US3216894A - Phosphonic acid esters and process for their production - Google Patents

Phosphonic acid esters and process for their production Download PDF

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Publication number
US3216894A
US3216894A US17487A US1748760A US3216894A US 3216894 A US3216894 A US 3216894A US 17487 A US17487 A US 17487A US 1748760 A US1748760 A US 1748760A US 3216894 A US3216894 A US 3216894A
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United States
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grams
methyl
mol
compounds
oil
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US17487A
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Lorenz Walter
Schrader Gerhard
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Bayer AG
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Bayer AG
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
    • 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
    • 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
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4018—Esters of cycloaliphatic acids
    • 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
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650905—Six-membered rings having the nitrogen atoms in the positions 1 and 2
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

Definitions

  • the present invention relates to and has as its objects new and useful phosphonic acid esters and processes for their production.
  • the new compound of this invention may be called phosphonic acid esters of the enolic ester type and thus they may be represented by the following formula
  • R stands for aliphatic or aromatic radicals
  • R stands for aliphatic radicals
  • X and Y stand for oxygen or sulfur
  • Z stands for further atoms necessary to complete a compound which is able to react in the ketoor enol-form, and which in the instant case as said above is present in the state of the enolic ester type.
  • Phosphoric acid esters of the above mentioned type recently have become of importance of the insecticidal or generally pesticidal type.
  • US. Patents No. 2,754,243 and No. 2,854,244 a number of compounds have been described which may .be considered as somewhat related to the above said formula with the exception that instead of phosphoric acid esters the compounds of the present invention are derivatives of the phosphonic acid ester type.
  • the new and valuable class of insecticidal phosphonic acid esters can be obtained by reacting enolisable ketoor thioketo-compounds with O- alkyl-thionophosphonic acid halides or phosphonic acid halides.
  • enolisable ketoor thioketo-compounds belong above all to the heterocyclic group and are for example (the designation means in the following either the enolor keto-form,'the notation which has become most familiar in organic chemistry): dioxotetra hydrofuran derivatives, and pyrazolones, such as e.g.,
  • enolisable are likewise suitable for the process of the present invention.
  • aceto-acetic acid esters and amides malonic esters, malonic ester seminitriles, halo-acetoacetic acid amides
  • chloro-acetic esters chloro-malonic esters
  • di-. hydroresorcinols such as, e.g., 5.5-dialkyl-dihydroresorcinol and similar compounds or their thio-analogues
  • the reaction is preferably carried out with the alkali metal salts of enolates or with enolates in the presence of alkali metal hydroxides in inert organic solvents at room temperature or slightly elevated temperature.
  • the new compounds are valuable insecticides, which for the most part possess the advantage over the corresponding phosphoric acid esters, that they are sometimes more readily crystallizable andtherefore simpler in handling and in formulation.
  • the invention concerns compounds which are new insecticides which in part are effective against resistant forms of insect pests.
  • the compounds obtained according to the invention are preferably applied in combination with the usual extending or diluent agents, as known for other phosphoric acid esters.
  • the usual extending or diluent agents as known for other phosphoric acid esters.
  • liquid combinations it is expedient to use commercial emulsifiers for improved distribution of the active compounds-especially in water.
  • the compounds of the following formulae have been tested against aphids. and flies respectively.
  • Aqueous solutions of the aforementioned compounds have been prepared by admixing them with the same amount of an auxiliary solvent (acetone).
  • a commercial emulsifier (benzyl hydroxy diphenyl polgylcol ether) is added in an amount of 20% referred to active ingredient. This premixture then is diluted with water to the desired concentration.
  • the tests have been carried out as follows: (a) against aphids (species Doralis fabae).
  • Heavily infested bean plants (Vitia faba) have been sprayed drip wet with solution of Compound I prepared as indicated above in a concentration of 0.01%. The effect has been determined by evaluation after 24 hours by counting the dead pests either on the surface of the soil or still remaining on the plants, thereby complete killing has been obtained; (b) against flies (Musca domestica). About 50 flies are placed under covered petri dishes in which drop wet filter paper has been placed which is sprayed with an insecticidal solution of Compound II prepared as shown above in a concentration of 0.00001%. The living status of the flies has been determined after 24 hours, and complete killing has been obtained.
  • the product is filtered ofi with suction, the filtrate poured into water and the oil taken up in benzene. After washing with water and drying over sodium sulfate and distilling oil the solvent 70 grams of a pale yellow oil are obtained, the oil being no longer distillable. Yield: 78.8% of the theoretical. The same ester is obtained if pyridine is used as solvent and acid-binding agent. The yield is then also 78-79% of the theoretical. Spider mites are killed completely With 0.01% solutions. Systemic action with 0.1% solutions: 100%. The compound shows an ovicidal action.
  • a phosphonic acid ester of the following formula 5 R1 X I wherein R stands for a member selected from the group consisting of phenyl, chlorophenyl, cyclohexyl, lower alkenyl, lower-alkoxy-lower-alkenylene and lower alkyl having up to 8 carbon atoms, R stands for lower alkyl having up to 4 carbon atoms, X and Y stand for members selected from the group consisting of oxygen and sulfur, R stands for lower alkyl having up to 4 carbon atoms and R stands for a member selected from the group consisting of lower alkyl having up to 4 carbon atoms and lower alkylmercapto having up to 4 carbon atoms.
  • the method of controlling insects which comprises contacting the insects with a toxic amount of a phosphonothioate of the structure IRVING MARCUS, MORRIS O. WOLK, WALTER A.

