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US2520393A - 2-nitrophenyl dialkyl phosphates and thiophosphates - Google Patents

2-nitrophenyl dialkyl phosphates and thiophosphates Download PDF

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US2520393A
US2520393A US795115A US79511547A US2520393A US 2520393 A US2520393 A US 2520393A US 795115 A US795115 A US 795115A US 79511547 A US79511547 A US 79511547A US 2520393 A US2520393 A US 2520393A
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diethyl
nitrophenyl
alkali
group
forming metal
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John H Fletcher
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Wyeth Holdings LLC
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American Cyanamid Co
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    • 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
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds

Definitions

  • R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals
  • X is a member of the group consisting of sulfur and oxygen
  • Z is a member of the group consisting of halogen and alkyl radicals
  • m represents an integer not greater than 2.
  • R1 and R2 may be the same or diflerent radicals. Furthermore, it is to be understood that when the Rs stand for alkyl radicals, they represent both the straight chain and branch chain, the saturated and unsaturated, and the eycloaliphatic hydrocarbon radicals.
  • the R1 and R2 radicals may also carry halogen substituents, particularly chlorine and bromine.
  • radicals are methyl, ethyl, n-propyl, isopropyl, isobutyl, sec.-amyl, n-hexyl, Z-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, bromomethyl, 2-chloroethyl, cyclohexyl, benzyl, phenyl, and i-chlorophenyl.
  • the compounds of this invention possess general pest-control characteristics, including insecticidal, rodenticidal, and fungicidal properties. Many of the members possess desirable flotation properties and have the characteristics of high pressure lubricants when used as oil additives. These compounds may also be employed as corrosion inhibitors.
  • organic phosphate esters may be readily prepared by reacting a chlorophosphate of the general formula in which R1, R2, and K have the meaning shown above, with an alkali-forming metal phenoxlde of the general formula 2 in which Z and m have the meaning shown above, and Y represents an alkali-forming metal, in the presence of an inert organic solvent.
  • 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.
  • chlorophosphate compounds employed in the present process as shown above namely the organic chlorophosphates and chlorothiophosphates, may be prepared according to the methods described in the Journal of the American Chemical Society, volume 67, No. 10, page 1663.
  • an inert organic solvent serving particularly as a solvent for the solid alkali-forming metal phenoxide.
  • Suitable inert solvents include the ketones such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, cyclohexanone, acetophenone, and the like; aliphatic esters such as ethyl acetate, amyl acetate, 2-ethy'1hexyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, and isopropyl butyrate; saturated aliphatic nitriles such as acetonitrile and propionitrile; dioxane, nitrobenzene, 1,2-dimethoxyethane, and the trialkyl phosphates such as trimethyl phosphate, triethyl
  • Organic liquids which are poor solvents for the alkali-forming metal phenoxides, and hence are less suitable in the present process, include chloroibenzene, toluene, xylene, diethyl ether, chloroform, carbon disulflde, and carbon tetrachloride.
  • Water and the alcohols in general may be used as solvents for the alkali-forming metal phenoxides. However, they are less satisfactory in the pro ss inasmuch as they tend to react with the chlorothiophosphate and chlorophosphate compounds,
  • the reaction is preferably carried out at a temperaturewithin the range of from about 30 to 150 C. However, temperatures outside of this range may be employed depending upon the type of reactants and solvents utilized.
  • An alternative method of preparing the compounds of the present invention consists in employing in lieu of the alkali-forming metal phenoxide the corresponding phenol and a basic alkali-forming metal compound, the latter having suiiicient alkalinity to neutralize the phenol. Obviously, this procedure avoids the initial preparation and isolation of the alkali-forming metal phenoxide.
  • Such basic alkali-forming metal compounds include sodium carbonate, potassium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, magnesium hydroxide, sodium borate, tripotassium arsenate, tripotassium arsenite, sodium pyrophosphate, magnesium pyrophosphate, potassium pyrophosphate, barium phosphate, trisodium phosphate, and the like.
