United States Patent Office E. 2 As individual phosphoric diester halides may be 2,754,302 listed: phosphoric acid or thiophosphoric acid dimethyl chloride, -diethylester chloride, -diethylester bro 2-6-DIMETHYLEENS-PHOSPHORIC mide, -dipropylester chloride, -di-isopropylester chloride, 5 -diamylester chloride. Hans Gysia and Alfred Margot, Basel, Switzerland, as- The following examples illustrate further the produc sigors to J. R. Geigy A. G., Basel, Switzerland, a tion of the new compounds. Parts are always given as Swiss firm parts by weight and the temperatures are in degrees centi No Drawing. Application April 4, 1952 graade. Sri.So.28666;" " " O EXAMPLE 1. Claims priority, applicationa Switzerlands April 20, 1951 parts12.3 of parts sodium of iny-lutidone 150 parts are of added abs. ethanol. to a solution 20 parts of 2.3 of 3 Claims. (CI. 260-297) di-isopropyl phosphoric acid chloride are added to the The present invention concerns new phosphoric acid theSolution whole of theis boiled sodium under salt of reflux y-lutidone for 9 so hours. obtained After and of the general formula: cooling, the which has precipitated from Chs the solution is filtered off and the is removed O- froin the filtrate in the vacuum. Any remaining ?y-lutidone N(, o-P^ 20 can be removed by shaking out with . The 2.6- N dimethyl pyridyl-(4)-di-isopropyl phosphoric acid ester CH X O-alky (I) obtained is suitable without further purification for the wherein X represents a member selected from the group production of agents for the control of pests. The ester consisting of and Sulphur, and wherein each alkyl can be distilled in a high vacuum. B. P.0.3 123. group contains a maximum of five carbon atoms. 25 It is advantageous to condense the sodium salt of y it has now been found that such compounds have a lutidone with phosphoric acid diester chloride in an inert very good insecticidal and acaricidal activity and, as ac gaseous atmosphere, e. g. in a nitrogenous atmosphere. tive ingredients, are excellently suitable for the produc The coinpounds shown in the following table can be tion of agents for the control of pests, in particular for produced in an analogous manner. Some of the phos the control of aphids and acarids. The new compounds 30 phoric acid esters can be distilled in a high vacuum with are active both as contact poisons and systemic insecti out decomposition, the boiling points are given in these cides. They are distinguished from the most active aro cases. On the other hand only a few of the thiophos matic aliphatic phosphoric acid esters such as p-nitro phoric acid esters can be distilled. phenyl-diethyl-thiophosphoric acid ester partly by their Table slighter toxicity to warm blooded animals and partly by 35 General formula: CH3 their stronger systemic action. O-alkyl Many of the compounds according to the present in- N^ O-P vention have a cholinesterase-inhibitant action and are -- X O-alkyl suitable, therefore, for the production of pharmaceutical ÖH, preparations. 40 The new compounds can be produced by reacting an aliphatic phosphoric acid diester halide or a thiophos No. X alkyl Boiling Point phoric acid diester halide of the general formula: mm. Ig o C. O-alkyl 88: 1182, Ha-P S 2His ------N X O-alkyl (II) The biological properties of the new compounds can wherein Hal represents chlorine or bromine and X and be applied in the most varied fields of and the alkyl have the meanings given above, with 2,6-dimethyl- 50 nature of the compositions used can be varied accord 4-pyridone or with a salt of the enol form of this com- ingly. The active compounds can be used as such, e. g. pound. in the form of powder or dispersed in the atmosphere as The reactions may be performed in either the presence gas, mist or Smoke. However, for most purposes it is or absence of inert solvents such as benzene, toluene, di- more economical to combine them with suitable carriers oxane, ethyl ester. It is advantageous to 55 or diluents. A number of such substances, suitable for add acid binding agents such as sodium or potassium the usual forms of application such as compositions for carbonate when free heterocyclic compounds are used. dusting or spraying (suspensions), solutions, aerosols, The alkali salts, and also e. g. the salts of monovalent emulsions and semi-solid preparations (ointments) are heavy metals are particularly suitable as salts of the enol listed below: forms. 60 Thus as solid, pulverulent carriers may be used, e. g.: In particular, compounds derived from alkanols with calcium carbonate in the form of whiting or ground lime 1 to 5 carbon atoms come into question as phosphoric Stone, koalin, bole, bentonite, talcum, powdered mag acid diester halides of the general Formula II. As alco- nesia, kieselguhr, boric acid, tricalcium phosphate, also hols inay be named for example: , ethanol, n- powdered wood, powdered cork and other materials of propanoi, isopropanol, butyl and amyl alcohols. a vegetable nature. By adding wetting agents and pro Some of the phosphoric acid diester halides are al- 65 tective colloids such pulverulent preparations may be ready known. The others can be produced in an anal- made to give suspensions in water suitable for use as ogous manner, e. g. by reacting phosphorus oxyhalides spraying agents. The active substances may be combined or phosphorus thiohalides with 2 mols of the correspond- with the carriers by, e. g., impregnating the latter with ing alcohols or mercaptains or metal compounds thereof Solutions of the active agents, by mixing the liquid active or some may be produced by sulphurisation of the corre- substances with the carriers or by milling the components sponding phosphorus acid diester halides. together. 