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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)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US17487A 1959-03-28 1960-03-25 Phosphonic acid esters and process for their production Expired - Lifetime US3216894A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF28060A DE1140580B (de) 1959-03-28 1959-03-28 Verfahren zur Herstellung von Thionophosphonsaeureestern

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US3216894A true US3216894A (en) 1965-11-09

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US (1) US3216894A (da)
BE (1) BE589122A (da)
CH (1) CH387004A (da)
DE (1) DE1140580B (da)
GB (1) GB926234A (da)
NL (2) NL249896A (da)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325492A (en) * 1964-03-26 1967-06-13 Bayer Ag Thiophosphoric (-phosphonic, -phosphinic) or dithiophosphoric (-phosphonic, -phosphinic) acid esters
US3336314A (en) * 1964-12-02 1967-08-15 Mobil Oil Corp O-quinolinyl s-alkyl-alkylphos-phonodithioates
US3384540A (en) * 1965-07-14 1968-05-21 Stauffer Chemical Co Pesticidal compositions and methods containing phosphorous-containing esters of 2-thiomethyl mercapto pyrimidines
US3700686A (en) * 1969-03-14 1972-10-24 Bayer Ag O-alkyl-o-pyrazolyl-phosphoric, phosphonic, thionophosphoric and thionophosphonic acid esters
US3700687A (en) * 1969-04-05 1972-10-24 Bayer Ag (thiono) phosphoric (phosphonic)-acid esters
US3723456A (en) * 1970-10-09 1973-03-27 Bayer Ag Pyrazolo-(thiono)phosphoric(phosphonic) acid esters
FR2162589A1 (da) * 1971-12-10 1973-07-20 Ciba Geigy Ag
US3759941A (en) * 1965-08-20 1973-09-18 Sankyo Co Insecticidal isoxazole derivatives
US3775057A (en) * 1969-02-24 1973-11-27 Petrolite Corp Use as corrosion inhibitors, nitrogen-heterocyclic phosphonates
US3862170A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylphosphoric acid esters
US3862124A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylthiophosphoric acid esters
US3880997A (en) * 1965-05-26 1975-04-29 Bayer Ag Insecticidal and acaricidal phosphorous-containing esters of 2-hydroxyquinoxaline
US3880584A (en) * 1971-08-19 1975-04-29 Petrolite Corp Use as corrosion inhibitors:acridine phosphoric compounds
US3888626A (en) * 1971-08-19 1975-06-10 Petrolite Corp Use as corrosion inhibitors: phenanthridine phosphonic compounds
US3952098A (en) * 1970-07-30 1976-04-20 Bayer Aktiengesellschaft Compositions and methods of combatting insects and acarids using pyrazolo-(thiono)-phosphoric(phosphonic) acid esters
