FUNGICIDAL DIOXOLANYL- AND DIOXANYL-METHAZOLIUM DERIVATIVES, COMPOSITIONS COMPRISING THEM, PROCESS FOR PREPARATION THEREOF, AND USES THEREOF

Abstract: The invention provides fungicidal dioxolanyl- and dioxan­ yl-methazolium derivatives of formula I in which X is -CH= or -N= and Y is the anion of an organ­ ic or inorganic acid, and a method for the preparation thereof. These compounds are used in pest control, especially for com­ batting phytopathogenic fungi.

Description: FUNGICIDAL DIOXOLANYL- AND DIOXANYL-METHAZOLIUM DERIVATIVES, COMPOSITIONS COMPRISING THEM, PROCESS FOR PREPARATION THEREOF, AND USES THEREDF This invention relates to fungicidal dioxolanyland dioxanyl-methazolium derivatives, to compositions comprising them, to a process for the preparation thereof, and to uses thereof. The present invention provides fungicidal compounds of Formula I EMI1.1 wherein R1, R2, R3 represent independently of one another hydrogen or a halogen, at least one residue being a halogen; A represents one af the following groups (a), (b), (c) and (d): EMI1.2 Z = O or S; R5 = hydrogen or C1-C6 alkyl, possibly substituted with a halogen; methyl z methyl or ethyl; R7 = methyl, ethyl, or propyl, or R and R7 together constitute a tetramethylene group that can be substituted by 1 or 2 methyl groups; R8 = C1-C6 alkyl, C3-C4 alkenyl, 2-propinyl-, 3-halo-2 propinyl, C1-C6alkoxy-C1-C6-alkyl, or phenyl or benzyl possibly substituted singly. doubly, or triply by a halogen, alkyl, alkoxy, nitro, cyano, or trifluoro methyl; ; R9 and R10 represent independently of one another hydrogen or C1 -C4 alkyl and R11 = hydrogen, C1 -C4 alkyl, or -CH2 OH, the total number of C--atoms in R9, R10-, and R11 not exceeding 10; X represents -CH= or -N=; ; R4 represents C1-C16 alkylt possibly substituted singly or multiply by a halogen, CH, SCN, COO(C1-C3)-alkyl, phenyl, or naphthyl and/or possibly interrupted by EMI2.1 or S02, C3-C6 alkenylmethyl possibly substituted by a halogen or an alkylthio group, or C3-C6-alkinylmethyl possibly substituted by a halogen, the phenyl or naphthyl group substituent possible in R4 being also possibly substituted singly or multiply by a halogen, NO1, CN, OH, C1 -C4 alkyl, methcxy, tri- fluoromethyl, ar phenyl, -and Y represents the anion of an organic or inorganic acid. In case A falls into one of the groups (a), (b) or (c), then the compounds in Formula I stand for quarternary dioxolane. In case A represents the group mentioned in (d)-, then the compounds stand for auarternary dioxane. By alkyl or an alkyl part of another substituent are meant, according to the number of carbon atoms specified, for example the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, and their isomers such as isopropyl, isobutyl, sec.butyl, tert.butyl, 3-ethylpentyl, and 3-methylbutyl. The O- or S-atoms and the CO- or S02-groups possibly present in residue R4 can occur in the alkyl residue itself, but also between the alkyl residue and a possible substituent. By alkenyl are meant for example allyl, 2-butenyl, and 3-methyl-2-butenyl, whereas alkinyl represents, inter alia, propargyl. The halogen stands for fluorine, chlorine, bromine, or iodine. The anions are derived, for example, from hydrohalic acids, such as hydrochloric, hydrobromic, or hydroiodic acid, fluoroboric acid, nitric acid, phosphoric acid, thiophosphoric or dithiophosphoric acid, sulfuric acid, methanesulfonic acid, ethanesulfonic acid, acetic acid, haloacetic acids, propionic acid, hnlopropionic acids, butyric acid, oxalic acid, picric acid,- p-toluenesulfonic acid, or benzensulfonic acid. The triazole compounds of Formula I (X=N) are clearly preferred as fungicides. The compounds of Formula I can be prepared by reacting a compound of Formula II EMI3.1 with a compound of Formula III Y R4 (III) where R1, R2, R3, R4, A, X, and Y have the same meanings as in Formula I. The reactions can be performed in the pre-sence or absence of protic or aprotic solvents inert to the reactants. For example, the following can be used: alcohols such as ethanol; nitriles such as acetonitrile; ethers such as dioxane, dimethoxyethane, or butyl methyl ether; halohydrocarbons such as chloroform, trichlorethane, etc. The reactions are performed at normal pressure or at a slightly elevated pressure and at temperatures between 0 and 1800C and preferably between 50 and 1200C. This method also constitutes a part of the invention. In a further variant of the process, and if so desired, the anion Y in an already obtained compound of Formula I in accordance with basically known methods can be exchanged for another anion, for example by converting a quarternary azalium halide of Formula I into the corresponding azolium hydroxide with a base or an anion exchangerand reacting it with an acid (cf. Houben-Weyl 11/2, 620). The starting compounds of Formula II are known in particular from U.S. Patents 3,575,999; 3,936,470; 4,101,666; 4,106,664; 4,156,008, Swiss Applications 7963/78; 8001/78;- 8005/78; 8041/78, and U.S. AppLication 53,640, and analogs can be prepared according to the methods described therein. The compounds of Formula I have a better action when compared with these starting substancos already familiar as fungicides. Thus, undesirable plant-regulatory excess effects and the phytotoxicity sometimes caused by the compounds of Formula- It can be largely eliminated. The Formula I compounds can be used on their own or together with suitable carriers and/or admixtures that cat be solid or liquid and correspond. to the substances usual in formulation techniques such as natural or regenerated minerals, solvents, dispersants, wetting