US3284546A - Thiophosphoric esters - Google Patents

Thiophosphoric esters Download PDF

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US3284546A
US3284546A US234541A US23454162A US3284546A US 3284546 A US3284546 A US 3284546A US 234541 A US234541 A US 234541A US 23454162 A US23454162 A US 23454162A US 3284546 A US3284546 A US 3284546A
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eggs
hours
leaves
water
discs
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Fusco Raffaello
Rossi Giogio
Tonelli Pietro De Pietri
Barontini Alberto
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Montedison SpA
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    • 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
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • 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
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • R, R and R represent the same or different alkyl radicals of low molecular Weight, having linear or branched chains, saturated or unsaturated, at least one of the R, R R radicals containing one or more fluorine atoms; and R is hydrogen or a phenyl radical, and X stands for oxygen or sulfur.
  • R and R stand preferably for CH C HA F, C H R is preferably a radical selected from the group consisting of CH C H CH CF CHF and C2H4F.
  • Another object of the present invention is to provide a new process for preparing the compounds of the formula (I). Said process consists in reacting the alkaline 3,284,546 Patented Nov. 8, 1966 R O I C R wherein R, R R R have the above indicated meaning, Me is an alkali metal, and Hal is chlorine or bromine.
  • the new compounds occur as oily substances which are insoluble in water and soluble in organic solvents. They are characterized by a high activity against parasites, particularly against mites. It is known that it is particularly desirable that substances employed for control of mites display an effective action either against adults or against the eggs, and moreover that they be end-owed with great persistance of activity, namely that they maintain their efficiency for a long time after application.
  • the compounds comprised in the claimed class act according to a special mechanism which inhibits the hatching of the eggs, which the females lay after having been in contact with the active compounds or after ingesting them (or their metabolites), on untreated leaves (see Example 31 Table XIII and Example 32Table XIV).
  • the aphid Acyrthosiphon onobrychl's (Emiphtera) is wholly destroyed, within 24 hours from treatment, by spraying with solutions containing l of active substances on broad bean seedlings, previously infested, said substances being those of Examples 5, 6, 7, 8.
  • N-methyl-l-naphthylcarbamate usually employed against larvae of Lepidoptera.
  • Example 8 mosquito which were left for 24 hours in a water solu-- tion containing one part per million of active substance, were 100% destroyed by the product obtained in Example 5, 33% by that of Example 6, 4% by that of Example 7, and 100% by that of Example 8.
  • the compounds in accordance with the present invention may be formulated without difficulty by conventional means.
  • the compounds of the invention may be used either as sole active ingredient or in admixture with each other or in admixture with other pesticides having a different activity.
  • compositions as emulsifiable liquids, which are obtained by dissolving the active substances or substances in suitable solvents or mixture of solvents, together with one or more surface active substances added to make the preparation emulsifiable in water.
  • the substances of the present invention may be formulated as powders for dry dusting, by direct admixture of the active substance or substances with inert substances such as talc, pyrophyllite or china clay, or as wettable powders by direct admixture of the active substance with inert substances such as kieselguhr, clay, attapulgyte, and surfactants, which make the formulated compound dispersible in water.
  • inert substances such as talc, pyrophyllite or china clay
  • wettable powders by direct admixture of the active substance with inert substances such as kieselguhr, clay, attapulgyte, and surfactants, which make the formulated compound dispersible in water.
  • Toxicity data toward cold-blooded animals is presented below. The indicated values represent the L.D. (lethal dose) 50 expressed in mg./kg. of treated animal (white mouse).
  • EXAMPLE 1 80 ml. of acetone solution of potassium salt of BB-difluoro-ethyl-dithiophosphoric acid of titer 2.5 mol/ lit. are added to 21.6 g. (0.2 mole) methyl chloroacetate; the solvent is kept at reflux for 1 hour. The reaction mixture is cooled and diluted with 200 ml. water; the organic phase is decanted, taken up again with 50 ml. methylene chloride and washed with water. After solvent removal under reduced pressure, 34.5 g. of oily substance are obtained as residue, said substance constituting the methylester of [3/3-difluorethyl-dithio-phosphorylacetic acid, i.e.
