US3875232A - AC Ketoxime carbamates - Google Patents

AC Ketoxime carbamates Download PDF

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US3875232A
US3875232A US229207A US22920772A US3875232A US 3875232 A US3875232 A US 3875232A US 229207 A US229207 A US 229207A US 22920772 A US22920772 A US 22920772A US 3875232 A US3875232 A US 3875232A
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Prior art keywords
dimethyl
methylcarbamyloximinobutane
methyl
methylcarbamyloximino
compound
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US229207A
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Thomas A Magee
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Diamond Shamrock Chemicals Co
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Diamond Shamrock Corp
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Priority to US229207A priority Critical patent/US3875232A/en
Priority to CA137,337A priority patent/CA984399A/en
Priority to FR7210622A priority patent/FR2136055A5/fr
Priority to AR241311A priority patent/AR192758A1/en
Priority to EG138/72A priority patent/EG10912A/en
Priority to ES401551A priority patent/ES401551A1/en
Priority to RO7282518A priority patent/RO72853A/en
Priority to IT49465/72A priority patent/IT954413B/en
Priority to IL39157A priority patent/IL39157A/en
Priority to CH436875A priority patent/CH585194A5/xx
Priority to RO70445A priority patent/RO61151A/ro
Priority to CH514972A priority patent/CH611275A5/xx
Priority to YU00944/72A priority patent/YU39065B/en
Priority to GB1618772A priority patent/GB1392111A/en
Priority to SU1886513A priority patent/SU466653A3/en
Priority to CH436975A priority patent/CH591433A5/xx
Priority to IE453/72A priority patent/IE36264B1/en
Priority to DE2216838A priority patent/DE2216838C2/en
Priority to NLAANVRAGE7204698,A priority patent/NL175989C/en
Priority to SU1887327A priority patent/SU466681A3/en
Priority to AU40916/72A priority patent/AU482663B2/en
Priority to SU1769624A priority patent/SU454735A3/en
Priority to HUDI222A priority patent/HU165184B/hu
Priority to RO7282519A priority patent/RO72827A/en
Priority to PL1972154659A priority patent/PL89001B1/en
Priority to AT299672A priority patent/AT316207B/en
Priority to JP3563572A priority patent/JPS5533410B1/ja
Priority to PL15918572A priority patent/PL89691B1/en
Priority to AT678173A priority patent/AT330197B/en
Priority to US05/391,329 priority patent/US3932471A/en
Priority to AT283274A priority patent/AT330198B/en
Priority to AT283374A priority patent/AT338282B/en
Priority to US05/553,648 priority patent/US4028413A/en
Publication of US3875232A publication Critical patent/US3875232A/en
Application granted granted Critical
Priority to BE157643A priority patent/BE830594Q/en
Priority to US05/966,390 priority patent/US4215075A/en
Priority to YU316/79A priority patent/YU42298B/en
Priority to YU00315/79A priority patent/YU39102B/en
Assigned to SDS BIOTECH CORPORATION, A DE CORP. reassignment SDS BIOTECH CORPORATION, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DIAMOND SHAMROCK CORPORATION
Assigned to DIAMOND SHAMROCK CHEMICALS COMPANY, A DE CORP. reassignment DIAMOND SHAMROCK CHEMICALS COMPANY, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SDS BIOTECH CORPORATION, A DE 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
    • C07D295/04—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms

