[1]Unite.d States Patent Office 2@9089605 2,908,605 NEW ORGANIC PHOSPHORUS COMPOLTNDS AND PROCESS FOR THEIR MANUFACTURE Ernst Beriger, ABschwil, neor Basel, and Richard Sall- 5 mann, Binningen, near Basel, Switzerland, assignors to Ciba Limited, Basel, Switzeriand@ a Swiss firm No Drawing. Application January 14, 1958 Serial No. 708,760@ io Claims priority, application Switzerland .No*ember 3, 1955 i8@ Clqms. (Cl. 167-22) This iriventionprovides new organic phosphorus com15 conipounds acting as contact poisons and stomach poipounds of the general formula R-(X).-i RS I P-C-R2 Rl-(Y)@-, izi R3 20 0 R, in which R, Rl, R3 and R4 represent alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radicals, which may contain 25 substituents, and R and Rl, on the one hand, and R3 and R4, on the other, may together forin Part of a ring ystem@, R3 and R4 may also represent hydrogen, R2 represents a halogen atom, R5 represents the group 30 0 (in which R6 represents an alkyl, aryl or heterogyclic radical),,X and Y represent -0-, -S@, >NH- or N-R, and Z represents oxygen or sulfur, and n and m 35 eacli represent a whole number not greater than 2, or compounds of the general formula R-(X)@@,p Rd -0-C II 40 R,-(Y) I z C-R2 R3 0 R4 in which R, RI, R2, R3, R4, R6, X, Y, Z, n and m have 45 the meanings given above. It has not yet been established with certainty which of the Formulae I and 11 should be ascribed to the compounds of the invention. It is possible that, depending on the method of preparation, tio only one or other of these forms is produced, or one form is produced preferentiary. It is known that in the reaction of trialkyl phosphites with certain halogencompounds according to-Michaelis and Arbuzow rearrangements occur, so that instead of the expected phosphonic acid derivatives isomeric phosphoric acid esters are formed. In the case of the present invention, for example, the condensation product of m:adichloroacetoacetic acid N-diethylamide and trimethyl phosphite can be given in the following two formulae 60 CH30 \ / c2]N5 P-OCHS + C113COC012--CON cHao/ C2HB cii3o cocipla CHBO CHs 65 P-OCI P-0- C]IBO 0 02H6 CH30 oci - N C 2US 0 c2EE5 CX/ 70 C2]Efa -Patented Oct. 13, 1959 2 Th present invention there@@ore includes compounds of the Forinulae I and 11, and also any mixtures thereof, since the isoiiierism of the compounds can be regarded as a keto-enol tautomerism. Whenever, hereinafter only one of these forms is given it is to be understood that the other form is included, provided that it appears to be capable of existing. This application is a continuation-inpart of now -abandoned application Serial Number 618,673, filed October 29 1956' The n@@ compounds are valuable agents for combating pests, especially animal pests. They are effective agaiiist the various stages of development, such as eggs, larvae and imagines (i.e. the adults of the insects), the sons. Suitably substituted compounds when applied to plants have an intra-therapeutic, or so-called systemic action. Especially valuable are compounds of the general forniula R-0 COCH3 R-0 CHs P-C-CL k---> P-0-C /11 I /11 11 l@1--o 0 R3 RI-0 0 cci R3 0 R4 C-N/ 11 \ 0 R4 in which R and R, represent lower alkyl radicals containing 1-4 carbon iatoms, and R3 and R4 represent hydrogen or lower alkyl radicals containing 1-4 carbon atoms. The invention also includes a process for the manufacture of the new compounds, wherein a compound of the formula R-(X).-I \P-Z-R7 Rl-(Y).-l m which R, RI, n, m, X, Y and Z have the meanings given above and R7 rep ents a lower alkyl radical conre@, taining 1-4 carbon atoms is condensed with a compound of the formula Rs it-l-@-R, Rs C-NI 0 R4 in which R2, R3, R4 and R5 have the meanings given above and Hal represents a halogen atom, such as bromine or advantageously chlorine, accompanied by the splitting off of a compound of the fokmula R7-Hal. The conipounds of the general fonnula P-Z-R7 used as starting materials are derivatives of trivalentphosphorus, whereas the products to be used in accordance with the invention are derivatives of pentavalent phosphorus. Among the compounds of the last mentioned formula the most easily accessible are those in which the symbols X, Y and Z represent oxygen. They correspond to the general formula R-0 P-0-Ri Rr-O and can be made by methods 'm themselves known.
