[1]Uni'ted States Patent Office 3,047,605 3,047,605 PHOSPHONIC AC-YD ESTERS AND THEIIR PRODUCTION Gerhard Schrader, Wuppertai-Cronenberg, Germany, assi-,nor to Farbeiifabriken Bayer Aktienge sellschaft, 5 Leverkusen, Germany, a corporation of Germany No Drawing. Filed May 20, 1958, Ser. No. 736,465 Claims priority, application Germany June 5, 1957 11 Claims. (Cl. 260-461) The present invention relates to and has as its objects 10 new and useful insecticidal phosphonic acid esters and their production. Generally the new compounds may be represented by the following formula Y ORI 15 II/ /A, R-X-CH=CTI-P \ ZR2 in which R and RI stand for alkyl radicals, R2 stands ior heraliphatic, araliphatic or aromatic radicals which furt 20 more may be substituted, and X, Y or Z stand for oxygen or sulfur. There are many ways of preparing the inventive compounds. Thus, if phosphonic or thionophosphonic acid esters -are desired the following way may lead to that 25 part of the inventive compounds. Vinylalky.I ethers or mercapta,ns are known to add on phosphorus pentachloride easily. The adducts thus formed may then be reacted with sulfurous acid to form the corresponding dichlorides: 3 0 (S) (S) R O-CH@CH2 + P C]5 @ RO-CHOI-CH2-PCI4 + S 02 0 ci (S) II/ RO-CH@CH-P + H01 + S OC12 35 These p - alkoxy - (or p-alkylmercapto-)-vinyl-phosphonic acid dichlorides thus formed may be @further converted by known methods i.e. by reacting with convenient alcohols to corresponding dialkyl esters of the following 40 ,general forniula 0 ORi (S) II/ RO-CH@CH-P \ OR2 4 5 These 3 - alkoxy - (or p-alkylmereapto-)-vinyl-phosphonic acid dialkyl esters may be converted by known methods with the aid of phosgene into the corresponding p-alkoxy-(or p-alkylmercapto-)-vin yl-phosphonic acid ester chlorides: 50 0 ORI (S) II/ RO-CII=Cl-I-P \ el The above shown adducts of phosphorus p.-ntachloride 55 and p-alkoxy-(or p-a@lkylmercapto-)-vinyl-ethers may be reduced with hydrogen sulfide so as to form 6-alkoxy(or 3-alkylmercapto-)-vinyl-thionophosphonic acid dichlorides: s ci 60 (S) II/ RO-CH=CH-P ci These easily obtainable dichlorides rnay also be con65 verted with appropriate alcohols by known methods into the corresponding p-alkoxy-(or g-alkylmerc apto-)-vinylthionophosphonic a-cid alkyl ester chlorides: S OR1 II/ RO-CH@CH-P \ 70 ci Patented July 31, 1962 These alkoxy - (or O-alkylmercapto@)-vinyl-phos-, phonic acid alkyl ester chlorides or p-alkoxy-(or p-alkylmercapto-)-vinyl thionophosphonic acid alkyl ester chlorides can be condensed with any alcohols or phenols to form the hitherto unknown esters which distinguish themselves by a very good contact-insecticidal action: 0 (S) 0 (S) (S) ii (S) RO-CH=CH-P-OR, @ RO-CH=CH-@l-ORI \ ci \ OR2 In all these above shown formulae R and R, and R2 have the first menitoned significance. The condensation of these phosphonic acid or thiophosphonic acid chlorides with alcohols or phenols may be carried out in the presence of suitable acid-binding agents. As acid-binding agents there are preferably used tertiary amines in the presence of inert solvents, at room temperature or slightly elevated temperature. When condensin.- phenols, it is also possible to start @from the a alk li metal salts of the phenols or from the phenols themselves and to bind the halogen with alkali metal carbonates. In the condensa-tion of phenols with p-alkoxy(or palkylmercapto-)vinyl-phosphonic acid- or -thionophosphonic acid ester chlorides, ketones have primarily proved to be particularly useful solvents (especially methyl ethyl ketone and methyl isobutyl ketone). If thiolphosphonic acid esters are desired p-alkoxy-(or6-alkylmercapto)vinylphosphonic, acid ester chlorides as described in the foregoing paragraph can be reacted with any aliphatic, aliphatic-aromatic or aromatic mercaptans so as to form likewise new 3-alkoxy-(or p-alkylmercapto-)-vinyl-phosphonic acid thiolesters of, the following formula 0 ORi (S) II/ RO-CH=CII-P SR2 In another way the p-alkoxy-(or p-alkylmereap@Q):. vinyl-thionophosphonic acid dichlorides also described in the first paragraph can be converted as described above into, the corresponding thionophosphonic acid monochlorides. When saponifying these p-alkoxy-(or 67alkylmercapto -)-vinyl-thionophosphonic acid monochlorides with alkaline reacting compounds chlorine is eliminated with the formation of the corresponding p-alkoxy-(or 6-alkyl mereapto-)-vinyl-thionophosphonic acid. These new thionophosphonic acids react, however, in thetautomeric Form 11: S ORt 0 ORI (S) II/ (S) II/ RO-CH=CH-P RO-CH=CH-P OH SH (I) (II) It has now been found that aliphatic, aliphatic-aromatic and in some cases also aromatic halides which may be substituted react with the Form II in such a @manner that palkoxy-(or p-alkylmereapto-)vinyl-thiolphosphonic acid esters of the general formula 0 ORi (s) II/ RO-CH@oll-F SR2 areformed. Thesep-alkoxy-(org-alkylmerc apto-)-vinylthiolphosphoiiic acid esters are identical with the compounds obtaiiiable by,the first mentioned process. When working according to the first described method for producing thiolphosphonic acid derivatives the reaction usually should be carried out at slightly elevated temperattires say up to about 50 to 70' C. The mercaptans are converted before reaction in their corresponding salts
[2]either by reaction of alkali metals in suitable inert or,ganic solvents such as benzene or toluene or by the reaction of alkali metal alcoholates also in suitable inert solvents; in this case especially low@-r ketones such as ;icetone or methyl ethyl ketone are most workable. If Working according to the second described method for producing thiolphosphonic acid esters the saponifying of the thionoester chlorides should be carried out usually with strong alkaline reactants such as e.g. potassium hydroxide. Without isola-ting the intermediates then the corresponding substituted halide is added. Reaction usually is carried out also in this case at elevated temperatures say up to about 100' C. and using suitable inert organic or aqueous organic solvents. Also these new thiolphosphonic ac@d esters distinguish themselves by an outstanding insecticidal action. The new compounds have chiefly a systemic action. If dithio-compounds are desired, the aforementioned palkoxy- (or p-alkylmercapto-) - vinyl@thioiiopho sphonic acid alkyl ester monochlorides are reacted with salts of any aliphatic, aliphatic-aromatic or aromatic mercaptans so as to form p-alkoxy-(or 6- alkylmercapto-)-vinyl-dithiophosphonic acid esters of the followin.- -encral formula s ORI (S) II/ RO-CH=CH-P SR2 The condensation of the p-alkoxy-(or p-alkylmercapt o-)-vinyl-thionophosphonic acid monochlorides with mercaptans is expediently carried out so that alkali metal alcoholates, especially sodium ethylate is used as an acidbinding agent. In this case most of the desired thiol esters are obtained nearly quantitatively without the formation of the corresponding oxygen esters as by-products. The condensation can expediently be carried out at a slightly elevated temperature, for example at 20-40' C., if desired also in the presence of suitable inert solvents. Also tfiese dithio-products distinguish then-iselves by a good contact-insecticidal action. The new esters are especially effective against red spiders and have chiefly an acaricidal action. T'hey are moreover also suitable for killing caterpillars of various species. I The new compounds of the present invention very effectively kill insec-ts like flies, mites, aphids, etc. They distinguish themselves especially by a good contact-insecticidal activity and at the same tin-ie by an activity on eating insects such as caterpillars. Most surprisingly they are of remarkable low toxicity against inammals. They may be used in the samemanner as other known phosphoric insecticides, i.e. in a concentration from about 0.00001% to about 1%, diluted or extended with suitable solid or liquid carriers or diljents. Examples of such solid carriers are talc, chalk, bentonite, clay -and the like, as liquid carriers there may be mentioned, water (if -necessary with a commercial emulsifier), alcohols, especially lower alcohols ;such as methanol ok ethanol, ketoiies, especially lower ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons and the like. The new compounds may furtherinore be used in combination with each other or with kn(ywn insecticides, fertilizers etc. The insecticidal activity of the inventive compounds May be seen from the following test results. Aqueous dilutions of the followin.