US2494284A - Cyanoalkyl phosphates and method of preparation - Google Patents

Cyanoalkyl phosphates and method of preparation Download PDF

Info

Publication number
US2494284A
US2494284A US70604A US7060449A US2494284A US 2494284 A US2494284 A US 2494284A US 70604 A US70604 A US 70604A US 7060449 A US7060449 A US 7060449A US 2494284 A US2494284 A US 2494284A
Authority
US
United States
Prior art keywords
parts
dithiophosphate
phosphate
cyanomethyl
diethyl
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
US70604A
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
Original Assignee
American Cyanamid Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to US70604A priority Critical patent/US2494284A/en
Application granted granted Critical
Publication of US2494284A publication Critical patent/US2494284A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • R1 or R2 may be the same or difierent 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.
  • radicals are methyl, ethyl, n propyl, isopropyl, isobutyl, sec.-amyl, nhewl, Z-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, cyclohexyl, phenyl and naphthyl.
  • 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 may be readily prepared by reacting a, phosphate of the formula H Z( ,--CN
  • Z is a. member Of of chlorine and bromine.
  • alkali-forming metal as used in this specification and in the appended claims is inthe group consisting 2 tended to cover the alkali metals (including am monium), and the alkaline earth metals.
  • Such solvents include the low molecular we ght aliphatic monohydric alcohols, 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-ethylhexy1, acetate, methyl proprionate, methyl butyrate, ethyl butyrate and isopropyl butyrate; dioxane, nitrobenzene, chlorobenzene, toluene, xylene, chloroform, carbon tetrachloride, 1,2-dimethoxyethane and the trialkyl phosphates such as trimethyl phosphate, triethyl phosphate and triis
  • the reaction is preferably carried out at a temperature within the range of from about 20 C. to, 0. However, temperatures outside of 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 suflicient alkalinity to neutralize said acid. Obviously, this procedure avoids the initial preparation and isolation of the alkali-forming metal phosphate.
  • 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 hydrosulfide, sodium borate, tripotassium arsenate, tripotassium arsenite, sodium pyrophosphate, magnesium pyrophosphate, potassium pyrophosphate, barium phosphate. trisodium phosphate, and the like.
  • Example 1 The procedure of Example 1 was employed, using 20.8 parts of sodium 0,0-diethyl dithiophosphate, 12 parts of monobromoacetonitrile and 100 parts of acetone. The mixture was allowed to stand at room temperature for 2 days.
  • the product S-cyanomethyl 0,0-diethyl dithiophosphate, was an amber-colored liquid, having a refractive index Np 1.5153.
  • Example 3 The procedure of Example 1 was employed, using 8.9 parts of potassium 0,0-diphenyl dithiophosphate, 2.2? parts of monochloroacetonitrile and 100 parts of acetone. The mixture was allowed to stand at room temperature for 2 days. The product, S-cyanomethyl 0,0-diphenyl dithiophosphate, was an amber-colored oily liquid having a refractive index ND 1.5180.
  • Example 4 The procedure of Example 1 was employed, using 15.4 parts of potassium 0,0-di-n-amyl dithiophosphate, 3.8 parts of monochloroacetonitrile and 100 parts of acetone. The product,
  • Example 7 The procedure of Example 6 was employed, using 41 parts of 0,0-di-n-decyl dithiophosphoric acid, 7.9 parts of sodium hydrosulflde (71%), 200 parts of acetone and 12 parts of monobromoacetonitrile. The mixture was not heated under reflux as in Example 6, but was allowed to stand for 2 days at room temperature. The product, 8- cyanomethyl 0,0-di-n-decyl dithiophosphate, was obtained in a 93% yield as a red 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 cock- 1 roach, 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 cock- 1 roach, Southern army worm, yellow fever mosquito, malarial mosquito, Mexican bean beetle, confused flour beetle, and black carpet bee
  • These new compounds may also be used in combination with insecticides such as lead atsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, 1,1,1 trichloro 2,2 di (p chlorophenyl) ethane, 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.
  • insecticides such as lead atsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, 1,1,1 trichloro 2,2 di (p chlorophenyl) ethane, dodecyl thiocyanate, phenothiazine, and the like
  • fungicides such as sulfur, various copper compounds, mercury salts, and the like
  • Example 5 The procedure of Example 1 was employed, using 20.8 parts of potassium 0,0-diethyl monothiophosphate, 12 parts of monobromoacetonitrile and 75 parts of methyl isobutyl ketone. The mixture was held at C. for 5 hours and then cooled and filtered to remove the precipitated potassium bromide. 12 parts of S-cyanomethyl 0,0-diethyl monothiophosphate were obtained as a brown oily liquid.
  • Example 6 40 parts of 0,0-diethyl ditbiophosphorlo (93%) were added slowly to a well-agitated mixture of 21.2 parts of anhydrous sodium carbonate thereto, but is to be construed. broadly and restricted solely by the scope of the appended claims.
  • Phosphate esters of the general formula R1 .5 H i-B-i-CN xt-s-Ju-ou it in which R1 and R2 are chosen from the group consisting of alkyl and aryl hydrocarbon radi cals', and X is a member of the group consisting of sulfur and oxygen, and Y represents an alkaliforming metal, with a halogen-substituted acetonitrile of the formula in which Z is a member of the group consisting of chlorine and bromine.
  • a method of preparing a phosphate ester of the general formula in which R1 and R2 are chosen from the up consisting of alkyl and aryl hydrocarbon radicals, and X is a member of the group consisting ol' sulfur and oxygen which includes the step oi reacting together a halogen-substituted aceto nitrile of the formula in which Z is a member of the group consisting of chlorine and bromine, an acid phosphate of the general formula in which R1 and R2 are chosen from the group consisting of alkyl and aryl hydrocarbon radicals, and X is a member of the group consisting of sulfur and'oxygen, and a basic alkali-forming metal compound having suflicient alkalinity to neutralize the acid phosphate.
  • a method of preparing S-cyanomethyl 0,0-diethyl -dithiophosphate which includes the step of reacting together 0,0-diethyl dithiophosphoric acid, sodium carbonate and monochloroacetonitrile in the presence of ethyl alcohol.
  • a method of preparing S-cyanomethyl 0,0-dipheny1 dithiophosphate which includes the step of reacting together potassium 0,0-diphenyl dithiophosphate and monochloroacetonitrile in the presence of acetone.
  • a method of preparing S-cyanomethyl 0,0-diethyl monothiophosphate which includes the step of reacting together potassium 0,0-dlethyl monothiophosphate and monobromoacetw nitrlle in the presence of methyl isobutyl ketone.

