US2961457A - New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids - Google Patents

New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids Download PDF

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US2961457A
US2961457A US783671A US78367158A US2961457A US 2961457 A US2961457 A US 2961457A US 783671 A US783671 A US 783671A US 78367158 A US78367158 A US 78367158A US 2961457 A US2961457 A US 2961457A
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parts
omicron
acid
butene
carbon atoms
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US783671A
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Pohlemann Heinz
Winderl Siegfried
Stummeyer Herbert
Adolphi Heinrich
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BASF SE
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BASF SE
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Classifications

    • 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
    • C07F9/20—Esters of thiophosphoric acids containing P-halide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/113—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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
    • 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
    • C07F9/173—Esters of thiophosphoric 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings

Definitions

  • This invention relates to a process for the production of .new esters of O .O-dialky1phosphoric or 0.0-dialkylthionophosphoric acids, and to the new esters themselves. It relates in particular :to-theproduction of esters of 0.0- dialkylphosphoric and 0.0-dialkylthionophosphoric acids with substituted butenols, and to the esters themselves.
  • the primary object of the present invention consists in the discovery and production of new halogen-free esters of 0.0-dialkylphosphoric acids and O;O-dialkylthionophosphoric acids which haveboth strong insecticidal and ovicidal properties but which on the contrary are less toxic for warm-blooded animals than the phosphoric acid esters hitherto known.
  • a further object consists in the discovery of new insecticides which do not contain any halogen atoms, which can be used against pests of all kinds and which above all have a systematic action.
  • Suitable butene-(3)-ol-(2) compounds substituted in l-position and in which Y is an oxygen atom combined with an alkyl radical are1-alkoxybutene-(3)-ols-(2)' with 1 to 4- carbon atoms in the alkoxy groups, such as l-methoxybutene-( 3 .-ol- (2) l-ethoxy-butene- 3 -ol-(2) and also l-propyland l-isopropyl-butene-(3)-o1-(2) and also the isomeric 1-butyl-butene-(3)-ols-(2).
  • butene- (3)-ols-(2) substituted in -1-position by an oxygen-containing radical are l allyloxy-butene-(3)-ol-(2) and also 1-phenoxy-butene-(3)rol-(2), and if'desired the phenoxy group .may be substituted by a nitro group.
  • butenols of this kind there may also be mentioned l-anilino-butene-(3')-ol-(2) and also l-substituted .butenols in which the N-atom of "the substituents is connected to a'cycloalkane'radical, for example cyclopentyl, cyclohexyl or cyclo-octyl, or is aconstituent of aheterocycliccompound which contains no further unsaturated linkages and further hetero atoms.
  • a'cycloalkane'radical for example cyclopentyl, cyclohexyl or cyclo-octyl, or is aconstituent of aheterocycliccompound which contains no further unsaturated linkages and further hetero atoms.
  • butenols are for example 1-cyclopentylamino-butene- (3 -ol- 2) 1-cyc1ooctylamino-butene- 3 -ol-(2) l-pyrrolidylbutene- 3 )-ol- (2) and 1-piperidino-butene-.( 3 -ol- (2)
  • those are especially suitable initial materialsof which the substitutent is an alkyl mercapto group containing up to 4 carbon atoms or a phenylmercapto group, and the sulfur atom may also be oxidized to a sulfonic acid group.
  • 0.0-dialkylphosphoric or 0.0-dialkylthionophosphoric acid monohalides serving as the second reaction component there may be mentioned the chlorides, bromides and iodides of 0.0-dialkylphosphoric and 0.0- dialkylthionophosphoric acids, the chlorides being the preferred compounds.
  • the ,alkyl groups may be identical or diiferent alkylradicals with 1 to.4 carbon atoms.
  • OD-dialkylphosphoric acid monohalides will hereinafter be referred to briefly as OD-dialkylphosphoric acid monohalides. They are readily accessible known compounds which are obtained for example by reaction of phosphorus oxychloride or thionophosphoric acid trihalides with the calculated amount of analiphatic monohydric alcohol.
  • the reaction takes place by introducing the two reaction components in an anhydrous medium and in general it is immaterial which component is introduced first. It is suitable to add the dialkylphosphoric acid monohalide to the substituted butenol.
  • the initial materials are used in about equivalent amounts. Sometimes it may be advantageous however to use one or other initial material in slight excess, for example 1.2 to 1.5 times the theoretically calculated amount.
  • diluents there may be used for example aromatic, aliphatic and cycloaliphatic hydrocarbons, such as benzene, toluene, xylene, gasolines and cyclohexane or aliphatic chlorohydrocarbons, as for example methylene chloride, chloroform, and also ethylene chloride and carbon tetrachloride.
  • aromatic, aliphatic and cycloaliphatic hydrocarbons such as benzene, toluene, xylene, gasolines and cyclohexane or aliphatic chlorohydrocarbons, as for example methylene chloride, chloroform, and also ethylene chloride and carbon tetrachloride.
