NZ200208A

NZ200208A - Pyridyl-thiazolines their preparation and pesticidal compositions containing such

Info

Publication number: NZ200208A
Application number: NZ200208A
Authority: NZ
Inventors: E Beriger
Original assignee: Ciba Geigy
Priority date: 1981-04-02
Filing date: 1982-04-01
Publication date: 1984-03-16
Also published as: TR21033A; ES8306748A1; ES511036A0; AU8226982A; ZA822270B; GB2096993A; EP0062612A1; JPS57176984A; BR8201873A; IL65394A0

Description

New Zealand Paient Spedficaiion for Paient Number £00208 2 002 0 8 Priority Dai^s): . $ yJf. $J...........

Corr.p-.elo Specification Filed: Class CQ7MP$.

Publication Date: .. .V."?9.V™\ V P.O. JcHirns!, No: ■ • • if! ^ || ii Jl'flf "< •$> [*~f APR 1982 £8 ivi5L Patents Form No.5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "NOVEL THIAZOLINE DERIVATIVES" -J ,WE CIBA-GEIGY AG, a Swiss Corporation, of Klybeckstrasse 141, 4002 Basle, Switzerland, hereby declare the invention, for which -i-/we pray that a patent may be granted to Hie/us,,and the method by which it is to be performed, to be particularly described in and by the following statement:— (followed by paee I a * 20020 - 1At Case 5-13362/+ NOVEL THIAZOLINE DERIVATIVES The present invention relates to 2-[pyridyl-(31)]-thiazolines and the tertiary and quaternary salts thereof, to processes for producing them, and to their use for combating pests.

The 2-[pyridyl-(3')]-thiazolines have the formula ■ 1 Ri\ . N CH~Ro ' R2-f Y\.A-R4 ' (A>n (I) V wherein and R2 are each hydrogen, halogen or C^-C^-alkyl, R^ and R^ are each hydrogen or C-^-C^-alkyl, A is an inorganic or organic acid, and n is the number 0, 1 or 2, with the proviso that R^, R2, R^ and R^ are not all simultaneously hydrogen.

By halogen in this case is meant fluorine, chlorine, bromine or iodine, particularly however chlorine. The C-^-C^-alkyl groups denoted by R^ to R^ are methyl, ethyl, propyl, isopropyl or n-, i-, sec- or tert-butyl. Preferred in the case of R^ and R2 is the methyl group. Inorganic acids for A are for example: HCl, l^SO^, HBr and H^PO^; and organic acids for A are for example: saturated and r ? 0 unsaturated mono-, di- and tricarboxylic acids, such as formic acid, acetic acid, oxalic acid, phthalic acid, succinic acid and citric acid.

Preferred compounds of the formula I are those wherein is hydrogen, R£ is chlorine or methyl, and R^ and R^ are each hydrogen, or R-^ and R2 are each hydrogen, R^ is hydrogen, and R^ is methyl or ethyl, or R^ is methyl or ethyl, R^ is hydrogen, A is an inorganic or organic acid, and n is the number 0, 1 or 2.

The compounds of the formula I can be produced by methods known per se, for example as follows: 1 • r s r. l\\ I' I4 S0C12 1 _ • •-c-nhch-choh > i , J. • ■ Kn '' I 1 2 • • 1 V R3 (ii) R1\ . R-> R/ \ ^ 13 14 0 • »-cn + h n-ch—ch—sh • ix _ II' I 2. 2 #w# *N' (iii) (iv) In the formulae II, III and IV, the symbols R^ to R^ and n have the meanings defined under the formula I.

The processes 1 and 2 are performed at a reaction temperature of between -50°C and +130°C, preferably between -10°C and +100°C, under normal or slightly elevated pressure, and in the presence of a solvent or diluent inert to the reactants.

Suitable solvents and diluents are for example: ethers and ethereal compounds, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran; aliphatic and aromatic 0020 hydrocarbons, especially benzene, toluene and xylenes; and ketones, such as acetone, methyl ethyl ketone and cyclohexanone.