- compounds (a) S OC2H5 (I/ C2H5O-CH=CH-P \ S-CT:I2--CHz-SC2Hs (b) s oc2H5 II/ C2H50-CIEI=CII-P sc2H5 (C) 0 oc2H5 II/ C2HsO-C]I=CH-P \ S-CH2--CHr-sc2H5 @q,047,605 4 (d) 0 OCH3 II/ C@H50-CH=cll-p s 002H5 C21150-CH=CH-P \O-cHz-OHr-SC2H5 s 0 C2115 10 II/ C61150-CH=CH-P \0 -@N02 (9) S 15 C2H5S-CH=CH-P S-0112--SC2H5 (h) S OC2H5 C2F[5S-CH@CH-P 20 0-<:D 0 OC3H5 II/ C2Fr5S-CH@CH-P 25 S-CHR s-e bave been prepared by mixin- the active in.-redient with the same amount of dimethyl'formamide as an auxiliary solvent adding thereafter 20% by wei,-ht referred to active 30 iiigredient of a cortimercial emulsifier consisting of a benzyl hydroxy polyglycol ether containing about 10 to 15 glycol residues, and dilutiiig at last this prem;xture with water to,tl-.e desired concentration indicated in the following para,-raphs. The tests have been carried out in the 35 fo,'owing manner: Against aphids (contact-insecticidal action) of the type doralis fabae (with cor@- lpounds (a), (c), (d), (f), (g), (h), and (i) ). Heavily infested bean plants (Yitia fciba) have been sprayed drip wet with solutions as prepared 40 above. The effect has been determined by evaluation after 24 hours by couriting the dead pests either on the surface of the soil or still remaining on the plants; With compounds (a), (g), and (i): solutions of 0.01% 45 kill aphids 100%, With compounds (d) and (f): solutions of 0.001% kill aphids 100%, With compounds (h): solutions of 0.1% kill aphids 100%; 50 Against caterpillars (with compound (b)). White cabba.-e has been sprayed drip wet with 0.1% aqueous emulsions as prepared above. Caterpillars of the type diamond back moth (10 each) have been placed on the sprayed leaves of the white cabbage. The living status 55 has been determined after 24 and 48 hours, and complete killing has been obtained; Against spider mites (contact-insecticidal action) of the type species Tetranychus telarius (two spotted spider) (with compounds (c), (d), and (e)). Bean plants 60 (Phaseolus vtilgaris) of about 15 inrhes height are sprayed drip viet with solutions prepared as indicated above. The bean plants have been infested heavily with the two spotted spider. Evaluation has been carried out after 24 hours, 4 8 hours and 8 days; 65 With compouiids (c) and (e): solutions of 0.01% kill spider inites 100%, With compound (d): solutions of 0.001% kill spider mites 90%; 70 Against flies (Mitsca domestica) (with compounds (g), (h), and (i)). About 50 flies were placed under covered Petri dishes in which drip wet filter paper has been placed which is sprayed with an insecticidal solution as prepared above. The living status of the flies has been 75 determined after 24 hours;
[3]5 With compounds (g) and (i): solutions of O.Ofl% kill flies 100%, With compound (h): solutions of 0.1% kill flies 100%. Further activities of the inventive compotinds are to be found in the following examples, wwch are -iven by way of illustration only without, however, limiting the present invention thereto. Exaniple 1 S Oc2H5 II/ C2H50.CH=CH-P S.CH2,CH2.S C2H5 25 grams of 6-ethylmereaptoethylmercaptan (B.P. 67' C@/12 mm. Hg) are dissolved in 100 millilitres of anhydrous alcohol. A sodium ethylate solution containiiig 0.2 mol of sodium is added thereto at about 30' C. The rnixture isafter-stirred at 30 C. for a half hour and 45 grams of p-ethoxyvinylethylthionophosphonic acid monochloride (B.P. 60' C.10.01 mm. Hg) a-re then added dropwise with further stirring at 30' C. The mixture is after-stirred at 300 C. for an hour, then poured into 300 millilitres of water, the separated oil is taken up in 200 millilitres of benzene and the benzenic solution is washed twice with 50-millilitre portions of water. The benzenic solution is then dried over sodium sulpb,ate. After distilling off the solvent, the residue is fractionated. 46 grams of the new ester of B.P. 118' C./O.01 mm. Hg are thus obtained. Yield: 77 percent of the theoretical. The new ester is a pale yellow water-insoluble oil. The new ester shows a toxicity on rats per os of about 25 milligrams per kilogram. Aphides are still killed completely at a concentration of 0.01 percent. Spider riaites are completely killed even at a concentration of 0.001 percent. 0.1 perceit solutions show a c<)mplete systemic action. Moreover, 0.1 percent solutions kill caterpillars with certainty. 0.1 percent solutions also have a positive ovicidal action on the ovae of red spiders. Example 2 S Oc2H5 II/ C2HsO.CH=CH-P \ s c2H5 13 grams of ethyl-inercaptan are dissolved in 60 millilitres of anhydrous alcohol. A sodium ethylate solution containing 0.2 mol of dissolved sodium is added thereto dropwise with stirring at 30' C. 45 grams of p-etho xyvinylethyl-thionophosphonic acid monochloride are then added with further stirring at 30' C. The mixture is after-stirred for an hour and then worked up as described in Example 1. 43 grams of the new ester of B.P. 90' C./ 0.01 mm. H- are thus obtained. Yield: 88 percent of the theoretical. The new ester is a colourless water-insoluble oil' The new ester shows i toxir-ity on rats per Os of 100 milligrams per kilogram. 0.1 percent solutions kill caterpillars completely. Example 3 s 0 e2HS II/ C2HBO.CH=CH-P \ S C ohia 24 grams of n-hexylmercaptan are dissolved in 50 millilitres of anhydrous alcohol. A sodium ethylate solutiori containing 0.2 mol of dissolved sodium are added thereto at 30' C. 45 grams of p-ethoxyvinylethyl-thionophosphonic acidmonochloride are added thereto dropwise with stirring at 30' C. and the mixture is heated to 3035' C. for a further 2 hours. The product is then worked up as described iii Example 1, and 52 grams of the new ester are thus obtained whicl@ distills under a pressure of 0.01 mm. Hg at 105' C. without decomposition. Yield: 88 percent of the theoretical. The ester is a colourless water-insoluble oil. The ester shows a toxicity on rats 8,047,606 6 per os of 5 milligrams per kilogram. 0.1 percent solutions kill red spiders completely. Exaniple 4 S oc2ns 5 II/ C2H50-CH=CH-P \ s -<@ Hi> 24 grams of cyclohexylmercaptan are dissolved in 50 10 millilitres of anhydrous alcohol. A sodium ethylate solution containing 0.2 mol of dissolved sodium is added dropwise thereto at 30' C. 45 grams of 3- ethoxyvinylethylthionophosphonic acid monochloride are added dropwise with further stirring at 30' C. and the mixture is 15 heated to 35-40' C. for a further 2 hours. The product is then worked up as described in Example 1, and 42 grams of the new ester of B.P. 120' C./O.01 rnm. Hg. are thus obtained. Yield: 72 percent of the theoretical. The new ester is a pale yellow water-insoluble oil which 20 shows a toxicity on rats per os of 250 milligrams per kilogram. 0.1 percent solutions kill caterpillars completely. Exaniple 5 S OC21-15 II/ 25 C2H3O.CH=CH-P 22 grams of thiophenol are dissolved in 50 millilitres of anhydrous alcohol. A sodium ethylate solution contain30 ing 0.2 rnol of dissolved sodium is added therdto with stirring at 30' C. 45 grams of p-ethoxyvinylethylthionophosphonic acid monochloride are then added dropwise with further stirring at 30' C. and the mixture is after-stirred at 40' C. for an hour. After working up 35 as usual, 47 grams of the new ester are obtained which boils under a pressure of O@01 mm. Hg. at 130 C. Yield: 82 percent of the theoretical. The new ester shows a toxioity on rats per os of 100 40 milligrams per kilogram. 0.1 percent solutionskill caterpillars completely. Aphides and spider mites are still completely killed at a concentration of 0.01 percent. Example 6 S 002H5 45 II/ C2H@@O.CH=CH-P \ 37 grarns of p-chlorophenylmercaptan are dissolved in 50 50 @millilitres of anhydrous alcohol. 0.2 mol of a sodium ethylate solut-ion is added thereto dropwise with stirring at 30' C. 45 grams of p-ethoxyvinylethylthionophosphonic acid monochloride are then added dropwise with further stirring at 30' C. The mixture is stirred at 35' 55 C. for a further 2 hours and then worked up as described in Example 1. 70 grams of the new ester are thus obtained as a pale yellow water-insoluble oil. On prolonged standing the crude product crystallises in colourless crystal,s which have a distinct melting point of 50' C. 6 . 0 The ester kills rats per os at 50 milligrams per kilogra m. Spider mites are completely killed at a concentration of 0.01 percent. Caterpillars are still killed with cert ainty by a 0.1 percent aqueous solution. Exa mple 7 65 S Oc2H5 II/ C2H 50.CH=CII-P \ ol 70 ci 45 grams of 3,4-dichlorophenylmercaptan are dissolved inl?Omillilitresofanhydrousalcohol. Asodiumethylate solution containing 0.3 mol of dissolved sodium is added thereto dropwise with stirring at 30' C. To this solution 75 there are added dropwise with further stiriing at 30' C.