Landscapes

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

Description

Patented Jan. 10, 1950 UNHTED STATES FATE CYANOALKYL PHOSPHATES AND METHOD OF PREPARATION Jack T. Cassaday assignor to and Erick I. Hoegberg, Stamford, and Bruce D. Gleissner,
Riverside, Comp,
American Cyanamld Company, New York, N. Y., a corporation of Maine No Drawing. Application January 12, 1949, Serial No. 7050i i. in which R1 and R2 are chosen from the group consisting of allql and aryl hydrocarbon radicals and X is a member of the group consisting of sulfur and oxygen.
In the new compounds R1 or R2 may be the same or difierent 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. Typical examples of these radicals are methyl, ethyl, n propyl, isopropyl, isobutyl, sec.-amyl, nhewl, Z-ethylhexyl, n-octyl, n-decyl, n-dodecyl, oleyl, cetyl, ceryl, allyl, cyclohexyl, phenyl and naphthyl.
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.
The phosphate esters of the above general formula may be readily prepared by reacting a, phosphate of the formula H Z( ,--CN
i in which Z is a. member Of of chlorine and bromine.
The term alkali-forming metal as used in this specification and in the appended claims is inthe group consisting 2 tended to cover the alkali metals (including am monium), and the alkaline earth metals.
A typical reaction in which potassium 0,0-diethyl dithiophosphate is reacted with monobromoacetonitrile to produce S-cyanomethyl 0,0- diethyl dithiophosphate may be illustrated as follows:
High yields of the desired products are obtained by carrying out the reaction in the presence of a solvent. Such solvents include the low molecular we ght aliphatic monohydric alcohols, 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-ethylhexy1, acetate, methyl proprionate, methyl butyrate, ethyl butyrate and isopropyl butyrate; dioxane, nitrobenzene, chlorobenzene, toluene, xylene, chloroform, 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 C. to, 0. However, temperatures outside of 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 suflicient alkalinity to neutralize said acid. Obviously, this procedure avoids the initial preparation and isolation of the alkali-forming metal phosphate. 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 hydrosulfide, 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 S -cyanomethyl 0,0-di-n-butyl dithiophosphate, the reaction may be illustrated as follows:
The following examples in which the parts are a by weight further illustrate the invention.
Example 1 The procedure of Example 1 was employed, using 20.8 parts of sodium 0,0-diethyl dithiophosphate, 12 parts of monobromoacetonitrile and 100 parts of acetone. The mixture was allowed to stand at room temperature for 2 days.
The product, S-cyanomethyl 0,0-diethyl dithiophosphate, was an amber-colored liquid, having a refractive index Np 1.5153.
Example 3 The procedure of Example 1 was employed, using 8.9 parts of potassium 0,0-diphenyl dithiophosphate, 2.2? parts of monochloroacetonitrile and 100 parts of acetone. The mixture was allowed to stand at room temperature for 2 days. The product, S-cyanomethyl 0,0-diphenyl dithiophosphate, was an amber-colored oily liquid having a refractive index ND 1.5180.
Example 4 The procedure of Example 1 was employed, using 15.4 parts of potassium 0,0-di-n-amyl dithiophosphate, 3.8 parts of monochloroacetonitrile and 100 parts of acetone. The product,
suspended in 100 parts of ethanol. 15.1 parts of monochloroacetonitrile were then added slowly and the mixture was heated under reflux with stirring for a period of 6 /2 hours. The reaction mixture was filtered and the filtrate was heatbd under vacuum to distill off the ethanol. The residual oily liquid was washed with cold water and dried over anhydrous sodium sulfate. 3'1 parts of the product, S-cyanomethyl 0,0-diethyl dithiophosphate, were obtained.
