Патент USA US3030275код для вставки
‘*1 "C ate 3,030,265 Patented Apr. 17, 1962 2 1 The new compounds of this invention may be readily prepared by reacting a metal or ammonium salt con 5,030,265 BUTYNYL PHGSE‘HATES taining the desired Z radical with the reaction product of Joseph ‘W. Baker ‘and John P. Chupp, Kirlrwood, Mo., assignors to Monsanto Chemical Company, St. Louis, a dihalogenated butyne and a salt of a phosphoric acid. The proportions of the reactants will vary in accordance Mo. a corporation of Delaware with the particular product to be obtained. The reaction of the Z radical salt, the butyne and the acid salt may No Drawing. Filed Nov. 9. 1959, Ser. No. 851,501 15 Claims. (Cl. 167--22) also be carried out in situ. This invention will be more fully understood by ref This invention relates to'new organic phosphorus com pounds and to insecticidal formulations comprising such 10 erence to the following examples. These examples, how ever, are given for the purpose of illustration only and compounds. More particularly, the invention is con are not to be construed as limiting the scope of the pres cerned with those phosphorus compounds which are de ent invention in any way. rived from the interaction of a metal or ammonium salt and a halogenated butynyl salt of phosphoric acid. EXAMPLE I It is an object of this invention to provide new and 15 0,0-Diethyl S-(4-Thiocyanato-Z-Butynyl) Phosphorothiolate useful compounds of phosphorus. It is a further object of this invention to provide a new class of highly useful insecticides. Still a further object is to provide new and useful formulations comprising such insecticides. The compounds of the present invention are phosphorus 20 derivatives of the general formula: no X A suitable reactor was charged with 7.6 grams (0.10 \I! mole) of ammonium thiocyanate dissolved in 100 ml. of, PX’CHzCECCHuZ R’O/ '25 wherein R and R’ represent like or unlike lower alkyl radicals or alkoxy substituted lower alkyl radicals, and X acetone. There was added 20.0 grams (0.078 mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphorothiolate with stirring. The mixture was heated at refluxing tem perature for 4 hours, after which it was cooled and and X’ are oxygen or sulfur. As employed herein, the ?ltered. The ?ltrate was stripped of acetone under vac term “lower” connotes radicals having from 1 to about 4 uum and water was added. There was then added 100 30 carbon atoms. In said general formula, Z represents a ml. of methylene chloride, and an aqueous layer sepa radical selected from cyano (--CN), thiocyano (—SCN), rated; The non-aqueous layer was washed with water and alkoxy (—OR"), sul?de (—SR"), mono or dithiocar then stripped under ‘vacuum to 100° C. at 10 mm. pres bamate sure to remove the methylene chloride. A yield of 15.3 S 35 grams (70.5% of theory) of 0,0-diethyl S-(4-thiocy H ll [I anato-2-butynyl) phosphorothiolate was obtained. Anal ysis showed 10.6% phosphorus and 22.1% sulfur as com (—S CNRZ", -s CNRg", or —0 CNRz”) xanthate pared with calculated values of 11.1% phosphorus and s l! ; 22.9% sulfur. (—- s o o R”) 40 benzothiazo - - When 23.4 grams (0.078 mole) of S-(4-chloro-2 butynyl) 0,0-dimethoxyethyl phosphorothiolate is sub stituted for the phosphorothiolate in the above charge, there is obtained 0,0~dimethoxyethyl S-(4-thiocyanato-2 butynyl) phosphorothiolate in good yield. L \. phthalimido, succinirnido and saccharinyl wherein R" is EXAMPLE II 45 4-(Diethoxyphosphinothioyllhio)-2-Butynyl Diethyldithiocarbamate an acyclic radical containing from 1 to about 8 carbon atoms or a phenyl radical. As employed in this applica tion, the term “saccharinyl” designates the radical derived 021150 from saccharin by removal of the hydrogen from the 50 nitrogen atom. ' ' s s \lll’sCHaCiCCHisgN/ C2H5O Exemplary of the radicals represented by R” are the C 21515 0211s A suitable reactor was charged with 9.12 grams (0.125 mole) of diethylamine and 70 ml. of acetone. There was alkyls