IL32635A - Dithiolanyl-or dithianyl-phosphoric or-thiophosphoric acid esters and processes for their preparation - Google Patents

Dithiolanyl-or dithianyl-phosphoric or-thiophosphoric acid esters and processes for their preparation

Info

Publication number
IL32635A
IL32635A IL32635A IL3263569A IL32635A IL 32635 A IL32635 A IL 32635A IL 32635 A IL32635 A IL 32635A IL 3263569 A IL3263569 A IL 3263569A IL 32635 A IL32635 A IL 32635A
Authority
IL
Israel
Prior art keywords
formula
compound
reaction
acid ester
active
Prior art date
Application number
IL32635A
Other versions
IL32635A0 (en
Original Assignee
Bayer 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
Priority claimed from DE19681793232 external-priority patent/DE1793232C3/en
Application filed by Bayer Ag filed Critical Bayer Ag
Publication of IL32635A0 publication Critical patent/IL32635A0/en
Publication of IL32635A publication Critical patent/IL32635A/en

Links

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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • 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
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • 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
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
    • 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
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655363—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a six-membered ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (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)

Description

32635/2 an JDH o'a'Vnm n'-naoisiK'n ur Dithiolanyl-or dithiaxiyX-phoaphorie or- hiophosphoric acid esters and processes for their preparation PAR SMPftBRIKSM BAYER AKTOTGESBILSCHAPT C. 30945 The present invention relates to certain new dithiolanyl-or dithianyl-phosphoric or -thiophosphoric acid esters, to a process for their preparation and to their use as insecticides or acaricides.
Published Japanese Patent Application 40-2073/65 describe insecticidally active dithiolanyl or dithianyl-phoephoric acid esters substituted in the heterocyclic ring. However, these compounds containing substituents in the nucleus possess only slight pesticidal potency.
The present invention provides dithiolanyl- or dithianyl-phosphoric or -thiophosphoric acid esters of the formula in which R and R' , which may be the same or different, are alkyl radicals with 1 to 6 carbon atoms, X and Y, which may be the same or different, are oxygen or sulphur, and n is 1 or 2.
The present invention also provides a process for the production of a dithiolanyl- or dithianyl-phosphoric or thiophosphoric acid ester of formula (1) in which (a) a 2-halomethyl-l,4-dithiolane or -dithiane of the formula Hal-CEL CH 2 i <2> RO Y II (3) R'O in the presence of an acid-binding agent or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt, or (b) a 2-hydroxymethyl-l,4-dithiolane or -dithiarie of the constitution is reacted, in the presence of a halogen hydride acceptor, with a O,0^dialkylphosphoric or -thionophos- phoric acid ester halide of the formula Y ^ P-Hal (5) R*0 in which Hal is a halogen atom, or (c) a 2-hydroxymethyl-l,4-dithiolane or -dithaae of formula (4) is first reacted, in the presence of a halogen hydride acceptor, with a 0,O-dialkylphosphorous acid ester halide of the formula RO P-Hal (8) R'O CLn which Hal is a halogen atom) and oxygen or sulphur is added on to the intermediately formed dithiolanyl- or dithianyl-phosphorous acid ester of the formula RO P-0-CH -C¾ OH V without isolation thereof by oxidation or reaction with elemental sulphur or a sulphur-yielding agent.
In formulae (2) to (8), the symbols R, R», T and n of course have the meaning stated for formula (1)· The courses of process variants (a) and (b) are illustrated by the following reaction schemes (a) (b) (7) The reaction according according to variant (c) proceeds according to the following equation RO / P-O-GH -GH CH ' 12 V (11) As there is no need to isolate the intermediate of formula (9) the process may be carried out as a "one-pot" process. The oxidation of the intermediate may for example be effected with hydrogen peroxide.
The dithiolanyl- or ditlSHnyl-phosphoric or -thiophosphoric acid esters according to the invention are clearly defined generally by the above formula (1) .
Preferably, R and R' are alkyl radicals with 1 to 4 carbon atoms, particularly methyl or ethyl, as well as n-propyl, iso-propyl, n-butyl, iso-butyl and sec.-butyl. Hal is preferably a chlorine atom.
