NZ209356A - N-(2-nitrophenyl)-4-aminopyrimidines and pesticidal compositions - Google Patents

N-(2-nitrophenyl)-4-aminopyrimidines and pesticidal compositions

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Publication number
NZ209356A
NZ209356A NZ209356A NZ20935684A NZ209356A NZ 209356 A NZ209356 A NZ 209356A NZ 209356 A NZ209356 A NZ 209356A NZ 20935684 A NZ20935684 A NZ 20935684A NZ 209356 A NZ209356 A NZ 209356A
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New Zealand
Prior art keywords
halogen
substituted
hydrogen
phenyl
alkyl
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NZ209356A
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A Hubele
W Eckhardt
E Sturm
H Zondler
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Ciba Geigy Ag
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Publication of NZ209356A publication Critical patent/NZ209356A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Description

New Zealand Paient Spedficaiion for Paient Number £09356 209356 Fri r- , C' ' COlO^i1^-.(AwfejA J$" .BOiOu?|t)!l v 8 JAN 1988.
V3C$ P* t 2 8 AUG 1984 RECEIVED Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "N-(2-Nitrophenyl)-4-aminopyrimidine derivatives, the preparation thereof arid use thereof" WE, CIBA-GEIGY AG of Klybeckstrasse 141, 4002 Basle, Switzerland, a Swiss Corporation, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement ffeflowei bv mm 1A1 - JC- 209356 -14567/= N-(2-Nitrophenyl)-4-aminopyriipidine derivatives the preparation thereof and use thereof The present invention relates to novel N-(2-nitrophenyl)-4-amino-pyrimidine derivatives of the formula I below. The invention further relates to the preparation of these compounds and to agrochemical compositions which contain at least one of said compounds as active ingredient. The invention relates also to the preparation of said compositions and to the use of the novel compounds or compositions for controlling harmful micro-organisms, in particular phytopathogenic fungi.
Specifically, the invention relates to compounds of the general formula I R, NO- R. R, \ / 2 6w« // \ / \ R,-» « N * N (I) 2 \ / I \\ // •=• R, N-* \ 4 \ Ri S wherein Rj is N02 or CF3, R2 is N02 or CF3, Rj is hydrogen or halogen, R^ is hydrogen or the -C(0)R^ group, in which Ry is an unsubstituted or substituted radical selected froa Che group consisting of Cj-C^alkyl, C^-C^alkenyl, C^-C^cycloalkyl, phenyl and heterocyclyl, 209356 R^, and Rg are each independently halogen, cyano, thiocyano, nitro or a group selected from -N(R^)(R^q), —^, R|2"°" or Rj3-S(0)n~, in which and R^ are each independently hydrogen or an unsubstituted or substituted radical selected from the group consisting of C^-C^alkyl, C^-C^alkenyl and phenyl, or together with the nitrogen atom form an unsubstituted or substituted heterocyclic ring, n is 0, 1 or 2, R11,R12 'n(* ^13 are eactl independently an unsubstituted or substituted radical selected from the group consisting of C,-C, - — 1 alkyl, Cj-C^alkenyl, C^-C^alkynyl, C^-C^cycloalkyl, phenyl or heterocyclyl; and in addition R^ may be hydrogen, may be hydrogen, or two of R^, R^ and Rg may be hydrogen.
Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent such as alkoxy, alkylmercapto, haloalkyl etc., comprises e.g. the following straight chain or branched groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl etc., and the isomers thereof, e.g. iBopropyl, isobutyl, tert-butyl, isopentyl etc. Throughout this specification, a substituent prefixed by "halo" will be understood as meaning that said substituent may be monohalogen-ated or perhalogenated. Halogen and halo signify F, CI, Br or I. Hence haloalkyl denotes a monohalogenated to perhalogenated alkyl radical, e.g. CHC12, C^F, CC13, CH^l, CHF^ C^CHjBr, C2C15I CHBrCl etc., with CF^ being preferred. Alkenyl is e.g. 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl, as well as chains containing several double bonds. Depending on the indicated number of carbon atoms, cycloalkyl denotes cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cyclohepty, cyclooctyl etc. Alkynyl is e.g. 2-propynyl, propargyl, 1-butynyl, 2-butynyl etc, with propargyl being preferred.
Throughout this specification the term "heterocyclyl" or "heterocyclic ring" shall be understood as meaning a saturated unsaturated heterocyclic radical containing one or more hetero . .. -V , 4k + • ^1 atoms, preferably a saturated or unsaturated 5- or 6-membered heterocyclic ring system containing 1 to 3 identical or different heteroatoms, e.g. oxygen, nitrogen or sulfur atoms. Typical representatives of such heterocyclic ring systems are: tetrahydrofuran, furan, tetrahydrothiophene, thiophene, pyrrolidine, pyrrole, pyrroline, pyrazole, imidazole, pyrazoline, oxazole, thiazole, isoxazole, isothiazole, pyran, dihydropyran, tetrahydropyran, thiopyran, dihydrothiopyran, tetrahydrothiopyran, pyridazine, dihydropyridazine, tetrahydropyridazine, pyrimidine, dihydropyrimidine, tetrahydropyrimidine, pyrazine, dihydropyrazine, tetrahyropyrazine, morpholine, thiazine, diyhdrothiazine, piperazine and triazine.
The compounds of formula I are oils, resins or mainly crystalline solids which are stable under normal conditions and have extremely valuable pesticidal properties. They can be used for example in agriculture or related fields preventively and curatively for controlling phytopathogenic pests, e.g. phytopathogenic fungi. The compounds of formula I have an excellent pesticidal activity and a broad activity spectrum when applied in wide ranges of concentration and their use poses no problems, especially in agriculture.
The following groups of compounds are preferred on account of their pronounced pesticidal, especially fungicidal, properties: Group la: Compounds of the formula I, wherein Rj is NO^ or CF^; is NO^ or CF^; R^ is hydrogen or halogen; R^ is hydrogen or the -C(0)R^ group, in which R^ is C^-C^alkyl which is unsubstituted or substituted by halogen, C^-C^alkoxy or C^-C^alkylthio, or is C^-C^-alkenyl which is unsubstituted or substituted by halogen, or is C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro or C^-C^alkyl, or is an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 identical or different hetero atoms and is unsubstituted or substituted by halogen, C^-C^alkyl or nitroj R^, R^ and R^ are each independently halogen, cyano, thiocyano, nitro, or a group selected from ► # » 2093 4 - -N(R9)(R10), -R11( r12"°" or R13~S^°^n"' in which Rg and Rio are each independently hydrogen, C^-Cj^alkyl which is unsubstituted or substituted by hydroxy or C^-C^alkoxy, or are C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, C^-C^alkyl or C^-C^alkoxy, or together with the nitrogen atom form an unsaturated or saturated 5- or 6-membered heterocyclic ring which can contain 1 or 2 additional hetero atoms and is unsubstituted or substituted by halogen, Cj-C^alkyl or Cj-C^alkoxy; n is 0, 1 or 2; Rjj, Rj2 and Rj3 are each independently C^C^alkenyl which is unsubstituted or substituted by halogen, C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted or substituted by halogen, nitro, C^-C^alkyl, C^-C^haloalkyl or C^-C^alkoxy, or are C^-C^alkynyl which is unsubstituted or substituted by halogen, or C^-C^cycloalkyl which is unsubstituted or substituted by halogen or C^-C^alkyl, or phenyl or phenyl which is substituted by halogen, C^-C^haloalkyl, C^-C^alkyl or C^-C^alkoxy, or are an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsubstituted or substituted by halogen, nitro, C^-C^alkyl, C^-C^halo-alkyl or Cj-C^alkoxy; and in addition R^ can be hydrogen, R^ can be hydrogen or two of R^, R^ and Rg can be hydrogen.