[4]7 55 grams of 6-ethoxyvinylethyl-thionophosphonic acid monochloride and the temperature is mairitained at 40' C. for a further 2 hours. The product is then worked up as described in Example 1. 77 grams of the new ester are thus obtained as a colourless crystalline powder Of 5 melting point 68' C. Yield: 87 percent of the theoretical. The DL50 on rats per os is 100 mill@igrams per kilogam. 0.1 percent solutions kill caterpillars with certainty. Example 8 S 0021-13 10 C2H50.CII=CH-P \ S.CH2- S 02E[5 22 grams of a-mercaptomethylthio ethyl ether (B.P. 50' C./12 mm. Hg) are dissolved in 75 niillilitres of an- 15 hydrous alcohol. A sodi-um ethylate solution containing 0.2 mol of dissolved sodium is added thereto. 45 grams of p-ethoxy-viiiylethyl-thionophosphonic acid monochloride are added thereto dropwise with further stirring at 35' C. and the temperature is kept at 30' C. for a further 20 hour. After working up as usual, 37 grams of the new ester of B.P. 115' C./O.01 mm. Hg are obtained. Yield: 65 percent of the theoretical. The ester is a colourless water-insoluble oil. 25 DL50 on rats per os: 10 milligrams per kilograni. 0.01 percent solutions kill aphids completely. Spider mites are still killed_completely at a concentration of 0.001 percent. 0.1 percent solutions have a strong systeinic action. Caterpillars are killed with certainty even 30 at a concentration of 0.1 percent. Spider mite ovae are also killed vnth certainty by 0.1 percent solutions. 13y the same way bu-t using instead of p-ethoxy-vinylethyl-thionophosphonic acid monochloride pethoxy-vinylmethyl-thionophosphonic acid monochloride or P-ethOxY35 vinylpropyl-thionophosphonic acid monochloride in equimolecular amounts there are obtained the following two compounds: s CH3 II/ C2HZO-C]I=CTI-P 40 S-CH2---S C2H5 s c3H7 C2TI50-CH=Cli-P S-CH2--S C2H5 45 Example 9 8 Oc2H5 II/ c@@H50.CH@CH-P 50 s -<@@ CHS 32 grams of p-tbiocresol are dissolved in 70 mihilitres of anhydrous alcohol. A sodium ethylate solution containing 0.2 mol of dissolved sodium is added thereto, 45 grams of p-ethoxyvinylethyl-thionophosphonle acid mono55 . chloride are then added dropwise with stirring and the mixture is after-stir@red at 40' C. for 2 hours. After working up as usual, 63 grams of the new ester are obtained. Yield: 84 percent of the theoretical. The new ester is not distillable even under high vaciium. 60 The new ester kius rats per os at 250 milligrams per kilogram. Flies are still killed with certainty at a concen@tratiori of 0.001 percent. Apbides are destroyed with certainty by 0.1 percent solutions. 65 Example 10 S OC2H5 II/ C2HsO.CH=CH-P \ S -CH2-C]12.N(C2H5)2 70 34 grams of p-diethylaminoethylmercaptan (B.P. 54' C./10 mm. Hg) are dissolved in 100 millilitres of methylethyl ketone. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto with stirring. To the solu-tion thus obtained tbere is added at 30' C. 75 3,047,605 8 55 grams of p-ethoxyvinylethyl-thionophosphonic acid monochloride. The mixture is after-stirred at 40' C. for two hours and then worked up in usual manner. 69 grains of the new ester are thus obtained as a yellow waterinsoluble oil. Yield: 88 percent of the @theoretical. The ester is not distillable even under high vacuum. Exatnple 11 s OCH3 II/ C2H50.CH=CH-P 38 grams of p-chlorothiophenol are dissolved in 100 millilitres of methanol. A sodium methylate solution containing 1/4 mol of dissolved sodium are added at 30' C. The mixture is after-stirred at 30' C. for a half hour and 53 -rams of p-ethoxyvinylthionophosphonic acid methyl ester chloride (B.P. 55' C./O.01 mm. Hg) are then added with stirring at the aforesaid temperature. The reaction product is heated at 30-35' C. for a further hour and then poured into plenty of water. The separated oil is t@aken up with benzene, washed neutral and dried. After distilling off the solvent, 45 grams of the new ester are obtained as a pale yellow water-insoluble oil. Yieid: 59 percent of the theoretical. Example 12 s OCH3 II/ C2H5O.CH=C]I-P \ SC6HI3 30 grams of n-hexylmereaptan are dissolved in 100 millilitres of methanol. A sodium methylate solution containing 1/4 mol of d:.Ssolved sodium is added thereto at 30' C. The mixture is after-stirred at 30' C. for a half hour and 53 grams of p-ethoxyvinylthionophosphonic acid methyl ester chloride are then added at this temperature. After working up as usual, 36 grams of the new ester are obtained as a colourless waterinsoluble oil of B.P. 98' C./O.01 mm. Hg. Yield: 51 percent of the -theoretical. Example 13 S OCH3 C2H50.CH=CH-P S-<-@i-> 30 -rams of cyclohexylmercaptan are dissolved in 100 millilitres of methanol. A sodium methylate solution containing 1/4 mol of dissolved sodium is added thereto. At 30' C., 53 grams of p-ethoxyvinyl-thionophosphonic acid methyl ester chloride are added dropwise with stirrin.- ' The mixture is stirred at 30-35' C. for an hour and then workedupinuusualmanner. 35gramsofthenewesterof B.P. 105' C./O.01 mm. Hg are thus obtained. Yield: 50 percent of the theoretical. Example 14 s oc2H5 II/ CH30.CH=CH-P S-CH2-CH2.SC2Hs 32 grams of p-ethylmereapto-thioethyl ether (B.P. 67' C./12 mm. I-Ig) are dissolved in 120 millilitres of anhydrous alcohol. A sodium ethylate solution cotitaining 1/4 mol of dissolved sodium is added thereto at 30' C. 52 grams of3-methoxyvinylthionophosphonic acid ethyl ester chloride (B.P. 55' C./O.01 mm. Hg) are then added dropwise with further stirring at 30' C. The mixttire is after-stirred at this temperature for another hour and then worked up in usual manner. 54 grams of the new ester of B.P. 94' C./O.01 rnm. H.-,are thus obtained. 'n-ie ester is barely water soluble. Yield: 76 percent of the theoretical.. Aphides are completely killed by 0.001 percent slispensions of this ester.
[5]9 Exaniple 15 s oc2H5 II/ CH30.CH=CH-P \ S.CH2.Sc2H5 28 grams of a-methylmercapto-thioethyl ether (B.P. 50' C./12 mm. Hg) are dissolved in 1?0 millilitres of anhydrous alcohol. A soditim ethylate solution containing I/ 4 mol of dissolved sodium is added thereto. The mixture is after-stirred at 30' C. for 30 minutes and 53 grams of p-methoxyvinvl-thionophosphonic acid ethyl ester chloride are added dropwise at the said temperature. The product is after-stirred for another hour and then worked up in usual manner. 49 grams of the new ester of B.P. 90' C./00.1 mm. Hg are thus obtained as a colourless waterinsoluble oil. Yield: 72 percent of the theoretical. Spider mites are stiu completely killed by 0.0001 percent solutions. Example 16 0 Oc2H6 II/ C2H5O.CI-I@CH-P S-CE[2-CH2.SC2H5 6 grams of finely divided sodium are suspended in 200 millilitres of benzene. 31 grams of 3- ethylmercaptoethylmercaptitn (B.P. 67' C./12 mm. Hg) are added thereto with'istirring. The mixture is heated to 50' C. for a further 4 hours. To the suspension of sodium mercaptide thus obtained there are added with stirring at 50-60' C. 50 grams of p-ethoxyvinyl-phosphonic acid ethyl ester chloride (B.P. 70' C.10.05 mm. Hg). The mixture is after-stirrej at 50' C. for 2 hours and then poured into 200 milfflitres of ice-water. The benzenic solution is separated off, washed twice with 50- millilitreportions of water and dried over sodium sulphate. After distilling off the benzene under vacuum the residue is fr@actionated. 51 grams of the now ester of B.P. 1 10' C./O.01 mm. Hg are thus obtained. Yield: 72 percent of the theoretical. The estex is a pale yellow water-insoluble oil. Example 17 0 Oc2H5 C2H6O.CH=CH-P 37 grams of. p-chlorophenylmercaptan are dissolved in 100 millilitres of ethyltnethylketone. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added dropwise with stiriing at 30' C. 50 grams of p-ethoxyvinyl-phosphonic acid eihyl ester chloride are then added dropwise with stirrin- at 30' C. The mixture is afterstirred at 30' C. for an hour and then worked up as indicated in ExaTnple 1. 70 grams of the new ester are thus obtained as a water-insoluble oil which is not distillable even under vacuunl Yield: 90 percent of the theoretical, Example 18 0 002H5 @l / C2H50.CH=CH-P ci 46 grams of 3,4-dichlorophenylmereaptan are dissolved in 100 millilitres of ethylmethylketone. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added dropwise with stirring at 30' C. 50 grams of 6ethoxyvinyl-phosphonic acid ethyl ester chloride are then added with stirring at 30' C. The mixture is kept at 30' C. for another hour and then worked up as described in Example 1. 