CA1254560A - N-(2-nitrophenyl)-4-aminopyrimidine derivatives, the preparation thereof and use thereof - Google Patents

N-(2-nitrophenyl)-4-aminopyrimidine derivatives, the preparation thereof and use thereof

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Publication number
CA1254560A
CA1254560A CA000461860A CA461860A CA1254560A CA 1254560 A CA1254560 A CA 1254560A CA 000461860 A CA000461860 A CA 000461860A CA 461860 A CA461860 A CA 461860A CA 1254560 A CA1254560 A CA 1254560A
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halogen
substituted
nitro
phenyl
hydrogen
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French (fr)
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Adolf Hubele
Wolfgang Eckhardt
Elmar Sturm
Helmut Zondler
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Syngenta Participations AG
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Ciba Geigy Investments Ltd
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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

Abstract

ABSTRACT OF THE DISCLOSURE

Novel N-(2-nitrophenyl)-4-aminopyrimidine derivatives of the general formula I

(I)

Description

s~

21~9-65 The present invention relates to novel N-(2-nitrophenyl)-4-aminopyrimidlne deri~atives of the formula I below. rrhe invention further relates -to the preparation of these compounds and -to ayro-chemical compositions which con-tain at least one of said compounds as active ingredient. The invention relates also to the prepara-tion of said compositions and to the use of the novel compounds or com-positions for controlling harmful micro-organisms, in particular phytopathogenic fungi.
Specifically, the invention relates to compounds of the general formula I

R3 NO2 R8~ / 6 _ O = --// ~ / \
R -~ -- N (I)
2 \
=- R N-~

Rl R5 wherein R3 is hydrogen or halogen R4 is hydrogen or the -C(O)R7 yroup, in which R7 is Cl-C12alkyl which is unsubstituted or substituted by halogen, Cl-C3alkoxy or Cl-C3alkylthio, or is C2-C6alkenyl which is unsubstituted or substituted by halogen, or is C3-C7cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro or Cl-C3 alkyl, or is an unsaturated or saturated 5- or 6-membered hetero-` ' 3 4~
. .~

i6~
2 214~g-65~3 cyclic ring which contains 1 to 3 identlcal or dlfferent hetero atoms and ls unsubstltuted or substituted by halogen, Cl-C3 alkyl or nltro, R5, R6 and R8 are each lndependently halogen, cyano, thio-cyano, nltro or a group selected from -N(Rg)(Rlo)~ -Rll, R12-O- or R13-S(O) -, ln whlch Rg and Rlo are each lndependently haloyen, Cl-C12alkyl which is unsubstltuted or substltuted by hydroxy or Cl-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl whlch ls substl-tuted by halogen, nltro, Cl-C4alkyl or Cl-C4alkoxy, or together wlth the nitrogen atom form an unsaturated or saturated 5- or 6-membered heterocycllc ring which can contain 1 or 2 additional hetero atoms and is unsubstituted or substituted by halogen, Cl-C4alkyl or Cl-C4 alkoxy, n is 0, 1 or 2 Rll, R12 and R13 are each independently Cl-C12alkyl which is unsubstituted or substituted by halogen, nltro, cyano, phenyl, phenoxy, phenylthlo or by a saturated or unsaturated 5- or 6-mem-bered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted by halogen, nitro, Cl-C4 alkyl, Cl-C4haloalkyl or Cl-C4alkoxy, or are C2-C6alkenyl which is unsubstituted or substituted by halogen, or are C3-C6alkynyl which is unsubstituted by halogen, or C3-C7cycloalkyl which is unsubsti-tuted or substituted by halogen or Cl-C3alkyl, or are phenyl or phenyl which is substituted by halogen, Cl-C4haloalkyl, Cl-C4alkyl or Cl-C4alkoxy, or are an unsaturated or satura-ted 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsub-~ .' ~ 2 -.,,~

~2~ 6~
- 2a - 2148g-6583 stituted or substituted by haloyen, nitro, Cl-C4alkyl, Cl-C4halo-alkyl or Cl-C4alkoxy; and in addltion R5 can be hydroyen, R6 can be hydrogen or two of R5, R6 and R8 can be hydroyen.
Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substitutent 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. isopropyl, isobutyl, tert-butyl, isopentyl etc. Throughout this specification, a substituent prefixed by "halo"
will be understood as meaning that said substituent may be monohalo-genated or perhalogenated. Halogen and halo signify F, Cl, Br or I.
Hence haloalkyl denotes a monohalogenated to perhalogenated alkyl radical, e.g. CHC12, CH2F, CC13, CH2Cl, CHF2, CH2CH2Br, C2C15, CHBrCl etc., with CF3 being preferred. Alkenyl is e.g. l-propenyl, allyl, l-butenyl, 2-butenyl or 3-butenyl, as well as chains contain-ing several double bonds. Depending on the indicated number of car-bon atoms, cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc. Alkynyl is e.g. 2-propynyl, propargyl, l-butynyl, 2-butynyl etc, with propargyl being preferred.
Throughout this specification the term "heterocyclyl" or "heterocyclic ring" shall be understood as meaning a ~aturated or a unsaturated heterocyclic radical containing one or more hetero-- 2a -"' ,.'' .i s~

atoms, preferably a saturated or unsaturated 5- or 6~neMbered 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, o~azole, 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 Ia: Compounds of the formula I, wherein Rl is N02 or CF3; R2 is NO~ or CF3; R3 is hydrogen or halogen; R~ is hydrogen or the -C(O)R7 group, in which R7 i8 Cl-C4alkyl which is unsubstituted or 9ubstituted by halogen, Cl-C3alkoxy or Cl-C3alkylthio~ or is C2-C4-alkenyl which is unsubstituted or substituted by halogen, or is C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro or Cl-C3alkyl, 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, Cl-C3alkyl or nitro; R5, R6 and R8 are each independently halogen, cyano, thiocyano, nitro, or a group selected from ~2~