such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, isoamyl, n-hexyl,‘ Z-methyl-l-pentyl, n 4.56 grams (0.06 mole) of carbon disul?de at ' heptyl, 3-ethyl-2-pentyl, n-octyl, 2-ethylhexyl, etc.; the 55 added 5-25” C. The mixture was stirred for one hour at 25 alkenyls and alkynyls such as vinyl,_allyl, n-butenyl-Z, 30° C., after which 15.0 grams (0.058 mole) of S-(4 diisobutenyl, propynyl, 2-butynyl, 3-hexynyl, etc.; other chloro-Z-butynyl) 0,0-diethyl phosphorodithioate was acyclics such as methoxyethyl, ethoxyethyl, , 2-chloro added. After heating for 5 hours at 65—70° C., the re ethyl, 2-chloroallyl, benzyl, etc.; and phenyl radicals such sultant mixture was cooled and ?ltered. The ?ltrate was as phenyl, xenyl, tolyl, chlorophenyl, nitrophenyl, cyano 60 stripped of acetone, and diethyl ether was added. After phenyl, methoxyphenyl, etc. washing with water and stripping to 75 ° C. at 5 mm. of Included within the above general structural formula pressure, a yield of 17.8 grams of 4-(diethoxyphosphino is a preferred group of compounds which have the thioylthio) -2-butynyl diethyldithiocarbamate was ob formula: ROX 65 R’O 1 tained EXAMPLE III 0,0-Diethyl S-(4-n-Pentylthi0) -2-Butynyl Phosphorodithioate where R and R’ are like or unlike lower alkyl radicals, and X and R" have the same meaning as above. Such 70 C2H5O against a wide variety of pests. I C2H5O compounds display an optimum degree of biocidal activity -> S PSCHzCEC CHzSCrHn 3,030,266 1% EXAMPLE VII A'suitable reactor was charged with 12.3 grams (0.1 mole) of 1,4-dichl0robutyne-2 and 20.3 grams (0.1 0,0-Diethyl S-(4-Berzz0thiaz0lethz'o)LZ-Butynyl mole) of ammonium 0,0-diethyl phosphorodithioate in Phosphorodithioate 200 ml. of acetone. .After heating at re?uxing tempera ture for 2 hours,~the mixture was cooled, and there was added 5.3 grams (0.05 mole) of sodium carbonate fol . C2H5O lowed by 10.4 grams (0.1 mole) of amyl mercaptan. The The \ S / A suitable reactor was charged with 20.3 grams (0.1 residue .was extracted with methylene chloride and washed 10 mole) of ammonium 0,0-diethyl phosphorodithioate in with water. The remaining solution was stripped to 80” C. at 3 mm. pressureto yield 23.2 grams (68% of theory) 200 ml..of acetone and 12.3 grams (0.1m01e) of 1,4 dichlorobutyne~2. _ The mixture was heated at re?uxing of 0,0-diethyl S-(4~n-pentylthio)-2-butynyl phosphorodi thioate as an amber liquid. PSCH2CECOH2SC/ l 1 022150 resultant mixture was heated at re?uxing temperature for 14 hours after which it was stripped of acetone. N S temperature for 2 hours and was then cooled. There 15 was added 16.7 grams (0.1 mole) .of mercaptobenzothia EXAMPLE IV zole followed by 6.2 grams (0.06 mole) of sodium car 0,0-Dz'ethyl S-(4-Thiocyanato-2~Butynyl) Phosphorodithioate bonate. This latter mixture was heated at re?uxing tem perature for 2.0 hours after which the solids were ?ltered out, and the ?ltrate was stripped of acetone. The resi 20 due was extracted with methylene chloride, and the or ganic solution was washed with water and stripped to olmo 0 \ll _ PSCHzCzCCHzSCN 021150 120° C. at 5 mm. of pressure. There was obtained 26.0 . A suitable reactor was charged with dichloride and am monium salt as in Example III. After cooling, 8.1 grams grams (65% of theory) of 0,0-diethyl S-(4-benzothia ‘16.3 grams 'of 0,0-diethyl S-(4-thiocyanato-2-butynyl) thioate. zo1ethi0)-2-butynyl phosphorodithioate as an amber .,(0.1 mole) of sodium thiocyanate was added, and the 25 liquid. When the mercaptan is 20.2 grams (0.1 mole) of 6 .resultant mixture'was heated at re?uxing temperature for chloromercaptobenzothiazole, and the second re?ux heat— - 15 hours. The reaction product was stripped of acetone, 'ing is shortened to 10 hours, the yield is 28 grams (92% of extracted with methylene chloride, and then stripped again theory) of the 6-chloro derivative of the phosphorodi to 98° C. at 10 mm. of pressure. There was obtained phosphorodithioate. vIn order‘ to obtain 0,0-dietl1yl S-(4-benzothiazolethio) ' Z-butynyl