IL93981A - 1-(imidazol-1-yl-) or (1,2,4-triazol-1-yl)-ethane derivatives and fungicidal and plant growth regulating compositions containing them - Google Patents

Description

n fungicidal and plant growth regulating compositions containing them BASF AKTIENGESELLSCHAFT ethane fungicidal and plant growth regulating compositions containing them BASF AKTIENGESELLSCHAFT 1 The present invention relates to processes for their and fungicides and growth regulators containing these It is known that triazolyIethane propane or can be used as fungicides Patent corresponding to Israel Patent Their fungicidal action is It is also known that triazoly derivatives can be used as fungicides 40 We have found that azolylethane derivatives of the general formula Γ i where A and B are each C tetrahydropyrany1 loalky1 or where these radicals may be to trisubstituted by alkoxy or each of 1 to 4 carbon D is which is unsubs t ituted or stituted by or unsubstituted or or where these radicals may be substituted to trisubstituted by alkyl or each of 1 to 4 atoms n is an integer of from 1 to 5 or and X is CH or and their acid addition salts or metal except for the compounds in which A is stituted B is D is X is and n is have a better fungicidal action than the known azole 2 compounds The compounds of the formula I contain asymmetric carbon atoms and can therefore occur as enantiomers and In the case of the novel the mixtures of diastereomers can be separated in a tional example on the basis of their ferent solubilities or by column and can be isolated in pure The racemates of the novel compounds can be resolved by known for example by salt formation with an optically active tion of the diastereomeric salts and liberation of the enantiomers by means of a Both the individual enantiomers or diastereomers and mixtures thereof can be used as fungicidal and active ingredients A and B are identical or different and are for chlorophenyl dichlorophenyl 2 2 butoxyphenyl hydropyranyl cyclohexenyl or n is 4 or Acid addition salts for the oxalates or dodecylbenzenesulfonates The activity of 3 the salts is due to the so that the anion is in general The novel active ingredient salts are prepared by reacting the azolylethane derivatives with the Metal complexes of the active ingredients I or their salts can be formed with cobalt or nickel by reacting the ethane derivatives with corresponding metal salts Compounds of the formula I can be prepared by reacting a compound of the formula II where B and X have the abovementioned meanings and Hal is chlorine or with a compound of the formula The reaction is carried out in the presence or absence of a solvent or with or without the addition of an inorganic or organic base and of a tion at from 10 to The preferred solvents and diluents include such as methyl ethyl ketone or such as acetonitrile or such as or such as ethyl methyl acetate or butyl such as diethyl dioxane or diisopropyl such as dimethylformamide or as well as dimethyl sulfolane or mixtures Suitable bases which may also be used as acid acceptors in the reaction for alkali metal such as lithium sodium hydroxide or potassium alkali metal such as sodium potassium carbonate or cesium alkali metal such as lithium sodium hydride and potassium alkali metal 4 such as sodium amide and potassium as well as pyridine or other conventional bases may also be Preferred reaction accelerators are metal such as sodium iodide or potassium quaternary ammonium such as tetrabutylammonium iodide or hydrogen sulfate or triethylammonium chloride or or crown such as or The reaction is carried out in general at from 20 to under atmospheric or superatmospheric continuously or The starting compounds II can be prepared by reacting a compound of the formula III where B and n have the abovementioned with a compound of the formula IV IV where X has the abovementioned in the presence of a thionyl The reaction is carried out in the presence or absence of a solvent or diluent