfonic acid/formaldehyde condensation product,
82 parts of kaolin.
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:
45 parts of 1-diethylamino-l-cyano-O-(N'-methylcarbamoyl)-formoxime,
5 parts of sodium aluminum silicate 15 parts of cetyl octaethylene glycol ether 2 parts of spindle oil,
10 parts of polyethyleneglycol of a molecular weight of about 400,
23 parts of water.
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;
b. 2 parts of l-dimethylamino-l-cyano-O-(N-(N'-methylcarbamoyD-formoxime are dissolved in 10 parts of xylene and 88 parts of petroleum;
c. 2 parts of l-diethylarnino-l-cyano-O-(N'-methylcarbamoyl)-formoxime and 3 parts of dichlorophenyl-trichloroethane are dissolved in parts of kerosene.
These solutions are sprayed with pressure sprayers. 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.
Insecticidal and acaricidal tests with the compounds of F ormula I have shown that the novel l-cyano-O-carbamoyl-formoximes have a very good systemic insecticidal action; in addition, they are good to very good stomach and contact poisons. Tests of their action were made with 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 family Pyralididae, e.g., Mediterranean flour moths (Ephestia kiihniella), as well as of the family Blattidae, e.g., Cockroaches (Phyllodromia germanica, Periplaneta americana Blatta orientalis), the family Aphididae, e.g., bean aphids (A- phis fabae); in addition, with insects of the family Pseudococcidae, e.g., citrus mealybugs (Planococcus citri) and of the family Locustidae, such as migratory locusts (Locusta migraton'a). The tests on the said bean aphids, citrus mealybugs and migratory locusts demonstrate a systemic action.
In addition, 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.
Furthermore the active substances of Formula I have excellent nematocidal and soil-fungicidal properties.
In admixture with synergists such as succinic acid dibutyl ester, piperonyl butoxide, and auxiliaries having a similar action such as olive oil, peanut oil, etc., the range of action of the 70 active substances according to the invention is broadened and,
in particular, the insecticidal and acaricidal action is improved. In the same way, the 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.
SYSTEMlC INSECTICIDAL ACTION In order to determine the systemic action of the new compounds, cabbage, tomato and horsebean plants in flower pots containing 600 cc of humus are watered with 50 ml of an aqueous emulsion containing 0.48 percent of active substance (prepared from a 10 percent emulsion concentrate).
After 24 hours the parts of the plants above ground are infested with the test animals. 10 Desert locusts (Locusta migrazon'a, 3rd stage) are placed on each cabbage plant, 10 citrus mealybugs (Pseudococcus citri) on each tomato plant, and 10 bean aphids (Aphis fabae) on each horsebean plant. All tests are duplicated. The time elapsing until all insects are in dorsal position is determined. (Test period 3 days, ambient temperature 2530) a. Tests with Locusla migratoria (3rd stage) time elapsed active substance (in hours) until 100% in dorsal position l-diethylaminol -cyano-0-( N'- methylcarbamoyl)-formoxime 24 l-isopropylaminol-cyano-O-(N 'methylcarbamoyD-fonnoxime 48 1-piperidin0-l-cyan0-0-(N'-methylcarbamoyl)-formoxime 72 1-norpholinol -cyano-0-( N'- methylcarbamoyl)-forrnoxime 24 1-methy1thi0- 1 -cyar|o-O-( N-methylcarbamoyl)-formoxime (known from South African patent No. 66/6759 or the French Patent No. 1,498,899) no effect b. Tests with Pseudococcus citri time elapsed active substance (in hours) until 100% in dorsal position l-morpholino- 1 -cyano-( N'-methylcarbamoyl)-formoxime 24 l -isopropylamin0-1-cyan0-0-(N'-methylcarbamoyl)-formoxime 72 l-methylthiol -cyano-O-( N-methylcarbamoyl)-formoxime (known from South African patent No. 66/6759 or the French Patent No. 1,498,899) no effect c. Tests with Aphisfabae time elapsed active substance (in hours) until 100% in dorsal position 1-diethylamino-l-cyano-O-(N- methylcarbamoyl)-formoxime 24 l -n-pr0pylarnino- 1-cyano-0-(N'-methylcarbamoyU-formoxime 24 l-isopropylamino-1cyan0-0-(N'-methylcarbamoyl)-fonnoxime 24 l-n-butylaminol -cyano-0-( N- methylcarbarnoyl)-fonnoxime 24 l-morpholinol -cyano-0-( N'-methylcarbamoyl)-forrnoxime 24 l-morpholinol-cyano-0-(N',N'- dimethyl-formoxime 24 l-piperidinol -cyano-0-( N-methylcarbamoyl)-formoxime 24 l-methylthiol -cyano-O-( N-methylcar- French Patent No. 1,498,899) no efl'ect STOMACH POISON TEST In order to determine the action of the new compounds as stomach poison, cabbage and potato plants in flower pots are sprayed until completely wet with an aqueous emulsion containing 0.05 percent of active substance (prepared from a 10 percent emulsion concentrate). For a first test a third of the treated plants are used. After 1 hour 10 Colorado beetle larvae (Leptinotarsa decemlineata, 3rd stage) are placed on each potato plant, and 5 desert locusts (Locusta migraton'a, 3rd stage) are placed on each cabbage plant. The test is repeated with the second and third portions of the treated plants after 3 and 8 days, respectively. All tests are duplicated. The time elapsing until all insects are in dorsal position is determined. (Test period 2 days, ambient temperature 25-30).