The 2-halomethyl- or 2-hydroxymeth l-l,4-dithiolanes or -dithianes of the formula (2) and (4) have not up to now been described in the literature, but are readily accessible according to known methods, even .on an industrial scale. Thus, the hydroxy compounds concerned can be prepared by first converting 2,3-dimercaptopropanol-(l) by means of alkali metal methylate, preferably sodium methylate, in methanolic solution at room temperature, to give the appropriate dimercaptide , sus endin the latter in acetonitrile under reduced ressure inorganic salts have been filtered off and the filtrate has been concentrated, the 2-hydrox methyl-l,4-dithiolane or dithiane (4) is obtained in the form of a non-distillable, water-soluble oil which is, however, pure enough for further reaction. The appropriate halomethyl compounds (2) can be obtained by reaction of 2-hydroxymeth l-l,4-dithiolane or dithiane (4) with halogenating agents, preferably thionyl chloride, in dichloromethane as solvent, at room temperature, washing of the mixture until there is a neutral reaction, and concentration of the former. The compounds (2) are water-insoluble oils which can only be distilled with partial decomposition but which as crude products are sufficiently pure for further reaction.
Besides according to the methods described, 2-chloromethyl-1,4-dithiolane and 2-hydroxymethyl-l,4-dithiolane can also be prepared by reaction of 2,3-dimerca opropanol-(l) with paraformaldehyde in dichloromethane. If, in this reaction, hydrogen chloride gas is used as depolymerisation and condensation agent, the desired 2-chloromethyl compound (2) is obtained in one operation, with simultaneous chlorination of the hydroxyl group; the use of p-toluenesulphonic acid instead of hydrogen chloride gives, on the other hand, the appropriate 2-hydroxymethyl derivative (4).
The 0,0-dialkyl-phosphoric, -phosphorous and -thiophos-phoric acid derivatives of the formulae (3), (5) and (8) are known substances readily accessible according to customary processes.
Preparation of the compounds of the invention takes place preferably in the presence of a solvent (this term includes a and water, are preferably used, but any other, inert solvent is suitable · On the other hand, the reactions according to the equations (7) and (10) are preferably carried out in non-polar solvents, especially aliphatic or aromatic hydrocarbons, for example benzene, toluene, xylene, chlorobenzene, di- and tri-chloromethane, as well as ethers such as diethyl and di-n-butyl ether.
-Furthermore, the reaction is preferably carried out in the presence of an acid acceptor. For this purpose, practically all customary acid-binding agents can be used, such as » alkali metal hydroxides and alkaline earth metal hydroxides, alcoholates and carbonates, for example potassium and sodium hydroxide, methylate or ethylate, sodium and potassium car-bonate, as well as tertiary aliphatic, aromatic or heterocyclic amines. Particularly suitable acid-binding agents are triethylamine, dimethylaniline and pyridine.
The reaction according to equation (7) is carried out with especial advantage in an excess of pyridine as solvent, which here acts simultaneously as halogen hydride acceptor.
The reaction temperatures can be varied within a fairly wide range.
In general, the reaction is carried out at 0 to 100°C, preferably at 30 to 70°C.
The starting materials and the auxiliary materials (acid-binding agents), are, in general, used in equimolar amounts.
In certain cases, however, it may be expedient to use the compounds of the formula (3) in excess.
The working up of the reaction mixture may take place in customary manner by pouring it into water, taking up in The products according .to the invention then remain behind as oily liquids which cannot, even under greatly reduced pressure, be distilled without decomposition, but which can, however, by so-called slight distillation (that is brief heating in a vacuum) be freed from the last volatile components and in this way can be purified.
For establishing their purity and more detailed characterisation, there serves, besides the elementary analysis, the chromatographic and spectroscopic investigation.
As already mentioned, the new products are distinguished by an outstanding insecticidal and acaricidal effectiveness, against eating and sucking insects as well as mites. In this respect, they are far superior to the products of analogous constitution described in the published Japanese Patent Application 40-2073/65 and therefore represent a genuine enrichment of the art.