at from to The preferred solvents or diluents include such as acetonitrile or such as diethyl dioxane or diisopropyl and in particular hydrocarbons and chlorohydrocarbons such as methylene carbon ethane or mixtures 5 The compounds III can be prepared by generally known methods of aldehyde synthesis Methoden der Organischen Georg Thieme Stuttgart The Examples which follow illustrate the tion of the active ingredients Preparation of the starting materials Method 1 2 2 butane g of thionyl chloride are added to a solution of g of triazole in 500 ml of methylene chloride at After the end of the the ture is stirred at room temperature for 30 minutes and g of are then The reaction mixture is stirred for 15 hours at room after which 400 ml of water are added to the solution and the organic phase is separated The remaining aqueous phase is extracted twice by shaking with methylene chloride and the collected organic phases are washed twice with saturated sodium bicarbonate The organic phase isolated is then dried over sodium sulfate and evaporated g of 2 being Preparation of the end products EXAMPLE 1 1 2 2 butane g of sodium methylate and g of potassium iodide are added to a solution of g of 2 in 200 ml of The reaction mixture is refluxed for 48 after which 100 ml of water are added to the solution and the mixture is extracted several times with methyl The organic phase isolated is washed twice with then dried over sodium sulfate 6 and evaporated down and the remaining residue is purified by chromatography over silica gel 1 ethyl g of are obtained as a 1 1 diastereomer mixture The compounds listed in the Table can be prepared similarly to Example Fungicidal azolylethane derivatives X A B D n X Isom 1 CH3 OCH3 1 N 1275 2 1 3 CH3 1 N 4 1 N 5 CH3 1 N 6 CH3 1 CH 7 CH3 NHCH3 1 N 8 CH3 1 N 9 CH3 1 N 10 CH3 1 N 11 CH3 1 N 12 CH3 1 N 13 CH3 1 N Table Isome 16 CH3 OCH3 0 17 CH3 OCH3 0 18 CH3 OC2H5 0 19 CH3 0 20 CH3 0 21 CH3 1 22 CH3 NH2 0 24 CH3 0 CH3 0 9 Table A B D n X Isome 27 CH3 OCH3 D 28 CH3 OCH3 29 CH3 OC2H5 30 CH3 OC2H5 31 CH3 32 CH3 SCH3 33 CH3 34 CH3 NH2 35 enant 36 CH3 37 CH3 38 CH3 41 CH3 10 Table A D n Isome 42 CH3 OCH3 3 43 CH3 3 44 CH3 OC2H5 3 45 CH3 OC4H9 3 46 CH3 SCH3 3 47 CH3 3 48 CH3 3 51 CH3 3 52 CH3 OCH3 4 53 CH3 0CH3 4 54 CH3 OCH3 5 55 CH3 0CH3 5 56 CH3 0CH3 0 57 CH3 OCH3 0 1 1 Table A B D n X Isom 58 CH3 0 N 59 C6H5 CH3 SCH3 0 N 60 CH3 0 N 61 CH3 0 N 64 0CH3 1 N 65 CH3 OC2H5 1 N 66 CH3 SCH3 1 N 68 CH3 OCH3 2 N 69 CH3 OC2H5 2 N 70 2 N 71 CH3 SCH3 2 N 12 Table A B D Isome CH3 CH3 CH3 OCH3 701 75 CH3 OC2H5 76 CH3 SCH3 77 C6H5 CH3 78 CH3 0CH3 79 CH3 0CH3 701 80 81 84 C6H5 OCH3 85 OCH3 86 87 OCH3 13 Table A B D n X Isome 88 OCH3 1 N 89 OCH3 1 N 90 OCH3 1 N 91 cyclohexyl OCH3 1 N 92 cyclohexyl OCH3 1 93 cyclohexyl OCH3 0 N 94 cyclohexyl SCH3 0 N 95 cyclohexyl 0 N 96 0CH3 0 N 97 0 N 98 SCH3 0 N 99 0 N 100 0 N 101 eye 1 OCH3 0 N 102 OCH3 0 N 104 CH3 0 N 105 CH3 SCH3 0 N 106 CH3 0 N Table A B D n iso 107 CH3 OCH3 1 108 CH3 SCH3 1 109 CH3 OC6H5 1 110 CH3 1 112 CH3 OCH3 2 113 CH3 SCH3 2 115 CH3 OCH3 3 116 CH3 SCH3 3 117 CH3 OCH3 5 118 OCH3 1 119 OCH3 1 120 OCH3 1 121 OCH3 1 122 OCH3 123 OCH3 1 124 SCH3 126 OCH3 15 Table 127 ohexenyl OCH3 0 N 128 CH3 OCH3 0 N 129 OC2H5 0 N 130 CH3 SCH3 0 N 131 CH3 0 N 132 CH3 OCH3 1 N 133 CH3 OC6H5 1 N 134 CH3 SC6H5 1 N 135 CH3 1 N 136 CH3 OCH3 2 N 137 CH3 SCH3 2 N 138 CH3 2 N 139 CH3 OCH3 3 N 0 SCH3 3 N 141 CH3 OCH3 5 N 142 OCH3 1 N 143 OCH3 1 N 144 1 N 145 i OCH3 1 N 146 OCH3 1 N 16 Table A B 0 11 X I 147 CH3 0CH3 0 N 148 CH3 0 N 149 CH3 SCH3 0 N 150 CH3 0 N 151 CH3 OCH3 1 N CH3 OC2H5 1 N 153 CH3 1 N 155 CH3 0CH3 2 N SCH3 2 N 157 2 N 158 CH3 0CH3 3 N 159 CH3 SCH3 3 N 160 CH3 0CH3 4 N 161 CH3 OCH3 4 CH 162 CH3 OCH3 5 N 163 CH3 0CH3 5 CH 164 CH3 0CH3 0 N 165 CH3 OCH3 0 CH 166 CH3 0 N 17 Table A B D n X Is 167 CH3 OCH3 1 N 168 CH3 SCH3 1 N 169 CH3 OCH3 2 N CH3 OCH3 3 N 171 CH3 OCH3 4 N 172 CH3 OCH3 0 N 173 CH3 OCH3 1 N 174 CH3 OCH3 1 CH 175 CH3 OCH3 2 N 176 CH3 OCH3 3 N 177 