phosphorothiolate, 18.7 ‘grams (0.1 mole) of EXAMPLE V ammonium 0,0-diethyl phosphorothioate was substituted 0,0-Diethyl ‘S-(p-Chlorophenyl) Thio-Z-‘Butynyl Phosphorothiolate O v / as an amber liquid. ‘ V . EXAMPLE VIII . ‘l \rsoHm-Eo oms< - for the dithioate in the charge. The yield was 21.3 grams \ >>>-o1 0,0—Diethyl S-(4-Allylthz'o) -2-Butynyl Phosphorothiolate —— 021-150 Asuitable reactor was charged with 18.7 grams (0.1 40 mole) of ammonium 0,0-diethyl phosphorothioate in 200 ml. ofacetone and‘ 12.3 grams (0.1 mole) of 1,4 dichlorobutyne-2. After heating at re?uxing temperature for 2 hours, the mixture was cooled, and 6.2 grams (0.06 mole) of sodium carbonate was added followed immedi C2H50\(?PSCH2CECCH2SCH2CH=GH2 7' CZH5O A suitable reactor was charged with 3.7 vgrams (0.05 mole) of allyl mercaptan in 100 ml. of ethanol and placed ately by 14.7 grams (0.1 mole) of p-chlorothiophenol. under a nitrogen atmosphere. There was slowly added 2.7 grams (0.05 mole) of sodium methylate. This mix The resultant mixture‘was heated at re?uxing temperature ture was stirred at room temperature for 1 hour, after The residue was extracted with methylene chloride, and ' which 12.8 grams (0.05 mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphorothiolate was added. The resultant the organic extract was washed with water and stripped to 120° C. at 5 mm. of pressure. A yield of 30.7 grams mixture was heated at re?uxing temperature for 3 hours, the alcohol then being removed under vacuum. The res (84% of theory) of 0,0-diethyl S-(p-chlorophenyl)thio .idue was extracted with methylene chloride, washed with for 13 hours after ‘which the acetone was stripped o?. dilute sodium carbonate solution and water, and ?nally 2-butynyl phosphorothiolate was obtained. stripped to 110° C. at '1 mm. of pressure. There was When 20.3 grams (0.‘1rnole) of ammonium 0,0-diethyl phosphorodithioate was substituted for the phosphorothi 55 obtained 10.2 grams (71% of theory) of 0,0-diethyl S .(4-allythio) -2-butyny1 phosphorothiolate. oate, a yieldof 36.8 grams (97% of theory) of 0,0-di When 13.6 grams (0.05 mole) of S-(4-chloro-2-butynyl) ethyl S-(p-chlorophenyl)thio-2-butynyl phosphorodithio 0,0¢diethy1 phosphorodithioate'was substituted for the rate was obtained. ‘EXAMPLE VI 0,0-Diethyl S-(4-n-Pentylthi0)<2~Butynyl Phosphorothiolate 021150 0 \u _ PSOHZC=OCIIZSC5HH 021150 phosphorothiolate, a yield of 7.1 grams of 0,0-diethyl 60 S-(4-ally1thio)-2-butyny1phosphorodithioate was obtained as an amber liquid. EXAMPLE IX 0,0-Diethyl S-(4-Ethylthio) -2-Butynyl Phosphorothiolate CsHa'O 0 Fsornozccmscun In the procedure of Example IV, 15.6 grams (0.15 Q mole) of amyl mercaptan was substituted for the chloro thiophenol, and the secondre?ux heating was continued, for an additional hour. The yield'was 32.0 grams (100% 021150 ' Following the procedure of Example VIII, 3.1 grams (0.05 mole) of ethyl mercaptan was substituted for the of theory) of 0,0-diethyl S-(‘4-n-pentylthi0)-2-butynyl 70 allyl mercaptan. The yield was 10.4 grams (75% of phosphorothiolate. . theory) of 0,0-diethyl S-(4-ethylthio)~2-butynyl phos When 12.2 grams (0.15 mole) of thiophenol was sub phorothiolate. Analysis showed 10.2% vphosphorus and stituted for the mercaptan, a yield of 25 grams (72% of theory) of 0,0-diethy1 S-(4-phenylthio)-2-butynyl phos phorothiolate was obtained. . 23.2% sulfur'as opposed to calculated values of 11.2% phosphorus and 23.0% sulfur. 