70 grams of the new ester are thus obtained as a water-insoluble oil which is not distillable even under vacuum. Yield: 82 percent of the theoretical. 3,047,605 10 Example 19 0 Oc2Hs II/ C2H5o.CH=CH-P 5 24 grams of p-thiocresol are dissolved in 100 millilitres of ethylmethylketone. A sodium ethylate solution containing 0.2 mol of dissolved sodium are added thereto at 30' C. 40 grams of p-ethoxyvinyl-phosphonic -acid ethyl 10 ester chloride are then added dropwise with stirring at 30' C. The mixture is heated at 30' C. @for another hour and then worked up in usual tnanner. 47 grams of a water-insoluble pale yellow oil are thus obtained. Yield: 15 82 percent of the theoretical. Example 20 0 002Ha II/ 02H50.CH=CH-P \ 20 S.CH2.CH2.sc2HS 43 grams of 9-ethoxyvinyl-thionophosphonic acid ethyl ester chloride (B.P. 60' C./O.01 mm. Hg) are dissolved in 100 millilitres of anhydrous alcohol. 25 millilitres of water are added thereto. 23 grams of potassium 25 hydroxide dissolved in 50 millilitres of water are then ;added with stirring and the reaction mixture, is kept at 70' C. for an hbur. 25 grams of 6-ethylmereaptoethylmercaptan are t@hereupon added withstirring and the mixture is heated to 75-80' C. for a further 2 hours. After 30 cooling, the reaction mixtlire is poured into 300 millilitres of water,,the separated oil is taken up with 200 millilitres of benzene and -the benzene solution is shaken twice with 50@millilitre-portions of a 4 percent sodium bicarbonate -solution. The benzene solution is dried over sodium sul35 phate. The benzene is distilled off and the residuefractionated under vacuum. 40 grams of the new ester of B.P. 110' C./O.01 mm. Hg -are thus obtained. Yield: 70 percent of the theoreti--al. The compound thus obtained is identical with the one 40 obtained according to Example 1. Example 21 0 oc2H5 c2H5o.clf=cH-p 45 \ S.CH2.COOC2HB 55 grams of,,6-ethoxyvinyl@thionophosphonic acid ethyl ester chloride are dissolved in 125 grams of anhydrous alcohol. 30 niillilitres of water are added thereto and then a solution of 29 grams of potassium hydroxide in 50 60 millilitres of water. The mixture is heated to 70' C. @for a further 2 hours and 32 grams of monochloracetic acid ethyl ester are then added. The mixture is heated with further stirring to 75' C. @for a further 1-2 hours. It is then cooled to foom temperature and poured into 55 300 miiiilitres of ice water. The separated oil is taken up with 300 niillilitres of benzene. The benzene solution is washed twice with 50 miltilitre-portions of a 4 percent sodium bicarbonate solution. The benzenic soliition is then dried over sodium sulphate. By fractionating 60 38 grams of the new ester of B.P. 115o C./O.01 mm. Hg are obtained. Yield: 54 percent of the theoretical. The new ester is a water-insoluble colourless oil. Eiample 22 65 0 oc2Ha [I/ C2HSO.CH=CH-P S.CH.COOC@H, I uli3 70 55 grarns of #@ethoxyvinyl-thionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of anhydrous alcohol@ 30 millilitres of water are added thereto and then a solution of 29 grams of potassiutft hydroxide in 60,mfflilitres of water. The mix-ture is heated to 75- C. 7,5 f<)r a further 2 hours and 47 grams of,8-bromopropionic
[6]acid ethyl ester are then added. The mixture is heated with further stirring at 75' C. for 2 hours and then worked up as described in Example 6. 40 grams of the new ester of 13.P. 120' C./O.01 mm. Hg are thus obtained. Yield: 54 percen-t of the theoretical. The ester is a cOlou,rless water-insoluble oil. Example 23 0 oc2HO II/ c2HSO.CH=CH-P \ SC6His(n) 55 grams of p-ethoxy-vinyl-thionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of anhydrous alcohol. 30 millilitres of water are added thereto with stirring and then a solution of 29 grams of potassiiim hydroxide in 60 milelitres of water. The mixture is heated to 75' C. for 2 hours and 55 gra@ms of n-hexyliodide are then added. The temperature is kept at 75' C. with stiiting -for a furLher 3 hours and then worked up as described in Example 6. 35 grams of the new ester of B.P. 110'/0.01 mm. Hg;are thus obtained. Yield: 50 percent of the theoretical. Example 24 0 oc2H5 C2H5o.oH=CE[-P S C 12H25 55 grams of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of 98 percent alcohol. 30 millilitres of water are added thereto and then a solution of 30@ graris of potassium hydroxide in 60 millilitr6s of water. The, mixture is heated with @stirring to 75' C. @for 2 hours and 74 grams of dodecyliodide are then added. Themixture is heated at 75' C. for a further 4 hours @and then worked up as described iri Example 6. 55 grams of the new ester of B.P. 160' C./O.01 m-m. Hg are thus obtained. Yield: 60 percent of the theoretical. Exaniple 25 0 oc2lr6 C2H5O.CH=CII-P B.CH2.CH2-N(C2H6)2 55 grams of p-ethoxyvinylthionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of 98 percent alcohol. 30 millilitres of water are added thereto and then a solution of 29 grams of potassium hyroxide in 60 millietres of water. T'he temperature is kept lat 75' C. for a further 2 hours and 68 grams of p-diethylaminoet,hyl-mercaptan are then added. The reaction product is then kept at an inside temperature of 75' C. for a further 4 hours. A@fter working up as usual, 54 grams of - the new ester are obtained. Yield: 73 percent of the theoretical. The colourless barely watersoluble oil is distillable under high vacuum only with decomposition. Example 26 0 OC2H6 II/ c2H5o.cEE=c]I-p 5 grams of p-ethoxyvinylthionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of 98 percent alcohol. 30 miuilitres of water are added thereto and ithen a solution -of 29 grams of potassium hydroxide in 60 millilitres of water. The temperature is kept at 75' C. for afurther 2 hours and 42 grams of p-chlorobenzyl chloride are then added. The reaction mixture is kept at an internal temperature of 75' C. for afurther 4 hours and then worked up in usual manner. 53 grams of the new ester are thus obtained as a pale yerow w-ater insoluble oil. Even under high vacuum the new compound is distillable only with deromposition. 3,047,605 12 Example 27 0 OC2H5 II/ CgH50.CH=CH-P \ 5 S-CI12.CN 55 grams of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of. anhydrous alrohol. 30 millilitres of water are added thereto and then a solution of 29 grams of potassium bydroxide in 60 10 milelitres of water. After having kept the reaction product at an internal temperature of 75' C. for Z hours, 20 grams of chloracetonitrile are added. The mixture is kept at 75' C. for a further 4 hours and then worked up in usual manner. 45 grams of the new ester are thus ob15 tained. Yield: 76 percent of the theoretical. The yellow water-insoluble ester is distillable only with decomposition even under high vacuum. Example 28 0 oc2HS 20 II/ C2H5o.cH=CII-P 55 grams of p-ethoxyvinyl-thionophosplionic acid ethyl 25 ester chloride are dissolved in 125 millflitres of 98 percent alcohol. 30 miflilitres of water are added thereto and then a solution of 29 grams of potassium hydroxide in 60 millilitres of water. The inix-ture is stirred at an internal temperature of 75' C. for a fiirther 2 hours and 50 grams 30 of a-chloromethyl-(4-chlorophenyl)-thioether are then added. The reaction product is kept at an internal temperature of 75' C. for a further 2 hours and then worked up in usual manner. 78 -ram of the new ester are thus obtained as a pale yellow water-insoluble oil. Yield: 89 35 percent of 4the theoretical. Example 29 0 oc2HS ii/ C2H50.CH=CH-P 40 55 grams of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are dissolved in 125 millilitres of 98 percent alcohol. 30 millilitres of water are added then and 45 then a solution of 29 grams of potassium hy&<)xide in 60 millilitres of water. The mixture is stirred at an internal temperature -of 75' C. for a furtlier 2 hours and 32 grams of benzyl chloride are then adde4,. The mixture is thereupon heated at 75' C. for a further 2 hours. After work50 ing up as usual, 37 grams of the new ester of B.P. 130' C/ 0.01 nim. Hg are obtained. Yield: 52 percent of the theoretical. The new @ester is a pale yellow water-insoluble oil. By the same way but using instead of p-ethoxyvinyl55 thionophosphonic acid ethyl ester chloride the equimoleeular amount of the p-n-butoxyvinylthionophosphon,c acid ethyl ester chloride there is obtained the ester of th'e following formula 0 Oc2H5 60 II/ c4HDO-CH=CH-P S-CHle Example 30 65 0 OCII3 C2IT50.CII=CH-P S.CH2.CH2.9(02Hb)2 70 53 grams of O-ethoxyvinyl-thionophosphonic acid methyl ester chloride are dissolved in 130 rnilliliters of methanol. 30 millilitres of water are added thereto and then a potassium hydroxide solution of 29 grams of potassium hydroxide in 60 mulilitres of water. The mixture is 75 heated to the boil for 2 hours and 25 grams of p-diethyl-