agents., adhesion agents, thickeners, binding agents, or- fertilizers. Substances of this kind are manufactured in a basically kno-wn- manner by intimate mixing and grinding of the components The Formula I compounds are found in the following practical forms (the data on the weight percentages representing ad-vantageous quantities of the active p-rinciple). Solid forms: dusting or spraying materials, (up to 10 a) granulates, coated granulates,- impregnation granulates and homogeneous granulates;- pellets (grains) (1 to 80R é) Liquid forms:. (a) dispersabic in water active principle- concentrates: wettable powders, pastes, 25-90, in the commercial pack, 0.01 to 15% in ready-for-use solution, emulsions; solution concentrates (10 to 50 0; 0.01 to 15 in ready-for-use solution) (b) Solutions: aerosols. The content of active ingredient in commercial products liesbetween 0.1 to 95 percent (w/w), the content of additives from 5 to 99.9 percent (w/w), whereby, in general, 0 to 30 percent (w/w) tenside can be found included in the additives. By tensides should hereby be understood contact surface- or surface- active agents which are mostly dissolved or dispersed in a liquid and are adsorbed particularly on contact surfaces. A tenside molecule contains at least one group which shows affinity to substances of stronger polarity - which in general causes the solubility in water and at least one other group with less affinity to water. Tensides are therefore molecules with one lipophil = hydrophob, i.e. molecule part which lacks affinity to water or has an affinity to lipids, mostly one carboxyl part with alkyl- and/or aryl-components and furthermore with one hydrophil = lipophob, i.e. molecular part which has an affinity to water and lacks affinity to lipids, e.g.. a perfluoralkyl part. Generally, products used in practical work are mostly mixtures of such compounds. Tensides not only make possible a good distribution of the active substance in a liquid, e.g. aqueous medium, but also an increased wettability of the plants. This leads to a reduction of the active ingredient in the finished product and thereby to a smaller environmental burden. The Formula I compounds can, of course, in order to suit the conditions obtaining, be used with other suitable pesticides to broaden the action spectrum, e.g. with fungicides, bactericides, insecticides, acaricides, herbicides, or agents that influence plant growth. The discovery covers also substances which contain at least one active substance as a component in Formula I, as well as the application of the substance to the fight against - and/or prevention of - an attack of microorganism. Furthermore, the present discovery also includes the manufacturing of the- substance, which can be recognized through the thorough mixing of the active substance with one or several substances described herein, respectively function groups Included is also a procedure for the fight against microorganisms, which distinguishes itself through the application of the compounds of Formula I, resp. the new substance Surprisingly, it has been found that compounds with the structure of Formula I exhibit a microbicide spectrum for the protection of cultivated plants that is very beneficial for practical r-equirements. The cultivated. plants within the scope of the present invention may be, for example: Cereal crops: (wheat, barley, rye, oats, rice); Beets: (sugar and fodder beets); pip fruits, stone fruits, and. berry fruits: (apples, pears, plums, peaches, almonds, cherries, strawberries-, raspberries, and blackberries); legumes:- (beans, lentils, peas., soya); oil cultures: (rape,. mustard,poppyseed, olives, sunflowers, coconut trees, castor-oil plants, cocoa tre-es, peanuts); cucumber plants: (pumpkins, cucumbers, melons); fibrous plants (cotton, flax, hemp,. jute.), citrus fruits: (oranges, lemons, grapefruits, tangerines); types of vegetables: (spinach, head lettuces, asparagus, types of cabbage, carrots, onions, tomatoes, potatoes, red peppers) or plants such as maize, tobacco, nuts, coffee, sugar cane, grapevines, hops, banana, natural rubber, and ornamental plants. The use of the active principles of Formula I on plants or parts (fruit, blossoms, foliage, stems, tubers, roots) of these and related useful cultures can check or destroy the occurrence of fungi, parts of the plant growing subsequently also being protected from such fungi. The active principles are effective against the phytopathogenic fungi of the following classes: ascomycetes (e.g. Erysiphaceae, Podosphaera, Venturia; basidomycetes, in particular rust fungi (e.g. Puccinia); fungi imperfecti (e.g. Botrytis and oniliales inter alia Cercospora), and the Omycetes of the class of Phycomycetes. In addition, the Formula I compounds sometimes have a systemic action. They can also be used as disinfectants for the treatment of seed (fruit, tubers, grains) and plant cuttings for protection against fungal infections and against phytopathogenic fungi occurring in the soil. The invention thus also comprises the use of the Formula I compounds to combat phytopathogenic microorganisms. The following substituents and combinations of these are preferred: with R1, R2, R3 2,4-dichloro-(the phenyl group is formed to the rest of the molecule in the 1-position) with a) R5 = hydrogen or C1 -C4 alkyl b) R6 and R7 methyl or (together) tetramethylene c) Z = O, R8 = C1-CT alkyl or phenyl with R4 EMI7.1 EMI7.2 (possibly substituted) or CH2CH (ii) CH2-CH=CH2, EMI7.3 -alkyl, EMI7.4 (possibly substituted by C1, NO2, CN, OH, CH3, OCH3, CF3); with X -N= with Y a halide, sulfate, nitrate, phosphate, methanesulfonate, ethanesulfonate, p-toluenesulfonate, or