Quinoline fungicides

Abstract: Compounds of the formula (1) <CHEM> wherein X is CR<5> or N, where R<5> is H, Cl, or CH3; Y is CR<5> min if X is N, and Y is CR<5> min or N if X is CR<5>, where R<5> min is H, Cl, or Br; Z is O, S, SO, SO2, NR<6>, where R<6> is H, (C1-C4) alkyl, or (C1-C4) acyl, or CR<7>R<8>, where R<7> and R<8> are independently H, (C1-C4) acyl, (C1-C4) alkyl, (C1-C4) alkenyl, (C2-C4) alkynyl, CN, or OH, or R<7> and R<8> combine to form a carbocyclic rirg containing four to six carbon atoms; R<1> to R<4> are independently H, OH, NO2, halo, I, (C1-C4) alkyl, (C3-C4) branched alkyl, (C1-C4) alkoxy, halo (C1-C4) alkyl, halo (C1-C4) alkoxy, or halo (C1-C4) alkylthio; or R<1> and R<2> or R<2> and R<3> combine to form a carbocyclic ring containing 4 to 6 carbon atoms; A is (a) a C1-C18 saturated or unsaturated hydrocarbon chain, straight chain or branched, optionally including a hetero atom selected from O, S, SO, SO2, or Si, and optionally substituted with halo, halo (C1-C4) alkoxy, hydroxy, or (C1-C4) acyl; (b) (C3-C8) cycloalkyl or cycloalkenyl; (c) a phenyl group of the formula (2) <CHEM> wherein R<9> to R<1><3> are independently H, CN, NO2, OH, halo, I, (C1-C4) alkyl, (C3-C4) branched alkyl, (C2-C4 ) acyl, halo (C1-C4) alkyl, hydroxy (C1-C4) alkyl, (C1-C4) alkoxy, halo (C1-C4) alkoxy, (C1-C4) alkylthio, halo (C1-C4) alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl (C1-C4) alkyl, substituted phenyl (C1-C4) alkyl, benzoyl, substituted benzoyl, SiR<2><0>R<2><1>R<2><2> or OSiR<2><0>R<2><1>R<2><2>, where R<2><0>, R<2><1>, and R<2><2> are H, a C1-C6 alkyl group, straight chain or branched, phenyl, or substituted phenyl, provided that at least one of R<2><0>, R<2><1>, and R<2><2> is other than H, or R<1><1> and R<1><2> or R<1><2> and R<1><3> combine to form a carbocyclic ring, provided that unless all of R<9> to R<1><3> are H or F, then at least two of R<9> to R<1><3> are H; (d) a furyl group of formula (3) <CHEM> wherein R<1><4> is H, halo, halomethyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or (C1-C4) alkoxy, (e) a thienyl group of formula (4) <CHEM> wherein R<1><5> is H, halo, halomethyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, or (C1-C4) alkoxy; (f) a group of formula (5) or (5a) <CHEM> wherein R<1><6> is H, halo, halomethyl, CN, NO2, (C1-C4) alkyl, (C3-C4) branched alkyl, phenyl, substituted phenyl, or (C1-C4) alkoxy, and F is N or CH and G is O, NR<1><9> or CH, provided that either F is N or G is NR<1><9>, where R<1><9> is H, (C1-C4) alkyl, (C1-C4) acyl, phenylsulfonyl, or substituted phenylsulfonyl; (g) a group selected from 1-naphthyl, substituted 1-naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl, 1,3-benzodioxolyl, tricyclo[3.3.1.1(3,7)]dec-2-yl, 1-(3-chlorophenyl)-1H-tetrazol-5-yl, pyridyl, pyridazinyl, or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH; provided Z is CR<7>R<8> if A is a group described in paragraph (d), (e), or (f); and provided that Z is S, SO, or SO2 if A is a group described in paragraph (a), are plant fungicides. o

Description: Background of the Invention Field of the Invention This invention provides new compounds that have excellent plant fungicide activity. Some of the compounds have also demonstrated insecticidal and miticidal activity The invention also provides compositions and combination products that contain a compound of the invention as active ingredient. Some of the combination products have shown synergistic activity against plant pathogens. The invention also provides fungicidal methods. There is an acute need for new fungicides, because target pathogens are rapidly developing resistance to known fungicides. Widespread failure of N-substituted azole fungicides to control barley mildew was observed in 1983, and has been attributed to the development of resistance. The field performance of DMI (demethylation inhibitor) fungicides, which are now widely relied on to protect cereal crops from powdery mildew, has declined since they were introduced in the 1970's. Similarly, the pathogen population responsible for grape Botrytis, the number one disease in grapes as well as in berry crops and in tomato and cucumber greenhouse crops, has shifted to strains that are resistant to benzimidazole and dicarboximide fungicides. The invention provides a fungicidal method which comprises applying to the locus of the fungus a fungicidally effective amount of a compound of the formula (1) wherein R 1 to R 4 are one of the following:- a) R 3 is Cl and R 1 and R 4 are H; b) R 3 is Br and R 1 and R 4 are H; c) R 1 and R 3 are Cl and R 4 is H; d) R 4 is Cl and R 1 and R 3 are H; A is a) (C 3 -C 8 ) cycloalkyl or cycloalkenyl; b) a phenyl group of the formula (2) wherein R 9 to R 13 are independently H, CN, NO 2 , OH, halo, I, (C 1 -C 4 ) alkyl, (C 3 -C 4 ) branched alkyl, (C 2 -C 4 ) acyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkylthio, halo (C 1 -C 4 ) alkylthio, an optionally substituted group phenyl-W-, where W is a bond, O, SiR 20 R 21 R 22 or OSiR 20 R 21 R 22 where R 20 , R 21 , and R 22 are H, a C 1 -C 6 alkyl group, straight chain or branched, phenyl or substituted phenyl, provided that at least one of R 20 , R 21 , and R 22 is other than H, or R 11 and R 12 or R 12 and R 13 combine to form a carbocyclic ring, provided that unless all of the R 9 to R 13 are H or F, then at least two of R 9 to R 13 are H; or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1); wherein the term "substituted" as used herein means substituted by up to three groups selected from halo, I, (C 1 to C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy, phenoxy, phenyl, NO 2 , OH, CN (C 1 -C 4 ) alkanoyloxy, or benzyloxy, but not including any such method for the therapeutic treatment of the human or animal body. The invention also provides novel compounds of formula (1) as defined above provided that the following compounds are excluded: 1) compounds wherein R 3 is Cl, R 1 and R 4 are H, and A is phenyl, 4-chlorophenyl, or 4-fluorophenyl; and 2) 7-chloro-4-(3-trifluromethyl)phenoxy)-quinoline; 3) 7-chloro-4-(4-chloro-3,5-dimethylphenoxy)-quinoline; 4) 7-chloro-4-(4-chloro-3-methylphenoxy)-quinoline; The fungicidal combinations of the invention comprise at least 1% by weight of a compound of formula (1), or an acid addition salt of a compound of formula (1) or an N-oxide of a compound of formula (1) where Y is CH, in combination with a second fungicidal compound. The fungicidal compositions of the invention comprise a compound of formula (1), or an acid addition salt of a compound of formula (1) or an N-oxide of a compound of formula (1) where Y is CH, in combination with a phytologically-acceptable carrier. Various quinoline ethers and quinolinamines are known. In particular:- JP 19548/68 and Derwent 66-33787 disclose 4-phenoxyquinolines having antimycotic activity. H. Gildemeister et al., Leibigs Ann. Chem. 1982, 1656-76 at page 1660 discloses certain phenoxyquinoline compounds as intermediates in preparing bactericides and fungicides. The disclosed compounds include 4-(3-methylphenoxy)quinoline, 4-(3-methoxyphenoxy)quinoline, 6-fluoro-2-methyl-4-(2,6-dinitro-4-trifluoromethylphenoxy)quinoline, 6-methoxy-2-methyl-4-(2,6-dinitro-4-trifluoromethylphenoxy)quinoline, 2-methyl-7-trifluoromethyl-(2,6-dinitro-4-trifluoromethylphenoxy)quinoline, and 2-methyl-4-(4-nitrophenoxy)quinoline. 