US3097128A - Phenol stabilized organo-phosphorous insecticides - Google Patents

Phenol stabilized organo-phosphorous insecticides Download PDF

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Publication number
US3097128A
US3097128A US80996A US8099661A US3097128A US 3097128 A US3097128 A US 3097128A US 80996 A US80996 A US 80996A US 8099661 A US8099661 A US 8099661A US 3097128 A US3097128 A US 3097128A
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US
United States
Prior art keywords
phosphate
phenol
insecticide
group
insecticides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US80996A
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English (en)
Inventor
Charles R Sprinkle
Leo F Sekula
Milton R Johnson
Bertram I Sparr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell USA Inc
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Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL273220D priority Critical patent/NL273220A/xx
Priority to BE612272D priority patent/BE612272A/xx
Priority to NL131123D priority patent/NL131123C/xx
Priority to US80996A priority patent/US3097128A/en
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to BR135470/62A priority patent/BR6235470D0/pt
Priority to CH10762A priority patent/CH437905A/de
Priority to ES0273412A priority patent/ES273412A1/es
Priority to DE1962S0077409 priority patent/DE1280001C2/de
Priority to GB372/62A priority patent/GB958421A/en
Priority to FR883860A priority patent/FR1332542A/fr
Priority to DK4062AA priority patent/DK102884C/da
Application granted granted Critical
Publication of US3097128A publication Critical patent/US3097128A/en
Priority to OA50490A priority patent/OA00413A/xx
Priority to MY33/65A priority patent/MY6500033A/xx
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/327—Esters with unsaturated acyclic alcohols
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4078—Esters with unsaturated acyclic alcohols

