CA1197248A - N-sulfenylated pyrrole derivatives - Google Patents

N-sulfenylated pyrrole derivatives

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Publication number
CA1197248A
CA1197248A CA000417974A CA417974A CA1197248A CA 1197248 A CA1197248 A CA 1197248A CA 000417974 A CA000417974 A CA 000417974A CA 417974 A CA417974 A CA 417974A CA 1197248 A CA1197248 A CA 1197248A
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group
phenyl
pyridyl
con
hydrogen
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French (fr)
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Robert Nyfeler
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Novartis AG
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Ciba Geigy Investments Ltd
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/42—Nitro radicals
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C07D207/48—Sulfur atoms
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
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    • 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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings

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  • Chemical & Material Sciences (AREA)
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  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Cosmetics (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Abstract The invention relates to novel N-sulfenylated pyrrole derivatives of the general formula I
(I), wherein R1 is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and Z
are each independently selected from the group consisting of hydrogen, halogen, C1-C4alkyl, C1-C3haloalkyl, di(C1-C4alkyl)amino, nitro, cyano, -COO(C1-C4alkyl), -CON(C1-C4alkyl)2 and the group -E-R4, where E is -O-, -S-, -SO-or -SO2-, R4 is C1-C6alkyl which is unsubstituted or sub-stituted by C1-C4alkoxy, C3-C5alkenyl which is unsub-stituted or substituted by halogen, C3-C5alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y,Z(phenyl)]; U, V and W are each independently selected from the group con-sisting of hydrogen, halogen and C1-C4alkyl, R2 is -COO(C1-C6alkyl), -CO(C1-C6alkyl), -CO-N(C1-C6alkyl)2, cyano, nitro, -SO2-(C1-C6alkyl), -P(O)-(C1-C6alkoxy)2, -SO (Cl-C6alkyl) or -S02-N(Cl-C3alkyl)2; and R3 is C1-C3haloalkyl.

The invention also relates to the preparation of these novel compounds by N-sulfenylation of corresponding pyrroles and to microbicidal compositions which contain a compound of the formula I as active ingredient. In addition, there is disclosed a method of controlling phytopathogenic micro-organisms, which comprises the use of the novel compounds.

Description

7~

Case 5-1371~

Microbicidal Compositions The present invention relates to novel N-sulfenylated pyrrole deriva~ives, to the preparation thereof, and to microbicidal compositions which contain at least one of these novel com-pounds. The invention relates ~urther to the preparation of the said compositions and to the use o~ the novel compounds and compositions for controlling harm~ul microorganisms, in particular phytopathogenic ~ungi.

The novel compounds of this invention have the general formula I
R ~
\N/ (I) wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,~,Z(biphenyl)], [U,V,W(pyridyl)], [U,~,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and Z
are each independently selected :Erom the group consisting oE hydrogen, halogen, Cl-C~alkyl, Cl-C3haloalkyl, di(Cl-C4alkyl)amino, nitro, cyano, -COO(Cl-C~alkyl), -CON(Cl-C~alkyl)2 and the group -E-R~, where E is -O-, -S-, -SO- or -S02-, R~ is Cl-C6alkyl which is unsub-stituted or substituted by Cl-C~alkox~?, C3-C5alkenyl which is unsubstituted or substituted by halogen, C3-C5-alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y?Z(phenyl)];
U, V and T~ are each independently selected ~rom the group consisting of hydrogen, halogen and Cl-C4alkyl, ~L9~

R2 ls -COO(Cl-C6alkyl), -CO(Cl-C6)alkyl), -CO-N(Cl-C6alkyl)2, cyano, nitro, -S02-(Cl-C6alkyl), -P(O)-(Cl-C6alkoxy)2, -SO-(Cl-C6alkyl) or -S02 N(Cl-C3alkyl)2; and Throughout this specification, the symbols [X,Y,Z~phenyl)~, [X,Y,Z(biphenyl)]-, [U,V,W(pyridyl)l, [U,V,W(furyl)] and [U,V,W(thienyl)~ are respectively the following groups:
x- ;~ v~ u ~.=.,- \.=./ \.=./ w o~ !
Z' Z~

V~ ! v ~o/ ' ~S/

Depending on the indicated number of carbon atoms, alkyl by itsel~ or as moiety of another substituent will be ~mder-stood as comprislng e.g. the Eollowing groups: methyl, ethyl, propyl, butyl, pentyl, hexyl etc., and the isomers thereo, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. Haloalkyl is a monohalogenated to perhalogenated alkyl subskituent such as C~12Cl, C~LC12, CC13, C~12Br, CHBr2, CBr3, CH2F, CHF2, ('F3, CC:L3F, CC:L2-CHC12, CH2CH2F, CI3 etc.
Throughout this speciEication, ha:l.ogen will be ~mderstood as sign:lEying fLuorine, ch:Lorine, bromine or iodine, with Eluorine, ch:lorine or bromine being pre~erred. C3-C5Alkenyl denotes an unsaturated aliphatic radical containing one or more double bonds and at most 5 carbon atoms, and is e.g.
propen-l-yl, allyl, buten-l-yl, buten-2-yl, buten-3-yl, CH3CH-CHCH=CH- etc. Pyridyl is 2-pyridyl, 3-pyridyl and 4-pyridyl, and furyl is 2-furyl and 3-Euryl. Thienyl is 724~3
2-thienyl ancl 3-thienyl and biphenyl is biphenyl-~-yl, biphenyl-3-yl and biphenyl-2-yl. Alkynyl is in parti.cular propargyl.

The compounds o~ formula I are oils, resins or mainly solids which are stable under normal conditions and have very valuable microbicidal properties. They can be used in agricuLture or related ~ields prevenLively and curatively for controlling phytopathogenic microorganisms. The com-pounds of the ~ormula I have excellent ~ungicidal activity in broad concentration ranges and their use is unproblematical.

On account o~ their pronounced microbicidal activity, pre~erred compounds o~ the formula I are those compounds which contain the ~ollowing substituents or combinations thereo~ with one another:
or Rl a) [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-~-yl)], [X,Y,Z(biphenyl-3-yl)]. [X,Y,Z(biphenyl-2-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(~-pyridyl)], [U,V,W(2-~uryl)], [U,V,W(3-furyl)], [U,V,W(2-thienyl)], [U,V,W(3-thienyl)]i b) [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-~-yl)], [U,V,Z(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-f~lryl)], [U,VJW(2-thienyl)];
c) [X,Y,Z(phenyl)], [U,V,W(2-furyl)]i d) [~,Y,Z(phenyl)]i or X,Y,Z: a) H, halogen, Cl-C3alkyl, Cl-C3haloalkyl, di(Cl-C3alkyl)amino, nitro, cyano, -COO(Cl-C3-alkyl), -CON(Cl-C3alkyl)2, Cl-C~alkoxy, Cl-C4alkylthio.^ C3-C5alkenyloxy, C3-C5halo-alkenyloxy, phenoxy, benzyloxy;
b) H, F, Cl, Br, CH3, C2H5, CF3, -N(CH3)2, -~(C2H5)2, -COOCH3, -COOC2H5, -CON(CH3)2, Cl-C~alkoxy, cl-c~alkylthio, C3-C5alken~10xy, C3-C5haloalkenyloxy, pheno~y, benzyloxyi c~ H, Cl, Br, CH3, C2H5, CF3, N(CH3)2~ 3 -CON(CH3)2, Cl-C4alkoxy, Cl-C~,alkylthio, C3alkenyloxy, phenoxy, benzyloxy;
d) H, Cl, Br, CH3, Cl-C~alkoxy, Cl--C4alkylthio, C3alkenyloxy .
or U,V,W: a) H, halogen, Cl-C4alkyl;
b) H, Cl, Br, Cl-C2alkyl;
c) H, Cl, Br, CH3;
or R2: a) -COO(Cl-C3alkyl), -CO-(Cl-C3alkyl), -CO-N(Cl-C3alkyl), cyano, nitro, -SO2(Cl-C3alkyl), ~P(o)(cl-c3alkoxy)2~ ~S2N(cl-c3alkyl)2;
b) -COOCH3~ ~COOc2Hs~ -COCH3~ -COC2H5~ -CON(C~I3) -CON(C2H5)2, cyano, nitro, -SO2-CH3, -SO2C2H5, -sO-cH3~ _p(o)(OCH3)2~ -P(O)(OC2H5)2' -so2-N(cH3)2~ -S02-N(C2H5)2;
c) -COOCH3, -COCH3, -CON(CH3)2, cyano, nitro, S2 CH3~ P(O)(OC2~Is)2, -SO2-N(CH3)2;
d) -COCH3, CNi or R3: a) Cl-C3haloalkyl;
b~ cl-c2haloalkYli c) CC13~ CC12F~ CC12H, CClH2, CF3, CF2H, C2C15, CC12C~IC12;
d) CC13, CC12F, CC12CMC12.

The Eollowing combinations a) to g) o:E these types oE sub-stituents result a) (Rl-a), (X,Y,Z-a), (U,V,W-a), (R2-a), (R3-a) b) (Rl-b), (X,Y,Z-b), (U,V,W-b), (R2-b), (R3-b) c) (Rl-c), (X,Y,Z-c), (U,V,W-c), (R2-c), (R3-c) d) (Rl-d), (X,Y,Z-d), (R2-d~, (R3-d) 1~7~

e) (Rl-a), (X,Y,Z-c), (U,V,W-c), (R2-b), (R3-c) f) (Rl-b), (X,Y,Z-c), (U,V,W-c), (R2-d), (R3-d) g) (Rl-d), (X,Y ,Z-~), (R2-a~, (R3-a) .
Accordingly, preferred groups of compounds are:

a) compounds of the ~ormula I, ~he,-ein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], ~X,Y,Z(biphenyl-3-yl)], [X,Y,Z(bi-phenyl-2-yl)], [U,V,W(2-pyridyl)~, [U,V,W~3 pyridyl)], [U,V,W(~-pyridyl)], [U,V,W(2-furyl)], [~,V,W(3-furyl)], [U,V,W(2-thienyl)] or [U,V,W-3-thienyl], wherein .Y,Y and Z
are each independently selected from the group consisting of hydrogen, Cl-C3alkyl, Cl-C3haloalkyl, di(Cl-C3alkyl)amino, nitro, cyano, -coo(Cl-C3alkyl), -CON(Cl-C3alkyl)2, Cl-C4-alkoxy, Cl-C4alkylthio, C3-C5alkenyloxy, C3-C5haloalkenyl.oxy, phenoxy and benzyloxy; U,V and W are each independently selected from the group consisting of hydrogen, halogen and Cl-C4alkyli R2 is -COO(Cl-C3alkyl), -CO-(Cl-C3alkyl), -CO-N(Cl-C3alkyl)2, cyano, nitro, -SO2-(Cl-C3alkyl), -P(O)(Cl-C3alkoxy)2 or -SO2-N(Cl-C3alkyl)2; and R3 is Cl-C3haloalkyl i b) compo-mds of the formula I, wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z('biphenyl-~-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-fury:L)] or [U,V,W(2-thienyl)], wherein X, Y and Z
are each independent'ly selected from the group consisting o:~
hydrogen, fluorine, chlorine, bromine, methyl, ethyl, tri-fluoromethyl, -N(CH3)2~ -N(C2~15)2' 3 2 5 -CON(C~I3)2, Cl-C4alkoxy, Cl-C~alkylthio, C3-C5alkenyloxy, C3-C5haloalkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and Cl-C2alkyl; R2 is R2-COOCH3, -Cooc2H5~ -COcH3~ -Coc2H5~ -CON(CH3)2, -CON(C2H5)2, cyano,
3 ~

2 3' 2 2 5~ ( )( 3)2' 3~
2 5 2 2 N(CH3)2 or -SO2-N(C2H5)2; and ~. is Cl-C2haloalkyl .