[2]2,908,605 3 The aliphatic radicals, which are represented by the symbols R and RI, may have straight or branched chains and may be saturated or unsaturated and they may be stibstituted or unsubstituted. There may be mentioned, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylbutyl, oetyl, 2-butyloctyl, dodecyl, octadecyl, allyl and 2-chloroetiiyl groups, and also radicals containingthiocyano, cyano or ester groups. The residues R and RI may be identical or different from one another. R7 is advantageously a lower alkyl radical containing 1-4 carbon atoms. For example, there may be mentioned the following compounds: Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, diethyl dodecyl phosphite, tri-(2-chloroethyl) phosphite and the ester of the formula CH2-0 P-oc2H6 ciiz-o The aromatic radicals, which R and R, may represent may be mononuclear or polynuclear and may, if desired, contain nuclear substituents. There may be mentioned phenyl, 2- or 4-chlorophenyl, 2:4-dichlorophenyl, 4 -methoxyphenyl, 4-nitrophenyl, naphthyl and 4-diphenyl groups, compounds such as 2 :4-dichlorophenyl diethyl phosphite or 4-chlorophenyl dimethyl phosphite. There may also be mentioned compounds in which one or two radicals are bound directly through a carbon atom to the phos phorus atom, for example, phenyl-phosphonous acid diethyl ester of the formula P-OC2II5 C@H@ Among the araliphatic radicals, which R and RI may represent, there may be mentioned the benzyl group, and among the cycloaliphatic radicals there may be mentioned the cyclohexyl group, and amon-, heterocyclic radicals there may be mentioned the tetrahydrofurfuryl group. Starting materials containing such radicals are, for exaiilple, cyclohexyl diethyl phosphite, tetrahydrofurfaryl dimethyl phosphite and dibenzyl propyl phosphite. Among the compounds, in which X and Y reprephite of the formula P-SC2115 c2H5s and among those in which X and Y represent nitrogen, there may be mentioned the compounds of the formula (c2H5)2N \ / P-OC2H5 (C2]15)2N T,he compounds of the general formula R2 0 Rs Rs- C N I Hal R4 are amides of halogenated acylacetic acids, and advantageously acetoacetic acids. The radicals R3 and R4 may have the meanings given above for the radicals R and 4 Rl. Advantageously they represent alkyl groups containing 1-4 carbon atoms, or form a heterocyclic ring together with the nitrogen atom, for example, the ring of morpholine or piperidine. 5 The radical R2 represents a halogen atom,- advantageously a chlorine.atom. As stated above, the radical RB represents a radical -CO-R6. RG may represent a heterocyclic radical, an aryl radical, for example, the phenyl, chlorophenyl or nitrophenyl group, or especially 10 an alkyl group containing 1-4 carbon atoms. Advantageously, the radical R6 is a methyl group and the radical R5 a -COCH3 group, that is to say, the starting compounds are advantageously aceto acetic acid amides. The products of the invention are produced by heating 15 the reaction component s at a 'raised temperatur e, for example, 50-200' C. and advantage ously at about 90- 150' C. It may be advantage ous or convenient to work in an inert solvent such as benzene, toluene, xylene, chlorobenz ene or benzine, and, if desired, in an inert gaseous 20 atmospher e, for example, under nitrogen, and/or redured