Example 7 The procedure of Example 6 was employed, using 41 parts of 0,0-di-n-decyl dithiophosphoric acid, 7.9 parts of sodium hydrosulflde (71%), 200 parts of acetone and 12 parts of monobromoacetonitrile. The mixture was not heated under reflux as in Example 6, but was allowed to stand for 2 days at room temperature. The product, 8- cyanomethyl 0,0-di-n-decyl dithiophosphate, was obtained in a 93% yield as a red 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 cock- 1 roach, 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 atsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, 1,1,1 trichloro 2,2 di (p chlorophenyl) ethane, 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.
This application is a continuation-in-part of our copending application Serial Number 6348, filed February 4, 1948.
While the invention has been described with particular reference to specific embodiments, it
is .tO be understood that it is not to be limited S-cyanomethyl 0,0-di-n-amyl dithiophosphate,
was a straw-colored liquid having a refractive index N19 1.4984.
Example 5 The procedure of Example 1 was employed, using 20.8 parts of potassium 0,0-diethyl monothiophosphate, 12 parts of monobromoacetonitrile and 75 parts of methyl isobutyl ketone. The mixture was held at C. for 5 hours and then cooled and filtered to remove the precipitated potassium bromide. 12 parts of S-cyanomethyl 0,0-diethyl monothiophosphate were obtained as a brown oily liquid.
Example 6 40 parts of 0,0-diethyl ditbiophosphorlo (93%) were added slowly to a well-agitated mixture of 21.2 parts of anhydrous sodium carbonate thereto, but is to be construed. broadly and restricted solely by the scope of the appended claims.
We claim: 1. Phosphate esters of the general formula R1 .5 H =i-B-i-CN xt-s-Ju-ou it in which R1 and R2 are chosen from the group consisting of alkyl and aryl hydrocarbon radi cals', and X is a member of the group consisting of sulfur and oxygen, and Y represents an alkaliforming metal, with a halogen-substituted acetonitrile of the formula in which Z is a member of the group consisting of chlorine and bromine.
6. The method of claim 5 in which the reaction is carried out in the presence of a solvent.
7. The method of claim 5 in which the reaction is carried out at a temperature within the range of from about 20 C. to 150 C.
8. A method of preparing a phosphate ester of the general formula in which R1 and R2 are chosen from the up consisting of alkyl and aryl hydrocarbon radicals, and X is a member of the group consisting ol' sulfur and oxygen, which includes the step oi reacting together a halogen-substituted aceto nitrile of the formula in which Z is a member of the group consisting of chlorine and bromine, an acid phosphate of the general formula in which R1 and R2 are chosen from the group consisting of alkyl and aryl hydrocarbon radicals, and X is a member of the group consisting of sulfur and'oxygen, and a basic alkali-forming metal compound having suflicient alkalinity to neutralize the acid phosphate.
9. The method of claim 8 in which the basic alkali-forming metal compound is sodium carbonate.
10. The method of claim 8 in which the reaction is carried out in the presence of a solvent.
11. A method of preparing S-cyanomethyl 0,0-diethyl -dithiophosphate which includes the step of reacting together 0,0-diethyl dithiophosphoric acid, sodium carbonate and monochloroacetonitrile in the presence of ethyl alcohol.
12. A method of preparing S-cyanomethyl 0,0-dipheny1 dithiophosphate which includes the step of reacting together potassium 0,0-diphenyl dithiophosphate and monochloroacetonitrile in the presence of acetone.
13. A method of preparing S-cyanomethyl 0,0-diethyl monothiophosphate which includes the step of reacting together potassium 0,0-dlethyl monothiophosphate and monobromoacetw nitrlle in the presence of methyl isobutyl ketone.
JACK T. CASSADAY.
ERICK I. HOEGBERG. BRUCE D. GLEISS.
No references cited.

