US2578652A - Addition product of diester of dithiophosphoric acid and maleic acid and its esters, and method of preparation - Google Patents

Addition product of diester of dithiophosphoric acid and maleic acid and its esters, and method of preparation Download PDF

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Publication number
US2578652A
US2578652A US147325A US14732550A US2578652A US 2578652 A US2578652 A US 2578652A US 147325 A US147325 A US 147325A US 14732550 A US14732550 A US 14732550A US 2578652 A US2578652 A US 2578652A
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United States
Prior art keywords
acid
diethyl
esters
dithiophosphoric acid
hydroquinone
Prior art date
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Expired - Lifetime
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US147325A
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English (en)
Inventor
Jack T Cassaday
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Wyeth Holdings LLC
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American Cyanamid Co
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Filing date
Publication date
Priority to BE501609D priority Critical patent/BE501609A/xx
Priority to NL80825D priority patent/NL80825C/xx
Priority to NL7604840.A priority patent/NL159376B/xx
Priority to US147325A priority patent/US2578652A/en
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to GB3808/51A priority patent/GB699522A/en
Priority to FR1033275D priority patent/FR1033275A/fr
Priority to ES0196779A priority patent/ES196779A1/es
Priority to CH292795D priority patent/CH292795A/fr
Priority to DEA12971A priority patent/DE847897C/de
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Publication of US2578652A publication Critical patent/US2578652A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1673—Esters of phosphoric or thiophosphoric acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5398—Phosphorus bound to sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • R1 and R2 are chosen from the group consisting of aliphatic and aromatic hydrocarbon radicals
  • R3 and R4 are chosen from the group consisting of hydrogen, aliphatic and aromatic hydrocarbon radicals.
  • R's may be the same or different radicals, and when they stand for aliphatic radicals it is to be understood that they represent both the straight chain and branch chain, the saturated and unsaturated, and the cycloaliphatic hydrocarbon radicals.
  • radicals are methyl, ethyl, npropyl, isopropyl, n-butyl, isobutyl, sec.-amyl, n-hexyl, 2-ethyl-hexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, cyclohexyl, phenyl, and naphthyl.
  • phosphate esters may be readily prepared by reacting an acid phosphate of the formula 1in which R1 and R2 have the meaning shown above, with an unsaturated compound of the formula in which R3 and R4 have the meaning shown above.
  • the unsaturated compounds utilized in the present process may be either malelc acid, the
  • the reaction is preferably carried out in the presence of a solvent.
  • solvents include the low molecular weight aliphatic monohydric alcohols, the ketones such as, Ior example, acetone, methyl ethyl ketone, methyl 'isobutyl ketone, methyl benzyl ketone, cyclohexanone, acetophenone, and the like; aliphatic esters such as ethyl acetate, amyl acetate, Z-ethylhexyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, and isopropyl butyrate; dioxane, benzene, nitrobenzene, chlorobenzene, toluene, xylene, chlorororm, carbon tetrachloride, 1,2-dimethoxyethane, and the trialkyl phosphates such as trimethyl phosphate
  • the reaction is preferably carried out at a temperature within the range of from about 20 to 150 C. However, temperatures outside of this range may be employed depending upon the type of reactants and solvents utilized.
  • the reaction may be accelerated by using an aliphatic tertiary amine catalyst, such as for example triethylamine, triisopropylamine, tri-nbutylamine, tri-Z-ethylhexylamine, and the like.
  • an aliphatic tertiary amine catalyst such as for example triethylamine, triisopropylamine, tri-nbutylamine, tri-Z-ethylhexylamine, and the like.
  • the amount of catalyst employed is usually within the range of from 0.2% to 2.0%, based on the total weight of the reactants.
  • An anti-polymerization agent such as hydroquinone may be employed to guard against polymerization of the maleate or fumarate compound.
  • Example 1 A mixture of 108 g. of 0,0-diethyl dithiophosphoric acid, 86 g. of diethyl fumarate, and 0.2 g. of hydroquinone was heated at C. for 24 hours, then allowed to cool to room temperature. The reaction mixture was taken up in 300 cc. of benzene, washed with 10% sodium carbonate solution and with water. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The residue, S-(1,2-dicarbethoxyethyl) 0,0-diethyl dithiophosphate, was a colorless liquid, having a refraetive index a 1.4895. weighing 170 g. (94% 1 (1).