The active compounds according to the invention which are mentioned in the following list have proved particularly effective: 0, 0-dimethyl-S-( 2-methyl-1, -di hiolanyl-) thionothiolphosphoric acid ester 0, 0-diethyl-S-( 2-methyl-1, -dithiolanyl-) thionothiolphosphoric acid ester 0,0-diethyl-S-( 2-methyl-1, 4-dithiolanyl-) thiolphosphoric acid ester 0, 0-dieth 1-0-( 2-methyl-1 , 4-dithiolanyl-) thionophosphoric acid ester 0,0-diethyl-0-(2-methyl-l,4-dithiolanyl-)phosphoric acid ester 0,0-dimethyl-S-( 2-methy1-1, 4-dithiany1-) thionothiolphosphoric cid este 0,0-diethyl-S-( 2-methyl-l,4-dlthianyl-)thiolphosphoric acid ester 0,0-diethy1-0-(2-methyl-l,4-dithianyl-)thionophosphoric acid ester 0,0-diethyl-0-(2-methyl-l,4-dithianyl-)phosphoric acid ester The compounds of the invention possess only a slight phytotoxicit . The pesticidal effect sets in rapidly and is long-lasting. For this reason, the compounds of the invention can be used with success in crop protection and the protection of stored products as well as in the hygiene field for the control of noxious sucking and eating insects and Diptera as well as against mites (Acarina) · To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalo-siphum padi.), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii) , the currant gall aphid (Cryptomyzus korschelti), the mealy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidio-tus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus) ; thrips (Thysanoptera) , such as Hercinothrips femoralis, and bugs, for example the beet bug (Pi'esma quadrata) , the cotton bug (Dysdercus intermedius) , the bed bug (Gimex lectularius) , the assassin bug (Rhodnius prolixus) and Chagas* bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus. nsects bove ll there shou V (Lymantria dispar), the brown-rtail moth (Euproctis chrysorr-hoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata) , the green oak tortrix moth (Tortrix viridana), the fall armyworm (laphygma frugiper-da) and cotton worm (Prodenia litura) , the ermine moth (Hypono-meuta padella) , the Mediterranean flour moth (Ephestia II uhniella) and greater wax moth (Galleria mellonella) .
Also to be classed with the biting insects are beetles (Goleoptera) , for example the granary weevil (Sitophilus granarius = Galandra granaria) , the Colorado beetle (Leptino-tarsa deceralineata) , the dock beetle (Gastrophysa viridula) , the mustard beetle (Phaedon cochleariae) , the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus)., the bean weevil (Bruchidius .= Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogo-derma granarium) , the flour beetle (Tribolium castaneum) , the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum) , the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzae-philus surinamensis) , but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica) , American cockroach (Periplaneta americana) , Madeira cockroach (Laucophaea or Rhyparobia madeirae), Oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia such as ants, for example the garden ant (Laslus niger) · The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster) , the Mediterranean fruit fly (Ceratitis capitata) , the house fly (Musca domestica) , the little house fly (Fannia canicularis) , the black blow fly (Phormia aegina) and bluebottle fly (Calliphora erythrocep-hala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).
With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius = Tetranychus althaeae or Tetrany-chus urticae) and the European red mite (Paratetranychus pilosus = Panonychus ulmi), blister mites, for example the currant blister mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata) .
The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. as mineral oil fractions, alcohols, such as methanol or butanol, or strongly polar solvents, such as dimethyl formamide or dimethyl sulphoxide, as well as water.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc or chalk, or ground synthetic minerals, such as highly-dispersed silicic acid or silicates.
Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpoly l col ethers, alkyl sulphonates and aryl sul-phonates; and preferred examples of dispersing agents include lignin, sulphite waste liquors and methyl cellulose.
The active compounds according to the invention may be present in the formulations in admixture with other active compounds .
The compositions contain, in general, from 0.1 to 95, preferably 0.5 to 90, per cent by weight of active compound.
For actual application, the concentration of active com-pound can be varied within a fairly wide range. In general, concentrations of 0.00001^ to 20°t preferably of O.Ol* to by weight are used.
The active compounds may be used as such or in the form of their formulations or of the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, spray powders, pastes, soluble powders, dusting agents and granulates. Application may take place in the usual manner, for example by watering, spraying, atomising, fumigation, scattering, dusting, compound according to the invention in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The invention also provides a method of combating insects or acarids which comprises applying to the insects or acarids or an insect or acarid habitat a compound according to the invention alone or in the form of a composition containing as active ingredient a compound according to the invention in admixture with a solid or liquid diluent or carrier.