  • Example 1 34.7 grams (0.2 mol) of 4-chloro-2-nitrophenol, 21.2 grams (0.2 mol) of anhydrous sodium carbonate, and 200 cc. of methyl ethyl ketone were mixed together at room temperature with good stirring in a vessel equipped with a reflux condenser. 37.7 grams (0.2 mol) of diethyl chlorothiophosphate were added, and the mixture was stirred and heated at reflux for three hours. After cooling to room temperature, the mixture was filtered to remove the sodium chloride and sodium bicarbonate, and the filtrate heated under reduced pressure to distill off the methyl ethyl ketone. The residual brown oil was dissolved in 200 cc.
  • Example 2 The procedure of Example 1 was employed using 34.7 grams of 4-chloro-2-nitrophenol, 21.2 grams of anhydrous sodium carbonate, 100 cc. of methyl ethyl ketone, and 34.5 grams 0i diethyl
  • Example 3 A mixture consisting of 0.2 mol of 2-nitro-D- cresol and 0.2 mol of anhydrous sodium carbonate was heated in cc. of methyl ethyl ketone until the orange-red sodium salt of 2-nitrop-cresol was formed. 0.2 mol of diethyl chlorothiophosphate was then added, and the reaction mixture refluxed for four and one-half hours.
  • Example 4 0.12 mol of 2,4-dichloro-6-nitrophenol was heated with concentrated aqueous alkali (containing 5 grams of sodium hydroxide) in 225 cc. of xylene until all the water had distilled azeotropically. 0.12 mol of diethyl chlorothiophosphate in cc. of methyl ethyl ketone was added to the cooled xylene slurry, followed by refluxing the resulting mixture for a period of twelve hours. The reaction mixture was filtered and the filtrate concentrated in vacuo. The residue was taken up in benzene, washed with dilute sodium hydroxide solution, and then with water, and dried over Drierite.
  • the solution was heated under reduced pressure to remove the benzene and any unreacted diethyl chlorothiophosphate.
  • 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 beetle, 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 beetle, confused flour beetle, and black carpet beetle.
  • These new compounds may also be used in combination with insecticides such as lead arsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, a,a-di(p-chlorophenyl) -B, B,B-trichloroethane, dodecyl thiocyanate, phenothiazine, and the like; with fungicides such as sulfur, various copper compounds, mercury salts, and the like; and
  • R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals
  • X is a member of the group consisting of sulfur and oxygen
  • Z is a member of the group consisting of halogen and alkyl radicals
  • m represents an integer not greater than 2
  • R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals
  • X is a member of the group consisting of sulfur and oxygen
  • a phenol of the general formula HOG in which Z is a member of the group consisting of halogen and alkyl radicals, and 122 represents an integer not greater than 2
  • a basic alkaliforming metal compound having suiicient alkalinity to neutralize the phenol, in the presence of an inert organic solvent in which the inert organic solvent is a, ketone.
  • a method of preparing 4-chloro-2-nitrophenyl diethyl thiophosphate which includes the step of reacting together 4-chloro-2-nitropheno1, sodium carbonate, and diethyl chlorothiophosphate in the presence of methyl ethyl ketone.
  • a method of preparing diethyl Z-nitro-- tolyl thiophosphate which includes the step of reacting together Z-nitro-p-cresol, sodium carbonate, and diethyl chlorothiophosphate in the presence of methyl ethyl ketone.
  • a method of preparing 4-chloro-2-nitrophenyl diethyl phosphate which includes the step of reacting together 4-chloro-2-nitrophenol, sodium carbonate, and diethyl chlorophosphate in the presence of methyl ethyl ketone.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)

Description

Patented Aug. 29, 1950 UNITED STATES PATENT OFFICE 2-NITBOPHENYL PHOSPHATES AND THIOPHOSPHATES John H. Fletcher, Riverside, Conn., assignor to 7 American Gyanamid Company, New York, N. Y.,
a corporation of Maine No Drawing. Application December 31, 1947, Serial No. 795,115
10 Claims.
in which R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, X is a member of the group consisting of sulfur and oxygen, Z is a member of the group consisting of halogen and alkyl radicals, and m represents an integer not greater than 2.