Definitions

  • the vinyl phosphates such as dimethyl Z-carbomethoxy-l-methylvinyl phosphate and dimethyl 2,2-dichloroyinyl phosphate, and related phosphonates and phosphinates, constitute a general class of highly effective insecticides.
  • applications-as in baits, dusts or the like-these insecticides must be used in the form of dry formulations wherein they are impregnated upon solid materials.
  • Such formulations have been prepared, and it has been found that these insecticides tend to be unstable when formulated in this manner. The reason for this instability has not been determined with certainty, but it is believed to involve in substantial part hydrolysis of the insecticides. It does not appear from examination of a variety of typical members of these insecticides impregnated upon a variety of solid carrier materials that the instability of the insecticides is due to the nature of the carrier material, but that the instability occurs irrespective of the carrier material.
  • insecticides which have been found to exhibit instability in dry formulations on solid carriers, and which are stabilized according to this invention, have the formula:
  • R represents hydrocarbon or substituted hydrocarbon
  • R represents hydrogen, halogen or one of the groups represented by R
  • R" represents halogen, one of the groups represented by R or a functional organic group
  • n is 0, l or 2
  • the halogen be middle halogen-that is, bromine or chlorine.
  • the organic groups represented by the symbols, R and R preferably are low molecular Weight hydrocarbon or substituted hydrocarbon groups, for example, containing from one to ten carbon atoms each. They may be aliphatic, cycloaliphatic, aromatic or of mixed structure. When aliphatic, they may be either straight-chain or branched-chain in configuration. "lype-wise, the preferred organic groups include alkyl, cycloalkyl, aryl, alkaryl, and like groups.
  • Illustrative examples include the methyl, ethyl, nand isopropyl groups, the various isomeric butyl, hexyl and like alkyl groups; the cyclopentyl, cyclohexyl and like cycloalkyl groups, the phenyl group; the na-phthyl group; the benzyl, phenethyl, p-methylbenzyl and like aralkyl groups; the isomeric tolyl groups, the isomeric xylyl groups, the ethylphenyl group, the 2,4-dimethyland 3,5- dimethylphenyl and like alkaryl groups, and the like.
  • n 2that is, in the phosphate insecticidesthe two symbols, R, may together represent a divalent hydrocarbon group, each of the symbols representing one valence bond thereof.
  • R may represent such a divalent hydrocarbon group.
  • the substituted hydrocarbon groups represented by R and R are those of the above-mentioned hydrocarbon groups which are substituted by one or more non-hydro carbon substituents.
  • the preferred substituents are mid- :dle halogen, the nitro group and amine groups represented by the formula:
  • non-hydrocarbon groups include monohaloalkyl groups, such as the chloromethyl and bromomethyl groups, the 2-chloroethyl, l-bromopropyl, 3-chloropropyl and the like; polyhaloalkyl groups, such as the dichloromethyl, tribromomethyl, 1,2-dichlor0- ethyl, 2,2 dibromoethyl, 3,3 dichloro 2 bromo'propyl groups, and the like; nitroalkyl groups such as the 2- nitroethyl group; halo-substituted aromatic groups such as the various isomeric chloroand bromophenyl groups, the various isomeric polyhalophenyl groups, such as the 2,6-dichlorophenyl group, the 3,5-dibromophenyl group and the like; amino-substituted groups, such as the 2- aminoethyl group, the Z-dimethylandnoethyl group
  • R may also represent a functional organic group, such as a carboaliphaticoxy group, particularly a carboalkoxy or an alkoxyalkyleneoxycarbonyl group of up to ten carbon atoms; it may represent an ether group, RO-, wherein R has the meaning already set out; it may represent an acyloxyalkoxycarbonyl group wherein the acyl group is 3 or it may represent an amide group having the amino moiety set out above.
  • a functional organic group such as a carboaliphaticoxy group, particularly a carboalkoxy or an alkoxyalkyleneoxycarbonyl group of up to ten carbon atoms
  • R may represent an ether group, RO-, wherein R has the meaning already set out
  • R may represent an acyloxyalkoxycarbonyl group wherein the acyl group is 3 or it may represent an amide group having the amino moiety set out above.
  • each R is lower hydrocarbonparticularly alkyl of up to seven carbon atoms, aryl of up to ten carbon atoms or aralkyl of up to 10 carbon atoms, particularly the phenyl or benzyl group;
  • R bonded to the alpha carbon atom is hydrogen or one of the groups represented by R and (a) R bonded to the beta carbon atom is middle halogen and R" is middle halogen;
  • R bonded to the beta carbon atom is hydrogen, middle halogen or one of the preferred groups represented by R, and R is a group of the formula H a.
  • alky1-O i 0- hal hi1 (I) wherein alkyl represents an alkyl group of from 1- to 4 carbon atoms and hal represents middle halogen-Le, bromine or chlorine;
