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US2494283A - Carbamylalkyl phosphates and method of preparation - Google Patents

Carbamylalkyl phosphates and method of preparation Download PDF

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Publication number
US2494283A
US2494283A US6348A US634848A US2494283A US 2494283 A US2494283 A US 2494283A US 6348 A US6348 A US 6348A US 634848 A US634848 A US 634848A US 2494283 A US2494283 A US 2494283A
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US
United States
Prior art keywords
grams
diethyl
group
phosphate
dithiophosphate
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
US6348A
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English (en)
Inventor
Jack T Cassaday
Erick I Hoegberg
Bruce D Gleissner
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.)
Wyeth Holdings LLC
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American Cyanamid Co
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Filing date
Publication date
Priority to CA494562A priority Critical patent/CA494562A/en
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to US6348A priority patent/US2494283A/en
Priority to GB2271/49A priority patent/GB663270A/en
Priority to FR979746D priority patent/FR979746A/fr
Priority to DEP32961D priority patent/DE819998C/de
Priority to CH287139D priority patent/CH287139A/fr
Application granted granted Critical
Publication of US2494283A publication Critical patent/US2494283A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • 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
    • 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
    • C10M2223/042—Metal salts thereof
    • 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 B may be the same or different radicals. Furthermore, it is to be understood that when R1 and R2 stand for alkyl radicals, they represent both the straight chain and branch chain, the saturated and unsaturated, and the cycloaliphatic hydrocarbon radicals.
  • the R1 and R: radicals may also carry halogen subs'tituents, particularly chlorine and bromine. Typical examples of these radicals are methyl, ethyl, n-propyl, isopropyl, isobutyl, sec.- amyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl.
  • ndodecyl oleyl, cetyl, ceryl, allyl, bromomethyl, z-chloroethyl, cyclohexyl, benzyl.
  • the compounds of this invention possess general pest-control characteristics, including insecticidal, rodenticidal, and fungicidal properties. They may also be employed as corrosion inhibitors, plasticizers, flotation agents, and petroleum additives.
  • phosphate esters of the above general formula when the symbol m stands for oiwgen. may be readily prepared by reacting a. phosphate of the general formula:
  • R1, R2, X1, and X2 have the meaning shown above
  • Y represents an alkali-forming metal, with a halogen-substituted amide of the general formula in which R3, R4, and m have the meaning shown above
  • Z is a member of the group consisting of chlorine and bromine.
  • alkali-forming metal as used in this specification and in the appended claims is intended to cover the alkali metals (including ammonium), and the alkaline earth metals.
  • High yields of the desired products are obtained by carrying out the reaction in the presrate, and isopropyl butyrate; saturated aliphatic nitriles such as acetonitrile and propionitrile; dioxane, nitrobenzene, chlorobenzene, toluene, xylene, chloroform, carbon tetrachloride, 1,2- dimethoxyethane, and the trialkyl' phosphates such as trimethyl phosphate, triethyl phosphat and triisopropyl phosphate.
  • the reaction is preferably carried out at a temperature within the range of from about201 to C. However, temperatures outside-got this range may be employed depending upon the type of reactants and solvents utilized.
  • An alternative method of preparing the above compounds consists in employing in lieu of the alkali-forming metal phosphate the corresponding acid and a basic alkali-forming metal compound, the latter having sufllcient alkalinity to neutralize said acid. Obvious1y, this procedure avoids the initial preparation and isolation of the alkali-forming metal phosphate.
  • Such basic A3131 The phosphate esters of the above general formula, when the symbol X1 stands for sulfur. may be prepared by reacting a cyanoalkyl phosphate of the general formula in which R1, R2, X1. X2, and m have the meaning shown above, with either hydrogen sulfide or a mercaptan, preferably in a closed vessel under pressure.
  • the cyanoalkyl phosphates utilized in the preceding reaction may be prepared by reacting a phosphate of the general formula in which R1, R2, X1, X2, and Y have the meaning shown above, with a halogen-substituted nitrile of the general formula Z--(CH2) m-CN in which m and Z have the meaning shown above.