Claims (1)

1. PHOSPHATE ESTERS OF THE GENERAL FORMULA
US70604A 1949-01-12 1949-01-12 Cyanoalkyl phosphates and method of preparation Expired - Lifetime US2494284A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US70604A US2494284A (en) 1949-01-12 1949-01-12 Cyanoalkyl phosphates and method of preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US70604A US2494284A (en) 1949-01-12 1949-01-12 Cyanoalkyl phosphates and method of preparation

Publications (1)

Publication Number Publication Date
US2494284A true US2494284A (en) 1950-01-10

Family

ID=22096318

Family Applications (1)

Application Number Title Priority Date Filing Date
US70604A Expired - Lifetime US2494284A (en) 1949-01-12 1949-01-12 Cyanoalkyl phosphates and method of preparation

Country Status (1)

Country Link
US (1) US2494284A (en)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2632020A (en) * 1951-07-07 1953-03-17 American Cyanamid Co Dithiophosphate 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
US2759010A (en) * 1952-08-01 1956-08-14 Bayer Ag Alkylmercaptoalkyl-o, o-dialkyldithiophosphate
US2766208A (en) * 1953-02-18 1956-10-09 Tidewater Oil Company Additive-containing mineral oil compositions
DE1024509B (en) * 1956-03-03 1958-02-20 Bayer Ag Process for the preparation of O, O-dialkyl-thiol-phosphoric acid and thiol-thionophosphoric acid esters
DE1047776B (en) * 1958-03-28 1958-12-31 Bayer Ag Process for the preparation of thionophosphoric acid esters
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US2947662A (en) * 1955-06-14 1960-08-02 Montedison Spa Alpha-substituted diethoxy-dithiophosphorylacetic esters
US2957019A (en) * 1958-02-14 1960-10-18 Eastman Kodak Co O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
US2965533A (en) * 1956-04-26 1960-12-20 Shell Oil Co Phosphate esters of cyanohydrins
US2994638A (en) * 1958-02-20 1961-08-01 Bayer Ag Agent for combating rodents
US3004996A (en) * 1956-04-09 1961-10-17 Lubrizol Corp Phosphorus and sulfur containing compositions and method for preparing same
US3020304A (en) * 1955-12-31 1962-02-06 Hoechst Ag Chloromethylated omicron, omicron-dialkyl-thiophosphoric acid esters
US3047459A (en) * 1954-11-09 1962-07-31 Montedison Spa New pesticidal compounds and methods of making same
US3080277A (en) * 1959-11-11 1963-03-05 Montedison Spa Alpha-dialkylthio-(dithio)-phosphoryl alpha-phenylacetic esters of cyanohydrin, and parasiticidal composition containing said esters
US3082240A (en) * 1960-04-16 1963-03-19 Bayer Ag Process for the production of phosphoric acid esters
US3092649A (en) * 1959-09-05 1963-06-04 Bayer Ag Thiophosphoric acid esters and process for their production
US3117151A (en) * 1961-10-30 1964-01-07 Dow Chemical Co Omicron-(2, 2-dichloro-1-cyanovinyl) omicron, omiron-diethyl phosphate
US3275501A (en) * 1963-06-04 1966-09-27 Bayer Ag Fungitoxic agents
US3294874A (en) * 1962-01-24 1966-12-27 Bayer Ag Omicron-alkyl-omicron-cycloalkyl-s-alkylthiolphosphoric acid esters
US3349103A (en) * 1963-12-20 1967-10-24 Universal Oil Prod Co S-(dithiophosphatyl) epoxyalkanes
US3408425A (en) * 1964-04-23 1968-10-29 Bayer Ag S-phenylmercaptocyanomethyl phosphoric-onic or-inic acid esters
US3507953A (en) * 1959-03-28 1970-04-21 Bayer Ag Pesticidal dithiophosphonic acid esters