9 10 ~ R12 or R13-S(O)n-, in which E~g and R are each independently hydrogen, Cl-C12alkyl which is unsubstituted or substituted by hydroxy or Cl-C~alkoxy, or are C3-C6alkenyl, phenyl or phenyl which is substituted by halogen, nitro, Cl-C4alkyl or Cl-C4alkoxy~ or together with the nitrogen atom forrn 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, Cl-C4alkyl or Cl-C4alkoxy; n is 0, 1 or 2; Rll, R12 and R13 are each independently C2-C6alkenyl which is unsubstituted or substituted by halogen, Cl-C12alkyl 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, Cl-C4alkyl, Cl-C4haloalkyl or Cl-C4alkoxy~ or are C3-C6alkynyl which is unsub-stituted or substituted by halogen, or C3-C7cycloalkyl which is unsubstituted or substituted by halogen or Cl-C3alkyl~ or phenyl or phenyl which is substituted by halogen, Cl-C4haloalkyl, Cl-C4alkyl or Cl-C4alkoxy, or are an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsub-stituted or substituted by halogen, nitro, Cl-C4alkyl, Cl-C4halo-alkyl or Cl-C4alkoxy; and in addition R5 can be hydrogen, R6 can be hydrogen or two of R5, R6 and R8 can be hydrogen.

Group Ib: Compounds of the formula I, wherein Rl is N02 or CF3; R2 is N02 or CF3; R3 is hydrogen or halogen; R4 is hydrogen; R5, R6 and R8 are each independently halogen, cyano, thiocyano, nitro, or a 9 10)' 11~ 12 or R13 S()n , in which Rg and Rlo are each independently hydrogen, Cl-C12alkyl which is unsubstituted or substituted by hydroxy or Cl-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl which is substituted by halogen, nitro, Cl-C4alkyl or Cl-C4alkoxy~ 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 unsubsti-tuted or substituted by halogen, Cl-C4alkyl or Cl-C4alkoxy; n is 0, 1 or 2; Rll, R12 and R13 are each independently C2-C6alkenyl which
3"Z~

is unsubstituted or substituted by halogen, Cl-Clzalkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-member-ed heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted or substituted by halogen, nitro~ Cl-C4alkyl, Cl-C4haloalkyl or Cl-C4alkoxy, or are C3-C6alkyn-yl which is unsubstituted or substituted by halogen, or C3-C7cyclo-alkyl which is unsubstituted or substituted by halogen or Cl-C3alk-yl, or are phenyl or phenyl which is substituted by halogen, Cl-C4-haloalkyl, Cl-C4alkyl or Cl-C4alkoxy~ 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, Cl-C4alkyl, Cl-C4haloalkyl or Cl-C4alkoxy; and in addition R5 can be hydrogen, R6 can be hydrogen or two of R5~ R6 and R8 can be hydrogen.

Group Ic: Compounds of the formula Il wherein Rl is N02 or CF3; R2 is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is halogen, cyano, thiocyano, nitro or a group selected from 9 10 ~ R12 or R13-S(O)n-, in which Rg and R are each independently hydrogen, Cl-C4alkyl, C3-C4alkenyl, 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; Rll, R12 and R13 are each independently C3-C4alkenyl or Cl-Cl2alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an unsatu-rated 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 substitute(l by halogen, nitro~ methyl, CF3 or methoxy~ or are C3-C4alkynyl, C3-C6-cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R6 and R8 are hydrogen-Group Id: Compounds of the formula I, wherein Rl is N02 or CF3; R2is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen, cyano, thiocyano, nitro or a group 5~

9 ( 10)' Rll' R12-- or R13-S~o) -, in whic~ R
and Rlo are each independently hydrogen, Cl-C3alkyl, or together with the nitrogen atom are piperidine; n is 2; Rll, R12 and R13 are each independently C3-C4alkenyl, Cl-C4alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenyl-thio, or C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen~ CF3~ Cl-C2alkyl or Cl-C2alkoxy; and R8 is hydrogen.

Group Ie:compounds of the formula I, wherein Rl is N02 or CF3; R2 is N02 or CF3; R3 is hydrogen or chlorine; R4, R5 and R6 are hydrogen; R8 is halogen, cyano, thiocyano, nitro or a group selected 9 10)' Rl1, R12 0 or R13-S(O)n-, in ~"hich Rg and R1o are each independently hydrogen, Cl-C3alkyl, or together with the nitrogen atom are piperidine; n is 2; Rll, R12 and R are each independently C3-C4alkenyl~ Cl-C4alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, CF3, Cl-C2alkyl or Cl-C2alkoxy.

Group If: Compounds of the formula I, wherein R1 is N02 or CF3; R2 is N02 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 and R8 are each independently halogen, cyano, thiocyano, nitro or a group selected from -N(Rg)(Rlo)~ -Rll, R12 or 13 n 9 and Rlo are each independently hydrogen, Cl-C4alkyl, C3-C4alkenyl, 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 i8 2; Rl1, R12 and R13 are each independently C3-C4-alkenyl or Cl-C12-alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by an un-saturated 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, CF3 or methoxy, or are C3-C4-alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R6 is hydrogen.

Group Ig: Compounds of the forrnula I, wherein Rl is N02 or CF3; R2 is N02 or CF3 ; R3 is hydrogen or chlorine; R4 is hydrogen; R6 and R8 are each independently halogen, cyano, thiocyano, nitro or a group selected from -N(R9)(Rlo)l Rll, R12 13 n which Rg and Rlo are each independently hydrogen, Cl-C4alkyl, C3-C4-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; Rll, R12 and R13 are each independently C3-C4alkenyl or Cl-C4alky1 which is unsubsti-tuted 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, CF3 or methoxy, or are C3~C4-alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, Cl-C2alkyl, CF3 or Cl-C2alkoxy; and R5 is hydrogen.