  • Example 1 41.6 rams (0.2 mol.) of sodium 0,0-diethyl dlthiophosphate, 18.7 grams (0.2 mol.) of chloroacetamide, and 250 cc. of acetone were mixed together and allowed to stand at room temperature (20 C.) for 24 hours. The precipitated sodium chloride was filtered oil and the filtrate heated under vacuum to remove the acetone. The resid- 4 us] crystalline product, S-carbamylmethyl, 0.0- diethyl dithiophosphate, weighing 46 grams (95% yield) was recrystallized from 125 cc. of carbon tetrachloride. The recrystallized product was a colorless crystalline solid, meltingat 5748" C.
  • Example 2 The procedure of Example 1 was employed, using 62.4 grams of sodium 0,0-diethyl dithiophosphate, 51 grams of chloroacetanilide, and 400 cc. of acetone. 91 grams of crude 0,0-diethyl S- (N-phenylcarbamyl) methyl dithiophosphate were obtained. After recrystallization from heptane, the product was a colorless crystalline material melting at 8547" C.
  • Example 3 The procedure of Example 1 was employed using 41.6 grams of sodium 0,0-diethyl dithiophosphate, 42.9 grams of alpha-chloro-4-nitroacetanilide, and 250 cc. of acetone. 69 grams (95% yield) of 0.0-diethyl S-(N-p-nitrophenyl carbamyl) methyl dithiophosphate were obtained. After recrystallization from 500 cc. of carbon tetrachloride, the product was a colorless crystalline material melting at 109-110 C.
  • Example 4 62.4 grams of sodium 0,0-diethyl dithiophosphate, 32.3 grams of beta-chloropropionamide, and 400 cc. of acetone were mixed together and allowed to stand at room temperature for 24 hours. The precipitated sodium chloride was filtered off and the filtrate heated under vacuum to remove the acetone. The residual product, 8- 2-carbamylethyl 0.0-diethyl dithiophosphate, weighing grams, was a clear, light brown liquid having a refractive index a 1.5230.
  • Example 5 The procedure of Example 4 was employed using 14.4 grams of sodium 0,0-diethyl dithiophosphate, 7.4 grams of beta-chloropropionanilide, and 100 cc. of acetone. The residual product, 0,0-diethyl S-(2-N-phenylcarbamyl) ethyl dithiophosphate, weighing 20.8 grams (90% yield) was an amber-colored oil having a refractive index n 1.5468. 4
  • Example 6 The procedure of Example 4 was employed using 62.4 grams of sodium 0,0-diethy1 dithio- .phosphate, 37.1 grams of alpha-chloro N-(hydroxymethyl) acetamide, and 250 cc. of acetone. The mixture was heated under reflux for a period of 6 hours. The residual product, 0,0-diethyl B-(N-hydroxymethyl) carbamylmethyl dithiophosphate, was a straw-colored, viscous liquid having a refractive index a 1.5372.
  • Example 7 42.9 grams of 0,0-dimethyl dithiophosphoric acid were added slowly to a well-agitated mixture of 28.7 grams of anhydrous sodium carbonate suspended in 100 cc. of methyl isobutyl ketone. The mixture was then heated to about 65 C. and 25.3 grams of chloroacetamide were added. The resulting mixture was held at 80 C. for one hour with continued stirring, then cooled to room temperature and filtered. The filtrate was washed twice with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was heated under vacuum to remove the methyl isobutyl ketone. The residual product, S-carbamylmethyl 0,0-dimethyl dithiophosphate, was a colorless crystalline solid melting at 60-'-62 C.
  • Example 8 48.4 grams of 0,0-dibutyl dithiophosphoric acid were added slowly to a well-agitated mixture of 21.2 grams of anhydrous sodium carbonate suspended in 200 cc. of acetone. 18.7 grams of chloroacetamide were then added. The reaction mixture was stirred for two hours, allowed to stand at room temperature (20-22 C.) for 24 hours, filtered, and the filtrate stripped of solvent under vacuum. The residual brown oil was washed twice with dilute sodium carbonate solution, then with water, and dried over anhydrous sodium sulfate. The product, 0,0-di-n-butyl S-carbamylmethyl dithiophosphate, was an amoer-colored, viscous oil having a refractive index a 1.5111.