Within the subgroup b), particularly pre:~erred compounds of the formula I are those wherein Rl is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)] or [U,V,W(2-thienyl)], wherein X, Y and Z are each independently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, Cl-C3alkoxy and Cl-C3alkyl-~hlo; U, V and W are each independently selected from the gro up consisting of hydrogen, chlorine, bromine, methyl and ethyl; R2 is -COOCH3, COC~I3, NO2 or CN; and R3 is CFCl2 or CCl3.

c) Compounds of the formula I, wherein Rl is a fragment selected from the group consisting o:E [X,Y,Z(phenyl)] and [U,V,W(2-furyl)], wherein X, Y and Z are each independently selected from the group conslsting of hydrogen, chlorine, l~romine, methyl, ethyl, trifluoromethyl, N(C~13)2, -COOCH3, -CON(CH3)2, Cl-C~alkoxy, Cl-C4alkylthio, C3alkenyloxy, phenoxy and benzyloxyi U, V and W are each independently selected :Erom the group consisting of hydrogen, chlorine, bromine and Cl-C2a:lkyli ~2 is -COOC~13, -COC~13, -CON(CH3)2, S2 C~13~ P(O)(OC2H5)2 or -SO2-N(C~13)2; and R3 is CC13, CCl2F, CCl2H, CCl~l2, CF3, CF2H, C2Cl5 or CC12C~IC12 i d) compounds of the formula I, wherein Rl is the ragment [X,Y,Z(phenyl)], wherein X, Y and Z are each independently selected from the group consisting of llydrogen, chlorine, bromine, methyl, Cl-C4alkoxy, Cl-C~+alkylthio and C3alkenyloxy;
R2 is -COCH3 or cyano; and R3 is CCl3, CCl3F or CCl2CHCl2.

~g~z'~

Within the scope o:E the present invention, the Eollowing individual compounds are especially preferred:

a) intermediates of the formula II', in particular on account of their advantageous properties in storage and plant protection:

3-(2-methylthiophenyl)-4-cyanopyrrole, 3-(2-methoxyphenyl)-4-cyanopyrrole;

b) final products of the formula I, in particular on account o~ their pronounced fungicidal properties:

N-fluorodichloromethylsulfenyl-3-(2-allyloxyphenyl)-4-cyano-pyrrole, N-~luorodichloromethylsul~enyl-3-(2-chlorophenyl)-4-cyano-pyrrole, N-fluorodichloromethylsul:~enyl-3-phenyl-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetyl-pyrrole, N-Eluorodichloromethylsulfenyl-3-(4-methylphenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulEenyl-3-(3-chlorophenyl)-4-acetyl-pyrrole, N-1uorodichloromethylsulenyl-3-(3-methylphenyl)-4-acetyl-pyrrole, N-Eluorodichloromethylsul:Eenyl-3-(3-chlorophenyl)-4-methoxy-carbonylpyrrole, N-~luorodichloromethylsulEenyl-3-(2-ch:Lorophenyl)-4-methoxy-carbonylpyrrole, N-fl-torodichloromethylsulEenyl-3-(2-chlorophenyl)-4-nitro-pyrrole, N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole, N-trichloromethylsulEenyl-3-(2-pyridyl)-4-cyanopyrrole, N-~luorodichloromethylsulfenyl-3-(2,3-dichlorophenyl)-4-cyanopyrrole.

~9~7~

In the practice of this invention, the compounds o~ formula I
are prepared by sulfenylating a free pyrrole of the ~ormula IL
R ~ -R ( I I ) \N/

H
at the pyrrole nitrogen~ with a reactive acid derivative o~ a sul~enic acid o:~ the ~ormula III-R3-S-OH (III) in the presence o~ a base. In the above formulae, Rl, R2 and R3 are as de~ined ~or formula I.

Suitable reactive sul~enic acid derivatives for this sulfenylation reaction are e.g. the lower alkyl esters and, pre~erably, the sulfenic acid halides, in particular the chlorides and bromides, with the chlorides being especially preferred. Lower alkyl will here be understood as meaning Cl-C6alkyl .

Both organic and inorganic bases may be successfully employed in the above reaction. Examples o~ suitable inorganic bases are alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate etc. Examples o~ suitable organic bases are ter~iary amines such as trialkylamines (triethylamine, methyl diethylamine), N,N-dimethoxycyclo-hexylamine, N-methylpiperidine, N,N-dimethylaniline or pyridines. Trialkylamines are preferred. It is advantageous to use the base in stoichiometric proportion or in excess thereo~, e.g. in up to 100% excess oE stoichiometric proportion, based on the pyrrole o~ the ~ormula II. The reactive derivative o~ the sul~enic acid of the formula III
is also used in stoichiometric proportion or in excess thereo~.

The sul~enylation reaction may be carried out in the presence or absence, preferably in the presence, o~ an inert solvent 2~8 _ 9 _ or mixture of inert solvents. In principle, the c~tstomary organic solvents are suitable for this reaction, provided they contain no reactive hydrogen atoms. Examples oE
suitable solvents are: aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ethers, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; e~hers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl-methyl ether etc.), ethylene glycol di- and monoether and diethylene glycol di- and monoether, containing 1 to ~
carbon atoms in each of the alkyl moieties, for example ethylene glycol dimethyl, diethyl and di-n-butyl ether, diethylene glycol diethyl and di-n-butyl ether, ethylene glycol monoethyl ether and diethylene glycol monomethyl ether; furan, dimethoxyethane, dioxan, tetrahydrofuran, anisole; sulfones such as dimethylsulfoxidei ketones such as acetone, methyl ethyl ketone; esters such as ethyl acetate, propyl acetate, butyl acetate; and mixtures of such solvents with one another. In some cases the sulEenylating reagent of the formula III may itsel act as solvent.

To hasten khe reaction rate, a catalyst such as ~-dimethyl-aminopyridine may be added, if appropriate.

The sulEenylation reaction is normally carried out in the temperature range from -30 to -~100C, preferably from -10 to -~ 20C, The reaction time is then generally Erom about ~ hour to 20 hours. However, addition o~ a reaction catalyst will on occasion often reduce the reaction time to less than ~ hour.

At normal temperatures, the free sulfenic acids of :Eormula III
are generally relatively unstable substances which have a tendency to self-oxidation. The known sulfenic acid halldes, ~7~4~3 howe-ver, which can be obtained e.g. by halogenation ~rom the corresponding mercaptans or dialkyl disulfides. are stable.
Also known are lower alkylsul~enic acid esters, which can be obtained e.g. hy reacting sul~enic acid chlorides with alkali alcoholates. At elevated temperature they undergo rearrangement to form the corresponding sulfoxides, but can be handled at lower temperatures.

Some o~ the pyrroles of the ormula II are known ~rom the literature. For example, the method o~ preparing and the chemical properties of 4-cyano-3-phenylpyrrole are described in Tetrahedron Letters No. 52, pp. 5337-53~0 (1972). Nothing is reported on the biological properties o~ the compoun~.

DifEerently substituted 3-phenyl-~-cyanopyrrole derivatives are known from the literature. For example, pyrroles o~ the ~ormula IV
. _ .
-CW (IV), ~n \N/

wherein X is a halogen atom, a lower alkyl group or a lower haloalkyl group, and n is 0, 1 or 2, are described in German O~fenlegungsschri~t 29 27 ~80 as in~ermediates having insigni~icant ~ungicidal activity.

Novel pyrro:le derivatives are those o~ the ~ormula II' R - o---.o . 1~ ( I I ' ) \N/' ' Il wherein Rl is a ~ragment selected ~rom the group consisting of [X~Y,Ztphenyl)], l~,Y,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(Euryl)] and [U,V,W(thienyl)], wherein X, Y and Z are each independently selected ~rom the group consisting of ~9~2~1~

hydrogen, halogen, Cl-C~alkyl, Cl-C3haloalkyl, di(Cl-C4alkyl)-amino, nitro, cyano, -COO(Cl-C~alkyl), -CON(Cl-C~alkyl)2 and the group -E-R~, wherein E is -O , -S-, -SO- or -S02-, R4 is Cl-C6alkyl which is unsubstituted or substituted by Cl-C4alkoxy, C3-C5alkenyl which is insubstituted or sub-stituted by halogen, C3-C5alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[~,Y,Z(phenyl)], and U, V and W are each independently selected ~rom the group consisting of hydrogen, halogen or Cl-C4alkyl; R2 is -COO(Cl-C~,alkyl), -CO-(Cl-C6alkyl), -CO-N(Cl-C4alkyl)2, nitro~ S02-(Cl-C6alkyl), -P(O)(Cl-C6-alkoxy)~, -SO-(Cl-C6alkyl) and -S02-N(Cl-C3alkyl)2, and, where Rl is a fragment [X,Y,Z(biphenyl)], [IJ,V,W(pyridyl)], [U,V,W(furyl)] or [U,V,W(thienyl)], R2 is additionally cyano.
These compounds are specially developed intermediates for obtaining the valuable compo~mds o~ the ~ormula I. Because of their structure they can be readily converted by N-sulfen-ylation into the compounds of the formula I. In addition, the compounds of Eormula II' have ~ungicidal activity against important harmful fungi in plant protection, as well as e~cellent storage protection properties. The novel com-pounds o~ ~ormula II', including the preparation thereof and use thereof, therefore fall within the province o~ ~his invention.

