IL35153A - N-phenylcarboxylic acid amidines,their preparation and their use as acaricides - Google Patents

Description

acid amidines preparation and their use as acaricides A 2 invention relates to certain new acid to a process for their and to their use for the control of animal ectoparasites of the acarid It is known that some show an activity against animal ectoparasites French Patent cation 1 504 which not always satisfactory first compound of the table on page The Israeli Patent Specification discloses compounds of the aforesaid kind of the general formula which represents the same or different substituents which may be lower cyano or thiocyano and n is 2 or is a alkyl radical and and are the same or different are each hydrogen or lower These compounds are useful as herbicides and also for combatting harmful aoarids and Preferred compounds of formula A above are those in which is hydrogen or and are methyl or ethyl radicals and the phenyl ring is unsubstituted or stituted with one lower nitro or trifluorome hyl 2a present Invention consists in certain selected compounds and which belong to the group covered by the general formula A above but have not yet been and also in some other compounds not covered by the above formula The compounds of the present invention are acid amidines or salts of the formula in which X and are Independently chlorine or methyl either is alkenyl is hydrogen and R is or is alk Rtt hydrogen and R methyl or or is alky1 is methyl or ethyl R is methyl or provided and are both ethyl then R is also and if X and are not the same then and together must contain at least 4 carbon a 2b Preferably is with or alkenyl with carbon a and is preferably alkyl with 1 or 2 carbon atoms or It has surprisingly that these compounds have excellent acaricldal properties as compared with that of the most olosely related compound of formula A above and are especially good for the 4 in the presence of an agent which splits off water if the compound is to be a the aiaidine obtained is converted thereto by means of an If chloride and are used as starting the course of the reaction according to process varient can be represented by the following formula If and are used as starting the reaction course according to process variant can be represented by the following formula scheme The imide chlorides used as starting materials in process variant are already known and are defined by formula Among the chlorides which are suitable for the preparation of the active compounds according to the there may be mentioned for example the butyric and valeric imide chlorides which can be derived from the following aromatic The amines used as starting materials are already known and are unambiguously characterised by formula Among these amines there may be diethylamine and The anilines used as starting materials in process variant are generally The carboxylic acid amides are wise generally The reactions according to the invention can be carried out in the presence of an inert solvent term includes a mere Suitable solvents for aromatic such as toluene and and such as dichlorobenzenes and tetrachloroe hylene It may be desirable to use an in process variant All customary agents can be Particularly suitable are tertiary such as An excess of the amine of the formula can also be used as the As agents which split off water in process variant inorganic halides are preferably such as phosphorus thiophosphoryl phosphorus thionyl silicon tetrachloride and tin The reaction can be varied within a fairly wide In the Work is carried out at 10 to 20 to carrying out the the starting be vised in approximately equiraolar amounts and an equimolar amount the process or of the agent splits off water process variant may be The work carried out in the presence or absence a In all reactants are first and not until the reaction mixture heated elevated for example The working up can take place by pourin into drying and distillation of the end The active acid have a basic can be used as free bases or in the form of their for example nitrates or acetates The substances according to the invention exhibit strong acaricidal particularly against acarids as animal infest domesticated animals as sheep and At the same the compounds have only a low toxicity to They are therefore suited for the control of animal ectoparasites the Order the As economically important ectoparasites from the Family of the which play a large part in subtropical and there are mentioned for the Australian and South host cattle tick the Central and North cattle the African cattle and sheep ticks Rhipicephalus endiculatus Bhipicephalus simus 5 the same there can also be from the Family such as sheep sca the rabbit ear mite and representatives from Family such as the red poultry mite 10 In the course of ticks particular have become resistant the phosphoric acid carbamates used