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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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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acid
diethyl
esters
dithiophosphoric acid
hydroquinone
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Jack T Cassaday
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Wyeth Holdings LLC
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American Cyanamid Co
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Priority to GB3808/51A priority patent/GB699522A/en
Priority to CH292795D priority patent/CH292795A/en
Priority to ES0196779A priority patent/ES196779A1/en
Priority to DEA12971A priority patent/DE847897C/en
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    • 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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Description

Patented Dec. 18, 1951 ADDITION PRODUCT OF DIESTER OF DI- THIOPHOSPHORIC ACID AND MALEIC ACID AND ITS ESTERS, AND METHOD OF PREPARATION Jack '1. Cassaday, Stamford, Conn., assignor to American Cyanamld Company, New York, N. Y., a corporation of Maine No Drawing. Application March 2, 1950, Serial No. 147,325
Claims.
in which R1 and R2 are chosen from the group consisting of aliphatic and aromatic hydrocarbon radicals, and R3 and R4 are chosen from the group consisting of hydrogen, aliphatic and aromatic hydrocarbon radicals.
In the new compounds the 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. Typical examples of these 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.
These 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.
A typical reaction in which 0,0-dimethyl dithiophosphoric acid is reacted with diethyl maleate to produce S-(1,2-dicarbethoxyethyl) 0,0-dimethyl dithiophosphate may be illustrated as follows:
f 3110000111. CHO/ HCOOCaHl crno s i -scnoooo,m
omo H.000 0.11
The unsaturated compounds utilized in the present process may be either malelc acid, the
acid maleate esters, the neutral maleate esters,
or their isomers, fumaric acid, the acid fumarate esters and the neutral fumarate esters. Therefore, it is to be understood that the formula onoooR.
cnoooR.
used in this specification and the appended claims is intended to represent both the maleate and fumarate compounds.
When one or both of the reactants are solids, the reaction is preferably carried out in the presence of a solvent. Such 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, triethyl phosphate, and triisopropyl 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. 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.
The following examples will further illustrate the invention.
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.
using 40 g. of diisopropyl maleate, 40 g. of 0,0- dimethyl dithiophosphoric acid, 0.5 cc. of triethylamine, and 0.2 g. of hydroquinone. The
reaction mixture was heated at 65 C. for 24" hours. 63 g. (88% yield) of S-(L2-dicarbisopropoxyethyl) 0,0 dimethyl dithiophosphate was obtained. The product was a clear pink liquid having a refractive index n 1.4862.
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.
The residue, S-(1,2-dicarbometh-' Emample 8 A mixture of 24.1 g. of bis(2-chioroethyl) fumarate, 22.3 g. of 0,0-diethyl dithiophosphoric acid, 50 cc. of xylene, 0.3 cc. of triethylamine, and 0.2 g. of hydroquinone was heated at 65 C. for a period of 84 hours. The reaction mixture was cooled to room temperature, diluted with 50 cc. of xylene, washed with 5% sodium carbonate solution and with water. ganic layer was dried over Drierite, filtered, and heated in vacuo to remove the xylene. The residue, S {1,2 bis[carbo(2 chloroetho'xyH- ethyl} 0,0-diethyl dithiophosphate, was a pale yellow liquid having a refractive index 11 1.5110 weighing 31.9 g. (75% yield).
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.
The or- Example 14 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.
While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.
I claim: 1. Phosphate esters of the general formula mo s i -s-on c o 0 B.
R: 0 HgC 0 0 B4 s-onc 0 OR:
R20 H30 0 CR4 in which R1 and R: are chosen from the group consisting of aliphatic hydrocarbon and aromatic hydrocarbon radicals, and R3 and R4 are chosen from the group consisting of hydrogen, aliphatic hydrocarbon and aromatic hydrocarbon radicals,
which includes the step of reacting an acid phosphate of the general formula v i -sn 330 in which R1 and R: are chosen from the group consisting of aliphatic hydrocarbon and aromatic hydrocarbon radicals, with an unsaturated compound of the general formula oncooai in which R: and R4 are chosen from the group consisting of hydrogen, aliphatic hydrocarbon and aromatic hydrocarbon radicals.
8. The method of claim 7 in which the reacapnoea tion is carried out in the presence of an aliphatic tertiary amine catalyst. REFER cum The th r claim); n which t The following references are of record in the tion is carried out in the presence of a. solvent. me Of this P t 10. The method 01 claim '7 in which the. reac- I UNITED STATES \p ms tion is carried out at a temperature within the Number Name mm 7 ranae of from about20 C.to150 C. 2,528,132 A fine Nov. 7. mm
JACK T. CASSfADAY.