53 Chem. Abst. 2229i (1959) discloses 4-(2,6-dinitro-4-methylphenoxy)quinoline N-oxide as having bacteriostatic properties. 57 Chem. Abst. 16760e (1962) discloses a series of 2-methyl-quinolines that were tested for fungistatic activity. 61 Chem. Abst. 5609h (1964) discloses a number of 2-methyl-4-phenoxyquinolines having various chlorine, methyl, and methoxy substitutions on the phenoxy ring. No utility is disclosed for the compounds. 73 JACS 2623-26 (1951) discloses 7-chloro-4-phenoxyquinoline as an intermediate for antivirals. 21 Eur. J. Med. Chem.-Chim. Ther., 5-8 (1986) discloses 4-(4-aminophenoxy)-7-chloroquinoline as a compound tested for antimalarial activity but found to be inactive. US 3075981 discloses a number of 4-(substituted anilino) quinolines as intermediates. Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated. The term halo, used alone or in combination with other terms, such as alkyl or alkoxy, refers to F, Cl, or Br. The term "(C1-C4) alkyl" refers to straight chain alkyl radicals. The term "branched (C3-C4) alkyl" refers to all alkyl isomers containing the designated number of carbon atoms, except the straight chain isomers. The term "(C1-C4) alkoxy" refers to straight or branched chain alkoxy groups. The term "halo (C1-C4) alkyl" refers to a (C1-C4) alkyl group, straight chain or branched, substituted with one or more halo atoms. The term "halo (C1-C4) alkoxy" refers to a (C1-C4) alkoxy group, substituted with one or more halo atoms. The term "halo (C1-C4) alkylthio" refers to a (C1-C4) alkylthio group, straight chain or branched, substituted with one or more halo groups. The term "(C 1 -C 4 ) acyl" refers to straight chain or branched acyl groups. The term "substituted phenyl" refers to phenyl substituted with up to three groups selected from halo, I, (C 1 -C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, phenoxy, phenyl, NO 2 , OH, CN, (C 1 -C 4 ) alkanoyloxy, or benzyloxy. The term "substituted phenoxy" refers to phenoxy substituted with up to three groups selected from halo, I, (C 1 -C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, phenoxy, phenyl, NO 2 , OH, CN, (C 1 -C 4 ) alkanoyloxy, or benzyloxy. The term "substituted phenylthio" refers to a phenylthio group substituted with up to three groups selected from halo, I, (C 1 -C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, phenoxy, phenyl, NO 2 , OH, CN, (C 1 -C 4 ) alkanoyloxy, or benzyloxy. The term "substituted phenylsulfonyl" refers to a phenylsulfonyl group substituted with up to three groups selected from halo, I, (C 1 -C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, phenoxy, phenyl, NO 2 , OH, CN, (C 1 -C 4 ) alkanoyloxy, or benzyloxy. The term "unsaturated hydrocarbon chain" means a hydrocarbon chain containing one to three multiple bond sites. The term "carbocyclic ring" refers to a saturated or unsaturated ring of four to seven carbon atoms. "HPLC" refers to high-performance liquid chromatography. Compounds While all of the compounds of the invention are useful fungicides, certain classes are preferred for reasons of greater efficacy or ease of synthesis, viz: 1) Compounds of formula (1) where at least one of R 1 , R 3 and R 4 is H; 2) Compounds of preferred class (1) wherein two of R 1 , R 3 and R 4 are hydrogen, and one is other than hydrogen; 3) Compounds of preferred class 2 wherein R 3 is Cl and R 1 and R 4 are H; 4) Compounds of preferred class 2 wherein R 4 is Cl and R 1 and R 3 are H. 5) Compounds of preferred class 1 wherein R 1 and R 3 are both Cl or both CH 3 and R 4 is H; 5a) Compounds of preferred class 5 wherein A is unsubstituted phenyl; 6) Compounds of formula (1) wherein A is substituted phenyl; 7) Compounds of preferred class 6 wherein R 11 is F; 8) Compounds of preferred class 6 wherein A is phenyl ortho-substituted with an electron-withdrawing group; 9) Compounds of preferred class 8 wherein R 9 is halo, CF 3 , CN, or NO 2 ; 10) Compounds wherein A is 4-fluorophenyl; 11) Compounds wherein A is phenyl ortho-substituted with an electron withdrawing group; For curative as well as protective powdery mildew control, compounds of formula (1) wherein R 3 is Cl (i.e., 7-chloro-4-quinolinyl ethers) are especially preferred, and most preferred within this class are 7-chloro-4-(4-fluorophenoxy)quinoline (a compound not claimed per se, but, included in the claimed methods and compositions), 7-chloro-4-(2-nitrophenoxy)-quinoline, 4-(2-bromophenoxy)-7-chloroquinoline, 7-chloro-4-(2-chlorophenoxy)quinoline, 2-[(7-chloro-4-quinolinyl)-oxy]benzonitrile, 7-chloro-4-(2,4-difluorophenoxy)quinoline, 7-chloro-4-(2-cyanophenoxy)quinoline, and 7-chloro-4-[2-(trifluoromethyl)phenoxy]quinoline. For protective, as well as some curative powdery mildew control, compounds of formula (1) wherein R 1 and R 3 are Cl (i.e., 5,7-dichloro-4-quinolinyl ethers are especially preferred. Most preferred within this class are 5,7-dichloro-4-(4-fluorophenoxy)quinoline, 5,7-dichloro-4-(4-fluorophenoxy)-quinoline,hydrochloride, 5,7-dichloro-4-(phenoxy)-quinoline, and 5,7-dichloro-4-(4-fluorophenoxy)quinoline, 1-oxide. Another preferred compound for control of powdery mildew is 7-chloro-4-[(4-fluorophenyl)methyl]quinoline. For activity against Botrytis, compounds of formula (1) wherein R 4 is C1 (i.e., 8-chloro-4-quinolinyl ethers) are especially preferred. Most preferred within this class are 8-chloro-4-(2-chlorophenoxy) quinoline, 8-chloro-4-(2-chloro-4-fluoro-phenoxy)quinoline, and 4-(2-bromophenoxy)-8-chloroquinoline. Although powdery mildew and Botrytis have been mentioned as being of particular interest, the data presented hereinafter will demonstrate that the compounds of the invention control many other plant pathogens aswell. Synthesis The compounds of this invention are made using well known chemical procedures. The required starting materials are commercially available, or they are readily synthesized using standard procedures. The compounds of formula (1) can be made by condensing a compound of formula (7) : wherein R 1 to R 3 and R 4 are as previously defined, with a compound of the formula (8) HO-A where A is as previously defined. The reaction can be carried out neat, at a temperature in the range of 80 to 150°C, preferably 130 to 140°C. An excess of the compound of formula (8) for example a two-fold excess, is typically used. Reaction time is typically two to 48 hours. The starting compound of formula (8) is then removed by diluting the reaction mixture with ethyl acetate, and washing with aqueous NaOH. Drying the organic layer over MgSO 4 , and reducing pressure to remove solvent delivers the product. In a preferred procedure, the