AMINO ETHERS AND THEIR USE AS FUNGICIDES

Abstract: Amino ethers of formula (I), wherein (R<1>)n represents up to three substituents selected from optionally substituted alkyl and aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, or 3, or (R<1>)n together with the benzene ring forms a naphthyl group, X is O or S, R<2> and R<3> is each hydrogen or alkyl, both of R<2> and R<3> not being hydrogen, however, when X is O, or R<2> and R<3> when taken together with the carbon atom to which they are attached form a ring of up to 7 carbon atoms, R<4> and R<5> each is optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl or optionally substituted aryl or arylalkyl, or NR<4>R<5> forms a saturated or unsaturated, optionally substituted heterocyclic ring optionally containing one or more additional hetero atoms selected from O, N and S, and m is 2 or 3, and quaternary ammonium salts and N-oxides thereof, are prepared in a manner known per se. The compounds have fungicidal, particularly plant-fungicidal activity and are therefore applicable in fungicidal compositions and in methods for combating fungi, particularly phytopathogenic fungi.

Description: Amino ethers and their use as fungicides. The present invention relates to novel amino ethers and quaternary ammonium salts and N-oxides thereof, and the invention also relates to the use of said compounds as fungicides. It is already known that quaternary ammonium compounds such as benzethonium chloride have fungicidal activity, confer, e.g., Japaness unexamined patent ap¬ plication Jpn Ko ai Tokkyo Koho JP/l12902 A2 (84/112902), 29th June, 1984. However, the plant- fungicidal activity of benzethonium chloride and of the corresponding base is considerably lower than that of the amino ethers of the invention. The novel amino ethers now provided have the general formula I wherein (R^-Jn represents up to three substituents which are the same or different and selected from straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, 2 or 3, or (R*)n to¬ gether with the benzene ring forms a naphthyl group, X represents 0 or S, R2 and R3 each independently represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, both of R^ and R3 not being hydrogen, however, when X is 0, or R2 and R3 when taken together with the carbon atom to which they are attached form a ring of up to 7 carbon atoms, R 4 and R5 each independently represents straight or branched chain, substituted or unsubstituted alkyl hav- ing up to 12 carbon atoms, cycloalkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, or substituted or un¬ substituted arylalkyl, or R 4 and R^ when taken together with the nitrogen atom to hich they are attached form a saturated or unsaturated, substituted or unsubstituted heterocyclic ring which may optionally contain one or more dditional hetero atoms selected from O, N and S, and is 2 or 3. The symbols R^-R^ in the above formula I have preferably, or by way of example, the following meanings: R- '. alkyl is preferably alkyl having 4-10 carbon atoms, more preferably branched chain alkyl having 4-8 carbon atoms, aryl is preferably phenyl, aryloxy is preferably phenoxy, alkoxy is, e.g., methoxy or propoxy, arylalkyl is preferably benzyl, alkyl in haloalkyl, dialkylamino and alkylthio is each preferably alkyl having up to 12 carbon atoms, and halogen is preferably fluoro, chloro or bromo, R2 and R 3 : alkyl is,e.g., methyl, and the carboxylic ring is, e.g., cyclopro- pyl, cyclobutyl or cyclohexyl, R 4 and R 5 : alkyl is preferably alkyl having up to 5 carbon atoms and more preferably up to 3 carbon atoms, cycloalkyl is preferably cyclohexyl, alkenyl is preferably allyl, 3 alkynyl is preferably propargyl aryl is preferably phenyl , arylalkyl is preferably benzyl , and the optionally substituted hetero- cyclic ring is preferably piperidino, dimethylpiperidino, ethylpiperidino, morpholino, 2 , 6-dimethylmorpholino ( cis/trans or cis or trans ) or hexa- methyleneimino . The corresponding quaternary ammonium salts are prefer¬ ably prepared by reaction with alkyl , alkenyl , suitable aryl or arylalkyl halides , e . g . benzyl chloride , methyl iodide or allyl iodide . The corresponding N-oxides are prepared by generally known methods . It has been found that the novel amino ethers of formula I and the corresponding quaternary ammonium salts and N-oxides have fungicidal properties . Thereby, the amino ethers of formu la I according to the invention and the said derivatives thereof surprisingly show a considerably superior fungicidal activity to that of the known benzethonium chloride and the corresponding base , which from a chemical point of view are compounds closely related to the compounds of the invention . The active compounds of the invention can