pressure. As stated above flie products of the invention are valuable agents for combati ng pests. Accordi ngly, the invention also provides preparat ions for combati ng pests 25 which comprise such a product as active substance in admixture with a carrier. There are advantage ously used compounds of the - eneral formula R-0 cocils R-0 CE[3 30 \ I I P-C-CL P-0-C /101 /11 11 R=Cl I-N R3 RI-0 0 11 35 0 RI I-NI 8 \R, in which R and RI represen t alkyl groups containin g 1-4 carbon atoms, and R3 and R4 represen t hydroge n 40 or ff desired alkyl groups containing 1-4 carbon atoms. A very wide variety of material s can be protecte d against pests, a gaseous, liquid or solid material being used as carrier for the active substanc e. The material to be protecte d or to be used as carriers may be, for 45 example, air, especially in rooms, or liquids, for example, water in ponds, or any non4iving substratum , for example, any objects in living rooms, in cebars, in plaster floors, stables, and also pelts, feathers, wool or the like and also sent sulfur, there may be mentioned triethyl thiophos- ,living organisms of the vegetable and animal kingdom 50 in very wide variety of stages of developme nt, provided that they are not sensitive to the pestcontrolling agent. The usual methods can be used for combati ng pests, for exampie, by treating the material to be protecte d with the active compou nd in the form of vapor, for ex55 ample, in the form of a smoke, or in the form of a dusting or spraying preparatio n, for example, a solution or suspension which has been prepared with water or a suitable organic solvent, for example, alcohol, petroleum, a tar distillate or the like. 60 There may also be used for brushing, spraying or immersing the materials to be protected aqueous solutions of the active substances or aqueous emulsions of organic solvents which contain the active substances. The spraying or dusting preparations may contain the 65 usual inert fillers or identifying agents, for example, kaolin, gypsum or bentonite, or further additions such as sulfite cellulose waste liquor, cellulose derivatives or the like and they may also contain the usual wetting or adherent agents for improving their wetting capacity and 7o adhesive power. The pest combati ng preparat ions may be made up in powdere d form, in the form of aqueous dispersio ns or pastes or as selfemulsifyi ng oils. The compounds of the invention may constitute the sole active substance in the pest combating preparatio ns 75 or they may be present together with other insecticides
[3]and/or fungici(res. 'nese preparatibns nlay be used'fbr protecting plants by; the usuall@ spraying, casting@ dusting or fumig@atio methods. A The. following examples, illustrate the - invention,, the parts and percentages being by weight unless otherwise 5 stated and the relationship of parts by weight to parts 'by volume, being the same as that of the kilogram to the liter: Example 1 10 11.3 parts of dichloracetoacetic acid diethylamide (boiling at 92.5-93' C. under 0;118 mm. ]@ressure) and 8.3 parts of triethyl phosphite are mixedi together at room temperature. In order to initiate the reaction the mixture. is heated to 90' C. At that tem@erature a violent. evolu- 15 tion of gas sets in, and the reaction solution heats up to 1601 C@ without external heatin,a. When the reactioin is finished@the7product is subjected for a short time longer at 95' C. to the reduced pressure of a water jet pump. There remains behind a red, -reen iridescent oil (16.1 20 parts), which can be purified by distillation in a high vacuum. It boils at 144' C. under @0.1 mm@ pressure. C12H2105NCIP.-Calculated: N, 4.27%; Cl,.!10.