The invention also provides crops protected from damage by insects or acarids by being grown in areas in which, immediately prior to and/or during the time of the growing, a compound according to the invention was applied alone or in admixture with a solid or liquid diluent or carrier„ The outstanding insecticidal and acaricidal effectiveness of the compounds of the invention can be seen from the following application Examples A to C.
Example A Phaedon larvae test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alk laryl pol lycol ether To produce a suitable preparation of active compound, 1 part by weight of the active substance concerned is mixed with the stated amount of the respective solvent containing the above-mentioned amount of emulsifier, and the concentrate thus obtained is diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) are sprayed with this preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochleariae) .
After the periods of time stated in the following Table, the degree of destruction of the pests is determined and expressed as a percentage: 100 means that all, and 0$ means that none, of the beetle larvae are killed.
The active compounds tested, the concentrations used of the active compounds, the times of evaluation and the experimental results obtained can be seen from Table A: Table A (Phaedon larvae test) Active compound Concentration Degree of (constitution) of active destruction compound in in i<> after 3 days S (12) (02H50)2P-0-CH2-CH- 0.1 100 0.01 0 (Comparative compound known from Japanese Patent Application No.2073/65) S II (CE-.0)2P-S-CH2 S II (G2H50)2P-S-CH2- (15) (09Hc0) P-S-CH -CH CH 0.1 100 0.01 100 s ^ s ^CH^ s tl (16) (C HK0) P-0-CH -CH CH 0.1 100 ά 5 d ύ » » ά n 0.n01 100 s . s 3^ (17) (CH,0) P-S-CH -CH ' CE- 0.1 100 Example B Myzus test (contact action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.
Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction is determined as a percentage: 10C$ means that all the aphids are killed whereas Oo means that none of the aphids are killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from Table B.
Table B (Myzus test) Active compound Concentration Degree of ( constitution) of active destruction compound in in i after 24 hours S II (Comparative compound known from Japanese Patent Application No. 2073/65) \ CH (12) 0.1 60 0.01 0 (Comparative compound known from Japanese Patent Application No. 2073/65) S II (CH50)2P-S-CH2 S (13) 0.1 100 0.01 98 lable B (continued) (M zus test) Active compound Concentration Degree of (constitution) of active destruction compound in in < after 24 hours S II (C2H50)2P-S-CH2-CH- -CH 3 s 0.1 100 0.01 100 CH2 (14) 0.001 90 (OgHjO s ft (C2H50) 2P-0-CH2-CH CH2 I t (20) 0.1 100 cm 0.01 100 Table B (continued) Concentration Degree of of active destruction compound in in o after 24 hours 0 II s (C2H50)2P-S-CH2-CH 0.1 100 CH CH. 0.01 9.9 0.001 80 (18) (22) 0 II / \ (C2H50)2P-0-CH2-CH CH t « 0.1 100 0.01 75 / (23) t Example C Tetranychus test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alk laryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris), which have a height of approximately 10-30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus telarius) in all stages of development.
After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 10C$> means that all the spider mites are killed whereas 0$ means that none of the spider mites are killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from Table C.
Table C (Tetranychus teet) Active compound Concentration Degree of des- (constitution) of active truction in $£ compound in after 48 hours S It (C^O) 2P-S-CH2-CH CH2 S 3 XnW^ (19) 0.1 (Comparative compound known from Japanese Patent Application No. 2073/65) S It (C^O) 2P-0-CH2-CH CH2 S S (12) CH (Comparative compound known from Japanese Patent Application No. 2073/65) (C2H50) (C^O) 0 tl (C2H50)2?-0-CH2-CH CH2 (20) 0 1 85 t t The process of the invention is illustrated by the following process Examples.
Example 1 S It (CH30) 2P-S-CH2-CH -CH2 (13) S S 77.5 g 2-chloromethyl-l,4-dithiolane are added at 40°C, with stirring, to a solution of 90.0 g sodium 0,0-dimethyl-thionothiolphosphate in 600 ml acetonitrile. The mixture is allowed to continue reacting overnight at 40°C; the reaction mixture is then poured into water, the separated oil is taken up in benzene, the organic phase is washed neutral with water, dried over anhydrous sodium sulphate, the drying agent is filtered off, the filtrate is concentrated, and the residue is slightly distilled. In this way, the 0,0-dimethyl-S-(2-methyl-l,4-dithiolanyl)-thionothiolphosphoric acid ester is obtained as yellow oil with the refractive index n^1 = 1.6070. The yield is 107» 2 g (77.6$ of the theory).