  • alkyl represents alkyl of from 1 to 4 carbon atoms.
  • Typical species of these insecticides include:
  • dioxaphospholane 2 (m nitrobenzyloxycarbonyl) -1-methylvinyl dimethyl phosphate 2 (p nitrobenzyloxycarbonyl) 1 l-methylvinyl dimethyl phosphate Dimethyl 1-methyl-2- (p-tolyloxycarbonyl)vinyl phosphate Dimethyl Z-phenethyloxycarbonyl-l-me-thylvinyl phosphate 2-(p methoxybenzyloxycarbonyl)-1-methylvinyl dimethyl phosphate 2-phenoxyethoxycarbonyl-l-methylvinyl dimethyl phosphate 2 (p chlorophenoxycarbonyl) l-methylvinyl dimethyl phosphate 2 (p chlorobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate Diethyl Z-carboethoxy-l-rnethylvinyl phosphate Dimethyl 2-carbomethoxy-Z-phenylvinyl phosphate Diethyl Z-carb
  • phenol itself is a suitable stabilizer, as are other mononucle'ar phenols such as alkyl-substituted phenols.
  • the stabilizer suitably may be a polynuclear phenol, such as alph and beta-naphthols.
  • Polyphenols such as hydroquinone and 2,2-bis(p-hydroxyphenyl)propane, also are suitable.
  • Those phenols which are known to be antioxidants are suitable.
  • kryptophenols--phenols substituted at one or both of the carbon atoms of the aromatic ring in position ortho to the carbon atom thereof to which is bonded the phenolic hydroxyl group-in which a stereo-chemical efiect shields or protects the phenolic hydroxyl group.
  • These also include the polyphenols with ortho and para hydroxyl groupswhich can undergo hydroquinone-quinone transformation. It must be noted, however, that the property of being an antioxidant is not essential to the utility of a phenol as a stabilizer in the present invention, since phenol itself, and beta-naphthol, which are not considered to be antioxidants, are quite suitable as stabilizers in the present invention.
  • phenols which may be used to stabilize these insecticides include catechol, pyrogallol, resorcinol, phloroglucinol, sesamol, B-phenylisocoumarone, the tocopherols, p-aminophenol, phenol ethers, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-alpha-dimethylamino-p-cresols, the cresols, 4,4-bis(2,6-di-tertbutylphenol), 4,4 methylene bis(6-tent butyl-o-cresol), 2,6-di-tert-butyl-alpha-methoxy-p-creso1, 2,6-di-tert-butylp-cresol, 2,2-methylenebis( t-methyl-6-tert-butylphenol), butylated hydroxyanisoles, propyl gallate, butyl ated hydroxytoluenes,
  • the invention thus is applicable to the stabilization of solid formulations of the herein defined insecticides, im-
  • Attapulgite clays diatomaceous earths, vermiculites, synthetic calcium silicates, crushed rock, rock flour, sand,
  • talc powdered calcium carbonate, lime, gypsum, pyrophyllite, powdered carbn-i.e., charcoal-and the like, upon sugar or like solid materials which are useful as baits, upon organic fibrous materials, such as crushed corncobs, bagass'e, crushed or powdered nut shells, or the like.
  • the preferred carrier materials for use with those insecticides defined in Formula I, column 3 are the montm-orillonite clays, particularlythat known as Pikes Peak clay.
  • Sand, sugar, pyrophyllites, particularly that known as Pyrax ABB and talc, particularly that known as Emtal 23A, are preferred carriers foruse with those insecticides defined in Formula II, column 3. 7
  • the phenol stabilizer is incorporated in the formulation in any manner, which will enable it to be intimately contactedwith the insecticide therein.
  • the phenol may be dissolved in the insecticide, or vice versa, depending upon the relative concentrations and solubilities of the two materials.
  • it may be merely intimately mixed in the already formed mixture of carrier and insecticide.
  • the phenol, or the phenol and insecticide together can be dissolved in a suitable solvent, and the solution mixed with the carrier or the carrier-insecticide mixture, as the case may be.
  • the solvent then may be removed wholly, or in part; or in some cases, it may be desirable to include the solvent in the formulation.
  • the formulations are otherwise compounded by techniques well known and generally practiced by the art.
  • the formulation may be in'the form of a dust, in the form of granules, in the form of wettable powders, or in other forms suitable to the intended use.
  • the formulation can contain other materials to provide necessary physical characteristics-thus, stickers, emulsifiers, spreading or wetting agents, fertilizers, other insecticides, other biocides (for example, fungicides or the like) can be incorporated in the formulation by known means.
  • any of the materials known to the prior art can be used, as desirable to impart the desired characteristic(s) to the final formulation.
  • sticking agents there may be used casein, gelatine, cellulose derivatives such as carboxymethylcellulose, sulfite waste liquor, a guru, a water-dis- I called concentrates which contain typically from about persible synthetic resin, mineral oil, or equivalent adhesives all of which are well known in the art.