Examples of particularly preferred individual compounds are:
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-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'-trifluoromethylphenyl)-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-arnino-2-methoxy-5-fluoropyrimidine (compound 5.6);

N-(3'-chloro-2',6'-dinitro-4'-tr;fluoromethylphenyl)-4-amino-5-nitro-6-methoxypyrimidine (coMpound 6.1);
N-~3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-arnino-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'-trifluoromethylphenyl)-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

~o // ~
2 \ / ~Z (II) \
Rl with a pyrimidine derivative of the formula III
R R
8\ / 6 / \
Y-- N (III) ~ //
N--in the presence of a base, to give a compound of the formula I' =. =-/ \ / \
R -- ~---N~---- N (I') 2 ~ // ~ //
o_- N--Rl R5 _ 9 _ and, to obtain an N-acylated derivative, N-acylating the compound of the formula I' with a reactive derivative of the carbo~ylic acid of the formula IV
R4COOH (IV) in which formulae above the substituents Rl to R8 are as defined for formula I and Z and Y are NH2 or halogen, with the proviso that, if Z is halogen, Y is NH2 and, if Z is NH2, Y is halogen.

The following reaction conditions are advantageous for the prepara-tion of the compounds of formula I and/or I':

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 the range from -20 to +150C, preferably from -20 to +30C, and that for the N-acylation is in the range from 0 to +180C, preferably from 0 to +150C or at the boiling point of the solvent or solvent mixture. In both reactions it is convenient to use an acid acceptor or a condensing agent. ~xamples of suitable acid acceptors or condensing agents are organic and inorganic bases, e.g. tertiary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidyl-aminopyridine etc.), oxides, hydroxides, carbonates 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. ~xamples of suitable solvents and diluent3 are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetra-chloride, tetrachloroethylene; ethers and ethereal compoullds 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 dimethylformamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents.
In some cases the acylating or alkylat;ng 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 catalysisO

The following solvents fGr 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:
tetraalkylammonium halides, hydrogen sulfates or hydroxides, e.g.
tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl-ammonium iodide, triethylbenzylammonium chloride or triethylbenzyl-ammonium 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 ~130C 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: alipllatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylenel 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 formamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone~ methyl ethyl ketone; and rnixtures o~ such solvents with each other. It can often be convenier-t 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 irtlportant 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 against 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 against 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.

s~

Accordingly, the invention also relates to microbicidal compositions and to the use thereof in agriculture or related fields for control-ling phytophatogenic microorganisms, for exarnple fungi.

The invention further embraces the preparation of these cornposi-tions, 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 forrnula 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) 7 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, sun-flowers, 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, bacterici-des, 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 5~
.~

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 sub-stances, solvents, dispersants, wetting agents, tackifiers, thick-eners 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 plan~ 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. selec-tive 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 lO0 g to 2 kg a.i./ha~ most preferably from 200 g to 600 g a.i./ha.

.

The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the ~ormula ~ and, where appropriate, a solid or liquid adjuvQnt, are prepared in kno~r1 mannerl e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers andl where appropriatel surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbonsl 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 cyclohexanone, 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, sphingomyelinel phosphat-idyl 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 56~

beans. Examples of useful physical forrns are phosphatidyl choline mixtures. Examples of synthetic phospholipids are dioctanoylphos-phatidyl choline and dipalmitoylphosphatidyl choline.

Depending on the nature of the compound of the fo~nula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic sufactants 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 salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium 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 sub-stituted ammonium salts and contain a C8-C22alkyl radical which also 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 sulfona-ted 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-lenesulfonic acid, or of a naphthalenesulfonic acid/forrnaldehyde condensation product. Also suitable are correspondillg pho~phates~
e.g. salts of the phosphoric acid ester of an adduct of p-norlyl-phenol with 4 to 1~ 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 ~mit.

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 C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. rhe salts are preferably in the forrn of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

5~i~

The surfactants custornarily emp10ye~l in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1981; ~lelMut Stache, "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, lg81.

The agrochemical compositions usually contain 0.1 to 99 ~, prefer-ably 0.1 to 95 ~, of a compound of the formula I, 99.9 to 1 ~, preferably 99.8 to 5 ~, of a solid or liquid adjuvant, and O to 25 ~, preferably 0.1 to 25 ~, of a surfactant.

Whereas commercial products are preferably formulated as concen-trates, 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 what is described therein. Parts and percentages are by weight.

Preparatory Example Example Pl: Preparation of C\ No2 No2 oc~3 0 = ~
/ \ / \
F C~ N - . N (6.1) -- H N--N-(3'-Chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-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 chloro-form. 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 eluant 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:

Table 1: Compounds of the forrnula // ~ / \
R -~ ~-iN--- N
2 \ /
o=~ H N--Rl R5 .__ _ .. __ _ _ _ . Compound Rl R2 ~ R3 R5 Physlcal data ~C] .
1.1NO2 CF3 Cl H m.p. 156 1.2NO2 CF3 H C3H7~n 1.3 NO2 CF3 Cl CH3 1.4CF3 NO2 H C6H5 1.5 NO2 CF3 Cl C3H7~n 1.6NO2 CF3 Cl Cl viscous substance 1.7CF3 No2 H Cl viscous substance 1.8CF3 No2 H OC2H5 1.9 NO2 CF3 Cl OC2H5 1.10CF3 NO2 H SCH3 1.11 No2 CF3 Cl OCH3 1.12 No2 CF3 Cl SCH3 1.13No2 CF3 H Cl 1.142 CF3 Cl 2 5 Table 1 (Continuation) ~ _ _ ~ ,_ _____ _ Compound RlR2 R3 R5 Physical data _ _ _ .
1.15 No2 CF3 Cl CF3 resin 1.16 CF3 N02 H H resin 1.17 No2 CF3 Cl OC3H7-i 1.18 No2 CF3 H C2H5 1.19 No2 CF3 Cl CH20CH3 1.20 No2 CF3 Cl SCH2-C6H5 1.21 No2 CF3 H CF3 re~in 1.22 N02 CF3 Cl _ Table 2: Compounds of the formula ~R6 ._. ~=.
// ~ / \
R ~ N-- N
2 \
~=- H N-~
Rl 1 1 . _ ._ .
Compound Rl R2 - 3 - 6 _ _ _ Physical data 2.1N02 CF3 H H
2.2N02 CF3 Cl Cl m.p. 97-99 2.3CF3 No2 H C6H5 2.42 3 1 1 ¦ OCH3 m.p. 128-129 2.5No2 CF3 Cl SCH3 m P~ 135-137 iL~5~