US3980777A (en) * 1974-07-02 1976-09-14 Bayer Aktiengesellschaft O-alkyl-O-[2-alkylthio-imidazol(4)yl](thiono)-phosphoric(phosphonic) acid esters and ester-amides
US4014996A (en) * 1974-08-24 1977-03-29 Bayer Aktiengesellschaft O-Alkyl-O-pyrimidin (2)yl-thionophosphonic acid esters
US4035487A (en) * 1973-09-10 1977-07-12 Ciba-Geigy Corporation Pesticidal 2-phenyl-1,2,3-triazolyl-(4) and-triazox-(1)-yl-(4) phosphate and thiosphosphate esters
US4059696A (en) * 1975-05-27 1977-11-22 Bayer Aktiengesellschaft Pyrimidine (4,6)diyl-bis-(thiono)(thiol)-phosphoric(phosphonic)acid esters
US4104375A (en) * 1977-02-24 1978-08-01 Stauffer Chemical Company Isoxazole phosphates and phosphonates
US4115542A (en) * 1976-05-20 1978-09-19 Bayer Aktiengesellschaft O-Alkyl-O-(6-alkanesulphonyloxy-pyrimidin(4)yl)-(thiono) (thiol) phosphoric (phosphonic) acid esters and ester-amides and arthropodicidal compositions and methods of combating arthropods using them
US4155999A (en) * 1976-09-02 1979-05-22 Bayer Aktiengesellschaft Pesticidally active O-alkyl-O-[6-tert.-butyl-pyrimidin(4)yl]-(thiono)(thiol)-phosphoric(phosphonic) acid esters
US4159323A (en) * 1976-05-03 1979-06-26 Bayer Aktiengesellschaft O,O'-Dialkyl-4,6-diphosphorylated pyrimidines and compositions and methods for combating arthropods containing them
US4163052A (en) * 1976-09-01 1979-07-31 Bayer Aktiengesellschaft Pesticidal O-[3-t-butylpyrazol-5-yl]phosphoric and thionophosphoric acid esters
US4168304A (en) * 1977-01-27 1979-09-18 Bayer Aktiengesellschaft Combating pests with 4-substituted-pyrimidin-6-yl (thiono)-phosphoric (phosphonic) acid esters or ester amides
EP0007466A1 (de) * 1978-07-15 1980-02-06 Bayer Ag 2-Cyclopropyl-pyrimidin(4)yl-thionophosphonsäureester, Verfahren zu ihrer Herstellung, ihre Verwendung als Insektizide und Akarizide, diese enthaltende Schädlingsbekämpfungsmittel und Verfahren zu deren Herstellung
US4940698A (en) * 1987-09-02 1990-07-10 Bayer Aktiengesellschaft Insecticidal thionophosphonates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2343931A1 (de) * 1973-08-31 1975-04-03 Bayer Ag Pyrimidin(4)-yl-(thiono)-(thiol)-phosphor(phosphon)-saeureester bzw. -esteramide, verfahren zu ihrer herstellung sowie ihre verwendung als insetktizide und akarizide
AU511744B2 (en) * 1976-09-25 1980-09-04 Bayer Aktiengesellschaft Pyrimidin(5)yl-(thiono) (thiol) phosporic-(phosphonic) acid esters and ester-amides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT489937A (da) * 1951-04-20 1900-01-01
US2867646A (en) * 1956-04-09 1959-01-06 Shell Dev Complex arylphosphonates
BE568698A (da) * 1957-06-24