Group lb: Compounds of the formula I, wherein R^ is NO^ or CF^; R^ is NO or CF_; R_ is hydrogen or halogen; R. is hydrogen; R , R and i 5 J H DO Rg are each independently halogen, cyano, thiocyano, nitro, or a group selected from -NCR^XRjq) , Ri2~°~ °r R13~S^n~' which R^ and R^Q are each independently hydrogen, Cj-C^alkyl which is unsubstituted or substituted by hydroxy or C^-C^alkoxy, or are C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, Cj-C^alkyl or C^-C^alkoxy, or together with the nitrogen atom form an unsaturated or saturated 5- or 6-membered heterocyclic ring which can contain 1 or 2 additional hetero atoms and is unsubstituted or substituted by halogen, C^-C^alkyl or C^-C^alkoxy; n is 0, 1 or 2; Rjj, R^2 and R^ *re each independently Cj-C^alkenyl which "" 0 91 ' is unsubstituted or substituted by halogen, C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted or substituted by halogen, nitro, C^-C^alkyl, C^-C^haloalkyl or C^-C^alkoxy, or are C^-C^alkyn-yl which is unsubstituted or substituted by halogen, or C^-C^cyclo-alkyl which is unsubstituted or substituted by halogen or Cj-C^alk-yl, or are phenyl or phenyl which is substituted by halogen, C^-C^-haloalkyl, C^-C^alkyl or C^-C^alkoxy, or are an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsubstituted or substituted by halogen, nitro, Cj-C^alkyl, Cj-C^haloalkyl or Cj-C^alkoxy; and in addition can be hydrogen. R, can be hydrogen or two of Rc, R, and R„ can be t> j o o hydrogen.
Group Ic: Compounds of the formula I, wherein R^ is NO^ or CF^; R^ is NO^ or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R^ is halogen, cyano, thiocyano, nitro or a group selected from -N(R^)(Rjq)I -IIJJI Ri2~°~ or R13~S^°^n~' *n wh*ch R9 and Rio are each independently hydrogen, C^-C^alkyl, C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together they form an unsubstituted or methyl-substituted piperidine ring; n is 2; an<* R13 are eac^ independently C^-C^alkenyl or Cj-Cj^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur, each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^alkynyl, C^-C^-cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cj-C^alkyl, CF^ or C^-C^alkoxy; and R^ and are hydrogen.
Group Id: Compounds of the formula I, wherein is NO^ or CF^; R^ is NO^ or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R^ is hydrogen; R is hydrogen, cyano, thiocyano, nitro or a group o 1 selected from -N(R^)(Rj0>, -R^, R^-O- or R^-S(0)n-, in which R^ and R^Q are each independently hydrogen, Cj-C^alkyl, or together with the nitrogen atom are piperidine; n is 2; R^, Rj2 and R^ are each independently C^-C^alkenyl, Cj-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, CF., C-C.alkyl or C.-C.alkoxy; and Ra is hydrogen. J 1 Z 12 o Group Ie:compounds of the formula I, wherein R^ is N02 or CF^; R^ is N0o or CF ; R is hydrogen or chlorine; R. , R. and R, are til ft 5 0 hydrogen; R is halogen, cyano, thiocyano, nitro or a group selected Q from -N(R^)(Rjq) i ~Rn» Ri2~°~ or R13~S^n~' 1,11 *ch R9 and Rio are each independently hydrogen, C^-C^alkyl, or together with the nitrogen atom are piperidine; n is 2; R^, R^ and are each independently C^-C^alkenyl, C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C_-C,cycloalkyl, phenyl or phenyl which is substituted by J o halogen, CF^, C^-C^alkyl or C^-C2alkoxy.
Group If; Compounds of the formula I, wherein R^ is NC>2 or CF^; Rj is NOj or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R^ and Rg are each independently halogen, cyano, thiocyano, nitro or a group selected from -N(Rg)(R^ ), -R^i rj2~0~ or R13~S^n~' wh^ch Rg and R^0 are each independently hydrogen, C^-C^alkyl, C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together they form an unsubstituted or methyl-substituted ring selected from piperidine, tetrahydrofuryl and morpholine; n is 2; Rj2 and Rj^ are each independently C^-C^- alkenyl or C^-C^-alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur, each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^- alkynyl, C,-C,cycloalkyl, phenyl or phenyl which is substituted by 3 6 halogen, nitro, C^-C^alkyl, CF^ or C^C^lkoxy; and R^ is hydrogen. 4 20935 Group Igt Compounds of the formula I, wherein Rj is NOj or CF^I Rj is NOj or CF^ j R^ is hydrogen or chlorine; R^ is hydrogen; R^ and Rg are each independently halogen, cyano, thiocyano, nitro or a group selected from -N(Rg)(Rj0), -R^. Ri2~°~ or R13~S^n~* *n which Rg and R^Q are each independently hydrogen, C^-C^alkyl, Cj-C^-alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together they form an unsubstituted or methyl-substituted piperidine ring) n is 2; R^, R^ and R^ are each independently C^-C^alkenyl or Cj-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, or by an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur, each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^-alkynyl, C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, C^-C^alkyl, CF^ or C^-Cjalkoxy; and R^ is hydrogen.
Examples of particularly preferred individual compounds are: N-(3'-chloro-2',6'-dinitro-4'-trifluoromethy1phenyl)-4-amino-6-chloropyrimidine (compound 2.2); N-( 3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methylmercaptopyrimidine (compound 2.5); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methoxypyrimidine (compound 2.4); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-(2,2,2-trifluorethoxy)pyrimidine (compound 2.6); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-chloropyrimidine (compound 5.1); N-(3'-chloro-2',6'-dinitro-4'-trifluororaethylpheny1)-4-amino-2,5-dichloropyrimidine (compound 5.3); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-chloro-5-fluoropyrimidine (compound 5.4); N-( 3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-fluoropyrimidine (compound 5.6); 2 0 91 N-(3'-chloro-2',6'-dinitro-4'-trifluororaethylphenyl)-4-amino-5-nitro-6-methoxypyrimidine (compound 6.1)J N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-aminopyrimidine (compound 6.2); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methylmercapto-5-nitro-6-methoxypyrimidine (compound 7.1); N-(3'-chloro-2',6'-dinitro-4'-trif1uoromethylphenyl)-4-amino-2-methyl-5-ethyl-6-chloropyrimidine (compound 7.3); The compounds of formula I are prepared by reacting a compound of the formula II H NO N / 1 •—• / \ R -• '-Z (II) 2 \ / •r • \ Ri with a pyrimidine derivative of the formula III r8V h •S* / \ Y-* N (III) \ / N-* \ R5 in the presence of a base, to give a compound of the formula I' R_ NO, R. R, \ / 2 "v /6 / \ / \ R--» • NH • N (I') 2 \ // \\ // N-* \ \ R1 R5 2 G v: "4 > and, Co obtain an N-acylated derivative, N-acylating the compound of the formula I1 with a reaccive derivative of Che carboxylic acid of the formula IV R.COOH (IV) 4 in which formulae above Che substituents Rj Co Rg are as defined for formula I and Z and Y are NH^ or halogen, wich Che proviso ChaC, if Z is halogen, Y is NH^ and, if Z is NH^, Y is halogen.