  • Example 10 The procedure of Example 9 was employed ising 28.2 grams of 0,0-diphenyl dithiophos- :horic acid, 10.6 grams of anhydrous sodium :arbonate, 100 cc. of methyl isobutyl ketone. and i4 grams of chloroacetamide. The reaction mixvure was stirred and heated at 75-80 C. for a :eriod of 4 hours. 23 grams of S-carbamylmethyl ),O-diphenyl dithiophosphate were obtained. the product was a red, viscous oil having a reractive index a 1.5988.
  • Example 11 18.3 grams of n-butyl amine, 26.5 grams of anhydrous sodium carbonate, and 200 cc. oi methyl isobutyl ketone were mixed together and ooled in an ice-bath. 28.3 grams of chloroacetyl hloride were added with stirring during a period f one hour, the temperature being held at 10- 2" C. The mixture was then warmed slowly to 5 C. and maintained at this temperature for V2 hours, after which it was allowed to cool to 6 C. 26.5 grams of anhydrous sodium carbonate rere then added, followed by the addition of 50 rams of 0,0-diethyl dithiophosphoric acid. The iixture was held at 85 C.
  • Example 12 56.1 grams of potassium hydroxide were dislved in 400 cc. of ethyl alcohol cooled in an e-bath. 86 grams of diethyl chlorophosphate ere added drop-wise with stirring, the temperalre being held at i0-15 C. The mixture conining potassium diethyl phosphate and precipi- .ted potassium chloride was warmed to 35 0. 1d 46.8 grams of chloroacetamide were then ided. The reaction mixture was heated to 50 C. 1d stirred for /2 hour, then allowed to stand room temperature (26-22 C.) for 36 hours.
  • Example13 62.6 grams of potassium 0,0-diethyl thiophosphate and 28.1 grams of-chloroacetamide were dissolved in 250 cc. of methyl ethyl ketone.
  • Example 14 50 grams of S-cyanomethyl 0,0-diethyl dithio- Phosphate and 7.6 grams of hydrogen sulfide were reacted together in a closed vessel in 100 cc. of
  • the phosphate esters of this invention may be employed in controlling many types of insects and mites such as, for example, the black bean aphid, green peach aphid, pea aphid, chrysanthemum aphid, greenhouse thrips, California red scale, citrus red spider, greenhouse red spider, 'milkweed bug, mealy bug, sow bug, German cockroach, southern army worm, yellow fever mosquito, malarial mosquito, Mexican bean bettle, confused flour beetle, and black carpet beetle.
  • insects and mites such as, for example, the black bean aphid, green peach aphid, pea aphid, chrysanthemum aphid, greenhouse thrips, California red scale, citrus red spider, greenhouse red spider, 'milkweed bug, mealy bug, sow bug, German cockroach, southern army worm, yellow fever mosquito, malarial mosquito, Mexican bean bettle, confused flour beetle, and black carpet beetle.
  • R1 and R2 are chosen from the group consisting of alkyl, arallryl, and aryl radicals
  • R3 and R4 are members of the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, and nitroaryl radicals
  • X1, X2, and X are members of the group consisting of sulfur and owgen
  • m be precipitated poum chloride was removed ?5 represents a small whole num.
  • Z is a member of the group consisting of chlorine and bromine, an acid phosphate of the general formula in which R1 and R: are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, and X1 and & are members of the group consisting of sulfur and oxygen, and a basic alkali-forming metal compound having sufllcient alkalinity to neutralize the acid phosphate.

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  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Environmental Sciences (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
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  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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US6348A 1948-02-04 1948-02-04 Carbamylalkyl phosphates and method of preparation Expired - Lifetime US2494283A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA494562A CA494562A (en) 1948-02-04 Carbamylalkyl phosphates and method of preparation
US6348A US2494283A (en) 1948-02-04 1948-02-04 Carbamylalkyl phosphates and method of preparation
GB2271/49A GB663270A (en) 1948-02-04 1949-01-27 Improvements relating to the preparation of phosphate esters
FR979746D FR979746A (fr) 1948-02-04 1949-01-28 Perfectionnements à la préparation d'esters phosphoriques
DEP32961D DE819998C (de) 1948-02-04 1949-02-01 Verfahren zur Herstellung von Estern der Phosphor- oder Thiophosphorsaeure
CH287139D CH287139A (fr) 1948-02-04 1949-02-04 Procédé de préparation d'un ester phosphorique.