The starting materials of the formulae II, III and IV are known, or they can be produced by methods analogous to known methods.

The compounds of the formula I, and~2-[pyridyl-(3')]-thiazoline and salts thereof, are suitable for combating pests on animals and plants.

The compounds of the formula I, and 2-[pyridyl-(3')]-thiazoline and salts thereof, are thus suitable for combating insects for example of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, and phytopathogenic mites and ticks of the order Acarina.

It is to be emphasised in this connection that the stated compounds are characterised both by a strongly marked systemic as well as contact action against sucking insects, especially against sucking insects of the order Homoptera, and particularly against insects of the Aphididae family (for example Aphis fabae, Aphis craccivora and Myzus persicae), which are very difficult to control by means hitherto known. These active substances exhibit also a favourable action against flies, such as Musca domestica, and against mosquito larvae. They are in addition characterised by a broad ovicidal and ovilarvicidal action, and have a valuable action against ectoparasitic mites and ticks, for example of the families: Ixodidae, Argasidae and Dermanyssidae.

The compounds of the formula I, and 2-[pyridyl-(3')]-thiazoline and salts thereof, are used either in an unmodified form or preferably together with auxiliaries customarily employed in formulation practice, and are 200208 thus processed in a known manner for example into the form of emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, dusts or granulates, and also encapsulations in for example polymeric substances. The application processes, such as spraying, atomising, dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objects to be achieved and the given conditions.

The formulations, that is to say, the compositions or preparations containing the active substance and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active substances with extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions Cg to C-^j such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl-or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethyl-formamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated 2 002 08 adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite; and suitable non-sorbent carriers are materials such as calcite or sand. A large number of pre-granulated materials of inorganic or organic nature can also be used, such as in particular dolomite or ground plant residues.

Suitable surface-active compounds are, depending on the nature of the active substance to be formulated, nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties. By 'tensides' are also meant mixtures of tensides.

Suitable anionic tensides are both so-called water-soluble soaps, as well as water-soluble, synthetic, surface-active compounds.

Soaps which may be mentioned are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids ' ^0r examP-'-e sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for" example from coconut oil or tallow oil. Also to be mentioned are the fatty acid-methyl-taurine salts.

So-called synthetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and contain an alkyl group having 8 to 22 C atoms, 'alkyl' including also the alkyl moiety of acyl groups, for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are also the salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. :2 0 0 2 0 The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid group having 8 - 22 C atoms. Alkyarylsulfonates are for example the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product. Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct.

Suitable nonionic tensides are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups, and 10 to 100 propylene glycol ether groups, with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of nonionic tensides which may be mentioned are: nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylene-sorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally 2002 halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described, inter alia, in the following publication: "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey, 1979.

The pesticidal preparations contain as a rule 0.1 to 99%, particularly 0.1 to 95%, of active substance , 1 to 99.97o of a solid or liquid additive, and 0 to 25%, especially 0.1 to 25%, of a tenside. Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted.

The compositions can also contain additives such as stabilisers, antifoam agents, viscosity regulators, binders and adhesives, as well as fertilisers or other active substances for obtaining special effects.

Formulation examples for liquid active substances (% = per cent by weight) 1. Emulsion concentrates a) b) c) active substance % 40% 50% calcium dodecylbenzenesulfonate % 8% 6% castor-oil-polyethylene glycol ether (36 mols of ethylene oxide) % - - tributylphenol-polyethylene glycol ether (30 mols of ethylene oxide) - 12% 4% cyclohexanone - % % xylene mixture 65% % % Emulsions of any required concentration can be produc from such concentrates by dilution with water. 2A U <*-? 2. Solutions a) b) c) d) active substance 80% 10% 5% 95% ethylene glycol-monomethyl ether 207> - polyethylene glycol M G 400 - 70% N-methyl-2-pyrrolidone - 20% epoxidised coconut oil - - 17, 5% ligroin (boiling limits 160-190°C) - - 94% The solutions are suitable for application in the form of very fine drops. 3. Granulates a) b) active substance 5% 10% kaolin 947, highly dispersed silicic acid 1% attapulgite - 907, The active substance is dissolved in methylene chloride, the solutions is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. 4. Dusts a) b) active substance 2%, 5% highly dispersed silicic acid 1% 5% talcum 97% kaolin - 907> Ready-for-use dusts are obtained by the intimate mixing together of the carriers with the active substance.