The following reaction conditions are advantageous for the preparation of the compounds of formula I and/or I't The N-alkylation of (II) with (III) to give (I') and the N-acylation of (I') with (IV) to give (I) take place with dehydrohalogenation. The reaction temperature of the N-alkylation is in Che range from -20* to +150*C, preferably from -20* to +30*C, and thaC for the N-acylation is in the range from 0* to +180*C, preferably from 0" to +150*C or at the boiling point of the solvent or solvent mixture. In boch reactions it is convenient to use an acid acceptor or a condensing agenc. Examples of suicable acid acceptors or condensing agencs are organic and inorganic bases, e.g. cerciary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidyl-areinopyridine etc.), oxides, hydroxides, carbonaces and bicarbonates of alkali metals and alkaline earth metals, as well as alkali metal acetates.
The reactions may be conducted in the presence of inert solvents or diluents. Examples of suitable solvents and diluents are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, cecrachloroechylene; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisole, dioxan, tetrahydrofuran; nitriles such as acetonitrile and propionitrile; N,N-dialkylated amides such as dimethylfonnamide; dimethylsulfoxide; ketones such as acetone, ' Mb* ^ ** diethyl ketone, methyl ethyl ketone; and mixtures of such solvents. In some cases the acylating or alkylating agent itself may be used as solvent.
The reaction of (II) with (III) can also be carried out in an aqueous two-phase system in accordance with the generally known principle of phase transfer catalysis.
The following solvents for example are suitable for the organic water-immiscible phase: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes etc.; halogenated hydrocarbons such as dichloro-methane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, tetrachloroethylene and the like, or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether etc. Examples of suitable phases transfer catalysts are: tetraalkylamroonium halides, hydrogen sulfates or hydroxides, e.g. Cetrabutylammoniuin chloride, tetrabutylammonium bromide, tetrabutyl-ammonium iodide, triethylbenzylammonium chloride or triethylbenzyl-aamonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide or tetrapropylammonium iodide etc. Suitable phase transfer catalysts are also phosphonium salts. The reaction temperatures are generally in the range from -30* to +130*C or may also be at the boiling point of the solvent or mixture of solvents.
Unless otherwise expressly specified, one or more inert solvents or diluents may be present in the preparation of all starting materials, intermediates and final products mentioned herein. Examples of suitable inert solvents or diluents are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene| ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisole, dioxane, tetrahydrofurane; nitriles such as aceto-nitrile, propionitrile; N,N-dialkylated amides such as dimethyl 7093 5 - li - fonnamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other. It can often be convenient to carry out the reaction, or partial steps of a reaction, under an inert gas atmosphere and/or in absolute solvents. Suitable inert gases are nitrogen, helium, argon etc.
The above described preparatory process, including all partial steps, constitutes an important object of the present invention.
Surprisingly, it has been found that the compounds of formula I have for practical purposes a very useful biocidal spectrum againBt harmful micro-organisms, especially against phytopathogenic fungi. They have very advantageous curative, systemic and, in particular, preventive properties, and can be used for protecting numerous cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the microorganisms which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.
As microbiocides, the compounds of formula I are effective againat the phytopathogenic fungi belonging to the following classes) Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. of the genera Hemileia, Rhizocotonia, Puccinia); and, in particular, against the class of the Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula). In addition, the compounds of formula I have a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic microorganisms which occur in the soil. ->093 56 Accordingly, the invention also relates to microbicidal composition* and to the use thereof in agriculture or related fields for controlling phytophatogenic microorganisms, for example fungi.
The invention further embraces the preparation of these compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.
Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites).
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These further compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art 2093 56 of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners binders or fertilisers.
A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen (type of fungus). However, the compound of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation. In special cases, further types of application are also possible, e.g. selective treatment of the plant stems or buds.
The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha. 2093 56 The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as eyelohexanone, strongly polar solvents such as N-methyl-2-pyrro-lidone, dimethylsulfoxide or dimethylformamide, as well as epoxid-ised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorp-tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. Particularly advantageous application promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the series of the cephalins and lecithins, e.g. phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphatidyl inisotol, phosphatidyl glycerol, lysolecithin, plasmalogenes or cardiolipin, which can be obtained e.g. from animal or plant cells, in particular from the brain, heart, liver, egg yokes or soya 2093 beans. Examples of useful physical forms are phosphatidyl choline mixtures. Examples of synthetic phospholipids are dioctanoylphos-phatidyl choline and dipalmitoylphosphatidyl choline.
Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic aufactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal saltB or unsubstituted or substituted ammonium salts of higher fatty acids e'®* t*le sod^um or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimid-azole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C0-C„„alkyl radical which also o 22 includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or tri-ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha- 2093 56 lenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Alao suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/ polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one CQ-C alkyl radical and, as o Lc further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, mechylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide. 2093 56 17 - The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and EmulsifierB Annual", MC Publishing Corp. Ringwood, New Jersey, 1981; Helmut Stache, "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981.
The agrochemical compositions usually contain 0.1 to 99 X, preferably 0.1 to 95 Z> °£ a compound of the formula 1, 99.9 to 1 JJ, preferably 99.8 to 5 Z% of a solid or liquid adjuvant, and 0 to 25 Zt preferably 0.1 to 25 Z> a surfactant.
Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Such agrochemical compositions also constitute an object of the present invention.
The invention is illustrated in more detail by the following Examples, without implying any restriction to tfiat is described therein. Parts and percentages are by weight.
Preparatory Example Example PI; Preparation of CI NO. NO. OCH. \ / 2 \2 / 3 / \ / \ F,C-» •—«—• N (6.1) 3 W I w H N-» \ NO- * ? 093 56 - 18 - * N-(3'-Chloro-2',6'-dinitro-4trifluoromethylphenyl)-4-amino-(5-nitro-6-methoxy)pyrimidine With stirring, 3.2 parts of 4-amino-5-nitro-6-methoxypyrimidine are added, in portions and at room temperature, to a solution of 6.1 parts of 2,4-dichloro-3,5-dichloro-3,5-dinitrobenzotrifluoride in 50 ml of dimethylsulfoxide. With cooling, a solution of 4.5 parts of potassium tert-butylate in 25 ml of dimethylsulfoxide is added dropwise at room temperature to the suspension over 1/2 hour and stirring is continued for 12 hours at room temperature. The red reaction mixture is then poured into 700 ml of water, acidified with * 3 ml of hydrochloric acid, and extracted with 3 x 200 ml of chloroform. The combined extracts are washed with 2 x 100 ml of water, dried over sodium sulfate, filtered and dried. The brown crystalline residue is purified by column chromatography through silica gel eluted with a 3:2 mixture of petroleum ether/ethyl acetate. The eluaat is evaporated off and the product is recrystallised from toluene/cyclohexane, affording the title compound with m.p. 184"-186*C.