H4 CH3 OCH3 4 N 178 CH3 OCH3 5 N 179 CH3 OCH3 0 N 180 CH3 OCH3 1 N 181 CH3 SCH3 1 N 183 CH3 OCH3 2 N 184 CH3 OCH3 3 N 185 CH3 OCH3 0 N 186 CH3 OCH3 1 N 187 CH3 SCH3 1 N 188 CH3 1 N 18 Table A B D n X 189 CH3 0CH3 3 N 192 CH3 OCH3 0 N CH3 OCH3 1 N 194 CH3 OCH3 2 N 195 CH3 SCH3 2 N 196 CH3 0 N 197 1 CH3 OCH3 0 N 198 0CH3 1 N 199 CH3 SCH3 1 N 200 CH3 1 N 201 CH3 OCH3 2 N 202 CH3 0CH3 3 N 203 0CH3 4 N 20 CH3 5 N 19 Table A B D n x Iso 205 OCH3 0 N 206 OC2H5 0 N 207 SCH3 0 N 208 0 N 209 OCH3 0 N 210 OC2H5 1 N 211 SCH3 0 N 212 0CH3 0 N 213 OC2H4 0 N 214 0 215 OCH3 0 N 216 OCH3 1 N 217 OCH3 2 N 218 1 N 219 OCH3 0 N 220 OCH3 1 N 221 OCH3 1 N 222 OCH3 0 N 223 eye OC2H5 0 N 224 OCH3 N 20 Table A B D is 225 2 822 226 C6H5 CH3 1 700 227 1094 700 228 CH3 4 691 229 C6H5 0 697 230 CH3 700 231 CH3 232 0 690 233 CH3 0 en of the formed 21 Table A B D n X Isom 234 OCH3 0 N 235 C6H5 OCH3 0 CH 236 C6H5 OC2H5 0 N 237 OCH3 0 N 238 OCH3 0 N 239 OCH3 0 N 240 OCH3 0 N 241 0 N 242 OC2H5 0 243 OCH3 0 N 244 OCH3 0 N 245 OCH3 0 N 246 OCH3 0 N 247 C6H5 OCH3 0 N 248 C6H5 OCH3 0 N 249 OCH3 0 N 250 OCH3 0 N 251 OCH3 0 CH 252 OC2H5 0 N 253 2 0 N 254 OCH3 0 N 255 OCH3 0 CH 256 OC2H5 0 N 22 Table A B n 257 OC2H5 0 CH 258 2 0 N 259 0CH2C6H5 0 N 260 OCH3 0 N 261 OCH3 0 CH 262 OC2H5 0 N 263 0C2H5 0 CH 264 2 0 N 265 0 CH 266 OCH3 0 N 267 OCH3 0 CH 268 OC2H5 0 N 269 OC2H5 0 CH 270 0 N 271 OCH3 0 N 272 0CH3 0 CH 273 6H3 OC2H5 0 N 274 0 N 275 2 0 N 276 0CH3 0 N 277 OC2H5 0 N 278 OCH3 0 N 279 OCH3 0 CH 23 Table Ex A B 0 n X Iso 280 0 N 281 0 N 282 OCH3 0 N 283 OCH3 0 CH 284 OC2H5 0 N 285 2 0 N 286 OCH3 0 N 287 0 288 OCH3 0 N 289 OC2H5 0 N 290 OCH3 0 N 291 0 N 292 OCH3 0 N 293 OC2H5 0 N 294 0 N 295 OC2H5 0 N 296 0 N 297 OCH3 0 CH 298 OC2H5 0 N 299 OC2H5 0 CH 300 2 0 N 301 0 CH 302 OCH3 0 N 24 Table A B D n X Iso 303 OC2H5 0 N 304 OCH3 0 N 305 C OC2H5 0 N 306 OCH3 0 N 307 OC2H5 0 N 308 OCH3 0 N 309 0 N 310 OCH3 0 N 311 OC2H5 0 N 312 OCH3 0 N 313 OCH3 0 CH 314 OC2H5 0 N 315 OCH3 0 N 316 OCH3 0 N 317 OCH3 0 N 318 OCH3 0 N 319 OCH3 0 N 320 OCH3 0 N 321 OCH3 0 N 322 OCH3 0 CH 323 OC2H5 0 N 324 OC2H5 0 CH 325 2 0 N 326 OCH3 0 N 25 Table A B D n X Iso 327 OC2H5 0 N 328 OCH3 0 N 329 OCH3 0 N 330 0 N 331 OCH3 0 N 332 OCH3 0 N 333 OCH3 0 N 334 0 N 335 0CH3 0 N 336 OCH3 0 CH 337 OC2H5 0 N 338 OC2H5 0 CH 339 0 N 340 OCH3 0 N 341 OCH3 0 N 342 OCH3 0 N 343 OCH3 0 N 344 OCH3 0 N 345 OCH3 0 N 346 OCH3 0 CH 347 0 N 348 OC2H5 0 CH 349 0 N 26 Generally the novel compounds are extremely effective on a broad spectrum of phytopathogenic in particular those from the and Basidiomycetes Some of them have a systemic action can be used as foliar and soil The fungicidal compounds of particular interest for controlling a large number of fungi in various crops or their especially Indian sugar fruit and ornamentals in horticulture and in vegetables such as beans and The novel compounds are particularly useful for controlling the following plant Erysiphe in Erysiphe c ichoracearum and Sphaerotheca fuliginea in Podosphaera leucotricha in Uncinula necator in Puccinia species in hizoctonia species in cotton and Ustilago species in cereals and sugar Venturia inaequalis in Helminthosporium species in Septoria in Botrytis cinerea in strawberries and Cercospora arachidicola in Pseudocercosporel herpotrichoides in wheat and Pyricularia oryzae in Phytophthora infestans in potatoes and and species in various Plasmopara viticola in Alternaria species in fruit and The compounds are applied by spraying or dusting the plants with the active or treating the seeds of the plants with the active They may be applied before or after infection of the plants or seeds by the The novel compounds may exercise a variety of influences on practically all plant development and are therefore used as growth The diversity of action of growth regulators depends especially on 27 the type and variety of the time with reference to the development stage of the plants and the time of the the place and method of