benzenesulfonate anion. Thus, it is found that the following groups are preferred: R1 R 2= chlorine R3 = hydrogen EMI8.1 where R5 is hydrogen or C1 -C4 alkyl R8 is C1-C3 alkyl or phenyl R9 and R10 are independently of one another hydrogen or C1 C4 alkyl, and R11 is hydrogen, C1-C4 alkyl, or CH20H, the total number of carbon atoms in R9, R10, and R11 not e-xceeding ten, X r-epresents -N=, R4 is C3-C6-alkenylmethyl, C3-C6alkinylmethyl, EMI8.2 alkyl, EMI8.3 (possibly substituted by Cl, N02, CN, OH, CH3r OCH3), or CH2CN and Y represents a halide, sulfate, nitrate, phosphate, methanesulfonate, ethanesulfonate, p-toluenesulfonate, or benzenesulfonate anion Furthermore, the compounds of the following subgroup Ib are favoured: R1 = hydrogen or chlorine = chlorine R3 = hydrogen EMI9.1 wherein R5 means ethyl or n-propyl, R8 represents C1 -C3 alkyl or phenyl, Rg means hydrogen or methyl, and R10 means hydrogen or C1-C3 alkyl, X = N = -CH2 -CO-R12 or -CH(COOR13), wherein R12 is C1-C4 alkyl or one unsubstituted phenylradical or one phenyl-radical substituted by alkyl, halogen, NO2, CN, OH, OCH3, CF3 singly or multiple; wherein R12 further means -CH2-CO 13 -CH2-COOR13 or -OR14; R13 stands for C1 -C4 alkyl; and R14 means alkyl, alkenyl or alkinyl each with maximum of 6 C-atoms or an unsubstituted phenyl radical or a substituted one by C1-C4 alkyl and/or halogen. In the structure element R4 = -CH2-CO-R12 either the hydrogen can be substituted by lower alkyl or the CO-group can be substituted by S02. In principle such groups R4 will behave comparably to the groups R4 in the subgroup Ib. The activity progression of a compound of Formula I in relation to a compound of Formula II cannot be derived from the molecular structure, because compounds R4V of Formula III do not contain this fungicide activity. One equimolar mixture of a compound of Formula II and one compound of Formula III exhibits, as expected, a weaker fungicide activity than a compound of Formula II by itself. It is therefore surprising that the quarternarization of compounds of Formula II with fungicidally inactive compounds leads R4Y to fungicides with favourable activity spectrum and decreasing phytotoxic side effects Favoured active substances are, e.g. the below listed compounds no. 1.9, 1.10, 1.15, 1.18,1.20, 1.47, 1.48, 1.49, 1.57,. 1.80, 1.81, 1.84, 1.85-, 1.86,. 1.88,. 2.10, 2.11, 2.12, 4.7, 4.23. These preferred groups are obviously part of the invention as well. The following Examples serve the purpose of explaining the- invention without limiting its scope. The data on temperature are in degrees centigrade, the data on pressure in millibars, and the data on parts and percentages refer to weight. Preparation Example Example 1 : Process for the manufacture of the quaternary salt of 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1 ,3-dioxolan-2- ylmethyl]-1H-1 ,2,4-triazole of formula EMI11.1 19 g of the compound 1-[2-(2,4-dichlorophenyl)-4-n-propyl- 1,3-dioxolan-2-yl-methylj-lH-1,2,4-triazole and 9 g of bromomethyl tert.butyl ketone were boiled in 700 ml of ethanol overnight under reflux. The mixture was then boiled down, the resin left behind was digested with ether, filtered under suction, and washed well with ether. The white precipitate melted at 156-1580C. The following Formula I compounds can be prepared in a similar fashion by using one of the methods described herein. EMI11.2 Table 1. (R1 = R2 = chlorine, R3 = H; EMI12.1 EMI12.2 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.1 <SEP> H <SEP> N <SEP> -CH3 <SEP> I <SEP> M.p. <SEP> 196 <tb> <SEP> O <tb> <SEP> 1.2 <SEP> H <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 175.3 <tb> <SEP> O <tb> <SEP> 1.3 <SEP> H <SEP> N <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 187 <tb> <SEP> O <tb> <SEP> 1.4 <SEP> H <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 205.9 <tb> <SEP> Cl <tb> <SEP> 1.5 <SEP> H <SEP> N <SEP> -CH2CH2-# <SEP> Br <SEP> M.p. <SEP> 241.1 <tb> EMI13.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> O <tb> <SEP> 1.6 <SEP> H <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 227-8 <tb> <SEP> OH <tb> <SEP> 1.7 <SEP> C3H7-n <SEP> N <SEP> -CH2-# <SEP> Cl <SEP> M.p. <SEP> 214-9 <tb> <SEP> NO2 <tb> <SEP> 1.8 <SEP> C2H5 <SEP> N <SEP> -CH2-C#CH <SEP> Br <SEP> M.p. <SEP> 145-8 <tb> <SEP> OH <tb> <SEP> 1.9 <SEP> C2H5 <SEP> N <SEP> -CH2-# <SEP> Cl <SEP> M.p. <SEP> 213-7 <tb> <SEP> NO2 <tb> <SEP> 1.10 <SEP> C3H7-n <SEP> N <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 152-160 <tb> <SEP> O <tb> <SEP> Cl <tb> EMI14.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> NO2 <tb> <SEP> 1.11 <SEP> C2H5 <SEP> CH <SEP> -CH2-# <SEP> Cl <SEP> M.p. <SEP> 99-115 <tb> <SEP> OH <tb> <SEP> O <tb> <SEP> 1.12 <SEP> C2H5 <SEP> N <SEP> -CH2-C-CH3 <SEP> Cl <SEP> M.p. <SEP> 194-5 <tb> <SEP> 1.13 <SEP> C2H5 <SEP> CH <SEP> -CH3 <SEP> I <SEP> M.p. <SEP> 168-70 <tb> <SEP> O <tb> <SEP> 1.14 <SEP> C2H5 <SEP> CH <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 165-9 <tb> <SEP> Cl <tb> <SEP> O <tb> <SEP> 1.15 <SEP> C2H5 <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 136-9 <tb> <SEP> (Dec.) <tb> EMI15.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> O <tb> <SEP> 1.16 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 130-4 <tb> <SEP> Cl <tb> <SEP> 1.17 <SEP> C2H5 <SEP> N <SEP> -CH2-CH=CH2 <SEP> Br <SEP> M.p. <SEP> 145-9 <tb> <SEP> O <tb> <SEP> 1.18 <SEP> C2H5 <SEP> CH <SEP> -CH2C-CH3 <SEP> Cl <SEP> M.p. <SEP> 182-190 <tb> <SEP> 1.19 <SEP> C2H5 <SEP> CH <SEP> -CH2-C#CH <SEP> Br <SEP> M.p. <SEP> 90-120 <tb> <SEP> O <tb> <SEP> 1.20 <SEP> C3H7-n <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 136-9 <tb> <SEP> 1.21 <SEP> C2H5 <SEP> CH <SEP> -CH2-CH=CH2 <SEP> Br <SEP> M.p. <SEP> 170-195 <SEP> (Dec.) <tb> <SEP> 1.22 <SEP> C3H7-n <SEP> N <SEP> -CH2-CH=CH2 <SEP> Br <SEP> M.p. <SEP> 132-8 <tb> <SEP> 1.23 <SEP> C3H7-n <SEP> N <SEP> -CH2-C#CH <SEP> Br <SEP> M.p. <SEP> 151-4 <tb> EMI16.