  • Example 2 72 g. of dimethyl maleate was added in small portions to a mixture of 94.5 g. of 0,0-dimethyl dithiophosphoric acid, 1 cc. of trie'thylamine, and 0.5 g. of hydroquinone. Cooling was applied as needed to keep the temperature of the reaction mixture below 60C. After the initial exothermic reaction had subsided, the mixture was heated at 65 C. for 16 hours, allowed to cool to room temperature, and dissolved in benzene. The benzene solution was washed with sodium carbonate solution and with water. The
  • v organic layer was dried over anhydrous sodium sulfate, filtered, and heated in vacuo to remove the benzene.
  • oxyethyl 0,0-dimethyl dithiophosphate was a clear colorless liquid having a refractive index a 1.5080, weighing 138 g. (91% yield.)
  • Example 3 The procedure of Example 2 was employed using 34.4 g. of diethyl fumarate. 37.8 g. of 0,0- dimethyl dithiophosphoric acid, 0.3 cc. of triethylamine, and 0.2 g. of hydroquinone. 50.8 g. (77% yield) of S-(1,2-dicarbethoxyethyl) 0,0-dimethyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index 11 1.4970.
  • Example 4 The procedure of Example 2 was employed.
  • Example 6 I The procedure of Example 2 was employed using 72 g. of dimethyl maleate, 108 g. of 0,0- diethyl dithiophosphoric acid, 1 cc. of triethylamine. and 0.2 g. of hydroquinone. The reaction mixture was heated at 65 C. for 24 hours. 155.5 g. (94% yield) of S-(1,2-dicarbomethoxyethyl) 0,0-diethyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index 11 1.4970.
  • Example 7 The procedure of Example -2 was employed using 86 g. of diethyl furnarate, 111 g. of 0,0- diethyl dithiophosphoric acid, 1 cc. of triethylamine, and 0.2 g. of hydroquinone. 165 g. (92% yield) of S-(1,2-dicarbethoxyethyl) 0,0-diethyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index a 1.4887.
  • Example 9 Example 10 The procedure of Example 2 was employed using 40 g. of diisopropyl maleate, 43.2 g. of 0,0-diethyl dithiophosphoric acid, 0.5 cc. of triethylamine, and 0.2 g. of hydroquinone. The reaction mixture was heated at 65 C. for 24 hours. 76 g. (98% yield) of S-(1,2-dicarbisopropoxyethyl) 0,0-diethyl dithiophosphate was obtained. The product was a pale yellow liquid having a refractive index 11 1.4805.
  • Example 11 39.2 g. of diallyl maleate was added slowly to a mixture of 44.5 g. of 0,0-diethyl dithiophospho'ric acid, 0.5 cc. of triethylamine, and 0.5 g. of hydroquinone. After a mildly exothermic reaction had subsided, the mixture was heated at 65 C. for 16 hours. The reaction mixture was cooled to room temperature, washed with 5% sodium carbonate solution and with water, dried over Drierite, and filtered to give 31.4 g. of S-(LZ-dicarballoxyethyl) 0.0-diethyl dithiophosphate, a colorless liquid having a refractive index 11 1.5000.
  • Example 12 The procedure of Example-11 was employed using 22.8 g. of di-n-butyl fumarate, 22 g. of 0,0-diethy1 dithiophosphoric acid, 0.3 cc. of triethylamine, and 0.2 g. of hydroquinone. The reaction mixture was heated at 65 C. for 21 hours. 31 g. (75% yield) of S-(1,2-dicarbo-n-butoxy ethyl) 0,0-diethyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index 11 1.4814.
  • Example 13 The procedure of Example 11 was employed using 22.8 g. of diisobutyl. fumarate, 22 g. of 0,0-diethyl dithiophosphoric acid, 0.3 cc. of triethylamine, and 0.2 g. of hydroquinone. The reaction mixture was heated at 65 C. for 24 hours. 25.3 g. (61% yield) of S-(1,2-dicarbisobutoxyethyl) 0,0-diethyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index n 1.4793.
  • Example 15 The procedure of Example 2 was employed using 45.2 g. of bis(2-butyloctyl) maleate, 22.3 g. of 0,0-diethyl dithiophosphoric acid, 0.5 cc. of triethylamine, and 0.2 g. of hydroquinone. 58.1 g. (91% yield) of S- ⁇ 1,2-bis[carbo(2-butyloctyloxy)] ethyl ⁇ 0,0-diethyl dithiophosphate was .obtained. The product was a clear yellow liquid having a refractive index a 1.4755.