-82%. Found: N, 4.24%; Cl, 10.97%. The dichloracetoacetic acid diethylamide used for mak- 25 ing the above condensation prpduct can be obtained by chlorinatin g acetoacetic acid diethylamide with 2 mols of suffuryl chloride, Example 2 30 A mixture@ of 33.8 parts of dichloracetoacetic acid diethylamide and 34 parts of chlorobenzene are heated to the boil. 20.5 parts of trimpthyl phosphite are added dropwise in the course of 5 minutes. A vigorous evolution of gas sets in, which ceases after boiling the mix- 35 ture for one hour under reflux. The easily volatile pOrtion and the chlorobenzene are removed under the reduced pressure of a water jet pump; and there are obtained as residue 45.0 parts of an orange colored oil, which can be distilled under a high vacuum. It boils at 40 @138-1-42' C-. undtr 0';I' mm. pressure (@7'.2 parts= 82-.6 percent of the theoretical,@ield@)'. C oNl9Q5NCI -Calculated: C 40.0 %; H, 6 39%;, 1 . p 1_ 7 N, 4i67%; Cl, 11.83%;,P, l@0.34.%., Found: C, 39.90%@;@ H, 6.61 %; N, 4.709'o; Cl. 1- 1.7.8 %; P, lo.3 8 %. Example 3 8.5 parts of dicworacetoacetic acid, amide (melting at !65' C.) are covered with 20 parts by volume of xylene. The mixture is heated to 90' C. and' @8.3 parts of triethyl phosphite are added dropwise. The temperature remains at 1110-120' C. without external heating and ethyl chloride escapes from the reaction. mixture. The sol@.. vent is then removed in, vacuo at 95' C. !13.6 parts of a reddish, green opalescent oil remain behind as residue. The product dissolves. well- in acetone and alcohol and is less soluble in ether. The dichloracetoac6iic acid amid'e can be@ obtained from acetoacetic -acid- amide2 by@ chlorination in chloroform with 2 mols of sulfuryl chloride. Example 4 6.2 parts of trimethyl phosphite -are slowly added to a mixture of 8.5 parts of dichloracetoacetic acid amide and 20 parts by volume of, xylenei which@ has been heated to 90-100' C., the addition being made in such manner that the temperature remains at 110-120' C. without external heating. When the evolution of gas ccases, the xylene is removed, at a bath lempcrature of 95' C. under the reduced pressure of a water jtt pump. The reaction product is a rpddish,gree-n iridescent oil (1@1.5 parts) and dissolves well in acetone and alcohol. In. an analogous manner the halogenated 8-keto-acid amides mentioned, in the, following table can be reacicd with tertiary phosphites. Only a part of the resulting esters of which the prbperties are also given in the table, can be distilled in a. high vacuum without di@composition. However, for the production of pest combating preparations purification of the compounds by distillation can be dispensed witli. No. Acid amide Halogenated acid amide Phosphite components and properties of the e s t e r s o b t a i n e d 1-2 --------- CH3COCH2CONHCH3 ()Il3CO001 2CONHOHo (CHBO)P (C2H6O)3P bo.Us at 100-102' C. (0.8 mm. pressure). melting at 59-601 C. Oil, d@ss s well in 011, soluble in water, 1 olve .ter, alcohol, ace- aicohol, acetone. boils at 135' tcon(e i.5 mm. pressure) with decompositio n. 3-4 --------- CHSCOCH2CONH02Hs CH3000CI 20ONHOgHS (CHSO)SP (02H&0)3p boils at 1201 C. (1.8 mm. pressure). boffs at Oll (). (0.15 mm. pressure). Oil, soluble in alcobol OJI, soluble In ale ol and seetonei poorly aud acetoiie, poorly solubl e in water. soluble in water. 5-6@ -------- CH3COCH2CONHC3H7 CHsOOC C12CONHC3H7(U) (CIIIO)3p (CIHBO)3 p boils at 104-106' C. (0.4 mm. pressure), viscous oil. viscous oil, soluble in Oil soluble in alcohol crystamile. alcohol aiid-abetoiae. 'and acetone. 7-8 --------- on3coCH2coNHc3H7- (iso) CH3COCC12CONHCsH7.(Iso) (cH3o)3R (c2HBO)gp boils at 91-94' C. (0.2 mm. pressure) orysmelting at 51, 011, soluble in alcohol sparingly mobile oil, tauine. and acetone. soluble in alcohol and acetoiie. 