N-(N{40 substituted-aminomethylidene)-O,S-dialkylthiol-phosphoric acid diester-imides
United States Patent 1 Hoffmann et al.  
 [4 1 Apr. 29, 1975 Ingeborg Hammann, Cologne, both of Germany [73] Assignee: Bayer Aktiengesellschaft,  
 Leverkusen, Germany 221 Filed: Mar. 5, 1973 211 Appl. No.: 338,010  
 [30] Foreign Application Priority Data Mar. 9 1972 Germany 2211338 [52] US. Cl. 260/944; 260/950; 260/968;  
  424/200; 424/211; 424/220 [51] Int. Cl C07i 9/24; AOln 9/36 [58] Field of Search 260/944 [56] References Cited UNITED STATES PATENTS 3,281,321 10/1966 Malz et a1. 260/944 3.801.679 4/1974 Hoffmann et al 260/945 Primary ExaminerAnton H. Sutto Attorney, Agent, or FirmBurgess, Dinklage &amp; Sprung [57] ABSTRACT N-(N&#39;-substituted-aminomethylidene)-O,S-dialkylthiolphosphoric acid diester-imides of the formula /P-N=OH-NER&#34; (I) R&#39;O in which R and R each independently is lower alkyl, and R&#34; is alkyl or alkenyl with up to 6 carbon atoms,  
 cycloalkyl with 4 to 6 carbon atoms or a nitrogen-containing heterocyclic structure,  
 which possess insecticidal and acaricidal properties.  
 &#39; 7 Claims, No Drawings N-(N &#39;SUBSTlTUTED-AMINOMETl-lYLllDENE )-O,S-  
  DIALKYLTHIOL-PHOSPHORIC ACID DlESTER-IMIDES The present invention relates to and has for its objects the provision of particular new N-(N&#39;- 5 substitutedaminomethylidene)-O,S-dialkylthiolphosphoric acid diester-imides which possess insecticidal and acaricidal properties, active compositions in the form of mixtures of such compounds with solid and NH R&#34; (lll) in which R&#34; has the abovementioned meaning. lf N-(O,S-dimethylthiol-phosphoryl)-iminoformic acid ethyl ester and isopropylamine are used as the starting substances, the course of the reaction can be represented by the following formula scheme:  
 (Ila) of the general formula P-N=CH-NHR&#34; R&#39;O in which R and R each independently is lower alkyl, and R&#34; is alkyl or alkenyl with up to 6 carbon atoms,  
 cycloalkyl with 4 to 6 carbon atoms or a nitrogen- 40 containing heterocyclic structure.  
  Preferably R and R represent straight-chain or branched alkyl with l to 4, especially 1 to 3 carbon atoms, and R represents straight-chain or branched lower alkyl with 1 to 4 carbon atoms, alkenyl with 3 or 4 carbon atoms, cyclohexyl or the pyridine radical.  
  Surprisingly, the N-(aminomethylidene)-thiolphosphoric acid ester imides according to the invention possess a substantially better insecticidal and acaricidal action than the previously known O.S-dialkyl-N-acety1- thiol phosphoric acid ester amides of analogous structure and same type of action. The substances according to the invention thus represent a genuine enrichment of the art.  
  The invention also provides a process for the production ofa N-(amino-methylidene)-thiol-phosphoric acid ester imide of the formula (I) in which a phosphorylated iminoformic acid alkyl ester of the general formula The following may be mentioned as examples of amines of formula (III): methylamine, ethylamine, npropylamine, isopropylamine, n-butylamine, sec.-, tert.- and iso-butylamine, allylamine, butenylamine, cyclohexylamine and 2-aminopyridine.  
  The phosphorylated iminoformic acid alkyl esters of formula (II) are new and may be prepared in accordance with a new process from the O,S-dialkyl-thiolphosphoric acid ester amides known from the literature, viz, US. Pat. No. 3,309,266, and orthoformic acid alkyl esters. Their preparation is the subject of Application Ser. No. 240,282, filed Mar. 31, 1972, now pending. As examples of phosphorylated iminoformic acid alkyl esters of formula (11) there may be mentioned: N- (O,S-dimethyland N-(O,S-diethyland N-(O,S- dipropylthiolphosphoryl)-iminoformic acid ethyl esters.  