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CA (1) CA494562A (de)
CH (1) CH287139A (de)
DE (1) DE819998C (de)
FR (1) FR979746A (de)
GB (1) GB663270A (de)

Cited By (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US2645657A (en) * 1949-03-30 1953-07-14 Standard Oil Dev Co Thiophosphate esters
US2690450A (en) * 1951-03-23 1954-09-28 Allied Chem & Dye Corp Method for preparation of sulfur-containing esters of phosphoric acid
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
US2736726A (en) * 1952-03-28 1956-02-28 Geigy Ag J R Basic phosphoric acid esters
US2743235A (en) * 1952-06-27 1956-04-24 Exxon Research Engineering Co Mineral oil composition
US2757118A (en) * 1951-11-20 1956-07-31 Monsanto Chemicals Method for controlling mollusks with diethyl thiophosphoryl bis (dimethylamido) phosphate
DE954960C (de) * 1955-07-30 1956-12-27 Bayer Ag Verfahren zur Herstellung des O, O-Dimethyl-S-(isopropylcarbaminyl-methyl)-thiolthionophosphorsaeureesters
US2802855A (en) * 1953-04-27 1957-08-13 Shell Dev Carbamylalkenyl phosphoruscontaining esters
US2818364A (en) * 1953-10-26 1957-12-31 Monsanto Chemicals Alkyl phosphite esters of perchloromethyl mercaptan and insecticidal compositions comprising the same
DE1024509B (de) * 1956-03-03 1958-02-20 Bayer Ag Verfahren zur Herstellung von O, O-Dialkyl-thiol-phosphorsaeure- und -thiol-thiono-phsphorsaeureestern
US2854469A (en) * 1956-03-02 1958-09-30 Stauffer Chemical Co Pesticidal composition of matter
US2861023A (en) * 1955-09-06 1958-11-18 Collier Carbon & Chemical Co Fungicidal compositions and methods of destroying fungi employing trialkyl tetra-thiophosphates
US2862949A (en) * 1953-11-16 1958-12-02 Ethyl Corp Organic phosphorus compounds
US2863901A (en) * 1952-11-19 1958-12-09 Ici Ltd Basic esters of dialkylthiolo phosphonic acid
US2879283A (en) * 1955-06-06 1959-03-24 Monsanto Chemicals Sulfoalkyl phosphorothioates and metal salts thereof
US2881196A (en) * 1956-05-16 1959-04-07 Standard Oil Co Thiophosphoryl derivatives of hexachlorocyclopentadiene-unsaturated alcohol adducts
US2884431A (en) * 1956-06-08 1959-04-28 Exxon Research Engineering Co Fluorinated diesters of phosphorodithioic acid and salts thereof
US2884354A (en) * 1955-08-30 1959-04-28 Hercules Powder Co Ltd Dithiophosphate insecticides
US2884353A (en) * 1955-08-30 1959-04-28 Hercules Powder Co Ltd Dithiophosphate insecticides
US2890947A (en) * 1956-11-14 1959-06-16 Pure Oil Co Gasoline motor fuel
US2897227A (en) * 1956-04-04 1959-07-28 Dow Chemical Co S-(chlorophenyl) o,o-dialkyl phosphorodithioates
US2901481A (en) * 1955-07-14 1959-08-25 Montedison Spa Process for preparing dialkyldithiophosphoric acid ester derivatives having two amide groups in the molecule and the insecticidal compounds obtained thereby
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US2912452A (en) * 1956-04-21 1959-11-10 Bayer Ag Thiophosphoric acid esters and their production
US2915546A (en) * 1955-05-13 1959-12-01 Bayer Ag Process for the manufacture of thiophosphoric acid esters
US2915429A (en) * 1957-09-17 1959-12-01 Hoechst Ag O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides
US2917533A (en) * 1954-05-12 1959-12-15 Virginia Carolina Chem Corp Dialkylaminoalkyl esters of phosphonic acid and method of preparing same
US2924615A (en) * 1954-01-13 1960-02-09 Searle & Co Aminoalkyl esters of aryl- and aralkyl-substituted phosphinic acids and their salts
