US3035079A - New organic phosphorus compounds and their manufacture and use - Google Patents

New organic phosphorus compounds and their manufacture and use Download PDF

Info

Publication number
US3035079A
US3035079A US691163A US69116357A US3035079A US 3035079 A US3035079 A US 3035079A US 691163 A US691163 A US 691163A US 69116357 A US69116357 A US 69116357A US 3035079 A US3035079 A US 3035079A
Authority
US
United States
Prior art keywords
parts
radical
compounds
acetone
residue
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
US691163A
Inventor
Beriger Ernst
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.)
BASF Schweiz AG
Original Assignee
Ciba AG
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 Ciba AG filed Critical Ciba AG
Application granted granted Critical
Publication of US3035079A publication Critical patent/US3035079A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/28—Titanium compounds
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • 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 System
    • 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
    • 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 System
    • 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
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
    • 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 System
    • 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
    • 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 System
    • 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
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2412—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic alcohols
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3264—Esters with hydroxyalkyl compounds
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems

Definitions

  • This invention provides new organic phosphorus compounds of the general formula in which R, R and R represent alkyl, cycloalkyl, aralkyl, aryl or heterocyclic residues which may contain substituents, and of which R and R may together form part of a ring system, R represents hydrogen or an alkyl residue or a halogen atom, R represents an alicyclic, aromatic or heterocyclic residue, X and Y represent -O, S, NH- or ITT R and Z represents oxygen or sulfur, and n and m each represent the whole number 1 or 2 or compounds of the general formula in which R, R R R R X, Y, Z and n and m have the meanings given above.
  • the condensation product of a:a-dichlorobenzoylacetic acid ethyl ester with trimethyl phosphite can be given the following formulae CH3-O
  • the invention therefore includes compounds of the above Formulae I and II and also any mixtures of these compounds, since the isomerism of the compounds can be considered as keto-enol tautomerisms. Accordingly, when one form is given in this specification it is to be understood that the other form is included, provided that that form is capable of existing.
  • the new compounds are valuable agents for combating pests, especially animal pests. They are active against the various stages of development, such as eggs, larvae and imagines, so that they are both contact and stomach poisons. Suitably substituted compounds of this invention exhibit an inner-therapeutic, so-called systemic, action when applied to plants. Especially valuable are compounds of the general formulae in which R, R and R represent lower alkyl residues containing l-4 carbon atoms, R represents a hydrogen atom or a chlorine atom, and R represents a cyclohexyl, phenyl, furyl or tetrahydrofuryl residue which may contain substituents.
  • the compounds of the general formula P-ZR Ri-(Y)m-i which may be used as starting materials are derivatives of trivalent phosphorus, whereas the products of the invention are derivatives of pentavalent phosphorus.
  • the aliphatic residues which the symbols R and R may represent, may have straight or branched chains and may be saturated or unsaturated. They may be substituted or unsubstituted. There may be mentioned, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2- ethylbutyl, octyl, 2-butyloctyl, dodecyl, octadecyl, allyl and 2-chloroethyl groups, and also radicals containing thiocyano, cyano or ester groups.
  • the residues R and R may be identical or different from one another.
  • R is advantageously a lower alkyl residue containing 1-4 carbon atoms.
  • Trimethylphosphite triethylphosphite, tripropylphosphite, diethyl-dodecylphosphite, tri-(2-chlorethyl)-phosphite and the ester of the formula CHr-O P-O C2115 GHQ-O
  • the aromatic radicals, which R and R may represent may be mononuclear or polynuclear, and may contain nuclear substituents. There may 'be mentioned, for example, phenyl, 2- or 4-chlorophenyl, 2:4-dich1orophenyl, 4-methoxyphenyl, 4-nitrophenyl, naphthyl and 4-diphenyl groups.
  • compounds such as 2:4-dichlorophenyl .diethylphosphite and 4-ch1orophenyl dimethyl phosphite may be mentioned.
  • compounds in which one or two residues are bound directly by a carbon atom to the phosphorus atom for example, phenyl-phosphorous acid diethyl ester of the formula 021150
  • araliphatic radicals which R and R may represent, there may be mentioned the benzyl radical, among the cycloaliphatic radicals the cyclohexyl radical, and among the heterocyclic radicals the tetrahydrofurfuryl radical.
  • Starting materials containing such radicals are, for example, cyclohexyl diethylphosphite, tetrahydrofurfuryl dimethylphosphite and dibenzylpropylphosphite.
  • triethylthiophosphite of the formula CaHsS cz as and among those in which X and Y represent nitrogen, the compound of the formula 4
  • the compounds of the general formula PMe 1( )m-1 Z are salts of disubstituted phosphites or phosphinic acids for example, sodium salts of dimethylphosphite, diethylphosphite, dodecylethylphosphite, cyclohexylrnethylphoe phite, tetrahydrofurfurylethylphosphite or benzyl ethyl phosphite.
  • the compounds of the general formula P-Hal R1( m-l Z are phosphoric acid monohalides, for example, phosphoric acid diethylester monochloride, thiophosphoric acid diethylester monochloride or bis-(dimethylamido)-phosphoric acid monochloride.
  • the compounds of the general formula are esters of halogenated acylacetic acids derived from alicyclic aromatic or heterocyclic carboxylic acids advantageously benzoyl-, hexahydrobenzoyl-, furoylor tetrahydrofuroylacetic acid.
  • the residue R may have the meanings given above for the residues R and R Advantageously it consists of a lower alkyl group containing 1-4 carbon atoms.
  • the residue R may be a halogen atom, advantageously a chlorine atom, or a hydrogen atom or an alkyl residue advantageously containing l-4 carbon atoms, such as the methyl group.
  • R may be a heterocyclic residue, such as the furyl residue or tetrahydrofuryl residue, an aryl residue, for example, the phenyl, chlorophenyl, nitrophenyl group, or a cycloalkyl residue, such as the cyclohexyl group.
  • reaction components are heated together at a raised temperature, for example, within the range of 50-200 C., and advantageously about 150 C. It may be of advantage or convenient to work in an inert solvent, such as benzene, toluene, xylene, chlorobenzene or benzine and, if desired in an atmosphere of an inert gas, for example, under nitrogen, and/ or under reduced pressure.