[7]i3 amincethyl chloride are then added, The reaction pirodur,t is then further heated to the beil for 2 hours. After working @up as usual, 17 grams of the new ester are obtained as a yellowish br4own-water-irisoluble oil. Yield: 25 percent of the theoretical. Example 31 0 OCH3 II/ C2H5O.CH=CH-P S.CH,E 53 grams of p-ethoxyvinyl-thionophosphomc acid methyl estet chloride (B.P. 55' C./O.01 mm. Hg) are dissolved in 130 millilitres of methanol. 30 millilitres of water are added thereto and then a solution of 29 grams of potassium hydroxide in 60 millilitres of water. The water is h,-ated to 70' C. for 2 hours and 33 grams of benzyl chloride are then added. The reaction product is afterstir-red at 70-75' C. for a further 2 hours and then poured into water. The separated oil is taken up with benzene, washed neutr@al and dried. After distilhng off the solvent, 38 grams @of the new ester are obtained as a pale yellow water-insoluble oil. Yield: 56 percent of the theoretical. Example 32 0 OCH3 II/ C2H50.CH=CH-P S.CH2.CH2 S C2Hs 53 grams of p-ethoxyvinylthionophosphonic acid methly ester chloride are dissolved in 130 mihilitres of methanol. 30 millilitres of waterare added thereto and then a solution of 29 grams of potassium hydroxide in 60 millilitres of water. The mixtuxe is heated to 70-75- C. for 2 hours and 32 grams of p-c hlorethylthioethyl ether are then added. The reaction product is kept at 7075' C. for a further 2 hours and then worked up in usual manner. 32 grams of the new ester are thus obtained as a yellow water-insoluble oil. Yield: 48 percent of the theoretical. Example 33 s oc2H5 II/ C2H5O.CH=CH-P \ O.CH2.CC13 38 grams of trichlorethylalcohol are dissolved in 22 grams of lanhydrous pyridine. 55 grams Gf 6-othoxyvinylthionophosphonic acid ethyl ester chloride (B.P. 60' C./ 0.01 mm. Hg) are added thereto with stitring. The temperature is kept at 45-50' C. for 8 hours and the mixture is then poured into 200 millilitres of ice-water to which 20 millilitres of dilute hydrochloric acid have been added. The separa@ted oil is taken up with benzene a-nd neutralised with sodium bicarbdnate. The bonezene solution is dried over sodium sulphate and then fractionated. 35 grams of the new ester of B.P. 105' C./O.01 mm. Hg are -then obtained. Yield: 43 percent of the theoretical. Example 34 S 002Hs II/ C2HsO.CH=CH-P \ O-CH2-CH2-S C2H5 To a suspension of 30 grams of anhydrous ground potassium carbonate in 1310 igrams of ethyl methyl ketone there are added with stirring 22 grams of 6-ethyl mercapto ethanol@ 45 grains of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are then added at an internal temperature of 75' C. with further stirring. The reaction product is heated to 75-80' C. for 3-4 hours and then cooled to room temperature. The Teaction product is poured into 300 millititres of water. The precipitated oil is taken up with 200 millilitres of benzene. The benzene solution is washed twice with 50millilitre portions of water and then dried over sodium 8,047,606 14 sulp-hate@ After distilling off the solvent under vacuum, 38 grams of the new ester remain behind as a colourless water-insoluble oil. B.P. 110' C./O.01 mm. Hg. Yield: 67 percent of the theoretical. Toxicity on rats per Os DL50: 100 milligrams per kilogram. Spider mites are killed completely with 0.0)1% solutions. 0.1% solutions have a systeniie action on aphides. Example 35 S Oc2H5 10 C2H5O.CH@CH-P o-e 27 grams of p-nitrophenol are dissolved in 200 milli15 litres of anhydrous eth3il alco-hol. 45 grams of a sodium ethylate solution containing 'Is mol of sodium are added thereto with stirring. The mixture is stirred at 25-30' C. for half an hour and 43 grams of p-eth oxyvinyl-thionophosphonic ;acid ethyl ester chloride are then added at 20 30' C. with further stirring. After a short time the reaction product shows a neutral reaction. The reaction product is then poured into 300- millilitres of water and the precipitated oil is taken up with benzene. The benzeiie solution is washed twice with 25 millilitre portions 25 of water and then dried over sodium sulphate. On fractionating, 50 grams of the new ester of B.P. 85' C./0;01 mm. Hg are obtained. Toxicity on Tats per os DL50: 25 mil-ligrams per kilogram. Aphides are destroyed with certainty with 0.00 I% solu30 tions. The new ester kills spider mites completely at a concentration of 0.001%. Moreover, the new ester has a strong ovicidal action on the eggs of red spiders. Example 36 35 S OC2H5 II/ C2HsO.CH=CH-P 0- <:@-NO2 40 ci 43 grams of 3-chloro-4-nitrophenol are dissolved in 150- millilitres of ethyl methyl ketone. 40 grams of dry ground potassium carbonate are added to this solution, The mixture is heated with stirring to an internal temperature of 75' C. and 55 grams of 6-ethoxyvinyl-thiono45 phosphonic acid ethyl ester chloride are added at this temperature. The mixture is heated at 75-80' C. for a further 4 hours and then worked up in usual manner. After distilling off the solvent, 57 grams of the new ester are obtained as a pale yellow water-insoluible oil. The 50 ester is disti@llable only with decomposition, even under high vacuum. Yield: 65 percent of the theoretical. Example 37 S OC2H5 55 C2H50.CH=CH-@l/ 0 ci N02 60 43 grams of 4-chloro-3-nitrophenyl are dissolved in 150 millilitres Of ethyl methyl ketone. 40 grams of dry and ground potassium carbonate are added thereto. 55 grams of O-ethbxyvinylthionophosphonic acid ethyl ester -chloride are added dropwise at an internal temperature 65 of 75' C. and the mixture is then heated at 75-80' C. for a further 4 hours. After working up as usual, 46 grams of the new ester are obtained as a yellow waterinsoluble oil which is not distillable even under high vacuum. Yield: 52 percent of the theoretical. 70 Example 38 S Oc2H5 C2H5O.CH=CH-P 0-< H 75 _>
[8]15 6 @rams of powdered sodium are suspended in 50 millilitres of benzene. 27 grams of cyclohexanol are added thereto with stirring at 50' C. The mixture is heated at 50' C. for an hour. The sodium has then dissolved. 55 grams of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are then added with further stirring at 50-55' C. The Teaction product is heated at 50-55' C. for another @hour and then worked up in usual manner. 50 grams of the new ester are thus obtained as a pale yehow water-insoluble oil of B.P. 105' C./O.01 mm. Hg. Yield: 72 percent of the theoretical. Example 39 S OC2Hs II/ C2H5O-CH=CII-P 0- /0\ @o cci C@/ I uH3 52 grams of 3-chloro-4-niethyl-7-hydroxycoumarin are dissolved in 150 millilitres of ethyl methyl ketone. 40 grams of dry and screened potassium carbonate are added therto. 55 grams of p-ethoxyvinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 75' C. to the suspension. The mixture is heated to -an internal temperature of 75-80' C. for 12 hours and then worked up in usual manner. 50 grains of the new ester are thus obtained as colourless crystalline needles melting at 76' C. Yield: 52 percent of the theoretical. Example 40 0 OC2Hs C2H50.CH=CH-P O-e--'@--NO2 N-/ 35 grams of p-nitrophenol are dissolved in 150 millilitres of ethyl methyl ketone. 40 grams of dry and screened potassium carbonate are then added with stirring. 50 grams of p-ethoxyvinylphosphonic acid ethyl ester chloride (B.P. 70' C./O.05 mm. Hg) are then added dropwise at an internal temperature of 75' C. The mixture is heated at 75-80' C. for a further 4-5 hours and then worked up in usual manner. 511 grams of the new ester are thus obtained as a yellow water-insoluble oil. Yield: 68 percent of the theoretical. The ester boils under a pressure of 0.01 mm. Hg at 135' C. Toxicity on rats per os DL50: 25 milligrams per kilogram. 0.01% solutions kill Colorado beetles with certainty- 0-01% 80lutions destroy aphides.. Example 41 0 002H5 II/ 021150.CH=CH-P \ O.CH2-CH2-S C2H5 6 grams of powdered sodium are suspended in 100 rnillilitres of benzene. 