IE54311B1 - Microbicidal compositions - Google Patents

Microbicidal compositions

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Publication number
IE54311B1
IE54311B1 IE3001/82A IE300182A IE54311B1 IE 54311 B1 IE54311 B1 IE 54311B1 IE 3001/82 A IE3001/82 A IE 3001/82A IE 300182 A IE300182 A IE 300182A IE 54311 B1 IE54311 B1 IE 54311B1
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IE
Ireland
Prior art keywords
alkyl
group
formula
phenyl
compound
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IE3001/82A
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IE823001L (en
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Ciba Geigy Ag
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Publication of IE823001L publication Critical patent/IE823001L/en
Publication of IE54311B1 publication Critical patent/IE54311B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D207/32—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
    • 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
    • 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
    • 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
    • A01N43/36—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D207/36—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D207/42—Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D207/46—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Cosmetics (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)

Abstract

1. Claims for Contracting States BE, CH, DE, FR, GB, IT, LI, NL Compounds of the general formula I see diagramm : EP0096142,P25,F1 wherein R1 is a fragment [X, Y, Z(phenyl)], [X, Y, Z(biphenyl)], [U, V, W(pyridyl)], [U, V, W(furyl)] or [U, V, W(thienyl)], wherein X, Y and Z are each independently hydrogen, halogen, C1 -C4 alkyl, C1 -C3 haloalkyl, di(C1 -C4 alkyl)amino, nitro, cyano, -COO(C1 -C4 alkyl), -CON(C1 -C4 alkyl)2 or the group -E-R4 , wherein E is -O-, -S-, -SO- or -SO2 -, R4 is C1 -C6 alkyl which is unsubstituted or substituted by C1 -C4 alkoxy, unsubstituted C3 -C5 alkenyl, 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 W are each independently hydrogen, halogen or C1 -C4 alkyl ; R2 is -COO(C1 -C6 alkyl), -CO-(C1 -C6 alkyl), -CO-N(C1 -C6 alkyl)2 , cyano, nitro, -SO2 -(C1 -C6 alkyl), -P(O)-(C1 -C6 alkoxy)2 or -SO2 -N(C1 -C6 alkyl)2 ; and R3 is C1 -C3 haloalkyl. 1. Claims for Contracting State AT A microbicidal composition for controlling or preventing an attack on living plants and/or for preserving perishable storable goods of vegetable or animal origin, which composition contains, as at least one active component, one of the compounds of the general formula I see diagramm : EP0096142,P27,F1 wherein R1 is a fragment [X, Y, Z(phenyl)], [X, Y, Z(biphenyl)], [U, V, W(pyridyl)], [U, V, W(furyl)] or [U, V, W(thienyl)], wherein X, Y and Z are each independently hydrogen, halogen, C1 -C4 alkyl, C1 -C3 haloalkyl, di(C1 -C4 alkyl)amino, nitro, cyano, -COO(C1 -C4 alkyl), -CON(C1 -C4 alkyl)2 or the group -E-R4 , wherein E is -O-, -S-, -SO- or -SO2 -, R4 is unsubstituted C1 -C6 alkyl, C3 -C5 alkenyl 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 W are each independently hydrogen, halogen or C1 -C4 alkyl ; R2 is -COO(C1 -C6 alkyl), -CO-(C1 -C6 alkyl), -CO-N(C1 -C6 alkyl)2 , cyano, nitro, -SO2 -(C1 -C6 alkyl), -P(O)-(C1 -C6 alkoxy)2 or -SO2 -N(C1 -C6 alkyl)2 ; and R3 is C1 -C3 haloalkyl.

Description

The present invention relates to novel N-sulfenylated pyrrole derivatives, to the preparation thereof, and to microbicidal compositions which contain at least one of these novel compounds. The invention relates further to the preparation of the said compositions and to the use of the novel compounds and compositions for controlling harmful microorganisms, in particular phytopathogenic fungi.