Table 2 (Continuation) Compound L R2 n3 6 ~ Physlcal data .
2.6 N02 CF3 Cl 2 3 m.p. 98-100 2.7 CF3 No2 H CF3 2.8 N02 CF3 Cl -C(CH3)3 2.9 CF3 No2 H Cl resin 2.10 No2 CF3 Cl -N(C2H5)2 2.11 No2 CF3 Cl C2H5 2.12 No2 CF3 Cl -N(CH3)2 2.13 No2 CF3 Cl C6H5 /~
2.14 No2 CF3 Cl -N\. ! -2.15 No2 CF3 H -N(C3H7-n)2 2.16 No2 CF3 Cl CF3 viscous substance 2.17 No2 CF3 Cl CH3 2.18 No2 CF3 H OC4Hg-n 2.19 No2 CF3 Cl OC3H7-i 2.20 No2 CF3 Cl OCH3 2.21 CF3 30z 3 2 5 _ _ Table 3: Compound of the formula . . ~ .= ~
// ~ / \
R ~ N - N
2 \ / I ~ D
=- H N--Rl Co~po~nd d~ ~ 3 8 _ Physical data 3.1 CF3 No2 H H semicrystalline 3.2 NO2 CF3 Cl CN
3.3 NO2 CF3 H Cl resin 3.4 NO2 CF3 Cl Br 3'5 CF3 NO2 H CN
3.6 NO2 CF3 Cl Cl 3'7 NO2 CF3 Cl Cl resin 3.8 CF3 No2 H Br 3~9 NO2 CF3 Cl C3H7-i 3.10 NO2 CF3 Cl CH20C2H5 3.11 NO2 CF3 Cl CH20C6H5 3.12 NO2 CF3 Cl C2N5 3.13 CF3 No2 H CH3 3.14 NO2 CF3 Cl OCH3 3.15 NO2 CF3 Cl CH3 3.16 CF3 No2 H CH20CII3 3.17 ~O~ CP3 Cl C6~l5 _ _ _ Table 3: (Continuation) CDmpo~md R~R2 R3 8 3.18 N02 CF3 Cl CH2C6H4Cl(4) 3.19 N02 CF3 Cl C6H13-n 3.20 N02 CF3 Cl C5H4Cl(4) 3.21 N02 CF3 Cl CH2Cl 3.22 mo CF3 Cl OC6H3C12(3 ,4) Table 4: Compounds of the formula \ / 2 8\ / 1 =~, ._0 / \ // ~
CF -~ N~-~ N
3 ~ // I \ /
G_- R4 N-~

_ .................. .... _ l .
Compound R4 R8 R5
4.1 C(O)CH=CH2 F SCH3 4.2 C(O)CH=CH2 C1 CN
4.3 C(o)ccl=ccl2 F SCH3 4.4 C(O)Cyclopropyl F SCH3 4.5 C(O)CH=CH2 CN CF3 4.6 C(O)C6H4Cl(4) F SCH3 ~.
4.7 C(0)-- OCH3 CN

5i6~

Table 4: (Continuation) .. __ . . ,_. _. __ , Compound R4 R8 R5 . ~ ......... __ .

//~~
4.8 C(O)~- N F SCH3 ,,_, Cl,_ _ Table 5: Compounds of the formula // ~ / \
R ~ N-- N
2 \ /
.=. H N-Rl R5 I __ _ _ _ . _ __ Compound Rl R2 R3 R5 R8 data [C]
. . _ _ . .. __ . .
5.1 NO2 CF3 Cl OCH3 Cl m.p. 157-158 5.2 NO2 CF3 Cl CH3 C4H9-n 5.3 NO2 CF3 Cl Cl Cl m.p. 176-177 5'4 NO2 CF3 Cl Cl F m.p. 167-168 5.5 NO2 CF3 Cl CH3 CH2N(CH3)2 5.6 NO2 CF3 Cl OC113 F m.p. 158-159 ~ ~2 CF3 Cl SCH3 _ Table 5: (Continuation) _ __ __ Compound Rl R2 R3 R5 8dPhysical . __ _ _ ___ . . _ .
5.8 CF3 No2 H CH3 C6H13-n 5 9 N02 CF3 Cl 3 7 CH2Br 5.10 N02 CF3 Cl CH2C6H5 CH2~r 5.11 N02 CF3 Cl CH3 CHzSCN
5.12 CF3 No2 H -N(CH3)2 CN
5.13 N02 CF3 Cl C1 CH2Cl 5.14 CF3 No2 H CH3 CH2CN
5.15 N02 CF3 Cl C2F5 CN
5.16 N02 CF3 C1 S02C2H5 CH3 5.17 CF3 No2 H SCH3 CH3 5.18 N02 CF3 C1 CF3 CN resin 5.19 N02 CF3 Cl OCH3 CN
5.20 N02 CF3 Cl 2 5 C6H5 5.21 CF3 No2 H CF3 CN
5.22 N02 CF3 C1 C1 OCH3 5.23 N02 CF3 C1 CF3 CH20C2H5 5.24 CF3 No2 H 3 7 CN
5.25 N02 CF3 C1 CH20CH3 CH20C2H5 5.26 N02 CF3 Cl S2CH3 CN
/'~-\
l 5 27 ~02 ~ L ~