The compounds oE Eor~lula II, and thereEore also those o~
:Eormula II', can be prepared in alkaline medi~ by a Michael cycloaddition reaction oE a compound o~ Eormula V with tosylmethyl isocyanide, aecompanied by the elimination of p-tol~lenesulfinic acid or the salt thereof:

1 R21 3 \ / So2-c~l2-Nc/base (V) p R ~ -R

C113~ --SOZ(~) ~) I (II,II ') .

. .

In ~he above formulae, Rl and R2 have meanings assigned to~hem previously.

Both here and subsequently, the tosyl group s~ands for a large number of groups which are able to activate the methylene group in the methyl isocyanide radical for a Michael addition reaction. Further preferred examples o~
such activating groups are benzenesul~onyl, p-chlorobenzene-sul~onyl, lower alkylsul~ony-l such as mesyl.

The cycloaddition is carried out in the presence o a non-nucleophilic base. Suitable bases are alkali metal hydrides such as sodium hydride, or alkali metal carbonates or alkaline earth metal carbonates such as ~a2C03, K2C03, or alkali alcoholates such as (CH3)3C0 K and others. The base is advantageously used in at least equimolar amount, based on the starting materials.

As in all reactions, it is convenient also in this case to conduct the reaction in an inert solvent. Examples oE
pre~erably anhydrous solvents suitable ~or the cycloaddition are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ethers, ligroin, cyclohexane;
ethers and ethereal compounds such as dialkyl ethers (di-ethyl ether, cliisopropyl ether, tert-butyl methyl ether etc.) dimethoxymethane, ~etrahydro~uran, aniso:Lei sulfones such as dimethylsul~o~lde; climethylEormamidei and m-lxtures oE such so:lvents w:lth one another.

The cycloaclclition is normally carried out in the temperature range Erom -30 to -~120C, preEerably ~rom -30 to -~50C, or at the boiling point oE the solvent o~ solvent mixture.

When choosing suitable bases, the cycloaddition can also conveniently be carried out in aqueous medi~m. Suitable bases ~9~

are water-soluble inorganic and organic bases, in particular alkali metal hydroxides such as LiO~I, NaOH or KOH, and ammonium bases, e.g. tetraalkylammonium hydroxides such as (CH3)~NOH. At least an equimolar amount o~ base is used, based on the starting materials. When using aqueous bases, it is advantageous to conduct the reaction in a heterogeneous two-phase system.

Examples o~ suitable organic solvents for the organic water-immiscible phase are: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes etc.,; halogenated hydro-carbons such as dichloromethane, chloro~orm, carbon tetra-chloride, ethylene dichloride, 1,2-dichloroethane, tetra-chloroethylene etc.; or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.

The presence o~ a phase trans~er catalyst can be o~
advantage in this mode of carrying out the reaction in order to hasten the rate of reaction. Examples o~ such catalys~s are: tetraalkylammonium halides, hydrogen sul~ates or hydroxides such as tetrabutylammonium chloride, tetra-butylammonium bromide or tetrabutylammonium iodide; tri-ethylbenzylammonium chloride or bromide; tetrapropylammonium chloride, bromicle or ioclicle etc. Phosphonium sa:lts are also suitable Eor use as phase trans~er catalysts.

The phase trans~er catalysed cycloaddit:lon can be carried out in the temperature range ~rom 0 to -~80C, pre~erably ~rom -10 to -~50C or at the boiling point oE the solvent mixture. The cycloaddition can be carried out in the described embodiment of the process under normal pressure.
The reaction time is in general ~rom 1 to 16 hours, and in phase trans~er catalysis ~rom ~ hour to 10 hours.

~L97Z~3 Surprisingly, it has been found that the compounds of form~lla I and the compositions containing them have for practical purposes a very useEul microbicidal spectrum against phytopathogenic fungi and bacteria. They can be used bo~h in plant protection for controlling harmful microorganisms on cultivated plants and in storage protection for preserving perishable goods. The compounds of Eormula I
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 diferent crops oE useful plants, while at the same time the parts of plants which grow later are also protected Erom attack by such mlcro-organisms. The intermediates oE Eormula II' also have a corresponding activity.

The compounds of Eormula I are effective against the phytopathogenic fungi belonging to the following classes:
Ascomycetes (e.g. Erysiphe, Sclerotinia, Fusarium, Monilinia, Helminthosporium; Basidiomycetes, e.g. Puccinia, Tilletia, Rhizoctonia; and the Oomycetes belonging to the class of the Phycomycetes such as Phytophthora. As plant protective agents the compounds of formula I can be used with particular success against important harmEul fungi oE the family of the Fungi imperEecti, e.g. against Cercospora, Piricularia and, in particular, against ]30trytis. Botrytis spp. (B. Cinerea, B.
alli:i) and the grey mould on vines, strawberries, apples, onions and other varieties oE fruit and vegetables, are a source of significant economic damage. In addition, the compounds oE formula I can be used successfully for protecting perishable goods of vegetable or animal origin. They combat mould fungi such as Penicillium, ~spergillus, Rhizopus, Fusarium, Helminthosporium, Nigrospora and Alternaria as 7~

well as bacteria such as butyric acid bacteria and yeast fungi such as Candida. Furthermore, these compounds have excellent activity against fungi which occur on seeds or in the soil.

As plant protective agents, the compounds of formula I have for practical application in agriculture a very advan~ageous activity spectrum for protecting cultivated plants without adversely affecting said plants by unwanted side-effects.
They can therefore 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.

Accordingly, the invention also relates to microbicidal compositions and to the use of compounds of the formula ~
for controlling phytopathogenic microorganisms, especially harmful fungi, and for the preventive treatment o~ plants and storable goods of vegetable or animal origin to protect them from attack by such microorganisms.

The invention further embraces the preparation of aggro-chemical compositions which comprises homogeneously mixing an active ingredient with one or more substances or groups of substances described herein. The invention Eurthermore relates to a method o treating plants or storable goods, which comprises applying to plants, parts o~ plants, the locws thereof or the substrate, 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, :1~97~

strawberries, rasberries and blackberries), leguminous plants (beans,lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons),fibre plants (cotton, ~lax, 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, nu-ts, co~fee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites).

In storage protection, the compounds of formulae I and II' are used in unmodified ~orm or, pre~erably, together with the adjuvants conventionally employed in the art of ~ormulation, and are therefore ~ormulated in known manner to e.g.
emulsifiable concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. pol~ner substances. The methods of application, 9uch as spra~ing, atomising, dusting, scattering or pouring, and the ~ormulation o~ the composition, are chosen in accordance with the intended objectives and the prevailing circumstances. Suitable rates o~ application are in general in the range Erom 0.01 to at most 2 kg o~ active ingredient per 100 kg of substrate to be protected. However, they depend very materially on the nature (surace area, consistency, moisture content) o~ the substrate and its environmental inEluences.

~i.thin the scope o~ this invention, s~orable goods will be understood as meaning natural substances of vegetable and/or animal origin and the prod~lcts obtained therefrom by further processing, for example the plants listed below whose natural life cycle llas been interrupted and the parts thereo~ (stalks, ~g7Z~8 leaves, tubers, seeds, fruit, grains) which are in Ereshly harvested or further processed form (predri.ed, moistened, crushed, ground, roasted). The following produce may be cited by way oE example, without any restriction to tlle Eield of use within tlle scope of this invention: cereals (wheat, barley, rye, oats, rice, sorghum and related crops); beet (carrots, sugar beet and fodder beet); drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherrLes, strawberries, rasberries and blackberries); leguminous plants (beans, lentils, peas, soybeans)i 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,ramie);
citrus fruit; vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika);
lauraceae (avocados, cinnamon, camphor), or maize, tobacco, nu~s, coffee, sugar cane, tea, vi.nes, chestnuts, hops, bananas, grass and hay.

Examples of natural products of animal origin are, in particular, dried meat and processecl Eish products such as dry-cured meat, dry-cured fish, meat extracts, bone meal, fish meal and animal dry feeds.
The treated storable goods are given lasting protection from attacl~ by mould Eungi and other harmEul microorganis~s. The Eormation of toxic and in some cases carcinogenic mould :Eungi (aElato~ins and ochratox:Lns) ls :inhibited, the goocls are preserved ~rom deteriorati.on, and their quality is main-tained over a prolonged period of time. The method oE the inven~i.on is susceptible of appLication to all forms oE dry and moist storable goods~Llich are liable to attack by microorganisms such as yeast Eungi, bacteria and, in particular, mould fungi.

1 ~ 7 preferred mettlod of applying active ingredient comprises spraying or wetting the substrate with a liquid formulation, or mixing the substrate with a solid formulation, of the active ingredient. The invention also relates to the described method of preserving storable goods.

The compounds of ~ormula I are normally applied in the Eorm of compositions and can be applied to the crop area, plant or substrate 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 of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in ~ormulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackiEiers, binders or fertilisers. Phospholipids are particularly useful adjuvants.

pre~erred m~thod oE applying a compound of the formula I
or an agrochemical composition which contains at least one of said compounds, is Eoliar (leaf) application The number oE applications and the rate o:E application depcnd on the intensity oE inEestation by the corresponding pathogen (type of fungus). ~lowever, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus oE 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 impregnatlng the seeds either with a liquid ~ormulation containin~ a compo~lnd o~
the Eormula I, or coating them with a solid formulation.
In special cases, further types o~ application are also possible, e.g. selective treatment o~ the plant stems or budso The compounds o~ the ~ormula I are used in unmodified form or, pre~erably, together with the adjuvants conventionally employed in the art o~ ~ormulation, and are therefore ~ormula-ted in known manner to emulsi~iable concentrates, coatable pastes, direc-tly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the na~ure o:E the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosed in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates o~ applicati.on are normally ~rom 50 g to 5 kg o~ active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most pre~erably ~rom 200 g to 600 g a.i./ha.

The form-~lations, i.e. the compositions containing the com-pound (active ingredient) o~ the formula I and, where appropriate, a solid or liq~licl adjuvant, are prepared in known manner, e g. by homoger~eo~lsly mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compo~mds ( s ~Ir:Eac tanl:s ) .

Suitable solvents are: aromatic hydrocarbons, pre~erably the ~ractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalates or dioctyl phthalate, aliphatic hydro-z~

carbons such as cycloheY~ane or parafEins, 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-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epo~idised 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 adsorptive carriers are poxous types, for exa~ple pumice, broken brick, sepoli-te or bentonite; and suitable nonsorbent earriers are materials such as ealcite or sand. In addition, a great number of preganulated materials oE inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues, e.g. cork powder or sawdust.