The novel compounds of this invention have the general formula 1 II II V SR. '3 (I) wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)], (X ,Ύ,Ζ(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, C^-C^alkyl, C^-Cghaloalkyl, di(C^-C^alkyl)amino, nitro, cyano, -COO(C-^-C^alkyl), -CON(C^-C^alkyl)2 and the group -E-R^, where E is -0-, -S-, -SO- or -S02-, R^ is G^-Cgalkyl which is unsubstituted or substituted by C^-C^alkoxy, C^-C^alkenyl which is unsubstituted or substituted by halogen, Cg-C,.alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl) ] or -C^- [Χ,Υ,Ζ(phenyl) 1,« U, V and W are each independently selected from the group consisting of hydrogen, halogen and C^-C^alkyl, R2 is -COOCC^-Cgalkyl), -CO(C1-C^)alkyl), -CO-N(C:L-Cgalkyl)2, cyano, nitro, -SO2-(C^-C^alkyl), -P(0)-(C^-C^alkoxy)2, -SO-(C^-Cgalkyl) or -SC^-NCCi-C^alkyl)^ and Rg is C^-C^haloalkyl. · Throughout this specification, the symbols (X,Y,Z(phenyl)], [X,Y ,Z(biphenyl)], [U,V,W(pyridyl)], [U,V,W(furyl)] and [U,V,W(thienyl)] are respectively the following groups: Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent will be understood as comprising e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl etc., and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. Haloalkyl is a monohalogenated to perhalogenated alkyl substituent such as CHjCl, CHC12, CCl^, CHgBr, CHBr2, CBr^, CH2F, CHF2, CF3, CC13F, CC12-CHC12, CH2CH2F, CI3 etc. Throughout this specification, halogen will be understood as signifying fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. C^-C^Alkenyl 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-furyl. Thienyl is - 3 2-thienyl and 3-thienyl and biphenyl is biphenyl-4-yl, biphenyl-3-yl and biphenyl-2-yl. Alkynyl is in particular propargyl. The compounds of 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 fields preventively and curatively for controlling phytopathogenic microorganisms. The compounds of the formula I have excellent fungicidal activity in broad concentration ranges and their use is unproblematical.
On account of their pronounced microbicidal activity, preferred compounds of the formula I are those compounds which contain the following substituents or combinations thereof with one another: for a) [X,Y,Z(phenyl)], (X,Y,Z(hiphenyl-4-yl)3, (X,Y,Z(biphenyl-3-yl)]. (X,Y,Z(biphenyl-2-yl)], [U,57,^( 2-pyridyl) ], [U,V,W(3-pyridyl) ], [U,V,W(4-pyridyl)], (O,V,W(2-furyl)], (U,V,W(3furyl)], IU,V,W(2-thienyl)], (U,V,W(3-thienyl)]; b) [X,Y,Z(phenyl)3, (X,Y,Z(biphenyl-4-yl)], [U,V,Z(2-pyridyl)1, [U,V,W(3-pyridyl)], lU,V,W(2-furyl)J, (U,V,W(2-thienyl)]; c) (X,Y,Z(phenyl)], (U,V,W(2-furyl)]; d) [X,Y,Z(phenyl)]; for Χ,Υ,Ζ: a) H, halogen, G^-C^alkyl, Cj-Cghaloalkyl, di(C^-C^alkyl)amino, nitro, cyano, -000(0^-0^alkyl) , -CONiC^-Cjalkyl^, C^-C^alkoxy, Cj-C^alkylthiQ, C^-G^alkenyloxy, C^-C^haloalkenyloxy, phenoxy, benzyloxy; b) H, F, Cl, Br, CH3> 0^, CF3> -Ν(0Η3)2> -n(c2h5)2, -cooch3, -cooc2h5, -con(ch3)2, - 4 C^-C^alkoxy, C^-C^alkylthio, Cg-C^alkenyloxy, Cg-C^haloalkenyloxy, phenoxy, benzyloxy; c) H, Cl, Br, CH3, C^, CF3> -N(CH3)2> -C00CH3> -00Ν(0Η3)2> C^-C^alkoxy, C^-C^alkylthio, C3alkenyloxy, phenoxy, benzyloxy; d) H, Cl, Br, CH3> C^-C^alkoxy, C^-C^alkylthio, C3alkenyloxy. for U,V,W: a) H, halogen, C^-C^alkyl; b) H, Cl, Br, Ci^alkyl; c) H, Cl, Br, CH3; for R2: a) -COO(C1-C3alkyl) , -CO-CC^C^lkyl) , -CO-N(C·^ C3alkyl), cyano, nitro, -SO2(C^-C3alkyl), -P (0) (C^-C^lkoxy) 2, -SO^CC^-C^lkyl) 2; b) -cooch3, -cooc2h5, -coch3, -coc2h5> -con(ch3)2, -C0N(C2H3)2> cyano, nitro, -SOg-CILj, -SO^H^, -so-ch3, -p(o)(och3)2, -p(o)(oc2h5)2, -S02-N(CH3)2, -S02-N(C2H5)2; c) -C00CH3> -C0CH3> -CON(CH3)2> cyano, nitro, -SO2-CH3, -P(O)(OC2H5)2, -SO2-N(CH3)2; d) -C0CH3, CN; for R3: a) C^-C-jhaloalkyl; b) C^-C2haloalkyl; c) cci3> cci2f, cci2h, ccih2, cf3> cf2h, c2ci5, CC12CHC12; d) cci3, cci2f, cci2chci2.