60 grams of p-ethoxy ethanol are added with stirr.;ng at 45' C. The sodium is then dissolved. 50 grams of 6- ethoxyvinylphosphonic acid ethy 1 ester chloride are then added with further stirring at 0 to +10' C. The nlixture is stirred at 10' C. for a further hour and then poured in 200 millilitres of water. After working up as usual, 47 grams of the new ester of B.P. 108' C./O.01 mm. Hg are obtained. Yield: 70 percent of the theoretical. Toxicity on rats per os DL50: 1000 milligams per kilogram. Example 42 s oc2H5 II/ C1130-CH=Cll-p 3,047,605 16 millilitres of beiizene. 30 grams of benzyl alcohol are added with stirring to this suspension at 50' C. The mixture is stirred for a further 2 hours. The sodium is then dissolved. 27 grams of p-methoxyvinyl-,thionophosphonic acid ethyl ester chloride (B.P. 55' C./O.01 mm. Hg) are added at 50' C. to the sol-ution thus obtained. The mixture is heated;at 50' C. for another hour, then cooled to room temperature and poured into 300 millilitres of ice-water. The separated oil is taken up with benzene, 10 separated from water and dried. On fractionating, 26 grams of the now ester are obtained as a pale yellow water-insoluble oil of B.P. 115o C./O.01 mm. Hg. Yield: 76 percent of the theoretical. By the same way but using the equirnolecular amount ][5 of p-n-propoxyvinyl-thionophosphonic acid ethyl ester chloride instead of pmethoxyvinyl-thionophosphonic acid ethyl ester chloride there is obtained the following compound S Oc2H5 II/ 20 C3H70-CH=CH-P O-CHle Example 43 25 s oc2H5 II/ CH30.CH=CH-P \ O.CH2.CH2.sc2H5 28 grams of j3-oxethyl-thioethylether are suspended in 30 150 millilitres of methyl ethyl ketone with the addition of 40 grams of anhydrous powdered potassium carbonate and of 1 gram of powdered cooper. 53 grams of p-niethoxyvinyl -thionophosphonic acid ethylester chloride,are added with stirrin.- at 80' C. to this suspension there. The mix35 ture is kept at 80' C. with stirring for a further 4 hours and then worked up in usual manner. 55 grams of the new ester are thus obtained as a water-insoluble yellow oil. Yield: 81 percent of the theoretical. In a concentration of 0.1 perce-.it, the estcr shows a 40 marked systemic ae-tion on aphids. Example 44 s 002,15 ii/ C2H5S-CH=CH-P \ 45 S-CHZ-cHr--Sc,IIS 36 grams of,3-ethylmereapto-ethylmercaptan (B.P. 67' C./12 mm. Hg) are dissolved in 100 n-iillilitres of anhydrous ethanol. At 30' C. there is added while stirring a -sodium ethylate solution in ethanol containing 1/4 mol 50 of sodium. At the same temperature there are added 59 grams of,3-ethylmereapto-vinylthionophosphonic acid ethyl ester chloride. The temperature is kept for I futher hour and the mixture is worked up in the usual manner. There are obtained 62 grams of the new ester boiling 55 at 0.01 mm. Hg at 118' C. The new ester is a colourless and water-insoluble oil. The yield amounts 87 percent of the theoretical. The toxicity on rats is 100 mg./kg. LD50. Example 45 60 S 0 C2116 II/ C2H5S-CH=CH-P S-CH2--CH2--N(C2H5)2 34 grams of p-diethylamino-ethylmercaptan (B.P. 54' 65 C./10 mm. Hg) are dissolved in 100 millilitres of anhydrous alcohol. There is added at 30' C. a sodium ethylate solution in anhydrous alcohol containing 1/4 mot of sodium. At the same temperature there are added dropwise while stirring 59 gtams of p-ethylmercapto-vinyl70 thionophosphonic acid ethylester chloride. The sametemperatlire is kept for 1 further hour and the mixture is worked up in the usual manner. There are obtained 77 grams of the new ester of the above shown formula as a slightly yellow water-insoluble oil. The yield is 94 30 grams of powdered sodium are suspended in 100 75 percent of the theoretical. The ne-w ester is undistillable
[9]3,047,606 17 even in high vacuum. The toxicity on rats orally is 25 mg./kg. LD95. Exaii?ple 46 s oc2H5 II/ 5 C2H5s-cH=CH-P\ SCOH13 30 grarns of n-hexylmereaptan are dissolved in 1GO cc. of anhydrous alcohol. There is added at 30' C. a sodium ethylate solution containing 1/4 mol of anhydr6us sodium. lo At the same temperature and wHe stirring there are added 59 grams of 6-ethylmercapto-vinyl-thionophosphonic acid ethylester chlor-ide. The temperature is kept for I further hour and the mixture is worked up in the usual manner. There are obtained 57 grams of the new ester as a colour- 15 less water-insoluble oil, boiling at 104' C./O.01 mm. Hg. Yield 73 percent of the theoretical. Example 47 S Oc2H5 20 11 / C2H5S-CH@CH-P \ S-CH2--SC2Hs 28 grams of a-methylmercapto-thioethyl ether (B.P. 50' C./12 mm. Hg) axe dissolved in 100 millilitres of 25 anhydrous alcohol. There is added while stirring and at a temperature of 30' C. a solution of sodium ethylate containing 1/4 mol of @anhydrous sodium. Thereafter are added while stirring at the same teriiperature 60 granis of P-ethyl-mercapto-vinyl-thionophosphonic - acid-ethyl30 ester ehloride. The temperature is kept for 11/2 hours at 30' C. and the mixture worked up as usual. There are obtained 74 percent of the new ester as a water-insoluble light brown oil. Yield 98 percent of the theoretioal. The toxicity on rats orally is 100 mg./kg. LD95. 35 Example 48 S Oc2Hs C2H5s-CH@CH-P SC12H25 4 0 51 grams lof dodecyl inercaptan are dissolved in 100 millilitres of -anhydrous alcohol. There isad@ded at 30' C. a solution of sodium ethylate containing 1/4 moi Of anhydrous sodium. Theroafter there,are added dropl%q'se at the same temperature 59 grams of 6-ethylmercapto45 vi--.ayl-thiono-phosphonic acid ethyl ester chloride. The tem,perature is kept for I further hour while sfuting and the m@ix@ture is worked up in the usual manner. There are obt,ained 85 grams of the new ester as a yellow waterinsoluble oil. Yield 86 percent of the theoretical. 50 Example 49 S OC2H5 II/ c2H5S-CH=CH-P S-CH@COOC2H5 55 I u-u3 34 grams of a-salfhydryl propionic acid ethyl estef (B.P. 48' C.111 mm@ Hg) are dissolved, in 100 millilitres of anhydrous alcohol. There is added while stir60 ring andat a temperature of 30' C.,a s<)Iution of sodium ethyla@te containing 1/4 mol of anhydrous sodiu@ni. Thereafter there are added at the same temperature 5@9 grams of p-ethyl mercapto-vinyl-thionophosphonic acid ethyl ester chloride. The temperature is kept for 2 further 65 hours and the niixture is worked up inthe iisual'manner. There are obtained 66 grams of the new ester as a yellow water-insoluble oil@ Yi@,ld 80% of@ the theotetic@dl. lbe toxicity on rats orally is 500 mg./kg. LD95. Exwnple 50 70 S OC2H5 II/ C2H5S-CH=CH-P > 75 is 29 gratns of cyclohexyl mercaptan,are dissolved in 100 millilitres of anhydrous alcohol. There is added to this solutiona solution of sodiuiii ethylate containing 1/4 mol of sodium. Thereafter there are added w@hile stirring and at a temperature of 30' C. 59 gra= of pethyl mercapto-vin-yl-thionophosphonic acid ethyl esterchlo@ride. The temperature is kept for further 2 hours and the mixture then is -worked up -as usual. There are ob. tained 65 grams of the new ester as a light brown waterinsoluble oil. Yield 83 percent of the theoretical. Example 51 s 0 02115 C2H5S-CH=CH-P S-CHz-CO002HS 30 grams of thioglycol acid ethyl ester are dissolved in 100 millilitr&s of anhydrous alcohol. At 30' C. there i6 iadded a solution of sodium othylate containing 1/4 iiiol of sodium. Thereafter there are,added drdpwise 59 gr@ams of [3-ethylmereapto-vi nyl-thionophosphonic acid ethyl ester enloride. The tenipera@ture is kept for 2 further hours at 30' C. and the mixture is worked up in a usual manndr. There are obtained 60 grams of the new ester as a yellow water-insoluble oil. Yield 76 percent of the thdoretieal. The toxicity on rats orally is 500 mg./kg. LD50@ Example 52 s 0 C 2115 02Hsg-CH=C)H-P 38 grams of p-chloro phenol mereaptein are dissolved in 120 mirilitres of anhydrous alcohol. Thereto is added while stirring a solution of sodium ethylate containing V4 mol of sodium. Thereaf@te:r there are add&d dropwise while stirring@ and at a temper@ature of 30' C. 60 grarns of 6-ethylmercapto-vinyl-thionophosphonic acid ethyl ester chloride. The temperature i8 kept for further 2 hours at 30' C. and the nuxture is then werked up in: a usual manner. There are obtained 68 grams of the new ester as a yellow water-insoluble oil. Yiel-d 80 perce:nt of the theoretical. Exanzple 53 S Oc2HSI C2H59-CH--CHO-CHCH2-N(c2H5)t 6 grams of sodium powder are suspended into 100 millilitres of dry benzene. At 50' C. there are added while stirring 60 grams of diethyl amino ethanol. After about 2 hours of stirring at said temperature the sodium has be&n converted into a corresponding alcoh6late. While stirrin,a there are added 60 grams of 6-eibyl riiercapto@ vinyl@thionophosphonic acid ethyl est6r chloride. Afti,-r stirring for 1 further hour at 60' C. the mixtuie'is poured into 400 millilitres of ice-water. The oil which precipitates is taken iip in 200 millilitres of benzene. The benzenic layer is dried overanhyd,@oiis sodiiini sul@haic andthe benzene then is distilled off. There are o-btained 50 grams of th@@ new este@ @s a colourless water-insoluble oil which distils at 0.01 mm. Hg at I - 18 " C. The yield is 64 percent of the theoretical. 'fhe toxicity on@ rats or,@lly is 10 mg.lkg. LD50. Example 54 S OC2H, - if/ CiHsS-CH=CH@-P