9-10 -------- CHacoCI12CONHC411g(n) CH3COC C12COIqII04H9(n) (CH30)gp (c2H5o)sp boils at 110-114' C. (0.2 mm. pressure crysviscous off. oil, soluble In alcohol viscous oil, solubie iia talline. and acetone. alcohol aiid 6cet6iie. 11-12 ------- CH3cocH20ON(Olla)i CH3COCC12CON(CH3)2 (CH30)p (c2HIO)SP boils at 76-771 C@ (L8 mm. pressure) boils at 681 C. (0.035 mTn. pressure). oll, soluble in alcohol oll, boils at 162- 1561 and acetone. 0. (0.35 mTn. prossure) soluble inialco13 ---------- CHaCOCH2CON(02Ho)2 CH3C OCC12CON(C2115)2 I(Clit)2cHo]ip hol aud acetonei boils at 68.6-701 0. (0.58 mm. pressare). boils at 92.5- 931 C. (0.18 mm. pressure). tbinly liquid oil, solubl e In alconol and acetone. 14-15 ------- ---------------------------------------------- CHaCOCIBr2CON(CjH6)j (OH30)IP (c3HIO)ip boils at 88-89.51 0. (0.4 mTn@ pressure),. Ofl, soluble in w,ateri OH, solubie In water, alcohol and acetone. alcohol and'acetone,
[4]@Aii, analogous manner the following phosphites, aie ireacted with- dichloracetoacetic acid diethyl aimde: Reaction prodtict of. the phosPhosphite phite with dichloracetoacetic .,d diethylamide (oZE40)gp-OCH,Clr=CH, light oil, soluble in alcohol and boilsat64-669 C. (12mTn pressure). acet.one. (C)2H5O)2P-002H&SC2]16 viscous oil@ soluble in alcohol boils at 69--611 C. (0.1 mm. pres- aAa acetoiae. sure). oil, soluble in alcohol and ace(,c3H5o)2p-OCBI@e \-/ tone. boils at 841 C. (0.3 mm,. pressure). (c2u5o) P-0 easily mob.Ue oil, soluble in alcohol and acetone. -boils at 50' 0. (0.3- mm. p,res-e) (02H5o)2p-ol-z-@@Cl viscous oil, soluble in alcohol and@acetone. boils at 70-75' C. (0.1 mm. pressure) - Example 6 11.3 parts of dichloracetoacetic acid diethylamide are he I ated to 150 C. and 7.5 parts of ethyl-ethylene phosphite O-CH2 02HSOP O-OH2 (,boring at 49,' C. under 10 mm. pressure) are added Oropwise in@ the course of 5 minutes. The mixture is maintained at 160' C. for a further IV4 hours until the evolution of ethyl chloride ceases. 1.2 parts of ethyl chloride are collected. The reaction does not proceed solely with the splitting Off of ethyl chloride but there is also a partial splitting of the ethylene phosphite ring. T,he starting materials still present are removed in@ a high vacuum at a bath temperature of 180' C., and there is obtained as residue a viscous oil (10.8 parts), which dissolves well in alcohol and acetone and less w ell 'n water. Example 7 11.3 p,arts of dichlbracetoacetic acid diethylamide are heated to 180' C. 11.7 I>arts of trithioethyl phosphi-te (C2HBS)3P are added dropwise in t@he course of 5 minutes, and the evolution of ethyl chloride is allowed to subside by heating the mixture for 1/4 hour at 180' C. The starting materials still present are removed in a high vacuum at 1-50' C., and there is obtained as residue a viscous mass (17.6 parts), which dissolves easily in chloroform and less well in alcohol and acetone. Example 8 10@6 parts of 0-diethylN-dieth@lamido-phosphite@ (C2H5()2PN(C2H5)@2 @axe added in the course of 5 minutes to a mixture 6f 11.3 parts of dirhloracetoacetic ,acid diethylamide @and 15 parts by volume of xylene at the. boilihg temperature. After 10, minutes the evolution of ethyl' chloride (3.0 parts) coases. The xylene is remo-ved under the reduced pressure of a water jet pump and a small@ aniount of starting material present is remo.ved in- a high vacuum at a bath temperature of 1-80' C. As residue there is obtained a light colored easfly mobile oil@ which dissolves well in acetone',and alcohol and is less soluble in water. Example 9@ 1--'1.3 parts of dichloracetoacetic acid dimethylamide are heated to the boil with 1-5 parts by volume of xylene and: 10.9 parts of phenyl-phosphbnous @cid diethyl. dste'. (O C2H5)2 -114' C.) are added dropwise. The re(boiling. at 108 action @is complete in about 1 hour, during which 2.8 parts of ethyl chloride are collected. After removingthe xyjene in vacuo and a small amount of star-ting material in a hi.