  • an inert solvent such as benzene, toluene, xylene, chlorobenzene or benzine and, if desired in an atmosphere of an inert gas, for example, under nitrogen, and/ or under reduced pressure.
  • the products of this invention are valuable agents for combating pests
  • the invention also provides preparations for combating pests, which contain a product of the invention as active substance, and a process for combating pests With such preparations.
  • R, R and R represent alkyl residues containing l-4 carbon atoms
  • R represents a hydrogen atom or a chlorine atom
  • R represents a cyclohexyl, phenyl, furyl or tetrahydrofuryl group which may contain substituents.
  • a very Wide variety of materials can be protected against pests, and gaseous, liquids or solid materials may be used as carriers for the active substances.
  • materials to be protected or to be used as carriers there may be mentioned, for example, air, especially in rooms, and liquids, for example, water in ponds, and any non-living or living solid substratum, for example, any objects in living rooms, in cellars, in plaster, floors, stables, and also pelts, feathers, wool or the like, and living organisms of the vegetable and animal kingdom at all stages of development, so far as they are not sensitive to the pest combating agent.
  • the compounds are used for combating pests by the usual methods, for example, by treating the material to be protected with the compound in the formula of vapour, for example, in the form of a fumigating preparation or in the form of a dusting powder or spraying liquor, for example, in the form of a solution or suspension, which may be prepared with water or a suitable organic solvent, for example, alcohol, petroleum, tar distillates or the like.
  • Aqueous solutions of the active substances or aqueous emulsions of organic solvents containing the active substances may be used or coating, spraying or immersing the objects to be protected.
  • the spraying preparations or dusting powders may contain the usual inert fillers or identifying agents, for example, kaolin, gypsum or bentonite or other additions, such as sulfite cellulose waste liquor, cellulose derivatives or the like, and also the usual wetting agents or adherent agents for improving the wetting capacity and adherence of the preparations.
  • the pest combating preparations may be made up in powdered form or in the form of aqueous dispersions or pastes or as self-dispersing oils.
  • the preparations may contain compounds of the invention as the sole active substances or in admixture with other insecticides and/or fungicides. Such preparations may he used for the protection of plants by the usual spraying, pouring, dusting or fumigating methods.
  • Example 1 A solution of 13.05 parts of uza-dichlorobenzoyl-acetic acid ethyl ester (boiling at 110 C. under 0.008 mm. pressure) in 15 parts by volume of chlorobenzene is heated to the boil. 6.8 parts of trimethyl phosphite are added dropwise in the course of 5 minutes, and the reaction is completed by boiling the mixture for one hour under reflux. 2.1 parts of methyl chloride are collected. By evaporating the volatile constituents at 95 C. under reduced pressure produced by a water jet pump there is obtained as residue 15.9 parts of a bright yellow oil, which dissolves well in acetone and alcohol and scarcely dissolves at all in water.
  • Example 2 A solution of 13.05 parts of am-dichlorobenzoyl-acetic acid ethyl ester in 15 parts by volume of chlorobenzene is heated to the boil and 9.1 parts of triethylphosphite are added dropwise in the course of 5 minutes. The initially vigorous evolution of ethyl chloride is completed by boiling for one hour under reflux. The solvent and the excess of triethyl phosphite are removed in vacuo at 95 C. The residue (18.8 parts) is an oily liquid which boils at 168 C. under 0.3 mm. of mercury.
  • Example 3 A solution of 12.35 parts of azu-dichlorobenzoyl-acetic acid methyl ester (boiling at IOU-102 C. under 0.2 mm. pressure) in 13 parts by volume of chlorobenzene is heated to the boil and 6.8 parts of trimethyl phosphite are added dropwise in the course of 5 minutes. In order to complete the reaction the mixture is maintained at the boil for a further hour. The volatile constituents are then removed in vacuo at 95 C., and there is obtained a residue consisting of 16.7 parts of a very mobile oil, which dissolves in acetone and isopropyl alcohol, and which boils at 154-158 C. under 0.04 mm. pressure.
  • Example 4 To a mixture of 12.35 parts of aza-dichlorobenzoylacetic acid methyl ester and 13 parts by volume of chlorobenzene at the boiling temperature there are added dropwise 9.1 parts of triethyl phosphite. When the addition is complete, the solution is maintained at the boil for a further hour. The solvent and volatile constituents are then removed in vacuo at a bath temperature of C. There is obtained as residue a bright yellow oil, which is soluble in acetone and isopropyl alcohol.
  • Example 5 A mixture of 14.07 parts of am-dichloro-para-chlorobenzoyl-acetic acid methyl ester (boiling at 121129 C. under 0.2 mm. pressure) and 15 parts by volume of chlorobenzene is mixed dropwise at the boil with 6.82 parts of trimethyl phosphite. When the dropwise addition of the trimethyl phosphite is complete, the solution is maintained at the boil for a further hour. At the end of this period 2.4 parts of methyl chloride will have been collected in the receiver cooled with Dry Ice and acetone. The volatile constituents are removed in vacuo, and there are obtained as residue 18.4 parts of a thickly liquid oil, which is easily soluble in acetone and isopropyl alcohol.
  • Example 6 14.07 parts of a-monochloro-ortho-chlorobenZoyl-acetic acid methyl ester in 16 parts by volume of chlorobenzene are heated to the boil. 6.8 parts of trimethyl phosphite are added dropwise, and the reaction is completed by boiling the mixture for a further /2 hour. After distilling oil the volatile constituents in vacuo, there are obtained 16.9 parts of a poorly mobile oil, which is soluble in acetone and isopropyl alcohol.
  • Example 7 12.87 parts of a-chloro-para-nitrobenzoyl-acetic acid methyl ester (melting at 106107 C.) and 13 parts by volume of chlorobenzene are heated to the boil, and 6.8 parts of trimethyl phosphite are added dropwise. The mixture is boiled under reflux for a further hour to complete the reaction. The volatile constituents are then removed in vacuo at a bath temperature of 95 C. 'The residue is a yellow oil (16.85 parts) which is easily soluble in isopropyl alcohol and acetone.
  • Example 8 7.45 parts of triethyl phosphite are added in the course of 5 minutes to a mixture of 10.5 parts of a-chloro-paranitrobenzoyl-acetic acid methyl ester and 12 parts by volume of chlorobenzene maintained at the boil. When the addition is complete, the reaction mixture is boiled under reflux for a further hour, and then the solvent and excess of phosphite are removed in vacuo at a bath temperature of 95 C. The residue is a yellow oil (14.8 parts), which dissolves well in alcohol and acetone.
  • Example 9 12.55 parts of aza-dichlorofuroyl-acetic acid ethyl ester are diluted with 15 parts by volume of chlorobenzene. The mixture is brought to the boil, and 6.8 parts of trimethylphosphite are added. After boiling the mixture under reflux for /2 hour 2.2 parts of methyl chloride are collected. The volatile constituents are removed at 95% C. under the reduced pressure of a water jet pump, and the residue consists of 14.1 parts of a very mobile oil, which dissolves in acetone and isopropyl alcohol.