Formulation examples for solid active substances (7o = per cent by weight) . Wettable powders a) b) c) active substance 25% 50% 75% sodium lignin sulfonate 5% 57> sodium lauryl sulfate 3% - 5% 2 002 a) b) c) sodium diisobutylnaphthalene sulfonate - 6% 10% octylphenolpolyethylene glycol ether - - 2% (7-8 mols of ethylene oxide) highly dispersed silicic acid 5% io% 10% kaolin 62% 27% The active substance is well mixed with the additives and the mixture is thoroughly ground in a suitable mill. Wettable powders which can be diluted with water to give suspensions of the required concentration are obtained. 6. Emulsion concentrate active substance 10% octylphenol polyethylene glycol ether 3% (4-5 mols of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (36 mols of ethylene oxide) cyclohexanone 30% xylene mixture 50% Emulsions of the required concentration can be obtained from this concentrate by dilution with water. 7. Dusts a) b) active substance 5% 87, talcum 95% kaolin - 92% Dusts ready for use are obtained by mixing the active substance with the carrier and grinding the mixture in a suitable mill. 8. Extruder granulate active substance 10% sodium lignin sulfonate 27« 2 002 carboxymethylcellulose 1% kaolin 87% The active substance is mixed and ground with the additives, and the mixture is moistened with water. This mixture is extruded and then dried in a stream of air. 9. Coated granulate active substance 3% polyethylene glycol (M G 200) 3%, kaolin 94% The finely ground active substance is evenly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Dustfree coated granulates are obtained in this manner.

. Suspension concentrate active substance 40%, ethylene glycol 10% nonylphenolpolyethylene glycol 6% ether (15 mols of ethylene oxide) sodium lignin sulfonate 10% carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 0.8% 75% aqueous emulsion water 32% The finely ground active substance is intimately mixed with the additives. There is thus obtained a suspension concentrate from which can be prepared, by dilution with water, suspensions of the concentration required. 2002 Example 1: Production of 2-[pyridyl-(3')]-thiazoline A solution of 10.4 g of nicotinic acid nitrile and 8 g of cysteamine in 40 ml of absolute alcohol is refluxed for 3 hours. The solution is subsequently concentrated in vacuo at 50°C bath temperature, and the residue is distilled under high vacuum.

There is obtained the compound of the formula . n ch / V 11 1 " "-c ch ij I v 2 (1) V having a boiling point of 90°C at 0.1 mm/Hg.

The following compounds are produced in an analogous manner: (2) N- 1h2 / ^ II ch3",i r\/CH2 m.p. 53-55°C N CH A 11 1 ■ -r-cv ,ch^ (3) ci-'i i V 2 m.p. 77-78°C n ch I /% I" I 2 • t~c ch (4) ■ ch -'J J V 2 m.p. 52-54°C V 200208 (5) ch3 I /\ -CH, V r\/CH2 • S b.p. 95-98°C/0.05 Pa (6) n ch, /\ 11 I . Y<\ .CH » • / 2 V CH„ ° = 1.5930 (7) N CHr / ^ 11 1 • X?-C CH-CH, ■j i V v b.p. 68°C/0.07 Pa (8) / V N CH II I —C. CH-CH„ HCl V 3 m.p. 148-150°C (9) / ^ \r N CH II I z i"VCH2 • s HCl m.p. 193°C (10) . N CH /% II I i r\/CH2 • s V . h2so4 2h 0 m.p. 150-153°C Example 2: Insecticidal systemic action: Aphis craccivora Rooted bean plants were transplanted to pots each containing 600 ccm of soil; and 50 ml of a test solution containing 25 ppm, 5 ppm and 1 ppm, respectively, of the compound to be tested was subsequently poured directly onto the soil. After 24 hours, aphids (Aphis craccivora)