-h vacuuni at a bath temperature of 180' C', there 10 are obtained 15.4 parts of. :a. viscous oil, which dissolves well in alcohol and acetone. Example 10 2 parts of -the condensation product of Exaniple I 15 or 2 are mixed with I part of t-he condensation product of 1 mol of tertiary oetyl-phenol and 8 mols of ethylene oxido, iand 7@ parts of isopro anol A clear soliltion is . p ADbtained which can be used as a concentrate for- prepan'ng spray liquors and can be emulsified by pouring it into 20 water. A. In order to demonstrate the, intra-therapeut,ic, socalled systemic, -action of the preparation the following experiment wa@s carried out with the use of spray liquors having contents of activc@ substance of 0.08 pereenti 0.04 25 percent, -and 0.02 percent. I The lower leaves were removed from broad bea n plants (Vicia fabae) which were heavily infested with aphids (Doralis fabae), and@ a color mark was applied 30 halfway up the stalk of each plant. Then the lower half of the stalk of two plants was sprayed with one of the spraying liquors of one of the above concentrations. After 24 hours the extent to which the aphids had been controlled in the upper non-sprayed part of the plants was examined@ The results obtained are given in the 35 following table: Effect on the aphids after 48 hoars 40 Spray liquor concentration Compound Compound of Example of Example 1 2 ++ ++ 4.5 00.- 0084%% --------- ------------------------------------------- ++ ++ 0.02% --------- ------ ------------------------- ++, ++ For each plant,a sign was used. + means that no living aphids were present, I means a good action such that 50 o@ly a few aphids were still alive, and - means an insufficient action or no action. B. In order to demonstrate the contact action on aphids the following experiment was carried out with 55 the use of spray liquors having contents of -active stibstance of 0.08 percent, 0.04 percent and 0.02 percent ' . Broad bean plants, which were heavily infested with aphids, were sprayed on all sides and after 48 hours the effect was examined. When a 100% control had been achieved@, the plants were freshly infested with 60 aphids,, -and the effect was examined after a further 48 hours. The results obtained are set out in the following -table: 65 Effeot on the aphids after48 hours 48 hoars fresh inSpray liquor concentration fection 70 Example Example Example Example 1 2 1 2 '08% ------------------------ ++ ++ ++ ++ 0.04 9 ------ -------------------- ++ ++ ++ + o@0 2f@ ------ ------------------ ++ ++ ++ 75
[5]C. In order to demonstrate the effect on aphids by 'diffusion through the leaves the following experiment was carried out with the use of spray liquors having contents of active substance of 0.08 percent, 0.04 percent and 0.02 percent. The aforesaid spray liquors were sprayed only onto the upper sides of the leaves of broad bean plants of which the undersides of the leaves only were infested with -aphids, and after 48 hours -the effect on the undersides of the leaves was exaniined. The resul.ts obtained are set out in the following table: Effect on the aphids Spray liquor concentration Example I Example 2 o.os% ----------------------------------------- ++ ++ 0.04% ----------------------------------------- ++ ++ 0.02% ------------------------------------ ++ . ++ - D. In order to demonstrate the action of the compounds of Example-s I and 2 as stomach poisons poplar leaves were inunersed in the spray liquor containing 0.04 percent of active substance. After drying the leaves the caterpillars in the fourth larval stage of t-he poplar spider (Stilpizotia caticis) were fed on the leaves. After 36 hours the stomach poisoning effect was determined. In the case of the compound of Example 1, all the caterpillars were killed; and in the case of the compound of Example 2, 9 out of 10 caterpillars were