The following combinations a) to g) of these types of substituents result a) (Rj-a), (Χ,Υ,Ζ-a), (U,V,W-a), (R2~a), (R^a) b) (Rj^-b), (X,Y,Z-b), (U,V,W-b), (R2-b), (R3~b) c) (Rj^-c), (X,Y,Z-c), (U,V,W-c), (R2-c), (R3‘c) d) (Rj-d), (X,Y,Z-d), (R2-d), (Rg-d) 543 11 - 5 e) (Rj-a), (X,Y,Z-c), (U,V,W-c), (R2-b), (R3~c) f) (Rj-b), (X,Y,Z-c), (U.V.W-c), (R2-d), (R3~d) g) (R^d). (Χ,Υ.Ζ-d), (R2-a), (R3~a).
Accordingly, preferred groups of compounds are: a) compounds of the formula I, wherein R^ 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(biphenyl-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)] or [U,V,W-3-thienyl], wherein X,Y and Z are each independently selected from the group consisting of hydrogen, C^-C^alky!, C^-Cghaloalkyl, di(C|-C3alkyl)amino, nitro, cyano, -COO(C^-C3alkyl), -CON(C|-C3alkyl)2> C^-C^alkoxy, C-^-C^alkylthio, Cj-C^alkenyloxy, C^-C^haloalkenyloxy, phenoxy and benzyloxyj U,V and W are each independently selected from the group consisting of hydrogen, halogen and C^-C^alkyl; R2 is -C00(C^-C3alkyl) , -CO-iC^-C^lkyl) , -CO-R(C^-C3alkyl)2> cyano, nitro, -SC^-iC^-C^alkyl), -P(0)(C^-C3alkoxy)2 or -SC^MC^-C^alkyl^; and R3 is C^-C^haloalkyl; b) compounds of the formula I, wherein R^ is a fragment 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)] or [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, tri. fluoromethyl, -N(CH3)2, -COOCH3, -COOC^, -CON(CH3)2» C^-C^alkoxy, C^-C^alkylthio, Cj-C^alkenyloxy, C^-C^haloalkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C^^alkylj R2 is R2-COOCH3, -COOC2H5, -COCH3, -COC2H5, -CON(CH3)2> -CON(C2H5)2> cyano, 5431 l - 6 nitro, -SO2-CH3, -SO2C2H5, -P(0)(OCH3)2, -SO-CH3, -P(O)(OC2H5)2, -SO2-N(CH3)2 or -SO2-N(C2H5)2; and R3 is C^-C2haloalkyl.