  The process according to the invention can be carried out in the presence or absence of solvents or diluents. As such, practically all inert organic solvents can be used. These include above all aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene. toluene, xylene, benzine, chlorobenzene, methylene chloride, chloroform or carbon tetrachloride; ethers, such as diethyl ether, dibutyl ether or dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone; and nitriles, sich as acetonitrile or .propionitrile.  
  The reaction temperature can be varied over a wide range. in general the reaction is carried out at about 0 to C, preferably about 10 to 25C.  
 The reaction is generally carried out at normal pressure.  
  ln carrying out the process, the components may be brought together, with stirring, in the presence or absence of one of the above-mentioned solvents or diluents; thereafter the mixture may be stirred for several hours at the indicated temperatures and subsequently the easily volatile constituents, such as solvents, which may still be present, may be distilled off.  
  The substances according to the invention are in most cases obtained in the form of colorless to slightly colored oils which cannot be distilled without decomposition but can be freed of the last volatile constituents, and in this way purified, by so-called slight distillation,&#34; that is prolonged heating under reduced pressure to a moderately elevated temperature. The refractive index is especially useful for their characterization. If they are obtained in a crystalline form, they are characterized by the melting point.  
 As has already been mentioned, the new N- -(aminomethylidene)-thiol-phosphoric acid ester imides are distinguished by excellent insecticidal and acaricidal activity towards plant pests. Herein, they possess a good action both against sucking and against biting insects and mites (Acarina), coupled with low phytotoxicity.  
  To the sucking insects there belong, in the main. aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Dvralis falme), the bird cherry aphid (Rlwpalosiphum padi), the pea aphid (Macrosiplzum pisi) and the potato aphid (Mac&#39;rosiplzum solanzfolii), the currant gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerusi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium liesperidum) as well as the grape mealybug (pseudocuccus maritimus); thrips (Thysanoptera), such as Herc-inothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilubatus and Neplwtettix bipunctalus.  
  In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidop- Iera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorclwea) and tent caterpillar (Malacosoma neuslria); further, the cabbage moth (Mamestra brassicue) 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 (Laplzygma frugiperda) and cotton worm (Prodenia Iitura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kulmiella) and greater wax moth (Galleria mellonella).  
  Also to be classed with the biting insects are beetles (Coleoprera), for example the granary weevil (Situphilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineuta), the dock beetle (Gasrropliysa viridulu), the mustard beetle (P/iaedon coclzleariae), the blossom beetle (Meligetlies aeneus), the raspberry bettle (Byturus tomentosus), the bean weevil (Brucliidius Acanthoscelides oblecrus), the leather beetle (Dermestes frischi), the khapra beetle (Trogvderma granarium), the flour beetle (Tribolium caslaneum), the northern corn billbug (Calundra or Situplu&#39;lus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain bettle (Oryzaep/zilus Surinamensis), and also species living in the soil, for example wireworms (Agrioles spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplanem americana), Madeira cockroach (Leuocoplzaea or Rhyparobia maderae), oriental cockroach (Blulla orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Hensclmuledeniaflexirilla; further, Ortlwprera, for example the house cricket (Gryllus domestic-us); termites such as the eastern subterranean termite (Reticulilermesflaripes) and Hymanoplera such as ants, for example the garden ant (Lasius niger).  
  The Diptera comprise essentially the flies, such as the vinegar fly (Drosop/zila melanogasrer), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Must-a domestic-u), the little house fly (Fannia caniculuris), the black blow fly (Plwrmia regina) and bluebottle fly (Calliplzora erythrocepliala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypli), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles sreplzensi).  
  With the mites (Acari) there are classed, in particular, the spider mites (Tetranyc/zidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paraletranychus pilosus Panonychus ulmi), gall mites, for examples the blackcurrant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus larus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornitlzodorus moubala).  