  • Wetting agents and dispersing agents which may be employed include the various naturally occurring or synthetic surfaceacting materials known for the purpose, such as, inter alia, soaps, saponins, lecithins, fatty acid salts, long-chain alcohols, sulfonated aliphatic and/ or aromatic hydrocarbon derivatives, hydroxy esters, such as sorbitan monolaurate, pine oil, and the like.
  • insecticidal agents of natural or synthetic, of mineral or organic origin, among which come into consideration sulfur, copper arsenate, pyrethrum, allethrin, DMC, HETP, malathion, DDT, BHC, lindane, and others well known to those skilled in the art.
  • Suitable fertilizers would include ammonium sulfate, urea, ammonium phosphate, potassium nitrate, and the like.
  • concentration of the insecticide in the final formulation can vary widely, depending upon the use to which the formulation is to be placed.
  • the insecticide concentration can be as little as 0.1 percent of the weight of the formulation or it can be as great as 50% or even more, in the case of the so-called concentrated formulations which are to be diluted before use.
  • a granular formulation may contain from about 2% to about 35% insecticide by weight. This type of formulation is generally'used as such without further dilution with an insecticidally inert carrier.
  • a dust formulation can contain about 0.25% insecticide up to about 75% insecticide by weight.
  • the dust formulations are first prepared as so- 10% to about 50% insecticide dispersed in the dust, and such concentrate is further diluted to a so-called field strength dust typically having an insecticide concentration of about 0.25 to about 5'%, varying with the use desired and the potency of the toxicant.
  • the wettable powders typically contain a concentration of toxicant on the order of that contained in dust doctrinees as above described. However, they are diluted to field strength by dispersing in water rather than by dispersing in dust.
  • the insecticide was dimethyl 2,2-dichlorovinyl phosphate. It was first formulated with powdered sugar as a bait for houseflies. The insecticide concentration was 1 percent by weight of the formulation. In one formulation, no stabilizer was added. In two other formulations, 2 percent by weight of the formulation of a phenol was present as stabilizer. The amount of the insecticide remaining was determined by analysis after the formulations were held at 130 F., for 2 weeks. The following data were obtained:
  • Toxicant Percent dosage decomposi- (percent tion after by weight 2 weeks at of formula- 130 F.
  • Carrier Stabilizer percent by weight of formulation None 2,6-di-tert-butyl 4-methyl phenol (2%). Pyrax ABB None Do Alpha-naphthol (5% N one 2,6-di-tert-bntyl 4-methyl phenol (5 Alpha-naphthol (5%) Beta-naphthol (5%) Phenol (5%) U! cum CnUrOr cncrgogo pp Percent decomposition after 2 weeks at; 130 F.
  • Carrier Stabilizer (percent by Weight of formulation) None 25 Hydroquinone added as 25 stabilizer (5%). 2,2 Bis(p-hydroxy-phenyl)- 25 propane (5%).
  • a stable solid insecticidal composition comprising in combination:
  • a stable solid insecticidal composition comprising in combination:
  • alky1-O -0( 3 ( ]ha1 wherein alkyl is lower alkyl and hal is a member of the group consisting of chlorine and bromine, (c) a phenol,
  • a stable solid insecticidal composition comprising in combination:
  • a stable solid insecticidal composition comprising in combination:
  • a stable solid insecticidal composition comprising in combination:
  • composition according to claim 6 wherein the phenol is phenol.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
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US80996A 1961-01-06 1961-01-06 Phenol stabilized organo-phosphorous insecticides Expired - Lifetime US3097128A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
NL273220D NL273220A (de) 1961-01-06
BE612272D BE612272A (de) 1961-01-06
NL131123D NL131123C (de) 1961-01-06
US80996A US3097128A (en) 1961-01-06 1961-01-06 Phenol stabilized organo-phosphorous insecticides
CH10762A CH437905A (de) 1961-01-06 1962-01-04 Insektizide Zubereitung
ES0273412A ES273412A1 (es) 1961-01-06 1962-01-04 Mejoras introducidas en la fabricaciën de composiciones insecticidas
BR135470/62A BR6235470D0 (pt) 1961-01-06 1962-01-04 Aperfeicoadas composicoes inseticidas estabilizadas
DE1962S0077409 DE1280001C2 (de) 1961-01-06 1962-01-04 Verwendung phenolischer Stabilisatoren fuer Vinylphosphate enthaltende Schaedlings-bekaempfungsmittel
GB372/62A GB958421A (en) 1961-01-06 1962-01-04 Insecticide formulations
FR883860A FR1332542A (fr) 1961-01-06 1962-01-04 Compositions insecticides constituées par des vinyl phosphates et des phosphonates et des phosphinates apparentés
DK4062AA DK102884C (da) 1961-01-06 1962-01-04 Insektbekæmpelsesmiddel.
OA50490A OA00413A (fr) 1961-01-06 1964-10-28 Compositions insecticides constituées par des vinyl phosphates et des phosphonates et des phosphinates apparentés.
MY33/65A MY6500033A (en) 1961-01-06 1965-12-30 Insecticide formulations