Claims (1)

1. PHOSPHATE ESTERS OF THE GENERAL FORMULA
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)

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GB3808/51A GB699522A (en) 1950-03-02 1951-02-16 Improvements relating to the preparation of phosphate esters
CH292795D CH292795A (en) 1950-03-02 1951-03-01 Process for preparing a phosphorus ester.
ES0196779A ES196779A1 (en) 1950-03-02 1951-03-01 A METHOD FOR PREPARING PHOSPHATE ESTERS
DEA12971A DE847897C (en) 1950-03-02 1951-03-01 Process for the preparation of dithiophosphoric acid triesters
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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 (en) * 1955-08-12 1958-01-30 American Cyanamid Co Process for the production of a deodorized and stabilized pest repellent based on O, O-dialkyl-1,2-di-carboxyaethyl-dithiophosphoric acid esters
US2844620A (en) * 1955-04-12 1958-07-22 Escobar Juan Nebrera Process for the deodorization of omicron, omicron-dimethyl-dithiophosphate of diethyl mercaptosuccinate
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
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DE1112338B (en) * 1956-05-03 1961-08-03 Pfizer & Co C Pest repellent with insecticidal and especially miticidal effects
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 (en) * 1958-10-31 1964-11-05 Ciba Geigy Process for the production of unsaturated thiophosphoric acid esters
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 (en) * 2018-09-27 2022-08-15 ケミノバ アクティーゼルスカブ Malathion catalyzed environmentally friendly production method

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DE1063154B (en) * 1950-05-09 1959-08-13 Bayer Ag Process for the preparation of thiophosphoric acid esters
DE956503C (en) * 1953-07-22 1957-01-17 Geigy Ag J R Process for the production of new phosphoric or thiophosphoric acid esters
DE942988C (en) * 1953-12-11 1956-05-09 Bayer Ag Process for the preparation of thiolphosphoric acid triesters
DE951717C (en) * 1953-12-19 1956-10-31 Bayer Ag Process for the production of thionothiol-phosphoric acid triesters
DE1006854B (en) * 1955-02-10 1957-04-25 Bayer Ag Process for the preparation of thionophosphoric acid esters
DE1011416B (en) * 1955-02-10 1957-07-04 Bayer Ag Process for the production of 0, 0-dialkyl-thiol and thiol-thiono-phosphoric acid triesters
NL110218C (en) * 1958-11-07
DE1188859B (en) * 1960-12-10 1965-03-11 Basf Ag Preparations for the control of insects
FR1310158A (en) * 1960-12-10 1963-03-06
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US2675321A (en) * 1951-06-12 1954-04-13 American Cyanamid Co Coated pigment and mineral oil ink containing same
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
US2630451A (en) * 1951-12-08 1953-03-03 American Cyanamid Co Dithiophosphate esters
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
US2863902A (en) * 1954-09-08 1958-12-09 American Cyanamid Co Preparation of phosphate esters
US2976308A (en) * 1954-10-13 1961-03-21 Lubrizol Corp Preparation of phosphorodithioate triesters
US2876244A (en) * 1954-12-30 1959-03-03 Union Carbide Corp Production of heterocyclic dithiophosphoric esters
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
US2844620A (en) * 1955-04-12 1958-07-22 Escobar Juan Nebrera Process for the deodorization of omicron, omicron-dimethyl-dithiophosphate of diethyl mercaptosuccinate
DE1023626B (en) * 1955-08-12 1958-01-30 American Cyanamid Co Process for the production of a deodorized and stabilized pest repellent based on O, O-dialkyl-1,2-di-carboxyaethyl-dithiophosphoric acid esters
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US2876156A (en) * 1956-05-03 1959-03-03 Pfizer & Co C Insecticides-derivatives of itaconic acid
DE1112338B (en) * 1956-05-03 1961-08-03 Pfizer & Co C Pest repellent with insecticidal and especially miticidal effects
US2861093A (en) * 1956-09-24 1958-11-18 Eastman Kodak Co Reaction products of dialkyl phosphorothiolothionates and mucohalic acids
US2937194A (en) * 1956-09-28 1960-05-17 Basf Ag Production of esters of phosphoric acid and thionophosphoric acid
US2948682A (en) * 1956-12-24 1960-08-09 Pure Oil Co Formyl triesters of dithiophosphoric acid and lubricating oil compositions containing same
US2947775A (en) * 1957-11-25 1960-08-02 Eastman Kodak Co O, o-dialkyl s-(2-acetoxy-2-cyanoethyl) phosphorothiolothionates
US2957019A (en) * 1958-02-14 1960-10-18 Eastman Kodak Co O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
DE1180736B (en) * 1958-10-31 1964-11-05 Ciba Geigy Process for the production of unsaturated thiophosphoric acid esters
US3074990A (en) * 1958-12-29 1963-01-22 Universal Oil Prod Co Alkylthiophosphoric acid salt of polymeric condensation product and use thereof
US2980723A (en) * 1959-06-16 1961-04-18 American Cyanamid Co Process for reducing objectionable odor of phosphorodithioate compounds
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
US3109770A (en) * 1961-04-10 1963-11-05 Stauffer Chemical Co Dialkoxyphosphinyl carbalkoxyalkyl disulfide pesticides
US3092543A (en) * 1961-05-09 1963-06-04 Velsicol Chemical Corp Allyl phthalate pesticidal compositions
US3185723A (en) * 1961-08-03 1965-05-25 Ici Ltd O-alkyl, s, 1-phenyl-2-alkoxycarbonylethyl alkylphosphonothioates
US3515782A (en) * 1964-11-27 1970-06-02 American Cyanamid Co Method for controlling insects
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
US3470272A (en) * 1966-10-24 1969-09-30 Mobil Oil Corp Process for making phosphorothioates
US3463841A (en) * 1966-11-01 1969-08-26 American Cyanamid Co Malathion manufacture
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
US5709890A (en) * 1996-03-14 1998-01-20 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
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