a. Tests withLeptinorarsa decemlr'neata (3rd stage) Time elapsed (in hours) until in dorsal position, when plants have been infected by insects active substance (3rd stage) Time elapsed (in hours) until 100% in dorsal position, when plants have been infected by insects active substance after 1 hour 3 days 8 days methylcarbamoyl)-formoxime 24 48 48 l-morpholino- 1 -cyano-0-( N -methylcarbamoyl)-formoxime 24 24 24 l-piperidino-l-cyano-(l-(N' -methylcarbamoyl)-formoxime 24 48 48 l-methylthiol-cyano-O-(N- methylcarbamoyl )-formoxime (known from South African patent No. 66/6759 or the no no no French patent No. 1,498,899 effect effect effect CONTACT POISON TEST a. Tests with Cotton Stainers (Dysdemusfasciatus) In order to determine the action as contact poison of the new compounds, cotton plants in flower pots are sprayed until completely wet with an aqueous emulsion containing 0.025 percent of active substance (prepared from a 10 percent emulsion concentrate). After 1 hour, the plants are infested with 10 adult cotton stainers each. All tests are duplicated. The time elapsing until all insects are in dorsal position is determined. (Test period 2 days, ambient temperature 25-30 a)- Time elapsed (in hours) until 100% in dorsal active substance position 1-diethylamino-1-cyano-O-(N'- methylcarbamoyl)-fonnoxime 24 1 -di-n-propylaminol-cyano--( N -methylcarbamoyl)-formoxime 24 l-tert-butylamino-l-cyano-0-(N'- methylcarbamoyl)-fonnoxime 24 l-piperidinol -cyano-0-( N '-methylcarbamoyl )-formoxime 24 1 -methylthiol-cyano-O-( N-methylcarbamoyl)-formoxime (known from South African patent No. 66/6759 or the French patent No. 1,498,899) no effect b. Tests with Citrus Mealybugs (Pseudococcus Citri) Tomato plants infested with citrus mealybugs are sprayed until completely wet with an aqueous emulsion containing 0.025 percent of active substance (prepared from a per cent emulsion concentrate). All tests are duplicated. The time elapsing until all insects are in dorsal position is determined. (Test period 2 days, ambient temperature 30.)
Time elapsed active substance (in hours) until 100% in dorsal position 1-diethylamino-1-cyano-0-(N'- methylcarbamoyl)-formoxime 24 l-isopropylamino-l-cyano-0-(N'-methylbamoyl)-formoxime 48 l-methylthio-l-cyano-O-(N-methylcarbamoyl)-formoxime (known from South African patent No. 66/6759 or the French patent No. 1,498,899 no eflect days, and then used for planting more tomato seedlings. After a test period of 28 days the number of root knots is determined. The minimum concentration of active substance preventing the formation of root knots is given in the table.
effective concenactive substance tration in tomato seedlings planted on the lst day 8th day 1-dimethylamino-l-cyano-ll-(N methyl carbamoyD-formoxime 0.005 0.0025
1-diethylamino-1-cyano0-(N'- methylcarbamoyl)-formoxime 0.001 0.001
effective concentration in tomato seeds active substance ACARICIDAL ACTION ON Tetranychus Urticae In order to determine the acaricidal properties of the new compounds, a test is carried out with bean leaves infested with adults, quiescent stages and eggs of the red spider mite (Tetranychus urticae). The bean leaves are treated until completely wet with aqueous emulsions in concentrations of 0.1 and 0.05 percent of active substance (prepared from a 25 percent emulsion concentrate). The concentrations of active substance used which lead to 100 percent mortality after 6 days are determined.
Red spider mites which are resistant to phosphoric acid esters are used as test animals. The test results are given in the following table.
Concentrations (in of active substance leading to 100% mortaactive substance NEMATOCIDAL ACTION ON MELOIDOG YNE ARENARIA The amount of active substance calculated to give concentrations for application of 0.02, 0.01, 0.005 and 0.0025 percent is thoroughly mixed with sand and subsequently mixed with humus, infested with Meloidogyne arenaria. Tomato seedlings are immediately planted in the fresh humus prepared as described above. Part of the prepared humus is stored for 8 ACUTE TOXICITY (LDM p.o. Rat) LD p.o. rat
active substance in mg/kg 1 -methylamino- 1 -cyano-0-( N '-methylcarbamoyl )-forrnoxime l-dimethy1amino-1-cyano-0(N -methylcarbamoyl)-formoxime 1 -di-n-propylamino- 1 -cyano-0-( N -methylcarbamoyl)-formoxime 1 -n-butylamino- 1 -cyano-0-(N methylcarbamoyl)-fonnoxime 1 -tetrahydrofurfurylarnino-1-cyano-O- (N-methylcarbamoyl)-formoxime 1 -methylthio- 1-cyano-0-(N-methylcarbamoyl)-formoxime (known from the South African patent No. 66/6759 or the French patent No. 1,498,899)
We claim: 1. Basically substituted l cyano-0-carbamoyl-forrnoximes of the Formula I wherein R, represents hydrogen, a substituted or unsubstituted lower alkyl radical with one to five carbon atoms, wherein said substitutents are hydroxy, halo, lower alkoxy, alkylthio, alkylamino or dialkylamino wherein alkyl is lower alkyl of from 1 to carbon atoms,
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.
2. A compour'd as defined in claim 1 which is ldiethylaminol -cya.no-O-( N -methylcarbamoyl )-formoxime.
3. A compound as defined in claim 1 which is lisopro pylaminol -cyano-O-( N -methylcarba.moyl )-formox- 12 ime.
4. A compound as defined in claim 1 which is l-npropylaminol-cyano-O-( N'-methylcarbamoyl )-formoxime.
5. A compound as defined in claim 1 which is l-n-butylaminol -cyano-O-( N -methylcarbamoyl )-formoxime.
6. A compound as defined in claim 1 which is lmethylaminol-cyano-O-( N'-methylcarbamoyl )-formoxime.
7. A compound as defined in claim 1 which is ldimethylamino-l-cyano-0-(N-methylcarbamoyl)-formoxime.
8. A compound as defined in claim 1 which is ldimethylamino-l-cyano-O-(N'-dimethylcarbamoyl)-formoxlme.
9. A compound as defined in claim 1 which is l-ethylaminol -cyano-O-( N -methylcarbamoyl )-formoxime.
10. A compound as defined in claim 1 which is l-isobutylamino- 1 -cyano-( N-methylcarbamoyl )-formoxime.
II l I I