Within the subgroup b), particularly preferred compounds of the formula I are those wherein R^ is a fragment selected from the group consisting of [x,Y,Z(phenyl)], [U,V,W(2pyridyl)], fU,V,W(3-pyridyl)], (U,V,W(2-furyl)] or [U,V,W(2thienyl)], wherein X, Y and Z are each independently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, C^-C^lkoxy and C^-C3alkylthio; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl; R2 is -COOCH3> COCH3> N02 or CN; and R3 is CFC12 or CC13· c) Compounds of the formula I, wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)] and [U,V,W(2-furyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl, N(CH3)2> -COOCH3> -CON(CH3)2> C^-C^alkoxy, C^-C^alkylthio, C3alkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C^-C^lkyl; R2 is -C00CH3> -COCHj, -CON(CH3)2> cyano, nitro, -SO2-CH3> -P(0)(OC2H3)2 or -SO2"N(CH3)2; and R3 is CC13, CC12F, CC12H, CCIHj, CF3> CF2H, C2C15 or CC12CHC12; d) compounds of the formula I, wherein R^ is the fragment tX,Y,Z(phenyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl, C^-C^alkoxy, C^-C^alkylthio and C3alkenyloxy; R2 is -COCH3 or cyano; and R3 is CC13> CCljF or CC12CHC12. 4 3 11 - 7 Within the scope of the present invention, the following 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 of their pronounced fungicidal properties: N-fluorodichloromethyIsulfenyl-3-(2-allyloxyphenyl)-4-cyanopyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-cyanopyrrole, N-fluorodichloromethylsulfenyl-3-phenyl-4-acetylpyrrole, N-fluorodichloromethylsulfeny1-3-(2-chlorophenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(4-methylphenyl)-4-acetylpyrrole , N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(3-methylphenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-methoxycarbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-methoxycarbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-nitropyrrole, N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole, N-trichloromethylsulfenyl-3-(2-pyridyl)-4-cyanopyrrole, N-fluorodichloromethylsulfeny1-3-(2,3-dichlorophenyl)-4cyanopyrrole.
In the practice of this invention, the compounds of formula I are prepared by sulfenylating a free pyrrole of the formula II '1 II II V I H (II) at the pyrrole nitrogen, with a reactive acid derivative of a sulfenic acid of the formula III R3-S-OH (III) in the presence of a base. In the above formulae, R^, R2 and R3 are as defined for formula I.
Suitable reactive sulfenic acid derivatives for this sulfenylation reaction are e.g. the lower alkyl esters and, preferably, the sulfenic acid halides, in particular the chlorides and bromides, with the chlorides being especially preferred. Lower alkyl will here be understood as meaning C|-Cgalkyl.
Both organic and inorganic bases may be successfully employed in the above reaction. Examples of suitable inorganic bases are alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate etc. Examples of suitable organic bases are tertiary amines such as trialkylamines (triethylamine, methyl diethylamine), N,N-dimethoxycyclohexylamine, N-methylpiperidine, Ν,Ν-dimethylaniline or pyridines. Trialkylamines are preferred. It is advantageous to use the base in stoichiometric proportion or in excess thereof, e.g. in up to 100% excess of stoichiometric proportion, based on the pyrrole of the formula II. The reactive derivative of the sulfenic acid of the formula III is also used in stoichiometric proportion or in excess thereof.
The sulfenylation reaction may be carried out in the presence or absence, preferably in the presence, of an inert solvent 4311 - 9 or mixture of inert solvents. In principle, the customary organic solvents are suitable for this reaction, provided they contain no reactive hydrogen atoms. Examples of 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; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), ethylene glycol di- and monoether and diethylene glycol di- and monoether, containing 1 to 4 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 dimethylsulfoxide; 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 sulfenylating reagent of the formula III may itself act as solvent.
To hasten the reaction rate, a catalyst such as 4-dimethylaminopyridine may be added, if appropriate.
The sulfenylation reaction is normally carried out in the temperature range from -30° to +100°C, preferably from -10° to + 20°C. The reaction time is then generally from about % hour to 20 hours. However, addition of a reaction catalyst will on occasion often reduce the reaction time to less than % hour.
At normal temperatures, the free sulfenic acids of formula III are generally relatively unstable substances which have a tendency to self-oxidation. The known sulfenic acid halides, 4 3 11 - 10 however, which can be obtained e.g. by halogenation from the corresponding mercaptans or dialkyl disulfides, are stable. Also known are lower alkylsulfenic acid esters, which can be obtained e.g. by reacting sulfenic acid chlorides with alkali alcoholates. At elevated temperature they undergo rearrangement to form the corresponding sulfoxides, but can be handled at lower temperatures.
Some of the pyrroles of the formula II are known from the literature. For example, the method of preparing and the chemical properties of 4-cyano-3-phenylpyrrole are described in Tetrahedron Letters No. 52, pp. 5337-5340 (1972). Nothing is reported on the biological properties of the compound.
Differently substituted 3-phenyl-4-cyanopyrrole derivatives are known from the literature. For example, pyrroles of the formula IV \ = / II II (IV), Xn - V I H 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 Offenlegungsschrift 29 27 480 as intermediates having insignificant fungicidal activity.