Table 5: (Continuation) _ _ __ .. _ Compound Rl R2 R3 K5 R8 dPhyical , __ _ . _ .. __ .
5.28 NO2 CF3 Cl C2F5 Br 5.29 NO2 CF3 Cl CF3 CH2Br 5.30 NO2 CF3 Cl SCH3 CH2Cl 5.31 NO2 CF3 Cl 2 5 CN
5.32 CF3 No2 H CF3 CH2Cl 5.33 NO2 CF3 Cl 2 5 F
5.34 NO2 CF3 Cl C5Hg-n CN
5.35 NO2 CF3 Cl -N(CH3)2 Br 5.36 NO2 CF3 Cl SCH3 NO2 5.37 CF3 NO2 H C4Hg-n CN
5.38 CF3 No2 H Cl NO2 5 39 NO2 CF3 H C6H4Cl(4) CN
5.40 CF3 NO2 H SCH2C6H5 CN
5.41 NO2 CF3 Cl -CH=CH2 CN
5.42 NO2 CF3 Cl SCH3 CH2Br 5.43 CF3 NO2 H Cl ~H ~r 5.44 NO2 CF3 H SCH2C6~5 I Ct~CH 2 5.45 NO2 CF3 Cl CH2F CH3 5.46 NO2 CF3 Cl OCH3 NO2 ~n.p. 178-179 5 47 NO2 CF3 Cl OC2~15 Cl m.p. 149-151 5.48 NO2 CF3 ¦ Cl 2CF3 Cl m.p. 146-147 5.49 ~ N2 CF3 Cl j (CH2)2cl~3 No2 m.p, 125 126 Table 5: (Continuation) _ ~ _ Compound ~ Rl R2 R3 R5 8 data ~C]
. .. _ _ .. _ .
5.50 N02 CF3 Cl 2 3 N02 m.p. 138-140 5.51 N02 CF3 Cl 2 3 F m.p. 135-138 5.52 N02 CF3 Cl SCH3 CH3 5'53 N02 CF3 H SCH3 CH3 5'54 N02 CF3 H SCH3 Cl 5'55 N02 CF3 Cl OCH3 CH3 5.56 CF3 No2 H OCH3 CH3 5.57 CF3 N02 H Cl CH3 5.58 N02 CF3 H OCH3 CH3 5.59 CF3 N02 H OCH2-CH=CH2 Cl 5.60 N02 CF3 Cl Cl CH3 5.61 N02 CF3 H Cl CH3 5.62 CF3 No2 H SCH3 Cl 5.63 N02 CF3 H OCH2CH=CH2 Cl 5.64 N02 CF3 Cl SCH3 Cl . 5.65 N02_ CF3 Cl OCH2CH=CH2 Cl ~ ~5 4~

Table 6: Compounds of the formula R3 N2 R8\ / 6 _O - ~
// ~ / \
R2~ N~-- N
\ / I ~ //
=o H N--Rl _ _______ Rl R2 R3 R6 R3 data [C]
6.1 NO2 CF3 Cl OCH3 NO2 m.p. 184-186 6.2 NO2 CF3 Cl -NH2 NO2 m.p. 184-189 6.3 CF3 No2 H CH20C2H5 CH3 6.4 NO2 CF3 Cl Cl No2 6.5 NO2 CF3 Cl CH3 CN
6.6 NO2 CF3 Cl -N(C3H7-n)2 No2 6.7 CF3 No2 H 2 4 2 5C6H5 6.8 NO2 CF3 Cl Cl OC4Hg-n 6.9 NO2 CF3 Cl F NO2 6.10 NO2 CF3 Cl Cl CH3 6.11 NO2 CF3 Cl Cl OCH3 6.12 CF3 No2 H 2 5 No2 6.13 NO2 CF3 Cl Cl C2H5 6.14 N~2 CF3 Cl CH3 Br 6.15 CF3 No2 H CH3 Cl 6.16 NO2 CF3 Cl Cl C6H5 6.17 NO2 CF3 Cl C21l40C2H5 OC4Hg-n 6.18 NO2 CF3 Cl Cl OC3H7-i 6.19 CF3 NO2 H CH3 CN

- 2g -Table 6: (Continuation) _ _ _~ , Compound Rl R2 R3 6 8 dPhtyai[al,]
. ._ _ _ _ , 6.20 CF3 No2 H C1 OC3H7-i 6.21 CF3 No2 H CH3 6.22 N02 CF3 HCl C2H5 6.23 N02 CF3 Cl SCH3 N02 m.p. 185 6.24 N02 CF3 Cl 2 3 N02 m.p. 164-167 6.25 N02 CF3 Cl OCH3 Cl 6.26 CF3 No2 H2 3 C1 6.27 N02 CF3 C1 OCH2-CH=CH2 C1 6.28 N02 CF3 Cl SCH3 Cl 6.2930~ CF3 U Cl Cl . . _ _ _ Table 7: Compounds of the formula 3\ / 2 8\ / 6 // ~ / \
R ~ N--- N

=- H N--Rl R5 C]
. ... _ .
7.1 No2 CF3 Cl SCH3 OCH3 No2 m.p. 181-183 7.2N02¦ CF31 C1 ¦ C1 ¦ C1 ¦ N02 7.3 ~ __ _ __ m.p. 134-136 D