  The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide for mulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, 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 pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes. etc.), halogenated, especially chlorinated. aromatic hydrocarbons (e.g. chlorobenzenes, etc.) cycloalkanes (e.g. cyclohexane, etc.) paraffms (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.) alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone. cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: 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 sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, 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 insecticides and acaricides, or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, 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.  
  As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier 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 0.000 ll0%, preferably 0.0l-1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as.( l) a dispersible inert finely divided carrier 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 surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.000l95%, 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 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to&#39; at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g/hectare, preferably 40 to 600 g/hectare, 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 by weight of the active compound or even the active substance alone, e.g. about 20-100% by weight of the active compound.  
  Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrustation, and the like.  
  It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aformentioned concentration ranges.  
  The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by  
  the following examples:  
 EXAMPLE 1 Phaedon larvae test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To manufacture an appropriate preparation of active compound, 1 part by weight of active compound was mixed with the indicated amount of solvent which contained the indicated amount of emulsifier, and the concentrate was diluted with water to the desired concentration.  
  Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochleariae).  
  After the indicated times, the degree of destruction was determined as a percentage. 100% means that all beetle larvae were killed. 0% means that no beetle larvae were killed.  
  The active compounds, the concentrations of the active compounds, the times of evaluation and the results can be &#39;seen from the following Table 1.  
 Table 1 (Insects harmful to plants) Phaedon larvae test Active compounds Active compound Degree of concentration in destruction by weight in after 3 days -NH-C-CH CH 3 0.01 0  
 :labJm L -Continued Phaed on larvae to st Active compound s Active compound concentration in 7; by weight Degree or (known) (B) 5 )P-N-CH-NH-C -n CH 0 0 1 3 CH S -N=CH-NH-CH(CH3)2 3 -N=CH-NH-C -cH(CH E 2 3 2 h 0.01  
  CHBS/P N-CH NH C(CH3)5 04 I 3 (4) 8 81 cn s EXAMPLE 2 Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.  
 Active compounds Table 2 Myzus teat Degree of due- Letive eomp traction in f conoontrat ion in 96 by weight after- 1 m.  
 c H O 9 9 0.01 20 2 5 0.001 0 (EH 3 (known) (3) O. 01 100 CH 0.001 35 0 8 P-NaCH-NH-C CH 3 EXAMPLE 3 Rhopalosiphum test (systemic action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.  
  Oat plants (Arena sativa) which had been strongly infested with the bird cherry aphid (Rhopalosiphum padi) were watered with the preparation of the active compound so that the preparation penetrated into the soil without wetting the leaves of the oat plants. The active compound was taken up by the oat plants from the soil and thus reached the infested leaves.  
  After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the aphids were killed whereas 0% means that none of the aphids were killed.  
  The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3.  
 Table 3 (Insects harmful to plants) EXAMPLE 4 Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained was diluted with water to the desired concentration.  
  Bean plants (Phaseolus vulgaris), which had a height of approximately 10-30 cm, were sprayed with the preparation of the active compound until dripping wet. These bean plants were heavily infested with the twospotted spider mite (Tetranychus urlicae) in all stages of development.  
  After the specified periods of time, the effectiveness of the preparation of active compound was determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites were killed whereas 0% means that none of the spider mites were killed.  
 Rhopalosiphum test (systemic action) Active compounds Active compound concentration in Degree of destruction in i 9% by weight after 4 days 16H 0 I o 01 100 3 )r un-c-cu 0.001 0 cn s (known) (A) 0 on o 0.01 100 3 P-N=CH-NH-CH CH=cH 0.001 8 011 s 9 on o 3 a 0.01 100 CH N CH(cH3)2 0.001 100 CH k 0 01 100 3 =-u=cH--ua -c(cs 0:001 80 cn s 9 o 01 0 cu 10 p...N=CH-NH\l 0.001 70 cn s 1 1 12 The active compounds, the concentrations of the acdistilled off and the residue was distilled. 56 g tive compounds. the evaluation times and the results (57% of theory) of the desired N-(O,S- can be seen from the following Table 4. dimethylthiolphosphoryl)-iminoformic acid ethyl Table 4 (Mites harmful to plants) Tetranychus test resistant Active compounds Active compound Degree of concentration destruction in $4 by weight in after 2 days.  