Analysis; p Calculated for CgH^O^S^ (molecular weight 276.5)*. 11.20 Pound: 11.07 1* Example 2 (CHjO g The compound is prepared in manner analogous with that described in Example 1 from sodium 0,0-dimethylthionothiolphos-phate and 2-chloromethyl-l,4-dithiane at 60 to 70°C. The 0,0- refractive index =.1.6081. The yield is 77·2$ of the .theory.
Analysis: P Calctilated for C ¾502 S4 (molecular weight 290.5): 10,68$ Pound: 10.24$ Example 3 S II 65 g sodium O,0-diethylthionothiolphosphate are dissolved in 400 ml acetonitrile. 38.8 g 2-chloromethyl-l,4-dithiolane are added to this solution at 40°C, with stirring. The reaction mixture is stirred overnight at 40°C; it is then poured into water, the separated oil is taken up in benzene, the organic phase is washed with water until there is a neutral reaction, it is dried over anhydrous sodium sulphate, the mixture is filtered and the filtrate is largely concentrated and the residue is slightly distilled. The 0,0-diethyl-S- (2-methyl-l,4-dit olanyl)-thionothiolphosphoric acid ester is obtained as brown oil with the refractive index n 21j = 1.5870. The yield is 58.6 g (77$ of the theory).
Analysis; p Calculated for caH1702PS4 (molecular weight 30.45): 10.18$ Pound: 9.73$ Example 4 \ The product is obtained in manner analogous with that in Example 3 from sodium 0,0-diethylthionothiolphosphate and 2-chloromethyl-l,4-dithiane at 50°C. The 0,0-diethyl-S-(2-meth l-l,4-dithianyl)-thionothiolphosphoric acid ester is obtained in the form of a yellow oil with the refractive index n2J = 1.5825. The yield is 98.4 of the theory.
Analysis : P Calculated for C9Hig02PS4 (molecular weight 318.5): 9.73$ Found: 9.20$ Example ^ 0 (C2H50) 2P-S-CH2 100 g ammonium 0,0-diethylthiolphosphate are dissolved in 500 ml acetonitrile. 77.5 g 2-chloromethyl-l,4-dithiolane are added to the solution at 40°G, with stirring. The reaction mixture is subsequently stirred overnight at room temperature; it is then poured into water, the separated oil is taken up in benzene, the organic phase is washed with water until it reacts neutral, the benzene solution is dried over anhydrous sodium sulphate, the mixture is filtered, the filtrate is concentrated and the residue is slightly distilled. The 0,0-diethyl- S-(2-methyl-l,4-dithiolanyl)-thiolphosphoric acid ester is 21 obtained as brown oil with the refractive index n = 1.5528. The yield is 125.6 g (87.2$ of the theory).
Analysis : P Calculated for (molecular weight 288.4): 10.76$ Found: 10.32$ Example 6 /3\ (C2H50)2P-S-CH2-CH CH2 t t (18) CH CH, 2 "2 \ / s In manner analogous with Example 5» from ammonium 0,0-diethylthiolphosphate and 2-chloromethyl-l, 4-dithiane at 60 to 70°c there is obtained the 0,0-dieth l-S-(2-methyl-l,4-dithianyl)-thiolphosphoric acid ester as brown oil with the refractive index n20) * 1.5460. The yield is 90.5# of the theory.
Analysis: P Calculated for CqH,Q0,PS, (molecular weight 302.4): 10.25 i Found: 10.30 io Example 7 0 It 86 g 0,0-diethylphosphoric acid ester chloride are added at 30 to 40°C, with stirring, to a solution of 68.1 g 2-hydroxymethyl-l,4-dithiolane in 400 ml of anhydrous pyridine; stirring of the mixture is continued overnight at room temperature, the excess pyridine is then largely distilled off under reduced pressure, the residue is taken up in benzene, the benzene solution is washed with water until there is a neutral reac-tion, it is dried over anhydrous sodium sulphate, the mixture is filtered, the filtrate is concentrated and the residue is slightly distilled. In this way, 109.3 g (80$ of the theory) of 0,0-diethyl-0-(2-methyl-l,4-dithiolanyl)-phosphoric acid ester are obtained in the form of an orange-coloured oil with the refrac-tive index n^0,5 = 1.5145.
Bxample 8 GH CH S The compound is prepared in manner analogous with Example 7 from 2-hydroxymeth l-l,4-dithiane, 0,0-diethylphosphoric acid ester chloride and pyridine at 30°C. The 0,0-diethyl-0-(2-methy1-1,4-dithianyl)-phosphoric acid ester is obtained as brown oil with the refractive index n 20 = 1.5090. The yield is 85 of the theory.