Table 7: (Continua~ion) pound ~1 R2 R3 R5 d6 8 Ph~si[al dat~
.. _ _ _ . _ .
7.4 N02 CF3 C1 Cl C113 No2 7.5 N02 CF3 Cl CH2CN CH2CN CN
7.6 No2 CF3 Cl F F F
7.7 CF3 N02 H ClCl No2 7.8 CF3 N02 H ClCl Br 7 9 N02 CF3 Cl CH3 CH3 S2CH3 7.10 No2 CF3 Cl Cl Cl Br 7.11 No2 CF3 Cl SCH3 C1 Br 7.12 No2 CF3 Cl Cl Cl CH3 m.p. 184-187 7.13 CF3 N02 H SCH3 Cl C8H17-n 7.14 CF3 N02 H Br Br CH3 7.15 No2 CF3 Cl Cl Cl CH2C6H5 7.16 No2 CF3 Cl Cl CH3 CH3 7.17 CF3 N02 H CF3 CF3 CN
7.18 No2 CF3 Cl Cl Cl Cl 7.19 CF3 N02 H Cl Cl CH3 m.p. Z07-208 7.20 No2 CF3 Cl B~ Br CH3 7.21 No2 CF3 Cl CH3 Cl CH2N(CH3)2 7.22 CF3 N02 H Cl Cl Cl 7.23 CF3 N02 H Cl Cl C2H5 7.24 CF3¦ N02¦ H SCH3CH3 No2 7.25 ~ ~ CF3 H ~ Cl Cl ¦ Cl Table 7: (Continuation) Cum-Rl R~ 3 ~ 5 ~ R8 Physical data . . ._ _ __ _ _ .
7.26 No2 CF3 Cl -N(CH3)2 Cl CN
7.27 No2 CF3 Cl CF3 CF3CN
7.28 CF3 N02 H Cl CH3C2H5 7.29 No2 CF3 Cl SCH3 OCH3 Br 7.30 N02 CF3 Cl SCH3 Cl C4Hg-n 7.31 No2 CF3 Cl Cl Cl C2H5 7.32 No2 CF3 Cl SCH3 CH3 CN
7.33 N02 CF3 Cl SCH3 Cl CH3 m.p. 169-172 7.34 N02 CF3 Cl CH20CH3 Cl C2H5 7.35 N02 CF3 Cl SCH3 NH2 N02 m.p. 250 (dec.) 7.36 No2 CF3 Cl OCH3 OCH3 N02 m.p. 164-166 7.37 N02 CF3 H SCH3 Cl CH3 m.p. 213-216 7.38 CF3 N02 H SCH3 Cl CH3 m.p. 150-160 7 39 N02 CF3 Cl CH3 CH3 7.40 N02 CF3 Br CH3 CH3 7.41 CF3 N02 H CH3 CH3 7.42 No2 CF3 Cl SCH3 Cl Cl 7.43 CF3 N02 H C2H5 OCH3 Cl 7.44 N02 CF3 Cl OCH3 Cl Cl 7.45 N02 CF3 Cl C2H5 SCH3 Cl 7.46 N02 CF3¦ Cl 2CF3 Cl Cl j 7.47 ~ 3 H OcH2-cH-cH2 Cl Cl Table 7: (Continuatiorl) C m- ~1 R2 R3 R5 n6 8 . 7.48 N02 CF3 Cl C2H5Cl Cl .
7 49 N02 CF3 Cl OCH~CH Cl Cl 7.50 N02 CF3 Cl ClCF3 Cl 7.51 No2 CF3 Cl OCH3CF3 Cl N02 CF3 Cl ~ _ CF3 Cl 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 25 ~ 40 ~ 50 calcium dodecylbenzenesulfonate 5 ~ 8 ~ 6 castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 ~ - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) 12 ~ 4 cyclohexanone - 15 ~ 20 xylene mixture 65 ~ 25 ~ ZO ~

Emulsions of any required concentration can be produced from such concentrates by dilution with water.

F2. Solutions a) b) c) d) _ a compound of tables 1 to 7 80 ~ 10 ~ 5 ~ 95 ethylene glycol monomethyl ether 20 ~
polyethylene glycol 400 - 70 ~ - -N-methyl-2-pyrrolidone - 20 ~ - -s~

epoxidised coconut oil ~ 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 I to 7 5 ~ 10 kaolin 94 ~ ~
highly dispersed silicic acid 1 ~ -attapulgite - 90 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent i6 subsequent-ly evaporated off in vacuo.

F4. Dusts a) b) a compound of tables 1 to 7 2 ~ 5 highly dispersed silicic acid 1 ~ 5 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 25 ~ 50 ~ 75 sodium lignosulfonate 5 % 5 ~ -sodium lauryl sulfate 3 ~ - 5 sodium diisobutylnaphthalenesulfonate - 6 ~ 10 5~

octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - Z ~ -highly dispersed silicic acid 5 ~ 10 % 10 kaolin 62 ~ 27 ~ -The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

F6. Emulsifiab e 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 cyclohexanone 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 10 sodium lignosulfonate 2 carboxymethylcellulose 1 kaolin 87 5~

The active ingredient is mixed and ground with the adjuvants, and the mixture is subse4uently moistened with water. The rni~ture is extruded and then dried in a streTn of air.

F9. Coated granulate a compound of tables 1 to 7 3 polyethylene glycol 200 3 kaolin 94 ~

The finely ground acTtive 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 ethylene glycol 10 nonylphenol polyethylene glycol (15 moles of ethylene oxide) 6 sodium lignosulfonate 10 carboxymethylcellulose 1 37 ~ aqueous formaldehyde solution 0.2 silicone oil in the form of a 75 aqueous emulsion 0.8 water 32 ~

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.

~25~

Biological Examples Example Bl: Action apainst Puccinia graminia 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 20C
and then stood in a greenhouse at about 22C. Evaluation of rust 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 fungus. The plants were then incubated for 48 hours at 95-100 ~
relative humidity and about 20C and then stood in a greenhouse at about 22C. 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 100~.
Compounds of Tables 1, 2, 5 and 7 and others inhibited Puccinia attack to 0 to 5~.
xample 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 of the fungus. The infected plants were incubated for 72 hours at about 21C and high humidity and then stood in a greenhouse until the typical leaf specks occurred. Evaluation of the fungicidal action was made 12 days after infection an(l 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 22C. 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 22C and evaluation of infesta-tion was made after 10 days.