  • Example 10 A solution of 12.6 parts of aza-dichloro-hexahydrobenzoyl-acetic acid methyl ester (boiling at 102-103 C.
  • Example 11 7 dropWise in the course of 5 minutes.
  • the mixture is mainl3.05 parts of dichlorobenzoyl-acetic acid ethyl ester in 15 parts by volume of xylene are heated to the boil, and 12.2 parts of diethyl allyl phosphite tained fora further hour at 180 C. 2 parts of ethyl chloride are collected.
  • the volatile constituents are removed in vacuo at C., and the residue consists of 20.8 parts of an easily mobile oil, which dissolves well in (boiling at 6466 C. under 12 mm. pressure) are added 75 alcohol and acetone.
  • ozn or oorn (boiling at 49 C. under mm. pressure) are added dropwise.
  • the mixture is slowly heated to 215 C. and maintained at that temperature for a further hour.
  • 0.9 part of ethyl chloride is collected.
  • the reaction does not take place solely with the splitting off of ethyl chloride, but partially involves splitting up of the ethylene phosphite ring.
  • the easily volatile constituents are removed in vacuo at 180 C., and the residue is an easily mobile oil (17.8 parts), which dissolves well in alcohol and acetone and hardly at all in water.
  • Example 14 9.9 parts of phenyl-phosphonous acid diethyl ester (boiling at 108114 C. under 10 mm. pressure) are added dropwise to a mixture of 13.05 parts of dichlorobenzoyl-acetic acid ethyl ester with 15 parts by volume of chlorobenzene, the mixture being heated to the boil. The reaction is finished in the course of hour, and 2.0 parts of ethyl chloride are collected. After removing the xylene in vacuo there are obtained 19.3 parts of a thinly liquid oil which dissolves well in alcohol and acetone.
  • Example 16 21.4 parts of the sodium salt of benzoyl-acetic acid ethyl ester are stirred well in 50 parts by volume of chlorobenzene. Beginning at 20 C. 189 parts of diethyl thiophosphoric acid ester chloride are added dropwise in the course of 20 minutes while stirring, the temperature being raised to 30 C. The mixture is allowed to react completely overnight at 50-60 C. After being cooled, the solution is washed three times with a small amount of water, dried over sodium sulfate, and then the solvent it is removed in vacuo. The residue consists of 25.8 parts of a mobile oil, which dissolves well in alcohol and acetone.
  • Example 17 2 parts of the condensation product obtained as described in Example 1 or 2 are mixed with 1 part of the condensation product of 1 mol of tertiary octyl phenol and 8 mols of ethylene oxide, and 7 parts of isopropanol.
  • Example 1 Example 2 For each plant a mark is used. means that no living aphids are present, means a good action, only a few aphids alive, and means an insufficient or no action.
  • Example 1 Spray liquor Action of concentration, aphids percent Example 1 (C)
  • leaves were immersed in spray liquors containing 0.04% of the active substance. When dry the leaves were fed to locusts.
  • the compounds of Examples 1 and 2 also exhibit a good action against the eggs of Ephestia kiihniella. They may be used in dormant spray preparations as active substances against the wintering stages of pests.
  • wetting and emulsifying agents there may be used wetting and emulsifying agents other than those mentioned above.
  • non-ionic products for example, condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon radical of about l030 carbon atoms with ethylene oxide, such as the condensation product of octadecyl alcohol with 25-30 mols of ethylene oxide, or the condensation products of soya bean fatty acid with 30 mols of ethylene oxide, or that of commercial oleylamine with 15 mols of ethylene oxide, or that of dodecyl mercaptan with 12 mols of ethylene oxide.
  • condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon radical of about l030 carbon atoms with ethylene oxide such as the condensation product of octadecyl alcohol with 25-30 mols of ethylene oxide, or the condensation products of soya bean fatty
  • anion-active emulsifying agents which may be used, there may be mentioned the sodium salt of dodecyl alcohol sulfonic acid ester, the sodium salt of dodecylbenzene sulfonic acid, the potassium or triethanolarnine salt of oleic acid or abietic acid, or a mixture of these acids, or the sodium salt of a petroleum sulfonic acid.
  • isopropanol there may be used other solvents for making up the spray concentrates, for example, ethyl alcohol, methanol, butanol, acetone, methyl ethyl ketone, methyl-cyclohexanol, benzene, toluene, xylene, kerosene or petroleum fractions. There may, of course, be used mixtures of these solvents.
  • Example 18 2 parts of the product of Example 2 are mixed with 9 parts of chalk and 1 part of a wetting agent. There is obtained a spray powder, which can be used for making spray liquors by suspending it in water. By treating the walls of stables with such a spray liquor containing 0.4% of active substance, good results are obtained against flies and gnats.
  • Example 19 1 part of the product of Example 2. is mixed with 99 parts of tale.
  • the resulting mixture is an insecticidal dusting powder, which is suitable for dusting vines to combat Pyralis caterpillars and Conchylis caterpillars.
  • the talcum may be replaced wholly or in part by sulfur, in which case the preparation is also active against Oidium.
  • other pulverulent carriers may be used, such as chalk, bentonite, kaolin or mixtures thereof.
  • R and R is each selected from the group consisting of an alkyl radical containing at most 18 carbon atoms, an allyl radical, a tetrahydrofurfuryl radical, a benzyl radical, a phenyl radical and a chlorophenyl radical;
  • R represents an alkyl radical containing at most 18 carbon atoms;
  • R represents a member selected from the group consisting of a chlorine atom and a bromine atom;
  • R represents a member selected from the group consisting of a phenyl radical, a chlorophenyl radical, a cyclohexyl radical, a furyl radical, a benzene radical which is substituted by a lower alkyl radical, a benzene radical which is substituted by a lower alkoxy radical, a benzene radical which is substituted by a nitro group and a benzene radical which is substituted by a nitro group and
  • R and R is each selected from the group consisting of an alkyl radical containing at most 18 carbon atoms, an allyl radical, a tetrahydrofurfuryl radical, a benzyl radical, a phenyl radical and a chlorophenyl radical;
  • R represents an alkyl radical containing at most 18 carbon atoms;
  • R represents a member selected from the group consisting of a chlorine atom and a bromine atom;
  • R represents a member selected from the group consisting of a phenyl radical, a chlorophenyl radical, a cyclohexyl radical, a furyl radical, a benzene radical which is substituted by a lower alkyl radical, a benzene radical which is substituted by a lower alkoxy radical, a benzene radical which is substituted by
  • R represents a lower alkyl radical
  • Y represents an oxygen atom
  • m and 12 each represents an integer of at most 2
  • Z represents a member selected from the group consisting of an oxygen atom and a sulfur atom; in admixture with an insecticidally inactive carrier.