  • Example 16 The procedure of Example 2 was employed using 26.8 g. of diphenyl fumarate, 22.3 g. of 0,0-diethyl dithiophosphoric acid, 1 cc. of triethylamine, and 1 g. of hydroquinone. The reaction mixture was heated at 65 C. for a period of 76 hours. 41 g. (90% yield) of S-(1,2-dicarbophenoxyethyl) 0,0-diethyl dithiophosphate was obtained. The product was a viscous brown liquid.
  • Example 17 The procedure of Example 2 was employed using 17.2 g. of diethyl fumarate, 23.5 g. of 0.0- diisopropyl dithiophosphoric acid, 0.5 cc. of triethylamine, and 0.5 g. of hydroquinone. The reaction mixture was heated at 65 C. for 18 hours. 34.0 g. (88% yield) of S-(1,2-dicarbethoxyethyl) 0,0-diisopropyl dithiophosphate was obtained. The product was a colorless liquid having a refractive index 11 1.4811.
  • Example 18 The procedure of Example 2 was employed using 11.2 g. of diethyl fumarate, 28 g. of 0,0-din-decyl dithiophosphoric acid, 0.2 cc. of triethylamine, and 0.2 g. of hydroquinone. The reaction mixture was heated at 65 C. for 23 hours. 33.5 g. (88% yield) of S-(1,2-dicarbethoxyethyl) 0,0-di-n-decyl dithiophosphate was obtained. The product was a pale yellow liquid having a refractive index a 1.4769.
  • Example 19 The procedure of Example 14 was employed using 17.2 g. of diethyl fumarate, 32.3 g. of 0,0- diphenyl dithiophosphoric acid, 150 cc. of benzene, 0.3 g. of triethylamine, and 0.2 g. of hydroquinone. The reaction mixture was allowed to stand at room temperature for a period of 7 days. 33 g. (83% yield) of S-(l,2-dicarbethoxyethyl) 0,0-diphenyl dithiophosphate was obtained. The product was a pale brown liquid having a refractive index a 1.5532.
  • Example 20 A mixture of mono-2-ethylhexyl maleate (0.50 mol) and 0,0-diethyl dithiophosphoric acid (0.52 mol) was heated at 93-94 C. for 6 hours, and then allowed to stand at room temperature for 16 hours. Titration of a portion of the product 6 with 0.1 N sodium hydroxide indicated the reaction to be 99% complete. The product was a yellow, viscous liquid.
  • Example 21 A mixture of mono-n-octadecyl maleate (0.20 mol) and 0,0-diethyl dithiophosphoric acid (0.21 mol) was heated at C. for 4 hours. Titration of a portion of the product with 0.1 N sodium hydroxide indicated the reaction to be 97% complete. The product was a yellow, viscous liquid.
  • the phosphate esters of the present invention are adapted for various uses. More particularly as insecticides, and in this connection show remarkably low warm-blooded animal toxicity. They are also useful as fungicides, plasticizers, corrosion inhibitors, flotation agents, and petroleum additives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dentistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
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US147325A 1950-03-02 1950-03-02 Addition product of diester of dithiophosphoric acid and maleic acid and its esters, and method of preparation Expired - Lifetime US2578652A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BE501609D BE501609A (en, 2012) 1950-03-02
NL80825D NL80825C (en, 2012) 1950-03-02
NL7604840.A NL159376B (nl) 1950-03-02 Werkwijze voor de bereiding van een waterige emulsie of suspensie van een organisch peroxyde, alsmede gevormde voortbrengselen, geheel of gedeeltelijk bestaande uit een bevroren waterige organische peroxyde-emulsie of -suspensie, verkregen volgens deze werkwijze.
US147325A US2578652A (en) 1950-03-02 1950-03-02 Addition product of diester of dithiophosphoric acid and maleic acid and its esters, and method of preparation
GB3808/51A GB699522A (en) 1950-03-02 1951-02-16 Improvements relating to the preparation of phosphate esters
FR1033275D FR1033275A (fr) 1950-03-02 1951-03-01 Perfectionnements à la préparation des esters phosphatés
ES0196779A ES196779A1 (es) 1950-03-02 1951-03-01 Un método para preparar ésteres de fosfatos
CH292795D CH292795A (fr) 1950-03-02 1951-03-01 Procédé de préparation d'un ester phosphoré.