  • solvents is especially recommended when one or both of the reactants is solid.
  • reaction already takes place appreciably even in the cold, but it is preferable to work at room temperature or at higher temperatures, for example at about to 130 C., advantageously at about to 75 C., if necessary in closed vessels.
  • Example 1 56.4 parts of diethoxythionophosphoric acid monochloride are allowed to react with a mixture of 37.7 parts of l-propyl-amino-butene-(3)-ol-(2) and 23.7 parts of anhydrous pyridine slowly while stirring vigorously. The temperature thereby rises to 50 C. After the completion of the addition, the whole is stirred for another 4 to 5 hours at 45 to 50 C. to complete the reaction. The reaction product is cooled to room temperature, parts of water and 100 parts of benzene are added thereto, stirred well and the aqueous layer separated from the non-aqueous layer in a separator. The latter is dried with sodium sulfate. After distilling off the solvent, 72 parts of a non-distillable oil remain.
  • the compound has the formula:
  • the compound has the following formula:
  • Example 6 CzHoO olrno
  • Example 7 68 parts of diethoxythionophosphoric acid monochloride are allowed to drip while stirring well into a mixture of 60 parts of 2-hydroxybutene-(3)-yl ethyl sulfone, 30 parts of anhydrous pyridine and 250 parts of benzene. After the addition had been completed, the whole is stirred for another 5 hours at 45 to 50 C. After the reaction matterial has been cooled it is Washed with Water and then the organic layer is dried over sodium sulfate. After distilling off the solvent there remain behind 91 parts of a pale brown readily mobile oil. The compound has the formula:
  • Example 11 37.6 parts of diethoxythionophosphoric acid chloride are allowed to flow into a mixture of 40 parts of l-cyclooctylaminobutene-(3)-ol-(2) and 16 parts of anhydrous pyridine while stirring well. Stirring is then continued for another 5 hours at 50 C. and the whole worked up as in Example 7 after the addition of 100 parts of benzene. After distilling on the solvent, there remain 46 parts of a viscous red-brown oil of the formula:
  • Example 14 36.6 parts of diethoxythionophosphoric acid monochloride are added while stirring well to 26.4 parts of l-ethylmercaptobutene-(3)-ol-(2), 50 parts of toluene and 21.2 parts of finely powdered sodium carbonate. The whole is then stirred for another 5 hours at 70 to C. The reaction mixture is cooled to room temperature and worked up as in Example 7. After distilling off the solvent, 30.7 parts of a brownish liquid are obtained having the formula:
  • Example 15 28.2 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring well into a mixture of 27 parts of 1-phenylmercaptobutene-(3)-ol-(2) and 12 parts of anhydrous pyridine. When the addition is completed, the whole is stirred for another 5 hours at 50 C. Then it is cooled to room temperature. 50 parts of benzene are added and the product worked up as in Example 7. After distilling off the solvent there remain 40 parts of a golden yellow oil. The compound has the formula:
  • Example 16 32.4 parts of di-isopropoxythionophosphoric acid chloride are allowed to fiow While stirring into a mixture of 27 parts of l-phenylmercaptobutene-(3)-ol-(2), 50 parts of methylene chloride and 12 parts of anhydrous pyridine. The whole is stirred for another hours at 40 C., then cooled to room temperature and worked up as in Example 7. After distilling off the solvent there remain 43.3 parts of a yellowish oil of the formula:
  • Example 20 37.6 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring into a mixture of 42 parts of l-(para-nitrophenoxy)-butene-(3)ol-(2) and 16 parts of anhydrous pyridine. The whole is stirred for another 5 hours at 50 C., then cooled to room temperature and 50 parts of benzene added. It is Worked up as in Example 7. After distilling off the solvent, there remains as a residue 25 parts of a red-brown oil of the formula:
  • RO O-CH-CH2Y CH CHz in which R and R stand for alkyl groups having 1 to 4 carbon atoms, X stands for a member of the group consisting of oxygen and sulfur and Y stands for a radical from the group consisting of alkoxy with 1 to 4 carbon atoms, allyloxy, phenoxy, nitrophenoxy, monoand dialkylamino with 1 to 4 carbon atoms in the alkyl groups, cycloalkylamino, anilino, pyrrolidyl, alkylmercapto and alkylsulfonyl with 1 to 4 carbon atoms in the alkyl groups, phenylmercapto and phenylsulfonyl.
  • R-O s CH CH2 in which R and R are alkyl groups with 1 to 4 carbon atoms and Y stands for an alkylmercapto radical containing 1 to 4 carbon atoms.
  • R-O s CH CH2 in which R and R stand for alkyl groups with 1 to 4 carbon atoms and Y for an alkylsulfonyl group which contains 1 to 4 carbon atoms in the alkyl radical.
  • RO ⁇ s ⁇ OCH-CH2Y CH OH2 in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y for a monoalkylamino group containing 1 to 4 carbon atoms in the alkyl radical.
  • R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for a dialkylamino group containing from 1 to 4 carbon atoms in the alkyl radicals.
  • R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenylmercapto.
  • R--0 O-GH-CHa-Y CH CH in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenoxy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US783671A 1958-01-02 1958-12-30 New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids Expired - Lifetime US2961457A (en)

