US3929883A

US3929883A - Phenylformamidine derivatives

Info

Publication number: US3929883A
Application number: US344461A
Authority: US
Inventors: Dieter Durr; Georg Pissiotas
Original assignee: Ciba Geigy Corp
Current assignee: Novartis Corp
Priority date: 1972-03-29
Filing date: 1973-03-23
Publication date: 1975-12-30
Anticipated expiration: 1992-12-30
Also published as: DE2315041A1; ZA732129B; CS189605B2; GB1422216A; AT320611B; YU36156B; FR2178117A1; YU82473A; BR7302283D0; CA1051027A; KE2917A; IT988616B; DD107907A5; AR217029A1; BE797442A; IL41823A0; JPS496124A; SU651643A3; AU5368873A; IL41823A

Abstract

Compounds of the formula

WHEREIN R1 represents alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms, R2 represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms, R3 represents alkyl having 1 to 4 carbon atoms, R4 represents alkyl having 1 to 4 carbon atoms, and R5 represents hydrogen, or alkyl having 1 to 4 carbon atoms, and X represents an inorganic or organic acid radical and their acid addition salts, process for the manufacture of these compounds, compositions containing these compounds as active ingredients and use of these compounds for the control of parasitic pests on domestic and productive animals.

Description

United States Patent 11 1 Dan at al.

[ Dec. 30, 1975 [5 4] PHENYLFORMAMIDINE DERIVATIVES [73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Mar. 23, 1973 21 Appl. No.: 344,461

[30] Foreign Application Priority Data Mar. 29, l972 Switzerland... 4730/72 Mar. 29, 1972 Switzerland 4731/72 [52] U.S. Cl. 260/564 RF; 260/50l.l4; 260/3l6;

OTHER PUBLICATIONS Japanese Publication No. 2198/70, (l-24-70), Nippon Gijutsu Bochi Co. Ltd.

Primary ExaminerGerald A. Schwartz Attorney, Agent, or Firm-Harry Falber; Frederick H. Rabin [57] ABSTRACT Compounds of the formula wherein R represents alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms,

R represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms,

R represents alkyl having 1 to 4 carbon atoms,

R represents alkyl having 1 to 4 carbon atoms, and

R represents hydrogen, or alkyl having 1 to 4 carbon atoms, and

X represents an inorganic or organic acid radical and their acid addition salts, process for the manufacture of these compounds, compositions containing these compounds as active ingredients and use of these compounds for the control of parasitic pests on domestic and productive animals.

2 Claims, No Drawings PHENYLFORMAMIDINE DERIVATIVES R R 4 /R1 N CH N I R NH l H l or to the formula R 4. 1 (I R N =-ca N ax wherein R represents alkyl having 1 to 4 carbon atoms, alkenyl having 3 to 5 carbon atoms, or alkynyl having 3 to 6 carbon atoms,

R represents alkyl having 1 to 4 carbon atoms,

R represents alkyl having 1 to 4 carbon atoms, and

R represents hydrogen, or alkyl having 1 to 4 carbon atoms, and

X represents an inorganic or organic acid radical.

The alkyl, alkenyl, alkynyl or alkoxy groups applicable for formula I can be straight-chain or branched, interrupted with hetero atoms, unsubstituted, or substituted, e.g. with halogen. Halogen is fluorine, chlorine, bromine and/or iodine.

Examples of such groups are inter alia: methyl, methoxy, trifluoromethyl, ethyl, ethoxy, 2-chloroethyl, propyl, propoxy, isopropyl, isopropoxy, n-butyl, nbutoxy, i, sec.- or tert.-butyl, allyl, methallyl, lchloroallyl, 2-chloroallyl, l-butenyl, 2-butenyl, 3-butenyl, propargyl or isobutynyl.

Compounds of formula I and la preferred because of their action are such compounds wherein R represents methyl, ethyl, propyl, isopropyl, or nbutyl,

R represents hydrogen, methyl, ethyl, propyl, isopropyl or n-butyl,

R represents methyl, ethyl or isopropyl,

R represents methyl, ethyl, propyl, isopropyl, sec.-

butyl or tert.-butyl, and

X represents an inorganic or organic acid radical.