chloride of formula (7) is reacted overnight with 1.2 to 1.4 equivalents of starting material of formula (8) in xylene at reflux. Derivatives N-oxides of the compounds of formula (1) are prepared by reacting the compound of formula (1) with an oxidizing agent, such as 3-chloroperoxybenzoic acid or hydrogen peroxide, in a non-reactive organic solvent, such as methylene chloride or chloroform, at -20°C to room temperature, preferably at about 0°C. The acid addition salts of compounds of formula (1) are obtained in the usual way. Thus, the invention also provides a process for preparing a compound of formula (1) which comprises (a) condensing a compound of formula (7) wherein R 1 , R 3 and R 4 are as defined in formula (1) with a compound of formula (8) HO-A where A is as defined in formula (1) to provide a compound of formula (1) Starting Materials Phenol starting materials of formula (8) are commercially available or can be synthesized from the corresponding aniline via the Bucherer reaction, in which the aniline is reacted with aqueous sodium bisulfite. Ang. Chem. Int. Ed. Eng. 6 , 307, 1967 . In the case of ortho -hydroxy-benzotrifluoride, a preferred preparation method is to react ortho -chlorobenzotrifluoride with sodium benzylate. The resulting ether is then hydrogenylized to provide the desired product. Thiol starting materials of formula (9) are similarly commercially available or are synthesized using conventional procedures. Preparation of Quinoline Starting Materials Quinoline starting materials can be synthesized using a variety of known procedures. Organic Syntheses, collective volume 3, 1955, pp. 272-75, gives a procedure for preparing 4,7-dichloroquinoline, and other polysubstituted quinolines. Another general procedure is described in Tetrahedron, vol. 41, pp. 3033-36 (1985). Many of the quinoline starting materials used in the following examples were prepared as shown in the following reaction scheme In cases where mixtures of isomeric products were obtained, the mixture of substituted 4-quinolones was chlorinated under standard conditions, and the isomeric 4-chloroquinolines were separated by liquid chromatography. 4,5-dichloroquinoline was prepared by reacting 3-chloroaniline with acrylic acid in water at ambient temperature for two days. The crude product was then isolated and heated to 100°C in solution with an excess of polyphosphoric acid, thereby furnishing a mixture of 5- and 7-chlorotetrahydroquinolin-4-ones. Chromatographic separation of the 5-chloro analog, followed by treatment with iodine in hot glacial acetic acid provided 4-hydroxy-5-chloroquinoline, which was halogenated to provide the desired intermediate. French Patent Number 1514280. Other 4-chloro-5-substituted quinolines were prepared by converting the corresponding 5-substituted quinoline to the N-oxide, chlorinating, and separating the resulting mixture of 4-chloro and 2-chloro isomers using HPLC. The 5-fluoro and 5-bromo quinolines can be prepared using the same general procedure. J.A.C.S., vol. 71, 1785 (1949). The bromo-quinolines can then be lithiated and quenched with suitable electrophiles at low temperatures to provide other 5-substituted quinolines. Chem. Ber., vol. 696, pp. 98 (1966). Preparation of nitroquinolines is disclosed in J.A.C.S., vol. 68, pp. 1267 (1946). Nitration of 4-chloroquinoline proceeds cleanly to deliver a mixture of 5- and 8-nitro-4-chloroquinolines, which can be separated by liquid chromatography. The 6- and 7- nitro compounds can be made via decarboxylation of the silver salts of the appropriate nitroquinoline-3-carboxylic acid. EXAMPLES The following examples are compounds actually prepared by the above described general procedures. The melting point is given for each compound. Specific illustrative preparations for the compounds of Examples 2, 15, 17, 23, 26 and 30 follow the tabular listing. 4-(Aryloxy)quinolines EXAMPLE NUMBER COMPOUND M.P. 1 7-chloro-4-[3-(trifluoromethyl)phenoxy]quinoline 96-97°C 2 7-chloro-4-(4-fluorophenoxy)quinoline 94°C 3 7-chloro-4-(4-chlorophenoxy)quinoline 82°C 4 2-[(7-chloro-4-quinolinyl)oxy]benzonitrile 122-123°C 5 7-chloro-4-phenoxyquinoline 44-46°C 6 7-chloro-4-(4-fluorophenoxy)quinoline, 1-oxide 164-165°C 7 7-chloro-4-(3-chlorophenoxy)quinoline 99-101°C 8 4-(2-bromophenoxy)-7-chloroquinoline 71-73°C 9 7-chloro-4-(2,4-difluorophenoxy)quinoline 116-118°C 10 7-chloro-4-(2,3,5,6-tetrafluorophenoxy)quinoline 121-123°C 11 7-fluoro-4-(4-fluorophenoxy)quinoline 76-77°C 12 7-chloro-4-(2-chlorophenoxy)quinoline 69-70°C 13 7-chloro-4-(2,6-difluorophenoxy)quinoline 134-136°C 14 5,7-dichloro-4-(4-fluorophenoxy)quinoline, 1-oxide 139-140°C 15 7-chloro-4-(2-chloro-4-fluorophenoxy)quinoline, 1-oxide 177-178°C 16 5,7-dichloro-4-(4-fluorophenoxy)quinoline 213-220°C 17 7-chloro-4-(4-fluorophenoxy)quinoline, hydrochloride 221-224°C 18 8-bromo-4-(2-chlorophenoxy)quinoline 68-71°C 19 7-chloro-4-[2-( i -propyl)phenoxy]quinoline oil 20 4-(4-fluorophenoxy)-5,7-dimethylquinoline 92-94°C 21 7-chloro-4-(pentafluorophenoxy)quinoline 95°C 22 7-chloro-4-(3-chloro-4-fluorophenoxy)quinoline 124-127°C 23 5,7-dichloro-4-(4-fluorophenoxy)quinoline 82°C 24 7-chloro-4-(4-phenoxyphenoxy)quinoline 54-55°C 25 7-chloro-4-[4-( t -butyl)phenoxy]quinoline 144-145°C 26 8-chloro-4-(2-chlorophenoxy)quinoline 56-58°C 27 8-chloro-4-[2-(trifluoromethyl)phenoxy]quinoline 64-66°C 28 4-(2-bromophenoxy)-8-chloroquinoline 70-72°C 29 8-chloro-4-(2-fluorophenoxy)quinoline 60-62°C 30 8-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 99-101°C 31 5,1-dichloro-4-(2,4-difluorophenoxy)quinoline 110-111°C 32 5,7-dichloro-4-(2-nitrophenoxy)quinoline 84-86°C 33 5,1-dichloro-4-[2-(trifluoromethyl)phenoxy]quinoline 86-89°C 34 8-chloro-4-(4-fluorophenoxy)-5-methylquinoline 105-106°C 35 7-chloro-4-[4-( i -propyl)phenoxy]quinoline 52-55°C 36 8-chloro-4-[4-( i -propyl)phenoxy]quinoline 101-103°C 37 7-chloro-4-(3-fluorophenoxy)quinoline 71-73°C 38 7-chloro-4-(2-fluorophenoxy)quinoline 72-73°C 39 7-chloro-4-(4-methylphenoxy)quinoline 78-80°C 40 7-chloro-4-(4-methoxyphenoxy)quinoline 88-90°C 41 7-chloro-4-(2-methoxyphenoxy)quinoline 81-83°C 42 7-chloro-4-(2-methylphenoxy)quinoline 48-50°C 43 7-chloro-4-(3-nitrophenoxy)quinoline 149-151°C 44 7-chloro-4-(2-nitrophenoxy)quinoline 113-115°C 45 7-chloro-4-(4-nitrophenoxy)quinoline 157-159°C 46 7-chloro-4-[2-(trifluoromethyl)phenoxy]quinoline 59-61°C 47 7-chloro-4-[4-(trifluoromethyl)phenoxy]quinoline 81-82°C 48 4-(2-bromo-4-fluorophenoxy)-7-chloroquinoline 100-102°C 49 8-chloro-4-(2,4-dichlorophenoxy)quinoline 165-167°C 50 8-chloro-4-(2-cyanophenoxy)quinoline 119-121°C 51 8-chloro-4-(2-iodophenoxy)quinoline oil 52 7-chloro-4-(2,6-dibromo-4-fluorophenoxy) 128-130°C 53 7-chloro-4-[3-( t -butyl)phenoxy]quinoline oil 54 7-chloro-4-[2-( t -butyl)phenoxy]quinoline 90-92°C 55 4-[(7-chloro-4-quinolinyl)oxy]phenol 211-213°C 56 2-[(7-chloro-4-quinolinyl)oxy]phenol 209-211°C 57 4-([1,1'-biphenyl]-2-yloxy)-7-chloroquinoline oil 58 7-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 