Description

United States Patent 3,035,079 7 NEW ORGANIC PHOSPHORUS COMPOUNDS AND THEIR MANUFACTURE AND USE Ernst Beriger, Allschwil, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Filed Oct. 21, 1957, Ser. No. 691,163 Claims priority, application Switzerland Oct. 25, 1956 Claims. (Cl. 260461) This invention provides new organic phosphorus compounds of the general formula in which R, R and R represent alkyl, cycloalkyl, aralkyl, aryl or heterocyclic residues which may contain substituents, and of which R and R may together form part of a ring system, R represents hydrogen or an alkyl residue or a halogen atom, R represents an alicyclic, aromatic or heterocyclic residue, X and Y represent -O, S, NH- or ITT R and Z represents oxygen or sulfur, and n and m each represent the whole number 1 or 2 or compounds of the general formula in which R, R R R X, Y, Z and n and m have the meanings given above.
It has not yet been ascertained with certainty which of the above Formula I and II should be accorded to the compounds of this invention. It is probable that, depending on the method of preparation, the compounds have only one or other of these formulae or compounds of one of the formulae are preferentially formed. It is known that in the reaction of trialkyl phosphites with certain halogen-compounds in accordance with the Michaelis-Arbuzow reactions rearrangements occur so that instead of the expected phosphonic acid derivatives the isomeric phosphoric acid esters are formed. In the present invention, for example, the condensation product of a:a-dichlorobenzoylacetic acid ethyl ester with trimethyl phosphite can be given the following formulae CH3-O The invention therefore includes compounds of the above Formulae I and II and also any mixtures of these compounds, since the isomerism of the compounds can be considered as keto-enol tautomerisms. Accordingly, when one form is given in this specification it is to be understood that the other form is included, provided that that form is capable of existing.
The new compounds are valuable agents for combating pests, especially animal pests. They are active against the various stages of development, such as eggs, larvae and imagines, so that they are both contact and stomach poisons. Suitably substituted compounds of this invention exhibit an inner-therapeutic, so-called systemic, action when applied to plants. Especially valuable are compounds of the general formulae in which R, R and R represent lower alkyl residues containing l-4 carbon atoms, R represents a hydrogen atom or a chlorine atom, and R represents a cyclohexyl, phenyl, furyl or tetrahydrofuryl residue which may contain substituents.
The compounds of this invention can be obtained by condensing a compound of the formula in which R, R n, m, X, Y and Z have the meanings given above, and R represents a lower alkyl residue containing 1-4 carbon atoms, with a compound of the formula O=CR4 Ha1-URa 0-3, in which R R and R have the meanings given above, and Hal represents a halogen atom, such as bromine or preferably chlorine, the condensation taking place with the splitting olf of a compound of the formula R -Hal. The new compounds can also be obtained by reacting a compound of the formula /1[.[ Me 1 )m1 Z in which R, R n, m, X, Y and Z have the meanings given above, and Me represents an alkali metal, advantageously sodium, with a compound of the formula O=C-Rg Hal-O-Ra \OR: in which R R R and Hal have the meanings given above. For preparing those compounds in which R represents a hydrogen atom or an alkyl residue, the following condensation may be carried out:
The choice of one or other of the reactions mentioned above, depends on the accessibility of the starting materials.
The compounds of the general formula P-ZR Ri-(Y)m-i which may be used as starting materials are derivatives of trivalent phosphorus, whereas the products of the invention are derivatives of pentavalent phosphorus.
Among the compounds of the formula last given above the most easily accessible are those in which the symbols X, Y and Z represent oxygen. They correspond to the formula P-o-n.
and can be obtained by methods in themselves known.
The aliphatic residues, which the symbols R and R may represent, may have straight or branched chains and may be saturated or unsaturated. They may be substituted or unsubstituted. There may be mentioned, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2- ethylbutyl, octyl, 2-butyloctyl, dodecyl, octadecyl, allyl and 2-chloroethyl groups, and also radicals containing thiocyano, cyano or ester groups. The residues R and R may be identical or different from one another. R is advantageously a lower alkyl residue containing 1-4 carbon atoms.
There may be mentioned, for example, the following compounds:
Trimethylphosphite, triethylphosphite, tripropylphosphite, diethyl-dodecylphosphite, tri-(2-chlorethyl)-phosphite and the ester of the formula CHr-O P-O C2115 GHQ-O The aromatic radicals, which R and R may represent, may be mononuclear or polynuclear, and may contain nuclear substituents. There may 'be mentioned, for example, phenyl, 2- or 4-chlorophenyl, 2:4-dich1orophenyl, 4-methoxyphenyl, 4-nitrophenyl, naphthyl and 4-diphenyl groups. Thus, compounds such as 2:4-dichlorophenyl .diethylphosphite and 4-ch1orophenyl dimethyl phosphite may be mentioned. There may also be mentioned compounds in which one or two residues are bound directly by a carbon atom to the phosphorus atom, for example, phenyl-phosphorous acid diethyl ester of the formula 021150 Among araliphatic radicals, which R and R may represent, there may be mentioned the benzyl radical, among the cycloaliphatic radicals the cyclohexyl radical, and among the heterocyclic radicals the tetrahydrofurfuryl radical. Starting materials containing such radicals are, for example, cyclohexyl diethylphosphite, tetrahydrofurfuryl dimethylphosphite and dibenzylpropylphosphite. Among compounds in which X and Y represent sulfur there may be mentioned triethylthiophosphite of the formula CaHsS cz as and among those in which X and Y represent nitrogen, the compound of the formula 4 The compounds of the general formula PMe 1( )m-1 Z are salts of disubstituted phosphites or phosphinic acids for example, sodium salts of dimethylphosphite, diethylphosphite, dodecylethylphosphite, cyclohexylrnethylphoe phite, tetrahydrofurfurylethylphosphite or benzyl ethyl phosphite.
The compounds of the general formula P-Hal R1( m-l Z are phosphoric acid monohalides, for example, phosphoric acid diethylester monochloride, thiophosphoric acid diethylester monochloride or bis-(dimethylamido)-phosphoric acid monochloride.