Definitions

  • This invention relates to organic compounds useful as pesticides and more particularly to carbamate derivatives of ketoximes having insecticidal, mi'ticidal, and, in some cases, nematocidal activity comparable or superior to the most closely related commercial products while having significantly lower toxicity toward mam mals than these commercial products.
  • Ketoxime compounds of Formulas (l) and (II) below were virtually inactive when compared with the aldoxime derivative Ketoxime compounds of Formulas (l) and (II) below are reported in the reference as being essentially inactive compared to the aldoxime compound of Formula (Ill) below which is known commercially as aldicarb (Temik).
  • the compound of Formula (II) differs from the compound of Formula (Ill) only in that a methyl group has been substituted for the aldehydric hydrogen of Formula (Ill).
  • R -R hydrogen, lower alkyl, lower alkenyl. lower alkynyl, substituted lower alkyl, alkenyl, or alkynyl with the proviso that R and R may be connected to form a cycloaliphatic ring;
  • R R -R or X with the proviso that when R, and X are OR SR S(O)R,,, SO. ,R,,, or NR,,R,,, R and X may be connected to form a heterocyclic ring;
  • R -R hydrogen, lower alkyl, lower alkenyl, or
  • R hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, substituted aryl, carbamyl, substituted carbamyl, acyl, or substituted acyl with the proviso that the lower alkyl or alkenyyl groups may be further substituted with X;
  • R hydrogen or lower alkyl with the proviso that R R and N in the NR R group may form a heterocyclic ring.
  • lower alkyl radical means a radical having from one to about seven carbon atoms.
  • This invention specifically includes those carbamates of Formula (IV) where R and R are lower alkyl radicals such as methyl; R is either R or X; R and R are hydrogen; X is s( )nRg Where n O, 1, or 2; R is a lower alkyyl radical such as methyl; and R and R are individually hydrogen, a lower alkyl radical such as methyl or a lower alkenyl radical.
  • the oral toxicity of the compound of Formula (V), measured on albino rats and expressed as the LD was found to be 8.5 mgm/kg of body weight; the dermal toxicity, measured on albino rabbits, again expressed as the LD was 38.9 mgm/kg of body weight.
  • LD is a standard means of expressing toxicity and indicates the concentration required to kill 509'! of the test animals. In each case, the LD value is approximately eight times greater than the reported value for the carbamate derivative of the aldoxime compound of Formula (III).
  • a further object is to provide a method for producing these carbamates.
  • Another object is to provide pesticidal compositions containing these carbamates.
  • Still another object is to provide methods for combatting pests such as insects, mites, and nematodes using these carbamates. It is intended. however, that the detailed description and specific examples given herein do not limit this invention but merely indicate preferred embodiments thereof since various changes and modifications within the scope of this invention will become apparent to those skilled in the art.
  • Preferred compounds of Formula (IV) include carbamate derivatives of l-hydrocarbylthio(or l-azido)-2- alkanone oximes wherein the carbamate nitrogen can be substituted with zero, one, or two lower alkyl groups; the carbon atom (C substituted by the hydrocarbylthio(or azido) group is not further substituted; and the carbon atom (C not substituted by the hydrocarbylthio-(or azido) groups is preferably substituted with an alkyl group and is optimally completely alkylated to provide a maximum degree of branching on this carbon atom.
  • a second preferred group of Formula (IV) compounds include carbamate derivatives of lhydrocarbylthio(or l-azido)-2-alkanone oximes wherein the carbamate nitrogen can be substituted with zero, one, or two lower alkyl groups; the carbon atom (C substituted by the hydrocarbylthio(or azido) group is not further substituted; and the carbon atom (C is preferably substituted with a substituent of group X and is optimally further completely alkylated to provide a maximum degree of branching on this carbon atom.
  • these compounds include those wherein the sulfide linkage of the above compounds is replaced by an oxide linkage, a sulfinyl linkage or a sulfonyl linkage as, for example: l-methoxy-3,3-dimethyl-2-methylcarbamyloximinobutane; l-ethoxy-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(2-propenyloxy)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-methoxy-3-methyl-2-methylcarbamyloximinobutane; l-ethoxy-3-methyl-2-methylcarbamyloximinobutane; l-(2-propenyloxy)-3-methyl-2-methylcarbamyloximinobutane; l-methoxy-Z-methylcarbamyloximinobutane; l-ethoxy-2-methylcarbamyloximinobutane
  • X is N;;. l-azido-2-methylcarbamyloximinopropane; 1-azido-2-methylcarbamyloximinobutane; l-azido-2-methylcarbamyloximinopentane; l-azido-3-methyl-Z-methylcarbamyloximinobutane; l-azido-3-methyl-2-methylcarbamyloximinopentane; l-azido-4-methyl-2-methylcarbamyloximinopentane; l-azido-3,3-dimethyl-2-methylcarbamyloximinobutane; 1-azido-3,3-dimethyl-2-methylcarbamyloximinopentane; l-azido-3,3-dimethyl-2-methylcarbamyloximinohexane; l-azido-4,4'dimethyl-2-methylcarbamyloxi
  • R is X as, for example:
  • R is X as, for example:
  • the carbamate nitrogen of these compounds can be unsubstituted, as in the simple carbamates, or can be substituted with a single alkyl.
  • alkenyl or alkynyl substituent such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, allyl, propargyl, or the like, or can be substituted with two alkyl, alkenyl, or alkynyl groups, with the groups being the same or different, to give, for example, N,N-dimethylcarbamyloximes; N,N-diethylcarbamyloximes; N- methyl-N-ethylcarbamyloximes; N,N-di-npropylcarbamyloximes; N-methyl-N- propylcarbamyloximes; N,N-diallylcarbamyloximes; N,N,N-dimethylcarbamyloximes; N,
  • ketoxime derivatives of this invention may exist in two geometric forms, the syn and the anti, representing the cis and trans isomers around the oxime double 9 10 bond. Both isomers and their mixtures are intended to dimethylaniline. Reaction is carried out from about be included in the scope of this invention. -30 C to about 100 C, preferably at from about C These compounds can be prepared by one of several to about 50 C. The resulting reaction mixture, a solumethods.
  • One method involves reaction of an isocyation of the chloroformate in an inert organic solvent, nate with an oxime, as shown, for example, in the equacan be filtered or washed with water to remove amine tion: I hydrochloride before it is used in the reaction shown in RNOHR R noisyi a I t a I1 S I R I-C--( 1-X R NC0 R -C-C C-X R I R5 R3 R5 wherein R through R,; and X are as defined above.
  • the Equation (2) The Equation (2).
  • an amine is solvent from about 0 C to about 150 C, preferably added to the chloroformate solution in the presence of from about 20C to about 80C, and at a pressure from i an amine solvent such as water, at temperatures beabout 1 to about atmospheres, preferably from tween about 40 C and about 80 C, preferably at about 1 to about 3 atmospheres.
  • Reaction pressure is about 0 C to about 40 C. A larger than molar excess determined by reaction temperature, concentration of amine can be used so that the amine acts both as reand vapor pressure of the isocyanate.
  • Liquid or solid carbamates produced by the above include aliphatic and aromatic hydrocarbons, such as methods can be recovered from reaction mixtures by hexane, heptane, octane, benzene, toluene, xylene; conventional means.
  • they can be recovethers such as diethyl ether, dipropyl ether, ethyl proered by removal of solvent and excess amine or isocyapyl ethere; esters such as ethyl acetate, ethyl propionate by vacuum distillation.
  • esters such as ethyl acetate, ethyl propionate by vacuum distillation.
  • ketones such as acetone, methyl ethyl ketone
  • they can be further puchlorinated hydrocarbons such as methylene chloride, rified, if desired, by recrystallization, distillation, abperchloroethylene, and the like. sorption chromatography, or other known procedures.
  • Ketoxime intermediate useful in this invention can be from about 0.1 to about 1.0% by weight, based on the prepared by well known procedures such as reaction of weight of reactants, of a tertiary amine catalyst such as the ketone with hydroxylamine in aqueous ethanol.
  • a tertiary amine catalyst such as the ketone with hydroxylamine in aqueous ethanol.
  • drocarbyloxy or thio ketones can be prepared by reac-
  • the molar ratio of isocyanate to oxime can vary from tion of the haloketones with mercaptans or alcohols in about 0.111 to about 10:1.
  • reaction times can vary pared by oxidizing the appropriate sulfide linked comfrom a few minutes to several days.
  • reaction pound with sodium metaperiodate or acidic hydrogen times of from about one-half to about six hours are sufperoxide, respectively. ficient.
  • the compounds of this invention can be ap- A second method for preparing these compounds inplied in undiluted form to the plant or other material volves reaction of an oxime with phosgene to obtain an being treated, it is usually desirable to apply these comoxime chloroformate which is then reacted with an pounds in admixture with either solid or liquid inert, amine.
  • This method is illustrated in Equations (1) and pesticidal adjuvants.
  • the compounds can (2) below: be applied to plants for pesticidal purposes by spraying 9 1 1 I YOH 13 I'M l lOCC1 R (1) R ICC !--X coc1 R2--e--c :--x
  • ceptor such as a tertiary amine, e.g., N,N- toluene,xylene, kerosene,diesel oil, fuel oil, hydrocarbons, and naphthas; ketones such as acetone, methyl ethyl ketone and cyclohexanone; chlorinated hydrocarbons such as trichlorethylene, perchloroethylene; esters such as ethyl acetate, amyl acetate and butyl acetate; ethers of ethylene glycol such as the monomethyl and monoalkyl ethers of diethylene glycol, the monoethyl ether of propylene glycol; alcohols such as ethanol, isopropanol, pentanols, and the like.
  • a tertiary amine e.g., N,N- toluene,xylene, kerosene,diesel oil, fuel oil, hydrocarbons, and naphth
  • These compounds can also be applied to plants and other materials in conjunction with inert solid adjuvants or carriers such as talc, pyrophyllite, attapulgite, chalk, diatomaceous earth, koalinite, montmorillonite, other silicates, silica, lime, calcium carbonate, certain organic carriers such as walnut shell flour, wood flour, ground corn cobs, and the like.
  • inert solid adjuvants or carriers such as talc, pyrophyllite, attapulgite, chalk, diatomaceous earth, koalinite, montmorillonite, other silicates, silica, lime, calcium carbonate, certain organic carriers such as walnut shell flour, wood flour, ground corn cobs, and the like.
  • a surfactant a surface active agent
  • An anionic, nonionic or cationic surfactant can be used in the formulation of either solid or liquid compositions.
  • Typical surfactants include alkyl sulfonates, alkylaryl sulfonates.
  • Solid and liquid formulations can be prepared by any suitable method. Solid active ingredients, in finely divided form, can be tumbled together with a finely divided solid carrier. Alternatively, the active ingredient in liquid forms such as solutions, dispersions, emulsions or suspensions, can be admixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust compositions.
  • the formulation be in the form of a finely divided powder or dust sufficiently fine that substantially all of the solids will pass through a Tyler sieve having a mesh size between about 20 and about 200.
  • the active ingredient can be present in an amount of 5 to 50% of the total weight. However, concentrations outside this range are operative and compositions containing from 1 to 99% of active ingredient by weight are contemplated wherein the remainder is carrier and/or any other desired additive or adjuvant. It may be advantageous to add a small amount of surfactant, e.g., 0.5 to 1% by weight based on the total weight of the dust formulation.
  • the active ingredient may be dissolved or dispersed in a liquid carrier, such as water or other suitable liquid.
  • a liquid carrier such as water or other suitable liquid.
  • the active ingredient can be added in the form of a solution, suspension, dispersion or cmulsion in aqueous or nonaqueous medium. Desirably, 0.5 to 1.0% by weight of surfactant is present in the liquid composition.
  • any desired quantity of surfactant may be employed, such as up to 250% by weight of the active ingredient. If the surfactant is used only to impart wetting qualities to a spray solution, as little as 0.05% or less, by weight of the surfactant need be used. Larger quantities of surfactant are used because of biological behavior of the surfactant rather than its wetting properties. These considerations are particularly important in the treatment of plants.
  • active ingredient in liquid formulations often may not be more than 30% by weight of the total and may be 10% by weight of even as low as 0.01% by weight.
  • pesticidal granules include elimination of water during application, reduction of drift, penetration through vegetative coverage, easy handling, storage, and increased safety to handlers of the pesticides.
  • Useful granule base materials include attapulgite, montmorillonite, corn cobs, walnut shells, and expanded vermiculites. Depending on their physical properties, the pesticides are either directly sprayed on the preformed granular base or are dissolved in a suitable solvent and then sprayed onto the granular base after which the solvent is removed by evaporation.
  • Granule base materials are usually 60 to 14 US. sieve size particles, although other size particles may also be used.
  • pesticide and pesticidal as used herein are intended to refer to the killing and/or control of insects, mites, nematodes, or the like. It will be appreciated that applications commonly referred to as insecticidal, miticidal, nematocidal, or the like are contemplated in the employment of these terms.
  • EXAMPLE 6 1-Bromo-3,3-dimethyl-2-butanone oxime (Compound A solution of 69.5 g 1.0 m) of hydroxylamine hydrochloride in 100 ml of water is chilled in an ice bath as 90 g (0.5 m) of l-bromo-3,3-dimethyl-2-butanone is added. After addition of 100 ml of 95% ethanol, the mixture is stirred for 16 hours and allowed to warm to room temperature. The resulting white slurry is filtered, and the solid is washed with water and dried to give 55 g of the desired compound, in. 1 1 1-1 12 C.
  • EXAMPLE 8 3,3-Dimethyl-2-methylcarbamyloximinol -methylsulfinylbutane (Compound 7804)
  • a stirred mixture of 9.0 g (0.042 m) of sodium metaperiodate in 60 ml of water and 25 ml of methanol is cooled to 0 C as 8.7 g (0.04 m) of 3,3-dimethyl-2- methylcarbamyloximino-l-methylthiobutane is added in portions.
  • the mixture is allowed to warm to room temperature and stripped of volatiles on a rotary evaporator to give a residue which is extracted with ethyl acetate. The dried extrace is stripped to leave 9 g (96%) of viscous yellow oil, the desired compound.
  • This compound (7 g, 0.044 m) and 18 g (0.26 m) of hydroxylamine hydrochloride in ml of absolute ethanol containing 30 ml of pyridine are heated under reflux for 120 hours. Pouring the clear solution into ice water gives a solid which is collected and dried. This white solid, m. 128-129 C, is the desired compound, 2,Z-dimethyl-4-methylthio-3-pentanone oxime.
  • EXAMPLE 1 4,4-Dimethyl-3-methylcarbamyloximino-l-methylthiopentane (Compound 81 l l)
  • a solution of sodium thiomethoxide prepared from 5.8 g (0.25 gram atom) of sodium, 135 g (0.28 m) of methanethiol, and 170 ml of absolute ethanol, is treated with 36.6 g (0.25 m) of l-chloro-4,4-dimethyl- 3-pentanone at 3 to 8 C over 30 minutes. After being heated at 4045 C for 45 minutes, the mixture is filtered and distilled to give 12 g of colorless liquid, b. 73 C/2 mm, n 1.4623.
  • Methylcarbamyloximinol-( l-methylcyclohexyl)-2- methylthioethane (Compound 8179) 1 Methylthioacetyl 1 -methylcyclohexane is prepared by treating a solution of sodium thiomethoxide [from 3 g (013 gram atom) of sodium, 6.7 g (0.14 m) of methanethiol, and ml of absolute ethanol] with 22.5 g (0.13 m) of l-chloroacetyl-lmethylcyclohexane over 20 minutes at 4-9 C. After being heated at 4045" C for 1 hour, the reaction mixture is filtered and distilled to give 7 g of colorless liquid, b. 8687 C/0.8 mm, n 1.4954.
  • This ketone is converted to the oxime by heating a solution of5 g (0.027 m) of ketone, 3.8 g (0.054 m) of hydroxylamine hydrochloride, and 3 g (0.027 m) of anhydrous sodium carbonate in 30 ml of 95% ethanol and 26 ml of water for 95 hours. The resulting solution is stripped of volatiles, to give a two-layer liquid residue, which is extracted with ethyl acetate. The organic layer is dried, filtered, and stripped to give 3.4 g of amber liquid, n 1.5164.
  • EXAMPLE l3 1-( l-Adamantyl)- 1 -methylcarbamyloximino-2- methylthioethane (Compound 8191 A solution of 4 g (0.018 m) of l-methylthioacetyladamantane, 2.5 g (0.036 m) of hydroxylamine hydrochloride, and 1.9 g (0.018 m) of anhydrous sodium carbonate in 20 m1 of 95% ethanol and 18 ml of water is heated under reflux for 29 hours. Stripping of volatiles gives a slurry which is filtered to obtain 4.2 g of white solid oxime, m. l00-l03 C.
  • EXAMPLE 14 l-Chloro-4,4-dimethyl-2-methylcarbamyloximinopentane (Compound 8108) To a chilled, stirred mixture of 20.2 g (0.29 m) of hydroxylamine hydrochloride in 30 ml of water is added 21.5 g (0.145 m) of l-chloro-4,4-dimethyl-2- pentanone followed by 30 ml of 95% ethanol. The cooled mixture is stirred for six hours, allowed to stand overnight, and stripped of volatiles to obtain a residue which extracted with ethyl acetate. This extract is dried, stripped, and distilled to yield a colorless liquid, b. 76-77 C/l.3 mm, 11, 1.4672. which is the desired oxime.
  • thio 2 bumnone is dried over magnesium sulfate, filtered, and stripped 7860 1-ethy1thi0-3.3-dimethyl-2-butanone c 7900 l-methylthio-Z-butanone of YOldIllfiSjO give 6.7 g (63 /c) of amber. viscous liquid 7909 lldimethYlLmethyhhioamemnone resldue, "n 7965 4,4-dimethyl-l methylthio-3-pentanone Calcd.
  • the compounds are evaluated for biological activity against the following representative pests: Mexican bean bettle (Epilaclina varivestis), Southern army worm (Prodenia eridania), housefly (Musca domestica), bean aphid (Aphisfabue). and red spider mite (Terranyclms s1). The last two pests are treated both by contact and systemic application.
  • Example 2 Contact Activity Systemic Activity
  • the spray and systemic application methods described in Example are used to apply the test formulations to the infested plants and soil. After three days, two of the four leaves treated are examined and mortal- Bean Aphid Spray and Systemic Test This test determines the insecticidal activity of the compound being tested against the bean aphid Aphisfabae.
  • Stock formulations containing 500 ppm of each test chemical are prepared using 0.05 g of the test chemical (or 0.05 ml if a liquid), 4.0 ml acetone containing 0.25% (V/V) Triton X-l55, and 96.0 ml deionized water and are used in both soil drench and spray treatments.
  • the stock formulations are diluted to obtain the appropriate lower concentrations maintaining the concentration level of all adjuvants.
  • the bean aphid is cultured on nasturtium plants (var. Tall Single), no attempt being made to select insects of a given age in these tests.
  • Single nasturtium test plants growing in soil in individual 2% inch fiber pots are then infested with populations of 100 to 200 aphids.
  • EXAMPLE 16 Red Spider Mite Sptay and Systemic Test ity is determined. Should a compound be an effective miticide, the other two leaves are available to obtain information on the residual activity of the formulation. Results of this test are shown in Table 7 as M (mite contact spray test) and MS (mite systemic soil drench test).
  • EXAMPLE l7 Housefly Spray Test This test determines the insecticidal activity of the compound being tested against adult houseflies, Musca domestica. Stock formulations containing 500 ppm of each test chemical are prepared using the procedure described in Example 15 and are diluted to obtain the appropriate lower concentrations.
  • Ten adult flies are placed in a cylindrical screen cage 1%. by 4 inches fabricated from 20-mesh stainless steel screening and are sprayed with 50 ml of the stock or diluted formulation.
  • the flies are suplied food and drink from a dextrose solution by draping a paper wick over the outside of the screen cylinder and are able to feed and drink ad libitum.
  • Percent mortality obtained is determined three days after treatment. Results of this test are shown in Table 7 as HF (housefly spray test).
  • EXAMPLE is Southern Army Worm Spray Test Paired fully expanded primary leaves excited from I Scarlet runner bean plants are maintained in plastic tubes containing water and sprayed with the test formulation prepared as described in ExamplelS. After the spray deposit on the leaves is dry, the paired leaves are separated. One leaf is placed onto 1.5 percent water agar and infested with 10 newly hatched Southern army worm larvae. The covered test receptacle is held at 72.
  • EXAMPLE 19 e Mexican Bean Beetle Leaf Spray'Test This test determines the insecticidal activity of the compound being tested against the Mexican bean beetle (Epilaclzna rarirestis). The test procedure is the same as that described for the Southern army worm in Example 18 with the exception that one-day old larvae of the Mexican bean beetle instead of newly hatched Southern army worm larvae are used.
  • EXAMPLE 20 Systemic Test of Compound 7268 against Lygus Bug and Spotted Cucumber Beetle The techniques used are essentiallythesame for the systemic tests described above in Example-l 5.
  • the test compound is Compound 7268.
  • One plant is used for each test species. The checks showed no mortality during the tests.
  • test organism is a strain of Southern corn rootworm (Diabrotica undecimpunctala howardi) resistant to chlorinated hydrocarbon insecticides and the test compound is Compound 7268.
  • Duplicate samples of sand-soil mixtures are treated with appropriate volumes of test formulation to give the desired dosages.
  • the sand-soil samples are in covered paper cups, and several hours after drenching, all cups are given a thorough shaking to-provide complete and uniform mixing of the chemical throughout the soil.
  • One day after treatment two corn seedlings and five rootworms are placed into each cup and the lids replaced. Five days later, mortality is determined. The results are given below:
  • test plants are cucumber seedlings; the test compound is Compound 7268; and the pest is the melon aphid (Aplzis gosyppi).
  • Root-knot Nematocide Test This test is an evaluation of the effectiveness of the compound being tested against infection by root-knot nematodes (Meloidogyne spp.
  • Composted greenhouse soil diluted by one-third with clean washed sand. is infested with about two grams of knotted or galled tomato roots per pot. Treatment is accomplished by applying 25 ml of the formulated compound onto the infested soil.
  • the test formulation contains 0.056 g of Compound 7960, 1.0 ml stock emulsifier solution (0.25% Triton X-l55 in acetone by volume), and 24.0 ml deionized water, giving a concentration of 2240 ppm. Lower concentrations are achieved by dilution.
  • R is hydrogen or lower alkyl
  • b. R; R is lower alkyl with the proviso that R and R may be connected to form a cycloalkyl ring of 90 not more than 6 carbon atoms;
  • R R is hydrogen, lower alkyl or lower alkenyl
  • X is SR S(O)R or 50 R and,
  • R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, or aryl
  • composition of matter of claim 1 selected from the group consisting of:
  • composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximino-l-methylthiobutane.
  • composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol-methylsulfinylbutane.
  • composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol -methylthiopentane.
  • composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol -methylsulfonylbutane.