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.24 <SEP> C2H5 <SEP> N <SEP> -CH2-#-NO2 <SEP> Br <SEP> M.p. <SEP> 217-20 <tb> <SEP> 1.25 <SEP> C3H7-n <SEP> N <SEP> -CH2-#-NO2 <SEP> Br <SEP> M.p. <SEP> 213-5 <tb> <SEP> CH3 <tb> <SEP> 1.26 <SEP> C2H5 <SEP> CH <SEP> -CH2-#-CH3 <SEP> Br <SEP> M.p. <SEP> 140-146 <tb> <SEP> CH3 <tb> <SEP> O <tb> <SEP> 1.27 <SEP> C2H5 <SEP> CH <SEP> -CH2-C-# <SEP> Br <SEP> solid <tb> <SEP> 1.28 <SEP> C2H5 <SEP> CH <SEP> -C2H5 <SEP> I <SEP> M.p. <SEP> 151-1 <tb> <SEP> 1.29 <SEP> CH3 <SEP> N <SEP> -CH2-#-NO2 <SEP> Br <tb> EMI17.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> CH3 <tb> <SEP> 1.30 <SEP> C2H5 <SEP> CH <SEP> -CH <SEP> # <SEP> I <SEP> M.p. <SEP> 200-203 <tb> <SEP> CH3 <tb> <SEP> O <tb> <SEP> 1.31 <SEP> C2H5 <SEP> CH <SEP> -CH2-C-CH3 <SEP> Cl <SEP> oil <tb> <SEP> 1.32 <SEP> C2H5 <SEP> CH <SEP> -CH2(CH2)10CH3 <SEP> Br <SEP> M.p. <SEP> 105-108 <tb> <SEP> 1.33 <SEP> C3H7-n <SEP> N <SEP> -C2H5 <SEP> I <SEP> M.p. <SEP> 146-8 <tb> <SEP> Cl <tb> <SEP> 1.34 <SEP> C2H5 <SEP> CH <SEP> -CH2-#-Cl <SEP> Cl <SEP> solid <tb> <SEP> 1.35 <SEP> C2H7-n <SEP> N <SEP> -CH3 <SEP> I <SEP> M.p. <SEP> 143-6 <tb> <SEP> CH3 <tb> <SEP> 1.36 <SEP> C3H7-n <SEP> N <SEP> -CH2-#-CH3 <SEP> Br <SEP> M.p. <SEP> 155-6 <tb> <SEP> CH3 <tb> EMI18.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.37 <SEP> C2H5 <SEP> N <SEP> -C2H5 <SEP> I <SEP> M.p. <SEP> 120-3 <tb> <SEP> 1.38 <SEP> C2H5 <SEP> N <SEP> -CH3 <SEP> I <SEP> M.p. <SEP> 143-5 <tb> <SEP> Cl <tb> <SEP> O <tb> <SEP> 1.39 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#.-F <SEP> Br <SEP> M.p. <SEP> 150-152 <tb> <SEP> 1.40 <SEP> C3H7-n <SEP> CH <SEP> -CH3 <SEP> I <SEP> M.p. <SEP> 154-161 <tb> <SEP> Cl <tb> <SEP> O <tb> <SEP> 1.41 <SEP> C3H7-n <SEP> CH <SEP> -CH2-C-#.-Cl <SEP> Br <SEP> M.p. <SEP> 156-160 <tb> <SEP> 1.42 <SEP> C3H7-n <SEP> CH <SEP> -CH2-C#CH <SEP> Br <SEP> M.p. <SEP> 170-4 <tb> <SEP> O <tb> <SEP> 1.43 <SEP> C3H7-n <SEP> CH <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 59-70 <tb> EMI19.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.44 <SEP> C3H7-n <SEP> CH <SEP> -CH2-CH=CH2 <SEP> Br <SEP> M.p. <SEP> 109-121 <tb> <SEP> CH3 <tb> <SEP> 1.45 <SEP> C2H5 <SEP> N <SEP> -CH2-#.-#CH3 <SEP> Br <SEP> M.p. <SEP> 87-100 <tb> <SEP> CH3 <tb> <SEP> O <SEP> CH3 <tb> <SEP> 1.46 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#CH3 <SEP> Br <SEP> M.p. <SEP> 178 <tb> <SEP> CH3 <tb> <SEP> O <SEP> CH3 <tb> <SEP> 1.47 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-CH3 <SEP> Br <SEP> M.p. <SEP> 156-8 <tb> <SEP> CH3 <tb> <SEP> O <tb> <SEP> 1.48 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 148-150 <tb> EMI20.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> O <tb> <SEP> 1.49 <SEP> C3H7-n <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 143-7 <tb> <SEP> CH3 <tb> <SEP> 1.50 <SEP> C2H5 <SEP> N <SEP> -CH <SEP> # <SEP> I <SEP> oil <tb> <SEP> CH3 <tb> <SEP> 1.51 <SEP> C2H5 <SEP> N <SEP> -CH2CN <SEP> Cl <SEP> M.p. <SEP> 197-200 <tb> <SEP> CH3 <tb> <SEP> 1.52 <SEP> C3H7-n <SEP> CH <SEP> -CH <SEP> # <SEP> Cl <SEP> M.p. <SEP> 152-161 <tb> <SEP> CH3 <tb> <SEP> 1.53 <SEP> C3H7-n <SEP> CH <SEP> -CH2CN <SEP> Cl <SEP> M.p. <SEP> 197-200 <tb> <SEP> OH <tb> <SEP> 1.54 <SEP> C3H7-n <SEP> CH <SEP> -CH2-# <SEP> Cl <SEP> M.p. <SEP> 105-130 <tb> <SEP> NO2 <tb> EMI21.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.55 <SEP> C3H7-n <SEP> CH <SEP> -(CH2)11-CH3 <SEP> Br <SEP> solid <tb> <SEP> 1.56 <SEP> C3H7-n <SEP> CH <SEP> -CH-(CH2)5-CH3 <SEP> Br <SEP> oil <tb> <SEP> # <tb> <SEP> COOC2H5 <tb> <SEP> 1.57 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 170-2 <tb> <SEP> O <tb> <SEP> 1.58 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-CH3 <SEP> Br <SEP> M.p. <SEP> 150-5 <tb> <SEP> O <tb> <SEP> OCH3 <tb> <SEP> 1.59 <SEP> C3H7-n <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 95-130 <tb> <SEP> O <SEP> -OCH3 <tb> EMI22.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.60 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#.-F <SEP> Cl <SEP> M.p. <SEP> 91-94 <tb> <SEP> O <tb> <SEP> 1.61 <SEP> C3H7-n <SEP> N <SEP> -CH2SCN <SEP> Cl <tb> <SEP> O <tb> <SEP> 1.62 <SEP> C2H5 <SEP> N <SEP> -CH2-C-#-# <SEP> Br <tb> <SEP> 1.63 <SEP> C2H5 <SEP> N <SEP> -CH2SO2CH3 <SEP> Br <SEP> viscous <tb> <SEP> CH3 <tb> <SEP> 1.64 <SEP> C3H7-n <SEP> N <SEP> -CH2-C=CH2 <SEP> Cl <tb> <SEP> CH3 <tb> <SEP> 1.65 <SEP> C2H5 <SEP> CH <SEP> -CH2-C=CH2 <SEP> Cl <tb> EMI23.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> O <tb> <SEP> 1.66 <SEP> C3H7-n <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.p. <SEP> 178-180 <tb> <SEP> # <tb> <SEP> CH3 <tb> <SEP> 1.67 <SEP> C2H5 <SEP> N <SEP> -CH-CN <SEP> Br <tb> <SEP> O <tb> <SEP> 1.68 <SEP> C2H5 <SEP> N <SEP> -CH3CH2-C-#-Br <SEP> Cl <SEP> resin <tb> <SEP> O <tb> <SEP> 1.69 <SEP> C2H5 <SEP> N <SEP> -(CH2)2-C-C2H5 <SEP> Cl <tb> <SEP> 1.70 <SEP> C3H7-n <SEP> N <SEP> -CH2CH2I <SEP> I <tb> <SEP> CH3O <tb> <SEP> 1.71 <SEP> C2H5 <SEP> N <SEP> -CH-C-CH3 <SEP> Br <tb> EMI24.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.72 <SEP> C2H5 <SEP> N <SEP> -CH2CH2Cn <SEP> Br <tb> <SEP> 1.73 <SEP> C3H7-n <SEP> N <SEP> -CH2CH2CH2CN <SEP> Br <tb> <SEP> 1.74 <SEP> C3H7-n <SEP> N <SEP> -CH2CH2SO2CH3 <SEP> Cl <SEP> resin <tb> <SEP> 1.75 <SEP> C2H5 <SEP> N <SEP> -CH2CH2OCH=CH2 <SEP> Cl <tb> <SEP> 1.76 <SEP> CH3 <SEP> CH <SEP> -CH2CH2CN <SEP> Cl <tb> <SEP> O <tb> <SEP> 1.77 <SEP> C4H9-n <SEP> N <SEP> -CH2-C-CH3 <SEP> Br <SEP> M.p. <SEP> 161-163 <tb> <SEP> O <tb> <SEP> 1.78 <SEP> C4H9-n <SEP> CN <SEP> -CH2-C-#-NO2 <SEP> Cl <tb> <SEP> 1.79 <SEP> CH3 <SEP> N <SEP> -CH2C#CH <SEP> Cl <tb> EMI25.