The compounds of formula I and la can be produced I by methods known per se; for example, by the following method:

(III) In formulae II and III, the symbols R to R have the meanings given for formula I. The starting materials of formulae ll and III are known, and can be produced by methods analogous to known methods.

The compounds of formula I have a broad biocidal action, and can be used for the control of parastic pests on domestic and productive animals. The compounds of formula I possess, in particular, acaricidal properties.

Surprisingly, the compounds according to the invention are appreciably more stable than analogous compounds disclosed in the literature, and have therefore a clearly more persistent action against all development stages, such as eggs, larvae and adults of members of the order acarina, particularly of mites, red spider mites and ticks, such as, e.g. of the families lxodidae, Argasidae, Tetranychidae and Dermanyssidae.

The acaricidal action of the said compounds can be substantially broadened and adapted to suit the given circumstances by the addition of other biocidal compounds. Suitable additives include the following active substances:

ORGANIC PHOS PHORUS COMPOUNDS (THl- 3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)phenyl-N-methylcarbamate l,3-bis(carbamoylthio)-2-(N,N-dimethylamino)- propanehydrochloride ,5-dimethylhydroresorcinoldimethylcarbamate 2-[ethyl-propargylamino]-phenyl-N-methylcarbamate 2-[methyl-propargylamino]-phenyl-N-methylcarbamate Z-[dipropargylamino]-phenyl-N-methylcarbamate 4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylamino1-3,5-xylyl-N-methylearbamate 2-[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]-phenyl-N-methylcarbamate CHLORINATED HYDROCARBONS -y-hexachlorocyclohexane [GAMMEXANE; LINDAN;

'y HCH] l,2,4,5 ,6,7,8,8-octachloro-3a,4,7,7a'tetrahydro-4,7-

methylene indane [CHLORDAN] 1,4,5 ,6,7,8 ,8-heptachloro,3a,4,7,7a-tetrahydro-4,7-

methylene indane [HEPTACHLOR] 1,2,3,4, l O, l O-hexachloro-l ,4,4oz,5 ,8,8oz-hexahydroend o-l ,4-exo-5 ,8-dimethanonaphthalene [ALDRlN] 1 ,2,3,4, 1 0,1 O-hexachloro-6,7-epoxy-1 ,4,4oz,5 ,6,7,8 ,8aoctahydro-exo-1,4-endo-5 ,8-dimethanonaphthalene [DIELDRIN] 1,2,3 ,4, l 0, l O-hexachloro-S ,7-epoxy-1,4,4oz,5,6,7,8,8a-

octahydro-endo-endo-5 ,S-dimethanonaphthalene [ENDRIN].

The compounds of formulae l and la can be used on their own or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid, and correspond to the substances common in formulation practice, such as, eg natural and regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of formulae 1 and la can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays, or solutions, the formulation of these preparations being effected in a manner commonly known in practice. Also to be mentioned are cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are produced in a manner known per se by the intimate mixing and- /or grinding of active substances of formulae l and la with the suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following preparation forms:

solid preparations: dusts, scattering agents, granulates,

coated granulates, impregnated granulates and homogeneous granulates;

liquid preparations:

a. water dispersible active substance concentrates:

wettable powders, pastes, emulsions;

b. solutions.

The solid preparations (dusts, scattering agents) are produced by the mixing of the active substances with solid carriers. Suitable carriers are, e.g. kaolin, talcum, bole, locss, chalk, limestone, ground limestone, attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline-earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal, etc., alone or in admixture with each other. 1

Granulates can be very easily prepared by a process in which an active substance of formula I or la is dissolved in an organic solvent, the thus obtained solution applied to a granulated mineral, e.g. attapulgite, SiO granicalcium, bentonite, etc., and the organic solvent then evaporated off.