3,030,265 6 5 EXAMPLE XIV In the same manner, using 13.6 grams (0.05 mole) of 0,0-Diisopr0pyl S-(4-Ethoxythi0carb0nylthio-Z-Butynyi) S-(4-chloro-2-butynyl) 0,0-diethyl phosphorodithioate in stead of the phosphorothiolate, a yield of 4.0 grams T. ' I of 0,0-diethyl S-(4-ethylthio)-2-butynyl phosphorodithio ate was obtained as an amber liquid. (0119201110 0 ' EXAMPLE X s (CI-Is)2CHO A ‘suitable reactor was charged with 28.5 grams (0.1 0,0-Diis0pr0pyl S-(4-Ethylthio) -2-Butynyl Phosphorothiolate (C H3) 2 C H O Phosphorothiolate mole) of S-(4-chloro-2-butynyl) 0,0-diisopropyl phos 10 phorothiolate in 200 ml. of acetone, and 16.0 grams (0.1 mole.) of solid potassium ethylxanthate. The mixture O P SCHzCEC CH2SC2H5 was heated at re?uxing temperature for 12 hours and was then cooled and ?ltered. The ?ltrate was stripped Again following the procedure of Example VII, the of acetone, and the residue was‘extracted with methylene reactants were 2.5 grams (0.04 mole) of ethyl mercaptan, v 15 chloride. The extract was washed with water and stripped (0 Hz) 2 C H 0 100 ml. of ethanol, 2.2 grams ‘(0.04 mole) of sodium to 110° C. at 1 mm. of pressure methylate, and 11.4 grams (0.04 mole) of S-(4-chloro Z-butynyl) 0,0-diisopropyl phosphorothiolate. Heating "I There was obtained 0,0-diisopropyl S~(4aethoxythiocarbonylthio-Z-butynyl) at re?uxing temperature was carried out for 4 hours, and the ?nal stripping was to 120° C. at 1 mm. of pressure. 20 phosphorothiolate as an amber liquid. EXAMPLE XV A yield of 9.4 grams (76% of theory) of 0,0-diisopropyl S-(4-ethylthio)-2-butynyl phosphorothiate was obtained. N-(4-Diethoxyphosphinothioylthio-2~Butyny'l) v Phthalimide EXAMPLE XI 0,0-Diethyl S-(4-Cyan0-2-Butynyl) Phosphorodithioate 25 C2H5O\?PSCHzCECCHzCN 021150 021150 Y A suitable reactor was charged with 2.5 grams (0.05 30 mole) of sodium cyanate, 13.6 grams (0.05 mole) of S A suitable reactor was charged with 10.9 grams (0.04 mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro dithioate, 7.4 grams (0.04 mole) of potassium phthalimide, (4-chloro-2-butynyl) 0,0-diethyl phosphorodithioate, and and 150 ml. of acetone. After heating this mixture at refluxing temperature for 8 hours, it was cooled and ?l 35 tered. The ?ltrate was stripped of solvent. The residue the manner of Example IV to yield 0,0-diethyl S-(4 was extracted with methylene chloride, washed with water, cyano-Z-butynyl) phosphorodithioate. and stripped to 80° C. at 1 mm. of pressure. A' yield of 7.5 grams of N-(4-diethoxyphosphinothioylthio-Z-butynyl) EXAMPLE XII 100 ml. of acetone. The mixture is heated at re?uxing temperature for a period of 8 hours, and worked up in 0,0-Diethyl S- [4- (3-0x0-1,Z-Benzisothiazolin-Z-yl) -2 phthalimide was obtained as a dark viscous oil. 40 The speci?c activity of some of the individual com pounds disclosed herein is enumerated below. At the outset it should be made clear that such data is merely exemplary, and that similar results are obtained by em ploying any of the other compounds within the scope of this invention. Tests of systemic activity were made 45 by immersing the excised stems of bean plants in diluted emulsions of the compounds for three days. Leaves were thenlexcised, infested with the selected pest, and the per A suitable reactor was charged with 12.9 grams (0.05 cent kill was noted after 48 hours. Tested against the mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro thiolate, 10.2 grams (0.05 mole) of sodium saccharin 50 two-spotted spider mite, emulsions containing 100 p.p.m. of the ?rst compound of Example V or the ?rst compound and 100 ml. of acetone. The mixture was heated at re of Example'VI killed 100% of the test organisms. A ?uxing temperature for 12 hours, followed by cooling and kill of 90% was achieved using the third compound of ?ltration. The ?ltrate was stripped of acetone. The res Example VII. Systemic tests against the bean beetle idue was then extracted with methylene chloride, washed with water, and stripped to 110° C. at 1 mm. of pressure. 