[10]19 6 grams of sodium powder are suspended in 100 milliiltres of benzene. At 50' C. there are added 40 grams of cyclohexahol. After stirring for 2 hours at 50' C. the sodiifm has been converted into a corresponding alcoholate. Thereafter there are added while stirring and at a temperature of 50' C. 60 grams of p-ethylmerca ptovinyl-thionophosphonic acid ethyl ester chloride. The temperature is kept at 60' C. for I further hour and the mixture is worked up then as described in the foregoing example. There are obtained 42 grams of the new ester as a pale yellow water-insoluble oil (B.P. 108' C./O.01 mm. Hg). Yield 57 percent of the theoretical. Example 55 s oc2H6 [I/ C2H5S-CH=CH-p 0-<:-:>-SCHS CH3 39 grams of 4-methyl mereapto-3-methylphenol (M.P. 59' C.) are dissolved in 70 millilitres of benzene. This solution is added at 5'0' C. and while stirring to a suspension of 6 grams of sodium powder in 150 millilitres of benzene. After conversion of the sodium into a corresponding alcoholate there are added while stirring at 60' C. 60 grams of p-ethyl mercapto-vinylthionophosphonic acid ethyl ester chloride. The temperature is kept for I further hour at 60' C. and the mixture then is worked up as described in the foregoing examples. There ,are obtained 70 grams of water-insoluble yellow oil. Yield 81 percent of the theoretical. The new ester is undistillable even in high vacuum. Example 56 s oc2H5 c2H5s-cH=CH-P 0-// SCH3 35 grams of p-methylmercapto phenol (M.P. 87' C.) are dissolved in 70 millilitres of benzene. This solution is added while stirring to a suspension of 6 grams of sodium powder in 100 millilitres of benzene at 60' C. After reaction of the sodium there are added while stirring at the same temperature 60 grams of i3-ethylmercaPtO-VinYlthionophosphonic acid ethyl ester chloride. The temperature is kept for I further hour at 60' C. and the mixture is worked up as usual. The product obtained is kept at a temperature of 80' C. under vacuum of 0.01 mm. There are obtained 53 grams of a yellow waterinsoluble oil. Yield 64 percent of the theoretical. Example 57 s 0 (D2H5 r,2H5S-C)H=Cll-p \ 0-//-\\ -NO2 40 grams of the sodium salt of nitrophenol are dissolved in 150 niillilitres of ethyl methyl ketone. There are added while stirring at 40' C. 60 grams of p-ethylmercaptovinyl-thionophosphonic acid ethyl ester chloride. The temperature is kept for 1 further hour at 40' C. and the mixture then is worked up as usual. The raw product obtained is distilled off at 80' C. under a pressure of 0.01 mm. There are obtained 59 grams of the new ester as a yellowish brown water-insoluble oil. Yield 71 percent of the theoretical. The new ester is undistillable even in high vacuum. Example 58 S 0 C21IS C2HsS-CH=CH-Ipl/ ci 33047,605 20 43 grams of 3-chlor6-4-nitrophenol are dissolved in 100- millflitres of anhydrous alcohol. To this solution there is added while stirring a solution of sodium ethylate containing 1/4 mol of sodium. Thereby the tempe-rature rises to 45' C. Thereafter there are added dropwise while stirrin- at 50',C. 60 grams of pethyl mercapto-vinylthionophosphonic acid ethyl ester chloride. The temperature is kept at 50' C. for further 2 hours and then the mixture is worked up in usual manner. There are, ob10 tained 55'grams of the new ester as a water-insoluble yellowish-brown oil, which is kept at a temperature of 80' C. for a short period under vacuum of 0.01 mm. Yield 60 percent of the theoretical. Example 59 15 S 002H5 II/ C2H5s-CH=CH-P \ O-CH2--CHz-SC2H5 28 grams of p-ethylmercapto ethanol are dissolved in 20 150 millilitres of methyl ethyl ke-tone. To this solution there are added while stirring 40 grams of dried and finely divided potassium carbonate and I gram of copper powder. Thereafter while stirring there are added dropwise at 80' C. 60 -rams of ethyl mareapto-vinylthionophos25 phonic acid ethyl ester chloride. The temperature is kept at 80' C. while stirring for further 4 hours, then the reaction product is diluted with 500 millilitres of chloroform and the resultin- salts are filtered off with suction. The mixture is worked up in a usual manner. There are ob30 tained 45 @rams of the new ester as a yellow water-insoluble oil, which is kept shortly at a temperature of 60' C. and under vacuum of 0.01 mm. Yield 60 percent of the theoretical. Example 60 35 0 OC2Hs C2H5S-CH=CH-P S-CR2-cooc2H5 60 grams of p-ethylmereapto-vinyl-thionophospbonic 40 a id efhyl ester chloride are dissolved in 120 millilitres of anhydrous alcohol. While stirrino there are add,-d 20 millilitres of water. The temperature rises to 70' C. Then there is added dropwise at 70' C. a solution of 29 grariis of potassium hydroxide and 60 millil@',tres of wa@Ler. The 45 temperature is kept for further 2 hours at 70' C. and ther--after there are added 32 grams o. monoch'oro acetic acid ethyl ester. The teriiperature is kept for 2 furtlier hours at 70' C. and the mixture is wor'Ked up as usual. There are obtained 40 grams of the new ester as a yellow 50 water-insoluble oil (,B.P. 108' C./O.01 mm. Hg). Yield 54 perceht of the theoretical. Example 61 0 0 C 2115 C2H5S-CH=CH-P \ S-CHr-CH2--SC2Hs 60 grams of #-ethyl mereapto-vinyl-thionophosphonic acid ethyl ester chloride together with 120 millilitres of anhydrous alcohol, 20 niillilitres of water and a solution of 6o 29 grams of potassium hydroxide in 60 millilitres of water are saponified exactly as described in the foregoin.- exnmple. After saponification there are added while stirriiig at 70' C. 32 grams of g-chloroethyl thioethyl ether. The temperature is kept for 2 hours at 70' C. and the mixture 65 is worked up in a usual manner. There are obtained 44 grams of the new ester as a li,@ht yellow water-insoluble oil (B.P. 114' C./O.01 mm. Hg). Yield 59 percent of the theoretical. The toxicity on rats orally is 10 mg./kg. LD5o. 70 Example 62 0 0 02TTS II/ C2H5S-011=CH-P S.-CII-COOC2HB I 75 CE3
[11]2,1 60 grams of p-ethylmercapto-vinyl-thionophosphoiaic acid etliyl ester chloride are saponified as described in the foregoing examples. T@,-, the saponification prodict there are added 47 grams of a-bromopropionic icid ethyl ester chloride. The temperature is kept at 70' C. for ,further 2 hours, and the riiixture is worked t@-o as Lisi-ial. Tbore are obtained 32 grams of the n-.w est-,r as a yei'low water-insoluble oil. The new ester is undistillable even ,in high vacuum. The toxicity cti rats orally is 50 m,- .Ikg. LD95. Exaniple 63 0 0 C 21-15 II/ C2I-15S-CH@CH-P S-CHz-CH2--N(C2Hs)2 60 grams of p-etbylmcrcapto-vinvl-thiorophospl-.o,,ic ;acid ethyl ester chloride are sapon-iiqed as desci-lbed in the foregoing examples. To the saponification prodtict there are added while stirring and at a tempc,,rature of 70' C. 35 grams of p-chloroethyl diethylamin,-. The ternperature is kept for further 2 hours at 70' C. and the mixture is worlced up in usual manner. After lower boiling impurities have been distilled off under reduced pressure@ there are obtained 30 grams of the new ester as a yellow waterinsoluble oil. Yield 39 rjerceit of the tbeoretical. The toxicity on rats orally is 10 mg.lkg. LD50- Example 64 0 oc2EI5 II/ C2H5S-CH=01-T-P 60 grams of 6-ethylmercapto-vinyl-thionophosphonic acid ethyl ester chloride are saponified as described in the aforegoing exaniples. To the sapoiiification product there are added while stirrin.