killed. For preparing the spray liquor concentrates other wetting or emulsifying agents than those mentioned above may be used. There may be used non@ionic products, for example, condensation products of aliphatic alcohols, amines, or carboxylic acids containing a long-chained hydrocarbon radical having about 10-30 carbon atoms with ethylene oxide, such as the condensation product of octadecyl alcohol with 25-30 mols of ethylene oxide, or the condensation -product of soya bean fatty acid with 30 mols of ethylene oxide, or the condensation product of commercial oleylamine with 15 mols of ethylene oxide, or the condensation product of dodecylmercaptan with 12 mols of ethylene oxide. Among the anion-active emulsifying agents there may be mentioned the sodium salt of dodecyl alcohol sulfonic acid ester, the sodium salt of doderylbenzene sulfonic acid, the potassium or triethanol-amine salt of bleic acid or the triethanolamine salt of abietic acid or of a n-iixture of these acids, or the sodium salt of a petroleum sulfonic acid. Instead of isopropanol there may be used another solvent for preparing the spray liquor concentrates, for example, ethyl alcohol, methanol, butanol, acetone, niethyl ethyl ketone, methyl-cyclohexanol, benzene, toluene, xylene, kerosene, or a petroleum fraction. It wifl be understood that mixtures of the aforesaid solvents may be used. Example I 1 20 parts of the products obtained @as described in Example 1 are mixed with 9 parts of chalk and I part of wetting agent. There is obtained a spray powder, with which spray liquors can be prepared by suspending the powder in water. Plum trees were treated with such a liquor containing 0.04 percent of active substance, and gave good results against plum fly caterpillars (Hopoclampa flava et m;inuta). Example 12 1 part of the product obtained as described in Example 2 is mixed with 99 parts of talc. There is obtained an insecticidal dusting powder, which is suitable for dusting vines to control wine moths (Clysia ambiguella, Polychrosis botrana). The talc may be replaced wholly or in part by sulfur in which case the preparation is also effcotive against Oidium. Instead of talc another pul2igos,605 12 ver-ulent carrier may be used, such as chalk, bentonite, kaolin or a mixture of two or more of thes,e carriers. Example 13 5 There is used a spray liquor which contains, per liter, 1 gram of zinc dimethyldithiocarbamate, 0.04 gram of compound No. I of the table in Example 4 and 0.08 gram of the compound No. 18. Fruit trees are sprayed in the summer with the liquor and a good control is ob10 tained against aphids and scab (Fusicladium). Example 14 Hop plants are watered with a liquor containing 0.04 percent of the compound of Example 2. All the hop 15 plants were free from aphids and red spiders (Tetranychidae) after a short time. Example 15 Good results are obtained with the compound of Ex20 ample 2 by spraying plants with spray liquors containing 0.2 to 0.004 percent of active substance, against the following pests which are not mentioned in the preceding examples: Pear leaf psylla (Psylla pyricola), thrips (Heliothrips haemorrhoidalis), lecania (Eulecanium 25 1 corni), peach insect (Cydia molesta), cotton leaf worm (Prodenia litura), ermine moth (Hyponomeuta malinella et padella), cherry blossom moth(Argyresthia ephippella). Example 16 30 In tests on the action against aphids by the method described under B in Example 10 all the compounds given in the table of Example 4 gave good to excellent results. In stomach poison tests (experimental procedure D 35 in Example 10) the compounds of Example 4 and of Nos. 3 and 1 1 of the table in Example 4 were active to very active. 'fhe compounds given in Example 5, possess a systemic action, when tested according to the experiinental pro40 cedure A of Example 10. What is
