US3641224A - Bromoalkyl-(di)-thiolphosphoric acid esters - Google Patents

Bromoalkyl-(di)-thiolphosphoric acid esters Download PDF

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US3641224A
US3641224A US807106A US3641224DA US3641224A US 3641224 A US3641224 A US 3641224A US 807106 A US807106 A US 807106A US 3641224D A US3641224D A US 3641224DA US 3641224 A US3641224 A US 3641224A
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alkyl
phenyl
carbon atoms
percent
bromo
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Hellmut Hoffmann
Hans Scheinpflug
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Bayer AG
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Bayer AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • 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

Definitions

  • Y is oxygen or sulfur
  • R is, when Y is sulfur, alkyl of l4 carbon atoms, alkylmercapto-alkyl having l-4 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl moiety, phenyl, chlorophenyl, or alkylphenyl having 1-4 carbon atoms in the corresponding alkyl moiety whereas R is, when Y is oxygen, alkyl of 1-4 carbon atoms or cycloalkyl of -6 ring carbon atoms, and
  • n 0 or 1
  • the present invention relates to and has for its objects the provision for particular new bromoalkyl-(di)-thiolphosphoric acid esters, i.e. O-[(2-bromo-optionally 1 and/ or 2-alkyl and/ or chloroalkyl)-ethyl and (3-bromo-optionally l, 2 and/or 3-alkyl and/or chloroalkyl)-propyl]-S- [alkyl, chloroalkyl, phenyl, chlorophenyl and alkylphenyl]-[S-(alkyl, alkylmercaptoalkyl, phenyl, chlorophenyl and alkylphenyl) and O-(alkyl and cycloalkyl) ]-thioland -dithiol-phosphoric acid esters, which possess fungicidal, bactericidal, and arthropodicidal, especially insecticidal and acaricidal, properties, active compositions in
  • bromoalkyl-(di)-thiolphosphoric acid esters of the formula R to R each individually, is hydrogen, alkyl of 1-2 carbon atoms, or chloroalkyl of 1-2 carbon atoms,
  • R is alkyl of 1-4 carbon atoms, chloro-substituted alkyl of 1-2 carbon atoms, phenyl, chlorophenyl, or alkylphenyl having 1-4 carbon atoms in the corresponding alkyl moiety,
  • Y is oxygen or sulfur
  • R is, when Y is sulfur, alkyl of 1-4 carbon atoms, alkylmercapto-alkyl having l-4 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl moiety, phenyl, chlorophenyl, or alkylphenyl having 14 carbon atoms in the corresponding alkyl moiety whereas R is, when Y is oxygen, alkyl of 1-4 carbon atoms or cycloalkyl of 5-6 ring carbon atoms, and
  • n 0 r l
  • the compounds of Formula I above may be produced by a process which comprises reacting a bromoalkyl-S-alkylor -phenyl-thiolphosphoric acid diester chloride of the formula in which Y and R are the same as defined above, or a salt thereof.
  • the particular new compounds of Formula I above are distinguished by outstanding fungitoxic properties, in particular against fungal pathogenic agents on rice plants.
  • the instant compounds are in this respect clearly superior to comparable known active compounds of analogous constitution which have already been proposed for the same purpose.
  • the in stant compounds also possess effective bactericidah insecticidal and acaricidal activity, coupled with low toxicity to Warm-blooded creatures and concomitantly 'low'phytotoxicity to higher plants.
  • the new compounds of the present' invention therefore represent a genuine enrichment of the art.