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> Cl <tb> <SEP> C2H5 <tb> <SEP> 1.80 <SEP> C2H5 <SEP> N <SEP> -CH-CO-#-Cl <SEP> Br <SEP> M.p. <SEP> 211-213 <tb> <SEP> Cl <tb> <SEP> C2H5 <tb> <SEP> 1.81 <SEP> C3H7-n <SEP> N <SEP> -CH-CO-#-Cl <SEP> Br <SEP> M.p. <SEP> 218-221 <tb> <SEP> 1.82 <SEP> C2H5 <SEP> N <SEP> -CH(C6H5)2 <SEP> Br <SEP> resin <tb> <SEP> 1.83 <SEP> C2H5 <SEP> N <SEP> -CH2-CO-# <SEP> Br <SEP> M.p. <SEP> 128-132 <tb> <SEP> # <tb> <SEP> 1.84 <SEP> C3H7n <SEP> N <SEP> -CH2-CO-#-F <SEP> Cl <SEP> M.p. <SEP> 126-129 <tb> EMI26.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.85 <SEP> C3H7-n <SEP> N <SEP> -CH2-CH-#-F <SEP> Br <SEP> M.p. <SEP> 1500-155 <tb> <SEP> Cl <tb> <SEP> 1.86 <SEP> C3H7-n <SEP> N <SEP> -CH2-CO-CH2COOC2H5 <SEP> Cl <SEP> viscous <tb> <SEP> Cl <tb> <SEP> 1.87 <SEP> C2H5 <SEP> N <SEP> -# <SEP> Br <SEP> M.p. <SEP> 198-200 <tb> <SEP> Cl <tb> <SEP> 1.88 <SEP> C2H5 <SEP> N <SEP> -CH2-CO-CH2COOC2H5 <SEP> Cl <SEP> solid <tb> <SEP> 1.89 <SEP> C3H7-n <SEP> N <SEP> -CH2-CO-#-Cl <SEP> Br <SEP> M.p. <SEP> 184-188 <tb> EMI27.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.90 <SEP> C4H9-tert. <SEP> N <SEP> -CH2-CO-#-Cl <SEP> Br <SEP> M.p. <SEP> 190-192 <tb> <SEP> Cl <tb> <SEP> 1.91 <SEP> C4H9-tert. <SEP> CH <SEP> -CH2-CO-#-Cl <SEP> Br <SEP> M.p. <SEP> 115-120 <tb> <SEP> Cl <tb> <SEP> 1.92 <SEP> C3H7-n <SEP> N <SEP> -CH2-COOC2H5 <SEP> Br <SEP> resin <tb> <SEP> 1.93 <SEP> C3H7-n <SEP> N <SEP> -CH(CH3)-COOCH3 <SEP> Br <SEP> viscous <tb> <SEP> 1.94 <SEP> C3H7-n <SEP> N <SEP> -CH(COOC2H5)2 <SEP> Br <SEP> viscous <tb> <SEP> 1.95 <SEP> C3H7-n <SEP> N <SEP> -C4H9-n <SEP> Br <SEP> resin <tb> <SEP> 1.96 <SEP> C3H7-n <SEP> N <SEP> -CH3-COOC2H5 <SEP> Cl <SEP> viscous <tb> EMI28.1 Compound <SEP> R5 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys.data <tb> <SEP> No. <tb> <SEP> 1.97 <SEP> C2H5 <SEP> N <SEP> -CH2-CO-#-OCH3 <SEP> Br <SEP> M.p. <SEP> 95-103 <tb> <SEP> OCH3 <tb> <SEP> 1.98 <SEP> C3H7-n <SEP> N <SEP> -CH(CH3)-COOCH3 <SEP> Br <tb> <SEP> 1.99 <SEP> C2H5 <SEP> N <SEP> -CH2COOC2H5 <SEP> Br <tb> <SEP> 1.100 <SEP> C3H7-n <SEP> N <SEP> -CH(COCH3)-COOC2H5 <SEP> Cl <tb> <SEP> 1.101 <SEP> C2H5 <SEP> N <SEP> -CH2COOC4H9 <SEP> Br <tb> <SEP> 1.102 <SEP> C2H5 <SEP> N <SEP> -CH(CH3)-COOCH3 <SEP> Br <tb> <SEP> 1.103 <SEP> C3H7-n <SEP> N <SEP> -CH(COCH3)COOC2H5 <SEP> Cl <tb> Table 2. (R1 = R2 chlorine, R3 = H) EMI29.1 EMI29.2 <SEP> Compound <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> Br <SEP> viscous <tb> <SEP> 2.1 <SEP> # <SEP> N <SEP> -CH2-COOCH3 <tb> <SEP> (cistrens) <tb> <SEP> CH3 <SEP> CH3 <SEP> O <SEP> CH3 <tb> <SEP> 2.2 <SEP> # <SEP> N <SEP> -CH2-C#-CH3 <SEP> Br <tb> <SEP> CH3 <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 2.3 <SEP> # <SEP> N <SEP> -CH2-CH=CH2 <SEP> Cl <tb> <SEP> CH3 <SEP> C2H5 <SEP> Cl <tb> <SEP> 2.4 <SEP> # <SEP> N <SEP> O <tb> <SEP> -CH2-C-#-Cl <SEP> Cl <tb> EMI30.1 <SEP> Compound <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <SEP> OH <tb> <SEP> 2.5 <SEP> # <SEP> N <SEP> -CH2-# <SEP> Br <tb> <SEP> NO2 <tb> <SEP> CH3 <SEP> O <tb> <SEP> 2.6 <SEP> # <SEP> CH <SEP> -CH2-C-CH3 <SEP> Br <SEP> viscous <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 2.7 <SEP> # <SEP> CH <SEP> -CH2-CH=CH2 <SEP> Cl <tb> <SEP> CH3 <SEP> C2H5 <tb> <SEP> 2.8 <SEP> # <SEP> N <SEP> -CH2CH2-SO2CH3 <SEP> Cl <SEP> resin <tb> EMI31.1 <SEP> Compound <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <SEP> O <SEP> Br <tb> <SEP> 2.9 <SEP> # <SEP> -CH2-C-# <tb> <SEP> O <tb> <SEP> 2.10 <SEP> #-H <SEP> N <SEP> -CH2-C-CH3 <SEP> Br <SEP> amorphous <tb> <SEP> (trans) <tb> <SEP> O <tb> <SEP> 2.11 <SEP> #-H <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> M.P. <SEP> 176-178 <tb> <SEP> (cis) <tb> EMI32.1 <SEP> Compound <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> 2.12 <SEP> # <SEP> O <tb> <SEP> H-#-H <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 218-220 <tb> <SEP> (cis) <tb> Table 3. (R1=R2= chlorine, R3=H, Z=0; EMI33.1 EMI33.2 <SEP> Compound <SEP> R8 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> No. <tb> <SEP> O <tb> <SEP> 3.1 <SEP> CH3 <SEP> N <SEP> -CH2-C-# <SEP> Br <SEP> viscous <tb> <SEP> Cl <tb> <SEP> 3.2 <SEP> (CH2)2OCH3 <SEP> N <SEP> -CH2-C-#-Cl <SEP> Cl <SEP> viscous <tb> <SEP> O <tb> <SEP> 3.3 <SEP> # <SEP> CH <SEP> -CH2CN <SEP> Cl <tb> <SEP> 3.4 <SEP> # <SEP> N <SEP> -CH2CN <SEP> Cl <tb> <SEP> O <tb> <SEP> 3.5 <SEP> # <SEP> N <SEP> -CH2-C-CH3 <SEP> Cl <SEP> viscous <tb> EMI34.1 <SEP> Compound <SEP> R8 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> No. <tb> <SEP> 3.6 <SEP> # <SEP> N <SEP> -CH2-CH=CH2 <SEP> Cl <tb> <SEP> 3.7 <SEP> C2H5 <SEP> N <SEP> CH2COCH3 <SEP> Br <SEP> viscous <tb> Table 4. (R1=R2=chlorine, R3=H; EMI35.1 EMI35.2 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <SEP> HO <tb> <SEP> 4.1 <SEP> # <SEP> CH <SEP> -CH2-#- <SEP> CL <SEP> 152-68 <tb> <SEP> NO2 <tb> <SEP> 4.2 <SEP> # <SEP> N <SEP> -CH3 <SEP> I <tb> EMI36.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> R11 <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> C2H5 <tb> <SEP> 4.3 <SEP> # <SEP> N <SEP> -CH2-CH=CH2 <SEP> Br <SEP> 152-68 <tb> <SEP> C3H7-i <SEP> O <tb> <SEP> 4.4 <SEP> # <SEP> N <SEP> -CH2-C-CH3 <SEP> Cl <tb> <SEP> C2H5 <SEP> C2H5 <SEP> O <SEP> CH3 <tb> <SEP> 4.5 <SEP> # <SEP> CH <SEP> -CH2-C#-CH3 <SEP> Cl <tb> <SEP> CH3 <tb> EMI37.