DEA12971A DE847897C (de) 1950-03-02 1951-03-01 Verfahren zur Herstellung von Dithiophosphorsaeuretriestern

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US (1) US2578652A (en, 2012)
BE (1) BE501609A (en, 2012)
CH (1) CH292795A (en, 2012)
DE (1) DE847897C (en, 2012)
ES (1) ES196779A1 (en, 2012)
FR (1) FR1033275A (en, 2012)
GB (1) GB699522A (en, 2012)
NL (2) NL159376B (en, 2012)

Cited By (48)

* Cited by examiner, † Cited by third party
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US2630451A (en) * 1951-12-08 1953-03-03 American Cyanamid Co Dithiophosphate esters
US2632020A (en) * 1951-07-07 1953-03-17 American Cyanamid Co Dithiophosphate esters
US2644002A (en) * 1951-08-29 1953-06-30 American Cyanamid Co Thiophosphatosuccinimides
US2675321A (en) * 1951-06-12 1954-04-13 American Cyanamid Co Coated pigment and mineral oil ink containing same
US2713018A (en) * 1953-02-18 1955-07-12 American Cyanamid Co Omcron, omcron-dialkyl s-(1, 2-dicarbalkoxyethyl) monothiophosphates and miticide compositions containing the same
US2802856A (en) * 1953-09-08 1957-08-13 Lubrizol Corp Methods of preparing tri-esters of thiophosphoric acids
DE1023626B (de) * 1955-08-12 1958-01-30 American Cyanamid Co Verfahren zur Herstellung eines desodorisierten und stabilisierten Schaedlingsbekaempfungsmittels auf der Basis von O,O-Dialkyl-1,2-di-carboxyaethyl-dithiophosphorsaeureestern
US2844619A (en) * 1955-04-12 1958-07-22 Escobar Juan Nebrera Process for the deodorization of omicron, omicron-dimethyl-dithio-phosphate of diethyl mercapto-succinate
US2861093A (en) * 1956-09-24 1958-11-18 Eastman Kodak Co Reaction products of dialkyl phosphorothiolothionates and mucohalic acids
US2863902A (en) * 1954-09-08 1958-12-09 American Cyanamid Co Preparation of phosphate esters
US2876156A (en) * 1956-05-03 1959-03-03 Pfizer & Co C Insecticides-derivatives of itaconic acid
US2876244A (en) * 1954-12-30 1959-03-03 Union Carbide Corp Production of heterocyclic dithiophosphoric esters
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US2937194A (en) * 1956-09-28 1960-05-17 Basf Ag Production of esters of phosphoric acid and thionophosphoric acid
US2947775A (en) * 1957-11-25 1960-08-02 Eastman Kodak Co O, o-dialkyl s-(2-acetoxy-2-cyanoethyl) phosphorothiolothionates
US2948682A (en) * 1956-12-24 1960-08-09 Pure Oil Co Formyl triesters of dithiophosphoric acid and lubricating oil compositions containing same
US2957019A (en) * 1958-02-14 1960-10-18 Eastman Kodak Co O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
US2976308A (en) * 1954-10-13 1961-03-21 Lubrizol Corp Preparation of phosphorodithioate triesters
US2980723A (en) * 1959-06-16 1961-04-18 American Cyanamid Co Process for reducing objectionable odor of phosphorodithioate compounds
DE1112338B (de) * 1956-05-03 1961-08-03 Pfizer & Co C Schaedlingsbekaempfungsmittel mit insekticider und insbesondere miticider Wirkung
US3030264A (en) * 1960-03-11 1962-04-17 Monsanto Chemicals 1, 2-bis (oxycarbonyl) ethyl phosphinothioates
US3048517A (en) * 1960-05-12 1962-08-07 Monsanto Chemicals 2-nitroalkyl phosphorothioates
US3074990A (en) * 1958-12-29 1963-01-22 Universal Oil Prod Co Alkylthiophosphoric acid salt of polymeric condensation product and use thereof
US3092543A (en) * 1961-05-09 1963-06-04 Velsicol Chemical Corp Allyl phthalate pesticidal compositions
US3109770A (en) * 1961-04-10 1963-11-05 Stauffer Chemical Co Dialkoxyphosphinyl carbalkoxyalkyl disulfide pesticides