The compounds of the general formula are esters of halogenated acylacetic acids derived from alicyclic aromatic or heterocyclic carboxylic acids advantageously benzoyl-, hexahydrobenzoyl-, furoylor tetrahydrofuroylacetic acid. The residue R may have the meanings given above for the residues R and R Advantageously it consists of a lower alkyl group containing 1-4 carbon atoms. The residue R may be a halogen atom, advantageously a chlorine atom, or a hydrogen atom or an alkyl residue advantageously containing l-4 carbon atoms, such as the methyl group. R may be a heterocyclic residue, such as the furyl residue or tetrahydrofuryl residue, an aryl residue, for example, the phenyl, chlorophenyl, nitrophenyl group, or a cycloalkyl residue, such as the cyclohexyl group. Among the reaction components of the formula last mentioned above there may be mentioned, azwdichlorobenzoyl-acetic acid ethyl ester, a:a-dichlorobenzoyl-acetic acid methyl ester, a:a-dichloro-4-chlorobenzoyl-acetic acid methyl ester,.achloro-4-nitro-benzoyl-acetic acid methyl ester, aim-dichlorofuroyl-acetic acid ethyl ester and aioc-dichlOrOheXflhydrobenzoyl-acetic acid methyl ester.
In order to prepare the products of this invention the reaction components are heated together at a raised temperature, for example, within the range of 50-200 C., and advantageously about 150 C. It may be of advantage or convenient to work in an inert solvent, such as benzene, toluene, xylene, chlorobenzene or benzine and, if desired in an atmosphere of an inert gas, for example, under nitrogen, and/ or under reduced pressure.
As stated above, the products of this invention are valuable agents for combating pests, Accordingly, the invention also provides preparations for combating pests, which contain a product of the invention as active substance, and a process for combating pests With such preparations.
Especially advantageous are compounds of the general formula in which R, R and R represent alkyl residues containing l-4 carbon atoms, R represents a hydrogen atom or a chlorine atom, and R represents a cyclohexyl, phenyl, furyl or tetrahydrofuryl group which may contain substituents.
A very Wide variety of materials can be protected against pests, and gaseous, liquids or solid materials may be used as carriers for the active substances. As materials to be protected or to be used as carriers there may be mentioned, for example, air, especially in rooms, and liquids, for example, water in ponds, and any non-living or living solid substratum, for example, any objects in living rooms, in cellars, in plaster, floors, stables, and also pelts, feathers, wool or the like, and living organisms of the vegetable and animal kingdom at all stages of development, so far as they are not sensitive to the pest combating agent.
The compounds are used for combating pests by the usual methods, for example, by treating the material to be protected with the compound in the formula of vapour, for example, in the form of a fumigating preparation or in the form of a dusting powder or spraying liquor, for example, in the form of a solution or suspension, which may be prepared with water or a suitable organic solvent, for example, alcohol, petroleum, tar distillates or the like. Aqueous solutions of the active substances or aqueous emulsions of organic solvents containing the active substances, may be used or coating, spraying or immersing the objects to be protected.
The spraying preparations or dusting powders may contain the usual inert fillers or identifying agents, for example, kaolin, gypsum or bentonite or other additions, such as sulfite cellulose waste liquor, cellulose derivatives or the like, and also the usual wetting agents or adherent agents for improving the wetting capacity and adherence of the preparations. The pest combating preparations may be made up in powdered form or in the form of aqueous dispersions or pastes or as self-dispersing oils.
The preparations may contain compounds of the invention as the sole active substances or in admixture with other insecticides and/or fungicides. Such preparations may he used for the protection of plants by the usual spraying, pouring, dusting or fumigating methods.
The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:
Example 1 A solution of 13.05 parts of uza-dichlorobenzoyl-acetic acid ethyl ester (boiling at 110 C. under 0.008 mm. pressure) in 15 parts by volume of chlorobenzene is heated to the boil. 6.8 parts of trimethyl phosphite are added dropwise in the course of 5 minutes, and the reaction is completed by boiling the mixture for one hour under reflux. 2.1 parts of methyl chloride are collected. By evaporating the volatile constituents at 95 C. under reduced pressure produced by a water jet pump there is obtained as residue 15.9 parts of a bright yellow oil, which dissolves well in acetone and alcohol and scarcely dissolves at all in water.
Example 2 A solution of 13.05 parts of am-dichlorobenzoyl-acetic acid ethyl ester in 15 parts by volume of chlorobenzene is heated to the boil and 9.1 parts of triethylphosphite are added dropwise in the course of 5 minutes. The initially vigorous evolution of ethyl chloride is completed by boiling for one hour under reflux. The solvent and the excess of triethyl phosphite are removed in vacuo at 95 C. The residue (18.8 parts) is an oily liquid which boils at 168 C. under 0.3 mm. of mercury.
Example 3 A solution of 12.35 parts of azu-dichlorobenzoyl-acetic acid methyl ester (boiling at IOU-102 C. under 0.2 mm. pressure) in 13 parts by volume of chlorobenzene is heated to the boil and 6.8 parts of trimethyl phosphite are added dropwise in the course of 5 minutes. In order to complete the reaction the mixture is maintained at the boil for a further hour. The volatile constituents are then removed in vacuo at 95 C., and there is obtained a residue consisting of 16.7 parts of a very mobile oil, which dissolves in acetone and isopropyl alcohol, and which boils at 154-158 C. under 0.04 mm. pressure.
Example 4 To a mixture of 12.35 parts of aza-dichlorobenzoylacetic acid methyl ester and 13 parts by volume of chlorobenzene at the boiling temperature there are added dropwise 9.1 parts of triethyl phosphite. When the addition is complete, the solution is maintained at the boil for a further hour. The solvent and volatile constituents are then removed in vacuo at a bath temperature of C. There is obtained as residue a bright yellow oil, which is soluble in acetone and isopropyl alcohol.
Example 5 A mixture of 14.07 parts of am-dichloro-para-chlorobenzoyl-acetic acid methyl ester (boiling at 121129 C. under 0.2 mm. pressure) and 15 parts by volume of chlorobenzene is mixed dropwise at the boil with 6.82 parts of trimethyl phosphite. When the dropwise addition of the trimethyl phosphite is complete, the solution is maintained at the boil for a further hour. At the end of this period 2.4 parts of methyl chloride will have been collected in the receiver cooled with Dry Ice and acetone. The volatile constituents are removed in vacuo, and there are obtained as residue 18.4 parts of a thickly liquid oil, which is easily soluble in acetone and isopropyl alcohol.
Example 6 14.07 parts of a-monochloro-ortho-chlorobenZoyl-acetic acid methyl ester in 16 parts by volume of chlorobenzene are heated to the boil. 6.8 parts of trimethyl phosphite are added dropwise, and the reaction is completed by boiling the mixture for a further /2 hour. After distilling oil the volatile constituents in vacuo, there are obtained 16.9 parts of a poorly mobile oil, Which is soluble in acetone and isopropyl alcohol.