US4252660A (en) * 1979-11-23 1981-02-24 Mobil Oil Corporation Reaction products of organophosphorus halides with inorganic thiocyanates as load-carrying additives in lubricating oil compositions
EP0044214A2 (en) * 1980-07-16 1982-01-20 Union Carbide Corporation Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same
US9437901B2 (en) 2012-11-13 2016-09-06 Samsung Sdi Co., Ltd. Additive for electrolyte and electrolyte and rechargeable lithium battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2690450A (en) * 1951-03-23 1954-09-28 Allied Chem & Dye Corp Method for preparation of sulfur-containing esters of phosphoric acid
US2632020A (en) * 1951-07-07 1953-03-17 American Cyanamid Co Dithiophosphate esters
US2759010A (en) * 1952-08-01 1956-08-14 Bayer Ag Alkylmercaptoalkyl-o, o-dialkyldithiophosphate
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
US2766208A (en) * 1953-02-18 1956-10-09 Tidewater Oil Company Additive-containing mineral oil compositions
US3047459A (en) * 1954-11-09 1962-07-31 Montedison Spa New pesticidal compounds and methods of making same
US2947662A (en) * 1955-06-14 1960-08-02 Montedison Spa Alpha-substituted diethoxy-dithiophosphorylacetic esters
US2911335A (en) * 1955-09-27 1959-11-03 Allied Chem Thiophosphate ester fungicides
US3020304A (en) * 1955-12-31 1962-02-06 Hoechst Ag Chloromethylated omicron, omicron-dialkyl-thiophosphoric acid esters
DE1024509B (en) * 1956-03-03 1958-02-20 Bayer Ag Process for the preparation of O, O-dialkyl-thiol-phosphoric acid and thiol-thionophosphoric acid esters
US3004996A (en) * 1956-04-09 1961-10-17 Lubrizol Corp Phosphorus and sulfur containing compositions and method for preparing same
US2965533A (en) * 1956-04-26 1960-12-20 Shell Oil Co Phosphate esters of cyanohydrins
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
DE1047776B (en) * 1958-03-28 1958-12-31 Bayer Ag Process for the preparation of thionophosphoric acid esters
US3507953A (en) * 1959-03-28 1970-04-21 Bayer Ag Pesticidal dithiophosphonic acid esters
US3092649A (en) * 1959-09-05 1963-06-04 Bayer Ag Thiophosphoric acid esters and process for their production
US3080277A (en) * 1959-11-11 1963-03-05 Montedison Spa Alpha-dialkylthio-(dithio)-phosphoryl alpha-phenylacetic esters of cyanohydrin, and parasiticidal composition containing said esters
US3082240A (en) * 1960-04-16 1963-03-19 Bayer Ag Process for the production of phosphoric acid esters
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
US3275501A (en) * 1963-06-04 1966-09-27 Bayer Ag Fungitoxic agents
US3349103A (en) * 1963-12-20 1967-10-24 Universal Oil Prod Co S-(dithiophosphatyl) epoxyalkanes
US3408425A (en) * 1964-04-23 1968-10-29 Bayer Ag S-phenylmercaptocyanomethyl phosphoric-onic or-inic acid esters
US4252660A (en) * 1979-11-23 1981-02-24 Mobil Oil Corporation Reaction products of organophosphorus halides with inorganic thiocyanates as load-carrying additives in lubricating oil compositions
EP0044214A2 (en) * 1980-07-16 1982-01-20 Union Carbide Corporation Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same
EP0044214A3 (en) * 1980-07-16 1982-04-28 Union Carbide Corporation Novel phosphorous esters of cyanohydrins, pesticidal compositions including same, and methods of controlling pests using same
US9437901B2 (en) 2012-11-13 2016-09-06 Samsung Sdi Co., Ltd. Additive for electrolyte and electrolyte and rechargeable lithium battery