Claims (9)

  1. 2. A compound as defined in claim 1 which is 1-diethylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  2. 3. A compound as defined in claim 1 which is 1-isopropylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  3. 4. A compound as defined in claim 1 which is 1-n-propylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  4. 5. A compound as defined in claim 1 which is 1-n-butylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  5. 6. A compound as defined in claim 1 which is 1-methylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  6. 7. A compound as defined in claim 1 which is 1-dimethylamino-1-cyano-0-(N'' -methylcarbamoyl)-formoxime.
  7. 8. A compound as defined in claim 1 which is 1-dimethylamino-1-cyano-O-(N'' -dimethylcarbamoyl)-formoxime.
  8. 9. A compound as defined in claim 1 which is 1-ethylamino-1-cyano-O-(N'' -methylcarbamoyl)-formoxime.
  9. 10. A compound as defined in claim 1 which is 1-isobutylamino-1-cyano-(N'' -methylcarbamoyl)-formoxime.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4081550A (en) * 1976-05-20 1978-03-28 Union Carbide Corporation Ketoalkanesulfenyl and ketoalkanethiosulfenyl carbamates
US4138423A (en) * 1974-07-08 1979-02-06 Union Carbide Corporation N-dithio carbamoyl oximes
US4188401A (en) * 1977-06-04 1980-02-12 Bayer Aktiengesellschaft Combating fungi with 1-(ω-substituted pentyl)-3-(2-cyano-acetyl)-ureas

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466316A (en) * 1964-09-23 1969-09-09 Union Carbide Corp Alpha-cyano carbamoyloxime compounds

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CH484604A (en) * 1966-11-10 1970-01-31 Ciba Geigy Pesticides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466316A (en) * 1964-09-23 1969-09-09 Union Carbide Corp Alpha-cyano carbamoyloxime compounds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138423A (en) * 1974-07-08 1979-02-06 Union Carbide Corporation N-dithio carbamoyl oximes
US4081550A (en) * 1976-05-20 1978-03-28 Union Carbide Corporation Ketoalkanesulfenyl and ketoalkanethiosulfenyl carbamates
US4188401A (en) * 1977-06-04 1980-02-12 Bayer Aktiengesellschaft Combating fungi with 1-(ω-substituted pentyl)-3-(2-cyano-acetyl)-ureas

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