  • EXAMPLE 2 64 ml. of acetone solution of potassium salt of fiB-difiuorethyl-dithiophosphoric acid of titer 2.5 mol/lit. are added to 19.6 g. ethyl chloroacetate; the solvent is then kept at reflux for 30 minutes. The reaction mixture is then cooled at room temperature and filtered by suction from the formed KCl. The acetone solution is diluted with water; the separated oily phase is taken again with 40 ml. of methylene chloride and washed with water. After solvent evaporation under reduced pressure, 29 g. of an oily substance are obtained comprising the ethylester of ,Bfl-difluorethyl-dithio-phosphoryl acetic acid of the formula:
  • EXAMPLE 4 118 ml. of a water solution of sodium salt of flp-difluorethyl-dithiophosphoric acid of titer 1.98 mol/ lit. are added to 48.6 g. a-bromophenylacetate diluted with 70 ml. acetone; the mixture is stirred at room temperature (about 20 C.) for 50 hours. The reaction mixture separates in an organic phase which is concentrated to a small volume under reduced pressure, and in an aqueous phase which is extracted with 25 ml. methylene chloride. The evaporation residue is combined with chloromethylene extract, then washed with water, dried upon CaCl and reduced to dryness under reduced pressure. A 74 g. residue is obtained in the form of faint yellow oil, consist- 6 ing of ethyl ester of 5,8-difluorethyl-dithiophosphoryl-phem yl-acetic acid of the formula:
  • EXAMPLE 5 71.4 ml. of a water solution of sodium salt of diethylphosphoric acid (titer 3.22 mol/lit.) are added to 52.5 g. a-bromophenyl-acetate of ,B-fiuorethyl alcohol diluted with 70 ml. acetone; the mixture is stirred. Owing to the exothermic reaction, the temperature rises from 20 to 30 C. After stirring for 15 hours, the mixture separates in an organic phase which is concentrated to a small volume under reduced pressure, producing an aqueous phase which is extracted with 25 ml. methylene chloride.
  • EXAMPLE 6 118 ml. of an aqueous solution of the sodium salt of Bfl-difluoroethyl-dithiophosphoric acid (titer 1.98 mol/ lit.) are added to 52.2 to bromophenylacetate of fi-fiuorethyl alcohol diluted with 70 ml. acetone. The mixture is stirred at room temperature (2023 C.) for 15 hours. The organic layer which separates is poured into 50 ml. water, taken up again with 30 ml. methylene chloride, washed once more with water, then dried on CaCl and evaporated under reduced pressure. 72.7 g. -of an orangeyellow oil are left, constituted of the B-fiuorethylester of flB-difluorethyl-dithiophosphoryl phenylacetic acid of the formula:
  • EXAMPLE 7 41.6 g. potassium diethyl mono-thiophosphate and 52.2 g. bromophenyla-cetate of fl-fluorethyl alcohol are mixed with 70 ml. acetone.
  • the reaction is exothermic.
  • the reaction mixture is kept to solvent refluxing for 1 hour, then is stirred at room temperature for further 24 hours.
  • the formed KBr is filtered olf by suction, then most of the solvent is removed under reduced pressure.
  • the residue is poured into 50 ml. water, taken up again with methylene chloride, washed 'with water, then with a NaHCO dilute solution and finally once more with water.
  • EXAMPLE 8 92.7 ml. of a water solution of the sodium salt of dimethyl-dithiophosphoric acid (liter 2.48 mol/lit.) are added to 52.8 g. bromophenyl-acetate of B-fluorethyl alcohol, diluted with 80 ml. acetone; then the mixture is stirred at room temperature (20-23 C.) for 20 hours. The organic phase is separated :by decantation, and is reduced to a small volume under reduced pressure and poured into 50 ml. water. After being taken up again with 30 ml. methylene chloride, washed with water, dried on CaCl and evaporated under reduced pressure, 59.7 g. of a light reddish oil are obtained, consisting of the B-fiuorethylester of dimethyl-dithiophosphoryl phenylacetic acid of the formula:
  • EXAMPLE 9 49 ml. of a water solution of sodium salt of diethyl dithiophosphoric acid (titer 3.22 mol/ lit.) are added to 21 g. ohloroacetate of p-fluorethyl alcohol diluted with 50 ml. acetone; the mixture is stirred at about 25 C. for 10 hours. The reaction mixture is diluted with 70 ml. water, and the organic layer is separated by decantation and reduced to small volume under reduced pressure. The residue is taken up again with 30 ml. methylene chloride, washed with water, dried on CaCl and evaporated under reduced pressure. 38.5 g. of a light yellow oil are obtained as residue, consisting of the fi-fiuorethylester of diethyl dithiophosphorylacetic acid of the formula:
  • EXAMPLE 10 69 m1. of a water solution of the sodium salt of B 8difluorethyl-dithiophosphoric acid (titer 1.84 mol/lit.) are added to 15.5 g. chloroacetate of B-fiuorethyl alcohol diluted with 40 ml. acetone; the mixture is then stirred at room temperature for 30 hours. The organic phase is separated, evaporated under reduced pressure, and the residue poured into 35 ml. water. It is then separated, taken up again with methylene chloride and washed once more with water. After drying on CaCl and evaporating under pressure, 28 g. of [light yellow oil are obtained, consisting of the fl-fiuorethylester of BB-difluorethyl dithiophosphorylacetic acid, having the formula:
  • EXAMPLE 12 94 ml. of a Water solution of the sodium salt of Bfl-difluorethyl dithiophosphoric acid (titer 1.84 mol/lit.) are added to 49.2 g. bromophenylacetate of 2,2-3,3-tetrafluoropropyl alcohol diluted with 50 ml. acetone; the mixture is stirred at a temperature in the range 20-25 C. for 9 hours. The organic phase is separated and concentrated under reduced pressure; the residue is taken up again with 30 m1. methylene chloride and washed with water, then with diluted NaCHO solution and finally once more with water. After drying on CaCl and evaporation under reduced pressure, a residue is obtained of 61.5 g. oily product, consisting of the 2,2-3,3-tetrafluoropropylester of pfl-difluoroethyl dithiophosphoryl phenylacetic acid of the formula:
  • EXAMPLE 14 27 g. of potassium [3p-difluoroethyl-thiophosphate and 24.3 g. of a-ethyl bromophenylacetate are mixed in cc. of acetone while agitating. The mixture is heated to 40 C. for 2 hours and is kept at room temperature for 20 hours. Most of the solvent is eliminated under reduced pressure and the residue is poured into 60 cc. of H 0. The oil thus obtained is extracted with 50 cc. of methylene chloride and is dried on CaCl After complete elimination of the solvent under reduced pressure 29.5 g. of an oily liquid essentially consisting of the ethylene ester of flB-difluoroethyl thiophosphorylphenyl acetic acid, are obtained.
  • EXAMPLE 16 27 g. of potassium fiB-difluoroethyl-thiophosphate and 26 g. of fl-fluoroethyl a-bromophenylacetate are mixed with 100 cc. of acetone while agitating.
  • Example 2 By operating as indicated in Example 1, 26 g. of an oily liquid are obtained. This liquid is then purified by dissolving it in 50 cc. of CH Cl and then precipitating with 110 cc. of petroleum ether.
  • a spraying formulation which may be profitably employed in the control of acarids and the eggs thereof, may be prepared by dissolving 20 parts of the B-fluoroethylester of diethyl dithiophosphoryl phenylacetic acid in 77 parts xylene, and by adding 2 parts of an anionic surfactant selected from the class of alkylarylsulphonates or alkylsulphates, and 1 part of a non-ionic surfactant selected from the class of ethylene oxide condensation products with fatty acids or with fatty alcohols or alkylphenols.
  • a spraying formulation which may be employed against acarids and the eggs thereof, is prepared by dissolving 20 parts of fi-fluoro-ethylester of Bfl-difiuoroethyl dithiophosphorylacetic acid in 75 parts xylene and adding 2.5 parts of an anionic surfactant selected from the class of alkylarylsulphonates or alkylsulphates and 2.5 parts of a non-ionic surfactant selected from the class of ethylene oxide condensation products with fatty acids, or alcohols, or with alkyl-phenols.
  • an anionic surfactant selected from the class of alkylarylsulphonates or alkylsulphates
  • a non-ionic surfactant selected from the class of ethylene oxide condensation products with fatty acids, or alcohols, or with alkyl-phenols.
  • a spraying formulation which may be employed in the control of acarids and their eggs is prepared by dissolving parts of B-fluoro-ethylester of dimethyldithiophosphoryl phenylacetic acid and 20 parts of a-cyanisoproylamide of O,O-diethyl diphosphoryl acetic acid in 67 parts xylene, while adding 2 parts of an anionic surfactant selected from the class consisting of al-kylarylsulphonates or alkylsulphates, and 1 part of a non-ionic surfactant selected from the class consisting of the ethylene oxide condensation products with fatty acids or alcohols or with alkylphenols.