Analysis : P Calculated for ^Ηχ^ϊ^ (molecular weight 286.4): 10,825* Found: 10.77$ Example 9 S (C2H50) 2P-0-CH2-CH CH2 (16) s . s 1Q*5 g 0,0-diethylphosphorous acid ester chloride are added at 30 to 40°C, with stirring and nitrogen atmosphere, to a solution of 68.1 g 2-hydroxymethyl-l,4-dithiolane and 40 g of anhydrous pyridine in 400 ml dichloromethane. The mixture is allowed to continue reacting for 3 hours at 30 to 40°C, and 16 g sulphur powder are then added to the reaction mixture. The temperature of the latter is meanwhile kept likewise to between 30 and 40°C. Stirring of the mixture is continued overnight at room temperature; the salt-like precipitate is then filtered off with suction, the filtrate is washed with water until there is a neutral reaction, it is dried over anhydrous sodium sulphate, filtered, the filtrate is concen methyl-l,4^ithiolan l)-thionophosphoric acid ester is obtained as yellow oil with the refractive index n£ a 1,5665· The yield is 103 g (71.5$ of the theory).
Analysis; P Calculated for (molecular weight 288.4): 10.7 $ Pound: 10.20$ Example 10 CR% CH, \ S The product is prepared in manner analogous with Example 9 from 2-hydroxymethyl-l,4-dithiane, 0,0-dieth lphosphorous acid ester chloride, pyridine and sulphur at 30 to 40°C. The 0, 0-diethy1-0-( 2-me hy1-1, 4-dithianyl)-1hionophosphoric acid ester is obtained in the form of a light-brown oil with the refractive index n2^*5 = 1.5453. The yield is 76.5?° of the theory.
Analysisι p Calculated for (molecular weight 302.4): 10.26$ Found: 10.40$ The 2-hydroxymethyl- or 2-halomethy1-1, 4-dithiolanes or -dithianes required as starting materials for the preparation of the compounds according to the invention are accessible for example as follows: (a) 2 moles of sodium methylate dissolved in methanol are added to a solution of 124 g (1 mole) of 2, 3-dimercaptopropanol reduced pressure, benzene to be added afresh in each case.
During this time, a temperature of 50°G should not be exceededβ The dimercaptide is suspended in 800 ml acetonitrile and 174 g dibromomethane are added to the reaction mixture at 20 to 30°C, with stirring.. The latter is further stirred overnight; the precipitated sodium bromide is subsequently filtered off, the filtrate is concentrated, and the substance is freed from newly precipitated salt. After slight distillation of the residue, 2-hydroxymethy1-1, -dithiolane obtained as yellow, water-soluble oil with the refractive index n2^ = 1.6098.
The yield is 75.3 g {55· of the theory).
Analysis: Q ^ Calculated for C4HQ0S2 (molecular weight 136.2): 35.25 5.88$ Found: 35.67$ 5.85 (b) H0-CH-CH CH S S (24) \ / 74*4 g 2,3-dimercaptopropanol-l, 18 g paraformaldehyde and 2 g p-toluenesulphonic acid are stirred in 300 ml dichloro-methane at 40°G for 48 hours under nitrogen atmosphere. After completion of the reaction, the reaction mixture is diluted with 800 ml dichlorome hane, the solution is decanted from insoluble impurities, dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure at 40 to 50°C. After slight distillation of the residue, 2-hydroxymethyl-l,4-di-thiolane reraains behind as pale, turbid oil with the refractive index xf 2 D = 1.6027. The yield is 13.3 g.
-CH CH.
I I c (25) CH CH, S The compound is prepared in manner analogous with that described under (a) from 2,3-dimercaptopropanol-(l) , sodium methylate and dibromoethane at 25 to 30°C. 2-hydroxymethyl-1,4-dithiane is obtained in the form of a yellow, water-soluble oil with the refractive index 2^*5 = 1,5885. The yield is 91.9# of the theory.
Analysis: C H Calculated for G5H10OS2 (molecular weight 150.3): 40.01# 6.67$ Pound: 40.53$ 6.85$ (d) C1-CH-CH GH 102 g 2-hydroxymethyl-l,4-dithiolane are dissolved in 350 ml dichloromethane. 89.3 g thionyl chloride are added to this solution at 15°C, with stirring. The mixture is allowed to continue reacting for 2 hours at room temperature, washed with water until there is a neutral reaction, the solution is dried over anhydrous sodium sulphate, the mixture is filtered, the filtrate is concentrated and the residue is slightly distilled. 2-chloromethyl-l,4-dithiolane is obtained as brown oil with the refractive index n^5 = 1,6024. The yield is 83.8 g (72.6$ of the theory).
Analysis : Calculated for C^H^CI^ (molecular weight 154.9): 22.90$ Found: 22.21 (e) C1-CH~- 74.4 g 2,3-dimercaptopropanol-l and 18 g paraformaldehyde are stirred in 200 cc dichloromethane for 8 hours at 0°C, with the introduction; it is then washed with water until there is a neutral reaction, the organic phase is dried over anhydrous sodium sulphate, the mixture is filtered, the filtrate is concentrated and the residue is slightly distilled. 2-chloro-methyl-l,4-dithiolane is obtained as light-brown oil with the refractive index n2^ = 1.6013. The yield is 70.7 g (76.2# The product is prepared as described under (d) from 2-hydroxymethyl-l,4-dithiane and thionyl chloride at 15°C,, 2-chloromethyl-l,4-dithiane is obtained as yellow oil with the refractive index ^5 = 1.5917. The yield is 85.45» of the theory.
Analysis: C Calculated for C5HgClS2 (molecular weight 168.5) ί '21.02$ Pound: 20.57$