- at 70' C. 40 grams of a-chloromethyl thiophenylether. The temperature is kept for further 2 hours at 70' C. and the -mixlure is worked up as usual. The water-insoluble yellow raw product obtained is kept :shortly under pressure of 0.01 mm. at a temperature of 80' C. There are obtained 49 grams of the new ester. Yield 59 percent of the theoretical. The toxicity on rats orally is 25 mg./kg. LD50. Example 65 0 Oc2H5 ii/ C2T-TSS-CH=CH-P 9-CH2-// ci 60 grams of p-othylmercapto-vinyl-thionophosphonic acid@ethyl ester chloride are saponified as usual. To this solution there are added dropwise while stirring and at a temperature of@ 70-80' C. 42 grams of p-chlorobenzyl chloride. The temperature is kept at 70' C. for further 2 hours and the mixture then is worked up as usual. 'nie raw product obtained is kept shortly under a pressure of 0.01 mm. at a temperature of 75' C. There are obtained 55 grams of the new ester. Yield 65 percent of the theoretical. Example 66 0 oc2H5 if/ CH30.CII=CH-P \ S.C]12.CH2.SC2H5 53 grams of #-methoxyvinyl-thioiophosphonic acid ethyl ester chloride are dissolved in 130 niillilitres of anhydrous alcohol. 30 millilitres of water are added thereto and then a solution of 29 grams of potassium hydroxida in 60 -millilitres of water. The mixture is kept at 751 C. with stirring and 32 grams of p-chloroethyl thioethylether are then added dropwise. The temperature is maintained at 75' C. with further stirring for a further 3 hours 8,047,605 22 and the product is then worked up in usual manner. 50 grams of the new ester of B.P. 90' C./O.01 mm. Hg axe thus obtained. Yield: 74 percent of the theoretical. The ester is sparingly water-soluble. 5 Spider mites are completely killed by 0.01% solutions of this ester. Example 67 S OC2HS It/ 10 c2H50.CIEI@CH-P \ O-C]12.CH2.N(C2H$)2 6 grams of sodium powder are suspended in 50 millilitres of benzene. 60 grams of diethylamirio-ethanol are 15 added with stirring at 50, C. After the sodiuni is dissolved, 55 grams of 6- ethoxyvinyl-phosphonic acid ethyl ester chloride (B.P. 60' C./0,01 mm. Hg) are added dropwise with stirring. The mixture is after-stirred for an hour and then worked up in usual manner. 64 grams of 20 the new ester of B.P. 114' C.10.01 mm. Hg are thus obtai-@ied. Yield: 86 percent of the theoretical. 0.01% solutions of the ester have a marked ovicidal action on the ovae of red spiders. Example 68 25 s OC2H5 C2l-I6O-CH=CH-@// \ O.CH2.CH2.N(CH3)3 3o 6 grams of sodium powder are suspended in 100 millilitres of benzene. 50 grains of dimethylaniino-ethanol are added with stirring at 50' C. The mixture is heated at 50' C. for a further hour and 55 grams of,3@ethoxyv inylthiono-phosphonic acid ethyl ester chloride are added at 35 this temperature. The reaction product is kept at 60' C. for a further hour and then poured into 300 millilitres of water. The separated, oil is taken up with plenty of benzene, the benzenic layer is separated and dried. The solvent is removed under vacuum. 32 grarns of the new 40 ester are Lthus obtained. Yield: 49 percent of the theoretical. Example 69 s 0 C ]El, 45 C2H50-CH=CH-P \ 0- C H2-- 0 H2-N (C2]E[S) I 6 grams of sodium powder are suspended in 100 millilitres of benzene. 50 grams of diethylamino-ethanol are 50 added thereto with stirriftg at 5@0' C. The mixture is afterstirred at 50' C. for half an hour. The sodium dissolves. 53 grams of 3-ethoxyvinyl-thiono@phosphonic acid methyl ester chloride (B.P. 55' C./O.01 nun. Hg) are then added with stirring at the said temperature. The@ reaction prod55 uct is after-stirred for an hour then diluted with 300 milli itres of benzene and poured'into 300 millilitres of icewatcr. The benzenir- layer is separated, dried over sodium sulphate and the filtrate is fractionated. 67 grams of the new e@,ter of B.P ' 80' C./O.01 mm. Hg are thus obtained. 60 Yield: 94 percent of the theoretical. Example 70 0 OC2HS ii/ 65 C2HSO-CH=CH-P \ ci 83 grams of,3-ethoxy-vinyl-phosphonic acid diethyl ester (B.P. 70' C./O.01 mm. Hg) are reacted at 65' C. with 70 phosgene. Reaction is carried out in such way that the temperature is kept at 65 to 70' C. When the reaction temperature no loiger can be maintained by introducing phosgene the reaction mixture is heated for I further hour at 70' C. The reaction product is distilled in vacuum, 75 There are obtained 33 grams of the ester chloride distilling
[12]3,047,605 23 at 70' C.10.105 mm. Hg. Yield 45 percent of the t@ieoretical. From the following table there is to be seen the activity of some of the inventive compounds of the above shown examples: COMPOUND @,@la' per Os - --------------- LDo5 50 -g./kg. Example 17 ----- 'id,, - ii;; 0.001% 40% aphids ------ ---------------- 0.01%1 100% LD, ,,o 50 mg./Icg. Example 18 -------- iraptid",,ero"ii;;--::: 0. 1% 100% p -------------- -------- o.i%i 100% at per os -------------------- LDos 100 m@./kg. Example 19 --------- caterpillars ------------------ 0. 1% 100% aphids (syst. act.) ----------- o.i%i 100% rat per os -------------------- LDg5 25 ing./kg. Example 20 --------- spider mites ----------------- 0.01% 100% apbids ---------------------- o.ooi%i 507, rat per os -------------------- LD,@ 50 mg.ll:,q. Example 21 --------- spider mites ----------------- 0.01% IC07@ flies ------------------------- 0.601%1 100% rat per os -------------- LD@io 5 g./,-,g Exainple 22 --------- @fit - ----- ------ 0.001% 106% [aphids (sFs@. 0. J% 100% rat per os -------------------- LD95 250 mg./Izg. E, xample 23 --------- spider mites ----------------- 0.1% 100% laphids (syst. act.) ----------- 0.1%1 loollo I.ra 'r Os LD " t pp 16. Example 24 ---------- idr ii;; ----------------- 1700@o aphids (syst. act.) ----------- 0.1% 1007, @,t p,,.,, ----------------- LD5o kg. pid, --------------- 0.01 100% Example 25 ---------- i,;;__ tRPthi,ls-j; ---- --------------- 0.01 100% ,@ )r _ _: --------------- LD5o Example 26 --------- @ spider mites --- -- ----------- 0.1 1 [caterpillars ------------------ 0.1 1,1 100%, rat per os -------------------- LD,o2.5 g./kg. Exaniple 27 --------- apbi(Is ---------------------- 0.001%1 90% spider mites ----------------- 100% rat per os ---- ---------------- LD5o 50 mg./kg. Examp'@e 2S --------- aplaids ---------------------- 0.01%1 100% spider mites ----------------- 0.01%1 100% ---------------- LD95 50 nig./kg. Example 29 --------- ---------------- 0.1% 100% act.) ----------- 0.1% 100% Example 30 --------- ---------------- 0.001% 100% -------------- 0.1% 100% Example 31 --------- ----------- 0.1% 100% ---------------- 0.1% 100% -------------- 0.001% 100% Example 32 --------- -fcey ---------------- 0.001% 90% Exainple 44 --------- ---------------------- 0.1% 100% r mites ----------------- 0.01% low, Example 45 --------- 0.01% 100% 0. 1% 100% Example 49 --------- ---------------- 0.01% 50;1@ aterpillars ------------------ 0.1% 100% Example 50 --------- aterpiuars ------------------ 0.1% 100% Exa-mple 51 --------- pliids ---------------------- 0.1% 100% aterpillars ------------------ 0.1% 110% at per os -------------------- LD95 2,50 mg./l@g, Examplp 52 --------- ---------------------- 0. 100% e9 ---------- ")0% Ex,,imple 53 --------- -ffY --------- '0 100% m---------------- 0. 100% Exampl(,, 55 --------- @"P ---------------------- 0. % 100% flies ------------------------- 0. 0 @% 50% Example 56 --------- at per os -------------------- LD5o 100 Tng./kg. LD5o 250 iiat per os -------------------- Example 57 --------- aphids ---------------------- 0.01% 50%, spider mites ------------------ 0.01%1 50% rat per os -------------------- LD,o 500 nig./K-g. Example 58 --------- aphids ---------------------- 0. 1% 100% spider mites ----------------- 0.01%1 70% rat por os -------------------- LDbo 10 mg.ikg. ExaTnple 59 --------- apbids ---------------------- 0.1%1 100% spider-mites ----------------- 0.01%1 100% ---------------- LD95 IGO mg./kg. ------------- 0. 1% 100 Example 60 --------- 1.ptl,pid'F-O' - % caterpillars -- ---------------- o.i%i 100% Example 61 irat per Os-: ------ ------------ LD5o 10 mg./k@. --------- aphids --- ------------------ 0""%l 100% spidr mite ------------------ 0.01% 75% rat per os -------------------- LD@5 50 ing.,Ikg. Example 62 --------- aphids ---------------------- 0.1%1 ioo% caterpillars ------------------ 0.1%1 100% ...... irat per os -------------------- LD6o 10 mg./kg. Example 63 --- aphids ---------------------- io.oi%l 10(% aphids (syst. act.) ----------- 0.1%1 100% ...... Irat per os -------------------- LDus 500 nig-g@g. Example 65 --- aphids ---------------------- 0. 1% 100% spider mites ----------------- 0.01% 60% 24 I