86-89°C 59 7-chloro-4-(2-iodophenoxy)quinoline 68-70°C 60 8-fluoro-4-(4-fluorophenoxy)quinoline 85-87°C 61 7-bromo-4-(4-fluorophenoxy)quinoline 87-89°C 62 7-bromo-4-(2,4-difluorophenoxy)quinoline 110-112°C 63 5,7-dichloro-4-(2-fluorophenoxy)quinoline 99-101°C 64 5,7-dichloro-4-(2-chlorophenoxy)quinoline 78-79°C 65 5,7-dichloro-4-(2-cyanophenoxy)quinoline 88-90°C 66 5,7-dichloro-4-(2-chloro-4-fluorophenoxy)quinoline 83-85°C 67 8-chloro-4-(2,4-difluorophenoxy)quinoline 105-107°C 68 8-chloro-4-(3-chloro-2-nophenoxy)quinoline 86-88°C 69 4-(2-bromo-4-fluorophenoxy)-8-chloroquinoline 106-107°C 70 8-chloro-4-(3-chlorophenoxy)quinoline 82-84°C 71 7-chloro-4-[4-[(trifluoromethyl)thio]phenoxy]quinoline 90-91°C 72 4-(3-chloro-4-fluorophenoxy)-8-chloroquinoline 88-90°C 73 8-chloro-4-(2-methylphenoxy)quinoline 85-87°C 74 8-chloro-4-(2,6-dichlorophenoxy)quinoline 156-159°C 75 8-chloro-4-(2-methoxyphenoxy)quinoline 120-122°C 76 8-chloro-4-(4-methoxyphenoxy)quinoline 119-121°C Additional Compounds EXAMPLE NUMBER COMPOUND M.P. 77 7-chloro-4-(4-chloro-3,5-dimethylphenoxy)quinoline 102°C 78 7-chloro-4-(4-chloro-3-methylphenoxy)quinoline 85°C 79 5-chloro-4-[2,6-dinitro-4-(trifluoromethyl)phenoxy]-2,8-dimethylquinoline 189°C 80 8-chloro-2-methyl-4-[2-nitro-4-(trifluoromethyl)phenoxy]quinoline 184°C 81 7-chloro-4-(3-methylphenoxy)quinoline 77-79°C 82 4-[(7-chloro-4-quinolinyl)oxy]benzonitrile 142-144°C 83 3-[(7-chloro-4-quinolinyl)oxy]beazonitrile 133-134°C 84 4-(4-bromophenoxy)-7-chloroquinoline 82-84°C 85 7-chloro-4-(4-iodophenoxy)quinoline 110-113°C 86 4-(3-bromophenoxy)-7-chloroquinoline 89-91°C 87 7-chloro-4-(4-fluorophenoxy)-6-methoxyquinoline 123-125°C 88 8-chloro-4-(2,4-dichloro-6-fluorophenoxy)quinoline 90-92°C 89 8-chloro-4-(2-ethoxyphenoxy)quinoline 76-78°C 90 8-chloro-4-(4-fluoro-2-methylphenoxy)quinoline 103-105°C 91 7-chloro-4-(2-methyl-4-fluorophenoxy)quinoline 98-100°C 92 8-chloro-4-(4-chloro-2-fluorophenoxy)quinoline 142-144°C 93 4-(2,6-dibromo-4-nitrophenoxy)-8-chloroquinoline 232-233°C 94 4-(4-bromo-2-fluorophenoxy)-8-chloroquinoline 122-125°C 95 8-chloro-4-(2,4-dibromophenoxy)quinoline 115-116°C 96 8-chloro-4-(4-fluoro-2-nitrophenoxy)quinoline 133-135°C 97 8-chloro-4-(2,4,6-trichlorophenoxy)quinoline 153-155°C 98 7-chloro-4-(4-fluorophenoxy)-2-methylquinoline 141-142°C 99 8-chloro-4-(2-nitrophenoxy)quinoline 142-144°C 100 5,7-dichloro-4-(3-bromophenoxy) quinoline 120-121°C 101 8-bromo-4-(4-fluorophenoxy)quinoline 122-123°C 102 5,7-dichloro-4-(4-fluorophenoxy)-6-methylquinoline 110-112°C 103 7-chloro-4-(2,4-dinitrophenoxy)quinoline 181-183°C 104 8-chloro-4-(2,6-dibromo-4-fluorophenoxy)quinoline 195-197°C 105 5-chloro-2,8-dimethyl-4-(4-fluorophenoxy)quinoline 75-76°C 106 8-chloro-4-(3-methylphenoxy)quinoline 46-48°C 107 7-chloro-4-[2-(methylthio)phenoxy]quinoline 107-108°C 108 7-chloro-4-(4-ethoxyphenoxy)quinoline 113-115°C 109 8-chloro-4-(4-ethoxyphenoxy)quinoline 94-96°C 110 5,7-dichloro-4-phenoxyquinoline 97-99°C 111 7-chloro-4-(3-methoxyphenoxy)quinoline 69-70°C 112 8-chloro-4-(4-iodophenoxy)quinoline 114-116°C 113 8-chloro-4-(4-chloro-2-methylphenoxy)quinoline 143-145°C 114 4-(4-chloro-3,5-dimethylphenoxy)-8-chloroquinoline 128-129°C 115 4-(4-chloro-2-nitrophenoxy)-8-chloroquinoline 149-150°C 116 8-chloro-4-(2-ethylphenoxy)quinoline oil 117 4-[(1,1'-biphenyl)-4-yloxy]-7-chloroquinoline 139-141°C 118 3-[(7-chloro-4-quinolinyl)oxy]phenol 150-154°C 119 7-chloro-4-(2-phenoxyphenoxy)quinoline 84-86°C 120 8-chloro-4-(2-chlorophenoxy)quinazoline 127-129°C 121 8-chloro-4-(2-chloro-4-fluorophenoxy)quinazoline 172-173°C 122 8-chloro-4-[2-(methylthio)phenoxy]quinoline 67-69°C 123 8-chloro-4-(4-methylphenoxy)quinoline 97-98°C 124 8-chloro-4-(2,3-dimethylphenoxy)quinoline 118-120°C 125 8-chloro-4-(3,4-dimethylphenoxy)quinoline 88-90°C 126 7-chloro-4-[4-(trifluoromethoxy)phenoxy]quinoline 79-80°C 127 8-chloro-4-[4-(trifluoromethoxy)phenoxy]quinoline 131-133°C 128 8-chloro-4-(2,5-dichlorophenoxy)quinoline 70-73°C 129 8-chloro-4-(2,6-dimethylphenoxy)quinoline 125-127°V 130 8-chloro-4-(3,5-dimethylphenoxy)quinoline 85-87°C 131 8-chloro-4-(2-chloro-6-methylphenoxy)quinoline 154-156°C 132 8-chloro-4-(2,5-dimethylphenoxy)quinoline 51-53°C 133 8-chloro-4-[2-chloro-5-(trifluoromethyl)phenoxy]quinoline 120-122°C 134 4-(2-chloro-4-nitrophenoxy)-8-chloroquinoline 179-181°C 135 4-(2,4-dibromophenoxy)-7-chloroquinoline 134-136°C 136 4-(4-bromo-2-fluorophenoxy)-7-chloroquinoline 129-131°C 137 8-chloro-4-(4-ethylphenoxy)quinoline 70-72°C 138 7-chloro-4-(2,6-dimethylphenoxy)quinoline 54-56°C 139 8-fluoro-4-(2-phenylphenoxy)quinoline N/A 140 4-(2-chloro-4,6-difluorophenoxy)-8-chloroquinoline 99-101°C 141 8-chloro-4-[(1-methylcyclopentyl)oxy]quinoline 82-83°C 142 4-[(5,7-dichloro-4-quinolinyl)oxy]benzonitrile 161-163°C 143 3-bromo-7-chloro-4-(2,4-difluorophenoxy)quinoline 113-114°C 144 3-bromo-7-chloro-4-(4-fluorophenoxy)quinoline 96.5-98°C 145 3-bromo-4-(2-chloro-4-fluorophenoxy)-7-chloroquinoline 140-141°C 146 3-bromo-4-(2-chlorophenoxy)-7-chloroquinoline 146-148°C 147 3-bromo-4-(2-bromo-4-fluorophenoxy)-7-chloroquinoline 152-154°C The following detailed descriptions of the procedures used to prepare selected examples are representative of the procedures used to prepare the compounds of the other examples. Examples 2 and 17 7-Chloro-4-(4-fluorophenoxy)quinoline and 7-Chloro-4-(4-fluorophenoxy)quinoline, hydrochloride A slurry comprising 7.92 g (.04 mol) of 4,7-dichloroquinoline, 4.48 g (.04 mol) of 4-fluorophenol, and 24 ml of xylene was stirred and heated to reflux. The resulting clear orange solution was refluxed at 144°C for 17 hours, at which time an additional 0.90 g (.008 mol) of 4-fluorophenol was added, and refluxing was continued. The mixture was concentrated to a brown solid, which was dissolved in a mixture of CH 2 Cl 2 (50 ml) and IN NaOH (50 ml). The organic layer was washed four times with 50 ml of IN NaOH, then dried with Na 2 SO 4 , and concentrated to a brown oil (9.8 g), which crystallized. The product, 7-chloro-4-(4-fluorophenoxy)quinoline, was recrystallized from hexane, yielding a white crystalline solid. Yield: 8.01 g (73.2%). M.P. 91-92°C. The corresponding amine hydrochloride, was prepared using a similar procedure, except that after refluxing the reaction mixture for 18 hours, the mixture was cooled to room temperature, and anhydrous HCl was added over one half hour period. The mixture was then cooled to 0°C and held at 0°C for two hours. The mixture was then filtered and the product dried under vacuum at 40°C. The filtrate was stirred 48 hours at room temperature, during which time additional product precipitated. The product, 7-chloro-4-(4-fluorophenoxy)quinoline, hydrochloride, was recrystallized from 40 ml propanol. Yield: 9.10 g (73%). M.P. 220-224°C. Example 15 7-Chloro-4-(2-chloro-4-fluorophenoxy)quinoline, 1-oxide A mixture of 5.0 g (16.22 mmol) of 4-(2-chloro-4-fluorophenoxy)-7-chloroquinoline, 4.20 g (19.47 mmol) of 80% 3-chloroperoxybenzoic acid, and 50 ml of CH 2 Cl 2 was