be used in practice for combating phytopathogenic fungi as for example Plasmodiophoromycetes , Oomycetes , Chytridiomyce- tes , Zygomycetes , Ascomycetes , Basidiomycetes and Deute- romycetes . The active substances of the invention can be used, e . g . , for combating the plant diseases Puccinia recondita, Puccinia striiformis and other rust diseases on wheat , Puccinia hordei , Puccinia strii formis and other rust diseases on barley and rust on other host plants as for example coffee , apples , vegetables and ornamental plants . Erysiphe graminis (mi ldew) on barley and wheat and other true mildew species on various host plants such as Sphaerotheca fuliginea on cucumber, Podosphaera leuco- tricha on apples and Uncinula necator on vines. Helminthosporium spp., e.g. Pyrenophora teres (net blotch) on barley. Rhynchosporium βpp. and Pseudocercosporella herpotri¬ choides on cereals. Cercospora arachidicola on peanuts and other Cercospo- ra species on for example sugar beet, banana and soya bean. Botrytis cinerea (grey mold) on tomato, strawberry, vine and other host plants. Venturia inaequalis (scab) on apples. Pyricularia oryzae on rice. The active substances are active in vitro against a broad spectrum of fungi. The active substances are active as seed dressing agents against Fusarium spp., Septoria spp., Tilletia spp., Ustilago spp. , Helminthosporium spp. and Pseudocer-cosporella herpotrichoides on cereals, Khizoc- tonia solani on cotton and Corticium sasakii on rice. Besides an excellent curative activity the active substances of the invention also show extremely good protective properties as well as systemic activity. In addition to this some of the compounds are sufficiently volatile to be active in the gaseous phase against fungi on plants. In accordance with the above the invention also relates to a fungicidal composition, particularly a plant-fungicidal composition, which composition is characterised by containing as an active component at least one compound selected from the amino ethers of the above formula I and quaternary ammonium salts and N-oxides thereof. Moreover, the invention relates to the use of an amino ether of the above formula I and/or a quater- 5 nary ammonium salt thereof and/or an N-oxide thereof for combating fungi, particularly phytopathogenic fungi. Furthermore, the invention relates to a method of combating fungi, particularly phytopathogenic fungi, which method is characterised by allowing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N-oxide thereof to affect the fungi concerned and/or their biotope. Furthermore, the invention relates to a process of preparing a fungicidal composition, particulary a plant-fungicidal composition, which process is charac¬ terised by mixing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N- oxide thereof with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents. The amino ethers of formula I according to the invention can be prepared by any known process for pre¬ paring similar compounds, e.g. as illustrated in the following Preparation Example. Preparation Example Preparation of 2-(2, -dichlorophenoxy)-2-methyl-propyl N-benzyl-N-ethyl-2-aminoethyl ether, compound No. 1. A mixture of 2-(2,4-dichlorophenoxy)-2-methyl- 1-propanol (3.00 g, 0.013 mole) benzyltriethylammonium chloride (0.30 g) and 50% aqueous NaOH (15 g) is heated on an oil bath at 70°C with vigorous stirring. To this N-benzyl-N-ethy1-2-amino-1-chloroethane hydrochloride (4.46 g, 0.019 ole) is added in one portion. After 15 minutes additional benzyltriethylammonium chloride (0.30 g) is added and the mixture is stirred for 1 hour. Water (50 ml) is added to the reaction mixture and the mixture is extracted with ether (50 ml). The ether phase is separated and extracted with 4 N hydrochloric acid (50 ml). The acidic phase is separated and basified by adding 20% aqueous sodium hydroxide. Extraction with ether (2 x 50 ml), drying of the combined ether phases over sodium sulphate and removal of the solvent in vacuo leave an oil from which the desired product is isolated by kugelrohr distillation. Yield 3.45 g (68%); b.p. 190-195°C/0,08 mm Hg; n^ 6 : 1.5385. In addition to the compound mentioned in the Pre¬ paration Example there are emphasized the following ami- no ethers of formula I which have been prepared by the process described above, and the corresponding quater¬ nary ammonium salts, prepared by generally known processes by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, as well as the corresponding N- oxides, prepared by generally known processes. No. Formula n D M CIS/TRANS No. Formula n 26 10 α θr °— 1.1515 / W No. Formula 2* "t> • N 16 -€r°χ- \ 1.4856 < 18 J3°^ 1.5224 / 20 > N \ 1.4924 22 — N 1.5470 No. Formula _ _* Racemic mixture Racemic mixture β jθr » ~"- 1.5035 1.5166 11 No. Formula 1.4851 No. Formula n 26 43 - 1.5314 n 4_. O 4-. vO 4-. OO • . 