US2928862A (en) * 1956-07-16 1960-03-15 Fmc Corp Pesticidal phosphorus esters
US2943974A (en) * 1958-01-28 1960-07-05 Rhone Poulenc Sa Phosphorus esters
US2947662A (en) * 1955-06-14 1960-08-02 Montedison Spa Alpha-substituted diethoxy-dithiophosphorylacetic esters
US2954394A (en) * 1957-06-10 1960-09-27 Dow Chemical Co O-aryl o-alkyl o-hydrogen phosphorothioates and their salts
US2957016A (en) * 1954-11-24 1960-10-18 California Spray Chemical Corp Dialkyl iminyl thionophosphates
US2957019A (en) * 1958-02-14 1960-10-18 Eastman Kodak Co O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
US2959608A (en) * 1959-01-30 1960-11-08 Fisons Pest Control Ltd Chemical process for making omicron, omicron-dialkyl-5-carbamoylmethyl-phosphorodithioates
US2960525A (en) * 1958-03-28 1960-11-15 Bayer Ag Thionophosphoric acid esters
US2965533A (en) * 1956-04-26 1960-12-20 Shell Oil Co Phosphate esters of cyanohydrins
US2976312A (en) * 1956-12-13 1961-03-21 Bayer Ag Process for making thionophosphoric acid esters of alpha-hydroxy-methyl-thioethers
US2994638A (en) * 1958-02-20 1961-08-01 Bayer Ag Agent for combating rodents
US2995595A (en) * 1955-07-29 1961-08-08 Bayer Ag Omicron, omicron-dimethyl-s-(isopropylcarbaminylmethyl-)dithio-phosphoric acid ester
US2996531A (en) * 1957-07-01 1961-08-15 American Cyanamid Co Preparation of alkylcarbamoylmethyl dimethylphosphorodithioates
US3004055A (en) * 1955-02-16 1961-10-10 Montedison Spa Process for preparing o,o-dialkyl, s-n-alkyl-carbamylmethyl phosphorodithioates
US3007845A (en) * 1958-05-05 1961-11-07 American Cyanamid Co Dithiophosphates as systemic insecticides in mammals
US3013940A (en) * 1957-06-03 1961-12-19 Montedison Spa Organo-mercapto-methyleneamides of o, o-dialkyl-thio(or dithio)-phosphorylacetic acids having pesticidal activity
US3017321A (en) * 1959-04-22 1962-01-16 American Cyanamid Co Trichloromethyl 2-methoxy-5-phosphono-benzenethiolsulfonate pesticides
US3020304A (en) * 1955-12-31 1962-02-06 Hoechst Ag Chloromethylated omicron, omicron-dialkyl-thiophosphoric acid esters
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US7060692B2 (en) 2000-08-31 2006-06-13 Bayer Cropscience Ag Active ingredient combinations comprising insecticidal and acaricidal properties
DE102007045955A1 (de) 2007-09-26 2009-04-09 Bayer Cropscience Ag Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften
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US2912452A (en) * 1956-04-21 1959-11-10 Bayer Ag Thiophosphoric acid esters and their production
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US2884431A (en) * 1956-06-08 1959-04-28 Exxon Research Engineering Co Fluorinated diesters of phosphorodithioic acid and salts thereof
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US2890947A (en) * 1956-11-14 1959-06-16 Pure Oil Co Gasoline motor fuel
US2976312A (en) * 1956-12-13 1961-03-21 Bayer Ag Process for making thionophosphoric acid esters of alpha-hydroxy-methyl-thioethers
US3170835A (en) * 1957-04-15 1965-02-23 Monsanto Co Nitromethylbenzyl-phosphorothioic acid diesters and nematocidal methods employing same
US3013940A (en) * 1957-06-03 1961-12-19 Montedison Spa Organo-mercapto-methyleneamides of o, o-dialkyl-thio(or dithio)-phosphorylacetic acids having pesticidal activity
US2954394A (en) * 1957-06-10 1960-09-27 Dow Chemical Co O-aryl o-alkyl o-hydrogen phosphorothioates and their salts