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325492A (en) * 1964-03-26 1967-06-13 Bayer Ag Thiophosphoric (-phosphonic, -phosphinic) or dithiophosphoric (-phosphonic, -phosphinic) acid esters
US3336314A (en) * 1964-12-02 1967-08-15 Mobil Oil Corp O-quinolinyl s-alkyl-alkylphos-phonodithioates
US3880997A (en) * 1965-05-26 1975-04-29 Bayer Ag Insecticidal and acaricidal phosphorous-containing esters of 2-hydroxyquinoxaline
US3384540A (en) * 1965-07-14 1968-05-21 Stauffer Chemical Co Pesticidal compositions and methods containing phosphorous-containing esters of 2-thiomethyl mercapto pyrimidines
US3759941A (en) * 1965-08-20 1973-09-18 Sankyo Co Insecticidal isoxazole derivatives
US3775057A (en) * 1969-02-24 1973-11-27 Petrolite Corp Use as corrosion inhibitors, nitrogen-heterocyclic phosphonates
US3700686A (en) * 1969-03-14 1972-10-24 Bayer Ag O-alkyl-o-pyrazolyl-phosphoric, phosphonic, thionophosphoric and thionophosphonic acid esters
US3700687A (en) * 1969-04-05 1972-10-24 Bayer Ag (thiono) phosphoric (phosphonic)-acid esters
US3952098A (en) * 1970-07-30 1976-04-20 Bayer Aktiengesellschaft Compositions and methods of combatting insects and acarids using pyrazolo-(thiono)-phosphoric(phosphonic) acid esters
US3723456A (en) * 1970-10-09 1973-03-27 Bayer Ag Pyrazolo-(thiono)phosphoric(phosphonic) acid esters
US3862170A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylphosphoric acid esters
US3862124A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylthiophosphoric acid esters
US3880584A (en) * 1971-08-19 1975-04-29 Petrolite Corp Use as corrosion inhibitors:acridine phosphoric compounds
US3888626A (en) * 1971-08-19 1975-06-10 Petrolite Corp Use as corrosion inhibitors: phenanthridine phosphonic compounds
FR2162589A1 (da) * 1971-12-10 1973-07-20 Ciba Geigy Ag
US4035487A (en) * 1973-09-10 1977-07-12 Ciba-Geigy Corporation Pesticidal 2-phenyl-1,2,3-triazolyl-(4) and-triazox-(1)-yl-(4) phosphate and thiosphosphate esters
US3980777A (en) * 1974-07-02 1976-09-14 Bayer Aktiengesellschaft O-alkyl-O-[2-alkylthio-imidazol(4)yl](thiono)-phosphoric(phosphonic) acid esters and ester-amides
US4014996A (en) * 1974-08-24 1977-03-29 Bayer Aktiengesellschaft O-Alkyl-O-pyrimidin (2)yl-thionophosphonic acid esters
US4059696A (en) * 1975-05-27 1977-11-22 Bayer Aktiengesellschaft Pyrimidine (4,6)diyl-bis-(thiono)(thiol)-phosphoric(phosphonic)acid esters
US4159323A (en) * 1976-05-03 1979-06-26 Bayer Aktiengesellschaft O,O'-Dialkyl-4,6-diphosphorylated pyrimidines and compositions and methods for combating arthropods containing them
US4115542A (en) * 1976-05-20 1978-09-19 Bayer Aktiengesellschaft O-Alkyl-O-(6-alkanesulphonyloxy-pyrimidin(4)yl)-(thiono) (thiol) phosphoric (phosphonic) acid esters and ester-amides and arthropodicidal compositions and methods of combating arthropods using them
US4163052A (en) * 1976-09-01 1979-07-31 Bayer Aktiengesellschaft Pesticidal O-[3-t-butylpyrazol-5-yl]phosphoric and thionophosphoric acid esters
US4155999A (en) * 1976-09-02 1979-05-22 Bayer Aktiengesellschaft Pesticidally active O-alkyl-O-[6-tert.-butyl-pyrimidin(4)yl]-(thiono)(thiol)-phosphoric(phosphonic) acid esters
US4168304A (en) * 1977-01-27 1979-09-18 Bayer Aktiengesellschaft Combating pests with 4-substituted-pyrimidin-6-yl (thiono)-phosphoric (phosphonic) acid esters or ester amides
US4104375A (en) * 1977-02-24 1978-08-01 Stauffer Chemical Company Isoxazole phosphates and phosphonates
EP0007466A1 (de) * 1978-07-15 1980-02-06 Bayer Ag 2-Cyclopropyl-pyrimidin(4)yl-thionophosphonsäureester, Verfahren zu ihrer Herstellung, ihre Verwendung als Insektizide und Akarizide, diese enthaltende Schädlingsbekämpfungsmittel und Verfahren zu deren Herstellung
US4254113A (en) * 1978-07-15 1981-03-03 Bayer Aktiengesellschaft Combating arthropods with O-Alkyl-O-(2-cyclopropyl-6-methyl-pyrimidin-4-yl)-thionophosphonic acid esters
US4940698A (en) * 1987-09-02 1990-07-10 Bayer Aktiengesellschaft Insecticidal thionophosphonates

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GB926234A (en) 1963-05-15
CH387004A (de) 1965-01-31
NL249896A (da) 1900-01-01
DE1140580B (de) 1962-12-06
BE589122A (da) 1900-01-01
NL126404C (da) 1900-01-01

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