The following compounds of formula I are prepared in analogous manner: i Table 1; Compounds of the formula r, no \ / 2 // \ / \ r • .—n—• n 2 \ / I \\ / •=• h n-* \ \ R1 R5 Compound R1 r2 r3 R5 Physical data £*cQ 1.1 no, cf3 ci H m.p. 156 1.2 n°2 cf3 h c3h?-n 1.3 n°2 cf3 ci ch3 1.4 cf3 no2 H c6h5 1.5 no2 CF3 ci c3h7-n 1.6 n°2 cf3 ci ci viscous substance 1.7 cf3 n°2 h ci viscous substance 1.8 cf3 n02 h oc2H5 1.9 n°2 cf3 ci °c2h5 1.10 cf3 no, h SCH3 1.11 no2 cf3 ci OCH3 1.12 no2 cf3 ci SCH3 1.13 n02 cf3 h ci 1.14 no2 cf3 ci c2h5 2093 Table 1 (Continuation) Compound r1 r2 r3 r5 Physical data 1.15 n°2 cf3 ci cf3 resin 1.16 cf3 no2 H H resin 1.17 n°2 cf3 CI OC^-i 1.18 n°2 cf3 H oc2h5 1.19 n°2 cf3 CI CH2OCH3 1.20 no2 cf3 CI sch2-c6h5 1.21 no2 cf3 H cf3 resin 1.22 n02 cf3 ci -n(ch3)2 Table 2: Compounds of the formula r, no, r, N / 2 /' // \ / \ R -• •—N—• N 2 \ / I \ / •=• H \ R1 Compound R1 R2 R3 R6 Physical data 2.1 N02 CF3 H H 2.2 NO2 CF3 ci ci m.p. 97-99 2.3 cf3 N°2 H OC6H5 2.4 no2 cf3 ci 0CH3 m.p. 128-129 2.5 N°2 CF3 ci SCH3 m.p. 135-137 2 ^ 56 Table 2 (Continuation) Compound r1 r2 r3 r6 Physical data 2.6 n02 cf3 ci och2cf3 m.p. 98-100 2.7 cf3 no2 h cf3 2.8 n°2 cf3 ci -c(ch3)3 2.9 cf3 n°2 h ci resin 2.10 n°2 cf3 ci -n(c2h5)2 2.11 no2 cf3 ci c2h5 2.12 no2 cf3 ci -k(ch3)2 2.13 no2 cf3 ci c6«5 •— • / \ 2.14 n°2 cf3 ci / \ -n • \ / •— • 2.15 n02 cf3 h -N(C3H?-n)2 2.16 N02 cf3 CI cf3 viscous substance 2.17 n°2 cf3 ci ch3 2.18 no2 cf3 h 0C4Hg-n 2.19 no2 cf3 ci OC3H7-i 2.20 n°2 cf3 ci 0CH3 2.21 cf3 N°2 h OC2h5 209356 Table 3: Compound of the formula R, NO, R- \ / 1 \ // \\ / \ R -• •—N—• N 2 \ / I \\ / H N-» \ R, Compound R1 R2 R3 R8 Phyaical data 3.1 CF3 N°2 H H 8emicrystalline 3.2 N02 CF3 CI CN 3.3 N02 CF3 H CI resin 3.4 N°2 CF3 CI Br 3.5 CF3 N°2 H CN 3.6 N°2 CF3 CI CI 3.7 N°2 CF3 CI CI reain 3.8 cf3 n°2 h Br 3.9 no2 cf3 CI sv1 3.10 no2 cf3 CI ch2oc2h5 3.11 N°2 CF3 CI ch2oc6H5 3.12 no2 cf3 CI c2»5 3.13 cf3 n°2 h CH3 3.14 N°2 CF3 ci 0CH3 3.15 N°2 CF3 ci CH3 3.16 cf3 n°2 h ch2och3 3.17 n°2 cf3 ci C6H5 *K.-' -X- 2093 23 - Table 3: (Continuation) Compound r1 r2 r3 r8 3.18 no2 cp3 ci ch2c6h4c1(4) 3.19 n°2 cf3 ci c6h13"n 3.20 no2 cf3 ci c5h4c1(4) 3.21 n°2 cf3 ci ch2ci 3.22 no2 cf3 ci 0c6h3c12(3,4) Table 4i Compounds of the formula CI NO, R. CI \ / 2 \ / •s• / \ / \ CP -• •—N—• H \ / I \ / R. N=» \ 4 \ "°2 R5 Compound R4 r8 R5 4.1 C(0)ch=ch2 f sch3 4.2 C(0)CH=CH2 CI cn 4.3 C(0)CC1=CC12 f sch3 4.4 C(0)Cyclopropyl f sch3 4.5 c(o)ch=ch2 cn CF3 4.6 C(0)C,H.Cl(4) 6 4 f sch3 4.7 II II C(0)-» • \/ 0 och3 cn TT~ Table 4: (Continuation) Compound r4 r8 r5 4.8 CI / / \ C(0)-» n \ / \ ci f sch3 Table 5t Compounds of the formula R, NO, R_ *\ / 2 / \ / \ R„-» '—N—• N 2 \ / I \\ / •=• H N-» \ \ R1 R5 Compound r1 r2 r3 r5 r8 Physical data [*c] .1 no2 cf3 ci och3 ci m.p. 157-158 .2 no2 cf3 ci ch3 c4h9"d .3 no2 cf3 ci ci ci m.p. 176-177 .4 n°2 cf3 ci ci f m.p. 167-168 .5 no2 cf3 ci ch3 ch2n(ch3)2 .6 n02 cf3 ci och3 f m.p. 158-159 .7 N°2 cf3 ci sch3 f 2093 56 Table 5: (Continuation) Compound R1 R2 R3 R5 R8 Phytica1 data [*c] .8 CF3 N°2 h CH3 C6H13-n .9 N°2 CF3 ci C3H7 chjbr .10 N°2 CF3 ci CH2C6H5 chjbr .11 N°2 cf3 ci CH3 ch2scn .12 cf3 N°2 h -n(ch3)2 cn .13 N°2 cf3 ci ci ch2ci .14 cf3 N°2 h ch3 ch2cn .15 N°2 cf3 ci C2F5 cn .16 N°2 cf3 ci S02C2H5 ch3 .17 CF3 N°2 h sch3 ch3 .18 no, cf3 ci CF3 cn resin .19 no2 CF3 ci 0ch3 cn .20 ko2 CF3 ci SC2H5 C6H5 .21 CF3 N°2 h CF3 cn .22 N°2 CF3 ci ci och3 .23 n°2 CF3 ci CF3 ch2oc2h5 .24 cf3 N°2 h c3F7-n cn .25 no2 CF3 ci ch2och3 ch2oc2h 5 .26 N02 CP3 ci so2ch3 cn .27 no2 cf3 ci / \ -N • \ / no2 - - — - • ll ■ WWKWP*' ^ - + * 2093 56 Table 5: (Continuation) Compound R1 R2 R3 R5 R8 Physical data £*CQ .28 N°2 CF3 ci C2F5 Br .29 N°2 CF3 ci CF3 ch2br .30 N°2 CF3 ci SCH3 ch2ci .31 N°2 CF3 ci SC2H5 CN .32 CF3 N°2 H CF3 ch2ci .33 N°2 CF3 ci SC2H5 F .34 N°2 CF3 ci C5H9~n CN .35 N°2 CF3 ci -n(ch3)2 Br .36 N02 CF3 ci sch3 no2 .37 CF3 N°2 H C, H -n 4 9 CN .38 CF3 no2 H ci N°2 .39 N°2 CF3 H C6H4C1(4) CN .40 CF3 N°2 H SCH2C6h5 CN .41 N°2 CF3 ci -CH=CH2 cn .42 N°2 CF3 ci SCH3 ch2br .43 CF3 H°2 H ci ch2br .44 N°2 CF3 H SCH2C6H5 CH-CH=CH2 .45 K°2 cf3 ci ch2f ch3 .46 N°2 CF3 ci 0CH3 no2 m.p. 178-179 .47 N°2 CF3 ci OC2H5 ci m.p. 149-151 .48 N02 cf3 ci och2cf3 ci m.p. 146-147 .49 n°2 CF3 ci o(ch2)2och3 n°2 m.p. 125-126 \ * i. ; / % '<■ / • - « 27 - Table 5: (Concinuation) Compound r1 r2 r3 r5 00 Physical data [*c] .50 n02 cf3 ci 0ch2cf3 n02 m.p. 138-140 .51 no2 cf3 ci och2cf3 f m.p. 135-138 .52 n°2 cf3 ci sch3 ch3 .53 n°2 cf3 h sch3 ch3 .54 no2 cf3 h sch3 CI .55 n°2 cf3 ci 0ch3 CH3 .56 cf3 no2 h 0ch3 ch3 .57 cf3 n°2 h ci ch3 .58 n°2 cf3 h 0ch3 ch3 .59 cf3 n°2 h och2-ch=ch2 ci .60 n°2 cf3 ci ci ch3 .61 n02 cf3 h ci ch3 .62 cf3 n°2 h sch3 ci .63 n°2 cf3 h och2ch=ch2 ci .64 no2 cf3 ci sch3 ci .65 no2 cf3 ci och2ch=ch2 ci £093 56 Table 6: Compounds of the foraula r NO, r_ r, \ / 2 *w6 // \ / \ r -• •—n—• n 2 ^ • S' \ \ / I \ / •=• h n-* Compound r1 r2 r3 r6 r8 Physical data £*C] 6.1 n02 cf3 CI 0ch3 n°2 m.p. 184-186 6.2 n°2 cf3 CI -nh2 N°2 m.p. 184-189 6.3 CF3 n02 h ch2oc2h5 ch3 6.4 no2 cf3 CI ci n°2 6.5 no2 cf3 CI ch3 cn 6.6 N°2 cf3 CI -n(c3h?-n)2 no2 6.7 cf3 n°2 h oc2h4°c2h5 c6h5 6.8 N°2 cf3 ci CI 0c4h9-n 6.9 N°2 cf3 CI f n°2 6.10 n°2 cf3 CI CI ch3 6.11 N°2 cf3 CI CI och3 6.12 cf3 N°2 h oc2h5 n°2 6.13 n°2 cf3 ci CI oc2h5 6.14 no2 cf3 CI ch3 Br 6.15 cf3 N°2 h ch3 CI 6.16 N°2 cf3 ci CI c6h5 6.17 no2 cf3 ci c2h4°c2h5 <*4Vn 6.18 n°2 cf3 CI ci °c3h7-i 6.19 cf3 n°2 h ch3 cn 2093 56 Table 6: (Continuation) Compound R1 R2 R3 R6 R8 Physical data [*c] 6.20 CF3 N°2 H ci °c3H7-i 6.21 cf3 N02 h CH3 i 6.22 N°2 CF3 h ci OC2H5 6.23 N°2 CF3 CI sch3 no2 m.p. 185 6.24 N°2 CF3 ci OCH2CF3 no2 m.p. 164-167 6.25 N02 CF3 ci 0CH3 CI 6.26 CF3 N°2 H 0CH2CF3 ci 6.27 N°2 CF3 ci 0CH2-CH=CH2 ci 6.28 N°2 cf3 ci SCH3 ci 6.29 N°2 CF3 H ci ci Table 7 s Compounds of the formula »3\ /"°2 R8\ /' // \ / \ R -• *—N—• H 2 \ / I \ / •=• H N-* \ \ R, R, Compound r1 r2 r3 r5 r6 r8 Physical data C-c] 7.1 n°2 cf3 CI SCHJ 0CH3 n°2 m.p. 181-183 7.2 no2 cf3 CI CI ci no2 7.3 no2 cf3 CI ch3 CI c2h5 m.p. 134-136 ✓ " 209356 Table 7: (Continuation) Compound R1 R2 R3 R5 R6 R8 Physical data [•c] 7.4 N°2 CF3 ci ci ch3 N02 7.5 no2 CF3 ci ch2cn ch2cn cn 7.6 n°2 cf3 ci F f f 7.7 CF3 n°2 H CI ci n°2 7.8 CF3 h°2 h ci ci Br 7.9 n°2 CF3 ci CH3 ch3 so2ch3 7.10 N°2 CF3 ci CI CI Br 7.11 N°2 CF3 ci SCH3 ci Br 7.12 N°2 CF3 ci CI ci ch3 m.p. 184-187 7.13 CF3 n°2 h SCH3 ci C8H17"n 7.14 CF3 N°2 h Br Br CH3 7.15 N°2 CF3 ci CI CI CH2C6H5 7.16 N°2 CF3 ci CI ch3 CH3 7.17 CF3 N°2 h cf3 CF3 CN 7.18 H°2 CF3 CI CI ci ci 7.19 CF3 n02 h CI ci CH3 m.p. 207**208 7.20 h°2 CF3 ci Br Br ch3 7.21 n°2 cf3 ci CH3 ci ch2n(ch3)2 7.22 CF3 no2 h ci ci ci 7.23 CF3 N°2 h ci CI C2H5 7.24 CF3 N°2 H sch3 ch3 N°2 7.25 no2 CF3 H ci ci CI 209356 Table 7i (Continuation) Compound r1 r2 r3 r5 r6 r8 Physical data [•c] 7.26 n°2 cf3 ci -n(ch3)2 ci cn 7.27 «o2 cf3 ci cf3 cf3 cn 7.28 cf3 N°2 h ci ch3 c2h5 7.29 n°2 cf3 ci sch3 0ch3 Br 7.30 n°2 cf3 ci sch3 ci c4»9~n 7.31 n°2 cf3 ci ci ci c2h5 7.32 n02 cf3 ci sch3 ch3 CN 7.33 n°2 cf3 ci sch3 ci ch3 m.p. 169-172 7.34 n°2 cf3 ci ch2och3 ci c2h5 7.35 n°2 cf3 ci sch3 nh2 n°2 m.p. 250 (dec.) 7.36 n°2 cf3 ci 0ch3 0ch3 N°2 m.p. 164-166 7.37 N°2 cf3 h sch3 ci ch3 m.p. 213-216 7.38 cf3 n°2 h sch3 ci ch3 m.p. 150-160 7.39 N°2 cf3 ci ch3 ch3 I 7.40 h°2 cf3 Br ch3 ch3 1 7.41 cf3 n02 h ch3 ch3 i 7.42 n°2 cf3 ci sch3 ci ci 7.43 cf3 n°2 h c2h5 0ch3 ci 7.44 n°2 cf3 ci 0ch3 ci ci 7.45 n02 cf3 ci c2h5 sch3 ci 7.46 no2 cf3 ci och2cf3 ci ci 7.47 no2 cf3 h och2"ch=ch2 CI CI 32 Table?: (Continuation) Compound r1 r2 r3 r5 r6 r8 7.48 CM O Z cf3 ci c2«5 CI CI 7.49 no2 cf3 ci 0ch2"ch = ch CI CI 7.50 N°2 cf3 ci CI cf3 CI 7.51 n°2 cf3 ci 0ch3 cf3 CI 7.52 N°2 cf3 ci sch3 cf3 CI Formulation Examples Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) Fl. Emulsifiable concentrates a) b) c) a compound of tables 1 to 7 Z 40 Z 50 X calcium dodecylbenzenesulfonate Z 8 X 6 X castor oil polyethylene glycol ether (36 moles of ethylene oxide) X - - tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) 12 X hX eyelohexanone - * X xylene mixture 65 X X X Emulsions of any required concentration can be produced from such concentrates by dilution with water.