Depending on the nature of the compound of the formula I
to be formulated, suitable surface-active eompounds are nonionic, cationic and/or anion:ic surfactants having good emulsi:Eying, dispersing and wetting properties. The term "surEaetants" will also be understood as comprising mixtures of swrfactants, Suitable anionie sur~aetants ean be both water-soluble soaps and water-soluble synthetie surfaee-active eompounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts 7;2 ~

o~ higher fatty acids (C10-C22), e.g. the sodium or potassium salts o~ oleic or stearic acid, or oE natural fatty acid mixtures which can be o~tained e.g. ~rom coconut oil or tallow oil. Mention may also be made of fatty acid methyl ~urin salts.

More ~requently, however, so called synthetic surfactants are used, especially fatty sul~onates, fa~ty sul~ates, sulfonated benzimidazole derivatives or alkylarylsul~onates.

The ~atty sulfonates or sulfates are usually in -the ~orm of alkali metal sal~s, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety o~ acyl radicals, e.g. the sodium or calcium salt o~ lignosul~onic acid, o~ dodecylsulfate or of a mixture of fatty alcohol sul~ates obtained ~rom natural ~atty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids o~ ~atty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives pre~erably contain 2 sulfonic acid groups and one ~atty acid radical containing 8 to 22 carbon atoms Examples o~ alkylarylsulfonates are the sodium, calcium or triethanolamine salts o~ dodecylbenzenesul~onic acid, dibutylrlaphthalenesul~onic acid, or o~ a naphthalene-sulfonic acid/~ormaldehyde condensation product. ~lso suitable are corresponding phosphates, e,g. salts o~ the phosphoric acicl ester o~ an add~ct o~ p-nonylphenol with ~ to 1~ moles o~ ethylene oxicle.

Non-ionic sur~actants are preferably polyglycol ether derivatives o~ aliphatic or cycloaliphatic alcohols, or saturated or unsaturated ~atty acids and alkylphenols, said derivatives containing 3 to 30 glycol`ether groups 7Z4~3 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 glycolg ethylenediamine propylene glycol and ~lkylpolypropylene 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 groupsO These compounds usually contain 1 to 5 ethylene glycol ~InitS
per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic suractants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22-alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benæyl or lower hydroxy-alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e,g. stearyl-tr:imethylammonium chloricle or benæy:ldi(2-chloroethyl)-ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsi~iers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co , Inc.
New York, ]980.

The agrochemical compositionsusually contain 0.1 to 99%, preferably 0.1 to 95%, o-f a compound of the formula I, 1 to 99 9% to 1%, preferably 99.8 to 5%~ of a solid or liquid adjuvant, and 0 to 25%~ preferably 0.1 to 25% of a surfactant.

Whereas commercial products are preferably ~ormulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such as stabilisers, anti~oams, viscosi-ty 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 Eollowing Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.

Preparatory Examples a) Startin~ materials Example a: Preparation of ~SCH3 ~SCH3 CII=CH-CN ~ ~ ~--1; il-CN (compound 2~) , .

~7;~

3-(2-Methylthiophenyl)-4-cyanopyrrole A solution of 123 g (0.7 mole) oE E/Z-3-(2-thiomethylphenyl)-acrylonitrile and 192 g (0.98 mole) of tosylmethyl isocyanide in 800 ml of tetrahydroEuran is added slowly dropwise at -13 to ~8C to a solution of 158 g (1.4 moles) of potassium tert-butylate in 400 ml of tetrahydrof~lran. The mixture is then stirred for 2 1/4 hours at room temperature, poured into 3 litres of ice/water and extracted twice with ethyl acetate. The combined extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, decolorised with silica gel and activated carbon, Eiltered and the filtrate is concentrated. The residue is crystallised from dichloromethane/petroleum ether to give 95 g of beige-coloured crystals with a melting point of 121-124C. The mother liquor is worked up to give another 21 g of substance. Repeated recrystallisation from dichloro-methane/petroleum ether yields an almost colourless product with a melting point o~ 128-134C.

Example b: Preparation of ~Cl ` ~Cl CH=CH-COCH3 D ~ COCH
~ (compound 49) 3-(2-Chlorophenyl)-4-acetylpyrrole A solution of 60 g (0.33 mole) of E/Z-4-(2-chlorophenyl)-3-buten-2-one and 75 g (0.38 mole) of tosylmethyl isocyanide in ~00 ml of tetrahyclrofuran is slowly added dropwise at -10 to -~30C to a solution of 48 g (o,L~3 mole) of potassium tert-butylate in 100 ml o~ tetrahydrofuran. The reaction mixture is stirred Eor 2~ hours at 5-10C, then warmed to room temperature, poured into 2 litres of ice/water and extracted twice with ethyl acetate. The combined extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, decolorised with silica ~7~
- ~5 -gel and fuller's earth, filtered and the filtrate is con-centrated. The residue is digested in dichloromethane under reflux, cooled and :Eiltered. Yield: 40 g of beige-coLoured crystals with a melting point of 198-201C.
Example c: Preparation of Cl~ Cl~
-CH=C~I-N02 ~ j -NO
~ ~ (compound 41) 3-(3-Chlorophenyl)-~-nitropyrrole 1.6 g (0.036 mole) of an approx. 55% dispersion of sodium hydride in mineral oil are digested under nitrogen twice with petroleum ether and then 50 ml of diethyl ether are added. With e:Eficient stirring, a solution of 5.5 g (0.03 mole) of 2-(3-chloxophenyl)-1-nitroethene and 5.9 g (0.03 mole) of tosylmethyl isocyanide in 20 ml oE dimethylsulEox-ide and 40 ml of diethyl ether is added dropwise to the above mixture such that the reaction mixture constantly boils under reflux. After the exothermic reaction has sub-sided, stirring is continued for 15 minutes at room temperature. First ice/water is cautiously added to the mixture, followed by the addition of saturated sodium chloride solution. The batch is extracted twice with ethyl acetate and the combined extracts are washed ~ times with semi-saturated sodium chloride solution, dried over sodium sulfate, Eiltered and the :Eiltrate is concentrated. The residue is recrystallised from dichloromethane/petroleum ether to give yellow crystals with a melting point of 133-135C.

~xample d: Preparation o:E
C~ C~
~ ~--C~I=C~I-CN ~ CN ( compound 10) .= . .= . . --~:~g~2~

3-(3-Methylphenyl)-~-cyanopyrrole 6.1 g of a 55% dispersion of sodium hydride in mineral oil are washed with petroleun- ether and then 60 ml o~ dimethoxy-ethane and 10 ml o~ dimethylsulEoxide are added. With stirring, a sol.ution o~ .3 g o~ 3-methylcinnamonitrile and 21.5 g of tosylmethyl isocyanide in 60 ml o~ dimethoxyethane and 10 ml o~ dime-thylsulEoxide are added slowly dropwise at -25 to -20C. The mixture is stirred for 1~ hours in a thawing ice bath, then poured onto ice and extracted twice with ethyl acetate. The organic phase is washed with aqueous sodium chloride solution, dried over sodium sulfate, ~iltered and the filtrate is concentrated, to give 19 g oE a viscous oil which, after recrystallisation from di~hloromethane/
petroleum ether~ yields crystalline 3-(3-methylphenyl)-4-cyanopyrrole with a melting point o 109-111C.

Example e: Preparation oE
c~ ~
-C~I=CH-CN ~ J~ -CN
~ (compound 1 3-(3-Chlorophenyl)-~-cyanopyrrole a) 10.5 g of a 55% dispersion o sodium hydride in mineral oil are washed with petroleum ether and then 120 ml oE
tetrahydrofuran are added. A solution oE 30.7 g o:E 3-chloro-cinnamonitrile and ~1 g oE tosylmethyl isocyanide in 180 ml oE tetrahydrofuran and 20 ml oE dimethylsul~oxide is then added dropwise at-25 to -20C, and the mixture is stirred ~or 2 hours in a thawed ice bath. The mixture is then poured onto ice and extracted twice with ethyl acetate. The organic phase is washed repeatedly with aqueous sodium chloride solution, dried over sodium sulEate and ~iltered.
The ~iltrate is concentrated and the residue is recrystallised Erom dichloromethane, a~Eording crystalline 3-(3-chloro-phenyl~-4-cyanopyrrole with a melting point o~ 138-130C.

Example f: Preparation of Cl ~/ \C~I=CH-COOC~13 C~ COOCH3 (compo~md ~0) ~/
3-(3-Chlorophenyl)-~-methyloxycarbonylpyrrole With stirring, a solution of 136 g of methyl E/Z-3-(3-chloro-phenyl)-acrylate and 155 g of tosylmethyl isocyanide in 500 ml of tetrahydrofuran and a solution of 109 g of potassium tert-butylate in 700 ml of tetrahydrofuran are each added dropwise simultaneously at 0-10C from two drip unnels to 400 ml of tetrahydrofuran. The mixture is stirred for 1~ hours at 0-5C and for % hour at 25C, then poured onto ice and extracted twice with ethyl acetate. The extracts are washed 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, decolorised with silica gel and activated carbon, filtered and the filtrate is concentrated. The residue is digested with dichloromethane ~mder reflux and the mixture is left to stand overnight at -18C and filtered, yielding 13]. g of colourless product with a melting point of 187-189C.

Example ~: Preparation o~
.~'\. .~-\.

~N CH=CH-CN ~ CN
(compound 63) ~
With stirring, a solut-Lon o;E 12$.8 g oE 3-(2-pyridyl)-prop-2-ene nitrile and 200 g oE tosylmethyl isocyanide in 1500 ml oE tetrahydrofuran and a solution oE 140 g o~ potassium tert-butylate in 1500 ml of tetrahydrofurane are each added dropwise simultaneously from two drip funnels at -10 to 0C to 200 ml o~ tetrahydro~uran. The mixture is stirred for 1 hour at 0-5C and for 1 hour at 25C, then poured onto ice and extracted twice with ethyl acetate. The organic ~l~9~48 phase is washed twice with aqueous sodium chloride solution, dried over sodi~ sulfate, stirred with silica gel and activated carbon, filtered and the filtrate is concentrated.
The dark residue is crystallised from dichloromethane at -20C, afEording 75.5 g of brown crystals with a melting point of 148-151C.

All intermediates, also those listed in the table, can be prepared in corresponding manner. The compounds 8, 9, 11, 13 to 76 marked with an asterisk (*) are novel and some have fungicidal properties. Compounds 16 and 24 in particular are very active against Deuteromycetes, especially Botrytis fungi, as well as against harmful microorganisms in storage protection. These novel compounds constitute an important embodiment of the present invention.