2,754,802 3 4. Solutions (for spraying) in high boiling solvents, such ent and 10 parts of solid puverised residue of sulphite as kerosene and similar oil fractions or in methyl waste liquor are homogeneously ground with 80 parts of naphthalenes, xylenes and the like, are best suited for carrier. Should a greater wetting action be required, the the direct spraying of the object treated, but also for Sulphite waste liquor residue can be replaced by 5 parts impregnating wood. Solutions in low boiling solvents of the sodium salt of dibutylnaphthalene sulphonic acid such as trichlorethylene, tetrachlorethane, ethylene chlo and 5 parts of blood albumin. The carrier may consist of ride are suitable for spreading the active ingredient in one or a mixture of several of the following substances: the form of a mist. The latter solvents as well as, e. g. chalk, kaolin, bentonite etc. benzine, xylene and chlorobenzene are also suitable in EXAMPLE 4 the impregnation of packing materials. 0 Fluoro-trichloromethane and difluoro-dichloromethane Emulsion.-20 parts of active ingredient are dissolved are examples of solvents and propellant agents suitable in 40 parts of a solvent and mixed with 40 parts of an for use in aerosols. emulsifying agent. Mixture of benzene, toluene, xylene, As emulsifying agents there come into consideration , lower aliphatic alcohols, petroleums may, for those of a cation active nature, such as quaternary am 5 example, be used as solvent. The emulsifiers may be monium compounds, as well as anion active agents such anicn active, cation active or non-ionogenic. As ex as soap, resin soap, soft soap, caseinate, aliphatic mono amples may be given: sulphonates of fatty acid esters, the esters of sulphuric acid and aliphatic aromatic sulphonic Sulphonate of ricinoleic acid butyl ester, quaternary com , furthermore, non-ionogenic emulsifiers such as high pounds or the condensation products of ethylene oxide molecular condensation products of ethylene oxide. They 20 and alkyl phenols or fatty alcohols. The concentrates are mixed with the active ingredients to form emulsion can be emulsified into ready-for-use emulsions with water. concentrates or are emulsified to form dilutable emulsion EXAMPLE 5 concentrates with or without the addition of suitable solvents such as e. g. acetone, alcohols, cyclohexanone, Solution (spray)-1 part of active ingredient either as benzene, toluene, xylene, tetrahydronaphthalene, alkylat 25 Such or after the addition of a solvent, e. g. an aromatic ed naphthalenes, phthalic acid esters, mineral and vege hydrocarbon, is dissolved in 99 parts of petroleum. table oils and, if required, water. (Boiling point 180-220.) White petroleum jelly and other ointment bases in What we claim is: which the active ingredient can be incorporated are suit 1. A phosphoric acid ester corresponding to the formuia able semi-solid extenders. 30 O-alkyl The active compounds may also be used together with O-P attractives or lures such as Sugar to form a bait, for in IN stance as a dusting agent with sugar as the main carrier, X O-alkyl or as sprays or fly catchers. 35 The different formulations can be better adapted for HC C the various uses intended in the usual way, i. e., by the NN 3 admixture of additives improving the distribution, ad wherein each alkyl group contains a maximum of five hesive power and resistance to rain on the treated surface. carbon atoms, and X represents a member selected from Examples of such additives are: fatty acids, resins, arti the group consisting of O and S. ficial resins, wetting agents, glue, casein, blood albumin, 40 2. A phosphoric acid ester corresponding to the formula sulphite waste liquor or alginates. Similarly, their bio O-alkyl logical activity can be extended by the addition of sub stances with bactericidal, fungicidal or insecticidal O-P properties. YO-Olkyl As bactericides there come into consideration, for 45 example, chlorinated phenols and quaternary ammonium compounds, suitable fungicides include e. g. sulphur in HC s all its various forms of application such as lime sulphur liquid, copper compounds such as copper oxychloride or wherein each alkyl group contains a maximum of five Bordeaux liquid, and fluorides. As examples of further 50 carbon atoms. insecticidal compounds there may be named: synthetic 3. A phosphoric acid ester corresponding to the formula products like 1.1-bis-(p-chlorophenyl)-2.2.2-trichloreth ane, y-hexachlorocyclohexane, , OCH tetraethyl pyrophosphate, chlorinated camphene and O-P 1.2.3.4.5.6.7.8.8-octachloro-4.7-methano-3a.4.7.7a-tetrahy 55 NOCH5 droindane and 5.5-dimethyl-dihydroresorcinol dimethyl ; suitable vegetable products are and C C. Totenone. In the following examples, parts are always given as parts by weight. 60 References Cited in the file of this patent EXAMPLE 2 UNITED STATES PATENTS Dusting agent.-1 part of active ingredient is homo 2,318,296 Dickey ------May 4, 1943 geneously ground with 99 parts of a carrier such as e. g. 2,583,744 Schrader et al.------Jan. 29, 1952 talcum. If desired, adhesives to improve the adhesive 65 properties of the dusted coating on plants may be added. FOREIGN PATENTS EXAMPLE 3 666,596 Great Britain ------Feb. 13, 1952 Suspension spraying agent.-10 parts of active ingredi