In the new compounds R1 and R2 may be the same or diflerent radicals. Furthermore, it is to be understood that when the Rs stand for alkyl radicals, they represent both the straight chain and branch chain, the saturated and unsaturated, and the eycloaliphatic hydrocarbon radicals. The R1 and R2 radicals may also carry halogen substituents, particularly chlorine and bromine. Typical examples of these radicals are methyl, ethyl, n-propyl, isopropyl, isobutyl, sec.-amyl, n-hexyl, Z-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, bromomethyl, 2-chloroethyl, cyclohexyl, benzyl, phenyl, and i-chlorophenyl.
The compounds of this invention possess general pest-control characteristics, including insecticidal, rodenticidal, and fungicidal properties. Many of the members possess desirable flotation properties and have the characteristics of high pressure lubricants when used as oil additives. These compounds may also be employed as corrosion inhibitors.
These organic phosphate esters may be readily prepared by reacting a chlorophosphate of the general formula in which R1, R2, and K have the meaning shown above, with an alkali-forming metal phenoxlde of the general formula 2 in which Z and m have the meaning shown above, and Y represents an alkali-forming metal, in the presence of an inert organic solvent.
The term 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.
The chlorophosphate compounds employed in the present process as shown above, namely the organic chlorophosphates and chlorothiophosphates, may be prepared according to the methods described in the Journal of the American Chemical Society, volume 67, No. 10, page 1663.
A typical reaction in which diethyl chlorophosphate is reacted with sodium 4-chloro-2-nitrophenoxlde to produce 4-chloro-2-nitrophenyl diethyl phosphate may be illustrated as follows:
High yields of the desired products are obtained by carrying out the reaction in the presence of an inert organic solvent, the latter serving particularly as a solvent for the solid alkali-forming metal phenoxide. Suitable inert solvents include the ketones such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, cyclohexanone, acetophenone, and the like; aliphatic esters such as ethyl acetate, amyl acetate, 2-ethy'1hexyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, and isopropyl butyrate; saturated aliphatic nitriles such as acetonitrile and propionitrile; dioxane, nitrobenzene, 1,2-dimethoxyethane, and the trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, and triisopropyl phosphate.
Organic liquids which are poor solvents for the alkali-forming metal phenoxides, and hence are less suitable in the present process, include chloroibenzene, toluene, xylene, diethyl ether, chloroform, carbon disulflde, and carbon tetrachloride. Water and the alcohols in general may be used as solvents for the alkali-forming metal phenoxides. However, they are less satisfactory in the pro ss inasmuch as they tend to react with the chlorothiophosphate and chlorophosphate compounds,
The reaction is preferably carried out at a temperaturewithin the range of from about 30 to 150 C. However, temperatures outside of this range may be employed depending upon the type of reactants and solvents utilized.
An alternative method of preparing the compounds of the present invention consists in employing in lieu of the alkali-forming metal phenoxide the corresponding phenol and a basic alkali-forming metal compound, the latter having suiiicient alkalinity to neutralize the phenol. Obviously, this procedure avoids the initial preparation and isolation of the alkali-forming metal phenoxide. Such basic alkali-forming metal compounds include sodium carbonate, potassium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, magnesium hydroxide, sodium borate, tripotassium arsenate, tripotassium arsenite, sodium pyrophosphate, magnesium pyrophosphate, potassium pyrophosphate, barium phosphate, trisodium phosphate, and the like.
Employing the above procedure in the preparation of di-n-butyl 2-nitro-4-tolyl thiophosphate, the reaction may be illustrated as follows:
The following examples will further illustrate the invention.