_ ~9 _ Table of intermediates o~ the formula ~ -R

Com- R R m.p- [ c]
pound 2 2,4-C12 CN 150-152 3 4-Cl CN 153-155
4 2-C1 . CN 136-138 7 3-Br CN 132-134 8* 4-NtCH3)2 CN 180-182 9* 3-N (CH3) 2 CN 144-146 11* 3-N02 CN 232-234 13* 3-OC6H5 CN 124-126 14* 3-OC113 CN 125-128 15* 3-OCUF2 CN 95_97 lG* 2-OCll3 CN 'l35-136 17''~ 2-OC'IIF2 CN 105-:lO7 18''~ 2-OC2H5 CN 134-135 l9* 2-OCII(C~1 ) CN 80-81 20* 2-OCH2CH=CH2 CN 83-86 21* 2 6 5 CN 91-93 22* 2-OH CN 130-132 23* 3-SCH3 CN 115-117 72~8 Com~ R R m-p [ C]
pound n 24 * 2-SCil3 CN 128-134 25 * 2-SO-C113 CN 168-171 26 * 2 H3 CN 150-152 27 ~; 2-SC2H5 CN 121-123 28 * 2-SO-C H CN 144-145 29 * 2 2 5 CN 141-143 30 * 2-S-CII(CH ) CN 121-123 31 * 2-S02-CH(CH3)2 CN 139-141 32 * 2-S-C~Hg-n CN 61-65 33 * 2-SO-C4Hg-n CN 120-123 34 * 2-S2C~SH9-n CN 151-152 35 * 2-COOC2H5 CN 130-132 36 * 3-C~C-C(OH) (CH3)2 CN oil 37 * 3-C-C-H CN 132-134 38 * 2-C--C-C(OH) (CH3)2 CN 140-143 39 * 2-C-C-H CN 109-115 40 * 3-C1 CO-OC~13 187-189 4l * 3-Cl N02 133-135 42 ~: 2-Cl N02 137-139 ~3 * 3-Cl P(O) (OC2115)2 102-10~
* 3-C1 P(O) (OC~13)2 120-122 ~5 * 2-C1 P(O) (OC2~15)2 129-131 ~6 * 2-C1 P(O) (OC113)2 1~6 148 47 * 2,~l-CI2 r(o) (C2ll5)2 ~9~90 48 * 3-C1 CO-CH3 193-195 49 * 2-Cl CO-CH3 198-201 50* 2,4-Cl2 CO-C~13 184-186 51'~ H CO-CH3 156-158 52 * 3-CH3 CO-CH3 120-123 ~L97~

Com- Rn R m.p. [ C]
pound 53* 4-Cl C0-C~13 170-174
5~* 3,4-C12 C0-C~3 162-164 55* 4-OCIl C0-CH3 179-182 56*. 4-C~13 C0-CII 181-184 57* 3-Cl S0 -CH 125-127 58* 4-Cl S0 -CH 154-156 59* 2,4-C12 S0 -CH 174-177 6C* 3-N02 2 3 133-135~
61* 2-C1~ 4-~2 S0 -C~l 197-200 62* 2-Cl S0 -CH 178-180 63* 6 5 CN 249-254 64* 1I CN 120-123 65* 2 3 Table of intermediates of the formula R- j i-CN

Com- R m.p. ~c]
pound 66* 2-pyriclyl lll8-151 67* 3-pyridy:l . 160-l62 68* 4-pyridyl 200-203 69* 2-(5-chloropyridyl) 20~-206 70* 3-(2-chloropyrldyl) 217-220 71* 2-(3,5-dichloropyrLcyl) 176-179 72* 2-khienyl l22-124 73* 2-:E~tryl 98-100 74* 2-(N-methylpyrrole) 174-175 75* 2-(6-methylthienyl) 108-110 76* 2-(3-methylthienyl) 132-137 . .

~724~3 ~) Final products Example ~ Preparation of ~Cl ~Cl COCH3 ~ . - . -COCH
~ (compound 1- 24) ~CFC12 N-Fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetylpyrrole A solution o~ 6 ml (0.0575 mole) o~ fluorodichloromethyl-sulfenyl chloride in 20 ml of tetrahydrofuran is initially added dropwise at 3-5C to a solution of 11 g (0.05 mole) o~ 3-(2-chlorophenyl)-4-acetylpyrrole in 100 ml of tetra-hydrofuran, followed by the dropwise addition of 8 ml (0.0575 mole) of triethylamine in 20 ml of tetrahydrofuran at 5-8C. The mix-ture is then stirred for 16 hours in a thawing ice bath and filtered. The filtrate is concentrated and the residue is recrystallised from diethyl ether/petroleum ether. Yield: 9.4 g of beige crystals with a melting point oE 85-87C. A ~urther crop of beige crystals (4.5 g) with a melting point of 8~-86C is obtained after purification by chromatography over silica gel with dichloromethane/
petroleum ether (~:1) as eluant, concentration oE the mother liquor and recr~stallisation Erom cliethyl ether/petroleum ether.

Example ~1~: Preparation oE
C113~, CE13~
j-COCH3 ) ~ COCE13 E~ (compound 1.31) ~-CC13 ~-TrichloromethylsulEenyl-3-(3-methylphenyl)-4 acetylpyrrole 3.9 ml (0.036 mole) of trichlorometh~lmercaptan in 30 ml of tetrahydrofuran are initially added dropwise at 0-5C to a solution of 6 g (0.03 mole) of 3-(3-methylphenyl)-4-acetyl-pyrrole in 100 ml of tetrahydrofuran, followea by the drop-wise addition at 5-8C of 5 ml (0.036 mole) of triethylamine in 30 ml of tetrahydrofuran. The reaction mixture is then stirred for 16 hours in a thawing ice bath and filtered. The filtrate is concentrated and the residue is puri~ied by column chromatography over silica gel with dichlorome~hane/
petroleum ether (2:1) as el~lant. Recrystallisation from petroleum ether yields 5 g of colourless crystals with a melting point of 58-59C.

Example H3: Preparation of ~OC2115 ~OC2~15 \ ~~ -CN \ / ~
~ (compound 1.15) ~-cFCl2 N-Fluorodichloromethylsulfenyl-3-(2-ethoxyphenyl)-4-cyano-pyrrole A solution of 4 ml (0.039 mole) oE :Eluorodichloromethyl-sulfenyl chloride in 15 ml of ethyl acetate is initially added dropwise at 3-7C to a solution of 7.2 g (0.034 mole) o~ 3-(2-ethoxyphenyl)-4 cyanopyrrole in 100 ml oE ethyl acetate, followed by the dropwise addition of 5.4 ml (0.039 mole) oE triethylamine in 15 ml oE ethyl acetate. The reaction mixture is stirred ~or 16 hours in a thawing ice bath and then Eiltered. The filtrate is concentrated and the residue is recrystallised from petroleum ether, aEfording 9.9 g of beige crystals with a melting point o:E 80-83C.

Example H4: Preparation of il--il - CN ~ CN
~ (compound 2-1) I-CFcl2 ~g7~

N-Fluorodichloromethylsul~enyl-3-(2-furyl)-~-cyanopyrrole 3.9 ml (0.037 mole) o:E fluorodichloromethylsulfenyl chloride in 10 ml of tetrahydro~lran are ini~ially added dropwise at 0-5C to a solution of 5.2 g (0.33 mole) oE 3-(2-furyl)-~-cyanopyrrole in 100 ml of tetrahydro~uran, followed by the dropwise addition of 5.2 ml (0.037 mole) o~ trlethylamine in 10 ml of tetrahydrofuran at 5-8C. The reac~ion mixture is then stirred for 16 hours in a thawing ice bath and filtered.
The filtrate is concentrated and the residue is purified by column chromatography over silica gel with dichloromethane/
petroleum ether (3:1) as eluant. Recrystalllsation from petroleum ether yields 7 g of yellowish crystals with a melting point of 7~-76C.

Example H5: Preparation of ,~ \O .~ \

il li ~ \il--i1/
tCompound 2.3) ~

N-Trichloromethylsulfenyl-3-(2-pyridyl)-4-c~anopyrrole A solution oE 13.7 g of perchloromethylmercaptan in 20 ml of tetrahydrofuran is initially added dropwise at 0-10C to Q
solution of 16.9 g of 3-(2-pyridyl)-~-cyanopyrrole in 200 ml of tetrahydrofuran, followed by the dropwise addition of 17.~ ml oE triethylamine in 20 ml of tetrahydroEuran. The mixture is stirred Eor :l6 hours in a thawing ice bath and then concentral:ed~ The residue is partitioned between ethyl acetate and aqueous sodium carbonate solution. The aqueous phase is separated and the organic phase is washed once with saturated sodium bicarbonate solution and twice with semi-saturated sodium chloride solution~ dried over sodium sulfate, decolorised with silica gel and activated carbon, filtered and the filtrate is concentrated until the onset of crystallisation at a bath temperature oE 30C. The ~ ~ 7 residue is diluted with the same volume of petroleum ether and allowed to crystallise completely in a crystallisation cabinet. Yield: 27.5 g of colourless crystals which decompose between 131 and 140C.

Example H6: Preparat~on of C~ COOC~3 ~ COOCH3 ~ (compound 1.34~ ~/
~-CFC12 H

N-Fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-methoxy-carbonylpyrrole A solution of 20.4 g of fluorodichloromethylsulfenyl chloride in 15 ml of tetrahydrofuran is initially added dropwise at 0-5C to a suspension of 23.6 g of 3-(3-chlorophenyl)-4-methoxycarbonylpyrrole in 150 ml of tetrahydrofuran, followed by the dropwise addition of 12.2 g of triethylamine in 15 ml of tetrahydro~uran. The mixture is stirred for 16 ho-lrs in a thawing ice bath and then filtered. The ~iltrate is con-centrated and the residue is crystallised from ethyl acetate/
petroleum ether, afEording 28 g oE colourless product with a melting point of 77-79C.

The ~ollowing individual compounds of the Eormula I may be prepared in corresponding manner.