Example 7 12.87 parts of a-chloro-para-nitrobenzoyl-acetic acid methyl ester (melting at 106107 C.) and 13 parts by volume of chlorobenzene are heated to the boil, and 6.8 parts of trimethyl phosphite are added dropwise. The mixture is boiled under reflux for a further hour to complete the reaction. The volatile constituents are then removed in vacuo at a bath temperature of 95 C. 'The residue is a yellow oil (16.85 parts) which is easily soluble in isopropyl alcohol and acetone.
Example 8 7.45 parts of triethyl phosphite are added in the course of 5 minutes to a mixture of 10.5 parts of a-chloro-paranitrobenzoyl-acetic acid methyl ester and 12 parts by volume of chlorobenzene maintained at the boil. When the addition is complete, the reaction mixture is boiled under reflux for a further hour, and then the solvent and excess of phosphite are removed in vacuo at a bath temperature of 95 C. The residue is a yellow oil (14.8 parts), which dissolves well in alcohol and acetone.
Example 9 12.55 parts of aza-dichlorofuroyl-acetic acid ethyl ester are diluted with 15 parts by volume of chlorobenzene. The mixture is brought to the boil, and 6.8 parts of trimethylphosphite are added. After boiling the mixture under reflux for /2 hour 2.2 parts of methyl chloride are collected. The volatile constituents are removed at 95% C. under the reduced pressure of a water jet pump, and the residue consists of 14.1 parts of a very mobile oil, which dissolves in acetone and isopropyl alcohol.
Example 10 A solution of 12.6 parts of aza-dichloro-hexahydrobenzoyl-acetic acid methyl ester (boiling at 102-103 C.
under 0.12 mm. pressure) in 15 parts by volume of chlorobenzene is heated to the boil and 6.8 parts of trimethyl phosphite are added dropvvise in the course of minutes. In order to complete the reaction the mixture is heated under reflux for a further hour. The volatile constituents are then removed in vacuo at a bath temperature of 95 C., and the residue consists of an almost colorless thinly liquid oil (15.5 parts), which is soluble in acetone and isopropyl alcohol.
In an analogous manner the halogenated ,B-keto-acid esters set out in the following table can be reacted with tertiary phosphite. Only some of the resulting esters, of which the properties are also given in the table, can be distilled in a high vacuum without decomposition. However, for making pest combating preparations it is unnecessary to purify the compounds by distillation Example 12 13.05 parts of dichloroberlZoyl-acetic acid ethyl ester are heated to l-160 C. and 11.1 parts of diethyl tetrahydrofurfuryl phosphite,
(boiling at 59 C. under 0.4 mm. pressure) are added No. fi-Keto-ester Halogenated B-keto-ester Phosphite components and properties of their esters l-2.-- Q-o 0 01120 0 0 04m 0 o 0 0120 o o 0.11. (01 3013? easily mowgsog sr easily m0- 0 o e o B.P. 167.5l69 C. (0.07 B.P. 159-165 C. (0.04 BI. 108 C. (0.08 mm). mm). mm.).
3 1... 01@0 0 011200 0 cine--- 01-00 0 01,0 0 0 0,11 01130? easily mocinema easily mobile 0' bile oil soluble in a1- B.P. 164-170 O. (0.03 cohol, acetone. B.P. 118-422 C. (0.2 mm.). mm.).
01 Cl 5--. Q-COCHzCOOCHa COCHC1COOOH3 Do.
B.P. 113-118 C. (0.4mn1.). B.P. 130-134" C. (0.18 mm.) crystalline.
01 01 I l 6-7-.- -COCH1COOClH -COOC1 COOCH (CH OhP easily mo- Do.
bile oil soluble in alcohol acetone. B.P. 123126 C. (0.25 mm.).
I l -0 0 ones 0 0 0,115 Q-o 0 0 0120 o o 0iHi cnoionolsr easily mobile oil, soluble in alcohol, acetone. B.P. 123126 C. (0.25 mm.).
9-10.. omQ-o 0 onto 0 0 0,11 0 NG 0 011010 0 o cine. (OH O)3P thickly liq- (oiniohr thickly liquid oil, soluble in uid oil. alcohol, acetone. B.P. 200203 G. (0.1 M.P. (it- C. mm.).
11-12. Olc O GHZC 0 O C2H5 OlQ-O O 0 0120 O 0 0211 (CH3O)3P (021150).51 thickly liq- M.P. 71 O. soluble uid oil soluble in al- I I in alcohol, acetone. collol, acetone. OgN OnN M.P. 89- C. IlLP. 68459 C.
1314 moQ-c 0 01120 0 o C2H moQ-o 0 0 01,0 0 0 02mm- (CH O) P easily mo- (C2H5O)3P easily mobile oil in alcohol, bile oil soluble in al- BP- 110412 0 (03 mm.) cohol, acetone. cohol, acetone.
15-16- H3O oQ-o 0 01320 0 0 0 11 H30 oQ-o o o 0110 0 0 02m (OH3O)3P mobile oilin Do.
alcohol, acetone.
11.--- @COOHQCOOCH: @oooonoooom Do.
B.P. 9498 C. (0.4 mm.). B.P. 102103 O. (0.12 mm.). M.P. 62 0.
Example 11 7 dropWise in the course of 5 minutes. The mixture is mainl3.05 parts of dichlorobenzoyl-acetic acid ethyl ester in 15 parts by volume of xylene are heated to the boil, and 12.2 parts of diethyl allyl phosphite tained fora further hour at 180 C. 2 parts of ethyl chloride are collected. The volatile constituents are removed in vacuo at C., and the residue consists of 20.8 parts of an easily mobile oil, which dissolves well in (boiling at 6466 C. under 12 mm. pressure) are added 75 alcohol and acetone.
9 In an analogous manner the following phosphites can be reacted with dichlorobenzoyl-acetic acid ethyl ester.
Reaction Phosphite tempera- Reaction product ture, C.
180-210 Easily mobile oil, (C2H50)3PO CH soluble in alcohol,
acetone.
B.P. 84 C. (0.3 111111.).
(amour-Q 180 Bright. thinly liquid oil soluble in alcohol,
acetone.
B.P. 50 C. (0.3 mm.).
(021350 );1 0-o1 180 Easily mobile oil,
soluble in alcohol, acetone.
xample 13 13.05 parts of dichlorobenzoyl-acetic acid ethyl ester are heated to l50-160 C., and 6.8 parts of ethyl ethylene phosphite O-CH:
ozn or oorn (boiling at 49 C. under mm. pressure) are added dropwise. The mixture is slowly heated to 215 C. and maintained at that temperature for a further hour. 0.9 part of ethyl chloride is collected. The reaction does not take place solely with the splitting off of ethyl chloride, but partially involves splitting up of the ethylene phosphite ring. The easily volatile constituents are removed in vacuo at 180 C., and the residue is an easily mobile oil (17.8 parts), which dissolves well in alcohol and acetone and hardly at all in water.
Example 14 9.9 parts of phenyl-phosphonous acid diethyl ester (boiling at 108114 C. under 10 mm. pressure) are added dropwise to a mixture of 13.05 parts of dichlorobenzoyl-acetic acid ethyl ester with 15 parts by volume of chlorobenzene, the mixture being heated to the boil. The reaction is finished in the course of hour, and 2.0 parts of ethyl chloride are collected. After removing the xylene in vacuo there are obtained 19.3 parts of a thinly liquid oil which dissolves well in alcohol and acetone.
Example 16 21.4 parts of the sodium salt of benzoyl-acetic acid ethyl ester are stirred well in 50 parts by volume of chlorobenzene. Beginning at 20 C. 189 parts of diethyl thiophosphoric acid ester chloride are added dropwise in the course of 20 minutes while stirring, the temperature being raised to 30 C. The mixture is allowed to react completely overnight at 50-60 C. After being cooled, the solution is washed three times with a small amount of water, dried over sodium sulfate, and then the solvent it is removed in vacuo. The residue consists of 25.8 parts of a mobile oil, which dissolves well in alcohol and acetone.
Example 17 2 parts of the condensation product obtained as described in Example 1 or 2 are mixed with 1 part of the condensation product of 1 mol of tertiary octyl phenol and 8 mols of ethylene oxide, and 7 parts of isopropanol.
There is obtained a clear solution which can be used as a concentrate for making up spray liquors and emulsifies when poured into water.