55 showed 100% kill at a concentration of 0.004% of the There was obtained 11.0 grams (61% of theory) of 0,0 diethyl S- [4-( 3-oxo-1,2-benzisothiazolin-‘2-yl) -2-butynyl] phosphorothiolate, dioxide. EXAMPLE XIII 0,0-Diethyl S-(4-Meth0xy-2-Butynyl) Phosphorodithioate ?rst compound of Example I and 60% kill at 0.004% of the ?rst compound of Example VI. The insecticidal e?ectiveness of the new compounds was also demonstrated in contact tests on the mobile and 60 resting stages, as well as on the ova, of the two-spotted spider mite. Concentrations of 0.1% resulted in 100% kill using any of the following: the ?rst compound of Example I; the compound of Example IV; either com pound of Example V; the ?rst compound of Example VI; 65 and either of the ?rst and third compounds of Example CzHsO A suitable reactor was charged with 11.0 grams (0.04 VII. Further, at concentrations of 0.05% either com mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphorodi pound of Example V still gave 100% kill against the thioate, 2.2 grams (0.04 mole) of sodium methylate, and mobile stage. 100 ml. of methanol. The mixture was heated at re?ux . Using the compounds of this invention against yellow ing temperature for 3 hours, after which it was ?ltered. 70 fever mosquito larvae, concentrations of 0.001% of the active ‘ingredient gave 100% kill with any one of the The ?ltrate was stripped of solvent, and the residue was compounds of Examples II through V. At 0.0003%, extracted with methylene chloride and Washed with water. Stripping to 100° C. at 1 mm. of pressure yielded 7.4 grams (69% of theory) of 0,0-diethyl S-(4-methoxy-2 butynyl) phosphorodithioate. - 100% kill resulted by using the ?rst compound of Ex ample VI, while the ?rst cornpound, of Example I gave 100% kill even with the concentration reduced to 3,030,265 ‘diluent or carrier. Althoughit is not intended that this invention be limited‘to any‘speci?c proportions of active ingredient and ‘adjuvant,.it should be noted that ready to'use liquid formulations comprising from about 0.001 to 5% of the active ingredient based upon the weight of the formulation ‘are preferred. In such liquid formula tions it is also preferred that the 'adjuvant comprise less 0.00002%. The ?rstcompound ofExarnple I was also tested for residual action on ?lter paper. Against the red ?our beetle, kills of 100% and 90% were obtained with concentrations of 1.0% and 0.5% respectively. It will be understood that the terms “insect” and “in secticide” are used herein in theirbroad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus, than about 5% ‘based upon the weight .of the formulation. With ready to use solid formulations, the parts of con the usage herein conforms to the de?nitions provided by Congress in PubliciLaw 104, the “Federal Insecticide, I10 centrate and diluent or carrier are substantially the same as de?ned for the liquids. However, in such solid formu~ Fungicide, and Rodenticide Act” of 1947, section 2, sub lations, the use of from about 2.5 to 25% of the active ingredient based upon the weight of the formulation is preferred. The percentage of 'adjuvant preferred in the solids is substantially the same as in the liquid formula tions. Itis also intended that the term “adjuvant” ‘includes .solid carriers of the type of pyrophyllite, talc, clay di atomaceous earth, and the like; and various mineral pow section h, wherein the term “insect” is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged,‘ usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to their allied classes of arthropods whose members 'are Wingless and usually have more than sixlegs, ‘as spiders, mites, ticks, centipedes, and wood lice. For maximum effectiveness the active ingredients of the present invention are admixed in:.insecticidally e?ective 20 ders, such 'as calcium sulfate and the like, which act as a dispersant, as a carrier, and in some instances perform amount with an insecticidaladjuvant. In order to pro the-function of a surface-active agent. vide formulations particularly adapted for ready and‘ ef Another method of applying'these insecticides is in ficient application to insects using conventional equipment, such formulations comprise those of both the liquid and the form of a water'suspension. However, to obtain an solid types as Well as the “Aerosol” ‘type formulations. '1 " Application may be directly to the insects, to the plant active aqueous suspension, there should be employed ‘a surface-active agent in sutticient amount to disperse and suspend the