Abstract

Carbamate derivatives of ketoximes are useful in combatting pests such as insects, mites, and nematodes.

Description

O United States Patent 1191 1111 3,875 ,232 Magee Apr. 1, 1975 AC KETOXIME CARBAMATES [58] Field of Search 260/566 AC 75 I t: Th A.M M t .Oh' nven or omas agee, en or 10 e ces Cited [73] Assignee: Diamond Shamrock Corporation, UNITED STATES PATENTS Cleveland, Ohio 3,217,037 11/1965 Payne et a1 260/566 AC [22] Filed: Feb. 24, 1972 3,400,153 9/1968 Payne et 21].... 260/566 AC 3,454,642 7/1969 Friedman 1. 260/566 AC [21] 229,207 3,647,861 3/1972 Buchanan 260/566 AC x Rehted Application Data 3,681,386 8/1972 Fridinger et a1 260/566 AC X [63] Continuation-impart of Scr. No. 132,584, April 8, R N PA ENTS OR APPLICATIONS 1971, abandoned. 1,090,986 11/1967 United Kingdom [52] U.S. Cl 260/566, 260/244, 260/256.4 R, Primary Examiner Leon Zitver 260/343 R, 260/349, 260/454, 260/456 A, 260/463, 260/465.4, 260/482 R, 260/566 A, 424/244, 424/246, 424/248, 424/251, 424/272, 424/273, 424/275, 424/276, 424/278, 424/300, 424/302, 424/303, 424/304, 424/311, 424/327 Int. Cl. C07c 131/00 Assistant Examine'rGera1d A. Schwartz Attorney, Agent, 0r'FirmJohn C. Tiernan; L. G. Nunn [57] ABSTRACT Carbamate derivatives of ketoximes are useful in com batting pests such as insects, mites, and nematodes.
6 Claims, No Drawings 1 AC KETOXIME CARBAMATES CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of copending application. Ser. No. l32,584, Thomas A. Magee, filed Apr. 8, 1971 now abandoned.
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to organic compounds useful as pesticides and more particularly to carbamate derivatives of ketoximes having insecticidal, mi'ticidal, and, in some cases, nematocidal activity comparable or superior to the most closely related commercial products while having significantly lower toxicity toward mam mals than these commercial products.
2. Description of the Prior Art The outstanding pesticidal activity of the carbamate derivatives of the ketoximes disclosed in this invention is surprising and unexpected because the prior art indicates that carbamate derivatives only of substituted aldoximes have high pesticidal activity, whereas ketoxime derivatives were essentially inactive. For example, U.S. Pat. No. 3,217,037 and US. Pat. No. 3,507,965 show compounds, possessing pesticidal activity, of the structure:
wherein X O or S(O) when n 0, l, or 2 and the free valances are satisfied by hydrogen or hydrocarbyl radicals. In these two patents, the preferred compounds are aldoximes wherein the carbon atom (C attached to the oxime moiety in the above structure is substituted with hydrogen. In the J. Agr. Food Chem., 14, 356 1966), the patentees of these patents state, The data... demonstrate...the detrimental effect...of replacing the aldehydic hydrogen with an alkyl group. All of the ketoxime derivatives... were virtually inactive when compared with the aldoxime derivative Ketoxime compounds of Formulas (l) and (II) below are reported in the reference as being essentially inactive compared to the aldoxime compound of Formula (Ill) below which is known commercially as aldicarb (Temik). The compound of Formula (II) differs from the compound of Formula (Ill) only in that a methyl group has been substituted for the aldehydric hydrogen of Formula (Ill).
0 ll ens QIOCIM'HCIL- cm, s-g-c-ca clh m EOCIHKCEL; cm, s-e --0H The ketoxime derivatives of Formulas (l) and (II) have been resynthesized and tested and their reported lack of activity relative to that of the compound of Formula (lll) reconfirmed. Surprisingly, however, the ketoxime derivatives of the present invention have been found to possess high pesticidal activity, comparable or superior to that of the compound of Formula (Ill).
SUMMARY OF THE INVENTION The carbamates of ketoximes of the present invention can be represented by the formula:
R -R hydrogen, lower alkyl, lower alkenyl. lower alkynyl, substituted lower alkyl, alkenyl, or alkynyl with the proviso that R and R may be connected to form a cycloaliphatic ring;
R R -R or X with the proviso that when R, and X are OR SR S(O)R,,, SO. ,R,,, or NR,,R,,, R and X may be connected to form a heterocyclic ring;
R -R hydrogen, lower alkyl, lower alkenyl, or
lower alkynyl;
X SR S(O)R,,, SO R,,, OR OSO R NR R N0 CN, SCN, N or halogen;
R hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, substituted aryl, carbamyl, substituted carbamyl, acyl, or substituted acyl with the proviso that the lower alkyl or alkenyyl groups may be further substituted with X; and
R hydrogen or lower alkyl with the proviso that R R and N in the NR R group may form a heterocyclic ring.
The term lower alkyl radical means a radical having from one to about seven carbon atoms.
This invention specifically includes those carbamates of Formula (IV) where R and R are lower alkyl radicals such as methyl; R is either R or X; R and R are hydrogen; X is s( )nRg Where n O, 1, or 2; R is a lower alkyyl radical such as methyl; and R and R are individually hydrogen, a lower alkyl radical such as methyl or a lower alkenyl radical.
It is completely unexpected to discover that carbamate derivatives of ketoximes such as the carbamate of Formula (V) have pesticidal activity comparable to that of the carbamate derivative of the aldoxime of Formula (Ill):
0 sa oiimica CH3 -('1-C-CH2SCH3 and simultaneously exhibit significantly lower toxicity toward mannals than does the compound of Formula (Ill). Thus, the oral toxicity of the compound of Formula (V), measured on albino rats and expressed as the LD was found to be 8.5 mgm/kg of body weight; the dermal toxicity, measured on albino rabbits, again expressed as the LD was 38.9 mgm/kg of body weight. LD is a standard means of expressing toxicity and indicates the concentration required to kill 509'! of the test animals. In each case, the LD value is approximately eight times greater than the reported value for the carbamate derivative of the aldoxime compound of Formula (III).
It is an object of this invention to provide carbamates of substituted ketoximes, which are useful pesticides. A further object is to provide a method for producing these carbamates. Another object is to provide pesticidal compositions containing these carbamates. Still another object is to provide methods for combatting pests such as insects, mites, and nematodes using these carbamates. It is intended. however, that the detailed description and specific examples given herein do not limit this invention but merely indicate preferred embodiments thereof since various changes and modifications within the scope of this invention will become apparent to those skilled in the art.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred compounds of Formula (IV) include carbamate derivatives of l-hydrocarbylthio(or l-azido)-2- alkanone oximes wherein the carbamate nitrogen can be substituted with zero, one, or two lower alkyl groups; the carbon atom (C substituted by the hydrocarbylthio(or azido) group is not further substituted; and the carbon atom (C not substituted by the hydrocarbylthio-(or azido) groups is preferably substituted with an alkyl group and is optimally completely alkylated to provide a maximum degree of branching on this carbon atom.
A second preferred group of Formula (IV) compounds include carbamate derivatives of lhydrocarbylthio(or l-azido)-2-alkanone oximes wherein the carbamate nitrogen can be substituted with zero, one, or two lower alkyl groups; the carbon atom (C substituted by the hydrocarbylthio(or azido) group is not further substituted; and the carbon atom (C is preferably substituted with a substituent of group X and is optimally further completely alkylated to provide a maximum degree of branching on this carbon atom.
These compounds exhibit extremely high activity as insecticides and miticides, both as contact and as systemic toxicants. In some cases, they show high nematocidal activity.
As specific examples of these compounds, there may be mentioned l-hydrocarbylthio-3,3-dimethyl-2 methylcarbamylouminobutanes such as: l-methylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-ethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-n-propylthio-3,3-dimethyI-Z-methylcarbamyloximinobutane; l-isopropylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-n-butylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-tert.-butylthio-3,3-dimethyl-Z-methylcarbamyloximinobutane; l-sec.-butylthio-3,3-dimethyl-2methylcarbamyloximinobutane;
4 l-isobutylthio3 ,3-dimethyl-2-methylcarbamyloximinobutane; l-vinylthio-3,3-dimethyl'2-methylcarbamyloximinobutane; l-(Z-propenylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane; l(3-butenylthio)-3,3-dimethyl-Z-methylcarbamyloximinobutane; l-ethynylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-phenylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; l-benzylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; and the like; also the analogous l-hydrocarbylthio-3-methyl-2- methylcarbamyloximinobutanes such as: l-methylthio-3-methyl-2-methylcarbamyloximinobutane; l-ethylthio-3-methyl-2-methylcarbamyloximinobutane; l-n-propylthio-3-methyl-Z-methylcarbamyloximinobutane; l-isopropylthio-3-methyl'2-methylcarbamyloximinobutane; l-n-butylthio-3-methyl-2-methylcarbamyloximinobutane; 1-tert.-butylthio-3-methyl-2-methylcarbamyloximinobutane; l-sec.-butylthio-3-methyl-2-methylcarbamyloximinobutane; l-isobutylthio-3-methyl-2-methylcarbamyloximinobutane; l-vinylthio-3-methyl-2-methylcarbamyloximinobutane; l-(2-propenylthio)-3-methyl-Z-methylcarbamyloximinobutane; l-( 3-butenylthio )-3-methyl-2-methylcarbamyloximinobutane; l-ethynylthio-3-methyl-Z-methylcarbamyloximinobutane; 1-phenylthio-3-methyl-Z-methyIcarbamyloximinobutane; l-benzylthio-3-methyl-2-methylcarbamyloximinobutane; and the like; as well as analogous l-hydrocarbylthio-Z-methylcarbamyloximinobutanes such as: l-methylthio-2-methylcarbamyloximinobutane; 1-ethylthio-2-methylcarbamyloximinobutane; 1-n-propylthio-2-methylcarbamyloximinobutane; 1-isopropylthio-2-methylcarbamyloximinobutane; 1-n-butylthio-2-methylcarbamyloximinobutane; l-tert.-butylthio-2-methylcarbamyloximinobutane; l-sec.-butylthio-Z-methylcarbamyloximinobutane; l-isobutylthio-2-methylcarbamyloximinobutane; l-vinylthio-2-methylcarbamyloximinobutane; l-( 2-propenylthio )-2-methylcarbamyloximinobutane; l-( 3-butenylthio )-2-methylcarbamyloximinobutane; l-ethynylthio-2-methylcarbamyloximinobutane; l-phenylthio-Z-methylcarbamyloximinobutane; l-benzylthio-2-methylcarbamyloximinobutane; and the like; as well as analogous l-hydrocarbylthio-Z-methylcarbamyloximinopropanes such as: l-methylthio-2-methylcarbamyloximinopropane; l-ethylthio-2-methylcarbamyloximinopropane; l-n-propylthio-2-methylcarbamyloximinopropane; l-isopropylthio-Z-methylcarbamyloximinopropane;
1-n-butylthio-2-methylcarbamyloximinopropane; 1-tert.-butylthio-2-methylcarbamyloximinopropane; l-sec.-butylthio-2-methylcarbamyloximinopropane; l-isobutylthio-Z-methylcarbamyloximinopropane; l-vinylthio-2-methylcarbamyloximinopropane; l-(2-propenylthi0)-2-methylcarbamyloximinopropane; l-(3-butenylthio)-2-methylcarbamyloximinopropane; l-ethynylthio-2-methylcarbamyloximinopropane; l-phenylthio-2-methylcarbamyloximinopropane; l-benzylthio-2-methylcarbamyloximinopropane;
the like; as well as carbamates of oximes of other straight or branched methyl-alkyl ketones where the methyl group is substituted with a hydrocarbylthio group such as: l-methylthio-2-methylcarbamyloximinopentane; l-methylthio-2-methylcarbamyloximinohexane; l-methylthio-4,4-dimethyl-2-methylcarbamyloximinopentane; l-methylthio-3,3-dimethylZ-methylcarbamyloximinopentane; l-methylthio-3,3-dimethyl-2-methylcarbamyloximinohexane; and the like.
Further examples of these compounds include those wherein the sulfide linkage of the above compounds is replaced by an oxide linkage, a sulfinyl linkage or a sulfonyl linkage as, for example: l-methoxy-3,3-dimethyl-2-methylcarbamyloximinobutane; l-ethoxy-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(2-propenyloxy)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-methoxy-3-methyl-2-methylcarbamyloximinobutane; l-ethoxy-3-methyl-2-methylcarbamyloximinobutane; l-(2-propenyloxy)-3-methyl-2-methylcarbamyloximinobutane; l-methoxy-Z-methylcarbamyloximinobutane; l-ethoxy-2-methylcarbamyloximinobutane; l-(2-propenyloxy)-2-methylcarbamyloximinobutane; l-methoxy-Z-methylcarbamyloximinopropane; l-ethoxy-2-methylcarbamyloximinopropane; l-(2-propenyloxy)-2-methylcarbamyloximinopropane; and: l-methylsulfinyl-3,3-dimethyl-2-methylcarbamyloximinobutane; l-ethylsulfinyl-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(2-propenylsulfinyl)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-methylsulfinyl-3-methyl-Z-methylcarbamyloximinobutane; l-ethylsulfinyl-3-methyl-2-methylc2irbamyloximinobutane; 1-(2-propenylsulfinyl)-3-methyI-Z-methylcarbamyloximinobutane; l-methylsulfinyl-2-methylcarbamyloximinobutane; l-ethylsulfinyl-2-methylcarbamyloximinobutane; l-(2-propenylsulfinyl)-2-methylcarbamyloximinobutane; l-methylsulfinyl-Z-methylcarbamyloximinopropane; l-ethylsulfinyI-Z-methylcarbamyloximinopropane; 1-( 2-propenylsulfinyl )-2-methylcarbamyloximinopropane; and: 1-methylsulfonyl-3,3-dimethyl-2-methylcarbamyloximinobutane;
and
l-ethylsulfonyl-3 ,3-dimethyl-2-methylcarbamyloximinobutane;
l-(2-propenylsulfonyl)-3,3-dimethyl-2-methylcarbamyloximinobutane;
l-methylsulfonyl-3-methyI-Z-methylcarbamyloximinobutane;
1-ethylsulfonyl-3-methyl-2-methylcarbamyloximinobutane;
1-( 2-propenylsulfonyl )-3-methyl-2-methylcarbamyloximinobutane;
l-methylsulfonyl-2-methylcarbamyloximinobutane;
l-ethylsulfonyl-2-methylcarbamyloximinobutane;
l-(2-propenylsulfonyl)-2-methylcarbamyloximinobutane;
1-methylsulfonyl-2-methylcarbamyloximinopropane;
l-ethylsulfonyl-2-methylcarbamyloximinopropane;
l-( Z-propenylsulfonyl Z-methylcarbamyloximinopropane;
and the like.
Further examples of these compounds include those wherein X is N;;. l-azido-2-methylcarbamyloximinopropane; 1-azido-2-methylcarbamyloximinobutane; l-azido-2-methylcarbamyloximinopentane; l-azido-3-methyl-Z-methylcarbamyloximinobutane; l-azido-3-methyl-2-methylcarbamyloximinopentane; l-azido-4-methyl-2-methylcarbamyloximinopentane; l-azido-3,3-dimethyl-2-methylcarbamyloximinobutane; 1-azido-3,3-dimethyl-2-methylcarbamyloximinopentane; l-azido-3,3-dimethyl-2-methylcarbamyloximinohexane; l-azido-4,4'dimethyl-2-methylcarbamyloximinopentane; and the like.