(A) In order to demonstrate the contact action on aphids the following experiments were carried out. Spraying liquors were used at concentrations of active substance of 0.08%, 0.04% and 0.02%.
Broad beans, which were heavily infected with aphids, were sprayed from all sides and the effect was examined after 48 hours. The plants on which the action was were infected with fresh aphids, and the action was examined after a further 48 hours. The results obtained are given in the following table:
Action on aphids Spray liquor concentration, After 48 hours 48 hours after reinfection percent Example 1 Example 2 Example 1 Example 2 For each plant a mark is used. means that no living aphids are present, means a good action, only a few aphids alive, and means an insufficient or no action.
(B) In order to demonstrate the action on aphids by difiusion through the leaves the following experiment was carried out, with the use of a spray liquor containing 0.08% of active substance.
Broad beans, which were infected with aphids only on the undersides of the leaves, were sprayed with the above liquor only on the upper surfaces of the leaves, and after 48 hours the action on the aphids under the leaves was examined. The results obtained are given in the following table:
Spray liquor Action of concentration, aphids percent Example 1 (C) In order to demonstrate the action of the compounds of Examples 1 and 2 as stomach poisons, leaves were immersed in spray liquors containing 0.04% of the active substance. When dry the leaves were fed to locusts.
After a few days the locusts were killed. The compounds of Examples 1 and 2 also exhibit a good action against the eggs of Ephestia kiihniella. They may be used in dormant spray preparations as active substances against the wintering stages of pests.
For preparting the spray concentrates there may be used wetting and emulsifying agents other than those mentioned above. There may be used non-ionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon radical of about l030 carbon atoms with ethylene oxide, such as the condensation product of octadecyl alcohol with 25-30 mols of ethylene oxide, or the condensation products of soya bean fatty acid with 30 mols of ethylene oxide, or that of commercial oleylamine with 15 mols of ethylene oxide, or that of dodecyl mercaptan with 12 mols of ethylene oxide. Among the anion-active emulsifying agents, which may be used, there may be mentioned the sodium salt of dodecyl alcohol sulfonic acid ester, the sodium salt of dodecylbenzene sulfonic acid, the potassium or triethanolarnine salt of oleic acid or abietic acid, or a mixture of these acids, or the sodium salt of a petroleum sulfonic acid.
Instead of isopropanol there may be used other solvents for making up the spray concentrates, for example, ethyl alcohol, methanol, butanol, acetone, methyl ethyl ketone, methyl-cyclohexanol, benzene, toluene, xylene, kerosene or petroleum fractions. There may, of course, be used mixtures of these solvents.
Example 18 2 parts of the product of Example 2 are mixed with 9 parts of chalk and 1 part of a wetting agent. There is obtained a spray powder, which can be used for making spray liquors by suspending it in water. By treating the walls of stables with such a spray liquor containing 0.4% of active substance, good results are obtained against flies and gnats.
Example 19 1 part of the product of Example 2. is mixed with 99 parts of tale. The resulting mixture is an insecticidal dusting powder, which is suitable for dusting vines to combat Pyralis caterpillars and Conchylis caterpillars. The talcum may be replaced wholly or in part by sulfur, in which case the preparation is also active against Oidium. Instead oftalc, other pulverulent carriers may be used, such as chalk, bentonite, kaolin or mixtures thereof.
What is claimed is:
1. An organic phosphorus compound which is represented by one of the general formulae wherein R and R is each selected from the group consisting of an alkyl radical containing at most 18 carbon atoms, an allyl radical, a tetrahydrofurfuryl radical, a benzyl radical, a phenyl radical and a chlorophenyl radical; R represents an alkyl radical containing at most 18 carbon atoms; R represents a member selected from the group consisting of a chlorine atom and a bromine atom; R represents a member selected from the group consisting of a phenyl radical, a chlorophenyl radical, a cyclohexyl radical, a furyl radical, a benzene radical which is substituted by a lower alkyl radical, a benzene radical which is substituted by a lower alkoxy radical, a benzene radical which is substituted by a nitro group and a benzene radical which is substituted by a nitro group and a halogen atom; X represents a member selected from the group consisting of an oxygen atom and the group wherein R represents a lower alkyl radical; Y represents in which R, R and R each represents an alkyl radical containing 1 to 4 carbon atoms and R is the phenyl radical.
3. An organic phosphorus compound of the formula in which R, R and R each represents an alkyl radical containing 1 to 4 carbon atoms and R is a chlorophenyl radical.
4. An organic phosphorus compound of the formula in which R, R and R each represents an alkyl radical containing 1 to 4 carbon atoms and R is a nitrophenyl radical.
5. An organic phosphorus compound of the formula in which R, R and R each represents an alkyl radical containing 1 to 4 carbon atoms and R is the furyl radical.
6. The compound of the formula 7. The compounds of the formula 8. The compounds of the formula 14 and compounds of the formula R-(X)n1 R4 P-O-C 0R wherein R and R is each selected from the group consisting of an alkyl radical containing at most 18 carbon atoms, an allyl radical, a tetrahydrofurfuryl radical, a benzyl radical, a phenyl radical and a chlorophenyl radical; R represents an alkyl radical containing at most 18 carbon atoms; R represents a member selected from the group consisting of a chlorine atom and a bromine atom; R represents a member selected from the group consisting of a phenyl radical, a chlorophenyl radical, a cyclohexyl radical, a furyl radical, a benzene radical which is substituted by a lower alkyl radical, a benzene radical which is substituted by a lower alkoxy radical, a benzene radical which is substituted by a nitro group and a benzene radical which is substituted by a nitro group and a halogen atom; X represents a member selected from the group consisting of an oxygen atom and the group .N in
wherein R represents a lower alkyl radical, Y represents an oxygen atom, m and 12 each represents an integer of at most 2; and Z represents a member selected from the group consisting of an oxygen atom and a sulfur atom; in admixture with an insecticidally inactive carrier.
References Cited in the file of this patent UNITED STATES PATENTS 2,668,174 Horback et a1. Feb. 2, 1954 2,678,329 Gamrath et a1 May 11, 1954 2,685,552 Stiles Aug. 3, 1954 2,766,260 Kartinos Oct. 9, 1956 2,864,828 Russell et a1. Dec. 16, 1958 2,894,018 Lorenz July 7, 1959 FOREIGN PATENTS 167,432 Austria Jan. 10, 1951 523,521 Canada Apr. 3, 1956 OTHER REFERENCES Arbuzov et al.: Chem. Abst., vol. 45, column 1506 (1951).