  • R to R each individually, represents hydrogen; lower alkyl hydrocarbon of 1-2 carbon atoms such as methyl and ethyl, i.e. C alkyl, especially methyl;
  • chloro-substituted lower alkyl hydrocarbon of l-2 carbon atoms such as chloromethyl, 2-chloro-ethyl and l-chloro -ethyl, i.e. chloro-C alkyl, especially chloromethyl
  • R represents lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.butyl, and the like, i.e. C alkyl, especially C1-2 y chloro-substituted lower alkyl of 1-2 carbon atoms as defined above, i.e. chloro-C alkyl, especially 2- chloroethyl; phenyl; chlorophenyl such as 2-, 3- and 4-chlorophenyl, es-
  • pecially 2- and 4-chlorophenyl or lower alkyl phenyl having 1-4 carbon atoms in the alkyl moiety such as 2-, 3- and 4-methyl, ethyl, nand iso-propyl, n-, iso-, sec.- and tert.-butyl-phenyl, i.e. 2-, 3- and 4-C alkyl phenyl, especially 2- and 4-C or C alkyl phenyl, and more especially 2- and 4-methyl phenyl; Yrepresents oxygen; or sulfur; R represents, when Y is sulfur,
  • lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl to tart-butyl inclusive, andthe like, as defined above, i.e. C alkyl, especially C alkyl; lower alkyl hydrocarbon mercapto-substituted lower alkyl hydrocarbon having 14 carbon atoms in the alkylmercapto moiety and 1-4 carbon atoms in the alkyl hydrocarbon moiety such as methyl, ethyl, nand iso-propyl, n-, iso-, secand tert.-butyl, and the like, -mercapto-methyl to tert.-buty1 inclusive, as defined above, and the like, i.e.
  • C alkylmercapto- C alkyl especially C alkylmercapto-C alkyl, and more especially ethylmercapto-ethyl
  • phenyl chlorophenyl as defined above, especially 2- and 4- chlorophenyl
  • lower alkyl phenyl having 14 canbon atoms in the alkyl moiety such as 2-, 3- and 4-methyl to tert.- butyl inclusive, and the like, -phenyl, i.e. 2-, 3- and 4-C alkyl phenyl, especially 2- and 4-C r C alkyl phenyl, and more especially 2- and 4-methyl phenyl
  • R represents, when Y is oxygen
  • lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl to tert.-butyl inclusive as defined above, and the like, i.e. C alkyl, especially C alkyl; or cycloallcyl hydrocarbon of 5-6 ring carbon atoms such as cyclopentyl, cyclohexyl, and the like, i.e. C cycloalkyl, especially cyclohexyl; and n represents a whole number from 0 to 1, preferably 0; with the proviso that at least one of R and R is such phenyl, chlorophenyl or alkyl phenyl, i.e.
  • -R- will be such phenyl, chlorophenyl or alkyl phenyl when Y is oxygen, and R or R or both will be such phenyl, chlorophenyl or alkylphenyl when Y is sulfur.
  • R is hydrogen, or C alkyl, especially methyl;
  • R to R and R are hydrogen;
  • R is hydrogen, or C alkyl, especially methyl, or ch1oro-C alkyl, especially chloromethyl;
  • R is C or C alkyl, or chloro-C alkyl, especially 2-chloroethyl, or phenyl, or chloro-phenyl, especially 2- and 4-chloropheny1, or C alkyl-phenyl, especially methylphenyl, more especially 2- and 4-C alkyl-phenyl, and particularly 2- and 4-methylphenyl;
  • Y is oxygen or sulfur;
  • R is, when 'Y is sulfur, C or C alkyl, or C alkylmercapto-C alkyl, especially C alkylmercapto-C alkyl, or phenyl, or chlorophenyl, especially 2- and 4-chlorophenyl, or C alkyl-phenyl, especially methylphenyl, more especially 2- and 4-
  • R is C alkyl, chloro-C alkyl, phenyl or chlorophenyl; and R is, when Y is sulfur, C alkylmercapto-C alkyl, phenyl, chlorophenyl or C alkyl phenyl, whereas R is, when Y is oxygen, C alkyl or C cycloalkyl.
  • bromoalkyl-S-alkylor -phenyl thiolphosphoric acid diester chlorides of Formula II above usable as starting materials are not yet known from the literature. It has been found that the bromo-alkyl-S-alkylor phenylthiolphosphoric acid diester chlorides concerned are obtained with very good yields as well as in outstanding purity by precursor reaction of equimolar amounts of 2-chloro-phospholanes or 2-chloro-phosphorinanes of the formula with aliphatic or aromatic sulfenic acid bromides of the formula R --SBr v) In the aforesaid Formulae IV and V, R to R and n are the same as defined above.
  • the precursor reaction can be carried out in the presence or absence of solvents or diluents such as (optionally chlorinated) aliphatic and aromatic hydrocarbons, ethers or low-molecular-weight ketones and nitriles; and the like, at temperatures of substantially between about 20 to +50, preferably at between about 10 to +30 C.
