US3644600A - 2-halo-4-alkyl-phenyl-phosphoramidates - Google Patents

2-halo-4-alkyl-phenyl-phosphoramidates Download PDF

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Publication number
US3644600A
US3644600A US802627*A US3644600DA US3644600A US 3644600 A US3644600 A US 3644600A US 3644600D A US3644600D A US 3644600DA US 3644600 A US3644600 A US 3644600A
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compounds
formula
hal
parts
alkyl group
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Expired - Lifetime
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US802627*A
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English (en)
Inventor
Ernst Beriger
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BASF Schweiz AG
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Ciba AG
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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
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
    • 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
    • C07F9/22—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
    • C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds

Definitions

  • substituents R independently of one another, represent hydrogen, an alkyl group having 1 to 4 carbon atoms or possibly R R represents an alkyl group having 1 to 4 carbon atoms, R represents an alkyl or alkenyl group having 1 to 6 carbon atoms, R represents an alkyl group having 1 to 5 carbon atoms which may be linked with the phosphorus atom through oxygen or sulphur, X represents an oxygen or a sulphur atom and Hal represents a halogene atom, having a pronounced selective activity against monocotyledenous weeds for example Panicum, Poa, Digitaria or Alopecurus, While leaving important (including monocotyledenous) useful cultures for example grain crops, rice, maize, turnips, flax, soybeans, cabbages and others, and in the case of some cultures, they even display a useful growth-regulating effect.
  • Compounds that are especially active are those in which the substituents R, independently of one another, represent hydrogen or an alkyl group having 1 to
  • the weeds can be combated in the plant cultures both by the pre-emergent and the postemergent treatment, though the pre-emergent treatment is preferred.
  • the compounds of the Formula I display a good fungicidal activity when applied in small quantities.
  • R independently of one another, represent hydrogen or an alkyl group having 1 to 4 carbon atoms
  • R represents an alkyl group having 1 to 5 carbon atoms, which may be linked with the phosphorus atom through oxygen or sulphur
  • X represents an oxygen or a sulphur atom
  • Hal is a halogen atom.
  • a group of compounds of importance to the selective control of plants comprises the compounds of the formula' in which R represents a hydrogen atom or the methyl group, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R';, represents an alkyl group and Hal represents a halogen atom.
  • the compounds of the general Formula I are new. They can he -manufactured by various methods:
  • alkyldichloro-dithiophosphate may be used as starting material and reacted with the corresponding phenol and then with the desired alkylamine.
  • the parent phosphorus component (PCl PBr or PXCl may be reacted first with the alkylamine and the resulting with the lower alkanol or mercaptan and the phenol, in either order of sequence.
  • anhydrous hydrogencarbonates or carbonates also tertiary amines for example triethylamine, pyridine, picoline, lutidine, quinaldine, diethylaniline and dimethylaniline.
  • the new compounds of the general Formula I are used alone or in conjunction with additives in the form of herbicidal preparations.
  • the present invention also provides a selective herbicidal preparation which comprises a compound of the general Formula I given above together with a suitable carrier.
  • the known herbicides whose activity supplements that of the compounds of this invention may be employed, for example 2-methyl- 4-chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and/or ot-[Z-methyl-4-chlorophenoxy] -propionic acid, and growth hormones.
  • the preparations may also contain one or more of the following: a vehicle, a solvent, a diluent, a dispersant, an emulsifier, a thickener, an adhesive and/or a fertilizer and, if desired, further pesticidal agents from the same or other spheres of application.
  • Ready spray solutions of the compounds of the general Formula I can be prepared, for example, with petroleum fractions of a high to medium boiling range, for example diesel oil or kerosene, coal tar oil and oils of vegetable or animal origin, also hydrocarbons for example alkylated naphthalenes, tetrahydronaphthalene, if desired with the use of xylene mixtures, cyclohexanols, ketones or chlorinated hydrocarbons for example trichlorethane or tetrachlorethane, trichlorethylene, or trior tetrachlorobenzenes. It is advantageous to use organic solvents having boiling point above 100 C.
  • Aqueous forms of application are advantageously prepared from emulsion concentrates, pastes or wettable spray powders by the addition of water thereto.
  • Suitable emulsifiers or dispersants are nonionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon residue having about to carbon atoms, with ethylene oxide, for example the condensation product of octadecyl alcohol with to mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide.
  • anionic emulsifiers that can be used, there may be mentioned the sodium salt of dodecyl alcohol-sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid.
  • Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammonium chloride.
  • solid vehicles used in the manufacture of dusting and casting preparations there may be used: talcum, kaolin, bentonite, calcium carbonate, or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture the preparations in granular form, especially for treating rice cultures in water.
  • the different forms of application may contain the usual additives that improve the distribution, adhesion, stability to rain or the penetration; such substances are fatty acids, resins, casein or alginates.
  • EXAMPLE 1 36.5 parts of 2-bromo 5 tertiary butylphenylthiodichlorophosphate [boiling at l18l20 C. under 0.2 mm. Hg; prepared by reacting 2-bromo-S-tertiary-butylphenol in the usual manner with phosphorus trichloride and sulphur] in 50 parts by volume of methylene chloride and 6.4 parts of methanol are boiled under reflux for 16 hours. The readily volatile phase is evaporated under vacuum at 50 C. bath temperature, to leave 35 parts of O-methyl-2- bromo-5-tertiary butylphenylthiochlorophosphate.
  • Dusting agent --Equal parts of an active substance according to this invention and of precipitated silica are finely ground together. From this mixture, dusting preparations containing preferably 1 to 6% of active substance, can be manufactured by incorporation of kaolin or talcum.
  • Spray powder for example, the fOllOWing ingredients are mixed and finely ground together:
  • active substance of this invention 20 parts of Hisil (highly adsorptive silica) 25 parts of bolus alba (kaolin) 3.5 parts of an adduct of para-tertiary octylphenol With ethylene oxide 1.5 parts of sodium1-benzyl-2-stearylbenzimidazole-6.3'-
  • Emulsion concentrate Readily soluble active substances can also be formulated as emulsion concentrates in the following manner:
  • Granulate 7.5 grams of one of the active substances of Formula I are dissolved in cc. of acetone and the resulting acetonic solution is poured over 92 g. of granulated attapulgite (mesh size: 24/48:apertures/inoh). The whole is thoroughly mixed and the solvent extracted in a rotary evaporator, to furnish a granulate containing 7.5% of active substance.
  • EXAMPLE 3 In the preemergent treatment, the new active substances of the Formula I displayed an excellent activity against grass-like weeds, while leaving cultures of grain crops, rice and maize as well as of dicotyledenous plants unaffected.
  • the treatment was carried out with 5 and respectively 2.5 kg. of active substance per hectare on the day after seeding. Evaluation was carried out 20 days later.
  • the pre-swelled rice seed material in one case of the Caloro type and in the other of the Hatsunisiki type, in admixture with the abovementioned granulate of one of the active substances was sprinkled into the water.
  • the amount of active substance applied ranged from 1 to 6 kg. per hectare.
  • Beta Calendula chrysantha, Chrysanthemum segetum, Lin um usitatissimum, Brassica rapa, Ipomoea purpurea, Gossypiumhirsutum, Soja max., Galium aparine, and Stellaria media.
  • the solution of the active substance was replaced by a nutrient solution containing the same quantity of active substance (100 parts per million of active substance No. 3), while in the control experiments the distilled Water was replaced correspondingly by a nutrient solution which did not contain the active substance.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US802627*A 1968-03-01 1969-02-26 2-halo-4-alkyl-phenyl-phosphoramidates Expired - Lifetime US3644600A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH308368A CH493203A (de) 1968-03-01 1968-03-01 Herbizides Mittel
CH182069A CH509354A (de) 1968-03-01 1969-02-06 Verfahren zur Herstellung neuer Phosphorsäure- und Thiophosphorsäureesteramide und ihre Verwendung als Wirkstoffe zur Unkrautbekämpfung in Nutzpflanzenkulturen