so effective control in is becoming In order to safeguard an livestock husbandry the areas of there is an urgent need for agents 15 which that is to sa and adults of resistant for of the genus be controlled As examples of strains which are becoming have sistant to the hitherto existing phosphoric acid ester agents 20 there may be mentioned in Australia the Ridgeland Strain and the Biarra strain of Boophilus compounds according to the invention are e ually both against the normally and against the for example of applicatio to the host they act both directly lethally on forms parasitic on the animal on the adult strongly inhibitorily in regard to egg so that the propagation cycle of the ticks is interrupted both in the phase on the animal and in the Depositing of eggs is substantially development and are According to the application form the new active such for suspensio pastes and These are prepared in known by mixture of the compounds with solvents carrier possibly wit use of emuisifiers dispersin it being possible in the of the use of water as that organic solvents may be used as auxiliary sol the following are arornatics orthodichloroberizene paraffins petroleum alcohols strongly polar a dimethyl sulphoxid and As solid carrier there are mentioned natural mineral powders synthetic inorganic carrier substances highly dispersed silicic as and anionic or cationic such as polyoxyethylene fatty acid polyoxyethylene fatty alcohol alkylar polyglycol alkyl sulphonates arid aryl quate nary ammonium salts with longer alkyl as dispersing sulphite waste liquors and methyl cellulos The formulations in from to ferably to per cent by weight of active The application concentrations be prepared from the formulation by dilution with The depending on application be varied within a wide and are generally from 10 to ppm preferably between and may take place in customary for exampl by atomising or by means of a bath Other auxiliaries or active such as disinfectan The aqueous solutions or of the active compounds according to the invention have a good stability under prnctical so that the can remain effective for three months even in the case of standing for lengthy periods and at a pH range of The invention therefore provides an cbmpositioh containing as active ingredient a compound according to the invention in admixture a solid diluent or carrier or in admixture with a liquid or containing active The invention also provides a method combating acarid pests comprises applying to the pests a habitat thereof compound according to the invention alone or in the form composition containing as active a compound accordin to the invention in admixture a solid or liquid diluent or The is applicable the of ectoparasites of the acarid Order on domestic the active compound being applied to the domestic The invention is illustrated by the following Example A test ovicidal on 3g of active compound are 7g of a mixture of equal parts by weight of ethyleneglycol monomethyl ether and nonylphenyl polyglycol The emulsion concentrate so tained is diluted with water to the application concentration desired in each engorged female ticks of the species Bqophilus microplus are immersed for one minute in this paration of acitve After immersion in each 10 transferred onto plastics dishes the bottom of which is covered with a disc of filter After 35 the effectiveness of the preparation of active compound is determined by ascertaining the inhibition of tho depositing of fertile eggs compared with the egg deposition of untreated control The effect is stated in means that fertile eggs ceased be and denotes that the ticks have deposited eggs in normal manner like the untreated control The results obtained are in the following Table test for cidal effect on ticks Active compound Constants Ovicidal effect against Boophilus nicroplus Inhibition with the stated concentration active compound French Patent Specification 504 Le A 12 323 11 Table test for ovicidal effect on ticks Active compound Constants Ovicidal effect against Boophilus rnicroplus Inhibition with the stated concentration of active compound 12 Table test for ovicidal effect on ticks Active compound Constants Ovicidal effect against Boophilus microplus 1000 Inhibition with the stated concentration of active compound CH5 CI J 13 Example 1 50 g are stirred together with 300 ml 54 g phosphorus pentachloride are introduced and heating under reflux is subsequently until evolution of hydrogen chloride has The benzene and phosphorus oxychloride formed are t en distilled off a the residue consisting of chloride is dissolved in a solution of 44 g in 500 ml Heating under reflu effected for a further 30 minutes and the mixture is poured into water and excess solution of The benzene layer is mshed with water and dried over potassium By fractional 43 acetic acid of boiling point mm Hg are 14 Example 2 in the