  • solvents or diluents such as (optionally chlorinated) aliphatic and aromatic hydrocarbons, ethers or low-molecular-weight ketones and nitriles; and the like
  • the sulfenic acid bromide (possibly diluted with one of the above-mentioned solvents) dropwise to the solution or suspension of the phospholane or phosphorinane derivative at a temperature within the above-mentioned range with stirring and possible cooling of the reaction mixture.
  • the mixture is left to stand for about 1 to 3 hours to complete the reaction, the solvent is then drawn off and the residue may be subjected to fractional distillation under reduced pressure.
  • the starting materials are obtained in such high purity that their further reaction is possible without purification.
  • isolation of the bromoalkyl-S- alkylor -phenyl-thiolphosphoric acid diester chlorides concerned is dispensed with entirely and, instead, the reaction products of the above-mentioned 2-chloro-phospholanes or -phosphorinanes with the appropriate sulfenic acid bromides are immediately reacted in a one-pot process with the required alcohol, mercaptan or thiophenol of Formula III above.
  • the process according to the present invention can also be carried out in the presence of solvent or diluents.
  • solvent or diluents are suitable.
  • Particularly good results, however, have been obtained with (optionally chlorinated) aliphatic and aromatic hydrocarbons, such as methylene chloride, dichloroethane, di-, triand tetrachloroethylene, chloroform, carbon tetrachloride, benzine, benzene, chlorobenzene, toluene and xylene; ethers, for example diethyl and di-n-butyl ether, dioxan, tetrahydrofuran or low-molecular-weight aliphatic ketones or nitriles, for example acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone, acetonitrile and propionitrile; and the like.
  • the alcohols, mercaptans and thiophenols to be reacted according to the present process can be reacted in the form of their salts, preferably the appropriate alkali metal or ammonium salts. It is alternatively possible to work the process in the presence of acid-binding agents.
  • the usual acid acceptors are suitable, such as alkali metal carbonates, alcoholates and hydroxides, for example potassium and sodium carbonate, methylate, ethylate and hydroxide, as well as tertiary aliphatic, aromatic or heterocyclic bases, such as triethylamine, dimethylaniline, benzyldimethylamine or pyridine; and the like.
  • reaction temperatures in the case of the process according to the present invention can be varied within a fairly wide range.
  • the reaction is carried out at substantially between about -100 C. (or the boiling point of the mixture), preferably at between about 80 C.
  • the reaction mixture is, in order to complete the reaction, left to stand for some time (for example 1 to 3 hours) and/or heated at the above-mentioned temperatures until the reaction is complete, for example for several hours (or overnight), with stirring.
  • the working up of the mixture may take place, in known manner, by pouring the mixture into ice Water, optionally deacidifying the solution, taking up the separated reaction product (in most cases in oily form) in a water-immiscible solvent, preferably one of the abovementioned hydrocarbons, for example benzene, washing the organic layer until there is a neutral reaction, separation of the phases, drying of the solution, distilling olf the solvent and, if possible, fractional distillation of the residue under reduced pressure.
  • a water-immiscible solvent preferably one of the abovementioned hydrocarbons, for example benzene
  • the instant compounds are obtained in most cases in the form of colorless to slightly yellow-colored viscous oils, some of which can be distilled under greatly reduced pressure without decomposition. When this is not possible, the compounds obtained can, for purification, be slightly distilled, that is freed from the last volatile impurities by longer heating to slightly to moderately elevated temperatures in a vacuum.
  • the instant new compounds when compared to the closest active compounds of analogous constitution and the same type of activity previously known from the literature are distinguished by a substantially better bactericidal, insecticidal, acaricidal, but especially fungicidal, effectiveness, as well as a repellent effect against destructive birds, with only slight toxicity to warm-blooded animals and only slight phytotoxicity.
  • the effect sets in rapidly and is long-lasting.
  • the instant new compounds can be used with success in plant protection endeavors, especially against a multiplicity of the most diverse plant and animal parasites, such as fungi, sucking and eating insects, Diptera and mites.
  • the instant new active compounds exhibit an especially strong fungitoxic activity against phytopathogenic fungi. Likewise, diseases caused by bacteria can be controlled with these compounds. The good compatibility with warmblooded animals and with higher plants permits the use of such compounds as plant protection agents against fungal diseases. In the concentrations necessary for the control of fungi, the instant compounds do not damage cultivated plants.