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US80996A US3097128A (en) 1961-01-06 1961-01-06 Phenol stabilized organo-phosphorous insecticides

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US3097128A true US3097128A (en) 1963-07-09

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US80996A Expired - Lifetime US3097128A (en) 1961-01-06 1961-01-06 Phenol stabilized organo-phosphorous insecticides

Country Status (11)

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US (1) US3097128A (de)
BE (1) BE612272A (de)
BR (1) BR6235470D0 (de)
CH (1) CH437905A (de)
DE (1) DE1280001C2 (de)
DK (1) DK102884C (de)
ES (1) ES273412A1 (de)
GB (1) GB958421A (de)
MY (1) MY6500033A (de)
NL (2) NL273220A (de)
OA (1) OA00413A (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3197362A (en) * 1961-06-30 1965-07-27 Montedison Spa Pesticidal liquid formulations stable at low temperatures
US3235452A (en) * 1962-03-05 1966-02-15 Geigy Chem Corp Granular pesticidal compositions and methods of preparation
US3278369A (en) * 1962-11-16 1966-10-11 Ciba Ltd Dimethyldichlorovinyl phosphate compositions stabilized with carboxylic acid anhydrides
US3318937A (en) * 1962-11-22 1967-05-09 Ciba Ltd Carbamyl and thiocarbamyl phosphates
US3364105A (en) * 1963-02-11 1968-01-16 Ciba Ltd Vapour emissive compositions containing dimethyl dichlorovinyl phosphate
US3364109A (en) * 1963-06-21 1968-01-16 Ciba Ltd Hydroxyquinoline-stabilized biocidal organic phosphorus pesticides in finely dispersed silicic acid
US3832464A (en) * 1970-09-11 1974-08-27 Ciba Geigy Ag Pesticidal compositions containing phosphoric acid esters and elemental sulphur
US3846557A (en) * 1972-05-26 1974-11-05 Univ California Bait for synanthropic flies and method for making same
US3852439A (en) * 1970-09-11 1974-12-03 Ciba Geigy Ag Compositions with a base of phosphoric esters combined with a stabiliser
US3976769A (en) * 1970-09-11 1976-08-24 Airwick Industries, Inc. Pesticidal compositions containing phosphoric esters and divalent sulphur compounds
US4323556A (en) * 1980-01-23 1982-04-06 Montedison S.P.A. Solid formulations containing pheromones and method of using same
US4325941A (en) * 1979-11-29 1982-04-20 Montedison S.P.A. Solid formulations containing pheromones and method of using same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744128A (en) * 1952-02-29 1956-05-01 Shell Dev Olefinically unsaturated phosphates
US2865944A (en) * 1955-12-28 1958-12-23 Shell Dev Complex amido-substituted esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids
US2894014A (en) * 1955-12-28 1959-07-07 Shell Dev Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids
US2898341A (en) * 1956-11-22 1959-08-04 Boehringer Sohn Ingelheim Organic phosphoric and thiophosphoric acid esters
US2913367A (en) * 1956-03-09 1959-11-17 Thomas P Dawson Some phosphorus containing derivatives of alkyl acetothiolacetate
US2956073A (en) * 1960-04-13 1960-10-11 Shell Oil Co Insecticidally active esters of phosphorus acids and preparation of the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2967127A (en) * 1957-05-29 1961-01-03 Minerals & Chem Philipp Corp Toxicant carrier and pesticidal composition containing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744128A (en) * 1952-02-29 1956-05-01 Shell Dev Olefinically unsaturated phosphates
US2865944A (en) * 1955-12-28 1958-12-23 Shell Dev Complex amido-substituted esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids
US2894014A (en) * 1955-12-28 1959-07-07 Shell Dev Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids
US2913367A (en) * 1956-03-09 1959-11-17 Thomas P Dawson Some phosphorus containing derivatives of alkyl acetothiolacetate
US2898341A (en) * 1956-11-22 1959-08-04 Boehringer Sohn Ingelheim Organic phosphoric and thiophosphoric acid esters
US2956073A (en) * 1960-04-13 1960-10-11 Shell Oil Co Insecticidally active esters of phosphorus acids and preparation of the same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3197362A (en) * 1961-06-30 1965-07-27 Montedison Spa Pesticidal liquid formulations stable at low temperatures
US3235452A (en) * 1962-03-05 1966-02-15 Geigy Chem Corp Granular pesticidal compositions and methods of preparation
US3278369A (en) * 1962-11-16 1966-10-11 Ciba Ltd Dimethyldichlorovinyl phosphate compositions stabilized with carboxylic acid anhydrides
US3318937A (en) * 1962-11-22 1967-05-09 Ciba Ltd Carbamyl and thiocarbamyl phosphates
US3364105A (en) * 1963-02-11 1968-01-16 Ciba Ltd Vapour emissive compositions containing dimethyl dichlorovinyl phosphate
US3364109A (en) * 1963-06-21 1968-01-16 Ciba Ltd Hydroxyquinoline-stabilized biocidal organic phosphorus pesticides in finely dispersed silicic acid
US3832464A (en) * 1970-09-11 1974-08-27 Ciba Geigy Ag Pesticidal compositions containing phosphoric acid esters and elemental sulphur
US3852439A (en) * 1970-09-11 1974-12-03 Ciba Geigy Ag Compositions with a base of phosphoric esters combined with a stabiliser
US3976769A (en) * 1970-09-11 1976-08-24 Airwick Industries, Inc. Pesticidal compositions containing phosphoric esters and divalent sulphur compounds
US3846557A (en) * 1972-05-26 1974-11-05 Univ California Bait for synanthropic flies and method for making same
US4325941A (en) * 1979-11-29 1982-04-20 Montedison S.P.A. Solid formulations containing pheromones and method of using same
US4323556A (en) * 1980-01-23 1982-04-06 Montedison S.P.A. Solid formulations containing pheromones and method of using same

Also Published As

Publication number Publication date
NL273220A (de)
DK102884C (da) 1965-10-18
BE612272A (de)
GB958421A (en) 1964-05-21
BR6235470D0 (pt) 1973-05-10
ES273412A1 (es) 1962-06-01
OA00413A (fr) 1966-05-15
DE1280001C2 (de) 1969-06-04
NL131123C (de)
MY6500033A (en) 1965-12-31
CH437905A (de) 1967-06-15
DE1280001B (de) 1968-10-10

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