7~8 Table 1: Compounds of the formula R
~ 2 Rn \
~1~

Com- R R R ~ p [ C]
pound n 3 2 . .
1.1 3-OCH3 CC12F CN oil 1.2 2-S-C2H5 CC12F CN 59-60 1.3 2-S-C2~5 CC13 CN 90-92 1.4 2-S-CH(CH3)2 CC12F CN 64-66 1.5 2-S-CH(CH3)2 CC13 CN 100-102 1.6 2-SCH3 CC12F CN 86-87 1~7 2-SCH3 CC13 CN 125-127 1.8 4H9 CC12F CN 44-46 1.9 4 9 n CC13 CN 41-42 1.10 2-OCH(CH3)2 CC12F CN 95-98 1.11 2-OCH(CH3)2 CC13 CN 100-102 1.12 2-ben7.yloxy CC12F CN 127-129 1.13 2-ben7yloxy CC13 CN 111-113 lo 14 2-Br CC12F CN 69-71 1,15 2-OC2115 CC12F CN 80-83 1.16 2-OC2H5 CC13 CN 107-110 1,17 2 H2 CC12F CN 66-68 1.18 2-OCH2CII-CH2 CC13 CN 79-80 I.l9 3-Cl CC12F CN 87-89 L.20 3-Ct CC13 CN 81-84 1.21 2-Cl CC12F CN 59~61 1.22 H CC12F CO-CH3 43-45 1.23 H CCl~ CO-CH3 86-88 1.24 2-Cl CCl2F CO-CH3 86-88 1.25 2-Cl CC13 CO-CH3 104-109 :1 ~ $~2~3 Ta~le 1: (contin-lation) pound Rn R3 R2 m.p [C]
1.26 ~,-C~l3 CC12F CO-CH3 82~84 1.27 4-CH3 CC13 CO-CH3 100-102 1.28 3-C1 CC12F CO-CH3 63-64 1.29 3-C1 CC13 CO-CH3 82-84 1.30 3-CH3 CC12F CO-CH3 nD : 1.5871 1.31 3-CH3 CC13 CO-CH3 58-59 1.32 4-OCH3 CC12F CO-CH3 n~ : 1.5927 1.33 4-OC113 CC13 CO-CH3 nD : 1.6098 1.34 3-Cl CC12F COOCH3 77-79 1.35 3-Cl CC13 COOCH3 89-90 1.36 3-Cl CC12F S2CH3 oil 1.37 3-Cl CC13 2 3 104-107 1.38 2 4-C1 CC12F' S2CH3 106-108 1.39 2,4-C1 CC13 S02C~13 111-113 1.40 2-C1 CC12F S2CH3 86-88 1.41 2-OC2H5 CC12CHC12 CN 103 decompos.
1.42 2-Cl CC13 CN 93-95 1.43 2-OCH3 CC12F CN 39-42 1.44 2-OCH3 CC13 CN resill 1.46 2 OC3~17 n CC13 CN
7 2-OC~I119-n CC12F CN
l.48 4 9 CCI3 CN
1.49 2-SC3117-n CC12F CN
1.50 2-SC3117-n CC13 CN
1.51 2-CN CC12F CN 112-115 1.52 2-CN CC13 CN resin 1.53 2,3-C~2 CC12F CO-CH3 1.54 2,3-C12 CC13 CO-CH3 1.55 4-C1 CC12F CO-C~3 ~9~7;~

Table 1: (continuation) Com- R R R2 m.P.[oc]
pound n 3 1.56 ~-Cl CC13 CO-CH3 1.57 2-SCH3 CC12F CO-CH3 1.58 2-SCH3 CC13 CO-CH3 1.59 2-OCH3 CC12F CO-CH3 1.60 2-OCH3 CC13 CO-CH3 1.61 2-CN CC12F CO-CH3 1.62 2 CN CC13 CO-CH3 1.63 ~I-N(CH3)2 CC12F CO-CH3 1.6~ -N(CH3)2 CC13 CO-OE13 1.65 3-CF3 CC12F CO-CH3 1.66 3-cr~'3 CC13 CO-CH3 lo 67 2-Cl CC12F COOCH3 oil 1.68 2-Cl CC13 COOCH3 83-86 1.69 ~-Cl CC12F COOCH3 1.70 ~-Cl CC13 COOCH3 1.71 3,~l-C1 CC12F COOC~13 92-9~D
1.72 3,~-C12 CC13 COOC~13 89-90 1.73 ~-C~13 CC12F COOCH3 1.7~ -C~13 CC13 COOC113 1~75 ~-OCH3 CC12F COOCH3 97~99 1.76 4-OCH3 CC13 COOC113 1.77 2-OC~13 CC12F COOCH3 1.78 2-OCH3 CC13 COOCll3 1.79 2-CN CC12F COOC~13 1.80 2-CN CC13 COOC1l3 1.81 2-C1 CC12F CON(CH3)2 1.82 2-C1 CC13 CON(CH3)2 1.83 3-C1 CC12F CON(CH3)2 1.8~ 3-C1 CC13 CON(CH3)2 1.85 ~-C1 CC12F CON(CH3)2 ~7Z~

Table 1: (continuation) Com- Rn R3 R2 m.p.[ C~

1~86 4-C1 CC13 CON(CH3)2 1.87 ~-CH3 CC12F CON(CH3)2 1.89 ~,-CH3 CC13 CON(CH3)2 1.90 4-OCH3 CC12F CON(CH3)2 1.91 4-ocH3 CC13 CON(CH3)2 1.92 2-OC~3 CC12F CON(CH3)2 1.93 Z-OCH3 CC13 CON(CH3)2 1.94 2-OC2H5 CC12F CON(CH3)2 1.95 2-OC2H5 CC13 CON(CH3)2 1.96 2 CN CC12F CON(CH3)2 1.97 2-CN CCl3 CON(CH3)2 1.98 2-C1 CC13 S2CH3 118-121 1.99 4-C1 CC12F S2CH3 1.100 4-C1 CC13 S2CH3 1.101 4-CH3 CC12F S2CH3 1.102 4~CH3 CC13 S2CH3 1.103 4-OCH3 CC12F S2CH3 1.104 4-oCH3 CC13 S2CH3 1.105 3,4-C12 CC12F S2CH3 1.106 3,~l-C12 CC13 S02C~13 1.107 2-OCII~ CC12F S02C113 1.]08 2-OCH3 CC13 S2CH3 1.lO9 2-SC4ll9-n CC12F S2C~13 l.llO 2-SC~1l9-ll C~13 S02C~13 1.111 2-CN CC12F S2CH3 1.L12 2-CN CC13 S2CH3 1.113 2-C1 CC12F S02N(CH3)2 103-105 1.114 2-C1 CC13 S02M(CH3)2 1.115 3-C1 CC12F S02N(CH3)2 72~1 3 - ~o -Table 1: (continuation) Com- R R R2 m .p.r C]
pound ll 3 1.1163-C1 CC13 SO,N(CH3)2 1.117 4-CH3 CC12FSO2N(CH3)2 1.118 4-CH3 CC13SO2N(CH3)2 1.119 4_0CH3 CC12FSO2N(CH3)2 1.120 4-OCH3 CC13SO2N(CH3)2 1.121 4-C1 CC12FSO2N(CH3)2 1.122 4-Cl CC13SO2N(CH3)2 1.123 2-C1 CC12F( )( 2 5)2 1.124 2-C1 CC13-P(O)(OC2H5)2 oil 1.125 3-C1 CC12FP(O)(OC2H5)2 1.126 3-C1 CC13_P(O)(OC2H5)2 1.127 4-C1 CC12F-P(O)tOC2H5)2 1.128 4-C1 CC13 -P(O)(OC2~l5)2 1.129 2-C1 -CC12F 2 85-87 1.130 2-C1 -CC 13 -N2 1.131 3-C1 -CC12F _NO2 1.132 3-C1 ' -CC13 -NO2 1.133 2-C1 -CC12F -~-CH3 l.134 2-C1 -CC13 -~-CH3 1.135 2-C1 -CC12F

1.136 2-Cl CC12-CHC:L2 CN 123-125 1.137 4-C6HS CC13 CN 168-175 1.138 4-C6H5 CFC12 CN 173-177 1.139 H CC12F CN 96-98 1.140 H CC13 CN 102~103 1.141 H CFC12 SO2CH3 1.142 3-C1 CCI2CHC12 COOCH3 J~

Table 1: (continuation) Com- Rn R3 R2 m-p ~C]

1.143 2-Br CC13 CN 114-115 1.144 2-CH3 CC12F COCH3 85-89 1.145 2-CH3 CC13 COCH3 94-99 1.146 2,3-C12 CC12F CN 105-107 1.147 H CC12F S02N(CH3)2 124-126 1.148 H CC12F CON(CH3)2 oil 1.149 H CC13 CON(CH3)2 75-79 1.150 2,3-C12 CC12F COOCH3 56-61 - ~2 -Table 2: Compounds of the formula R -i -R

~Rq Com- R R R m.p. [~C]
pound 1 2 3 2.1 2-furyl CN CCl2F 74_76D
2.2. 2 pyridyl CN CCl2F 92-1oodeccmp 2.3 2-pyridyl CN CC13 131-140d~cllp.
2.4 2-pyridyl COOCH3 CC12F
2.5 2-pyridyl COOCH3 CC13 2.6 2-pyridyl CON(CH3)2 CCl2F
2.7 2-pyridyl CON(C~13)2 CC13 2.8 3-(2~1~opyridyl) CN CC12F
2.9 3-(2~ ~ropyridyl) CN CC13 142-144 2.10 3-(2-~loropyridyl) CO-CFI3 CC12F
2.11 3-(2~hloropyridyl) CO-CH3 CC13 2.12 2~6-chloropyridyl) CN CCl2F
2.13 2-(6-chloropyridYl) CN CC13 2.14 2-(6~loropyridyl) COOCH3 CC12F
2.15 2-(6-c~loropyridyl) COOCH3 CC13 2.16 2-thienyl CN CCl2F 72-77 2.17 2-thienyl CN CC13 85-89 2.18 2-thienyl CON(C1l3)2 CCl2F
2.~9 2-thienyl CON(C~13)2 CCl3 2.20 2-pyridyl CN CCl -CHCl 103-106 2. 21 3-pyridyl CN CC12F 123-126d~comp.
2.22 3-pyridyl CN CC13 dec~np.from 156 2.23 '~-pyridyl CN CC12F deccmp.frcm145 2.24 ~-pyridyl CN CC13 d~corr,p,fiom 154 I ~

~g~

~ormulation Exlm~)les for liq-lid active in~redien~s o~ the formu].a ~ (throughout, percentages are by weight) Fl Emulsiflable concentrates a) ~) c) a compound of the tables 25 % 40 % 50 %
calcium dodecylben~enesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % _ _ tributylphenol polyethylene glycol ether (30 moles o~
ethylene oxide) - 12 % 4 %
cycl.ohexanone ~ 15 % 20 %
xylene mixture 65 % 25 V/o 20 %

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

F2 Solutions a) b)l c) d) a compound of the tables ~0 % :L0 % 5 % 95 %
ethylene gLycol monomethyl ether ~0 % - ~ -polye~hylene glycol MG 400 , 70 % - -N-methyl-2-pyrrolidone - 20 %
epoxidlsed coconut oil - - 1 % 5 ~/0 ligroin (boi].lng ran~e 160-1')0) - - 9~ %

These solutions are suitable for appl:lcation in the ~orm oE microcrops.