US3210397A (en) * 1957-07-01 1965-10-05 American Cyanamid Co Alkylcarbamoylmethyl dimethyl-phosphorodithioates
US2996531A (en) * 1957-07-01 1961-08-15 American Cyanamid Co Preparation of alkylcarbamoylmethyl dimethylphosphorodithioates
US2915429A (en) * 1957-09-17 1959-12-01 Hoechst Ag O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides
US2943974A (en) * 1958-01-28 1960-07-05 Rhone Poulenc Sa Phosphorus esters
US2957019A (en) * 1958-02-14 1960-10-18 Eastman Kodak Co O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
US2994638A (en) * 1958-02-20 1961-08-01 Bayer Ag Agent for combating rodents
US2960525A (en) * 1958-03-28 1960-11-15 Bayer Ag Thionophosphoric acid esters
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US3134801A (en) * 1958-07-12 1964-05-26 Boehringer Sohn Ingelheim Process for the preparation of o,o-dialkyl-dithiophosphoryl-fatty acid compounds and pesticidal compositions containing the same
US3026243A (en) * 1958-09-04 1962-03-20 Montedison Spa Control of the olive fly by application of products containing omicron, omicron-dimethylthiophosphorylacetic acid monomethylamide
US3032579A (en) * 1958-11-20 1962-05-01 Montedison Spa Process for the preparation of an n-monoalkylamide of o,o-dimethyldithiophosphorylacetic acid
US2959608A (en) * 1959-01-30 1960-11-08 Fisons Pest Control Ltd Chemical process for making omicron, omicron-dialkyl-5-carbamoylmethyl-phosphorodithioates
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US3507953A (en) * 1959-03-28 1970-04-21 Bayer Ag Pesticidal dithiophosphonic acid esters
US3017321A (en) * 1959-04-22 1962-01-16 American Cyanamid Co Trichloromethyl 2-methoxy-5-phosphono-benzenethiolsulfonate pesticides
US3092649A (en) * 1959-09-05 1963-06-04 Bayer Ag Thiophosphoric acid esters and process for their production
US3213122A (en) * 1959-10-30 1965-10-19 Bayer Ag Thiophosphoric acid esters and process for the production thereof
US3033744A (en) * 1959-12-30 1962-05-08 Montedison Spa Thiophosphate esters, their insecticidal application, and process of preparation
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US3030264A (en) * 1960-03-11 1962-04-17 Monsanto Chemicals 1, 2-bis (oxycarbonyl) ethyl phosphinothioates
US3090719A (en) * 1960-04-28 1963-05-21 Montedison Spa High-stability insecticide compositions, emulsifiable or soluble in water, of nu-monomethylamide of omicron, omicron-dimethyldithiophosphorylacetic acid
US3102021A (en) * 1960-11-08 1963-08-27 Monsanto Chemicals Herbicidal method
US3102023A (en) * 1960-11-09 1963-08-27 Monsanto Chemicals Herbicidal method
US3259540A (en) * 1961-02-13 1966-07-05 Murphy Chemical Ltd Stabilized insecticidal composition containing an o, o-dimethyl s-(n-alkoxymethyl) carbamoylmethyl phosphorothiolothionate
US3197498A (en) * 1961-04-08 1965-07-27 Bayer Ag Alkyl-(mercapto, sulfoxy, sulfonyl)-acetic acid amide-s-esters of phosphorus acids
US3281507A (en) * 1961-04-10 1966-10-25 Stauffer Chemical Co Process for making dialkoxy phosphinyl carbamoyl disulfides
US3238202A (en) * 1961-05-02 1966-03-01 Montedison Spa Amides of o, o-dialkyldithiophos-phorylacetic acids
US3102019A (en) * 1961-08-16 1963-08-27 Monsanto Chemicals Method for inhibiting germination and preemergent growth of plants using s(n-aryl, n-aliphatic carbamoylmethyl) phosphorothiate triesters
US3126314A (en) * 1961-10-18 1964-03-24 S-chlorophenylsblfonylmethyl - o
US3117151A (en) * 1961-10-30 1964-01-07 Dow Chemical Co Omicron-(2, 2-dichloro-1-cyanovinyl) omicron, omiron-diethyl phosphate