Example 1 34.7 grams (0.2 mol) of 4-chloro-2-nitrophenol, 21.2 grams (0.2 mol) of anhydrous sodium carbonate, and 200 cc. of methyl ethyl ketone were mixed together at room temperature with good stirring in a vessel equipped with a reflux condenser. 37.7 grams (0.2 mol) of diethyl chlorothiophosphate were added, and the mixture was stirred and heated at reflux for three hours. After cooling to room temperature, the mixture was filtered to remove the sodium chloride and sodium bicarbonate, and the filtrate heated under reduced pressure to distill off the methyl ethyl ketone. The residual brown oil was dissolved in 200 cc. of toluene, washed with 5% sodium carbonate solution, and then with sodium chloride solution. The toluene extract was dried over Drierite, filtered, and the toluene removed by distillation at reduced pressure. A small amount of unreacted diethyl chlorothiophosphate was also removed by distillation in vacuo. The residual product, 4-chloro-2-nitrophenyl diethyl thiophosphate, weighing 53.5 grams, was a clear light brown liquid having a refractive index n 1.5402.
Example 2 The procedure of Example 1 was employed using 34.7 grams of 4-chloro-2-nitrophenol, 21.2 grams of anhydrous sodium carbonate, 100 cc. of methyl ethyl ketone, and 34.5 grams 0i diethyl Example 3 A mixture consisting of 0.2 mol of 2-nitro-D- cresol and 0.2 mol of anhydrous sodium carbonate was heated in cc. of methyl ethyl ketone until the orange-red sodium salt of 2-nitrop-cresol was formed. 0.2 mol of diethyl chlorothiophosphate was then added, and the reaction mixture refluxed for four and one-half hours. The resulting mixture was cooled to room temperature, filtered, and the filter cake washed with methyl ethyl ketone. The combined .flltrate and washings were heated under reduced pressure to remove the ketone and any unreacted diethyl chlorothiophosphate. The residue was taken up in 77 cc. of benzene, washed twice with dilute sodium hydroxide solution, once with water, and then dried over Drierite. Upon distillation, 39 grams of diethyl 2-nitro-4-tolyl thiophosphate were obtained, boiling at 175-185 C./0.5-1.0 mm.,
'and having a refractive index a 1.5283.
Example 4 0.12 mol of 2,4-dichloro-6-nitrophenol was heated with concentrated aqueous alkali (containing 5 grams of sodium hydroxide) in 225 cc. of xylene until all the water had distilled azeotropically. 0.12 mol of diethyl chlorothiophosphate in cc. of methyl ethyl ketone was added to the cooled xylene slurry, followed by refluxing the resulting mixture for a period of twelve hours. The reaction mixture was filtered and the filtrate concentrated in vacuo. The residue Was taken up in benzene, washed with dilute sodium hydroxide solution, and then with water, and dried over Drierite. The solution was heated under reduced pressure to remove the benzene and any unreacted diethyl chlorothiophosphate. The residual product, 2,4-dichloro-6-nitrophenyl diethyl thiophosphate, was a dark brown oily liquid.
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 beetle, confused flour beetle, and black carpet beetle.
These new compounds may also be used in combination with insecticides such as lead arsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, a,a-di(p-chlorophenyl) -B, B,B-trichloroethane, dodecyl thiocyanate, phenothiazine, and the like; with fungicides such as sulfur, various copper compounds, mercury salts, and the like; and
with various types of plant foods and fertilizers. Additives of high alkalinity are to be avoided, since the organic phosphates are unstable in vehicles' having a pH in water greater than about 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 in which R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, X is a member of the group consisting of sulfur and oxygen, Z is a member of the group consisting of halogen and alkyl radicals, and m represents an integer not greater than 2, which includes the step of reacting a ohlorophosphate compound of the general formula in which R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, and X is a member of the group consisting of sulfur and oxygen, with an alkali-forming metal phenoxide of the general formula in which Z is a member of the group consisting of halogen and alkyl radicals, m represents an integer not greater than 2, and Y represents an alkali-forming metal, in the presence of an inert organic solvent. I
6. The method of claim 5 in which the reaction is carried out at a temperature within the range of from about 30 to 150 C.