Claims (5)

1. I What we claim is:- 1. Dithiolanyl- or dithianyl-phosphoric or -thiophosphoric acid esters of the general formula RO Y in which R and R', which may be the same or different , are alkyl radicals with, in each case, 1 to 6 carbon atoms, X and Y, which may be the same or different, are oxygen or sulphur, and n is 1 or 2.
2. Compounds according to claim 1 in which R and R' have 1 to 4 carbon atoms.
3. The compound of the formula S S It ( C2H50) 2P-S-CH2- 5. The compound of the formula 0 (C2H50)2P-S-CH2-CH CH2 . S (15) CH2^ » The compound of the formula S I» ( C2H50) 2P-0-CH2-CH CH2 S^CH2"S The compound of the formula ( CH^O ) 2 CH2 CH CH S The compound of the formula 0 S CH CH, 9. The compound of the formula 0 It ( C2H50 ) 2P-0-CH2-CH CH2 (20) s s 10. The compound of the formula S S \ / S 11. The compound of the formula S S / \ ( C2H50) P-0-CH2-CH CH2 (22) \ / 2 S 12. The compound of the formula ° s (CjH-O^-O-OH^OH " ¾ (25) OH, OH, 13. A process for the production of a compound according to any of claims 1 - 12 in which (a) a 2-halomethyl-l,4-dithiolane or -dithiane of the formula Hal-CH -CH CH 2 , 2 (2) is reacted with a O,0-dialkylthiol-or -thionothiol- phosphoric acid of the formula RO (3) R'O in the presence of an acid-binding agent or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt, 2-hydroxymethyl-l,4-dithiolane or -dithiane of the constitution is reacted, in the presence of a halogen hydride acceptor, with a Ο,Ο-dialkylphosphoric or -thiono- phosphoric acid ester halide of the formula in which Hal is a halogen atom, or (c) a 2-hydroxymethyl-l,4-dithiolane or -dithdane of formula (4) is first reacted, in the presence of a halogen hydride acceptor, with a 0,0-dialkylphosphorous acid ester halide of the formula RO P-Hal (8) R'0/ (in which Hal is a halogen atom) and oxygen or sulphur is added on to the intermediately formed dithiolanyl- or dithianyl-phosphorous acid ester of the formula RO P-0-CH -CH CH R'O s <0W without isolation thereof by oxidation or reaction with elemental sulphur or a sulphur-yielding agent. 1 . A process according to claim 13 (a) in which the reaction is carried out in the presence of a polar solvent. 15· A process according to claim 13 (b) or (c) in which the reaction is carried out in the presence of a non-polar solvent. 16. A process according to claim 13 (b) in which the reaction is carried out in an excess of pyridine as solvent and halogen hydride acceptor. 17. A process according to any of claims 13 - 16 in which the reaction is carried out at 0 to 100°G. 18. A process according to claim 17 in which the reaction is carried out at 30 to 70°G. 19· A process for the production of a compound according Examples 1 - 10. 20. Compounds according to claim 1 whenever prepared by a process according to any of claims 13 - 19. 21. An insecticidal or acaricidal composition containing as active ingredient a compound according to any of claims 1 - 12 or 20 in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. 22. A composition according to claim 21 containing from 0.1 to 9$ of the active compound by weight. 23· A method of combating insects or acarids which comprises applying to the insects or acarids or an insect or acarid habitat a compound according to any of claims 1 - 12 or 21 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 - 12 or 21 in admixture with a solid or liquid diluent or carrier. 4 2
4. A method according to claim 23 in which a composition is used containing from 0.01 to of the active compound, by weight. 2
5. Crops protected from damage by insects or acarids by being grown in areas in which, immediately prior to and/or during the time of the growing, a compound according to any of claims 1 - 12 or 21 was applied alone or in admixture with a solid or liquid diluent or carrier. For the Applicants DR. REiHHOlD COKN AMD PARTNERS
IL32635A 1968-08-20 1969-07-16 Dithiolanyl-or dithianyl-phosphoric or-thiophosphoric acid esters and processes for their preparation IL32635A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681793232 DE1793232C3 (en) 1968-08-20 Dithiolanyl or. Dithianyl phosphorus or thiophosphoric acid esters, process for their preparation and agents containing them