Publications (1)

Publication Number Publication Date
US3644600A true US3644600A (en) 1972-02-22

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US802627*A Expired - Lifetime US3644600A (en) 1968-03-01 1969-02-26 2-halo-4-alkyl-phenyl-phosphoramidates

Country Status (9)

Country Link
US (1) US3644600A (de)
BE (1) BE729213A (de)
BG (1) BG16728A3 (de)
CH (2) CH493203A (de)
DE (1) DE1909108A1 (de)
ES (1) ES364246A1 (de)
FR (1) FR2002984A1 (de)
GB (1) GB1250227A (de)
NL (1) NL6903161A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846513A (en) * 1969-10-04 1974-11-05 Bayer Ag 2-chloroethane-(thiono)-phosphonic acid esters
US3923493A (en) * 1972-01-06 1975-12-02 Nikolai Nikolaevich Melnikov Herbicide
US3972705A (en) * 1974-01-16 1976-08-03 Bayer Aktiengesellschaft Amidothionophosphonic acid ester containing plant growth regulants
USRE28949E (en) * 1969-10-04 1976-08-31 Bayer Aktiengesellschaft 2-Chloroethane-(thiono)-phosphonic acid esters
US3996041A (en) * 1971-12-27 1976-12-07 Bayer Aktiengesellschaft Novel amidoth ionophosphoric acid esters and their use as herbicides
US4065288A (en) * 1970-03-04 1977-12-27 Bayer Aktiengesellschaft Novel 2-chloroethane-(thiono)-phosphonic acid amido compounds and plant growth inhibiting compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035449A (en) * 1975-10-23 1977-07-12 Mobay Chemical Corporation Process for the production of S-alkyl phosphoro dihalogenidodithioate

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846513A (en) * 1969-10-04 1974-11-05 Bayer Ag 2-chloroethane-(thiono)-phosphonic acid esters
USRE28949E (en) * 1969-10-04 1976-08-31 Bayer Aktiengesellschaft 2-Chloroethane-(thiono)-phosphonic acid esters
US4065288A (en) * 1970-03-04 1977-12-27 Bayer Aktiengesellschaft Novel 2-chloroethane-(thiono)-phosphonic acid amido compounds and plant growth inhibiting compositions
US3996041A (en) * 1971-12-27 1976-12-07 Bayer Aktiengesellschaft Novel amidoth ionophosphoric acid esters and their use as herbicides
US3923493A (en) * 1972-01-06 1975-12-02 Nikolai Nikolaevich Melnikov Herbicide
US3972705A (en) * 1974-01-16 1976-08-03 Bayer Aktiengesellschaft Amidothionophosphonic acid ester containing plant growth regulants

Also Published As

Publication number Publication date
CH493203A (de) 1970-07-15
ES364246A1 (es) 1971-02-16
FR2002984A1 (de) 1969-11-07
GB1250227A (de) 1971-10-20
BE729213A (de) 1969-08-28
BG16728A3 (bg) 1973-02-15
NL6903161A (de) 1969-09-03
CH509354A (de) 1971-06-30
DE1909108A1 (de) 1969-10-30

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