Additional examples of these compounds include those wherein two memebers of the group R,, R and R are joined together to form a ring as, for example:
l-cyclopropyll -methylcarbamyloximinc-2- methylthioethane;
l-methylcarbamyloximino-1-( l-methylcyclopropyl)-2- methylthioethane;
Z-azidol -methylcarbamyloximinol l-methylcyclopr0pyl)ethane;
l-cyclobutyll -methylcarbamyloximino-Z- methylthioethane;
l-methylcarbamyloximino-1-( l-methylcyclobutyl)-2- methylthioethane;
2-azidol -methylcarbamyloximinol lmethylcyclobutyhethane;
l-cyclopentyl- 1 -methylcarbamyloximino-2- methylthioethane;
l-methylcarbamyloximinol l-methylcyclopentyl)-2- methylthioethane;
l-cyclohexyl-l-methylcarbamyloximino-2 methylthioethane;
l-methylcarbamyloximinol l-methylcyclohexyl)-2- methylthioethane;
2-azidol -methylcarbamyloximinol l-methylcy- .clohexyl)ethane; and the like;
as well as compounds wherein R is X as, for example:
1,3-bis(methylthio)-3-methyI-Z-methylcarbamyloximinobutane;
3-methyl-Z-methylcarbamyloximinol -methylthio-3 nitrobutane;
3-methoxy-3-methyl-2-methylcarbamyloximinol methylthiobutane;
7 3-cyano-3-methyl-Z-methylcarbamyloximino-lmethylthiobutane; l-azido-3-methyl-2-methylcarbamyloximino-3- methylthiobutane; l-azido-3-methoxy-3-methyl-2-methylcarbamyloximinobutane; 3-azido-3-methyl-2-methylcarbamyloximinol methylthiobutane; 3-azido-l-methoxy-3-methyl-2-methylcarbamyloximinobutane; 1-methoxy-3-methyl-2-methylcarbamyloximino-S- nitrobutane; l-methoxy-3-methyl-2-methylcarbamyloximino-3- methylthiobutane; 3-cyano-l-methoxy-3-methyl-2-methylcarbamyloximinobutane; l,3-bis( methoxy )-3-methyl-2-methylcarbamyloximinobutane; l,3-bis(cyano)-3-methyl-Z-methylcarbamyloximinobutane; l-cyano-3-methyl-2-methylcarbamyloximino-3- methylthiobutane; l-cyano-3-methoxy-B-methyl-2-methylcarbamyloximinobutnne; l-nitro-3-mcthyl-2-methylcarbamyloximino-3- methylthiobutane; l-nitro-3-methoxy-3-methyl-Z-methylcarbamyloximinobutane; 3-methyl-3-dimethylamino-2-methylcarbamyloximinol-methylthiobutane; l-methoxy-3-methyl-3-dimethylamino-Z-methylcarbamyloximinobutane; 3-methyll-dimethylamino-Z-methylcarbamyloximino- 3-methylthiobutane; 3-methoxy-3 -methyl- 1 -dimethylamino-2-methylcarbumyloximinobutane; and the like;
as well as compounds wherein R is X as, for example:
l,l-bis(methylthio)-3,3-dirriethyL2-methylcarbamyloximinobutane;
l, 1 -bis( methoxy )-3 ,3-dimethyl-2-methylcarbamyloximinobutane;
l-methoxy-3 ,3-dimethyl-2-methylcarbamyloximinol methylthiobutane;
l, l -ethylenedithio-3,3-dimethyl-Z-methylcarbamyloximinobutane;
3,3-dimethyl-2-methylcarbamyloximinol ,1-( 1,2-
propylenedithio)-butane;
3,3-dimethyl-2-methylcarbamyloximino-1,l-(1,3-
propylenedithio)-butane;
l,1-ethylenedioxy-3.3-dimethyl-2-methylcarbamyloximinobutane;
3 ,3-dimethyl-2-methylcarbamyloximinol l 1,2-
propylenedioxy)-butane;
3,3-dimethyl-2-methylcarbamyloximino-l,l-(1,3-
propylenedioxy)-butane;
2,2-dimethyll -methylcarbamyloximinol 1,3-
oxathiolan-Z-yl)-propane;
2,2-dimethyl-l-methylcarbamyloximino-l-(1,3-
oxathian-2-yl)-propane;
2,2-dimethyll -methylcarbamyloximinol 3-methyll,3-oxazolidin-2-yl)-propane;
2,2-dimethyl l -methylcarbamyloximinol 3- methyltetrahydro-l ,3-oxazin-2-yl)-propane;
2,2-dimethyll -methylcarbamyloximinol 1,3-
dimethylimidazolidin-Z-yl)propane;
2,2-dimethyl-l-methylcarbamyloximino-1-(1,3-
dimethylpyrimidin-Z-yl)propane;
2,2-dimethyll -methylcarbamyloximinol 3- methylthiazolidin-2-yl)propane; 2,2-dimethyl-l-methylcarbamyloximino-l-(3- methyltetrahydro-l.3-thiazin-2-yl)propane; and the like. Additional examples of these compounds include: 3,3-dimethyl-2-methylcarbamyloximinol 2- methylthioethylthio)-butane; l-(Z-ethylthioethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(2-methoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(Z-ethoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;
- 3,3-dimethyl-2-methylcarbamyloximino-l-(2- methylsulfinylethylthio)butane; 3,3-dimethyl-Z-methylcarbamyloximino-l-(2- methylsulfonylethylthio)butane; l-(Z-methoxyethoxy)-3,3-dimethyl-2-methylcarbamyloximinobutane; 3,3-dimethyl-2-methylcarbamyloximino-l-(2- methylthioethoxy)-butane; 3,3-dimethyl-Z-methylcarbamyloximino-l-(2- methylthiomethylthio)-butane; l-(2-methoxymethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-(Z-methoxymethoxy)-3,3-dimethyl-2-methylcarbamyloximinobutane; 3,3-dimethyl-2-methylcarbamyloximino-l-(3,3,3-
trifluoropropylthio)butane; l-(3,3,3-trichloropropylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane; l-'( 2-cyan oethylthio )-3 ,3-dimethyl-2-methylcarbamyloximinobutane; 3,3-dimethyl-l-(Z-dimethylaminoethylthio)-2-methylcarbamyloximinobutane; 3,3-dimethyl-2-methylcarbamyloximino-l-(2- phenethylthio)butane; 3,3-dimethyl-Z-methylcarbamyloximino-l-(2-(2'- thenyl)ethylthio)-butane; 3 ,3-dimethyl-2-methylcarbamyloximinol -propargylthiobutane; I l-cyano-3 ,3-dimethyl-2-methylcarbamyloximinobutane;
3 ,3-dimethyl-2-methylcarbamyloximinol -nitrobutane;
and the like.
Although the above compounds are, for purpose of illustration, N-methylcarbamates, the carbamate nitrogen of these compounds can be unsubstituted, as in the simple carbamates, or can be substituted with a single alkyl. alkenyl or alkynyl substituent such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, allyl, propargyl, or the like, or can be substituted with two alkyl, alkenyl, or alkynyl groups, with the groups being the same or different, to give, for example, N,N-dimethylcarbamyloximes; N,N-diethylcarbamyloximes; N- methyl-N-ethylcarbamyloximes; N,N-di-npropylcarbamyloximes; N-methyl-N- propylcarbamyloximes; N,N-diallylcarbamyloximes; N,N-dipropargyloximes; N-methyl-N- allylcarbamyloximes; N-methyl-N-propargylcarbamyloximes; and the like.
It will be appreciated by those skilled in the art that the ketoxime derivatives of this invention may exist in two geometric forms, the syn and the anti, representing the cis and trans isomers around the oxime double 9 10 bond. Both isomers and their mixtures are intended to dimethylaniline. Reaction is carried out from about be included in the scope of this invention. -30 C to about 100 C, preferably at from about C These compounds can be prepared by one of several to about 50 C. The resulting reaction mixture, a solumethods. One method involves reaction of an isocyation of the chloroformate in an inert organic solvent, nate with an oxime, as shown, for example, in the equacan be filtered or washed with water to remove amine tion: I hydrochloride before it is used in the reaction shown in RNOHR R Noii a I t a I1 S I R I-C--( 1-X R NC0 R -C-C C-X R I R5 R3 R5 wherein R through R,; and X are as defined above. The Equation (2).
oxime and isocyanate are reacted in an inert organic In the reaction shown in Equation (2), an amine is solvent from about 0 C to about 150 C, preferably added to the chloroformate solution in the presence of from about 20C to about 80C, and at a pressure from i an amine solvent such as water, at temperatures beabout 1 to about atmospheres, preferably from tween about 40 C and about 80 C, preferably at about 1 to about 3 atmospheres. Reaction pressure is about 0 C to about 40 C. A larger than molar excess determined by reaction temperature, concentration of amine can be used so that the amine acts both as reand vapor pressure of the isocyanate. actant and as HCl acceptor and complete conversion of Any inert organic solvent used in the reaction should chloroformate is obtained. Alternatively, a separate not contain hydroxy, amino or other groups which will HCl acceptor, such as a tertiary amine, can be used. react with the isocyanate function. Useful inert solvents Liquid or solid carbamates produced by the above include aliphatic and aromatic hydrocarbons, such as methods can be recovered from reaction mixtures by hexane, heptane, octane, benzene, toluene, xylene; conventional means. For example, they can be recovethers such as diethyl ether, dipropyl ether, ethyl proered by removal of solvent and excess amine or isocyapyl ethere; esters such as ethyl acetate, ethyl propionate by vacuum distillation. Although these products nate; ketones such as acetone, methyl ethyl ketone; and are obtained in very pure form, they can be further puchlorinated hydrocarbons such as methylene chloride, rified, if desired, by recrystallization, distillation, abperchloroethylene, and the like. sorption chromatography, or other known procedures. Preferably, reaction is carried out in the presence of Ketoxime intermediate useful in this invention can be from about 0.1 to about 1.0% by weight, based on the prepared by well known procedures such as reaction of weight of reactants, of a tertiary amine catalyst such as the ketone with hydroxylamine in aqueous ethanol. Hytriethyl amine, N,N-dimethylaniline, or the like. drocarbyloxy or thio ketones can be prepared by reac- The molar ratio of isocyanate to oxime can vary from tion of the haloketones with mercaptans or alcohols in about 0.111 to about 10:1. An equimolar amount or the presence ofan acid acceptor,e.g., sodium alkoxide. slight excess of isocyanate is preferred to ensure com- Sulfinyl and sulfonyl linked compounds can be preplete reaction of the oxime. Reaction times can vary pared by oxidizing the appropriate sulfide linked comfrom a few minutes to several days. Usually reaction pound with sodium metaperiodate or acidic hydrogen times of from about one-half to about six hours are sufperoxide, respectively. ficient. Although the compounds of this invention can be ap- A second method for preparing these compounds inplied in undiluted form to the plant or other material volves reaction of an oxime with phosgene to obtain an being treated, it is usually desirable to apply these comoxime chloroformate which is then reacted with an pounds in admixture with either solid or liquid inert, amine. This method is illustrated in Equations (1) and pesticidal adjuvants. For example, the compounds can (2) below: be applied to plants for pesticidal purposes by spraying 9 1 1 I YOH 13 I'M l lOCC1 R (1) R ICC !--X coc1 R2--e--c :--x
0 0 II II R R NOCCl R R NOCN R (2) R ':g--t':-x HN R --'c'--- x I I 7 2 I I R3 R5 R3 R5 wherein R through R, and X are as defined above. The the plants with aqueous or organic solvent dispersions method is carried out in two steps following the reacof the compounds. Choice of an appropriate solvent is tions shown in Equations (1) and (2). deteremined by factors such as concentration of active In the reaction shown in Equation (1), a solution of ingredient, the volatility required in the solvent, cost of the oxime dissolved in an inert solvent such as diethyl the solvent, and nature of the material being treated. ether, is added slowly to a solution of phosgene dis- Solvents, which can be employed as carriers for these solved in an inert solvent in the presenceof an HCl accompounds, include hydrocarbons such as benzene,
ceptor such as a tertiary amine, e.g., N,N- toluene,xylene, kerosene,diesel oil, fuel oil, hydrocarbons, and naphthas; ketones such as acetone, methyl ethyl ketone and cyclohexanone; chlorinated hydrocarbons such as trichlorethylene, perchloroethylene; esters such as ethyl acetate, amyl acetate and butyl acetate; ethers of ethylene glycol such as the monomethyl and monoalkyl ethers of diethylene glycol, the monoethyl ether of propylene glycol; alcohols such as ethanol, isopropanol, pentanols, and the like.
These compounds can also be applied to plants and other materials in conjunction with inert solid adjuvants or carriers such as talc, pyrophyllite, attapulgite, chalk, diatomaceous earth, koalinite, montmorillonite, other silicates, silica, lime, calcium carbonate, certain organic carriers such as walnut shell flour, wood flour, ground corn cobs, and the like.
It is often desirable to use a surfactant (a surface active agent) in pesticidal compositions. An anionic, nonionic or cationic surfactant can be used in the formulation of either solid or liquid compositions. Typical surfactants include alkyl sulfonates, alkylaryl sulfonates. alkyl sulfates, alkylamide sulfonates, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols, ethylene oxide addition products of these esters; ethylene oxide addition products of long-chain mercaptans; sodium alkyl benzene sulfonates having 12 to 18 carbon atoms; ethylene oxide addition products of alkylphenols, such as phenol condensed with moles of ethylene oxide; cetyl pyridinium chloride; soaps such as sodium stearate and sodium oleate.
Solid and liquid formulations can be prepared by any suitable method. Solid active ingredients, in finely divided form, can be tumbled together with a finely divided solid carrier. Alternatively, the active ingredient in liquid forms such as solutions, dispersions, emulsions or suspensions, can be admixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust compositions.
When solid formulations are used, in order to obtain a high degree of coverage with a minimum dosage, it is desirable that the formulation be in the form of a finely divided powder or dust sufficiently fine that substantially all of the solids will pass through a Tyler sieve having a mesh size between about 20 and about 200.
In dust formulations, the active ingredient can be present in an amount of 5 to 50% of the total weight. However, concentrations outside this range are operative and compositions containing from 1 to 99% of active ingredient by weight are contemplated wherein the remainder is carrier and/or any other desired additive or adjuvant. It may be advantageous to add a small amount of surfactant, e.g., 0.5 to 1% by weight based on the total weight of the dust formulation.
For spray application, the active ingredient may be dissolved or dispersed in a liquid carrier, such as water or other suitable liquid. The active ingredient can be added in the form of a solution, suspension, dispersion or cmulsion in aqueous or nonaqueous medium. Desirably, 0.5 to 1.0% by weight of surfactant is present in the liquid composition.
For adjuvant purposes, any desired quantity of surfactant may be employed, such as up to 250% by weight of the active ingredient. If the surfactant is used only to impart wetting qualities to a spray solution, as little as 0.05% or less, by weight of the surfactant need be used. Larger quantities of surfactant are used because of biological behavior of the surfactant rather than its wetting properties. These considerations are particularly important in the treatment of plants. The