application soil or application to climatic average amount of sunshine and soil conditions the formulation of the active and the concentration at which the active ingredient is A description of some of the various possibilities of using the growth regulators according to the invention in agriculture and horticulture is given Vegetative plant growth can be inhibited to a considerable a fact which is manifested particularly in a reduction in plant The treated plants thus have a compact the leaf color is Of advantage in practice is for example the reduction in grass growth on canal embankments and on areas such as fruit lawns and thus reducing expensive and A further feature of economic interest is the increase in the rigor of crops which tend to such as Indian sunflowers and The shortening and strengthening of the stem thus caused reduces or eliminates the danger of lodging under unfavorable weather The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in It is thus sible for this important crop to be harvested completely Growth regulators may also increase or inhibit lateral This is of interest for instance in tobacco it is desired to inhibit the formation of lateral shoots in favor of leaf With growth it is possible for instance in winter rape to considerably increase the resistance to freeze On the one upward growth and the development of a too luxuriant thus particularly leaf or plant mass are on 28 the the young rape plants are in spite of favorable growth in the vegetative development stage before winter frosts The danger of freeze injury is thus eliminated in plants which tend to lose prematurely their inhibition to bloom pass into the generative In other winter it is advantageous if the plants are well tillered in the fall as a result of treatment with the compounds according to the but enter winter with not too lush a This is a preventive measure against increased susceptibility to freeze injury and because of the relatively low leaf or plant mass attack by various The inhibition of vegetative growth also makes closer planting possible in numerous which means an increase in based on the area Better yields both of plant parts and plant materials may be obtained with the novel It is thus for instance possible to induce increased formation of seed roots and to increase the sugar content of sugarcane and citrus to raise the protein content of cereals and and to stimulate the increased formation of latex in rubber The compounds of the formula I may raise the yield by influencing plant metabolism or by promoting or inhibiting vegetative generative plant It is also possible with growth regulators to shorten or lengthen growth stages and to accelerate or retard the ripening process in plant parts either before or after A factor of economic interest is for example the facilitation of vesting made possible by a temporally concentrated loosening of the adherence of stalks to the branches of citrus olive and other kinds of drupes and indehiscent The same promotion of the formation of ation layers between fruit or leaf and stem of the is also sential for a readily controllable defoliation of crop transpiration in crop plants may be reduced with growth This is particularly important for plants growing in agricultural areas which are expensive to in arid or Irrigation frequency can be reduced by using the compounds according to the making for lower As a 29 result of the use of growth the water available can be better inter the size of the opening is a thicker epidermis and cuticle are penetration of the soil by the roots is the in the stand is favorably influenced by the more compact The active ingredients according to the invention may be applied not only to the seed a but also to the via the and to the by As a result of the good tolerance by crop the application rate when the active ingredients are used as growth regulators may vary within wide When the active ingredients are used for treating amounts of