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CH (1) CH377331A (de)
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GB (1) GB846229A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151147A (en) * 1961-10-12 1964-09-29 Shell Oil Co Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates
US3206493A (en) * 1961-08-21 1965-09-14 Standard Oil Co Preparation of o, o, s-triesters of monothiophosphoric acid
US3359203A (en) * 1965-09-01 1967-12-19 Exxon Research Engineering Co Ashless dithiophosphoric acid derivatives
US3502677A (en) * 1963-06-17 1970-03-24 Lubrizol Corp Nitrogen-containing and phosphorus-containing succinic derivatives
US4493817A (en) * 1983-07-06 1985-01-15 Teck Corporation Process for recovering pyrochlore mineral containing niobium and tantalum
US6187723B1 (en) * 1993-09-13 2001-02-13 Exxon Research And Engineering Company Lubricant composition containing antiwear additive combination

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1173723B (de) * 1960-09-21 1964-07-09 Basf Ag Mittel zur Bekaempfung von Insekten

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736726A (en) * 1952-03-28 1956-02-28 Geigy Ag J R Basic phosphoric acid esters
US2777792A (en) * 1954-09-01 1957-01-15 Sandoz Ag Pest combating agents
GB789122A (en) * 1953-04-24 1958-01-15 Ciba Ltd New organic compounds containing phosphorus, processes for their manufacture and preparations containing them
GB795340A (en) * 1953-10-07 1958-05-21 Sandoz Ltd New insecticidal esters of dithiophosphoric acid
US2852513A (en) * 1956-04-27 1958-09-16 Bayer Ag Thiophosphoric acid esters and their production
US2865801A (en) * 1956-04-06 1958-12-23 Monsanto Chemicals Propargyl phosphorothioates

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394829A (en) * 1944-04-26 1946-02-12 Shell Dev Allyl-type phosphates and their preparation
US2536647A (en) * 1948-03-06 1951-01-02 Monsanto Chemicals Process of preparing bis (beta-chlorethyl)-para-nitrophenyl thiophosphate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736726A (en) * 1952-03-28 1956-02-28 Geigy Ag J R Basic phosphoric acid esters
GB789122A (en) * 1953-04-24 1958-01-15 Ciba Ltd New organic compounds containing phosphorus, processes for their manufacture and preparations containing them
GB795340A (en) * 1953-10-07 1958-05-21 Sandoz Ltd New insecticidal esters of dithiophosphoric acid
US2777792A (en) * 1954-09-01 1957-01-15 Sandoz Ag Pest combating agents
US2865801A (en) * 1956-04-06 1958-12-23 Monsanto Chemicals Propargyl phosphorothioates
US2852513A (en) * 1956-04-27 1958-09-16 Bayer Ag Thiophosphoric acid esters and their production

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3206493A (en) * 1961-08-21 1965-09-14 Standard Oil Co Preparation of o, o, s-triesters of monothiophosphoric acid
US3151147A (en) * 1961-10-12 1964-09-29 Shell Oil Co Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates
US3502677A (en) * 1963-06-17 1970-03-24 Lubrizol Corp Nitrogen-containing and phosphorus-containing succinic derivatives
US3359203A (en) * 1965-09-01 1967-12-19 Exxon Research Engineering Co Ashless dithiophosphoric acid derivatives
US4493817A (en) * 1983-07-06 1985-01-15 Teck Corporation Process for recovering pyrochlore mineral containing niobium and tantalum
US6187723B1 (en) * 1993-09-13 2001-02-13 Exxon Research And Engineering Company Lubricant composition containing antiwear additive combination

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DE1072616B (de) 1960-01-07
GB846229A (en) 1960-08-31
CH377331A (de) 1964-05-15

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