Publications (2)

Publication Number Publication Date
IL32635A0 IL32635A0 (en) 1969-09-25
IL32635A true IL32635A (en) 1972-07-26

Family

ID=5707626

Family Applications (1)

Application Number Title Priority Date Filing Date
IL32635A IL32635A (en) 1968-08-20 1969-07-16 Dithiolanyl-or dithianyl-phosphoric or-thiophosphoric acid esters and processes for their preparation

Country Status (7)

Country Link
BE (1) BE737721A (en)
CH (1) CH525243A (en)
ES (1) ES370641A1 (en)
FR (1) FR2016018A1 (en)
GB (1) GB1273770A (en)
IL (1) IL32635A (en)
NL (1) NL6912607A (en)

Also Published As

Publication number Publication date
ES370641A1 (en) 1971-05-01
DE1793232A1 (en) 1971-07-08
BE737721A (en) 1970-02-20
DE1793232B2 (en) 1976-04-01
NL6912607A (en) 1970-02-24
CH525243A (en) 1972-07-15
FR2016018A1 (en) 1970-04-30
IL32635A0 (en) 1969-09-25
GB1273770A (en) 1972-05-10

Similar Documents

Publication Publication Date Title
US3801679A (en) N-(dimethylaminomethylidene)thiol-(thiono)-phosphoric acid ester imides s
PL93687B1 (en)
US3697518A (en) Phosphorus acid esters of 3-hydroxy-benzo-1,2,4-triazine -1-n-oxide
US3687963A (en) Thiazolo-(thiono)phosphoric (phosphonic) acid esters
IL46687A (en) N-sulphenylated oxime-carbamates their preparation and insecticidal acaricidal and nematicidal compositions containing them
IL34985A (en) Triazolothiazole esters of phosphoric,phosphonic and phosphinic acids and of the corresponding thiono acids,their preparation and their use as insecticides and acaricides
IL29504A (en) 3,5,6-trichloropyridyl-2-thionophosphonic acid esters
US3547920A (en) Phosphoric,phosphonic,thionophosphoric and thionophosphonic acid esters
US3641223A (en) S-(2-chloro-2-bromo-ethyl-(di)thio-phosphoric and phosphonic acid esters
US3763285A (en) 1-phenyl-2-cyanovinyl(thio)-phosphoric or-phosphonic acid esters
IL31640A (en) Thionophosphonic acid esters,their preparation and use for pest control
US3740427A (en) Insecticidally active lower alkyl-substituted 2 - chloro - 2-thiono-1,3,2-dioxaphosphorinane
US3706820A (en) S-alkylmercaptomethylthiophosphoric or phosphonic acid esters
US3773766A (en) Cinnolinyl(thiono)phosphoric(phosphonic)acid esters and ester amides
US3828063A (en) Benzisoxazolo(thiono)phosphoric(phosphonic)acid esters
IL32635A (en) Dithiolanyl-or dithianyl-phosphoric or-thiophosphoric acid esters and processes for their preparation
IL34101A (en) O-alkyl-s-(n,n-dialkylaminocarbamyl)-methyl-n-monoalkylamido-thiolphosphoric and thionothiolphosphoric acid esters,their preparation and use as insecticides and acaricides
IL37223A (en) O-pyrazolopyrimidine-(thiono)-phosphoric and phosphonic acid esters,their preparation and their use as insecticides and acaricides
US3752871A (en) O - alkyl - n-monoalkyl-s-(n&#39;-acyl-carbamylmethyl) - thionothiolphosphoric acid ester amides
US3700686A (en) O-alkyl-o-pyrazolyl-phosphoric, phosphonic, thionophosphoric and thionophosphonic acid esters
IL33731A (en) O,o-dialkyl-s-(1,2,2-trichloroethyl)-thionothiolphosphoric acid esters and o-alkyl-s-(1,2,2-trichloroethyl)-alkane-thionothiolphosphonic acid esters,their preparation and use as insecticides
IL28249A (en) Thiophosphoric,thiophosphonic,dithiophosphoric and dithiophosphonic acid esters of 1,2,4-triazolinethione-(3) derivatives
IL32650A (en) Thionophosphonic acid esters,their preparation and use for combatting insects
IL47240A (en) O-triazolyl-(thiono)-phosphoric(phosphonic phosphinic) acid esters and ester-amides their preparation and their use as insecticides acaricides or nematicides
US3819644A (en) Benzisoxazolo(thiono)phosphoric(phosphonic)acid esters