7. A method of preparing a phosphate ester of the general formula NO: (z),-
in which R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, X is a member of the group consisting of sulfur and oxygen, Z is a member of the group consisting of halogen and alkyl radicals, and m represents an integer not greater than 2, which includes the step of reacting together a chlorophosphate compound of the genera/l formula in which R1 and R2 are chosen from the group consisting of alkyl, aralkyl, and aryl radicals, and X is a member of the group consisting of sulfur and oxygen, a phenol of the general formula HOG in which Z is a member of the group consisting of halogen and alkyl radicals, and 122 represents an integer not greater than 2, and a basic alkaliforming metal compound having suiicient alkalinity to neutralize the phenol, in the presence of an inert organic solvent in which the inert organic solvent is a, ketone.
8. A method of preparing 4-chloro-2-nitrophenyl diethyl thiophosphate which includes the step of reacting together 4-chloro-2-nitropheno1, sodium carbonate, and diethyl chlorothiophosphate in the presence of methyl ethyl ketone.
9. A method of preparing diethyl Z-nitro-- tolyl thiophosphate which includes the step of reacting together Z-nitro-p-cresol, sodium carbonate, and diethyl chlorothiophosphate in the presence of methyl ethyl ketone.
10. A method of preparing 4-chloro-2-nitrophenyl diethyl phosphate which includes the step of reacting together 4-chloro-2-nitrophenol, sodium carbonate, and diethyl chlorophosphate in the presence of methyl ethyl ketone.
' JOHN H. FLETCHER.
REFERENCES CITED The following references are of record in the file of this patent:
' UNITED STATES PATENTS Name Date Clemmensen Dec. 4, 1934 OTHER REFERENCES Number Developments in Methods and Materials for Control of Plant Pests and Diseases in Germany," by H. Martin et al., dated May-June 194:6,page 22.

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1. PHOSPHATE ESTERS OF THE GENERAL FORMULA
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Cited By (38)

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US2575225A (en) * 1948-09-29 1951-11-13 Us Rubber Co Preparation of o-alkyl dichlorothiophosphates
US2575224A (en) * 1948-07-17 1951-11-13 Us Rubber Co Thiophosphates
US2599375A (en) * 1950-04-21 1952-06-03 Lewis R Drake 2,4,6-trichlorophenyl dialkylphosphates
US2599512A (en) * 1950-04-21 1952-06-03 Dow Chemical Co O-2, 4, 6-trichlorophenyl o, o-dialkylthiophosphates
US2599515A (en) * 1950-03-30 1952-06-03 Dow Chemical Co O-2, 4, 5-trichlorophenyl o, o-dialkylphosphates
US2599516A (en) * 1950-03-30 1952-06-03 Dow Chemical Co O-2, 4, 5-trichlorophenyl o, o-dialkylthiophosphates
US2643265A (en) * 1950-09-15 1953-06-23 Victor Chemical Works Bis (dialkyl phosphate) esters of alkylidene diphenols
US2656374A (en) * 1950-05-01 1953-10-20 Monsanto Chemicals Process for the preparation of alkyl phenyl phosphoric acids and the salts thereof
US2656373A (en) * 1950-04-14 1953-10-20 Monsanto Chemicals Process for producing mixed diaryl esters of ortho-phosphoric acid
US2657229A (en) * 1950-12-08 1953-10-27 Pittsburgh Coke & Chemical Co Manufacture of thiophosphate esters
US2663721A (en) * 1949-05-16 1953-12-22 Monsanto Chemicals Preparation of o, o-dialkyl o-para nitrophenyl thiophosphate esters
US2678329A (en) * 1950-11-06 1954-05-11 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2692891A (en) * 1950-11-24 1954-10-26 Pittsburgh Coke & Chemical Co Production of thiophosphate esters