Claims

- 13 - were settled onto the parts of plants above the soil, and a plastics cylinder was placed over each plant and drawn to by tying at the bottom in order to protect the aphids from any contact or gas action of the test substance. An evaluation of the mortality rate achieved was made 48 hours after commencement of the test. Two plants, each in a separate pot, were used per concentration level of test substance. The test was carried out at 25°C with 70% relative humidity. The compounds according to Example 1 exhibited against insects of the species Aphis craccivora the activity shown in the following Table. Biological test results In the following Table are summarised test results based on the Examples given in the foregoing, the index of values with regard to the percentage mortality of the pests being as follows: A: 70-100% mortality with 1 ppm of active substance, B: 70-100% mortality with 5 ppm of active substance, C: 70-100% mortality with 25 ppm of active substance. Compound No. Action against Aphis craccivora 1 A 2 b 3 b 4 b 5 C 6 C 7 A 8 c 9 C 10 c 2 002 - 14 - WHAT +/WE CLAIM IS- WHAT IC CLAIMED-j-&:

1. A 2-[pyridyl-(31)]-thiazoline of the formula r n—ch-r X% 11 1 (I) -a ch-r, . (a) R^-~H- I \ / 4 2 • • 9 V n wherein and R2 are each hydrogen, halogen or C-^-C^-alkyl, R^ and R^ are each hydrogen or C-^-C^-alkyl, A is an inorganic or organic acid, and n is the number 0, 1 or 2, with the proviso that R^, R2, R^ and R^ are not all simultaneously hydrogen.

2. A compound according to Claim 1, wherein R^ is hydrogen, R2 is chlorine or methyl, and and R^ are each hydrogen, or R^ and R2 are each hydrogen, R^ is hydrogen, and R^ is methyl or ethyl, or R^ is methyl or ethyl, and R^ is hydrogen, A is an inorganic or organic acid, and n is the number 0, 1 or 2.

3. The compound according to Claim 2 of the formula n ch- A 11 1 ■ CV<, YC\/CH2 V *

,4. The compound according to Claim 2 of the formula . n ch / ^ II I 2 ci-5 rv™2 \r 21, f% 1 15 -

5. The compound according to Claim 2 of the formula n ch„ A 11 1 ■ ™ " '_cv/h2 ™3-v- '

6. The compound according to Claim 2 of the formula ch 1 I 3 N CH- , A 11 1 *i r\/CH2 : v

7. The compound according to Claim 2 of the formula ; n ch 1 /% » 1 2 ii rc\/ch2 o V v- CH3

8. The compound according to Claim 2 of the formula N—CH A 11 1 .ii rvch"ch3. j • ; \

9. The compound according to Claim 2 of the formula N CH A 11 1 Ycvch-ch3 • /• S . HCl V 2 o■ o ? n V. s: i$ # B » ^i.'/ %£/ *%is - 16 -

10. A process for producing a compound according to Claim 1, which process comprises a) cyclising a compound of the formula s R/ 1XX\ 11 '4 n • •-C-NHCH-CHOH R2~tf~ i I ■; V R3 with thionyl chloride, or b) reacting a compound of the formula R. V , - v™ with a compound of the formula h„n-ch—ch-sh 2 I I E3 E4 wherein to R^ have the meanings defined in Claim 1.

11. A pesticidal composition which contains as active ingredient a compound according to Claim 1, or 2-[pyridyl-(3')]-thiazoline or salts thereof with inorganic or organic acids, together with suitable carriers and/or additives.

12. A method of combating pests on animals and plants, which method comprises applying thereto or to the locus thereof an effective amount of a compound according to ^ ^ Claim 1, or of 2-[pyridyl-(31)]-thiazoline or of salts ^ thereof with inorganic or organic acids. ^

13. A method according to Claim 12 for combating insects. BALDWINTBQ!^ & CAREY ATTORNEYS FOR THE APPLICANTS