  • a wcttable powder may be suitably prepared by mixing 3-5% of a compound belonging to the claimed class together with 97-95% talc.
  • a wettable powder may be suitably prepared by mixing 20% of a compound belonging to the claimed class together with 75% diatomaceous earth and 5% of an anionic surfactant, selected from the class consisting of alkylarylsulphonates or alkylsulphates.
  • Tests on pot plants.--Discs having a diameter of 2.8 cm. are recovered from apple or bean leaves and sprayed with the products under tests before or after having been infested with the adults.
  • EXAMPLE 22 Activity against adults is determined by direct spraying at Metatetranychus ulmi S, on discs of apple tree leaves, in the laboratory.
  • Discs are infested, on the upper leaf face, each with 60 adult females, then sprayed with the products to be tested and kept for 48 hours in open Petri dishes as 24-26 C.
  • Ovicide activity is determined by direct spraying eggs of Metatetranychus ulmi S on discs of apple tree leaves, in the laboratory.
  • Discs are infested, each with 100 adult females; after 24 hours the females are removed, and the discs together with eggs are sprayed with the products to be tested and kept, at 2426 C., in open Petri dishes for a few days beyond the hatching date of unsprayed eggs (check).
  • Plants are sprayed with the products at 0.02% of active substance, then 1, 3, 6, 13 and 18 days after the day of treatment 8 leaves are gathered from each plant. From the leaves are obtained the discs, which are infested partly on the upper side and partly on the underlying side of the leaf, each with 100 adult females. After 24 hours the mites are removed, and the discs together with eggs are kept inside of open Petri dishes, for a few days beyond the hatching date of untreated eggs. The results are reported in Table IV.
  • Discs are sprayed with the products to be tested and after two and half hours are infested, each with 100 adult 25 Percentage unhatched egg-s females; after 24 hours the females are removed and the ogzgodugt dsldesiziggg In discs together with the eggs are sprayedav th the product ggfi Z? 1 3 6 13 18 to be tested and kept, at 242 6 C., inside open Petri day days days days days dishes, for several days beyond the hatching date of unsprayed eggs.
  • the ascertained percentages of unhatched 5 100 100 99 96 72 100 100 98 50 49 eggs are reported in Table III.
  • Persistance of activity against adults is determined by measuring percentage mortality, at diiferent time intervals after treatment (1, 3, 6 and 13 days), of the adults removed after 24 hours of contact with the surface of treated leaves, according to Example 22.
  • EXAMPLE 28 Activity against adults and eggs of Metatetranychus Table VI I Eggs Adults Number of adults observed Product obtained Percent on 100 leaves in Example Number of unof eggs hatched observed eggs Before 2 days 13 days treatment after after treatment treatment.
  • EXAMPLE 29 Activity against adults is determined by residual effect a short time (24 hours) after treatment, on Metaletranychus ulmi susceptible strain S and resistant strain R.
  • the test was carried out in the field by spraying (on July 25, 1961) young apple trees with the products under examination at a concentration 0.02% of active substance. 24 hours after treatment 5 leaves per plant are gathered; from said leaves the discs are obtained whereupon adult mites belonging to the two above-mentioned strains are allowed to rest for 24 hours. The results are reported in Table VIII.
  • ulmz' S is determined by direct spraying on apple tree plants, on the field. The plants are infested with mites in the field and after about one month are sprayed with the products under examination, at 0.02% concentration of active substance.
  • EXAMPLE 3O Persistence of activity is determined against eggs of Metatetranychus ulmi susceptible strain S and resistant strain R, said eggs being laid by untreated females on leaves of apple trees sprayed on the field.
  • EXAMPLE 31 Activity against adults of Tetranychus telarius, on discs of bean leaves, in the laboratory.
  • Discs are infested, each with 60 adult females, then sprayed with the products under examination and kept for 48 hours inside of open Petri dishes, at 2436 C.
  • Discs are infested, each with 50 adult females; after 24 hours the females are removed and the discs are sprayed with the products under examination and kept at 2426 C. inside of open Petri dishes for several days beyond'the hatching date of the untreated testimony eggs. The noted percentages of unhatched eggs are reported in Table XI.
  • the eggs are laid by untreated females on discs of bean leaves, in the laboratory.
  • the discs are sprayed with the product under examination, and after two and a half hours they are infested each with adult females. After 24 hours the mites are removed, and the discs are kept at 24-26 C. inside of open Petri dishes for several days beyond the hatching date of unsprayed eggs. The noted percentages are reported in Table XII.