US2701259A (en) * 1952-05-02 1955-02-01 Bayer Ag Omicron. omicron-dimethyl-omicron-4-nitro-3-chlorophenyl thiophosphate
US2732394A (en) * 1956-01-24 Manufacture of dialkyl aryl
US2739977A (en) * 1950-11-06 1956-03-27 Monsanto Chemicals Dialkyl phosphoryl monochlorides
US2739978A (en) * 1950-11-06 1956-03-27 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2757118A (en) * 1951-11-20 1956-07-31 Monsanto Chemicals Method for controlling mollusks with diethyl thiophosphoryl bis (dimethylamido) phosphate
US2758091A (en) * 1947-10-28 1956-08-07 Shell Dev Lubricating compositions
US2758954A (en) * 1952-01-04 1956-08-14 Fmc Corp Stable mixture of diethylparanitro-phenylthionophosphate and solid extender and method of making same
US2793224A (en) * 1954-02-03 1957-05-21 Stauffer Chemical Co P-chlorophenyl-mercaptomethyl di-alkyl dithiophosphates and their use as insecticides
US2866808A (en) * 1954-08-04 1958-12-30 Ethyl Corp Chemical process for producing tri (beta-haloaliphatic) esters of phosphorus acids
US2870187A (en) * 1955-07-29 1959-01-20 Bayer Ag O, o-dimethyl-o-(4-chloro-3-nitrophenyl)-thiophosphoric acid esters and their preparation
US2885429A (en) * 1956-04-02 1959-05-05 Dow Chemical Co O-biphenylyl o, o-dialkyl phosphoro-thioates
US2888481A (en) * 1957-02-04 1959-05-26 Ford Motor Co Perfluoroalkyl phosphite and phosphonate lubricants and lubricant additives
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US3004054A (en) * 1960-05-23 1961-10-10 Virginia Carolina Chem Corp Process for the manufacture of mixed phosphorothioate esters
US3006946A (en) * 1953-03-04 1961-10-31 Union Carbide Corp Production of heterocyclic phosphoruscontaining compounds and products
US3033667A (en) * 1957-05-09 1962-05-08 Pittsburgh Coke And Chemical C Composition and method for defoliating plants
US3085044A (en) * 1961-04-04 1963-04-09 Monsanto Chemicals Aryl alkylphosphonothioates
US3107164A (en) * 1962-03-27 1963-10-15 Stauffer Chemical Co Herbicidal methods employing omicron, omicron-diallyl omicron-aryl phosphate esters
US3135780A (en) * 1959-09-03 1964-06-02 Sumitomo Chemical Co O, o-dimethyl-o-(3-methyl-4-nitrophenyl) thionophosphate
US3155570A (en) * 1961-07-07 1964-11-03 Bayer Ag Synergistic mixture of parathion and its ortho-isomer
US3322863A (en) * 1963-09-09 1967-05-30 Dow Chemical Co Aminoalkyl phosphonates and preparation thereof
US3444274A (en) * 1964-10-29 1969-05-13 Bayer Ag Asymmetrical para-nitrophenyl phosphates
US3480697A (en) * 1966-02-02 1969-11-25 American Cyanamid Co Para-thiocarbamoylphenyl phosphorothioates
US3937765A (en) * 1970-10-12 1976-02-10 Stauffer Chemical Company Process for preparing 0,0-diaryl n,n-dialkyl phosphoramidates
US5034529A (en) * 1988-04-28 1991-07-23 Ciba-Geigy Corporation Process for the production of thiophosphoric acid esters of hydroxypyrimidines

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US2732394A (en) * 1956-01-24 Manufacture of dialkyl aryl
US2758091A (en) * 1947-10-28 1956-08-07 Shell Dev Lubricating compositions
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US2575225A (en) * 1948-09-29 1951-11-13 Us Rubber Co Preparation of o-alkyl dichlorothiophosphates
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US2599515A (en) * 1950-03-30 1952-06-03 Dow Chemical Co O-2, 4, 5-trichlorophenyl o, o-dialkylphosphates
US2599516A (en) * 1950-03-30 1952-06-03 Dow Chemical Co O-2, 4, 5-trichlorophenyl o, o-dialkylthiophosphates
US2656373A (en) * 1950-04-14 1953-10-20 Monsanto Chemicals Process for producing mixed diaryl esters of ortho-phosphoric acid