F2. Solutions a compound of tables 1 to 7 ethylene glycol monomethyl ether polyethylene glycol 400 N-methyl-2-pyrrolidone a) b) c) d) 80* 10 x 5X 95X 20 Z ~ 70 X - Z ~ 2093 56 - 33 epoxidiaed coconut oil - - 1 * 5 * petroleum distillate (boiling range 160-190*) - - 94* - These solutions are suitable for application in the form of micro* drops.
F3. Granulates a) b) a compound of tables 1 to 7 5 Z 10 * kaolin 94 * highly dispersed silicic acid 1 Z attapulgite - 90 * The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F4. Dusts a) b) a compound of tables 1 to 7 2Z * highly dispersed silicic acid IX * talcum 97 * - kaolin - 90* Ready-for-use dusts are obtained by intimately mixing the carriers with the acitve ingredient.
Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight) F5. Wettable powders a) b) c) a compound of tables 1 to 7 * 50* 75* sodium lignosulfonate * * - sodium lauryl sulfate 3* - * sodium diisobutylnaphthalenesulfonate - 6 * 10 * 34 - 209356 octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2* - highly dispersed silicic acid b% 10* 10* kaolin 62 * 27 * The active ingredient is thoroughly mixed with the adjuvants and tha mixtures is thoroughly ground in a suitable mill, affording wettabla powders which can be diluted with water to give suspensions of the desired concentration.
F6. Bnulsifiable concentrate a compound of tables 1 to 7 10 * octylphenol polyethlene glycol ether (4-5 moles of ethylene oxide) 3 * calcium dodecylbenzenesulfonate 3 * castor oil polyglycol ether (36 moles of ethylene oxide) 4* eyelohexanone 30 * xylene mixture 50* Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
F7. Dusts a) b) a compound of tables 1 to 7 5 * 8 * talcum 95 * kaolin - 92 * Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
F8. Extruder granulate a compound of tables 1 to 7 * sodium lignosulfonate 2* carboxymethylcellulose 1 * kaolin 87 * y V* - The active ingredient is mixed and ground with the adjuvant*, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a strera of air.
F9. Coated granulate a compound of tables 1 to 7 3 % polyethylene glycol 200 3 Z kaolin 94 Z The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethlene glycol. Non-dusty coated granulates are obtained in this manner.
F10. Suspension concentrate a compound of tables 1 to 7 40 Z ethylene glycol io Z nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6 Z sodium lignosulfonate z carboxymethylcellulose i Z 37 Z aqueous formaldehyde solution 0.2 Z silicone oil in the form of a 75 Z aqueous emulsion 0.8 Z water 32 Z The finely ground active ingredient is intimately mixed with the aduvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. 209356 Biological Examples Example Bl; Action against Puccinia grsminis on wheat ! a) Residual-protective action Wheat plants were treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.02*)- After 24 hours the treated plants were infected with a uredospore suspension of the fungus. The infected plants were incubated for 48 hours at 95-100 * relative humidity and about 20*C and then stood in a greenhouse at about 22'C. Evaluation of rust .
I pustule development was made 12 days after infection. | b) Systemic action Wheat plants were treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient ; (0.006* based on the volume of the soil). After 48 hours the treated plants were infected with a uredospore suspension of the j fungus. The plants were then incubated for 48 hours at 95-100* relative humidity and about 20*C and then stood in a greenhouse at about 22"C. Evaluation or rust pustule development was made 12 days after infection.
Compounds of the tables were very effective against Puccinia fungi.
Puccinia attack on untreated and infected control plants was 10()£. / Compounds of Tables 1, 2, 5 and 7 and others inhibited Puccinia attack to 0 to 5*.
Example B2; Action against Cercospora arachidicola in groundnut plants Residual protective action Groundnut plants 10-15 cm in height were sprayed with a spray mixture (0.006 *) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension j of the fungus. The infected plants were incubated for 72 hours at j about 21"C and high humidity and then stood in a greenhouse until 2 0 9 $ 6 the typical leaf specks occurred. Evaluation of the fungicidal action was made 12 days after infection and was based on the number and size of the specks.
Compared with untreated and infected controls (number and size of the specks = 100£), Cercospora attack on groundnut plants treated with compounds of the tables was substantially reduced. In the above tests, compounds 1.1, 1.6, 1.7, 1.16, 1.21, 2.2, 2.5, 2.6, 2.9, 2.16, 3.1, 3.3, 3.7, 5.1, 5.3, 5.6, 5.18, 5.46, 5.48, 5.50, 5.51, 6.1, 6.2, 6.23, 6.24, 7.1, 7.3, 7.12, 7.36, 7.37 and 7.38 inhibited the occurrence of specks almost completely (0-10*).
Example B3: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height were sprayed with a spray mixture (0.002 *) prepared from a wettable powder formulation of the test compound. The treated plants were dusted with conidia of the fungus after 3-4 hours. The infected barley plants were then stood in a greenhouse at about 22*C. The extent of the infestation was evaluated after 10 days. b) Systemic action Barley plants about 8 cm in height were treated with a spray mixture (0.006 *), based on the volume of the soil) prepared from a wettable powder formulation of compound. Care was taken that the spray mixture did not come in contact with the growing parts of the plants. The treated plants were infected 48 hours later with a conidia suspension of the fungus. The infected barley plants were then stood in a greenhouse at about 22°C and evaluation of infestation was made after 10 days.
Compounds of formula I were very effective against Erysiphe fungi. Erysiphe attack was lOQj on untreated and iunfected control plants. Compounds 1.1, 1.6, 1.7, 1.16, 1.21, 2.2, 2.5, 2.6, 2.9, 2.16, 3.1, 38 - 3.3, 3.7, 5.1, 5.3, 5.6, 5.18, 5.46, 5.48, 5.50, 5.51, 6.1, 6.2, 6.23, 6.24, 7.1, 7.3, 7.12, 7.36, 7.37, 7.38 and others, inhibited fungus attack on barley to less than 3q£.
Example B4: Residual-protective action against Venturia inaequalia on apple shoots Apple cuttings with 10-20 cm long fresh shoots were sprayed with a spray mixture (0.006 %) prepared from a wettable powder formulation of the test compound. The plants were infected 24 hours later with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20"-24*C. Scab infestation was evaluated 15 days after infection. Compounds of the tables inhibited attack to less than 2f£. On the other hand, attack on untreated and infected control shoots was 100%.
Example B5: Action against Botrytis cinerea on beans Residual protective action Bean plants about 10 cm in height were sprayed with a spray mixture (.0.02% concentration) prepared from a wettable powder formulation of the test compound. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. The infected plants were incubated for 3 days at 95-lOQj relative humidity and 21*C, and evaluation of fungus attack was then made. Numerous compounds of the tables very strongly inhibited fungal infection. At a concentration of 0.02Z, compounds I -1., 1.6, 1.7, 1.15, 2.4, 2.6, 2.16, 3.3, 3.7, 5.3, 5.6, 5.18, 5.46, 5.49, 6.2, 7.1, 7.12 and 7.33 were fully effective (0 to 8* attack). Botrytis attack on untreated and infected bean plants was 10Q£.