DE1180736B (de) * 1958-10-31 1964-11-05 Ciba Geigy Verfahren zur Herstellung von ungesaettigten Thiophosphorsaeureestern
US3185723A (en) * 1961-08-03 1965-05-25 Ici Ltd O-alkyl, s, 1-phenyl-2-alkoxycarbonylethyl alkylphosphonothioates
US3359203A (en) * 1965-09-01 1967-12-19 Exxon Research Engineering Co Ashless dithiophosphoric acid derivatives
US3440305A (en) * 1965-09-30 1969-04-22 American Cyanamid Co Process for upgrading malathion
US3463841A (en) * 1966-11-01 1969-08-26 American Cyanamid Co Malathion manufacture
US3470272A (en) * 1966-10-24 1969-09-30 Mobil Oil Corp Process for making phosphorothioates
US3515782A (en) * 1964-11-27 1970-06-02 American Cyanamid Co Method for controlling insects
US3887658A (en) * 1972-04-27 1975-06-03 Ciba Geigy Ag O-Alkyl-S-alkyl-S-{8 1,2-bis(alkoxycarbonyl)ethyl{9 dithiophosphates
US4058605A (en) * 1975-06-11 1977-11-15 Sun Ventures, Inc. Insecticides from dimethylmuconic acid
US4190650A (en) * 1977-04-09 1980-02-26 Basf Aktiengesellschaft Phosphonyl vinyl phosphorus compounds as pesticides
US4203977A (en) * 1977-10-13 1980-05-20 Basf Aktiengesellschaft Phosphoric acid esters, composition and use
US5614203A (en) * 1995-01-30 1997-03-25 Environmentally Safe Systems, Inc. Environmentally safe pesticide and plant growth accelerator
US5646133A (en) * 1996-03-14 1997-07-08 Donlar Corporation Polyaspartic acid and its analogues in combination with insecticides
US6046144A (en) * 1997-06-02 2000-04-04 R.T. Vanderbilt Co., Inc. Combination of phosphate based additives and sulfonate salts for hydraulic fluids and lubricating compositions
US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6576661B1 (en) 1999-11-09 2003-06-10 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US20070010496A1 (en) * 2005-07-06 2007-01-11 Daniella Gutman Process for Preparing Malathion for Pharmaceutical Use
US20070065474A1 (en) * 2004-07-12 2007-03-22 Sandhya Goyal Topical gel formulation comprising organophosphate insecticide and its preparation thereof
WO2009007998A1 (en) 2007-07-09 2009-01-15 Suven Life Sciences Limited Process for the preparation of malathion and its intermediate
US8012498B2 (en) 2004-07-12 2011-09-06 Sandhya Goyal Topical gel formulation comprising organophosphate insecticide and preparation thereof
US8846787B2 (en) 2010-01-20 2014-09-30 W. R. Grace & Co.-Conn. High curing inducing surface applied setting retarder
JP2022536218A (ja) * 2018-09-27 2022-08-15 ケミノバ アクティーゼルスカブ マラチオンの触媒による環境に優しい製造方法
WO2025136661A1 (en) * 2023-12-18 2025-06-26 Afton Chemical Corporation Thiophosphate esters as antiwear additives for lubricants

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DE1011416B (de) * 1955-02-10 1957-07-04 Bayer Ag Verfahren zur Herstellung von 0, 0-Dialkyl-thiol- und -thiol-thiono-phosphorsaeuretriestern
DE1006854B (de) * 1955-02-10 1957-04-25 Bayer Ag Verfahren zur Herstellung von Thionophosphorsaeureestern
NL110218C (en, 2012) * 1958-11-07
FR1310158A (en, 2012) * 1960-12-10 1963-03-06
DE1188859B (de) * 1960-12-10 1965-03-11 Basf Ag Mittel zur Bekaempfung von Insekten
NL282213A (en, 2012) * 1961-08-18

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NL80825C (en, 2012)
FR1033275A (fr) 1953-07-09
DE847897C (de) 1952-08-28
CH292795A (fr) 1953-08-31
GB699522A (en) 1953-11-11
ES196779A1 (es) 1953-04-01
NL159376B (nl)
BE501609A (en, 2012)

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