from to and preferably from to g per kg of seed are ly For foliage and soil amounts of from to and preferably from to are generally considered to be The novel substances may be converted into conventional formulations such as pastes and The application forms depend entirely on the purposes for which they are they should at all events ensure a fine and uniform distribution of the active The formulations are produced in known for example by extending the active ingredient with solvents with or without the use of and if water is used as it is also possible to employ other organic solvents as auxiliary Suitable auxiliaries for this purpose are solvents such as aromatics chlorinated paraffins crude oil alcohols amines and carriers such as ground natural minerals talc and and ground synthetic minerals highly disperse silica and emulsifiers and other such as nonionic and anionic emulsifiers polyoxyethy lene fatty alcohol alkyl and dispersants such as sulfite waste liquors and The fungicidal agents generally contain from to and preferably from to of active The novel compounds may also be used for protecting for example against 30 The agents and the formulations prepared from such as pastes and are applied in conventional for example by dressing or 5 Examples of formulations are given 90 parts by weight of compound 1 is mixed with 10 parts by weight of A mixture is obtained which is suitable for 10 application in the form of very fine 20 parts by weight of compound 27 is dissolved in a mixture consisting of 80 parts by weight of 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic 15 5 parts by weight of the calcium salt of dodecy sulfonic and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor By pouring the solution into water and uniformly distributing it an aqueous dispersion is 20 20 parts by weight of compound 42 is dissolved in a mixture sisting of 40 parts by weight of 30 parts by weight of 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor By pouring the solution into water and finely distributing it an aqueous dispersion is 25 20 parts by weight of compound 44 is dissolved in a mixture sisting of 25 parts by weight of 65 parts by weight of a mineral oil fraction having a boiling point between 210 and and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 30 of castor By pouring the solution into water and uniformly ing it an aqueous dispersion is 80 parts by weight of compound 1 is well mixed with 3 parts by weight of the sodium salt of 35 10 parts by weight of the sodium salt of a acid obtained from a sulfite waste and 7 parts by weight of powdered silica and triturated in a hammer By uniformly distributing the mixture in a spray liquor is 40 3 parts by weight of compound 27 is intimately mixed with 97 parts by weight of particulate A dust is obtained containing by weight of the active 31 30 parts by weight of compound 42 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica A formulation of the active ingredient is obtained having good 40 parts by weight of compound 44 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic formaldehyde 2 parts of silica gel and 48 parts of water to give a stable aqueous Dilution in water gives an aqueous 20 parts by weight of compound 1 is intimately mixed with 2 parts by weight of the calcium salt of dodecy Ibenzenesulfonic 8 parts by weight of a fatty alcohol polyglycol 2 parts by weight of the sodium salt of a phenolsulfonic condensate and 68 parts by weight of a paraffinic mineral A stable oily dispersion is In these application the agents according to the invention may also be present together with other active for example growth and and may furthermore be mixed and applied together with Admixture with other gicides frequently results in an increase in the fungicidal Use examples For comparison the compounds and pheny disclosed in EP were Use Example 1 Action on Pyricularia oryzae Leaves of rice seedlings of the variety were sprayed to runoff