preceding the is replaced by equimolar amounts of or crotylamine there are obtained acetic acid acetic acid Example 50g are stirred together with 300 ml 51g phosphorus pentachloride are and the mixture heated under reflux until the evolution of hydrogen chloride has The benzene and the phosphorus ox chloride formed are then distilled off in a the residue is ved in 100 ml benzene and added dropwise to solution of 31 and 50 ml triethylamine in 400 ml Heating under reflux is continued for a further 30 minutes and the ture is poured into ice water and excess solution of sodium benzene layer washed with water and dried over potassium By fractional 52g propionic acid of the boiling point are Example in the preceding the is replaoed by equimolar amounts of or there are 16 acetic acid propionic acid or Example 50g and 49g propionic acid amide are in 500 ml 58g phosphorus chloride are added and the mixture heated under reflux until the hydrogen chloride has Thereafter mixture is poured into ice water and excess solution of sodium the benzene layer is washed with water and dried over potassium By fractionnl 73g propionic acid amide of the point mmHg are Example 8 in the preceding Example laniline is by or there are obtained propionic acid amidine propionio aoid insufficientOCRQuality

Claims (1)

17 35153/3 CLAIMS. 1. N-phenylcarboxylic acid amidio.es of the general formula in whioh X and X* are independently chlorine or methyl and, either a) R' is alkenyl (O-j-O^ R" is hydrogen and R is methyl; or R' is alkyl (04-012) R" is hydrogen and R is methyl or ethyl; or o) R' is alkyl (02-.0Q) R" is methyl or ethyl R is methyl or ethyl; provided that: (i) if R' and R" are both ethyl then R is also ethyl; and (ii) if X and X1 are not the same then R, R' and £M together must oontain at least 4 oarbon atoms. - 18 - 35153/3 2. Compounds according to Claim 1 in which R is methyl or ethyl, R' is alkyl with 2-8 or. alkenyl with 3 or 4 carbon atoms,. R" is alkyl with 1 or 2 carbon atoms or hydrogen, and X and X' are chlorine, or methyl. 3. · The compound of the formula 4. The compound of the formula 35153 The compound of the formula The compound of. he formula The compound of the formula The compound of the formula compound of the formula The compound of the formula 55155/2 The compound of the formula The compound of the formula The compound of the formula The compound of the formula •J - 20 - 35 53/2 1 . 5. Salts of the compounda of any of Claims 3-1 · 1. 6. A process for the production of a compound according to any of Claims 1-15 in which (a) a H-phenylamide chloride of the formula in which R, X and X' have the meaning stated above is reacted with an amine of the formula R ' H-M< (III) R" in which R' and R" have the meaning stated above and, if the compound is to be a salt, the amidine obtained is converted thereto by means of an acid, or (b) an aniline of the formula X ^)-HH2 (*v> X· in which X and X' have the meaning stated above is reacted with a carboxylic acid amide of the formula R ' 0=C-¥< (?) R" in which R, R* and R" have the meaning stated above in the presence of an agent which splits off water and, if the compound is to be a salt, the amidine obtained is converted thereto by means of an acid. 35153/2 ÷ 17t A process according to Claim 16 in which the compound of formula (II) is one of those hereinbefore specifically identified. 18. A process according to Claim 16 and 17 in which the compound of formula (III) is one of those hereinbefore specifically identified. 19· A process according to any of Claims 16-18 in which the reaction is carried out in the presence of an inert solvent. 20. A process according to Claim 16 (b) or Claim 19 as dependant thereon in which the agent which splits off water is an inorganic acid halide. 21. A process according to any of Claims 16-20 in whic the reaction is carried out at 10-130°C. 22. A process for the production of a compound according to Claim 1, substantially as hereinbefore described in any of Examples 1-8. 23. Compounds according to Claim 1 whenever prepared by a process according to any of Claims 16-22. 24. An acaricidal composition containing an active ingredient according to any o Claims 1-15 or 23 in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent, 25. A composition according to Claim 24 containing from 0.1 to 95$ of the active compound by weight. 26. A method of combating acarid pests whidh comprises applyin to the pests or a habitat thereof a compound accordin to any of Claims 1-15 or S3 alone or in the form of a composition accord- 35153/2 • 4 ing to Claim 24 or 25. 27· A method according to Claim 26 in which a composition is used lepntainlng from 10 to 50,000 ppm of the active compound, by weight. 28. A method according to Claim 26 or 27 in which the active compound is applied to domestic animals for combating ectoparasites of the acarid order thereon. 23