  • lower alkyl means alkyl radicals having up to six carbon atoms.
  • RrO i i R in which R, R and R are taken from the group consisting of lower alkyl, lower alkenyl, lower alkyny l, fluorolower alkyl, fluoro-lower alkenyl, and fluorolower alkynyl; at least one of the R, R and R radicals being one of said fluoro radicals; R being taken from the class consisting of hydrogen and phenyl; X being taken from the class consisting of sulfur and oxygen. 2.
  • R, R and R are taken from the radicals consisting of lower alkyl, lower alkenyl, lower alkynyl, fluorolower alkyl, fluoro-lower alkenyl and fluoro-lower alkynyl; at least one of R, R and R being one of fluoro radicals, and X is taken from the group consisting of sulfur and oxygen.
  • Table XV Product Active suhst Total number Number of Percent unobtained in concentrationlos of eggs unhatched eggs hatched eggs
  • Example References Cited by the Examiner UNITED STATES PATENTS 2,927,882 3/1960 Trademan et al. 16722 2,939,876 6/1960 Cramer et al 260461 2,945,780 7/1960 Jones et al. 167--22 2,947,662 8/ 1960 Fusco et a1 260461 XR 3,032,579 5/1962 Losco et a1 260--461 XR 3,047,459 7/1962 Perini et al.

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US234541A 1961-11-03 1962-10-31 Thiophosphoric esters Expired - Lifetime US3284546A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3355522A (en) * 1965-01-25 1967-11-28 Olin Mathieson Bicyclic thiophosphate esters of omicron, omicron-dialkyl s-carboxymethyl phosphates

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2927882A (en) * 1957-11-18 1960-03-08 Velsicol Chemical Corp Insecticide formulations and method of making same
US2939876A (en) * 1958-10-28 1960-06-07 Friedrich D Cramer Preparation of acid anhydrides
US2945780A (en) * 1955-03-24 1960-07-19 Fmc Corp Synergistic insecticidal compositions
US2947662A (en) * 1955-06-14 1960-08-02 Montedison Spa Alpha-substituted diethoxy-dithiophosphorylacetic esters
US3032579A (en) * 1958-11-20 1962-05-01 Montedison Spa Process for the preparation of an n-monoalkylamide of o,o-dimethyldithiophosphorylacetic acid
US3047459A (en) * 1954-11-09 1962-07-31 Montedison Spa New pesticidal compounds and methods of making same
US3076009A (en) * 1955-02-10 1963-01-29 Bayer Ag Thiophosphoric acid esters and production
US3081332A (en) * 1962-03-01 1963-03-12 American Cyanamid Co Process for reacting trialkyl phosphites with disulfides to produce phosphorothiolate triesters

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047459A (en) * 1954-11-09 1962-07-31 Montedison Spa New pesticidal compounds and methods of making same
US3076009A (en) * 1955-02-10 1963-01-29 Bayer Ag Thiophosphoric acid esters and production
US2945780A (en) * 1955-03-24 1960-07-19 Fmc Corp Synergistic insecticidal compositions
US2947662A (en) * 1955-06-14 1960-08-02 Montedison Spa Alpha-substituted diethoxy-dithiophosphorylacetic esters
US2927882A (en) * 1957-11-18 1960-03-08 Velsicol Chemical Corp Insecticide formulations and method of making same
US2939876A (en) * 1958-10-28 1960-06-07 Friedrich D Cramer Preparation of acid anhydrides
US3032579A (en) * 1958-11-20 1962-05-01 Montedison Spa Process for the preparation of an n-monoalkylamide of o,o-dimethyldithiophosphorylacetic acid
US3081332A (en) * 1962-03-01 1963-03-12 American Cyanamid Co Process for reacting trialkyl phosphites with disulfides to produce phosphorothiolate triesters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3355522A (en) * 1965-01-25 1967-11-28 Olin Mathieson Bicyclic thiophosphate esters of omicron, omicron-dialkyl s-carboxymethyl phosphates

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CH440825A (de) 1967-07-31
DE1542939A1 (de) 1970-07-02
BE624355A (de)
NL284766A (de)
ES282122A1 (es) 1963-05-01
GB957829A (en) 1964-05-13
AT248795B (de) 1966-08-10
SE303633B (de) 1968-09-02

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