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <SEP> HO <tb> <SEP> 4.6 <SEP> # <SEP> N <SEP> -CH2C#CH <SEP> Br <SEP> M.p. <SEP> 138-142 <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 4.7 <SEP> # <SEP> N <SEP> -CH2-CH=CH2 <SEP> Br <SEP> amorphous <tb> <SEP> CH3 <SEP> C2H5 <SEP> O <tb> <SEP> 4.8 <SEP> # <SEP> CH <SEP> -CH2-C-CH3 <SEP> Cl <tb> EMI38.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> C3H7-n <SEP> O <SEP> CH3 <tb> <SEP> 4.9 <SEP> # <SEP> CH <SEP> -CH2-C#-CH3 <SEP> Br <SEP> viscous <tb> <SEP> CH3 <tb> <SEP> 4.10 <SEP> CH3 <SEP> C3H7-n <SEP> N <SEP> -CH2-CN <SEP> Cl <tb> <SEP> # <tb> <SEP> C2H5 <tb> <SEP> 4.11 <SEP> #-C3H7-n <SEP> N <SEP> Cl-#-CH2- <SEP> Cl <tb> EMI39.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> C2H5 <SEP> C4H9-n <SEP> CH3 <tb> <SEP> 4.12 <SEP> # <SEP> CH <SEP> -CH2-#-CH3 <SEP> Br <tb> <SEP> CH3 <tb> <SEP> O <tb> <SEP> 4.13 <SEP> #-CH3 <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 139-142 <tb> <SEP> CH3 <SEP> CH3 <SEP> O <tb> <SEP> 4.14 <SEP> # <SEP> N <SEP> -CH2-C-#-NO2 <SEP> Br <SEP> M.p. <SEP> 139-142 <tb> EMI40.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <SEP> Cl <tb> <SEP> 4.15 <SEP> #-C3H7-n <SEP> CH <SEP> O <SEP> Br <SEP> resin <tb> <SEP> -CH2-C-#-Cl <tb> <SEP> C2H5 <SEP> C4H9-n <SEP> OH <tb> <SEP> 4.16 <SEP> # <SEP> N <SEP> -CH2-# <SEP> Cl <tb> <SEP> NO2 <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 4.17 <SEP> # <SEP> N <SEP> -CH2-C-CH3 <SEP> Cl <SEP> stable <tb> <SEP> @ <tb> EMI41.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 4.18 <SEP> # <SEP> CH <SEP> -CH2-C-CH3 <SEP> Br <SEP> 152-68 <tb> <SEP> O <tb> <SEP> CH3 <tb> <SEP> 4.19 <SEP> # <SEP> CH <SEP> -CH2-C-CH3 <SEP> Br <tb> <SEP> O <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 4.20 <SEP> # <SEP> N <SEP> -CH2-# <SEP> Cl <tb> EMI42.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> CH3 <SEP> C2H5 <SEP> HO <tb> <SEP> 4.21 <SEP> # <SEP> CH <SEP> -CH2-CN <SEP> Cl <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> 4.22 <SEP> # <SEP> N <SEP> -CH2-CN <SEP> Cl <SEP> M.p. <SEP> 203-6 <tb> <SEP> CH3 <SEP> CH3 <SEP> O <tb> <SEP> 4.23 <SEP> # <SEP> N <SEP> -CH2-C-#-Cl <SEP> Br <SEP> M.p. <SEP> 149-152 <tb> EMI43.1 Compound <SEP> R9 <SEP> R10 <tb> <SEP> No. <SEP> # <SEP> X <SEP> R4 <SEP> Y <SEP> Phys. <SEP> data <tb> <SEP> C2H5 <SEP> C3H7-n <SEP> O <tb> <SEP> 4.24 <SEP> # <SEP> N <SEP> -CH2-C-Cl <SEP> Br <tb> <SEP> Cl <tb> <SEP> C3H7-i <SEP> O <tb> <SEP> 4.25 <SEP> # <SEP> CH <SEP> -CH2-C-#-Cl <SEP> Br <tb> <SEP> C3H7-i <SEP> OH <tb> <SEP> # <SEP> N <SEP> -CH2-# <SEP> Cl <tb> <SEP> NO2 <tb> EMI44.1 <tb> <SEP> x <SEP> ¯soil <SEP> T <SEP> Phys. <SEP> data <tb> <SEP> ?11 <SEP> I <SEP> X <SEP> S <SEP> p <SEP> hys. <SEP> data <tb> <SEP> Fizz <tb> <SEP> Fq <SEP> Q <SEP> <tb> <SEP> rt'5 <tb> <SEP> 4*ZE <SEP> 98 <SEP> N <SEP> S <SEP> -e <SEP> Cl <tb> 3 <tb> 4 <SEP> Cd <SEP> = <SEP> 9 <SEP> cry <SEP> - < 4-5¯: <SEP> 3r <tb> <SEP> C:¯ <SEP> C-¯ <tb> <SEP> '23 <SEP> '2¯5 <tb> 6.30 <SEP> I <tb> 4.'l <SEP> 8V8 <SEP> CH <SEP> -C--r.:-=CE2 <SEP> 3r <tb> <SEP> 4.n <SEP> t9n <SEP> CE <tb> <SEP> ./ <SEP> a <SEP> e=. <tb> <SEP> n <SEP> r- <SEP> a <SEP> - <SEP> <tb> <SEP> . <SEP> 4/ <tb> Formulation Examples Dusting agents: The following materials are used to manufacture a) a 5% and b) a 20Ó dusting agent: a) 5 parts of the active principle of Formula I 95 parts of talc; b) 2 parts. of the active principle 1 part of highly dispersed silica 97 parts of talc The active principles are mixed and ground with the carriers and can in this form be scattered as dust as necessary for the application. Granulate: The following materials are used to manufacture a 5% granulate: 5- parts of the active principle of Formula I 0.25 parts of epoxylated vegetable oil 0.25 parts of cetyl polygylcol ether 3.50 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3-0.8 mm). The active substance is mixed with epoxylated vegetable oil and dissolved. in 6. parts of acetone. The polyethylene glycol and cetyl polyglycol ether are added next. The resulting solution is sprayed onto kaolin and the acetone is evaporated off under vacuum. A microgranulate of this kind is used advantageously for combatting soil fungi. Wettable powder: The following components are used to manufacture a) a 70, b) a 40, c) and d) a 25, and e) a 10 ó wettable powder: a) 70 parts of the active principle of Formula I 5 parts of sodium dibutylnaphthylsulfonate 3 parts of naphthalenesulfonic acids-phenolsulfonic acids-formaldehyde condensate (3:2:1) 10 parts of kaolin 12 parts of Champagne chalk; b) 40 parts o-f the active principle of Formula I 5 parts of sodium ligninsulfonate 1 part of sodium dibutylnaphthalenesulfonate 54 parts of silica; c) 23 parts of the active principle of Formula I 4.5 parts of calcium ligninsulfonate 1.9 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1) 1.5 parts of sodium dibutylnaphthalenesulfonate 19.5 parts of silica 19.5 parts of Champagne chalk 28.1 parts of kaolin; d) 25 parts of the active principle of Formula I 2.5 parts of isooctylphenoxypolyoxyethyleneethanol 1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1) 8.3 parts of sodium- aluminum silicate 16.5 parts of kieselguhr 46 parts of kaolin; e) 10 parts of the active principle of Formula I 3 parts of a mixture of sodium salts of saturated fatty alcohol sulfates 5 parts of naphthalenesulfonic acid/formaldehyde condensate 82 parts of kaolin. The active principles are mixed thoroughly with the additives in suitable mixers and ground in appropriate mills and rollers. Wettable powders of excellent wettability and buoyancy are obtained, which can be diluted with water to suspensions of the desired concentration and are particularly