active ingredient in liquid formulations often may not be more than 30% by weight of the total and may be 10% by weight of even as low as 0.01% by weight.
For systemic application, it may be desirable to apply the pesticide to the soil in the form of granules of an inert material coated with or incorporating the active ingredient. Reasons for the use of pesticidal granules include elimination of water during application, reduction of drift, penetration through vegetative coverage, easy handling, storage, and increased safety to handlers of the pesticides. Useful granule base materials include attapulgite, montmorillonite, corn cobs, walnut shells, and expanded vermiculites. Depending on their physical properties, the pesticides are either directly sprayed on the preformed granular base or are dissolved in a suitable solvent and then sprayed onto the granular base after which the solvent is removed by evaporation. Granule base materials are usually 60 to 14 US. sieve size particles, although other size particles may also be used.
Terms pesticide and pesticidal as used herein are intended to refer to the killing and/or control of insects, mites, nematodes, or the like. It will be appreciated that applications commonly referred to as insecticidal, miticidal, nematocidal, or the like are contemplated in the employment of these terms.
For a fuller understanding of the nature and objects of this invention, reference may be made to the following examples which are given to illustrate the invention and are not to be construed in a limiting sense. The infrared spectrum for each product described herein is consistent with the assigned structure. All percentages, proportions, and quantities given in these examples are by weight unless otherwise indicated. Likewise, all references to temperature are as C unless otherwise indicated.
EXAMPLE 1 3,3-Dimethyl-l-tert.-butylthio-2-butanone (Compound 7569) To a solution of 5.8 g (0.25 m) of sodium metal in 175 ml of absolute ethanol is added, dropwise, 24.4 g (0.27 m) of 2-methyl-2-propanethiol. The stirred solution is heated for 20 minutes, cooled, and treated in a dropwise manner with 44.8 g (0.25 m) of lbromopinacolone, prepared according to the procedure ofJ. Am. Chem. Soc., 74, 4507 1952). This reaction mixture is heated at reflux for 20 minutes, cooled, and poured onto 200 g of ice and water. After being saturated with sodium chloride, the mixture is extracted with four portions of ether. The combined ether extracts are dried over anhydrous magnesium sulfate, filtered, and stripped of solvent. Distillation of the residue through a short Vigreaux column gives the desired product. Properties of this, and similar compounds prepared by substantially the same procedure using the appropriate mercaptans and a-haloketones, are given in Tables 1 and 2.
EXAMPLE 2 3,3-Dimethyl-l-tert.-butylthio-2-butanone oxime (Compound 7604) A solution of 27 g (0.14 m) of 3,3-dimethyl-l-tert.- butylthio-2-butanone, 19.5 g (0.28 m) of hydroxylamine hydrochloride and 14.8 g (0.14 m) of anhydrous sodium carbonate in a mixture of 200 ml of ethanol and ml of water is heated at reflux for 19.5
hours. Stripping of volatiles on a rotary evaporator gives a slurry which is filtered to obtain the white solid oxime product. Properties of this and related compounds prepared by substantially the same procedure are given in Tables 3 and 4. Where the oxime product is a liquid, isolation is accomplished by ethyl acetate extraction of the residue left after removal of the volatiles and subsequent stripping of the dried extract.
EXAMPLE 3 Carbamate Preparation Method A 3 ,3-dimethyl-2-methylcarbamyloximino-1-tert.- butylthiobutane (Compound 7619) A solution of 4.7 g (0.023 m) of 3,3-dimethyl-l-tert.- butylthio-2-butanone oxime, 1.4 g (0.025 m) of methyl isocyanate, and three drops of triethylamine in 35 ml of anhydrous ether is heated at reflux for 16.5 hours. Stripping of volatiles on a rotary evaporator gives the desired product as a white solid. Properties of this and analogous compounds prepared by substantially the same procedure are given in Tables 5 and 6.
EXAMPLE 4 Carbamate Preparation Method B 2-Carbamyloximino-3 ,3-dimethyll -methylthiobutane (Compound 7859) To a chilled solution of 5.4 g (0.055 m) of phosgene in 50 ml of anhydrous ether is added, dropwise 6.1 g (0.05 m) of N,N-dimethylaniline followed by a solution of 8.1 g (0.05 m) of 3,3-dimethyl-l-methylthio-2- butanone oxime in 50 ml of ether. The mixture is stirred for two hours, as it is allowed to come to room temperature, and then filtered. The chilled filtrate is treated over 15 minutes with ml (0.15 m) of 29% aqueous ammonia. After being stirred for an additional minutes, the organic layer is separated, washed with water, and dried. Stripping of solvent from the organic layer gives 10.1 g of a clear liquid residue which solidifies on standing. Properties of this and analogous compounds prepared by substantially the same procedure are shown in Tables 5 and 6.
EXAMPLE 5 Carbamate Preparation Method C 3 ,3-Dimethyl-2-methylcarbamyloximino-l-(1- pyrro1idinyl)-butane (Compound 7870) To a solution of 12.6 g of l-bromo-3,3-dimethy1-2- methylcarbamyloximinobutane in 100 ml of anhydrous ether is added, dropwise, 7.8 g (0. 11 m) of p'yrrolidine. The mixture is stirred at room temperature for 1 hour and at reflux for 0.5 hour, then cooled and washed with water. The ether solution is separated, dried, and stripped of solvent to give 11.8 g of amber oil which solidifes on standing to an amber solid, m. 43-46 C. Properties of this and analogous compounds prepared by substantially the same procedure are shown in Tables 5 and 6.
EXAMPLE 6 1-Bromo-3,3-dimethyl-2-butanone oxime (Compound A solution of 69.5 g 1.0 m) of hydroxylamine hydrochloride in 100 ml of water is chilled in an ice bath as 90 g (0.5 m) of l-bromo-3,3-dimethyl-2-butanone is added. After addition of 100 ml of 95% ethanol, the mixture is stirred for 16 hours and allowed to warm to room temperature. The resulting white slurry is filtered, and the solid is washed with water and dried to give 55 g of the desired compound, in. 1 1 1-1 12 C.
Calcd. for C H NBrO: N, 7.2%; Br, 41.2% Found: N, 7.1%; Br, 42.4%
EXAMPLE 7 3,3-Dimethyl-l-nitro-2-butan one oxime (Compound 7668) To a stirred solution of 18.2 g (0.26 m) of sodium nitrite in ml of dimethyl sulfoxide is added, in portions, 29.0 g (0.15 m) of l-bromo-3,3-dimethyl-2- butanone oxime. A mild exotherm results and external cooling is used to keep the temperature below 27 C. Additional solvent is added to maintain stirrability. After 20 hours stirring, the mixture is poured onto ice and water to give a solid which is collected on a filter. The 10 g of solid, in. 11 5-120 C, thus obtained is recrystallized from a hot benzene-petroleum ether mixture to give 7 g of white crystals, m. 124125C.
Calcd. for c -H gN- ogi C, 45.0%; H, 7.6%
Found: C, 45.2%; H, 7.8%
EXAMPLE 8 3,3-Dimethyl-2-methylcarbamyloximinol -methylsulfinylbutane (Compound 7804) A stirred mixture of 9.0 g (0.042 m) of sodium metaperiodate in 60 ml of water and 25 ml of methanol is cooled to 0 C as 8.7 g (0.04 m) of 3,3-dimethyl-2- methylcarbamyloximino-l-methylthiobutane is added in portions. After stirring at 0-l0 C for 18 hours, the mixture is allowed to warm to room temperature and stripped of volatiles on a rotary evaporator to give a residue which is extracted with ethyl acetate. The dried extrace is stripped to leave 9 g (96%) of viscous yellow oil, the desired compound.
Calcd. for C H N O S: C, 46.1%; H, 7.7%
Found: C, 45.2%; H, 7.5%
EXAMPLE 9 2,Z-Dimethyl-3-methylcarbamyloximino-4-methylthiopentane (Compound 8071 To a solution of sodium thiomethoxide prepared from 4.1 g (0.18 gram atom) of sodium, 8.7 g (0.21 m) of methanethiol and 1 10 ml of ethanol is added 34.5 g (0.18 m) of 4-bromo-2,2-dimethyl-3-pentanone over 25 minutes at 0 i 5 C. After being heated to 4045 C for 30 minutes, the solution is filtered, stripped of solvent and distilled to give 12 g (42%) of colorless liquid, b. 57 C/4.3 mm, n 1.4589.
Calcd. for C,,H ;OS: C, 59.9%; H, 10.1%
Found: C, 59.2%; H, 10.1%
This compound (7 g, 0.044 m) and 18 g (0.26 m) of hydroxylamine hydrochloride in ml of absolute ethanol containing 30 ml of pyridine are heated under reflux for 120 hours. Pouring the clear solution into ice water gives a solid which is collected and dried. This white solid, m. 128-129 C, is the desired compound, 2,Z-dimethyl-4-methylthio-3-pentanone oxime.
Calcd. for C H NOS: C, 54.8%; H, 9.8%; N, 8.0%
Found: C, 54.3%; H, 9.4%; N, 7.8%
A solution of 4.6 g (0.026 m) of this oxime, 1.7 g (0.029 m) of methyl isocyanate, and three drops of triethylamine in 60 ml of benzene is heated under reflux for 17 hours. Stripping of volatiles gives 6.2 g of solid residue, m. 9394 C, which is the desired compound.
Calcd. for C H N O S: C, 51.7%; H, 8.7%; N,
12.1% Found: C, 51.6%; H, 8.5%; N, 12.1%
EXAMPLE 1 4,4-Dimethyl-3-methylcarbamyloximino-l-methylthiopentane (Compound 81 l l) A solution of sodium thiomethoxide, prepared from 5.8 g (0.25 gram atom) of sodium, 135 g (0.28 m) of methanethiol, and 170 ml of absolute ethanol, is treated with 36.6 g (0.25 m) of l-chloro-4,4-dimethyl- 3-pentanone at 3 to 8 C over 30 minutes. After being heated at 4045 C for 45 minutes, the mixture is filtered and distilled to give 12 g of colorless liquid, b. 73 C/2 mm, n 1.4623.
Calc'd. for C,,H,,,OS: C, 59.9%; H, 10.1% I
Found: C, 60.1%; H, 10.0%
A solution of 22.5 g (0.14 m) of this ketone and 58.4 g (0.84 m) of hydroxylamine hydrochloride in 525 ml of absolute ethanol and 105 ml of pyridine is heated under reflux for 48 hours. Pouring the reaction mixture into ice water gives 17.8 g of a white solid, in. 84 C, which is the desired 4,4-dimethyl-l-methylthio-3- pentanone oxime.
Calcd. for C H NOS: N, 8.0%
Found: N, 8.1%
Refluxing a solution of 5.3 g (0.03 m) of this oxime, 1.9 g (0.033 m) of methyl isocyanate, and three drops of triethylamine in 50 ml of anhydrous ether gives, after stripping of volatiles, 7.6 g of white solid residue, m. 5658 C, which is the desired compound.
Calcd. for C,,,H ,,N O S: C, 51.7%; H, 8.7%; N,
12.1% Found: C, 51.6%; H, 8.5%; N, 12.5%
EXAMPLE 11 l -Cyc1ohexyl-1-methylcarbamyloximino-Z- methylthioethane (Compound 8169) To a solution of 10.8 g (0.47 m) of sodium in 330 ml of absolute ethanol is added 25 g (0.52 m) of methanethiol followed by 76 g (0.47 m) of chloroacetylcyclohexane. Both additions are carried out at about 0 C. After being heated at 4045 C for 1 hour, the reaction mixture is filtered, stripped, and distilled to give 29.8 g of colorless liquid, b. 88-89 C/0.6-1.3 mm, n 1.4970, the desired ketone.
Calc'd. for C H OS: C, 62.7%; H, 9.4%
Found: C, 63.0%; H, 8.6%
A solution of 26 g (0.15 m) of the l-methylthioacetylcyclohexane, 21 g (0.3 m) of hydroxylamine hydrochloride, and 16 g (0.15 m) of anhydrous sodium carbonate in 155 ml of 95% ethanol and 104 ml of water is heated under reflux for 41 hours. Stripping of volatiles gives 18 g of solid, m. 6364 C, which is the desired oxime.
Calcd. for C,,H, NOS: C, 57.7%; H, 9.2%; N, 7.5%
Found: C, 57.5%; H, 9.0%; N, 7.4%
Heating a solution of 5.6 g (0.03 m) of this oxime, 1.9 g (0.033 m) of methyl isocyanate, and three drops of triethylamine in 50 ml of absolute ether at reflux for 17 hours gives, after removal of volatiles, 7.3 g of solid which is recrystallized from ethanol-water to obtain a white solid, m. 70-7l C, which is the desired com- 1 pound.
Calcd. for C H N O S: C, 54.1%; H, 8.3%; N,
11.5% Found: C, 54.2%; H, 8.3%; N, 11.7%
EXAMPLE 12 l Methylcarbamyloximinol-( l-methylcyclohexyl)-2- methylthioethane (Compound 8179) 1 Methylthioacetyl 1 -methylcyclohexane is prepared by treating a solution of sodium thiomethoxide [from 3 g (013 gram atom) of sodium, 6.7 g (0.14 m) of methanethiol, and ml of absolute ethanol] with 22.5 g (0.13 m) of l-chloroacetyl-lmethylcyclohexane over 20 minutes at 4-9 C. After being heated at 4045" C for 1 hour, the reaction mixture is filtered and distilled to give 7 g of colorless liquid, b. 8687 C/0.8 mm, n 1.4954.
Calcd. for C H OS: C, 64.5%; H, 9.7%
Found: C, 64.0%; H, 9.6%
This ketone is converted to the oxime by heating a solution of5 g (0.027 m) of ketone, 3.8 g (0.054 m) of hydroxylamine hydrochloride, and 3 g (0.027 m) of anhydrous sodium carbonate in 30 ml of 95% ethanol and 26 ml of water for 95 hours. The resulting solution is stripped of volatiles, to give a two-layer liquid residue, which is extracted with ethyl acetate. The organic layer is dried, filtered, and stripped to give 3.4 g of amber liquid, n 1.5164.
Calcd. for C H NOS: C, 59.7%; H, 9.5%; N, 7.0%
Found: C, 59.8%; H, 9.5%; N, 7.0%
A solution of 2.2 g (0.011 m) of this oxime, 0.7 g (0.012 m) of methyl isocyanate, and three drops of triethylamine in 25 ml of anhydrous ether is heated at reflux for 16 hours. Stripping of volatiles gives 3.5 g of amber viscous liquid, n 1.5200, which is the desired compound.
Calcd. for C H N O S: C, 55.8%; H, 8.6%
Found: C, 55.7%; H, 8.6%
EXAMPLE l3 1-( l-Adamantyl)- 1 -methylcarbamyloximino-2- methylthioethane (Compound 8191 A solution of 4 g (0.018 m) of l-methylthioacetyladamantane, 2.5 g (0.036 m) of hydroxylamine hydrochloride, and 1.9 g (0.018 m) of anhydrous sodium carbonate in 20 m1 of 95% ethanol and 18 ml of water is heated under reflux for 29 hours. Stripping of volatiles gives a slurry which is filtered to obtain 4.2 g of white solid oxime, m. l00-l03 C.
Calcd. for,C H,NOS: C, 65.2%; H, 8.8%; N, 5.9%
Found: C, 65.5%; H, 8.8%; N, 5.6%
A solution of 3 g (0.013 m) of this oxime, 0.8 g
(0.014 m) of methyl isocyanate, and three drops of triethylamine in 50 ml of anhydrous ether is heated under reflux for 17 hours. Stripping of volatiles gives 3.9 g of white solid, m. 99-100 C, which is the desired compound.
Calcd. for C H N O S: C, 60.8%; H, 8.2%; N, 9.5% Found: C, 60.2%; H, 8.1%; N, 9.5%
EXAMPLE 14 l-Chloro-4,4-dimethyl-2-methylcarbamyloximinopentane (Compound 8108) To a chilled, stirred mixture of 20.2 g (0.29 m) of hydroxylamine hydrochloride in 30 ml of water is added 21.5 g (0.145 m) of l-chloro-4,4-dimethyl-2- pentanone followed by 30 ml of 95% ethanol. The cooled mixture is stirred for six hours, allowed to stand overnight, and stripped of volatiles to obtain a residue which extracted with ethyl acetate. This extract is dried, stripped, and distilled to yield a colorless liquid, b. 76-77 C/l.3 mm, 11, 1.4672. which is the desired oxime.
Calcd. for C H C1NO:C, 51.4%; H, 8.6%; N, 8.6%