Similar Documents

Publication Publication Date Title
US2494284A (en) Cyanoalkyl phosphates and method of preparation
US2520393A (en) 2-nitrophenyl dialkyl phosphates and thiophosphates
US2494126A (en) Organic phosphate esters and methods of preparation
US2494283A (en) Carbamylalkyl phosphates and method of preparation
US2759010A (en) Alkylmercaptoalkyl-o, o-dialkyldithiophosphate
US2731487A (en) Asymmetric tertiary alkyl trithiocarbonates
US3728381A (en) Production of 2-haloethylphosphonic acid
US2552541A (en) O-(halophenyl) o-alkyl amidothiophosphates
US2938831A (en) Control of nematodes using dialkyl pyrazinyl phosphorothioates
US2965533A (en) Phosphate esters of cyanohydrins
US2725328A (en) 2, 3-p-dioxanedithiol-s, s-bis (o, o-dialkylphosphorodithioate)
US2910501A (en) Thiophosphoric acid esters and process for their manufacture
US3371132A (en) O-alkyl o(s)-(n-alkoxy-n-alkyl-carbamyl methyl) phenyl (thiolo) (thiono)phosphonates
US2829111A (en) Azidoethyl-thiophosphoric acid esters
US3166581A (en) S-acyloxyalkyl and s-acyloxyalkenyl esters of o, o-diorgano-phosphorothiolic acids
US2729668A (en) Process for making diethoxyphosphoryl tetramethyldiamidothiophosphate
US2722479A (en) Triisooctyl phosphite and herbicides containing same
US2867646A (en) Complex arylphosphonates
US2865943A (en) Process of making o, o-dimethyl-o-(beta, beta-dichlorovinyl)-phosphate
US3321361A (en) Acaricidal method
US3553323A (en) Method of controlling rice blast with thiolphosphates
US3892694A (en) Substituted phosphorous containing alkyl thio methyl carboxylates
US3420919A (en) Nitrile amide phosphates and phosphonates
US3220922A (en) Amino-triazol derivatives
US3636206A (en) Certain thiolophosphonamides as insecticides and acaricides