US2599512A (en) * 1950-04-21 1952-06-03 Dow Chemical Co O-2, 4, 6-trichlorophenyl o, o-dialkylthiophosphates
US2599375A (en) * 1950-04-21 1952-06-03 Lewis R Drake 2,4,6-trichlorophenyl dialkylphosphates
US2656374A (en) * 1950-05-01 1953-10-20 Monsanto Chemicals Process for the preparation of alkyl phenyl phosphoric acids and the salts thereof
US2643265A (en) * 1950-09-15 1953-06-23 Victor Chemical Works Bis (dialkyl phosphate) esters of alkylidene diphenols
US2739978A (en) * 1950-11-06 1956-03-27 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2678329A (en) * 1950-11-06 1954-05-11 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2739977A (en) * 1950-11-06 1956-03-27 Monsanto Chemicals Dialkyl phosphoryl monochlorides
US2692891A (en) * 1950-11-24 1954-10-26 Pittsburgh Coke & Chemical Co Production of thiophosphate esters
US2657229A (en) * 1950-12-08 1953-10-27 Pittsburgh Coke & Chemical Co Manufacture of thiophosphate esters
US2757118A (en) * 1951-11-20 1956-07-31 Monsanto Chemicals Method for controlling mollusks with diethyl thiophosphoryl bis (dimethylamido) phosphate
US2758954A (en) * 1952-01-04 1956-08-14 Fmc Corp Stable mixture of diethylparanitro-phenylthionophosphate and solid extender and method of making same
US2701259A (en) * 1952-05-02 1955-02-01 Bayer Ag Omicron. omicron-dimethyl-omicron-4-nitro-3-chlorophenyl thiophosphate
US3006946A (en) * 1953-03-04 1961-10-31 Union Carbide Corp Production of heterocyclic phosphoruscontaining compounds and products
US2793224A (en) * 1954-02-03 1957-05-21 Stauffer Chemical Co P-chlorophenyl-mercaptomethyl di-alkyl dithiophosphates and their use as insecticides
US2866808A (en) * 1954-08-04 1958-12-30 Ethyl Corp Chemical process for producing tri (beta-haloaliphatic) esters of phosphorus acids
US2870187A (en) * 1955-07-29 1959-01-20 Bayer Ag O, o-dimethyl-o-(4-chloro-3-nitrophenyl)-thiophosphoric acid esters and their preparation
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US2885429A (en) * 1956-04-02 1959-05-05 Dow Chemical Co O-biphenylyl o, o-dialkyl phosphoro-thioates
US2888481A (en) * 1957-02-04 1959-05-26 Ford Motor Co Perfluoroalkyl phosphite and phosphonate lubricants and lubricant additives
US3033667A (en) * 1957-05-09 1962-05-08 Pittsburgh Coke And Chemical C Composition and method for defoliating plants
US3135780A (en) * 1959-09-03 1964-06-02 Sumitomo Chemical Co O, o-dimethyl-o-(3-methyl-4-nitrophenyl) thionophosphate
US3004054A (en) * 1960-05-23 1961-10-10 Virginia Carolina Chem Corp Process for the manufacture of mixed phosphorothioate esters
US3085044A (en) * 1961-04-04 1963-04-09 Monsanto Chemicals Aryl alkylphosphonothioates
US3155570A (en) * 1961-07-07 1964-11-03 Bayer Ag Synergistic mixture of parathion and its ortho-isomer
US3107164A (en) * 1962-03-27 1963-10-15 Stauffer Chemical Co Herbicidal methods employing omicron, omicron-diallyl omicron-aryl phosphate esters
US3322863A (en) * 1963-09-09 1967-05-30 Dow Chemical Co Aminoalkyl phosphonates and preparation thereof
US3444274A (en) * 1964-10-29 1969-05-13 Bayer Ag Asymmetrical para-nitrophenyl phosphates
US3480697A (en) * 1966-02-02 1969-11-25 American Cyanamid Co Para-thiocarbamoylphenyl phosphorothioates
US3937765A (en) * 1970-10-12 1976-02-10 Stauffer Chemical Company Process for preparing 0,0-diaryl n,n-dialkyl phosphoramidates
US5034529A (en) * 1988-04-28 1991-07-23 Ciba-Geigy Corporation Process for the production of thiophosphoric acid esters of hydroxypyrimidines

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