Found: C, 50.7%; H. 8.4%; N. 8.1% 1
A solution of 7 g (0.043 m) of the above oxime. 2.7. g (0.047 m) of methyl isocyanate, and three drops of triethylamine in 50 ml of anhydrous ether is heated under reflux for 17 hours. Stripping of volatiles gives the desired carbamate as a colorless, viscous liquid, n 1.4802.
Calcd. for C H C1N O N, 12.7%
18 having a reactive halogen radical Y, such as chlorine or bromine is reacted with HX having an X radical, as defined above. in the presence of an HY acceptor. Table 6 shows other compositions prepared by Method C.
TABLE 1 KETON ES FOUl'lClI N, 12.8% Compound EXAMPLE 14A Number Chemical Name 3,3-Dimethy1-2-methylcarbamyloximino-1'methy1su1- Z Z- 1 b g' 2 i gqiihpfi nonil I 1 b -C2ll' omet oxymet y! lO- lmet UlilllOflE fonyloxybumne (Compound 9350) 7533 1-methy|thio-2-propanone 7557 3-methy1-3-methylthio-Z-butanone A solution of 7.5 g (0.04 in) of 1-hydroxy-3,3- 755s 1-isopropy|thio-3,3dimethyl-2-butanone dimethy1-2-methylcarbamyloximinobutane and 5.0 g 20 7569 3,3-dimethyl-1-tert.:butylthio-Z-butanone (0.044 m) of methanesulfonyl chloride in 50 ml of benzene is treated dropwise with 4.6 g (0.044 m) of trieth- 77, 7 a 1 ylamine with cooling to keep the temperature below 7665 3345111611111-l-P11eny1thl0-3-hulflflm1e 35C Af h h d h d 7667 1,3-bis(methylthio)-3-methyl'2-butanone tert e a 1t1on,t e stirre mixture 1s eate 7765 33 dimethy| 1 phenoxy z bumnone at 35 C for two hours and then washed with aqueous 25 Z32 y l-l-progmnone .7 3-methyl-1-met ylthio-Z- utanone sodium bicarbonate and with water. The orgamclayer 7838 33 dimethyl I n propy|thio 2 bumnone is dried over magnesium sulfate, filtered, and stripped 7860 1-ethy1thi0-3.3-dimethyl-2-butanone c 7900 l-methylthio-Z-butanone of YOldIllfiSjO give 6.7 g (63 /c) of amber. viscous liquid 7909 lldimethYlLmethyhhioamemnone resldue, "n 7965 4,4-dimethyl-l methylthio-3-pentanone Calcd. for C H N O S: C, 40.6%; H, 6.8%; N, 30 8059 y p S17 8126 1-methy1-1-(methylthioacetyl)-cyclohexane l 8127 methylthioacetylcyclohexane Found: C, 41.2%; H, 6.8%; N, 10.5% 8373 methylthioacetylcyclopropane 8504 4,4-dimethyl-1-methylthio-2-pentanone Example 5 describes Method C for preparlng these 9011 4 methy| I methy|thi0 3 pemanone compositions whereln a compound of the formula 9061 l-methylthio-Z-pentanone 9274 1,1-bis(methylthio)-3,3-dimethy1-2-butanone 9 9275 1-( 2-ethylthioethylthio )-3,3-dimethyl-2-butanone R 9278 1 -methoxy-3.3-dimethy1-2-butanone R1 I f-OCK R4 9380 1-(3,3,3-trifluoropropylthio)-3.3-dimethyl-2-butanone l 7 I 9382 3,3,3-trich1oropropyl )-3 .3-dimethyl-2-butanone R -CC C Y 9383 3.3-dimethyl- 1 2-pheny1ethy1thio )-2-butanone rge is 9385 3 ,3-dimethy1- l -propargy1thio-2-butanone swig R 0 I! R --CC CH X Compound Boiling Range Refractive Percent Analysis Number R R R;, X in Clmm Hg Index/C Yield Calculated Found 7218 CH CH, 011,- cH .,s 73/93 1.4650/24 62 7443 CH;, CH;, CH CH;,OCOCH S 94/08 1.4720/24 64 C 52.9 C 52.6 H 7.9 H 7.5 7533 H H- H CH;,S 63-4/29 1.4691/24 45 C 46.1 C 46.9 H 7. H 7.9 7557 CH CH;, CH;,S H- 48/8.1 1.4625/24 57 C 54.5 C 54.2 H 9.2 H 9.2 7558 CH;, CH;. CH; (CH,-,) CHS 96/89 1.4568/24 68 C 62.0 C 61.8 H 10.4 H 10.2 7569 CH CH;, CH;. (CH;;);,CS- 84-92/9.8 1.4595/24 67 C 63.8 C 63.6 H 10.7 H 10.6 757 1 CH;, CH;, CH;; (CH;.)- CHCH S 101/98 1.4592/24 62 C 63.8 C 63.1 H 10.7 H 10.8 7573 CH;.- CH CH;, CH =CHCH S 589/1.2 1.4762/24 24 C 62.7 C 62.8 H 9.4 H 9.1 7637 CH;,- CH;, CH C H CH S 104.5-106/ 1.5306/24 57 C 70.2 C 70.9 0.5-0.6 H 8.2 H 9.0 7665 CH,-, CH;, CH;, C H,-,S- 102/05 1.5425/24 38 C 69.2 C 70.0 H 7.7 H 7.7 7667 CH;. CH;; CH -,S CH S 91-5/39 1.5138/23 56 C 47.2 C 46.8 H 7.9 H 7.8 7765"" cH, cH,, cH,, c,,1-1 -,o l06-8/1.8 1.5036/23 72 7807"" CH -,S- H H CH S IDS/9.5 1.5302/24 27 7837 01-1,- CH,, H- c1-1,.s* 61/8 48 c 54.6 C 54.9 H 9.1 H 9.7
The compounds are evaluated for biological activity against the following representative pests: Mexican bean bettle (Epilaclina varivestis), Southern army worm (Prodenia eridania), housefly (Musca domestica), bean aphid (Aphisfabue). and red spider mite (Terranyclms s1). The last two pests are treated both by contact and systemic application.
For purposes of comparison, results obtained with known Compound 7472. Compound 7577, and al- This test determines the acaricidal iactivity of the compound being tested against the red spider mite. Tetranyc/ms $1). Stock formulations containing 500 ppm of each test chemical are prepared by the procedure described in Example 15 and are used in both the soil drench and spray treatments. The stock culture of mites is maintained on Scarlet runner bean foliage. Approximately l8 to 24 hours before testing, mites are transferred to the primary leaves of two Lima bean dicarb are included in the test results. Each test com- 10 plants (var. Sieva) grown in 2% inch pots.
pound is rated using the following scale:
Contact Activity Systemic Activity The spray and systemic application methods described in Example are used to apply the test formulations to the infested plants and soil. After three days, two of the four leaves treated are examined and mortal- Bean Aphid Spray and Systemic Test This test determines the insecticidal activity of the compound being tested against the bean aphid Aphisfabae. Stock formulations containing 500 ppm of each test chemical are prepared using 0.05 g of the test chemical (or 0.05 ml if a liquid), 4.0 ml acetone containing 0.25% (V/V) Triton X-l55, and 96.0 ml deionized water and are used in both soil drench and spray treatments. The stock formulations are diluted to obtain the appropriate lower concentrations maintaining the concentration level of all adjuvants. The bean aphid is cultured on nasturtium plants (var. Tall Single), no attempt being made to select insects of a given age in these tests. Single nasturtium test plants growing in soil in individual 2% inch fiber pots are then infested with populations of 100 to 200 aphids.
In the spray application, 50 ml of stock or diluted formulation is uniformly sprayed onto the plants. in the. systemic application, 1 1.2 ml of stock or diluted formulation is applied to the soil containing the plant. A dosage of 11.2 ml of formulation containing 500 ppm of test chemical is equivalent to a dosage of the test chemical of 16 pounds per acre.
The plant test units under fluorescent lights are given bottom watering for the duration of the test. Percentage mortality is determined three days after treatment. Results of this test are shown in Table 7 asA (aphid contact spray) and AS (aphid systemic soil drench).
EXAMPLE 16 Red Spider Mite Sptay and Systemic Test ity is determined. Should a compound be an effective miticide, the other two leaves are available to obtain information on the residual activity of the formulation. Results of this test are shown in Table 7 as M (mite contact spray test) and MS (mite systemic soil drench test).
EXAMPLE l7 Housefly Spray Test This test determines the insecticidal activity of the compound being tested against adult houseflies, Musca domestica. Stock formulations containing 500 ppm of each test chemical are prepared using the procedure described in Example 15 and are diluted to obtain the appropriate lower concentrations.
Ten adult flies are placed in a cylindrical screen cage 1%. by 4 inches fabricated from 20-mesh stainless steel screening and are sprayed with 50 ml of the stock or diluted formulation. The flies are suplied food and drink from a dextrose solution by draping a paper wick over the outside of the screen cylinder and are able to feed and drink ad libitum. Percent mortality obtained is determined three days after treatment. Results of this test are shown in Table 7 as HF (housefly spray test).
EXAMPLE is Southern Army Worm Spray Test Paired fully expanded primary leaves excited from I Scarlet runner bean plants are maintained in plastic tubes containing water and sprayed with the test formulation prepared as described in ExamplelS. After the spray deposit on the leaves is dry, the paired leaves are separated. One leaf is placed onto 1.5 percent water agar and infested with 10 newly hatched Southern army worm larvae. The covered test receptacle is held at 72.
F for three days and then the percent mortality is determined. Results of this test are shown in Table 7 as AW (Southern army worm spray test).
EXAMPLE 19 e Mexican Bean Beetle Leaf Spray'Test This test determines the insecticidal activity of the compound being tested against the Mexican bean beetle (Epilaclzna rarirestis). The test procedure is the same as that described for the Southern army worm in Example 18 with the exception that one-day old larvae of the Mexican bean beetle instead of newly hatched Southern army worm larvae are used.
These tests are held at 72 F for three days when mortality and feeding inhibition are determined. The feeding inhibition is an indication of the repellent properties of the test material. Results of this test are shown in Table 7 as BB (Mexican bean beetle leaf spray test).
TABLE 7 Compound Number 7268 7472 7503 7577 7603 7718 7797 7799 7804 7859 7862 7867 7871 7897 79 l 6 7934 7960 799] 807] 81 l l 8465 8519 8520 8868 8997 9026 9057 9058 aldicarb BB Mexican hcan beetle AW Southcrn army worm HF houscfl M mite contact A aphid contact MS mite systemic 7 AS aphid systemic The high insecticidal and miticidal activity of Compound 7268 is further demonstrated by the results of special tests described below.
EXAMPLE 20 Systemic Test of Compound 7268 Against Lygus Bug and Spotted Cucumber Beetle The techniques used are essentiallythesame for the systemic tests described above in Example-l 5. The test compound is Compound 7268. There is one Sieva bean plant per pot and five adult insects are caged on each plant. One plant is used for each test species. The checks showed no mortality during the tests.
The test organism is a strain of Southern corn rootworm (Diabrotica undecimpunctala howardi) resistant to chlorinated hydrocarbon insecticides and the test compound is Compound 7268. Duplicate samples of sand-soil mixtures are treated with appropriate volumes of test formulation to give the desired dosages. The sand-soil samples are in covered paper cups, and several hours after drenching, all cups are given a thorough shaking to-provide complete and uniform mixing of the chemical throughout the soil. One day after treatment, two corn seedlings and five rootworms are placed into each cup and the lids replaced. Five days later, mortality is determined. The results are given below:
The techniques used are essentially the same as for the systemic tests described above in Example 15. The test plants are cucumber seedlings; the test compound is Compound 7268; and the pest is the melon aphid (Aplzis gosyppi).
Dosage. lb/A 0.5 0.25 0.125 0.062 Control 100 100 100 EXAMPLE 23 Residual Systemic Activity of Compound 7268 Against Mexican Bean BeetleLarvae Three furrows are opened in soil contained in 8 inch X 10 inch X 3 inch fiber pans and 12 Pinto bean seeds day-old bean beetle larvae. Mortality is determined three days later.
Weeks After 7? Mortality at Indicated Dosage. lh/A Treatment l 0.5 0.2.5 Check 3 100 100 100 7 I00 100 I00 l0 I0 95 100 I00 0 l l 95 70 95 0 EXAMPLE 24 Root-knot Nematocide Test This test is an evaluation of the effectiveness of the compound being tested against infection by root-knot nematodes (Meloidogyne spp.
Composted greenhouse soil, diluted by one-third with clean washed sand. is infested with about two grams of knotted or galled tomato roots per pot. Treatment is accomplished by applying 25 ml of the formulated compound onto the infested soil. The test formulation contains 0.056 g of Compound 7960, 1.0 ml stock emulsifier solution (0.25% Triton X-l55 in acetone by volume), and 24.0 ml deionized water, giving a concentration of 2240 ppm. Lower concentrations are achieved by dilution.
After treatment with the test formulation, the soil, inoculum, and formulation are thoroughly mixed, returned to the pot, and the mixture incubated for seven days at 20 C and constant moisture. After incubation, two seedlings of Rutgers tomato transplants and three garden nasturtium (Nasturtium spp.) seeds are set in each pot. Roots are removed from the soil after three weeks of growth and rated for gall (root-knot nematode infection) formation. Nasturtium roots are evaluated only when necrosis of the tomato host has occurred. A rating of infection from O to 10 is recorded:
no galls or complete control, and 10 heavily galled roots comparable to controls. Each of the root systems is rated separately and the average is multiplied by 10 and subtracted from 100 to give percent nematode control. Results of the test are shown below:
Compound Percent Control at Indicated Dosage. lb/A Number 8 4 2 1 0.5
7960 100 100 100 I 00 97 8423 I00 90 60 8997 100 100 0 9026 90 7O 60 30 34 fined by the appended claims.
What is claimed is: l. A composition of matter having the structural formula:
0 ll R6 R, N ocn H ll R t 2 C C C X l5 where:
a. R is hydrogen or lower alkyl; b. R; R is lower alkyl with the proviso that R and R may be connected to form a cycloalkyl ring of 90 not more than 6 carbon atoms;
c. R R is hydrogen, lower alkyl or lower alkenyl;
d. X is SR S(O)R or 50 R and,
e. R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, or aryl,
5 2. A composition of matter of claim 1 selected from the group consisting of:
3,3-dimethyl-2-methylcarbamyloximino-lmethylthiobutane;
3,3-dimethyl-2-methylcarbamyloximino-l-methylsulfinylbutane; 3.3-dimethyl-2-methylcarbamyloximinol methylthiohexane; 2-carbamyloximino-3,3-dimethyl-l-methylthiobutane; 3-methyl-2-methylcarbamyloximino l methylthiobutane; l-ethylthio-3,3-dimethyl-Z-methylcarbamyloximinobutane; v l-cyclopropyll -methylcarbamyloximinc-2- methylthioethane;
40 3,3-dimethyl-2-methylcarbamyloximino-l-methylthiopentane;
3,3-dimethyl-2-methylcarbamyloximino-l-methylsulfonylbutane,
2-ethylcarbamyloximino-3,3-dimethyl-lmethylthiobutane 2-allylcarbamyloximino-3,3-dimethyl methylthiobutane l-allythio-3,3-dimethyl-2-methylcarbamyloximinobutane 50 3,3-dimethyl-Z-methylcarbamyloximino- 1 -npropylthiobutane.
3. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximino-l-methylthiobutane.
4. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol-methylsulfinylbutane.
5. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol -methylthiopentane.
6. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2- methylcarbamyloximinol -methylsulfonylbutane.