F3 Granulates a) b) a compound of the tables 5 % 10 %
kaol.in 94 %
highly dispersed silicic acid1 %
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 vacuoA

F4 Dusts a) b) a compound of the tables 2 % 5 %
highly dispersed silicic acid 1 % 5 talcum 97 %
kaolin - 90 %

Ready Eor use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formula~ion examples for solid active in~redients oE the formula I (thro-lghout, percentages are by weight) F5 Wet~able powders a) b) c) a compound oE the tables 25 % 50 % 75 %
sodium lignosul:EonaLe 5 % 5 %
sod:ium lauryl.sulEate 3 % - 5 %
sodlum cllis0l~uty:1.naph~llalene-sul~onate - 6 % 10 %
octylphenol polyethyl.ene glycol ether (7-8 moles oE ethylene o~ide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %

~7;2~8 Tlle active ingredient is thorougllly mixed ~ith the adjuvants and the mi~ture is thoro~lghly ground in a s~litable mill, af~orcling ~ettable po~Jclers ~hich can be diluted with water to give suspensions of the desired concentration.

F6 Emulsi:~;able concentrate a compound o~ the tables 10 %
octylphenol polyethylene glycol ether (4-5 moles o~ ethylene oxide) 3 calcium cdodecylben~enesul~onate 3 %
castor oil polyglycol ether (36 moles o~ ethylene oxide) 4 cyclohexanone 30 ~/o xylene mixture 50 %

~mulsions of any required concentration can be obtained rom this concentrate by dilution ~ith water.

F7 Dusts, a) b) a compound of the tables 5 % 8 %
talc~m 95 %
kaol:in - 92 %

~eady fôr use dusts are obtained by rn:ix:ing the active ingredl.ent witll the .carr:lers~ ancl grlndl.ng the mlxture in a su:itable mil:l.

F8 E.xtrucler ~ranulate a compound o~ the tables 10 %
sodi~l lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %.

The active ingredient is mi~ed ~nd ~round ~ith ~he adjuvants, and the mi~ture is subscquently nloistened with wa~er. The mi~ture is e~truded and then dried in a stream oE air.

F9 Coated ~,ranulate a compound of the tables 3 %
polyethylene gylcoL MG 200 3 %
kaolin 94 %

The ~inely ground active ingredient is uniformly appliedg in a mixer, to the kaolin moistened w;th polyethylene glycol.
Non dusty coated granulates are obtained in this manner.

F10 Suspension concentrate a compound of the tables 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil ln ~he form oE a 75 %
aqueous emulsion 0.8 %
water 32 %.

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate Erom which suspensioTIs o~ any desired concentration can be obtained by dilution with water.

Both the final products of the ~ormula I and the intermediates o~ the formulae I and II' can be formulated in accor-Jance with Examples Fl to F10.

-- '~7 --Biological Examples Example Bl: Action a~alnst Puccinia graminia on wheat a) Residual-protective action Wheat pLants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active i~gredient (0.06 %). A~ter 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are 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 pustule development is made 12 days after infection.

b) Systemic action ~leat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (O.oO6% based on the volume of the soil).
~Eter ~8 hours the treated plants are infected with a uredos-pore suspension oE the ungus. The plants are then incubated Eor ~8 hours at 95-100 % relative humidity and about 20C and then stood in a greenhouse at about 22C, Evaluation oE rust pustule development is made 12 days aEter inection. Compouncls oE tables 1 and 2 are very eEfective against Puccinia Eungi. 100 % Puccinia attack is Eound on untreated and inEected control plants. ~mong others, compounds 16, 1.2~, 1.26, 1.3~, 1.75 and 1.1 inhibit f~mgus attack to 0-5 %.
xample B2: ~ction against Cercospora arachidicola in groundnut plants Residual-protective action Groundnut plants 10-15 cm in height are sprayed with a spray mi~ture prepared Erom a wettable powder Eormulation of the active ingredient (concentration o.oo6%) and infected ~72~

48 hours later wlth a conidia suspension of the fungus, The infected plants are incubatecl for 72 hours at about 21 C
and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection~ and is based on the number and size of the specks.

Compa~ed with un~reated and infected controls (number and size of the speclcs = 100%), Cercospora attack on the ground-nut plants ~reated with compounds of Tables 1 and 2 is greatly reduced. For example, compounds 23, 1.11, 1.15, 1.17, 1~ 2~ 26 ~ 0 ~ 1.75 and 1~ inhibit speck development almost completely (8%) in the above tests. Compound 24 has this activity even when diluted to a concentration of 0~002~/o~
Example B3: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about S cm in height are sprayed with a spray mixture (0~02 %) prepared ~rom the active ingredient Eormulated as a wettable powder. The treated plants are dusted with conidia of the fungus after 3-~ hours. The infected barley plants are then stood in a greenhouse at about 22C~ The Eungus attack is evaluated after lO days.

b) Systemic act:lon ~arley plants about 8 cm in height are treated with a spray mixture (0.006 %, basecl on the volume o~ the soil) preprared ~rom the active ingredient Eor~nulated as wettable powder. Care is talcen that the spray mixture does not come irl contactwith the parts of the plants above the soil. The treated plants are infected ~8 hours later with a conidia suspension of the E~mgus. The infected barley plants are then stood in a greenhouse at about 22C and ~7~8 evaluation of Eungus attack is made after 10 days. Compounds of the formula I are very effective against Erysiphe fungi.
Erysiphe attack is 100% on untreated and infected controls.
Compounds of Tables 1 and 2 strongly inhibit fungus attack.
For example, compounds 2, 16, 1.15, 1.21, 1.24, 1.26, 1.36 and 2.2 inhi~it attack almost completely (0-5%). The most active compounds are compounds 1.24 and 1.36.
xample B4: Residual-protective action a~ainst Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long Eresh shoots are sprayed with a spray mixture (0.06%) prepared from a w~ettable powder formulation of the active ingredient. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are 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 is evaluated 15 days after infection. Compounds 1, 4, 6, 7, 10, 24, 1.6, 1.8, 1.14, 1.17, 1.21, 1.2~, 1.26, 1.28, 1.3~, 1.36, l.~0, 1.52, 1.144, 2.3 and others inhibit attack to less than 10%. Venturia attack is 100% on untreated and infected controls. Com-pounds 1.24, 1.26, 1.40 and 2.3 are still fully effective (0% attack) when diluted to a concentration oE 0.006%.
xample B5: ~esidual protective action a~ainst Botrytis cinerea on beans ~ean plants about 10 cm in height are sprayed with a spray mixture (0.02%) prepared from the active :Lngredient ~ormulat~d as wettable powder. ~ter 4~ hours, the treated plants are infected with a conidia suspension oE the f~mgus.
The infected plants are incubated Eor 3 days at 95-100%
relative humidity and 21C, and evaluation of the fungus attack is then made. The compounds of Ta~les 1 and 2 inhibit fungus infection very strongly in many cases. For example, compounds 1, 4, 6, 7, 10, 24, 1.1 to 1.8, 1.14, 1.15, 1.17, ~'7~

1.19, 1,20~ 1.34 and 2,1 are fully effective at a con-centration of 0.02% (0 to 5% attack), Attack on untreated and infected plants is 100%, The intermediates 16 and 24 are also equally effective, Example B6: Action a~ainst Botrytis cinerea on apples Ar-tificially damaged apples are treated by dropping a spray mixture prepared from the respective active ingredient formulated as wettable powder onto the injury sites, The treated fruit is then inoculated with a spore suspension of Botrytis cinerea and incubated for 1 week at high humidity and abo~lt 20C.

Evaluation is made by counting the number of injury sites attacked by rot and deducing the fungicidal action of the test compound therefrom. Compared with untreated controls (100%
attack),compounds 1, 4, 6, 7, 10, 24, 1,1 to 1.8, 1.14 to 1.24, 1.26 to 1.34, 1,36 to 1.43, 1.51, 1.52, 1.67, 1.68, 1.71, 1,72, 1.75, 1.98, 1.113, 1.123, 1.129, 1.136 to 1.139, 1.144 -to 1.147, 1.150, 2.1, 2.2, 2.3, 2.9, 2.16, 2.17 and 2.21 to 2.24 and others inhibit f~mgus attack almost completely. The intermediates 16 and 24 are also equally effective.

Example B7: Action a~ainst Alternaria solani on tomato plants Tomato plants are sprayed~ aEter 3 weeks' cultivation, with a spray mixture prepared from the active ingredient formulated as a wettable powder (0.06%). AEter 24 ho~lrs, the treated plants are infested with a conidia suspension o~ the Eungus. Evaluation oE the fungus attack is made after incubation oE the inEested plants for 8 days at 18 to 22C
and high humidity. Compounds of Tablesl and 2 effect a strong reduction of Alternaria attack. For example, com-pounds 1.23, 1.24 and 1.26 inhibit attack completely (0.5%).

~7Z~3 Exam~le B8: Action a~ainst Piricularia oryzae on rice Rice plants are sprayed, after 2 weeks' cultivation, with a spray mixture prepared from the active ingredient formulated as a wettable powder (0.02%). After 48 hours, the treated plan-ts are infested with a conidia suspension of the fungus.
Evaluation of the fungus attack is made after incubation of the infested plants for 5 days at 24C and 95-100C
relative humidity. Compounds o~ the formula I effect good inhibition ofPiricularia attack. For example, compounds 1.23 1.24, 1.26, 1.75 and 1.1~4 inhibit attack to less than 10%.

Example B9: Grain preservative test a) Short-term test a~ainst mould fun~i on moist maize Dry maize kernels (80 g portions) intended for use as animal feed are thoroughly mixed in sealable plastic beakers with compounds of all Tables in the form o~ an aqueous suspension, emulsion or solution. The application of active ingredient is made so as to give a concentration oE 0.06%, based on the dry weight of the maize. A moistened sheet of paper ensures a saturated moist atmosphere in the beakers, which are filled with the maize and then sealed. After incubation Eor 2-3 weeks at about 20C, a mixed population of mould fungi develops spontaneously on the maize samples treated only with water. There is no need ko make an arti~icial infection. The eEfectiveness oE the compounds of the Eormulfle I and II' :is evaluated by determinin~ the e~tent of Eungus clevelopment aEter 3 weeks.

~) Lon~-term test a~ainst moulcl fun~i on moist maize I The mai~e samples exhibiting no f~mgus attack after 3 weelcs ar.e incubated for a further two months. A visual assessment is made after each month, applying the same criteria as in test a) ~7~

II The test procedure is in principle the same as in a) and b), except that the text compo-md o~ the formula I or II' is used in concentrations of 2000, 600 and 200 ppm a.i.
(based on the dry weight o~ the maize) over 6 months.

In all three tests a), bI) and bII), the Eormation of mould fungi on moist maize is inhibited completely both short-term (3 weeks) and long-term (6 months) by treatment with compounds of the ~ormula I of all Tables.