  • Fungitoxic agents in plant protection are used for the control of fungi from the most diverse classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.
  • the instant active compounds possess a broad spectrum of activity. They can be used against parasitic fungi on above-the-soil parts of plants, fungi which cause tracheomycosis, fungi which attack the plants from the soil and seed-borne as well as soil-inhabiting fungi.
  • the instant new compounds have given particularly good results in the control of rice diseases. Such compounds show an excellent activity against the fungi Piricularia oryzae and Pellicularia sasakii, by reason of which they may be used for the joint control of these two diseases. This represents a substantial advance in the art, since up to now agents of different chemical constitution were individually necessary to combat and control these two fungi, respectively. Surprisingly, the instant active compoundsshow not only a protective activity, but also a curative effect.
  • the instant new compounds also act against other fungi which infest rice or other cultivated plants, such as Cochliobolus miyabeanus, Mycosphaerella musicola, Cercosporw person ata, Botrytis cinema and Alternaria species, Fusarium species, Verticillium alboatrium and Phialophom cinerescens; and the like.
  • the active compounds according to the instant invention can be utilized, if desired, in the form of the usual pesticidal diluents or extenders, i.e. conventional pesticidal dispersible carrier vehicles such as solutions, emulsions, suspension,s emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticidal dispersible liquid diluent carriers and/r dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g.
  • carrier vehicle assistants e.g.
  • inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), clorinated aliphatic hydrocarbons (e.g.
  • methylene chloride, etc. methylene chloride, etc.
  • alcohols e.g. methanol, ethanol, propanol, butanol, etc.
  • amines e.g. ethanolamine, etc.
  • ethers e.g. glycol monomethyl ether, etc.
  • amides e.g. dimethyl formamide, etc.
  • sulfoxides e.g. dimethyl sulfoxide, etc.
  • ketones e.g. acetone, etc.
  • water as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e.
  • inert dispersible finely divided solid carriers such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e.
  • emulsifying agents such as non-ionic and/or anionic emulsifying agents (e.g.
  • polyethylene oxide esters of fatty acids polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
  • Such active compounds may be employed alone or in the form of mixtures with one another and/ or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicides, or bactericides, or herbicides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
  • plant protection agents such as other acaricides, insecticides, fungicides, or bactericides, or herbicides, etc.
  • composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.-0001%, preferably 0.011%, by weight of the mixture.
  • the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/ or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g.
  • a surfaceactive agent such as an emulsifying agent and/or a dis persing agent, and an amount of the active compound 8 which is effective for the purpose in question and which is generally between about 0.0001-%, and preferably 0.0195%, by weight of the mixture.
  • the active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.
  • the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, bacteria or arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of fungi, bacteria, insects and acarids which comprises applying to at least one of correspondingly (a) such pests, i.e. fungi, bacteria, insects or acarids, and (b) the corresponding habitat, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e.
  • pests e.g. fungi, bacteria or arthropods
  • fungi, bacteria or arthropods i.e. insects and acarids
  • methods of combating at least one of fungi, bacteria, insects and acarids which comprises applying to at least one of correspondingly (a) such pests, i.e. fungi, bacteria, insects or acarids, and (b)
  • the instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, squirting, fumigating, incrustations, dressings, and the like.
  • Piricularia test liquid preparation of active compound
  • Solvent 4 parts by weight acetone Dispersing agent: 0.05 part by weight sodium oleate
  • Other additive 0.2 part by weight gelatin
  • Water 95.75 parts by 'weight
  • the amount of the particular active compound required for the desired concentration of such active compound in the spray liquor is mixed with the stated amount of solvent, and the resulting concentrate is diluted with the stated amount of water containing the stated dispersive agent and other additive.
  • the infestation of all the leaves present at the time of inoculation is determined as a percentage of the untreated but also inoculated control plants. 0% means no infestation; 100% means that the infestation is exactly as great as in the case of the control plants.
  • the-degree of destruc- After the specified period of time, the-degree of destruc- After the specified tperiod of time the -effe etiveness tion is determined-as a percentage: -100% means that all of the given active compound preparationi s determined the aphids are ldlled whereasr0% means that none of the by counting the dead mites. The degree of destruction aphids are killed. thus obtained is expressed as a percentage. 100% means Th particular a tiv com o d ht sted, their concenthat all the spider mites are killed whereas 0% means that trations, the evaluation time and the results obtained can none of thespider mites are killed a.