Compounds of formula I were very effective against Erysiphe fungi.
Erysiphe attack was 100~ 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, 3.3, 3.7, 5.1, 5.3, 5.6, 5.18, 5.~6, 5.~8, 5.5U, 5.51, ~.1, 6.2, 6.23, 6.24, 7.1, 7.3, 7.12, 7.36, 7.37, 7.38 aad others, inhibited fungus attack on barley to less than 30~.
xample B4: Residual-protective action against Venturia inaequalis 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 20-24C. Scab infestation was evaluated 15 days after infection. Compounds of the tables inhibited attack to less than 25~. On the other hand, attack on untreated and infected control shoots was 100~.
xample 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 95-100~ relative humidity and 21C, and evaluation of fungus attack was then made. Numerous compounds of the tables very strongly inhibited fungal infection. At a concentration of 0.02~, compounds 1.1., 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 (O to 8~ attack). Botrytis attack on untreated and infected bean plants was 100~.

Example B6:Action against Ph to hthora infestans on tomato plants Y P

a) Residual protective action After a cultivation period of 3 weeks, tomato plants were sprayed with a spray mixture (0.06~) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants ~25~

were infected with a sporangia suspension of the fungus. ~valuation of fungus attack wa~s made after the plants had been incubated for 5 days at 90-100~ relative humidity and 20~C.

b) Systemic action A spray mixture (0.06~, 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 48 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 20C.

In the above tests, compounds 1.1, 1.6, 1.21, 2.Z, 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 to.o6~) 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 95-100~ relative humidity and 20C.

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 9S-100~ relative humidity and 20C, 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 coating had dried, the treated plants were re~urned to the humid chamber. Evaluation of fungus attack was made 6 days 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 (0.02~) 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 95-100 relative humidity and 24C.

Compared with 100~ attack on untreated controls, fungus attack was less than 10~ 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.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula I

(I), wherein R1 is NO2 or CF3 R2 is NO2 or CF3 R3 is hydrogen or halogen R4 is hydrogen or the -C(O)R7 group, in which R7 is C1-C12alkyl which is unsubstituted or substituted by halogen, C1-C3alkoxy or C1-C3alkylthio, or is C2-C6alkenyl which is unsubstituted or substituted by halogen, or is C3-C7cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro or C1-C3alkyl, or is an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 identical or different hetero atoms and is un-substituted or substituted by halogen, C1-C3alkyl or nitro, R5, R6 and R8 are each independently halogen, cyano, thio-cyano, nitro or a group selected from -N(R9)(R10), -R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C12alkyl which is unsubstituted or substituted by hydroxy or C1-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl which is substituted - 41a -by halogen, nitro, C1-C4alkyl or C1-C4alkoxy, 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, C1-C4alkyl or C1-C4 alkoxy, n is 0, 1 or 2, R11, R12 and R13 are each independently C1-C12alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy, phenylthio or by a saturated or unsaturated 5- or 6-mem-bered heterocyclic ring which contains 1 to 3 hetero atoms, each cyclic radical being in turn unsubstituted by halogen, nitro, C1-C4 alkyl, C1-C4haloalkyl or C1-C4alkoxy, or are C2-C6alkenyl which is unsubstituted or substituted by halogen, or are C3-C6alkynyl which is unsubstituted by halogen, or C3-C7cycloalkyl which is unsubsti-tuted or substituted by halogen or C1-C3alkyl, or are phenyl or phenyl which is substituted by halogen, C1-C4haloalkyl, C1-C4alkyl or C1-C4alkoxy, or are an unsaturated or saturated 5- or 6-membered heterocyclic ring which contains 1 to 3 hetero atoms and is unsub-stituted or substituted by halogen, nitro, C1-C4alkyl, C1-C4halo-alkyl or C1-C4alkoxy; and in addition R5 can be hydrogen, R6 can be hydrogen or two of R5, R6 and R8 can be hydrogen.