stirred at 0°C for six hours. The CH 2 Cl 2 was removed by reducing pressure, and the residue was dissolved in ethyl acetate and washed with base. After removing solvent from the organic layer by reducing pressure, a white solid formed. This was recrystallized in ethyl acetate. Yield 3.04 g (58%). M.P. 177-178°C. Analysis: Theory C, 55.58; H, 2.49; N, 4.32; Found C, 55.67; H, 2.46; N, 4.43. Example 23 5,7-Dichloro-4-(4-fluorophenoxy)quinoline A mixture of 29.11 g of 4,5,7-trichloroquinoline and 16.84 g of 4-fluorophenol was heated to 160°C. After approximately 40 minutes, the molten solution solidified. The solid was dissolved in ethyl acetate and 2N NaOH. The organic layer was washed with base to remove excess phenol, then dried. Solvent was removed by reducing pressure, and the residue was purified by recrystallizing in heptane to produce 29.49 g of the title product. M.P. 105-106°C. Analysis: Theory C, 58.47; H, 2.62; N, 4.55; Found C, 58.38; H, 2.52; N, 4.55. Example 26 8-chloro-4-(2-chlorophenoxy)quinoline A mixture of 2.0 g of 4,8-dichloroquinoline and 2.6 g of 2-chlorophenol was heated to 160°C and stirred. Progress of the reaction was monitored by TLC. When no 4,8-dichloroquinoline remained, the reaction mixture was diluted with ethyl acetate, and washed with base to remove most of the excess phenol. To remove phenol remaining after washing, the product was purified using HPLC. Fractions containing product were combined, and solvent was removed using reduced pressure. The oily product crystallized. Yield: 1.36 g (46%). M.P. 56-58°C. Analysis: Theory C, 62.09; H, 3.13; N, 4.83; Found C, 62.14; H, 3.11; N, 5.04. Example 30 8-chloro-4-(2-chloro-4-fluorophenoxy)quinoline A mixture of 2.0 g of 4,8-dichloroquinoline and 2.96 g of 2-chloro-4-fluorophenol was heated to 160°C and stirred. Progress of the reaction was monitored using TLC. When no 4,8-dichloroquinoline remained, the product was washed with base to remove phenol, then purified using HPLC. A brown solid resulted, which was recrystallized in heptane to give 1.54 g of the title product as yellow crystals. Yield: 49%. M.P. 99-101°C. Analysis: Theory C, 58.47; H, 2.62; N, 4.55; Found C, 58.39; H, 2.85; N, 4.49. Utility The compounds of formula (1) have been found to control fungi, particularly plant pathogens. When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount. The term "disease inhibiting and phytologically acceptable amount," as used herein, refers to an amount of a compound of the invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type formulation employed, the method of application, the particular plant species, climate conditions and the like. The compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal infestation. Greenhouse Tests The following experiments were performed in the laboratory to determine the fungicidal efficacy of the compounds of the invention. Test 1 This screen was used to evaluate the efficacy of the present compounds against a variety of different organisms that cause plant diseases. The test compounds were formulated for application by dissolving 50 mg of the compound in 1.25 ml of solvent. The solvent was prepared by mixing 50 ml of "Tween 20" (polyoxyethylene (20) sorbitan monolaurate surfactant) with 475 ml of acetone and 475 ml of ethanol. The solvent/compound solution was diluted to 125 ml with deionized water. The resulting formulation contains 400 ppm test chemical. Lower concentrations were obtained by serial dilution with the solvent-surfactant mixture. The formulated test compounds were applied by foliar spray. The following plant pathogens and their corresponding plants were employed. Pathogen Designation in Following Tables Host Erysiphe graminis tritici (powdery mildew) POWD MDEW wheat Pyricularia oryzae (rice blast) RICE BLAS rice Puccinia recondita tritici (leaf rust) LEAF RUST wheat Botrytis cinerea (gray mold) GRAY MOLD grape berries Pseudoperonospora cubensis (downy mildew) DOWN MDEW squash Cercospora beticola (leaf spot) LEAF SPOT sugar beet Venturia inaequalis (apple scab) APPL SCAB apple seedling Septoria tritici (leaf blotch) LEAF BLOT wheat The formulated technical compounds were sprayed on all foliar surfaces of the host plants (or cut berry) to past run-off. Single pots of each host plant were placed on raised, revolving pedestals in a fume hood. Test solutions were sprayed on all foliar surfaces. All treatments were allowed to dry and the plants were inoculated with the appropriate pathogens within 2-4 hours. The effectiveness of test compounds in controlling disease was rated using the following scale: 0 = not tested against specific organism - = 0-19% control at 400 ppm + = 20-89% control at 400 ppm ++ = 90-100% control at 400 ppm +++ = 90-100% control at 100 ppm Results are reported in the following Table 7: COMPOUND EX NO. POWD MDEW RICE BLAS LEAF RUST GRAY MOLD DOWN MDEW LEAF SPOT APPL SCAB LEAF BLOT 1 + - - - - - - + 2 +++ - - - + 0 - + 3 ++ - - - + 0 - + 4 +++ - - - - - - - 5 ++ + + - - + - - 6 +++ - + - + ++ - + 7 ++ - - - - - - - 8 +++ - - - + - - + 9 +++ - - - - + - - 10 + - + - + + - + 11 + - + - ++ - - - 12 +++ - + - - - - - 13 ++ - - - + - - - 14 +++ + - - - + - - 15 ++ - - - ++ + - + 16 +++ - - - + 0 0 0 17 +++ - - - - 0 0 0 18 +++ ++ - ++ ++ 0 0 0 19 ++ ++ - + + 0 0 0 20 +++ ++ ++ - - 0 0 0 21 + - - - - - - - 22 + - - - - 0 0 0 23 +++ - + - - + - - 24 +++ + - - + - - - 25 + - + - - 0 0 0 26 + ++ + +++ ++ + +++ - 27 + + - - - - - + 28 + + - +++ + - + - 29 + - - + - 0 0 0 30 + - + +++ + - +++ + 31 +++ - - - - 0 0 0 32 + + - - ++ 0 0 0 33 ++ + - - - 0 0 0 34 ++ - - - - 0 0 0 35 + - - - - 0 0 0 36 - - - + - 0 0 0 37 ++ + - - - - - + 38 +++ - - - - + - + 39 + - - - - 0 0 0 40 ++ - + - + - - - 41 + - + - ++ - + - 42 + + - - + - - - 43 + - - - - - - - 44 ++ - - - - - - + 45 ++ + - - - - - - 46 +++ + - - + - - - 47 + - - - + 0 0 0 48 +++ + + - - 0 0 0 49 + - - - - 0 0 0 50 + + - - + 0 0 0 51 ++ ++ + ++ + 0 0 0 52 + - - - - 0 0 0 53 ++ + + - + - - + 54 ++ + - - - - - + 55 - - + - + 0 0 0 56 - - - - - 0 0 0 57 + + - - + - - + 58 ++ - - - - - - + 59 +++ - + - - - - + 60 - + + + ++ - + + 61 +++ + + - - 0 0 0 62 +++ - - - - 0 0 0 63 + - - - - 0 0 0 64 +++ - - - - - - + 65 + ++ - - + - - + 66 +++ - - - + - - - 67 + + - ++ ++ 0 0 0 68 - ++ + ++ + 0 0 0 69 + + - ++ + 0 0 0 70 + - + + - 0 0 0 71 ++ - - - - 0 0 0 72 - - + ++ + 0 0 0 73 ++ ++ + ++ ++ 0 0 0 74 ++ - - + - 0 0 0 75 + + - + - 0 0 0 76 - - - ++ - 0 0 0 77 + - - - - 0 0 0 78 ++ - - - - - - - 79 - - + - - - - - 80 - - + - - 0 0 0 81 ++ - + - - - - - 82 - - - - - 0 0 0 83 + - - - + 0 0 0 84 + - - - - 0 0 0 85 - - - - - 0 0 0 86 - - + - - 0 0 0 87 - 0 - - - 0 0 0 88 ++ + - ++ + 0 0 0 89 + + - - + 0 0 0 90 ++ - - ++ - 0 0 0 91 +++ - - - - 0 0 0 92 - - - ++ - 0 0 0 93 - - - - - 0 0 0 94 + + - ++ + 0 0 0 95 - - - + - 0 0 0 96 - + - + + 0 0 0 97 - - - - - 0 0 0 98 + - - - - 0 0 0 99 - - - - - 0 0 0 100 + - - - - 0 0 0 101 - - - - - 0 0 0 102 - - - - - 0 0 0 103 + - - - - 0 0 0 104 - - - - - 0 0 0 105 - - - - + 0 0 0 106 ++ - - ++ - 0 0 0 107 + - - - - 0 0 0 108 + + + - - 0 0 0 109 - - - - - 0 0 0 110 +++ - + - - 0 0 0 111 + - + - + 0 0 0 112 - - - - - 0 0 0 113 - - - ++ - 0 0 0 114 - - - - - 0 0 0 115 + + + - + 0 0 0 116 +++ + - ++ ++ 0 0 0 117 + - - - - 0 0 0 118 - - - - - 0 0 0 119 + - - - - 0 0 0 120 + - + ++ - 0 0 0 121 - - - ++ - 0 0 0 122 - - - + - 0 0 0 123 + + - + - 0 0 0 124 + + - ++ - 0 0 0 125 - - - + - 0 0 0 126 ++ - - - - 0 0 0 127 - - - - - 0 0 0 128 - + - ++ ++ 0 0 0 129 ++ - - - + 0 0 0 130 - - - + - 0 0 0 131 + - - + - 0 0 0 132 ++ + + + ++ 0 0 0 133 - - - - + 0 0 0 134 - - - - - 0 0 0 135 + - - - - 0 0 0 136 + - - - - 0 0 0 137 ++ + + + - 0 0 0 138 ++ ++ + - + 0 0 0 139 ++ - + + ++ 0 0 0 140 +++ ++ - +++ - 0 0 0 141 + ++ + - ++ 0 0 0 142 - - - - - 0 0 0 143 - - - - - 0 0 0 144 + - - - - 0 0 0 145 - - - - - 0 0 0 146 - - - - - 0 0 0 147 - - + 0 - 0 0 0 Additional Plant Pathology Tests Selected compounds were further tested in the greenhouse against various pathogens. The compounds were formulated and applied as foliar sprays as in Test 1. Results are reported in the following Tables 8-10 using the rating scale of Table 7. The following abbreviations are used in the Tables: PMW = Wheat Powdery Mildew PMB = Barley Powdery Mildew PMG = Grape Powdery Mildew PMC = Cucumber Powdery Mildew PMA = Apple Powdery Mildew BG = Grape Botrytis BT = Tomato Botrytis BB = Bean Botrytis DMG = Grape Downy Mildew LRW = Wheat Leaf Rust LS = Wheat Leaf Spot LB = Wheat Leaf Blot AS = Apple Scab TB = Tomato Blight PCH = Pseudocercosporella herpotuchoides COMPOUND EX NO. PMW PMB PMG PMC PMA 1 0 0 0 0 +++ 2 +++ ++ +++ +++ +++ 4 +++ 0 0 0 0 6 ++ 0 0 0 0 8 +++ 0 0 0 0 9 +++ 0 0 0 0 11 - 0 0 0 0 12 +++ 0 0 0 ++ 13 ++ 0 0 0 0 14 +++ 0 0 0 0 16 +++ 0 0 0 0 17 +++ 0 0 0 0 20 +++ 0 0 0 0 23 +++ +++ 0 ++ +++ 30 ++ 0 0 0 0 31 +++ 0 0 0 0 38 +++ 0 0 0 0 44 +++ 0 0 0 ++ 43 +++ + 0 + ++ 48 +++ 0 0 0 0 58 +++ 0 0 0 0 61 +++ 0 0 0 0 62 +++ 0 0 0 0 91 ++ 0 0 0 0 98 - 0 0 0 0 109 +++ 0 0 0 0 140 + 0 0 0 0 COMPOUND EX NO. BG BT BB DMG LRW 2 0 0 0 + + 23 0 0 0 0 + 26 +++ ++ + ++ 0 27 0 - 0 0 0 28 - +++ 0 0 0 29 0 ++ 0 0 0 30 +++ +++ 0 0 0 44 0 0 0 0 - 46 0 0 0 0 - 60 0 0 0 ++ 0 67 0 +++ 0 0 0 94 0 + 0 0 0 99 0 - 0 0 0 106 0 + 0 0 0 120 ++ 0 0 0 0 121 ++ + 0 0 0 140 0 ++ 0 0 0 COMPOUND EX NO. LS LB AS TB PCH 2 0 + 0 0 0 6 + 0 0 0 0 23 0 0 0 0 + 30 + 0 +++ + 0 Combinations Fungal disease pathogens are known to develop resistance to fungicides. When strains resistant to a fungicide do develop, it becomes necessary to apply larger and larger amounts of the fungicide to obtain desired results. To retard the development of resistance to new fungicides, it is desirable to apply the new fungicides in combination with other fungicides. Use of a combination product also permits the product's spectrum of activity to be adjusted. Accordingly, another aspect of the invention is a fungicidal combination comprising at least 1% by weight of a compound of formula (1) in combination with a second fungicide. Contemplated classes of fungicides from which the second fungicide may be selected include: 1) N-substituted azoles, for example propiconazole, triademefon, flusilazol, diniconazole, ethyltrianol, myclobutanil, and prochloraz; 2) pyrimidines, such as fenarimol and nuarimol; 3) morpholines, such as fenpropimorph and tridemorph; 4) piperazines, such as triforine; and 5) pyridines, such as pyrifenox. Fungicides in these five classes all function by inhibiting sterol biosynthesis. Additional classes of contemplated fungicides, which have other mechanisms of action, include: 6) dithiocarbamates, such as maneb and mancozeb; 7) phthalimides, such as captafol; 8) isophthalonitrites, such as chlorothalonil; 9) dicarboximides, such as iprodione; 10) benzimidazoles, such as benomyl and carbendazim; 11) 2-aminopyrimidines, such as ethirimol; 12) carboxamides, such as carboxin; and 13) dinitrophenols, such as dinocap. The fungicide combinations of the invention contain at least 1%, ordinarily 20 to 80%, and more typically 50 to 75% by weight of a compound of formula (1). Certain combinations within the invention have been found to provide synergistic activity against a number of fungal pathogens. Synergism against powdery mildew and rust has been observed not only in greenhouse tests, but also under field conditions. More specifically, synergism has been observed for certain combinations in which the second fungicide component was nuarimol, benomyl, chlorothalonil, prochloraz, propiconazole, triademefon, or tridemorph. The compounds of Examples 2, 12, 23, 30, and 46 were tested in such combinations. In general, it is believed that synergism can be expected under appropriate conditions from combinations comprising a compound of the formula (1) in combination with a sterol inhibiting fungicide of the type that inhibits C-14 demethylation; but, as evidenced by the foregoing list, synergism has also been observed with other classes of fungicides. When it is stated that a composition displays synergism, we mean that the percent control of disease observed in a test of the composition exceeds the value predicted by the equation E = X + Y - XY 100 where X is the percent control observed in a test of component A applied at rate p, Y is the percent control observed in a test of component B applied at rate q, and E is the expected percent control for the combination of A + B applied at rate p + q. This test is based on an article by S. R. Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations" Weeds, vol. 15, 20-22 (1967). The test operates on the theory that if components A and B each independently kill 50% of disease organisms, then, if used together, after A kills 50% of disease organisms, the best B can be expected to do is kill 50% of the remaining organisms, for an expected total of 75% control. A given fungicidal composition may display synergism under certain conditions and not under others. Factors significant in determining whether synergism is displayed include, for example, the application rate, the timing of the application, and the genetic resistance of disease organisms to a component of the composition. When a combination is applied at a rate such that the applied amount of one component alone would afford nearly complete control of the organism, there is little room for improvement, and the synergistic potential of the combination may not be apparent. In regard to timing, if an application of fungicide is made before the fungal disease organism is well established, the organism is more susceptible, and there is less opportunity to show synergistic potential than in the case where the disease organism is well established. On the other hand, if a disease organism is genetically resistant to one component of a combination, so that the applied amount of the one component alone would afford little control of that particular organism, there is more opportunity for the combination to show synergism against that organism than in a case where a similar application