suitable for foliar application. Emulsifiable concentrates: The following materials are used to manufacture a 25 emulsifiable concentrate: 25 parts of the active principle of Formula I 2.5 parts of epoxydized vegetable oil 10 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture 5 parts of dimethylformamide 57.5 parts of xylene Emulsions of the concentration desired for use can be prepared from concen-trates of this type by dilution with water These are particularly suited for foliar application. Biological Examples Example 2: Action against Erysiphe graminis on barley a) Residual-pr-otective action Barley plants about 8 cm high were sprayed with a solution prepared from wettable powder of the active principle (0c02 of the active substance). After 4 h the treated plants were dusted with conidia of the fungus. The infected barley was kept in a greenhouse at about 220C and after 10 days the fungal infection was evaluated. b) Systemic action A spray solution made from wettable powder of the active principle (0.006 á of the active substance referred to the soil volume) was poured over barley plants some 8 cm high Care was taken that the spray solution did not come into contact with the parts of the plant above the ground. After 48 h the treated plants were dusted with conidia of the fungus. The infected barley was kept in a greenhouse at about 220C and the fungal infection was evaluated after 10 days. Example 3: Action against Cercospora arachidicola on peanut plants a) Residual-protective action Peanut plants 10-15 cm high were sprayed with a solution (0.02 á of the active substance) made from wettable powder of the active substance and infected with a fungal conidia suspension 48 h later. The infected plants were incubat.ed for 72 h at about 210C and a high relative humidity and were kept in a greenhouse until the appearance of the typical spots on the leaves. The fungicidal action was evaluated 12 days after the infection, on the basis of the number and size of the spots, Example 4: Action against Puccinia graminis on wheat Wheat p-lants were- sprayed with a. solution made from wettable powder of the active principle (0,062 of the active substance) 6 days after- sowing. After 24 h the treated plants were infected with a urediospore suspension of the fungus. After incubation for 48 h at 95-100% relative humidity and about 20 C the infected plants were kept in a- greenhouse at about 220C, The evaluation of the rust pustule development took place 12 days after the infection. b) Systemic action 5 da-ys after- sowing a solution prepared from the wettable powder of the active principle (0.006 ó of the active substance referred to the soil volume) was poured over wheat plants. After 48 h the treated plants were infected with a urediospore suspension of the fungus. After incubation for 48 h at 95-100% relative humidity and about 20 C, the infected plants were placed in a greenhouse at about 220C. The evaluation of the rust pustule development took place 12 days after the infection. Example 5: Action on Botrytis cinerea on broad beans Residual-protective action Broad bean plants about 10 cm in height were sprayed with a solution prepared from the wettable powder of the active substance (0,02% of the active substance). After 24 h the treated plants were infected with a fungal conidia suspension. After incubating the infected plants for 2-3 days at 95-100% relative humidity and 21 C, the fungal infection was evaluated. Example 6: Action of Venturia inaequalis on apple trees Residual-protective action Apple seedlings with about 5 developed leaves were sprayed with a solution prepared from wettable powder of the active substance (0.006%, 60 ppm) of the active substance. infected with a conidia suspension of the fungus. The plants were After 24 n the treated plants were/then inculbated at 90-100% relative humiduty for 5 days and kept in a greenhouse at 20-240C for a further 10 days. The scab formation was evaluated 15 days after the infection. According to the discovery, the prior experiments show in general a good fungicide activity. Among others the below listed compounds achieved a retardation of the attack of less than 20 ó in comparison with untreated but infected control plants. By the compounds marked with asterisk no attack occurred. By Erysiphe graminis: No. 1.2*, 1.7*, 1.8, 1.9*, 1.10*, -1.12*s 1.14, 1.15*, 1.16*, 1.17*, 1.18*, 1.20*, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.30, 1.31, 1.32, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39*, 1.40, 1.41, 1.43, 1.45, 1.46*, 1.47*, 1.48*, 1.49*, 1.50. 1.51, 1.52, 1.53, 1.57*, 1.58*, 1.60*, 1.69*, 1.80*, 1.81*, 1.8Z*, 1.84*, 1.85*, 1.86*., 1.88*, 1.92*, 1.94*, 1.97*, 2.1*, 2.6*, 2.10*, 2.11*, 2.12*, 3.7*, 4.1, 4.7* 4.14*, 4.17*, 4.23*. By Cercospora arachidicola: No. 1.7, 1.8, 1.14, 1.16*, 1.17*, 1.45, 1.46*, 1.47*, 1.48*, 1.49*, 1.50, 1.51, 1.52, 1.2*, 1.9*, 1.10*, 1.12*., 1.15*, 1.18*, 1.20*, 1.39*, 1.57*, 1.58*, 1.60*, 1.69*, 1.80*, 1.81*, 1.82*, 1.84*, 1.85*, 1.86*, 1.88*, 1.97#, 2.10#, 2.11#, 2.12#, 4.7#, 4.23. By Puccinia graminis: No. 1.2*, 1.7*, 1.8, 1.14, 1.16*, 1.17*, 1.18*, 1.19, 1.20*, 1.22, 1.23, 1.36, 1.39, 1.41, 1.43, 1.45, 1.46*, 1.47*, 1.48#, 1.49*, 1.9*, 1.10*, 1.12*, 1.15*, 1.57*, 1.85*, 1.60*, 1.69*, 1.80*, 1.81*, 1.84*, 1.85*, 1.86*, 1.88*, 1.92*, 1.93#, 1.94, 1.96, 197*, 2.10*, 2.11*, 2.12*, 47*, 4.14*, 4.23*. By Botrytis cinerea No. 1.14, 1.15, 1.34, 1.36, 1.48*, 1.49*, By Venturia inaequalis: No. 1.9*, 1.10*, 1.12*, 1.14*, 1.15*, 1.17*, 1.18*, 1.20*, 1.22#, 1.23*, 1.47*, 1.48*, 1.49*, 1.57*, 1.58#, 1.69*, 1.80#, 1.81*, 1.85*, 1.97*, 2.11*, 2.12*, 4.23#.