Example B6;Action against Phytophthora infestans on tomato plants a) Residual protective action After a cultivation period of 3 weeks, tomato plants were sprayed with a spray mixture (0.0(y£) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants 2093 56 were infected with a sporangia suspension of the fungus. Evaluation of fungus attack was made after the plants had been incubated for 5 days at 90-10$ relative humidity and 20*C. b) Systemic action A spray mixture (0.0^, based on the volume of the soil) prepared from a wettable powder formulation of the test compound was poured on tomato plants after a cultivation period of 3 weeks. Care was taken that the spray mixture did not come in contact with the growing parts of the plants. After 46 hours the plants were infected with a sporangia suspension of the fungus. Evaluation of fungus attack was made after the plants had been incubated for 5 days at 90-100* relative humidity and 20*C.
In the above tests, compounds 1.1, 1.6, 1.21, 2.2, 2.5, 2.9, 2.16, 3.1, 3.3, 3.7, 5.1, 5.3, 5.46, 5.48, 6.1, 7.1, 7.3 and 7.12 had a very good systemic action. These compounds inhibited fungus attack almost completely (0 to 5* attack) as against 100* attack on untreated control plants.
Example B7: Action against Plasmapora viticola on vines a) Residual protective action Vine cuttings in the 4-5 leaf stage were sprayed with a spray mixture (0.06*) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants were infected with a sporangia suspension of the fungus. Fungus attack was evaluated after incubation for 6 days at 95-lOQlJ relative humidity and 20*C. b) Residual curative action Vine cuttings in the 4-5 leaf stage were infected with a sporangia suspension of the fungus. After incubation for 24 hours in a humid chamber at 95-10$ relative humidity and 20*C, the infected plants were dried and sprayed with a spray mixture (0.06*) prepared from a wettable powder formulation of the test compound. After the spray

Claims (12)

- 40 - coating had dried, the treated plants were returned to the huaid chamber. Evaluation of fungus attack vaa made 6 daya after infection. Compounds of the tables exhibited a very good fungicidal action against Plasmopara viticola on vines. In particular, compounds 1.1, 1.6, 1.7, 1.21, 2.2, 2.5, 2.9, 2.16, 3.1, 3.3, 5.1, 5.3, 5.4, 6.1, 6.2, 7.1, 7.12 and 7.19 inhibited fungus attack completely (0 to 5*). Example B8: Action against Piricularia on rice plants Residual protective action After a cultivation period of 2 weeks, rice plants were sprayed with a spray mixture (0.0^) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants were infected with a conidia suspension of the fungus. Evaluation of fungus attack was made after incubation for 5 days at 95—lOCjf relative humidity and 24*C. Compared with 10Q£ attack on untreated controls, fungus attack was less than iq£ on rice plants which were treated with a spray formulation containing a compound of tables 2 or 7, e.g. compounds 7.1 and 7.19. 309356 - 41 - WHAT «tfWE CLAIM IS;
1. A compound of Che formula I R- NO A / 2 V / \\ \ / \ R, A / •—• / \ R, N \\ // N-* \ (I), wherein Rj is N02 or CF^, R2 is N02 or CFj, R. is hydrogen or halogen, R4 R, R. is hydrogen or a -C(0)R^ group, in which is an unsubscicuted or subsCiCuCed radical selected from Che group consisCing of C.-C,.alkyl, C -C alkenyl, C.-C cycloalkyl, 1 2 0 j 7 phenyl and heCerocyclyl, and Rg and Rg are each independencly halogen, cyano, thiocyano, nicro or a group selecCed from -N(Rg)(Rj0), "Rjji Ri2~°~ an<* Rj3-S(0)n-, in which R^ and R^^ are each independencly hydrogen or an unsubstituted or substituCed radical selecCed from the group consisting of C ,-C1(,alkyl, C,-C,alkenyl and phenyl, or X 1Z J o together with the nitrogen atom form an unsubstituted or substituCed heterocyclic ring, n it 0, 1 or 2, and R11,R12 8Il<* R13 are eac^ independently an unsubstituted or substituted radical selected from the group consisting of C^-C^alkyl, Cj-C^alkenyl, C^-C^alkynyl, C^-C^cycloalkyl, phenyl or heterocyclyl; and in addition R^ may be hydrogen, may be hydrogen, or two of R , R, and R may be hydrogen. -> O o
2. A compound of Che formula 1 according to claim 1, wherein R^ is N02 or CF^; R2 is N02 or CF^; R^ is hydrogen or halogen; R^ is hydrogen or a -C(0)R7 group, in which R^ is C^-C^alkyl which i 209356 - 42 - unsubstituted or substituted by halogen, C^-C^alkoxy or Cj-C^alkyl-thio, or is C^-C^alkenyl which is unsubstituted or substituted by halogen, or is C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro or C^-C^alkyl, or is an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 identical or different hetero atoms and is unsubstituted or substituted by halogen, Cj-C^alkyl or nitro; and 1*5, Rg and Rg are each independently halogen, cyano, thiocyano, nitro, or a group selected from -N(Rg)(R10), -Rllt r12"°" 30(3 R13"S(0)n~» in which R9 and R10 are each independently hydrogen, Cj-C^alkyl which is unsub&£itute£~o« substituted by hydroxy or C^-C^alkoxy, or are C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, C^-C^alkyl or C^-C^alkoxy, or together with the nitrogen atom form an unsaturated or saturated 5- or 6-membered heterocyclic ring which can contain 1 or 2 additional hetero atoms and is unsubstituted or substituted by halogen, Cj-C^alkyl or C^-C^alkoxyj n is 0, 1 or 2; and R^j, R^2 Rj^ are each independently C -C.alkenyl which is unsubstituted or 2 0 substituted by halogen, C^-C^&lkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted or substituted by halogen, nitro, C^-C^alkyl, Cj-C^haloalkyl or C^-C^alkoxy, or are C^-C^alkynyl which is unsubstituted or substituted by halogen, or C^-C^cycloalkyl which is unsubstituted or substituted by halogen or C^-C^alkyl, or are phenyl or phenyl which is substituted by halogen, C^-C^haloalkyl, Cj-C^-alkyl or C^-C^alkoxy, or are an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsubstituted or substituted by halogen, nitro, C^-C^alkyl, Cj-C^haloalkyl or C^-C^alkoxy; and in addition R,. can be hydrogen, R, can be hydrogen or two of R_, R,- and R can be hydrogen. 0 5 o o
3. A compound of the formula I according to claim 2, wherein R^ is NO^ or CF^; R2 is N02 or CF^; R^ is hydrogen or halogen; R^ is hydrogen; and R5, Rg and Rg are each independently halogen, cyano thiocyano, nitro, or a group selected from -N(Rg)(R^), -R^, 209356 _ 43 - and Ri3~s^°^n~' *n wh*-c'1 an<* Rj0 are eac^ independently hydrogen, Cj-C^alkyl which is unsubstituted or substituted by hydroxy or Cj-C^alkoxy, or are C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, C^-C^alkyl or Cj-C^alkoxy, or together with the nitrogen atom form an unsaturated or saturated 5- or 6-membered heterocyclic ring which can contain 1 or 2 additional hetero atoms and is unsubstituted or substituted by halogen, Cj-C^alkyl or C^-C^-alkoxy; n is 0, 1 or 2; and R^, Rj2 anc3 Ri3 axe each independently Cg-C^alkenyl which is unsubstituted or substituted by halogen, Cj-Cj2alkyl which is unsubstituted or substituted by hajpgen, qitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted or substitut- t ed by halogen, nitro, C^-C^alkyl, Cj-C^haloalkyl or Cj-C^alkoxy, or i are C^-C^alkynyl which is unsubstituted or substituted by halogen, j or C^-C^cycloalkyl which is unsubstituted or substituted by halogen j or Cj-C^alkyl, or are phenyl or phenyl which is substituted by ' halogen, C^-C^haloalkyl, C^-C^alkyl or C^-C^alkoxy, or are an j unsaturated or saturated 5- or 6-membered heterocyclic ring which j- contains 1 to 3 hetero atoms and is unsubstituted or substituted by halogen, nitro, C^-C^alkyl, C^-C^haloalkyl or Cj-C^alkoxy; and in addition R. can be hydrogen, R, can be hydrogen or two of Rc, R, and J 0 JO Rg can be hydrogen.