rate is used against a non-resistant disease organism. MITE/INSECT SCREEN The compounds of Examples 1-147 were tested for miticidal and insecticidal activity in the following mite/insect screen. Each test compound was formulated by dissolving the compound in acetone/alcohol (50:50) mixture containing 23 g of "Toximul R" (sulfonate/nonionic surfactant blend) and 13 g of "Toximul S" (sulfonate/nonionic surfactant blend) per liter. These mixtures were then diluted with water to give the indicated concentrations. Twospotted spider mites (Tetranychus urticae Koch) and melon aphids (Aphis gossypii Glover) were introduced on squash cotyledons and allowed to establish on both leaf surfaces. Other plants in the same treatment pot were left uninfested. The leaves were then sprayed with 5 ml of test solution using a DeVilbiss atomizing sprayer at 10 psi. Both surfaces of the leaves were covered until runoff, and then allowed to dry for one hour. Two uninfested leaves were then excised and placed into a Petri dish containing southern armyworm ( Spodopetra eridania Cramer). Activity on Southern corn rootworm ( Diabrotica undecimpuctata howardi Barber) was evaluated by adding two ml of tap water, a presoaked corn seed, and 15 g of dry sandy soil to a one ounce plastic container. The soil was treated with 1 mL of test solution containing a predetermined concentration of test compound. After six to 12 hours of drying, five 2-3 instar corn rootworm larvae were added to the individual cups, which were then capped and held at 23°C. After standard exposure periods, percent mortality and phytotoxicity were evaluated. Results for the compounds found to be active are reported in Table 11. The remaining compounds showed no activity. The following abbreviations are used in Table 11: CRW refers to corn rootworm SAW refers to Southern armyworm SM refers to twospotted spider mites MA refers to melon aphids. EXAMPLE NUMBER CRW RATE PPM CRW RESULTS % SAW SM & MA RATE PPM SAW RESULTS % SM RESULTS % MA RESULTS % 2 12.00 0 200 0 0 10 11 24.00 0 400 0 90 0 12.00 0 200 0 40 0 17 24.00 0 400 0 40 50 63 24.00 100 400 0 0 0 12.00 0 200 0 0 0 74 24.00 100 400 0 0 0 12.00 0 200 0 0 0 97 24.00 100 400 0 90 90 12.00 100 200 0 0 0 114 24.00 0 400 80 0 0 12.00 0 200 0 0 0 131 24.00 80 400 0 0 0 12.00 0 200 0 0 0 141 24.00 100 400 0 0 0 12.00 0 200 0 0 80 Compositions The compounds of this invention are applied in the form of compositions which are important embodiments of the invention, and which comprise a compound of this invention and a phytologically-acceptable inert carrier. The compositions are either concentrated formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment. The compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition. The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such water-soluble, water-suspendable or emulsifiable formulations are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually from about 10% to about 90% by weight. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols. Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 10% to about 50% by weight of liquid, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants such as those mentioned above. Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer. The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle size. Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock and the like. Dusts can suitably contain from about 1% to about 10% of the compound. The following formulations of compounds of the invention have been prepared, and are typical of compositions useful in the practice of the present invention. A. Emulsifiable Concentrate 7-chloro-4-(4-fluorophenoxy)quinoline 12.50% "TOXIMUL D" (nonionic/anionic surfactant blend) 1.75% "TOXIMUL H" (nonionic/anionic surfactant blend) 3.25% "PANASOL AN3N" (naphthalenic solvent) 64.50% "DOWANOL PM" (propyleneglycol momethyl ether) 18.00% B. Dry Flowable 7-chloro-4-(4-fluorophenoxy)quinoline 18.13% "STEPANOL M.E."(anionic surfactant) 2.50% gum arabic 0.50% "SELLOGEN HR" (anionic dispersant and wetting agent) 3.00% "HISIL 233" (silica carrier) 3.00% "POLYFON H" (lignosulfonate dispersing agent) 4.00% Barden clay 8.87% C. Wettable Powder 7-chloro-4-(4-fluorophenoxy)quinoline 78.125% "STEPANOL ME" 5.000% "HISIL 233" 5.000% "POLYFON H" 5.000% Barden clay 6.875% D. Aqueous Suspension 7-chloro-4-(4-fluorophenoxy)quinoline 12.5% "MAKON 10" (10 moles of ethyleneoxide nonyl phenol surfactant) 1.0% "ZEOSYL 200" (silica) 1.0% "POLYFON H" 0.2% "AF-100" (silicon based antifoam agent) 0.2% 2% xanthan gum solution 10.0% tap water 75.1% E. Aqueous Suspension 5,7-dichloro-4-(4-fluorophenoxy)quinoline 12.5% "MAKON 10" 1.0% "ZEOSYL 200" 1.0% "AF-100" 0.2% "POLYFON H" 0.2% 2% xanthan gum solution 10.0% tap water 75.1% F. Aqueous Suspension 5,7-dichloro-4-(4-fluorophenoxy)quinoline 12.5% "TOXIMUL D" 2.0% "TOXIMUL H" 2.0% "EXXON 200" (naphthalenic solvent) 83.5% G. Emulsifiable Concentrate 8-chloro-4-(2-chlorophenoxy)quinoline 17.8% "TOXIMUL D" 2.5% "TOXIMUL H" 2.5% "EXXON 200" 77.2% H. Emulsifiable Concentrate 8-chloro-4-(2-chlorophenoxy)quinoline 12.5% "TOXIMUL D" 2.5% "TOXIMUL H" 2.5% "EXXON 200" 82.5% I. Emulsifiable Concentrate 8-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 17.6% "TOXIMUL D" 2.5% "TOXIMUL H" 2.5% "EXXON 200" 77.4% J. Emulsifiable Concentrate 8-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 12.5% "TOXIMUL D" 2.5% "TOXIMUL H" 2.5% "EXXON 200" 82.5% K. Emulsifiable Concentrate 5,7-dichloro-4-(4-fluorophenoxy)quinoline 12.5% "TOXIMUL D" 2.0% "TOXIMUL H" 2.0% "EXXON 200" 83.5% L. Wettable Powder 8-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 25.8% "SELLOGEN HR" 5.0% "POLYFON H" 4.0% "STEPANOL ME DRY" 2.0% "HISIL 233" 3.0% Barden clay 60.2%

Claims: A fungicidal method which comprises applying to the locus of the fungus a fungicidally effective amount of a compound of the formula (1) wherein R 1 to R 4 are one of the following:- a) R 3 is Cl and R 1 and R 4 are H; b) R 3 is Br and R 1 and R 4 are H; c) R 1 and R 3 are Cl and R 4 is H; d) R 4 is Cl and R 1 and R 3 are H; A is a) (C 3 -C 8 ) cycloalkyl or cycloalkenyl; b) a phenyl group of the formula (2) wherein R 9 to R 13 are independently H, CN, NO 2 , OH, halo, I, (C 1 -C 4 ) alkyl, (C 3 -C 4 ) branched alkyl, (C 2 -C 4 ) acyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halo (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkylthio, halo (C 1 -C 4 ) alkylthio, an optionally substituted group phenyl-W-, where W is a bond, O, SiR 20 R 21 R 22 or OSiR 20 R 21 R 22 where R 20 , R 21 , and R 22 are H, a C 1 -C 6 alkyl group, straight chain or branched, phenyl or substituted phenyl, provided that at least one of R 20 , R 21 , and R 22 is other than H, or R 11 and R 12 or R 12 and R 13 combine to form a carbocyclic ring, provided that unless all of the R 9 to R 13 are H or F, then at least two of R 9 to R 13 are H; or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) ; wherein the term "substituted" as used herein