Claims: CLAIMS: 1. Compound of the formula I EMI51.1 wherein R1, R2 and R3 independently of one another denote hydrogen or halogen, but at least one radical. is halogen, A represents one of the following groups a), b), c) or d) wherein EMI51.2 Z = O or S, R5 denotes hydrogen or optionally halogensubstituted C1-C6-alkyl, R6 denotes methyl or ethyl, R7 denotes methyl, ethyl or propyl or R6 and R7 together form a tetramethylene group which can be substituted by 1 or 2 methyl groups, R8 denotes C1-C6-alkyl, C3-C4-alkenyl, 2-propinyl, 3-halogen-2-propinyl, C1-C6-alkoxy-C1- C6-alkyl, phenyl which is optionally monosubstituted, disubstituted or trisubstituted by halogen, alkyl, alkoxy, nitro, cyano or trifluoromethyl, orbenzyi Rg and R10 independently of one another denote hydrogen or. C1-C4-alkyl and R11 denotes hydrogen, C1-C4-alkyl or -CH2OH, with the proviso that the total number of C atoms in R9, R10 and R11 does not exceed 10, X represents -CH= or R4 denotes C1-C16-alkyl which is optionally monosubstituted or polysubstituted by halogen, CN, SCN, COO(C1-C3)-alkyl, phenyl or naphthyl, and/or is optionally interrupted by 0, S, EMI52.1 or SO2, or denotes optionally halogen- or alkylthio substituted C3-C6-alkenylmethyl or optionally halogen-substituted C3-C6-alkinylmethyl, the optional phenyl or naphthyl substituent in R4 also being optionally monosubstituted or poly substituted by halogen, NO2, CN, OH, C1-C4-alkyl, methoxy, trifluoromethyl or phenyl, and Y denotes the anion of an inorganic or organic acid 2. A compound of the formula I according to Claim 1, wherein R1 = R2 = chlorine, R3 = hydrogen, EMI52.2 wherein R5 denotes hydrogen or C1-C4-alkyl, R8 denotes C1-C3-alkyl or phenyl, R9 and R10 independently of one another denote hydrogen or C1-C4-alkyl and R11 denotes hydrogen, C1-C4-alkyl or CH2OH, with the proviso that the total number of C atoms in Rg, R10 and R11 does not exceed 10, X represents -N=, R4 denotes z z C3-C6-alkenylmethyl, C3-C6-alkinyl- methyl, EMI53.1 -alkyl, EMI53.2 (option ally substituted by C1, NO2, CN, OH, CH3 or OCH3) or CH2CN and Y denotes a halide, sulphate, nitrate, phosphate, methanesulphonate, ethanesulphonate, p-toluene sulphonate or benzenesulphonate anion. 3. A compound of the formula I according to Claim 1, wherein R1 = hydrogen or chlorine, R2 = chlorine, R3 = hydrogen, wherein EMI53.3 R5 denotes ethyl or n-propyl, R8 denotes Cl-C3-alkyl or phenyl, R9 denotes hydrogen or methyl and R10 denotes hydrogen or C1-C3-alkyl, X = N and R4 = -CH2-CO-R12 or -CH(COOR13) wherein R13 is Cl-C4-aIkyl or a phenyl radical which is unsubstituted or is monosubstituted or poly substituted by alkyl, halogen, NO2, CN, OH, OCH3 or CF3, R12 furthermore denotes -CH2-CO-R13, -CH2-COOR13 @@ or -OR14, R13 represents C1-C4-alkyl and R14 denotes alkyl, alkenyl or alkinyl, each of at most 6 C atoms , or an unsubstituted or C1-C4 alkyl- and/or halogen-substituted phenyl radical. 4. A compound from the group EMI54.1 EMI55.1 EMI56.1 5. Process for the preparation of compounds of the formula I, characterised in that a compound of the formula II EMI57.1 is reacted with a compound of the formula III Y - R4 (III) wherein R1, R2, RD, R4, A, X and Y have the meanings given under formula I. 6. Agent for combating and/or preventing attack by phytopathogenic fungi, characterised in that it contains as at least one active component, a compound of the formula I according to one of Claims 1 to 4. 7. Agent according to Claim 6, characterised in that it contains 0.1 to 95 per cent by weight of an active compound of the formula I according to one of Claims 1 to 4, 5 to 99.9 per- cent by weight of additives and 0 to 30 per cent by weight of a surfactant. 8. Process for the preparation of agents for combating and/or preventing attack by phytopathogenic fungi, characterised in that the active compound of the formula I according to one of Claims 1 to 4 is intimately mixed with carriers and/or surfactants. 9. Use of a compound of the formula I according to one of Claims 1 to 4 for combating phytopathogenic fungi. 10. Process for combating and/or preventing attack of the plants by phytopathogenic fungi, characterised in that a compound of the formula I according to one of Claims 1. to 4 is applied, in a diluted form, to the plant or to its locus.

Inventors: GLOOR, BERNHARD, HEERES, JAN, HUBELE, ADOLF, KUNZ, WALTER, STURM, ELMAR
Applicants: JANSSEN PHARMACEUTICA N.V.
Application year: 1980
Main classification: C07D405
IPC codes: A01N43, C07D405, C07D521