4-. ON a. f_ o T4 No. Formula „ 26 n D 57 1.5717 15 No. Formula n-) 26 64 •o. o CΛ ON VO CΛ OO -4 8. 8. o z No. Formula "D* N 74 1.4782 Cr°^° 1.5097 No. Formula "D* No. Formula n *D n M No. Formula n-) 26 a r-^O 1.5047 cis and trans 99 1.4994 No. Formula "D M No. Formula "D* - * >P ( ϊ > ~CQ 1.5460 No. Formula -_' 127 1.4896 to to CO O CO to CO o to t VO 00 o z -J cn tn tn O Cn a to cn co vO to tΛ σ to 00 co 00 No. Formula „ 26 No. Formula δ" Quat. Reag. 1) I3 C-N R chemical shift of α-carbon βf the entering group. No. Formula i l) Quat. Reag. 150 'O -n' I' 49.63 CH 3 I 1) 13 C-NMR chemical shift of α-carbon βf the entering group. 94 29 No. Formula δ'> Q ua t. Reag. T ' ^ 67.72 CH 2 =CH-CH 2 Br racemic Bf 1) 13 C-NMR chemical shift of α-carbon βf the entering group. No. Formula δ . ) Q ua t. Reag. 162 Q°κ°- 65.50 C,H, 3 I 166 "iQr 0 ^ ' -^ 51-" CH,B, chemical shift of α-carbon of the entering group. 3 1 No. Formula δ π Quat. Reag. 170 48.73 CH 3 I 1) I3 C-N R chemical shift of α-carboπ βf the entering group. No. Formula δ n Quat. Reag. 1) 13 C-N ' MR chemical shift of α-carbon of the entering group. No. Formula "D* 180 1.5477 ,_5- °~" _> 186 1.4696 No. Formula π D M 193 1.4964 No. Formula "D* 194 ^ ø -^ 1.5191 199 o " Cl0y O°x-s~" N J 1.5185 200 -^^O N ' « -^O^^ 15632 No. Formula „ u π D No. Formula "D M 1 1-5008 No. Formula "D* No. Formula n 26 228 1.4996 No. Formula n 26 235 1.5093 No. Formula 26 "D α 23 a l&xl, XV- O°.. . ^ 1.5402 'N" 242 No. Formula n 26 1.4799 to to to CΛ to to to Ul o <Λ s tn cn vo oo ? to to to t to o CΛ CΛ CΛ t to VO 00 ~ CΛ Ov Ov 2 Z Ul o No. Formula n D κ No. Formula δ° Quat. Reag. 277 n-K' )-0 ^ Λ N + T- 49.48 CH,I 1. !3 C-N ' MR chemical shift of α-carbon of the entering group. No. Formula Quat. Reag. 1) 13 C-N R chemical shift of α-carbon of the entering group. to to vO to to Ul vO t to vO s 00 to 00 t vo 00 Z 00 - o . 50 The compounds of the invention may be formulated as compositions such as wettable powders, dusts, gran¬ ules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Wettable powders are usually formulated to con¬ tain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a disper¬ sing agent and, where necessary 0-10% by weight of sta¬ bilisers and/or additives such as penetrants or stickers. Dusts are usually formulated as a dust concen¬ trate having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant. Gran¬ ules are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0-10% by weight of suspending agents such as protective collo¬ ids and thixotropic agents, 0-10% by weight of appro¬ priate additives such as defoamers, corrosion inhibi¬ tors, stabilisers, penetrants and stickers, and as car¬ rier, water or an organic liquid in which the toxicant is substantially- insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to 51 assist in preventing sedimentation or an antifreeze agents for water. Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the olie-in-water type, and may have a thick "mayonnaise"- like consistency. The compositions may also contain other ingredi¬ ents, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal pro¬ perties. The activity of the compounds of the invention is illustrated in detail by the following Application Examples. Application Examples In the following Application Examples the following compounds are used as reference substances Benzethonium chloride _ _ 52 Eksempel 1 Erysiphe graminis test (barley/protective spray) . Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of act¬ ive substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired . Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155. To test for protective activity young barley plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inocu¬ lated with mildew cσnidia by the brush method The plants are left 48 hours af 18°C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80% RH. 7 Days after inoculation the activity of the sub¬ stance is evaluated. In this test a clear superiority in activity is shown by, e.g., the compound of Preparation Example I and, e.g., the compounds 5, 7, 8, 9, 17, 36, 38, 41, 43, 45, 54, 58, 65, 67, 68, 69, 70, 71, 76, 78, 85, 86, 87, 91, 94, 95, 96, 99, 106, 110, 128, 138, 139, 141, 142, 144, 145, 146, 148, 151, 152, 154, 159 and 169. Eksempel 2 Erysiphe graminis test (barley/curative spray) . Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155. To test for curative activity young barley plants are sprayed to leaf wetness with the composition af act- ive substance 2 days after the plants have been inocu¬ lated with mildew conidia by the brush method. After inoculation and until spraying the plants are left at 18°C and 100% RH, and after spraying they are left in a growth chamber at 18°C and 70-80% RH. 7 Days after inoculation the activity of the sub¬ stance is evaluated. In this test a clear superiority in activity is shown by, e.g., the compounds listed in Tabel 1. The activity of the compounds is indicated as given below: 3 90-100% disease control 2 50- 89% disease control 1 11- 49% disease control 0 0- 10% disease control Table 1 Compound Erysiphe graminis No. test 64 ppm curative spray A 0 B 0 1 3 5 2 7 3 8 3 36 3 38 3 41 2 43 3 45 2 53 3 58 3 65 - 3 67 3 68 3 69 3 Table 1 (continued) Compound Erysiphe graminis No . test 64 ppm curative spray 5 70 3 71 3 76 3 78 3 85 3 10 86 3 87 3 91 2 94 3 95 15 96 3 99 3 1 10 3 128 3 138 2 20 139 3 141 3 142 3 144 3 145 2 25 146 3 148 2 151 3 152 3 154 3 30 159 3 167 3 181 3 183 3 184 _ 3 35 185 3 187 3 188 2 189 3 190 3 Table 1 (continued ) Compound Erysiphe graminis No . test 64 ppm curative spray 191 3 192 3 197 3 199 3 201 2 10 205 2 214 3 226 2 232 3 233 3 15 234 3 237 3 238 3 239 3 241 3 20 242 3 251 3 254 3 255 2 256 3 25 259 3 275 2 276 2 283 2 284 3 30 287 3 288 3 Example 3 Puccinia recondita test (wheat, protective spray) . Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentra¬ tion desired. Further dilution is carried out by a so¬ lution containing 10% acetone in water and 100 ppm Triton X-155. To test for protective activity young wheat plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inocu¬ lated with brown rust spores in an aqueous slurry which is sprayed on. The plants are left for 48 hours at 18°C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80% RH. 10 Days after inoculation the activity of the substances is evaluated. In this test a clear supe- riority in activity is shown by, e.g., the compounds listed in Tabel 2. The activity of the compounds is indicated as given below: 3 90-100% disease control 2 50- 89% disease control 1 11- 49% disease control 0 0- 10% disease control Table 2 Compound Puccinia recondita No . test 250 ppm protective spray A 1 θ 1 1 3 5 2 8 2 10 38 2 41 1 43 1 45 1 46 3 15 47 3 52 3 58 2 67 2 68 2 20 69 2 70 2 71 2 76 2 78 2 25 83 3 87 3 91 2 94 3 139 2 30 141 3 142 2 148 2 154 3 159 3 35 183 2 184 3 185 2 191 2 234 3

Claims: Patent Claims 1. Amino ethers, characterised by having the foll wherein (R ) n represents up to three substituents which are the same or different and selected from straight or branched chain substituted or unsubstituted alkyl having up to 12 carbon atoms, aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, 2 or 3, or (R^-Jn together with the benzene ring forms a naphthyl group, X represents O or S, R 2 and R 3 each independently represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, both of R 2 and R 3 not being hydrogen, however, when X is 0, or R 2 and R 3 when taken together with the carbon atom to which they are attached form a ring of up to 7 carbon atoms, 4 and R5 each independently represents straight or branched chain, substituted or unsubstituted alkyl hav- ing up to 12 carbon atoms, cycloalkyl, alkenyl, alkynyl, substituted or ubsubstituted aryl, or substituted or un¬ substituted arylalkyl, or R 4 and R 5 when taken together with the nitrogen atom to which they are attached form a saturated or unsaturated, substituted or unsubstituted heterocyclic ring which may optionally contain one or more additional hetero atoms selected from 0, N and S, and m is 2 or 3, and quaternary ammonium salts thereof, preferably pre- pared by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, and N-oxides thereof. 2. A fungicidal composition, particularly a plant-fungicidal composition, characterised by con¬ taining as an active component at least one compound selected from amino ethers of formula I as defined in claim 1 and quaternary ammonium salts and N-oxides thereof. 3. Use of an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof for combating fungi, particul- arly phytopathogenic fungi. 4. A method of combating fungi, particularly phytopathogenic fungi, characterised by allowing an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof to affect the fungi concerned and/or their biotope. 5. A process of preparing a fungicidal composi¬ tion, particularly a plant-fungicidal composition, characterised by mixing an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents.

Inventors: JACOBSEN NIELS, KLEMMENSEN PER DAUSELL, KOLIND-ANDERSEN HANS, SVENDSEN AXEL, WENGEL ANITA, JACOBSEN, NIELS, KLEMMENSEN, PER, DAUSELL, KOLIND-ANDERSEN, HANS, SVENDSEN, AXEL, WENGEL, ANITA
Applicants: CHEMINOVA AS, A/S CHEMINOVA
Application year: 1987
Main classification: A01N31
IPC codes: A01N39, A01N43, C07D209, C07D211, C07D215, C07D217, C07D249, C07D295, C07D521