4. A compound of the formula I according to claim 3, wherein R^ is NC>2 or CF^; R, is NO^ or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R^ is halogen, cyano, thiocyano, nitro or a group selected from -N(R9)(R1£)), -R , Rjj-O- and R13~S(0)n-, in which Rg and Rj0 are each independently hydrogen, C^-C^alkyl, C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together they form a<i unsubstituted or methyl-substituted piperidine ring; n is 2; and Rn» Rj2 a™* %3 316 each independently C^-C^alkenyl or C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or by an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen 209356 - 44 sulfur, each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^-alkynyl, C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cj-C,alkyl, CF^ or C^-C,alkoxy; and and Rg are hydrogen.
5. A compound of the formula I according to claim 3, wherein R^ is NO, or CF^; R, is NO, or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R^ is hydrogen; R^ is hydrogen, cyano, thiocyano, nitro or a group selected from -N(R9)(R1()), -Rn, Rj2"0- and R13rS(0)n-^in which and R^ are each independently hydrogen, C^-C^alkyl, or together with the nitrogen atom are piperidine; n is 2; and Rjj, Rj^ a**3 Rj3 are each independently C^-C^alkenyl, C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, CF^, Cj-C,alkyl or Cj-C,alkoxy; and two of R5, Rg and Rg can be hydrogen.
6. A compound of the formula I according to claim 3, wherein R^ is NO, or CF^; R, is NO, or CF^; R^ is hydrogen or chlorine; R^, R^ and Rg are hydrogen; and Rg is halogen, cyano, thiocyano, nitro or a group selected from -N(Rg)(R10), Ri2~°~ and R^3"S(0)-n, in which R^ and R^ are each independently hydrogen, C^-C^alkyl, or together with the nitrogen atom are piperidine; n is 2; and Rji, R^2 and Rj3 are each independently C^-C^alkenyl, C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C,-C,cycloalkyl, phenyl or phenyl J D which is substituted by halogen, CF^, Cj-C,alkyl or Cj-C,alkoxy.
7. A compound of the formula I according to claim 3, wherein R^ is NO, or CF^; R, is NO, or CF^; R^ is hydrogen or chlorine; R^ is hydrogen; R and R are each independently halogen, cyano, thio- J o cyano, nitro or a group selected from -N(R^)(R^q), -Rj^t Ri2~°~ 9013 Rj2~S(0)n-, in which R^ and R^ are each independently hydrogen, Cj-C^alkyl, C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together thev form an r HJLPATWHTOmCt to NOV 1987 209356 - 45 - unsubstituted or methyl-substituted ring selected from piperidine, tetrahydrofuryl and morpholine; n is 2; and Rjj, R^2 an<^ *4.3 are independently C^-C^alkenyl or Cj-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or by an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^-alkynyl, C^-C^cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, C^-C^alkyl, CF^ or C^-Cjalkoxy; and is hydrogen.
8. A compound of the formula I according to claim 3, wherein Rj is NO^ or CF^f Rj is NO^ or CF^ ; R^ is hydrogen or chlorine; R^ is hydrogen; R^ and Rg are each independently halogen, cyano, thiocyano, nitro or a group selected from -NCR^XR^), Ri2~®~ an<^ Rjj-S(0)n~, in which R^ and R^ are each independently hydrogen, Cj-C^alkyl, C^-C^alkenyl, phenyl or phenyl which is substituted by halogen, nitro, methyl or methoxy, or taken together they form an unsubstituted or methyl-substituted piperidine ring; n is 2; and Rll' Rj2 and R^ are each independently C^-C^alkenyl or C^-C^alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or by an unsaturated or saturated 5- or 6-metnbered heterocyclic ring which contains 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur, each heterocyclic radical being in turn unsubstituted or substituted by halogen, nitro, methyl, CF^ or methoxy, or are C^-C^alkynyl, C^-Cgcycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cj-Cjalkyl, CF^ or Cj-Cjalkoxy; and R^ is hydrogen.
9. A compound of the formula I selected from the group consisting of: N-(3'-chloro-2 *,6'-dini tro-4'-trifluoromethylphenyl)-4-amino-6-chloropyrimidine (compound 2.2); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methylmercaptopyrimidine (compound 2.5); h ^crvnomolt 10 NOV 1987 WSCBVEP J 209356 46 - N-(3 '-chloro-2*,6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methoxypyrimidine (compound 2.4); N-(3'-chloro-2',6'-dinitro-4'-trif1uoromethylphenyl)-4-amino-6-(2,2,2-trifluorethoxy)pyrimidine (compound 2.6); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-chloropyrimidine (compound 5.1); N-(3'-chloro-2',6'-d init ro-4'-t ri fluorome thylphenyl)-4-amino-2,5-dichloropyrimidine (compound 5.3); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-chJoro-5-fluoropyrimidine (compound 5.4); — N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-fluoropyrimidine (compound 5.6); N-(3*-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-methoxypyrimidine (compound 6.1); N-(3'-chloro-2',6'-dinitro-4'-tri fluoromethylphenyl)-4-amino-5-nitro-6-aminopyrimidine (compound 6.2); N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methylmercapto-5-nitro-6-*methoxypyrimidine (compound 7.1); and N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methyl-5-ethyl-6-chloropyrimidine (compound 7.3).
10. A process for the preparation of a compound of the formula I, vhich comprises reacting a compound of the formula II (II) \ R. with a pyrimidine derivative of the formula III MX PAT 10 NOV 1987 209356 - 47 - (III) \ /' •r • / \ y-* N \\ / N-« \ r, in the pretence of a base, to give a compound of the formula I1 R, NO, \ / 2 / \ \\ / \ R6 ®\ /6 / \ n \\ / n-» \ (I') 1 and, to obtain an N-acylated derivative, N-acylating the compound of the formula I' with a reactive derivative of the carboxylic acid of the formula IV R4C00H (IV) in which formulae above the substituents R. to R„ are as defined for X o formula I and Z and Y are NH^ or halogen, with the proviso that, if Z is halogen, Z is NH2 and, if Z is NH^, Y is halogen.
11. A composition for controlling or preventing attack by microorganisms, which contains at least one compound of the formula 1 together with conventional adjuvants.
12. A method of controlling phytopathogenic pests or of preventing cultivated plants from being attacked by such pests, rfiich comprises applying to said plants or to tne locus thereof an effective amount of a compound of the formula I. FO 7.5/Hl/am*" 2 8 AUG 1984 ,11 BALDWtltf^jfljN & CAREY attorneys for the applicants
NZ209356A 1983-08-29 1984-08-28 N-(2-nitrophenyl)-4-aminopyrimidines and pesticidal compositions NZ209356A (en)

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AU3245084A (en) 1985-03-07

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