active ingredient. Examples of such surface active agents which can be employed in forming disper hosts of such insects, to soil or other media used for grow ing plants. In the pure state the active ingredients may be too effective or too potent in some applications to sions include the soft or hard sodium or potassium soaps, contact but thoroughly dispersed on the surface “to be .taurides; the alkylarylpolyether alcohols; the fatty acid have practical utility. For example, for most ‘effective "30 tall-oil, salts'of the alkyl and alkylaryl sulfonates; alkyl sulfates; a-lkylamide sulfonates, including fatty methyl protection, it'is preferred to apply the materialsrin intimate . esters of .polyhydric alcohols; the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Still other surface-active agents can be employed, the above merely protected. Therefore, the active ingredients have incor~ porated therewith a relatively inert surface-active ‘agent or adjuvant as a dispersing medium. Furthermore, such adjuvants have the effect of requiring only minute quan showing a representative ‘list of the more common vmate rials. tities of said ingredients of some formulations to obtain effective protection. A further advantage of so extend It should be pointed out that the formulations of this invention may also include sticking or adhesive agents, indicators and other active biocidal ingredients.‘ Such ing this material is to permit'?eld application by methods readily employed and still obtain effectively complete coverage of the material being protected. Thus, the formulations of thisinvention comprise the other ingredients may be supplementary insecticides, fungicides, bacteriocides, nematocides or selective herbi above de?ned active ingredients and ‘a suitable material as an adjuvant therefor. cides. The important feature ‘of the While the invention has been speci?cally described with regard to several embodiments, it is not thereby limited, invention is to provide an adjuvant such that upon the preparation of'a formulation of a concentration appropri and it is to be understood that modi?cations and varia tions thereof obviousto those skilled in the art may be made without departing from the spirit or scope of the ate for any particular application, the adjuvant Will be present to provide the proper type .of contact with the material being protected. Thus, in one embodiment the invention. adjuvant can comprise a surface-active agent such as a 50 detergent, a soap, or other wetting agent. What is claimed ‘is: l. A compound of'the formula Such a formula tion then comprises the active ingredient incombination with a minor proportion of the surface-active agent or adjuvant. Such 'a formulation is of practical merit be cause of its concentrated form and ease of‘transportation, 55 storage, and the like. Such a formulation lends itself directly to further dilution with a diluent or carrier with where Rand R’ are selected‘from the group consisting of out resorting to complicated mixing and blending pro cedures. Thus, such a formulation can be further diluted with a solid carrier of the dust type by a simple mixing operation. Likewise, such a formulation can be directly suspended in water or can be further diluted with an oil lower alkyl and alkoxy substituted lower alkyl radicals, 60 X and X’ are selected from oxygen and sulfur, and Z is selected from the group consisting of cyano, thiocyano, phthalimido, 'suc'cinimido, ibenzothiazo, saccharinyl, OR”, SR", which upon mixing with water thereby forms .an oil-in i i | water emulsion containing the active ingredient. One fur- ' SCNRZ”, ooNm”, sdNRi”, and siioR" ther example of the utility of such a formulation com 65 where R" is‘selected fromalkyl and alkenyl radicals hav prises the preparation by further dilution with a solid ing '1 to 8 carbon atoms and'phenyl radicals. carrier of a Wettable powder which upon admixture with "2. A compound of the formula water prior to-application forms a dispersion of the active ingredient and the solid carrier in water. R0 X In the preparation of the above-described concentrates, PSCH2OECOH2SR" the active ingredient may comprise up to about 95% 0f ‘R’O the concentrated formulation. To obtain 100 parts of already to use liquid formulation, from 1 to 50 parts of whereR and R’ are ‘lower alkylradicals, X is selected _.a concentrate-is admixed with from 50 to 99parts of a 75 from oxygen and sulfur, and.R".