Claims (6)

1. A COMPOSITION OF MATTER HAVING THE STRUCTURAL FORMULA:
2. A composition of matter of claim 1 selected from the group consisting of: 3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane; 3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfinylbutane; 3,3-dimethyl-2-methylcarbamyloximino-1-methylthiohexane; 2-carbamyloximino-3,3-dimethyl-1-methylthiobutane; 3-methyl-2-methylcarbamyloximino-1-methylthiobutane; 1-ethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; 1-cyclopropyl-1-methylcarbamyloximino-2-methylthioethane; 3,3-dimethyl-2-methylcarbamylOximino-1-methylthiopentane; 3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfonylbutane, 2-ethylcarbamyloximino-3,3-dimethyl-1-methylthiobutane 2-allylcarbamyloximino-3,3-dimethyl -1-methylthiobutane 1-allythio-3,3-dimethyl-2-methylcarbamyloximinobutane 3,3-dimethyl-2-methylcarbamyloximino-1-n-propylthiobutane.
3. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane.
4. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfinylbutane.
5. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2-methylcarbamyloximino-1-methylthiopentane.
6. The composition of matter of claim 1 wherein the composition is 3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfonylbutane.
US229207A 1971-04-08 1972-02-24 AC Ketoxime carbamates Expired - Lifetime US3875232A (en)