- 41a -
2. A compound of the formula I according to claim 1, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or halogen; R4 is hydrogen or the -C(O)R7 group, in which R7 is C1-C4alkyl which is unsubstituted or substituted by halogen, C1-C3alkoxy or C1-C3alkyl-thio, or is C2-C4alkenyl which is unsubstituted or substituted by halogen, or is C3-C6cycloalkyl, phenyl or phenyl which is substitut-ed by halogen, nitro or C1-C3alkyl, or is an unsaturated or saturat-ed 5- or 6-membered heterocyclic ring which contains 1 to 3 ident-ical or different hetero atoms and is unsubstituted or substituted by halogen, C1-C3alkyl or nitro; R5, R6 and R8 are each independent-ly halogen, cyano, thiocyano, nitro, or a group selected from -N(R9)(R10), -R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C12alkyl which is unsubstituted or substituted by hydroxy or C1-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl which is substituted by halogen, nitro, C1-C4alkyl or C1-C4alkoxy, 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, C1-C4alkyl or C1-C4alkoxy; n is 0, 1 or 2; R11, R12 and R13 are each independently C2-C6alkenyl which is unsubstituted or substituted by halogen, C1-C12alkyl 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, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, or are C3-C6alkynyl which is unsub-stituted or substituted by halogen, or C3-C7cycloalkyl which is unsubstituted or substituted by halogen or C1-C3alkyl, or are phenyl or phenyl which is substituted by halogen, C1-C4haloalkyl, C1-C4-alkyl or C1-C4alkoxy, 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, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy; and in addition R5 can be hydrogen, R6 can be hydrogen or two of R5, R6 and R8 can be hydrogen.
3. A compound of the formula I according to claim 2, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or halogen; R4 is hydrogen; R5, R6 and R8 are each independently halogen, cyano, thiocyano, nitro, or a group selected from -N(R9)(R10), -R11, R12-O-or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C12alkyl which is unsubstituted or substituted by hydroxy or C1-C4alkoxy, or are C3-C6alkenyl, phenyl or phenyl which is substi-tuted by halogen, nitro, C1-C4alkyl or C1-C4alkoxy, 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, C1-C4alkyl or C1-C4-alkoxy; n is 0, 1 or 2; R11, R12 and R13 are each independently C2-C6alkenyl which is unsubstituted or substituted by halogen, C1-C12alkyl 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 substitut-ed by halogen, nitro, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy, or are C3-C6alkynyl which is unsubstituted or substituted by halogen, or C3-C7cycloalkyl which is unsubstituted or substituted by halogen or C1-C3alkyl, or are phenyl or phenyl which is substituted by halogen, C1-C4haloalkyl, C1-C4alkyl or C1-C4alkoxy, 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, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxy; and in addition R5 can be hydrogen, R6 can be hydrogen or two of R5, R6 and R8 can be hydrogen.
4. A compound of the formula I according to claim 3, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is halogen, cyano, thiocyano, nitro or a group selected from -N(R9)(R10), -R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C4alkyl, C3-C4alkenyl, 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; R11, R12 and R13 are each independently C3-C4alkenyl or C1-C12alkyl 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, CF3 or methoxy, or are C3-C4-alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, C1-C2alkyl, CF3 or C1-C2alkoxy; and R6 and R8 are hydrogen.
5. A compound of the formula I according to claim 3, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen, cyano, thiocyano, nitro or a group selected from -N(R9)(R10), R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C3alkyl, or together with the nitrogen atom are piperidine; n is 2; R11, R12 and R13 are each independently C3-C4alkenyl, C1-C4alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, CF3, C1-C2alkyl or C1-C2alkoxy; and R8 is hydrogen.
6. A compound of the formula I according to claim 3, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or chlorine; R4, R5 and R6 are hydrogen; R8 is halogen, cyano, thiocyano, nitro or a group selected from -N(R9)(R10), R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C3alkyl, or together with the nitrogen atom are piperidine; n is 2; R11, R12 and R13 are each independently C3-C4alkenyl, C1-C4alkyl which is unsubstituted or substituted by halogen, nitro, cyano, phenyl, phenoxy or phenylthio, or are C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, CF3, C1-C2alkyl or C1-C2alkoxy.
7. A compound of the formula I according to claim 3, wherein R1 is NO2 or CF3; R2 is NO2 or CF3; R3 is hydrogen or chlorine; R4 is hydrogen; R5 and R8 are each independently halogen, cyano, thio-cyano, nitro or a group selected from -N(R9)(R10), -R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C4alkyl, C3-C4alkenyl, 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; R11, R12 and R13 are each independently C3-C4alkenyl or C1-C12alkyl 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, CF3 or methoxy, or are C3-C4-alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, C1-C2alkyl, CF3 or C1-C2alkoxy; and R6 is hydrogen.
8. A compound of the formula I according to claim 3, wherein R1 is NO2 or CF3; R2 is NO2 or CF3 ; R3 is hydrogen or chlorine; R4 is hydrogen; R6 and R8 are each independently halogen, cyano, thio-cyano, nitro or a group selected from -N(R9)(R10), -R11, R12-O- or R13-S(O)n-, in which R9 and R10 are each independently hydrogen, C1-C4alkyl, C3-C4alkenyl, 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; R11, R12 and R13 are each independently C3-C4alkenyl or C1-C4alkyl 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, CF3 or methoxy, or are C3-C4alkynyl, C3-C6cycloalkyl, phenyl or phenyl which is substituted by halogen, nitro, C1-C2alkyl, CF3 or C1-C2alkoxy; and R5 is hydrogen.
9. A compound of the formula I selected from the group con-sisting of:
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-chloropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methylmercaptopyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methoxypyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-(2,2,2-trifluorethoxy)pyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-chloropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2,5-dichloropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-chloro-5-fluoropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-fluoropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-methoxypyrimidine;
N-(3'-chloro-2',6' dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-aminopyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methylmercapto-5-nitro-6-methoxypyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methyl-5-ethyl-6-chloropyrimidine.
10. A process for the preparation of a compound of the formula I, as defined in claim 1, which comprises reacting a compound of the formula II

(II) with a pyrimidine derivative of the formula III

(III) in the presence of a base, to give a compound of the formula I' (I') 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

R4COOH (IV) in which formulae above the substituents R1 to R8 are as defined for formula I and Z and Y are NH2 or halogen, with the proviso that, if Z is halogen, Y is NH2 and, if Z is NH2, Y is halogen.
11. A composition for controlling phytopathogenic pests, or for protecting cultivated plants from attack by such pests, which comprises an agriculturally acceptable carrier, and, as active in-gredient, a compound of the formula I, as defined in claim 1.
12. A composition according to claim 11 wherein the active ingredient is a compound selected from the group consisting of:

N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-chloropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methylmercaptopyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-methoxypyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-6-(2,2,2-trifluorethoxy)pyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-chloropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2,5-dichloropyrimidine;

N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-chloro-5-fluoropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methoxy-5-fluoropyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-methoxypyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-5-nitro-6-aminopyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methylmercapto-5-nitro-6-methoxypyrimidine;
N-(3'-chloro-2',6'-dinitro-4'-trifluoromethylphenyl)-4-amino-2-methyl-5-ethyl-6-chloropyrimidine.
13. A method of controlling phytopathogenic pests, or of preventing cultivated plants from being attacked by such pests, which comprises applying to said plants or to the locus thereof an effective amount of a compound of the formula I as defined in claim 1, or of an agriculturally acceptable composition containing such a compound.
CA000461860A 1983-08-29 1984-08-27 N-(2-nitrophenyl)-4-aminopyrimidine derivatives, the preparation thereof and use thereof Expired CA1254560A (en)

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US7825116B2 (en) 2002-07-29 2010-11-02 Rigel Pharmaceuticals, Inc. N2, N4-bis-aryl-5-fluoro-2,4-pyrimidinediamines
US7851480B2 (en) 2004-11-24 2010-12-14 Rigel Pharmaceuticals, Inc. Spiro 2,4-pyrimidinediamine compounds and their uses

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PT79137A (en) 1984-09-01
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NZ209356A (en) 1988-01-08
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