  0 ca 0 0.1 0 -mt-c-cr-t c H o 9 9 2 5 0.1 cn s 3 o u CH 3 -N-CH-NH-CH2-CH=CH2 95 9 on o 3 p...N=CH-NH-CH 0.1 98 011 s (6) 9 CH 0 CH s P-N=CH-NH-C H -n o 1 90 t -N=cH-NH-(2H(0H 04 95 3 o (1) CH 0 5 -N=CH-NH-CH2-CH(CH3)2 0.1 95 (5) o\&#34; 3 r-u-ca-un-cwn 0.1 99  
  3 3 ca s (2) 0.01 40 The process of this invention is illustrated by the folester of boiling point 84C/0.0l mm Hg and relowing preparative examples. fractive index m 1.4892 were obtained.  
  EXAMPLE 5 a. The N-(O,S-dimethylthiolphosphoryl)- CE 0 9 iminoformic acid ester used as the starting com- 3 P-n=QH-RH-(}H(QE3)2 (1) pound was prepared as follows: a  
 71 g (0.5 mole) of O,S-dimethylthi0l-ph0sphoric acid ester amide and 92 g of orthoformic acid ethyl ester were heated to the boil under reflux 14 g (0.2 mole) of isopropylamine in 50 ml of benfor 4 hours. Thereafter the alcohol formed was zene were added dropwise to 40 g (0.2 mole) of N- (O,S-dimethylthiol-phosphoryl)-iminoformic acid in which ethyl ester dissolved in 100 ml of benzene while cooling R and R each independently is lower alkyl, and the temperature being kept at to C and stir R&#34; is alkyl or alkenyl with up to 6 carbon atoms, cy-&#39; ring. Thereafter the mixture was stirred for 2 hours cloalkyl with 4 to 6 carbon atoms.  
 while cooling, the solvent was distilled off in vacuo and 5 2. A compound according to claim 1 in which R and the residue was subjected to slight distillation.&#34; g R each is alkyl with 1 to 3 carbon atoms, and R&#34; is (83% of theory) of N-(N-isoalkyl with l to 4 carbon atoms, alkenyl with 3 or 4 carpropylaminomethylidene)-O,S-dimethylthiolbon atoms, or cyclohexyl. phosphoric acid diester-imide of refractive index n,, 3. The compound according to claim 1 wherein such l.5l6l were obtained. 10 compound is N-(N&#39;-iso-propyl-aminomethylidene)- The following compounds were prepared analo- O,S-dimethylthiolphosphoric acid diester imide of the gously: formula Structure Physical properties (refractive index, melting point) 0 CH 0 &#39;I 5 P-N=CH-NH-C(CH n% 1.5129 CH S g 3 2) I 36 2s P-N=CH-NH-CH -CH=CH n ,5 CH S O CH O n P-N=CH-NH P-N=CH-N1-i-CH 5 1.5322 5 1) ctt s (6) O CH o n 28 3 P-N=CH-NH-C H n 1.5167 3 (7) c3 0 Melting point r- I 11a-122c CH S (8) It will be appreciated that the instant specification O and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit (EH 8.  
 and scope of the present invention.  
 what is claimed is: 4. The compound according to claim 1 wherein such 1. A N-(amlnomethyhdene)-th1ol-phosphor1c acid compound is N (NI tert butybaminomethyfidene) ester imide of the formula O,S-dimethylthiolphosphoric acid diester imide of the formula 0 0 R-S c 3 u /P-N=CH-NHR&#34; H- H 6. The compound according to claim 1 wherein such compound is N-(N&#39;-methylaminomethylidene) O.S-dimethylthiol-phosphoric acid diester imide of the formula rhea-M143 7. The compound according to claim 1 wherein such compound is N-(N&#39;-n-propylaminomethylidene) O,S-dimethylthiol-phosphoric acid diester imide of the formula