-is selected fromalkyl 3,030,265 10 X and X’ are selected from oxygen and sulfur, and Z is selected from the group consisting of cyano, thioc'yano, and alkenyl radicals having 1 to 8 carbon atoms and phenyl radicals. phthalirnido, succinimid-o, benzothiazo, saccharinyl, 3. 0,0-diethyl S-(p-chlorophenyl)thio-Z-butynyl phos phorothiolate. OR”, SR", 4. 0,0-diethyl S-(4-ethy1thio)-2-butynyl phosphoro s 0 thiolate. siiNRz", OiiNRZ", siiNRy’, and srlion" thioate. where R” is selected from alkyl and alkenyl radicals hav 5. 0,0-diethyl S-(4-ethylthio)-2-'butynyl phosphorodi 6. 0,0-diethyl S-(4emethoxy-2-butynyl) phosphoro 10 dithioate. 7. 0,0-diethyl S-(4-thiocyanato~2-butytnyl) phosphoro ing 1 to 8 carbon atoms and phenyl radicals. 13. A method of combatting insects which comprises treating the insects externally and the insect habitats with a composition containing as an essential active in thiolate. 8. 0,0-diethyl S-(4-allylthio)-2~butynyl phosphorodi thioate. 9. 0,0 - dimethoxyethyl S-(4-thiocyanato-2-butynyl) gredient thereof a compound of the formula ROX 15 \H rsornozoornsa" phosphorothiolate. 10. An insecticidal ‘formulation comprising an insecti cidal adjuvant and as an essential active ingredient there of a compound of the formula BOX R’O where R and R’ are lower alkyl radicals, X is selected 20 from oxygen and sulfur, and R" is selected from alkyl and alkenyl radicals having 1 to 8 carbon atoms and phenyl radicals. where R and R’ are selected from the ‘group consisting of lower alkyl and alkoxy substituted lower alkyl radicals, 14. A method of protecting plants from insects which comprises treating the plant with a composition contain 25 ing as an essential active ingredient a compound of the formula X and X’ are selected from oxygen and sulfur, and Z is RO\)“(PX'CHaCEOCHzZ selected from the group consisting of cyano, thiocyano, phthalimido, succinimido, benzothiazo, saccharinyl, OR”, SR”, s I! l! I] R'O 30 where R and R’ are selected from the group consisting of ll SONRZ”, OONRQ”, soNRl", and SCOR" lower alkyl and \alkoxy substituted lower alkyl radicals, where R” is selected from alkyl and alkenyl radicals hav ing 1 to 8 carbon atoms and phenyl radicals. 11. An insecticidal formulation comprising an insecti cidal adjuvant and as an essential active ingredient there of a compound of the formula X and X’ are selected from oxygen and sulfur, and Z is selected from the group consisting of cyano, thiocyano, 35 phthalimido, succinimido, benzothiazo, saccharinyl, OR”, SR”, s s siiNRw, Oil/NR2", scliNm", and srlion" ROX 40 where R” is selected from alkyl and alkenyl radicals hav R’O where R and R’ are lower alkyl radicals, X is selected from oxygen and sulfur, and R" is selected from alkyl and alkenyl radicals having from 1 to 8 carbon atoms and phenyl radicals. 12. A method of combatting insects which comprises treating the insects externally ‘and the insect habitats ing 1 to 8 carbon atoms and phenyl radicals. 15. A method of protecting plants from insects which comprises treating the plant with ‘a composition contain ing as an essential active ingredient a compound of the 45 formula with a composition containing as an essential active in gredient thereof a compound of the formula 50 R’O where R and R’ are selected from the group consisting of 55 lower alkyl and alkoxy substituted lower alkyl radicals, R’O where R and R’ are lower alkyl radicals, X is selected from oxygen and sulfur, and R” is ‘selected from alkyl and alkenyl radicals having ‘from 1 to 8 carbon atoms and phenyl radicals. No references cited.