  • O-(2-bromo-ethyl)-S-methyl-thiolphosphoric acid diester chloride boils at 130 C. under a pressure of 2 mm. Hg.
  • the yield is 87% of the theory.
  • the yield is 89% of the theory.
  • Atmlysia-C H BrClO PS (molecular weight 360). Calculated (percent): P, 8.6; Cl, 9.8. Found (percent): P, 8.47; Cl, 9.81.
  • arthropod, arthropodicidal and arthropodicide contemplate specifically both insects and acarids.
  • the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidal ly effective amount Which in eifect means an insecticidally or acaridically effective amount of the active compound for the desired purposes.
  • R is selected from the group consisting of hydrogen and C alkyl; R to R and R are hydrogen; R is selected from the group consisting of hydrogen, C alkyl and chloro-C alkyl; R; is selected from the group consisting of C alkyl, chloro- C alkyl, phenyl, chlorophenyl and C alkylphenyl; R is selected from the group consisting of C alkyl, C alkylmercapto-C alkyl, phenyl, chlorophenyl and C alkyl-phenyl; and n is 0-1; with the proviso that at least one of R and R is selected from the group consisting of said phenyl, chlorophenyl and C alkylphenyl.
  • Ester according to claim 1 wherein such compound is O- (Z-brorno-ethyl -S-methyl-S- (4'-chloro-phenyl) -dithiolphosphoric acid ester of the formula B!CHzCH2-O CH -S 8. Ester according to claim 1 wherein such compound is O-(2-bromo-ethyl)-S-ethyl S (4-chloro-phenyl)-dithiolphosphoric acid ester of the formula BlCHgCHz-O 0 ⁇ II CH3S 9.
  • Ester according to claim 1 wherein such compound is O-(Z-bromo-ethyl) S methyl-S-(2'-methyl-phenyl) dithiolphosphoric acid ester of the formula CH3 BI-CHz-CHz-O O ll CHa-S 10. Ester according to claim 1 wherein such compound is O-( l-bromo-prop-Z-yl) S methyl S phenyl-dithiolphosphoric acid ester of the formula Br-CHz /CH-0 ⁇ fl) CHJS 24 11.
  • Ester according to claim 1 wherein such compound is O-(l-brorno-prop-Z-yl) S methyl S (4'-chlorophenyl)-dithiolphosphoric acid ester of the formula CHaS 12. Ester according to claim 1 wherein such compound is O-(4-bromo-but-2-yl) S methyl S phenyl-dithiolphosphoric acid ester of the formula BrCHzCHz-CHO O i Q CH3-S 13. Ester according to claim 1 wherein such compound is O-( l-bromo-3-chloro-prop-2-yl) ,S methyl S phenyldithiolphosphoric acid ester of the formula CH: S

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US807106A 1968-03-25 1969-03-13 Bromoalkyl-(di)-thiolphosphoric acid esters Expired - Lifetime US3641224A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681768040 DE1768040A1 (de) 1968-03-25 1968-03-25 Verfahren zur Herstellung von Bromalkyl-(di)-thiol-phosphorsaeureestern

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US (1) US3641224A (fr)
JP (1) JPS5114577B1 (fr)
AT (1) AT290554B (fr)
BE (1) BE730354A (fr)
CH (1) CH515935A (fr)
DE (1) DE1768040A1 (fr)
DK (1) DK123271B (fr)
ES (1) ES365217A1 (fr)
FR (1) FR2004696A1 (fr)
GB (1) GB1219713A (fr)
IL (1) IL31611A0 (fr)
NL (1) NL6904578A (fr)

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FR2004696A1 (fr) 1969-11-28
IL31611A0 (en) 1969-04-30
CH515935A (de) 1971-11-30
DE1768040A1 (de) 1971-10-14
GB1219713A (en) 1971-01-20
JPS5114577B1 (fr) 1976-05-11
AT290554B (de) 1971-06-11
DK123271B (da) 1972-06-05
BE730354A (fr) 1969-09-24
NL6904578A (fr) 1969-09-29

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