For example~ compounds 16, 24, 1.14 and 1.15 in all three tests a), bI) and bII) inhibit mould fungus attack almost comp:Letely (0-5% attack) at a test concentration oE 600 ppm a.i.

Treatment with compounds oE the ~ormulae I and II' in similar tests using, alternatively, cereals (oats), hay, carrot chips or broad beans instead of ~odder maize, give similar results o~ long-term protection over several months.

Example B10: Action a~ainst Tilletia caries Tilletia spores are suspended Eor 15 minutes in a spray mixture containing 600 ppm o~ active ingredient. The spore/
compound mixture is pipetted dropwise onto the sur~ace oE
Einel.y sieved, moistened soil in Petri dishes. These prepared dishes are then kept at high humidity (95-100%) and 20C. Spore ~ormation is evaluated microscopically a;Eter about 10 clays. The flction oE the test compouTIds is determined in accordance with the number and length of the sporocysts.
Compounds oE the Eormulae I and II' are very eE~ective against Tilletia caries Eungi. For example, compounds 1, 4,
6, 7, 10, 24, 1.6, 1.1~, 1.15, 1.17, 1.21, 1.2~, 1.26, 1.28, 1.36, 1.40, 1.52 and 2.3 inhibit the formation of sporocysts completely.

Claims (17)

CLAIMS:
1. A compound of the general formula I

(I) wherein R1 is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl)] r [U,V,W(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)], wherein X, Y and Z are each independently selected from the group consisting hydrogen, halogen, C1-C4alkyl, C1-C3halo-alkyl, di(C1-C4alkyl)amino, nitro, cyano, -COO(C1-C4-alkyl), -CON(C1-C4alkyl)2 and the group -E-R4, where E is -O-, -S-, -SO- or -SO2-, R4 is C1-C6alkyl which is unsubstituted or substituted by C1-C4alkoxy, C3-C5alkenyl which is unsubstituted or substituted by halogen, C3-C5alkynyl which is unsub-stituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH2-[X,Y,Z(phenyl)];
U, V and W are independently selected from the group con-sisting of hydrogen, halogen ancl C1-C4alkyl, R2 is -COO(C1-C6alkyl), -CO(C1-C6alkyl), -CO-N(C1-C6alkyl)2, cyano, nitro, -SO2-(C1l-C6alkyl), -P(O)(C1-C6alkoxy)2, -SO-(C1-C6alkyl) or -SO2-N(C1-C3alkyl)2; and R3 is C1-C3haloalkyl.
2. A compound according to claim 1, wherein R1 is a frag-ment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], [X,Y,Z(biphenyl-3-yl)], [X,Y,Z(bi-phenyl-2-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(4-pyridyl)], [U,V,W(2-furyl)], [U,V,W(3-furyl)], [U,V,W(2-thienyl)] and [U,V,W(3-thienyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, C1-C3alkyl, C1-C3haloalkyl, di(C1-C3alkyl)-amino, nitro, cyano, -COO(C1-C3alkyl), -CON(C1-C3alkyl)2, C1-C4alkoxy, C1-C4alkylthio, C3-C5alkenyloxy, C3-C5halo-alkenyloxy, phenoxy and benzyloxy; U,V,W are each indepen-dently selected from the group consisting of hydrogen, halogen and C1-C4alkyl; R2 is -COO(C1-C3alkyl), -CO(C1-C3-alkyl), -CO-N(C1-C3alkyl)2, cyano, nitro, -SO2(C1-C3alkyl), -P(O)(C1-C3alkoxy)2 and -SO2-N(C1-C3alkyl)2; and R3 is C1-C3haloalkyl.
3. A compound according to claim 1, wherein R1 is a frag-ment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)] and [U,V,W(2-thienyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, -N(CH3)2, -N(C2H5)2, -COOCH3, -COOC2H5, -CON(CH3)2, C1-C4alkoxy, C1-C4alkylthio, C3-C5alkenyloxy, C3-C5haloalkenyloxy, phenoxy and benzyl-oxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C1-C2alkyl; R2 is -COOCH3, -COOC2H5, -COCH3, -COC2H5, -CON(CH3)2, -CON(C2H5)2, cyano, nitro, -SO2-CH3, -SO2-C2H5, -P(O)(OCH3)2, -P(O)(OC2H5)2, -SO-CH3, -SO2-N(CH3)2 and -SO2-N(C2H5)2; R3 is C1-C2haloalkyl.
4. A compound according to claim 3, wherein R1 is a frag-ment selected from the group consisting of [X,Y,Z(phenyl)], [U,V,W(2-pyridyl)], [U,V,W(3-pyridyl)], [U,V,W(2-furyl)]
and [U,V,W(2-thienyl)], wherein X, Y and Z are each inde-pendently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, C1-C3-alkoxy and C1-C3alkylthio; U, V and W are each independent-ly selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl; R2 is -COOCH3-, -COCH3, NO2 or CN; and R3 is CFCl2 or CCl3.
5. A compound according to claim 2, wherein R1 is a frag-ment selected from the group consisting of [X,Y,Z(phenyl)]
and [U,V,W(2-furyl)], wherein X, Y and Z are each inde-pendently selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl, -N(CH3)2' -COOCH3, -CON(CH3)2, C1-C4alkoxy, C1-C4alkylthio , C3alkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C1-C2alkyl; R2 is -COOCH3, -COCH3, -CON(CH3)2, cyano, nitro, -SO2-CH3, -P(O)(OC2H5)2 or -SO2-N(CH3)2; and R3 is CC13, CC12F, CC12H, CClH2, CF3, CF2H, C2Cl5 or CC12CHCl2.
6. A compound according to claim 5, wherein R1 is the fragment [X,Y,Z(phenyl)], wherein X, Y and Z are each in-dependently selected from the group consisting of hydrogen, chlorine, bromine, methyl, C1-C4alkoxy, C1-C4alkylthio and C3alkenyloxy; R2 is -COCH3 or cyano; and R3 is CCl3, CCl3F or CCl2CHCl2.
7. A compound according to claim 3, selected from the group consisting of:

N-fluorodichloromethylsulfenyl-3-(2-allyloxyphenyll)-4-cyanopyrrole, N-fluorodichlormethylsulfenyl-3-(2-chlorophenyl)-4-cyano-pyrrole, N-fluorodichloromethylsulfenyl-3-phenyl-4-acetylpyyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(4-methylphenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-acetyl-pyrrole, N-fluorodichloromethylsulfenyl-3-(3-methylphenyl)-4-acetyl-pyrrole, N-fluorodichlormethylsulfenyl-3-(3-chlorophenyl)-4-methoxy-carbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-methoxycarbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-nitro-pyrrole, N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanoopyrrole, and N-Trichloromethylsulfenyl-3-(2-pyridyl)-4-cyanopyrrole.
8. A process for the preparation of a compound of the formula I as defined in claim 1, which process comprises sulfenylating a free pyrrole of the formula II

(II) wherein R1 and R2 are as defined for formula I, at the pyrrole nitrogen with a reactive acid derivative of a sulfenic acid of the formula III

R3-S-OH (III) wherein R3 is as defined for formula I, in the presence of a base.
9. A process according to claim 8, wherein a lower alkyl acid ester or an acid halide of the acid of formula III is used as reactive sulfenic acid derivative.
10. A process according to claim 9, wherein the acid chloride of the acid of formula III is used.
11. A process according to claim 8, wherein an alkali metal carbonate or an alkaline earth metal carbonate or a tertiary amine is used as base.
12. A process according to claim 8, wherein the reaction is carried out in the presence of a reactive solvent.
13. A process according to claim 8, wherein 4-dimethyl-aminopyridine is used as catalyst.
14. A process according to claim 8, wherein the reaction is carried out in the temperature range from -30° to + 100°C .
15. A process according to claim 14, wherein the reaction is carried out in the temperature range from -10° to +20°C.
16. A method of controlling phytopathogenic microorganisms or protecting cultivated plants from attack by said micro-organisms, which method comprises applying to said plants, to parts of the plants or to the locus to be protected a microbicidally effective amount of a compound according to claim 1.
17. A method of preserving or protecting storable goods of vegetable or animal origin from attack by harmful micro-organisms, which method comprises treating said goods with a microbicidally effective amount of a compound according to claim 1.
CA000417974A 1981-12-18 1982-12-17 N-sulfenylated pyrrole derivatives Expired CA1197248A (en)

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EP0111452A1 (en) * 1982-12-10 1984-06-20 Ciba-Geigy Ag Use of pyrroles as biocides for the protection of materials
EP0174910B1 (en) * 1984-09-12 1990-04-04 Ciba-Geigy Ag Process for the preparation of 4-phenyl-pyrrole derivatives
EP0182737A3 (en) * 1984-10-16 1986-10-08 Ciba-Geigy Ag 3-phenyl-pyrrole derivatives, process for their preparation and their use as pesticides
US5234943A (en) * 1989-04-13 1993-08-10 Bayer Aktiengesellschaft Fungicidal 3-(2-chloro-3-trifluoromethylphenyl)-4-cyanopyrrole
DE4128132A1 (en) * 1991-08-24 1993-02-25 Bayer Ag 3- (2-CHLOR-3-TRIFLUORMETHYLPHENYL) -4-CYANOPYRROL, THEIR PRODUCTION AND USE AND NEW INTERMEDIATE PRODUCTS
EP0404721A3 (en) * 1989-06-20 1991-12-27 Ciba-Geigy Ag Microbicides
US5492925A (en) * 1993-08-31 1996-02-20 American Cyanamid Company Thienyl-and furylpyrrole insecticidal and acaricidal agents

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CA689434A (en) * 1964-06-23 Unterstenhofer Gunter Process for the production of derivatives of fluoro-dichloro-methane sulphenic acid
US2888462A (en) * 1957-11-07 1959-05-26 Lilly Co Eli Trichloromethylmercaptopyrazoles
BE616336A (en) * 1960-11-03
DE2614935C3 (en) * 1976-04-07 1980-02-21 Schuelke & Mayr Gmbh, 2000 Norderstedt N-Trichloromethylthio-alkenylsuccinic acid imides and fungicidal agents
DE2636076C3 (en) * 1976-08-11 1980-10-09 Schuelke & Mayr Gmbh, 2000 Norderstedt Substituted N-trichloromethylthio-succinic acid imides
IL56243A (en) * 1978-01-31 1982-07-30 Nippon Soda Co Phenylpyrrole derivatives,their production and their use as fungicides
JPS5511524A (en) * 1978-07-10 1980-01-26 Nippon Soda Co Ltd Cyanopyrrole derivative, its preparation and agricultural and horticultural fungicide
ES482591A1 (en) * 1978-07-20 1980-04-01 Basf Ag N-Arylsulfonyl pyrroles, their preparation and medicaments containing them.
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