Claims (1)

1. AN ORGANIC PHOSPHORUS COMPOUND WHICH IS REPRESENTED BY ONE OF THE GENERAL FORMULAE
US691163A 1956-10-25 1957-10-21 New organic phosphorus compounds and their manufacture and use Expired - Lifetime US3035079A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH875583X 1956-10-25

Publications (1)

Publication Number Publication Date
US3035079A true US3035079A (en) 1962-05-15

Family

ID=4544366

Family Applications (1)

Application Number Title Priority Date Filing Date
US691163A Expired - Lifetime US3035079A (en) 1956-10-25 1957-10-21 New organic phosphorus compounds and their manufacture and use

Country Status (7)

Country Link
US (1) US3035079A (en)
BE (1) BE563003A (en)
CH (1) CH353007A (en)
DE (1) DE1197271B (en)
FR (1) FR1190017A (en)
GB (1) GB875583A (en)
NL (1) NL222265A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3134775A (en) * 1957-10-25 1964-05-26 Ici Ltd New pesticidal triazine derivatives
US3136690A (en) * 1959-10-12 1964-06-09 Ciba Ltd Methods and compositions for combating pests with beta-phosphate esters of -2-butenoates of mono glyceriate heterocyclic acetals and glyceriate carbonates
US4088758A (en) * 1975-08-20 1978-05-09 Bayer Aktiengesellschaft O-(1-Phenyl-2-carbalkoxy-vinyl)-thionophosphoric (phosphonic) acid esters and ester-amides and method for combatting insects

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1155437B (en) * 1959-04-07 1963-10-10 Dr Friedrich Cramer Process for the preparation of phospho-enolpyruvic acid dibenzyl ester
NL256740A (en) * 1959-10-12

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT167432B (en) * 1946-10-12 1951-01-10 Bertha Braendli-Schafroth Pesticides
US2668174A (en) * 1950-08-15 1954-02-02 Celanese Corp Monopropyl dixylyl phosphate and process
US2678329A (en) * 1950-11-06 1954-05-11 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2685552A (en) * 1952-02-29 1954-08-03 Shell Dev Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate
CA523521A (en) * 1956-04-03 R. Whetstone Richard Complex arylphosphonates
US2766260A (en) * 1953-10-09 1956-10-09 Gen Aniline & Film Corp Methine dyestuff intermediates
US2864828A (en) * 1957-06-11 1958-12-16 Charles R Russell Esters of gamma-(tetrahydro-2-furyl) alkanols
US2894018A (en) * 1957-07-16 1959-07-07 Bayer Ag Di(lower alkyl)-mono(alpha-phenyl-beta-carbalkoxy-vinyl) phosphate esters

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE974569C (en) * 1951-09-25 1961-03-02 Ciba Geigy Pest repellants

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA523521A (en) * 1956-04-03 R. Whetstone Richard Complex arylphosphonates
AT167432B (en) * 1946-10-12 1951-01-10 Bertha Braendli-Schafroth Pesticides
US2668174A (en) * 1950-08-15 1954-02-02 Celanese Corp Monopropyl dixylyl phosphate and process
US2678329A (en) * 1950-11-06 1954-05-11 Monsanto Chemicals Dialkyl monoaryl esters of orthophosphoric acid
US2685552A (en) * 1952-02-29 1954-08-03 Shell Dev Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate
US2766260A (en) * 1953-10-09 1956-10-09 Gen Aniline & Film Corp Methine dyestuff intermediates
US2864828A (en) * 1957-06-11 1958-12-16 Charles R Russell Esters of gamma-(tetrahydro-2-furyl) alkanols
US2894018A (en) * 1957-07-16 1959-07-07 Bayer Ag Di(lower alkyl)-mono(alpha-phenyl-beta-carbalkoxy-vinyl) phosphate esters

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3134775A (en) * 1957-10-25 1964-05-26 Ici Ltd New pesticidal triazine derivatives
US3136690A (en) * 1959-10-12 1964-06-09 Ciba Ltd Methods and compositions for combating pests with beta-phosphate esters of -2-butenoates of mono glyceriate heterocyclic acetals and glyceriate carbonates
US4088758A (en) * 1975-08-20 1978-05-09 Bayer Aktiengesellschaft O-(1-Phenyl-2-carbalkoxy-vinyl)-thionophosphoric (phosphonic) acid esters and ester-amides and method for combatting insects

Also Published As

Publication number Publication date
GB875583A (en) 1961-08-23
BE563003A (en)
CH353007A (en) 1961-03-31
DE1197271B (en) 1965-07-22
NL222265A (en)
FR1190017A (en) 1959-10-08

Similar Documents

Publication Publication Date Title
US2908605A (en) New organic phosphorus compounds and process for their manufacture
US2959516A (en) Organic phosphate compounds and use thereof
US2861912A (en) Method for combating pests and preparations suitable therefor
US2885430A (en) Bis-(o:o-diethyl-dithiophosphoryl) 1:4-butylene-dimethyl ether
US3035079A (en) New organic phosphorus compounds and their manufacture and use
US2831014A (en) New compounds containing phosphorus and sulphur
US3763160A (en) Phosphorus containing esters of 2-hydroxyquinoxaline
US3055798A (en) New organic phosphorus compounds and their manufacture and use
US3361855A (en) Dithiophosphonic acid esters
US3136784A (en) Beta-phosphate esters of -2-butenoates of mono glyceriate heterocyclic acetals and glyceriate carbonates
US3248412A (en) Thiophosphonic acid esters
US3496178A (en) 2 - (o,o - dialkyl-phosphoryl)-6-carbalkoxy or carbalkenoxy-pyrazolo pyrimidines
US3092541A (en) New carbamoylalkyl phosphorus ester compounds
US2995486A (en) Method for combating pests and preparations suitable therefor
US3136690A (en) Methods and compositions for combating pests with beta-phosphate esters of -2-butenoates of mono glyceriate heterocyclic acetals and glyceriate carbonates
US3238202A (en) Amides of o, o-dialkyldithiophos-phorylacetic acids
US3733376A (en) Phosphoric acid esters
US2983748A (en) Thionophosphonic acid esters
US3060217A (en) Thiophosphoric acid esters
US3432599A (en) Organophosphorus insecticides
US2962518A (en) Phosphonic acid esters
US3644598A (en) 1 - alkoxy(-alkenyloxy -phenoxy) - 1-thiono-3-chloro(3-alkyl)phospholines
US3016326A (en) New organic phosphorus compounds
US2945054A (en) O, o-dialkyl s-[1-(2, 2-dihalocyclopropyl) ethyl] phosphorothiolothionates
US2931824A (en) Thiophosphoric acid esters and their production