means substituted by up to three groups selected from halo, I, (C 1 to C 10 ) alkyl, branched (C 3 -C 6 ) alkyl, halo (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl, C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy, phenoxy, phenyl, NO 2 , OH, CN (C 1 -C 4 ) alkanoyloxy, or benzyloxy, but not including any such method for the therapeutic treatment of the human or animal body. A compound of formula (1) as defined in Claim 1, provided that the following compounds are excluded: 1) compounds wherein R 3 is C1, R 1 and R 4 are H, and A is phenyl, 4-chlorophenyl, or 4-fluorophenyl; and 2) 7-chloro-4- [3-(trifluoromethyl)phenoxy]-quinoline; 3) 7-chloro-4-(4-chloro-3,5-dimethylphenoxy)-quinoline; 4) 7-chloro-4-(4-chloro-3-methylphenoxy)-quinoline; or an acid addition salt or an N-oxide of a compound of formula (I). A compound of claim 2 wherein R 1 is H or Cl, R 3 is Cl, and R 4 is H. The compound of claim 3 which is 5,7-di-chloro-4- (4-fluorophenoxy) quinoline, or the 1-oxide thereof. A compound of claim 2 wherein R 1 and R 3 are H and R 4 is Cl. A compound of claim 5 wherein A is 2-chlorophenyl or 2-chloro-4-fluorophenyl. 7-chloro-4-[2-(trifluoromethyl)phenoxy]quinoline, or the 1-oxide thereof. 5,7-di-chloro-4-phenoxyquinoline, or the 1-oxide thereof. 7-chloro-4-(2-nitrophenoxy) quinoline, or the 1-oxide thereof. A fungicidal formulation comprising as active ingredient a compound as claimed in any one of claims 2 to 9. A fungicidal combination comprising a compound as claimed in any one of claims 2 to 10, in combination with a second fungicide. A process for preparing a compound as claimed in claim 2, which comprises a) condensing a compound for formula (7) wherein R 1 , R 3 and R 4 are as defined in claim 1 with a compound of formula (8) HO-A wherein A is as defined in claim 1 to provide a compound of formula (1), or b) oxidizing a compound of formula (1) to provide the corresponding N-oxide. A compound of claim 2 which is: 2-[(7-chloro-4-quinolinyl)oxy]benzonitrile 7-chloro-4- (3-chlorophenoxy) quinoline 4-(2-bromophenoxy) -7-chloroquinoline 7-chloro-4- (2,4-difluorophenoxy) quinoline 7-chloro-4-(2,3,5,6-tetrafluorophenoxy)quinoline 7-chloro-4-(2-chlorophenoxy)quinoline 7-chloro-4- (2,6-difluorophenoxy) quinoline 7-chloro-4-(2-chloro-4-fluorophenoxy)quinoline, 1-oxide 7-chloro-4-(4-fluorophenoxy)quinoline, hydrochloride 7-chloro-4-[2-i-propyl)phenoxy]quinoline 7-chloro-4- (pentafluorophenoxy)quinoline 7-chloro-4-(3-chloro-4-fluorophenoxy)quinoline 7-chloro-4-(4-phenoxyphenoxy)quinoline 7-chloro-4-[4-(t-butyl)phenoxy]quinoline 7-chloro-4-[4-(i-propyl)phenoxy]quinoline 7-chloro-4- (3-fluorophenoxy) quinoline 7-chloro-4-(2-fluorophenoxy)quinoline 7-chloro-4-(4-methylphenoxy)quinoline 7-chloro-4-(4-methoxyphenoxy)quinoline 7-chloro-4-(2-methoxyphenoxy)quinoline 7-chloro-4-(2-methylphenoxy)quinoline 7-chloro-4- (3-nitrophenoxy) quinoline 7-chloro-4-(2-nitrophenoxy)quinoline 7-chloro-4- (4-nitrophenoxy) quinoline 7-chloro-4- (2- (trifluoromethyl)phenoxy]quinoline 7-chloro-4-[4-(trifluoromethyl)phenoxy]quinoline 4-(2-bromo-4-fluorophenoxy)-7-chloroquinoline 7-chloro-4-(2,6-dibromo-4-fluoro-phenoxy) quinoline 7-chloro-4-[3-(t-butyl)phenoxy]quinoline 7-chloro-4- [2-(t-butyl)phenoxy]quinoline 4- [(7-chloro-4-quinolinyl)oxy]phenol 2- [(7-chloro-4-quinolinyl)oxy] phenol 4-([1,1 '-biphenyl]-2-yloxy)-7-chloroquinoline 7-chloro-4-(2-chloro-4-fluorophenoxy)quinoline 7-chloro-4-( (2-iodophenoxy)quinoline 7-chloro-4-[4-[trifluoromethyl)thio]phenoxy] quinoline 7-chloro-4-(3-methylphenoxy)quinoline 4-[(7-chloro-4-quinolinyl)oxy]benzonitrile 3-[(7-chloro-4-quinolinyl)oxy]benzonitrile 4-(4-bromophenoxy)-7-chloroquinoline 7-chloro-4-(4-iodophenoxy)quinoline 4-(3-bromophenoxy)-7-chloroquinoline 7-chloro-4-(2-methyl-4-fluorophenoxy)quinoline 7-chloro-4- (4-fluorophenoxy) 2-methylquinoline 7-chloro-4-(2,4-dinitrophenoxy)quinoline 4-[(1,1'-biphenyl)-4-yloxy]-7-chloroquinoline 3-[(7-chloro-4-quinolinyl)oxy]phenol 7-chloro-4-(2-phenoxyphenoxy)quinoline 7-chloro-4-[2- (methylthio)phenoxy]quinoline 4-(2,4-dibromophenoxy)-7-chloroquinoline 7-chloro-4-(2,6-dimethylphenoxy)quinoline, or 4-(4-bromo-2-fluorophenoxy)-7-chloroquinoline A compound of Claim 4 which is: 5,7-dichloro-4-(4-fluorophenoxy)quinoline, 1- oxide 5 ,7-dichloro-4-(4-fluorophenoxy)quinoline 5,7-dichloro-4-(2,4-difluorophenoxy)quinoline 5,7-dichloro-4-(2-nitrophenoxy)quinoline 5,7-dichloro-4-[2-trifluoromethyl) phenoxy]quinoline 5,7-dichloro-4-(2-fluorophenoxy)quinoline 5,7-dichloro-4-(2-chlorophenoxy)quinoline 5,7-dichloro-4-(2-cyanophenoxy)quinoline 5,7-dichloro-4-(2-chloro-4-fluorophenoxy)quinoline 5,7-dichloro-4-(3-bromophenoxy)quinoline 5,7-dichloro-4-phenoxyquinoline, or 4-[(5,7-dichloro-4-quinolinyl)oxy]benzonitrile A compound of Claim 6 which is: 8-chloro-4-(2-chlorophenoxy)quinoline 8-chloro-4-[2-(trifluoromethyl)phenoxy]quinoline 4-(2-bromophenoxy)-8-chloroquinoline 8-chloro-4- (2-fluorophenoxy) quinoline 8-chloro-4-(2-chloro-4-fluorophenoxy) quinoline 8-chloro-4- (4- (i-propyl)pheroxy]quinoline 8-chloro-4-(2,4-dichlorophenoxy)quinoline 8-chloro-4-(2-cyanophenoxy)quinoline 8-chloro-4-(2-iodophenoxy)quinoline 8-chloro-4-(2,4-difluorophenoxy)quinoline 8-chloro-4-(3-chlorophenoxy)quinoline 8-chloro-4-(2-methylphenoxy)quinoline 8-chloro-4-(2,6-dichlorophenoxy)quinoline 8-chloro-4-(2-methoxyphenoxy)quinoline 8-chloro-4-(4-methoxyphenoxy)quinoline 8-chloro-4-(2,4-dichloro-6-fluorophenoxy)quinoline 8-chloro-4-(2-ethoxyphenoxy) quinoline 8-chloro-4-(4-fluoro-2-methylphenoxy)quinoline 8-chloro-4- (4-chloro-2-fluorophenoxy) quinoline 8-chloro-4-(2,4-dibromophenoxy)quinoline 8-chloro-4-(4-fluoro-2-nitrophenoxy)quinoline 8-chloro-4-(2,4,6-trichlorophenoxy)quinoline. 8-chloro-4- (2-nitrophenoxy)quinoline 8-chloro-4- (2,6-dibromo-4-fluorophenoxy)quinoline 8-chloro-4-(3-methylphenoxy)quinoline 8-chloro-4-(4-ethoxyphenoxy)quinoline 8-chloro-4-(4-chloro-2-methylphenoxy)quinoline 4-(4-chloro-3,5-dimethylphenoxy)-8-chloroquinoline 4-(4-chloro-2-nitrophenoxy)-8-chloroquinoline 8-chloro-4-(2-ethylphenoxy)quinoline 8-chloro-4-[2-(methylthio)phenoxy]quinoline 8-chloro-4-(4-methylphenoxy)quinoline 8-chloro-4-(2,3-dimethylphenoxy) quinoline 8-chloro-4- (3,4-dimethylphenoxy)quinoline 8-chloro-4-[(4-trifluoremethoxy)phenoxy]quinoline 8-chloro-4-(2,5-dichlorophenoxy)quinoline 8-chloro-4-(2, 6-dimethylphenoxy)quinoline 8-chloro-4-(3,5-dimethylphenoxy)quinoline 8-chloro-4-(2-chloro-6-methylphenoxy)quinoline 8-chloro-4-(2,5-dimethylphenoxy)quinoline 8-chloro-4-[2-chloro-5-(trifluoromethyl)phenoxy]-quinoline 4-(2-chloro-4-nitrophenoxy)-8-chloroquinoline, or 8-chloro-4-(4-ethylphenoxy)quinoline.

Inventors: ARNOLD WENDELL RAY, COGHLAN MICHAEL JOSEPH, JOURDAN GLEN PHIL, KRUMKALNS ERIKS VICTOR, SUHR ROBERT GEORGE, ARNOLD, WENDELL RAY, COGHLAN, MICHAEL JOSEPH, JOURDAN, GLEN PHIL, KRUMKALNS, ERIKS VICTOR, SUHR, ROBERT GEORGE
Applicants: DOW AGROSCIENCES LLC
Application year: 1989
Main classification: C07D215
IPC codes: A01N43, C07D401, C07D239, C07D237, C07D215, C07D221, C07D405