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US229207A US3875232A (en) 1971-04-08 1972-02-24 AC Ketoxime carbamates
CA137,337A CA984399A (en) 1971-04-08 1972-03-17 Ketoxime carbamates
FR7210622A FR2136055A5 (en) 1971-04-08 1972-03-27
AR241311A AR192758A1 (en) 1971-04-08 1972-04-05 CARBAMATES OF KETOXIMAS, METHODS FOR THEIR MANUFACTURE AND PESTICIDE COMPOSITIONS THAT CONTAIN THEM
EG138/72A EG10912A (en) 1971-04-08 1972-04-06 Carbamate derivatives of ketoximes compounds and their use as insecticides and acaricides
PL1972154659A PL89001B1 (en) 1971-04-08 1972-04-07 AC Ketoxime carbamates[US3875232A]
IT49465/72A IT954413B (en) 1971-04-08 1972-04-07 DISINFESTANT COMPOSITION AND RELATED PRODUCTION PROCESS
IL39157A IL39157A (en) 1971-04-08 1972-04-07 Ketoxime carbamates,their preparation and their use as pesticides
CH436875A CH585194A5 (en) 1971-04-08 1972-04-07
RO70445A RO61151A (en) 1971-04-08 1972-04-07
CH514972A CH611275A5 (en) 1971-04-08 1972-04-07
YU00944/72A YU39065B (en) 1971-04-08 1972-04-07 Process for obtaining ketoxime derivatives
GB1618772A GB1392111A (en) 1971-04-08 1972-04-07 Carbamyloximino compounds and their use in pesticidal compositions
SU1886513A SU466653A3 (en) 1971-04-08 1972-04-07 Method for preparing carbamate ketoxime derivatives
CH436975A CH591433A5 (en) 1971-04-08 1972-04-07
IE453/72A IE36264B1 (en) 1971-04-08 1972-04-07 Improvements in or relating to carbamyloximino compounds and their use in pesticidal compositions
DE2216838A DE2216838C2 (en) 1971-04-08 1972-04-07 Ketoxime carbamates, process for their preparation and their use
NLAANVRAGE7204698,A NL175989C (en) 1971-04-08 1972-04-07 METHOD FOR PREPARING PESTICIDE PREPARATIONS AND PROCESS FOR PREPARING CARBAMOYL KETOXIME DERIVATIVES SUITABLE FOR USE IN SUCH PREPARATIONS.
SU1887327A SU466681A3 (en) 1971-04-08 1972-04-07 Method for preparing carbamate ketoxime derivatives
AU40916/72A AU482663B2 (en) 1972-04-07 Ketoxime carbamates
ES401551A ES401551A1 (en) 1971-04-08 1972-04-07 AC Ketoxime carbamates
HUDI222A HU165184B (en) 1971-04-08 1972-04-07
RO7282519A RO72827A (en) 1971-04-08 1972-04-07 PROCESS FOR OBTAINING CETOXIME CARBAMATES
RO7282518A RO72853A (en) 1971-04-08 1972-04-07 PROCESS FOR THE PREPARATION OF CARBAMATES OF KETOXYMES
AT299672A AT316207B (en) 1972-02-24 1972-04-07 Insecticidal, acaricidal and nematocidal compositions
JP3563572A JPS5533410B1 (en) 1971-04-08 1972-04-07
PL15918572A PL89691B1 (en) 1972-02-24 1972-04-07 Ketoxime carbamates[au4091672a]
SU1769624A SU454735A3 (en) 1971-04-08 1972-04-07 Method for preparing carbamate ketoxime derivatives
AT678173A AT330197B (en) 1972-02-24 1973-08-02 METHOD FOR MANUFACTURING NEW KETOXIME CARBAMATES
US05/391,329 US3932471A (en) 1972-02-24 1973-08-24 Azide
AT283274A AT330198B (en) 1972-02-24 1974-04-04 METHOD FOR MANUFACTURING NEW KETOXIME CARBAMATES
AT283374A AT338282B (en) 1972-02-24 1974-04-04 METHOD FOR MANUFACTURING NEW KETOXIME CARBAMATES
US05/553,648 US4028413A (en) 1972-02-24 1975-02-27 Ketoxime carbamates
BE157643A BE830594Q (en) 1971-04-08 1975-06-24 CETOXIM CARBAMATES, METHODS FOR THEIR PREPARATION AND THEIR APPLICATIONS, ESPECIALLY AS INSECTICIDES.
US05/966,390 US4215075A (en) 1971-04-08 1978-12-04 Ketoxime carbamates
YU316/79A YU42298B (en) 1971-04-08 1979-02-12 Process for obtaining ketoxime derivatives
YU00315/79A YU39102B (en) 1971-04-08 1979-02-12 Process for obtaining ketoxime derivatives

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CH (3) CH591433A5 (en)
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US4640927A (en) * 1984-03-30 1987-02-03 Uniroyal Chemical Company, Inc. Substituted oxime carbamates
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Cited By (25)

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US4215075A (en) * 1971-04-08 1980-07-29 Diamond Shamrock Corporation Ketoxime carbamates
US3932471A (en) * 1972-02-24 1976-01-13 Diamond Shamrock Corporation Azide
US3968129A (en) * 1974-02-22 1976-07-06 Boehringer Mannheim G.M.B.H. Azidophenol amine compounds and therapeutic compositions
US4029688A (en) * 1974-06-27 1977-06-14 Union Carbide Corporation Carbamic pesticidal compositions
US3988357A (en) * 1975-01-20 1976-10-26 Stauffer Chemical Company Certain oxime carbonates
US4018894A (en) * 1975-01-20 1977-04-19 Stauffer Chemical Company Oxime carbonetes as fungicidal or bactericidal agents
US4009179A (en) * 1975-10-15 1977-02-22 E. I. Du Pont De Nemours And Company Di- and tri-substituted oxazolidin-2-one oximes
US4073930A (en) * 1976-06-01 1978-02-14 Union Carbide Corporation Carbamoyloximes and oximes and insecticidal and miticidal compositions and methods employing them
US4072750A (en) * 1976-06-01 1978-02-07 Union Carbide Corporation 1,3,5-Trithiane and 1,3,5-oxadithiane carbamoyloxime compounds and insecticidal and miticidal compositions and methods employing them
US4454134A (en) * 1976-06-14 1984-06-12 Union Carbide Corporation Amide carbamates and amide oxime compounds
US4119788A (en) * 1976-10-07 1978-10-10 International Flavors & Fragrances Inc. α-Oxy(oxo) sulfides and ethers
US4234514A (en) * 1978-12-04 1980-11-18 Diamond Shamrock Corporation Method of preparing ketoxime carbamates
US4264528A (en) * 1978-12-04 1981-04-28 Diamond Shamrock Corporation Method of preparing ketoxime carbamates
US4316910A (en) * 1979-08-18 1982-02-23 Bayer Aktiengesellschaft Combating arthropods with substituted 2-carbamoyloximino-butanes
US4387053A (en) * 1981-11-23 1983-06-07 Diamond Shamrock Corporation Stabilization of oxime carbamates with gallic acid, lower alkyl ester derivatives thereof
WO1983001773A1 (en) * 1981-11-23 1983-05-26 Diamond Shamrock Corp Stabilization of oxime carbamates with gallic acid, lower alkyl ester derivatives thereof
US4640927A (en) * 1984-03-30 1987-02-03 Uniroyal Chemical Company, Inc. Substituted oxime carbamates
US4785108A (en) * 1984-06-04 1988-11-15 Uniroyal Chemical Company, Inc. Substituted oxime carbamates
US5200427A (en) * 1984-07-27 1993-04-06 The Board Of Trustees Of The Univ. Of Illinois Porphyric insecticides
US20070037869A1 (en) * 2001-03-27 2007-02-15 Hsuan-Yin Lan-Hargest Histone deacetylase inhibitors
US7842727B2 (en) 2001-03-27 2010-11-30 Errant Gene Therapeutics, Llc Histone deacetylase inhibitors
US20040023944A1 (en) * 2002-05-22 2004-02-05 Beacon Laboratories, Inc. Histone deacetylase inhibitors based on alpha-chalcogenmethylcarbonyl compounds
US7214831B2 (en) 2002-05-22 2007-05-08 Errant Gene Therapeutics, Llc Histone deacetylase inhibitors based on alpha-chalcogenmethylcarbonyl compounds
US20100143961A1 (en) * 2002-05-22 2010-06-10 Hsuan-Lin Lan-Hargest Histone deacetylase inhibitors based on alpha-ketoepoxide compounds
US8138225B2 (en) 2002-05-22 2012-03-20 Errant Gene Therapeutics, Llc Histone deacetylase inhibitors based on alpha-ketoepoxide compounds

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CH591433A5 (en) 1977-09-15
RO72827A (en) 1982-10-11
NL175989B (en) 1984-09-03
YU42298B (en) 1988-08-31
SU466653A3 (en) 1975-04-05
YU94472A (en) 1982-05-31
NL175989C (en) 1985-02-01
DE2216838A1 (en) 1972-11-02
NL7204698A (en) 1972-10-10
YU39065B (en) 1984-04-30
CA984399A (en) 1976-02-24
RO72853A (en) 1982-02-26
BE830594Q (en) 1975-10-16
IE36264L (en) 1972-10-08
JPS5533410B1 (en) 1980-08-30
RO61151A (en) 1976-10-15
FR2136055A5 (en) 1972-12-22
IT954413B (en) 1973-08-30
SU466681A3 (en) 1975-04-05
EG10912A (en) 1976-12-31
YU31579A (en) 1982-06-30
ES401551A1 (en) 1975-10-01
GB1392111A (en) 1975-04-30
SU454735A3 (en) 1974-12-25
IL39157A0 (en) 1972-06-28
YU39102B (en) 1984-04-30
HU165184B (en) 1974-07-27
IL39157A (en) 1976-08-31
CH611275A5 (en) 1979-05-31
IE36264B1 (en) 1976-09-29
YU31679A (en) 1982-05-31
CH585194A5 (en) 1977-02-28
DE2216838C2 (en) 1985-05-09
AR192758A1 (en) 1973-03-14
PL89001B1 (en) 1976-10-30

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