It is possible also to produce polymer granulates; in this case the active substances of formula I or la are mixed with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde, or others); polymerisation is then carefully carried out in a manner which leaves the active substances unaffected, and granulation performed actually during the gel forming process. It is more favourable, however, to impregnate finished porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester and others), having a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, e.g. in the form of their solutions (in a low-boiling solvent), and to then remove the solvent. Polymer granulates of this kind can be also sprayed in the form of microgranulates, having bulk weights of preferably 300 g/liter to 600 g/liter, with the aid of spray apparatus. Spraying can be carried out over extensive areas of useful plant crops by the use of aeroplanes.

Granulates can also be obtained by the compacting of the carrier material with the active substances and additives, and a subsequent reducing operation.

Moreover, it is possible to add to those mixtures additives stabilising the active substance and/or nonionic, anion-active and cation-active substances which improve, e.g. the adhesiveness of the active substances on plants and parts of plants (adhesives and agglutinants), and/or ensure a better wettability (wetting agents) as well as dispersibility (dispersing agents).

The following substances are, for example, suitable: olein/lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, ligninsulphonic acid, the alkali metal and alkaline-earth metal salts thereof, polyethylene glycol ethers (carbowaxes), fatty alcohol polyglycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, as well as latex products.

Water-dispersible concentrates of active substances, i.e. wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to obtain any desired concentration. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substances, and anti-foam agents and, optionally, solvents.

The wettable powders and pastes are obtained by the mixing and grinding of the active substances with dispersing agents and pulverulent carriers, in suitable devices, until homogeneity is obtained. Suitable carriers are, c.g. those previously mentioned in the case of 3,929,883 1 1 1 2 solid preparations. It is advantageous in some cases to The active substance is mixed with epichlorohydrin use mixtures of different carriers. As dispersing agents and dis olved with 6 parts of acetone; the polyethylene it is possible to use, e.g.: condensation products of l l nd cetyl polyglycol ether are then added. The sulphonated naphthalene and sulphonated naphthalene thus obtained solution is sprayed on to kaolin, and the derivatives with formaldehyde, condensation products 5 t n subsequently evaporated in vacuoof naphthalene or of naphthalenesulphonic acids with w l powder;

Phenol l formaldehyde, as as alkali, ammonium The following constituents are used for the preparaand alkaline-earth metal salts of ligninsulphonic acid, tion f (a) a (b) and (C) a 2 and (d) a 0% also alkylarylsulphonates, alkali metal salts and alkawettable powderZ line-earth metal salts of dibutyl naphthalenesulphonic l0 acid, fatty alcohol sulphates such as salts of sulphated a 40 art: )f active substance. hexadecanols, heptadecanols, octadecanols, and salts 5 g gr sodium lignin sulphonatc, of sulphated fatty alcohol glycol ethers, the sodium salt I p of sodium dibutyl-naphthalene ulp 54 parts of silicic acid. of oleyl methyl tauride, ditertlary ethylene glycols, b 25 parts of active Substance.

dialkyl dilauryl ammonium chloride, and fatty acid alkali-metal and alkaline-earth metal salts.

Suitable anti-foam agents are, e.g. silicones.

5 parts of calcium lignin sulphonate .9 parts of Champagne chalk/hydroxyethyl cellulose mixture (l:l

1.5 parts of sodium dibutyl naphthalene sulphonate. The active substances are so mixed, ground, sieved 19.5 parts fsilicic a id.

and strained with the above mentioned additives that Champagne Chan" 28.] parts of kaolin. the solid constituent in the case of wettable powders c) parts of act ve substance, has a particle size not exceeding 0.02 to 0.04 mm, and P 22 p fiy figyg y yg n h parts 0 ampagnc c a y roxyet y in the case of pastes not exceeding 0.03 mm. For the ccnulnsc mixture (ML preparation of emulsion concentrates and pastes, dls- 8.3 parts of sodium aluminium silicate, persing agents are used such as those mentioned in the ,2 :gfif L preceding paragraphs, organic solvents and water. Suit- 25 d) 10 parts of active substance, able solvents are, e.g. alcohols, benzene, xylene, tolu- 3 P L a -71 Sal's saturate at y a c0 0 su p ates. dlmethylsulphoxldei and mmeral fractlons boll 5 parts of naphthalencsulphonic acid/formaldehyde ing 11'! the range of 120 to 350C. The solvents must be condensate. practically odourless, non-phytotoxic, and inert to the 82 pans of active substances.

Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose, the active substance, or several active substances, of the general formula 1 and/or la is dissolved in suitable organic solvents, solvent mixtures, or water. As organic solvents it is possible to use aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils on their own or in admixture with each other.

The content of active substance in the above de- 40 scribed agents is between 0.1 and 95%; it is to be men- The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to produce (a) a 10% and (b) a 25% emulsifiable concentrate:

' t a) 10 parts of active substance, tioned m this connection that m the case of application 3.4 pans of epoxidiscd vegetable oil of the agents from an aeroplane, or by means f s m 13.4 parts ofa combination emulsifier consisting other suitable application devices, concentrations of up g i g s giiel gg y g i' ether and y y to 99.5% can be used, or even the pure active sub- 4O pares of dimethylformafidey stance. 43.2 parts of xylene.

' b) 25 parts of active substance, The active substances of formulae I and la are pre 25 parts of epoxidised Vegetable 0" p -gas follows: l0 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide, Dusts' 57.5 parts of xylene.

The following substances are used for preparation of (a) a 5% dust, and (b) a 2% dust:

From these concentrates it is possible to produce, by

a) 5 parts of active substance dilution with water, emulsions of any desired concen- 95 parts of talcum. {ration h) 2 parts of active substance 1 part of highly dispersed silicic acid p y 97 parts fta um- The following constituents are used to prepare a 5% spray:

The active substances are mixed and ground with the carriers. 5 parts of active substance,

Granulate. 1 part of epichlorhyd r n,

94 arts of ll I'Olll (boilin limits HEW-190C The following substances are used to produce a 5% p g g granulate:

EXAMPLE 1 5 parts of active substance, 81%; zgfi'gg y 'g ether Production of N,N-dimethyl-N-(2,6-diethylphenyl)- 3.50 parts of polyethylene glycol, formamidine. Parts knoll (Pamclc Production of the compound of the formula 01-1 N cu N 40 ml of dimethylformamide and 40 ml of thionyl chloride are stirred for 2 hours in 200 ml of absolute toluene at 40C; an addition is then made dropwise at 40-50C of 59.8 g of 2,6-diethylaniline diluted with 200 ml of anhydrous toluene. The reaction mixture is heated slowly for 4 hours to the boiling point, and refluxed for a further 5 hours. The reaction mixture is cooled; ice water is added, the whole rendered alkaline with sodium hydroxide solution, and the organic phase separated and dried over sodium sulphate. Distillation yields the product in ca. 85% yield; B.P.: 7779C/0.03 Torr.

The following further compounds are produced in an analogous manner:

N,N-dimethyl-N'-(2,6-dimethylphenyl formamidine,

N-methyl-N-butyLN 2,6-dimethylphe nyl formamidine N-methyl-N'-( 2.6-dimethylphenyl formamidine, M.P. 82 83C N methyl-N'-(2,6-diisopropylphenyl)- formamidine. M.P. 62 63C oil EXAMPLE 2 Action against ticks A. R/iipicephalus bursa In each case, 5 adults or 50 tick larvae were placed RP. 132C/ll Torr B.P. 93C/0.02 Torr M.P. 165 166C M.P. 186 187C into a small glass test tube, and the test tubes them immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active substance emulsion could be absorbed by the cotton wool.

An evaluation in the case of the adults was made after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test.

The compounds according to Example 1 were effective, in the above test, against adults and larvae of Rhipicephalus bursa.

B. Boophilus microplus (larvae) With a dilution series analogous to that in Test A, tests were carried out in each case with 20 OP-sensitive larvae.

The compounds according to Example 1 were effective in the above test against sensitive larvae of Boophilus microplus.

We claim: 1. N,N-dimethyl-N-(2-methyl-6-ethyl-phenyl)-formamidine.

2. N-methyl-N-n-butyl-N(2,6-diethyl-phenyl)-formamidine.

Claims

1. N,N-DIMETHYL-N''-(2-METHYL-6-ETHYL-PHENYL)-FORMAMIDINE.

2. N-methyl-N-n-butyl-N''-(2,6-diethyl-phenyl)-formamidine.