US3294874A (en) * 1962-01-24 1966-12-27 Bayer Ag Omicron-alkyl-omicron-cycloalkyl-s-alkylthiolphosphoric acid esters
US3106510A (en) * 1962-04-24 1963-10-08 Stauffer Chemical Co Omicron, omicron-dialkyl s-carbamoylmethyl phosphorothioates and process for preparing same
US3327025A (en) * 1962-04-25 1967-06-20 Rhone Poulenc Sa O, o-dimethyldithiophosphoric esters
US3254105A (en) * 1963-02-26 1966-05-31 Diamond Alkali Co Polyhalo-cycloalkene isocyanate and imide carbonyl chloride compounds
US3349103A (en) * 1963-12-20 1967-10-24 Universal Oil Prod Co S-(dithiophosphatyl) epoxyalkanes
US3336420A (en) * 1964-01-04 1967-08-15 Bayer Ag Process for the production of asymmetric thionothiol-phosphoric acid esters
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US3317426A (en) * 1965-06-16 1967-05-02 Chevron Res Phospho-substituted urethane lubricating oil additives
US3385689A (en) * 1965-10-11 1968-05-28 Velsicol Chemical Corp Method of controlling undesirable plant growth
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US4168305A (en) * 1977-01-19 1979-09-18 Bayer Aktiengesellschaft Combating pests with S-alkyl-N-carbonyl-alkanedithiophosphonic acid ester-amides
US4162279A (en) * 1977-09-28 1979-07-24 Stauffer Chemical Company Phosphonoxycarboxamides
US4177300A (en) * 1977-09-28 1979-12-04 Stauffer Chemical Company Phosphonoxycarboxamide flame retarding compositions
US4333841A (en) * 1978-10-19 1982-06-08 Ciba-Geigy Corporation Dithiophosphate lubricant additives
US4525289A (en) * 1981-12-29 1985-06-25 The Procter & Gamble Company Alpha-phosphono lauramide lubricant additives
US4537730A (en) * 1982-08-03 1985-08-27 Bayer Aktiengesellschaft Preparation of O,S-dimethyl-thiolophosphoric acid amide
US4493817A (en) * 1983-07-06 1985-01-15 Teck Corporation Process for recovering pyrochlore mineral containing niobium and tantalum
US4844726A (en) * 1984-04-20 1989-07-04 Nitrokemia Ipartelepek Herbicidal compositions with prolonged action and improved selectivity
WO1989006492A1 (en) * 1988-01-05 1989-07-27 Fmc Corporation Safening of herbicidal clomazone applications with organophosphorus compounds
US6576661B1 (en) 1999-11-09 2003-06-10 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US6818670B2 (en) 1999-11-09 2004-11-16 Bayer Aktiengesellschaft Active ingredient combination having insecticidal and acaricidal characteristics
US20030100604A1 (en) * 2000-03-28 2003-05-29 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US6900190B2 (en) 2000-03-28 2005-05-31 Bayer Aktiengesellschaft Active substance combinations having insecticidal and acaricidal properties
US20050147639A1 (en) * 2000-03-28 2005-07-07 Reiner Fischer Active substance combinations having insecticidal and acaricidal properties
US7060692B2 (en) 2000-08-31 2006-06-13 Bayer Cropscience Ag Active ingredient combinations comprising insecticidal and acaricidal properties
DE102007045955A1 (de) 2007-09-26 2009-04-09 Bayer Cropscience Ag Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften
US8846567B2 (en) 2009-03-25 2014-09-30 Bayer Cropscience Ag Active compound combinations having insecticidal and acaricidal properties

Also Published As

Publication number Publication date
CH287139A (fr) 1952-11-30
DE819998C (de) 1951-11-08
GB663270A (en) 1951-12-19
FR979746A (fr) 1951-05-02
CA494562A (en) 1953-07-21

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