with aqueous emulsions consisting of of active ingredient and of and inoculated 24 hours later with an aqueous spore suspension of Pyricularia The plants were then set up in climatic cabinets at from 22 to and a relative humidity of 95 to The extent of fungus spread was assessed after 6 The results show that active ingredients 228 and applied as spray have a better fungicidal action than prior art active ingredients A and B 32 Use Example 2 Action on Pyrenophora teres Barley seedlings of the variety were sprayed to runoff at the stage with aqueous suspensions consisting of of active ingredient and of After 24 hours the plants were inoculated with a spore suspension of the fungus Pyrenophora and set up for 48 hours in a climatic cabinet at The plants were then cultivated for a further 5 days in the greenhouse at 20 to and a relative humidity of The extent of fungus spread was then The results show that active ingredients 226 and applied as spray have a better fungicidal action than prior art active ingredients A and B insufficientOCRQuality

Claims (1)

1. 93981 33 Azolylethane derivatives of the general formula I where A and B are each tetrahydropy rany c oa ky or c 1 oa 1 keny where these radicals may be to subst i tuted by alkoxy or each of 1 to 4 carbon 0 is amino which is unsubstituted or substituted by or unsubstituted or C t i tuted thiophen or where these radicals may be to i subst i tuted by alkyl or each of 1 to 4 carbon n is an integer from 1 to 5 or and X is or and their acid addition salts or metal except for the compounds in which A is unsubstituted B is D is x is N and n is A fungicidal agent containing a carrier a fungicidal ly effective amount of an azolylethane derivative of the general formula I where A and B are each tetrahydropy rany oa ky or c oa keny 1 where these radicals may be to tr i i tuted by alkoxy or each of 1 to 4 carbon D is amino which is unsubstituted or substituted by C or unsubstituted or C tuted aminophenyl or where these radicals may be to tr subst tuted by alkyl or each of 1 to 4 carbon n is an integer from 1 to 5 or and X is CH or or a acid addition salt or metal complex except for the compounds in which A is unsubstituted B is D is X is N and n is A process for combating wherein a fungicidal ly effective amount of an azolylethane derivative of the general formula I 34 where A and B are each C bipheny naphthy benzyl tetrahy rany oal ky 1 or oal where these radicals may be to subst i tuted by ni alkoxy or each of 1 to 4 carbon 0 is amino whi ch i s unsubst tuted or substituted by l or unsubst tuted or 1 ky 1 i tuted aminopheny l or where these radicals may be to i subst i tuted by n i alkyl or each of 1 to 4 carbon n is an integer from 1 to 5 or and X i s or or a ac id addi tion salt or metal complex except for the compounds in which A is unsubstituted phenyl 8 i s D is X is N and n i s is al lowed to act on the fungi or the materi plants or seed threatened by fungus A containing a carrier and a ory amount of an azolylethane deri vative of the general formula I where A and B are each naphthy tetrahydropy rany or c where these radicals may be to subst tuted by alkoxy or each of 1 to 4 carbon O amino which is unsubstituted or substituted by unsubstituted or ky aminophenyl or where these radicals may be to tr subst tuted by ni alkyl or each of 1 to 4 carbon n is an integer from 1 to 5 or and X is CH or or a ac id addition salt or metal complex except for the compounds in which A is tuted pheny l B is 0 is X is and n i s A compound of the formula I as set forth in c laim where A is dichlorophen B is 0 i s n is 1 and X is A compound of the formula I as set forth in claim where A is d c B is i s n is 2 and X is A compound of the formula I as set forth in c laim where A is dichloropheny 8 i s 0 i s n is 3 and X is A compound of the formula I as set forth in claim where A is chloropheny B is 0 i s n is 3 and X i s For the A KElNHOifb AND PARTNERS insufficientOCRQuality