Novel pyrrole derivatives are those of the formula II i_R2 (II') wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)J, [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 4 3 11 - 11 hydrogen, halogen, C^-C^alkyl, C^-C^haloalkyl, di(C^-C^alkyl)amino, nitro, cyano, -COO(C^-C^alkyl), -CON(C.j-C4alkyl)2 and the group -E-R^, wherein E is -0-, -S-, -SO- or -S02-, R^ is C^-C^alkyl which is unsubstituted or substituted by C^-C^alkoxy, Cg-C^alkenyl which is insubstituted or substituted by halogen, C^-C^alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is (X,Y,Z(phenyl)] or -CH2-lX,Y,Z(phenyl)], and U, V and W are each independently selected from the group consisting of hydrogen, halogen or C^-C^alkyl; R2 is -COO(C^-C^alkyl), -CO-(C^-C^alkyl), -CO-N(C1-C4alkyl)2, nitro, -S02-(C^C^lkyl) , -P(0) alkoxy)2> -SO-(G^-C^alkyl) and -SO2~N(C^-C3alkyl)2, and, where R^ is a fragment [X,Y,Z(biphenyl)], [U,V,W(pyridyl)], (U,V,W(furyl)] or tU,V,W(thienyl)], R2 is additionally cyano. These compounds are specially developed intermediates for obtaining the valuable compounds of the formula I. Because of their structure they can be readily converted by N-sulfenylation into the compounds of the formula I. In addition, the compounds of formula II1 have fungicidal activity against important harmful fungi in plant protection, as well as excellent storage protection properties. The novel compounds of formula II’, including the preparation thereof and use thereof, therefore fall within the province of this invention.
The compounds of formula II, and therefore also those of formula II', can be prepared in alkaline medium by a Michael cycloaddition reaction of a compound of formula V with tosylmethyl isocyanide, accompanied by the elimination of p-toluenesulfinic acid or the salt thereof: V=-r2 (v) / A CHj—S02-CH2-NCZbase ~ > \ ι'ι ΓΓ*2 CH3-< ).-80,0 V’ »=:· I H (II.II'). - 12 In the above formulae, and R2 have meanings assigned to them previously.
Both here and subsequently, the tosyl group stands 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 of such activating groups are benzenesulfonyl, p-chlorobenzenesulfonyl, lower alkylsulfonyl such as mesyl.
The cycloaddition is carried out in the presence of a nonnucleophilic base. Suitable bases are alkali metal hydrides such as sodium hydride, or alkali metal carbonates or alkaline earth metal carbonates such as NanC0o, KoC0,, or Π (+) 2 3 2 3 alkali alcoholates such as (CH^^CO 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 of preferably anhydrous solvents suitable for the cycloaddition are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ethers, ligroin, cyclohexane; ethers and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether etc.) dimethoxymethane, tetrahydrofuran, anisole; sulfones such as dimethylsulfoxide; dimethylformamide; and mixtures of such solvents with one another.
The cycloaddition is normally carried out in the temperature range from -30° to +120°C, preferably from -30° to +50°C, or at the boiling point of the solvent of solvent mixture.
When choosing suitable bases, the cycloaddition can also conveniently be carried out in aqueous medium. Suitable bases 4 3 11 - 13 are water-soluble inorganic and organic bases, in particular alkali metal hydroxides such as LiOH, NaOH or KOH, and ammonium bases, e.g. tetraalkylammonium hydroxides such as (CHp^NOH, At least an equimolar amount of 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 of suitable organic solvents for the organic waterimmiscible phase are: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes etc.,; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, tetrachloroethylene etc.; or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.
The presence of a phase transfer catalyst can be of advantage in this mode of carrying out the reaction in order to hasten the rate of reaction. Examples of such catalysts are: tetraalkylammonium halides, hydrogen sulfates or hydroxides such as tetrabutylammonium chloride, tetrabutylammonium bromide or tetrabutylammonium iodide; triethylbenzylammonium chloride or bromide; tetrapropylammonium chloride, bromide or iodide etc. Phosphonium salts are also suitable for use as phase transfer catalysts.
The phase transfer catalysed cycloaddition can be carried out in the temperature range from 0° to +80°C, preferably from -10° to +50°C or at the boiling point of 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 from 1 to 16 hours, and in phase transfer catalysis from % hour to 10 hours. 4 3 11 - 14 Surprisingly, it has been found that the compounds of formula I and the compositions containing them have for practical purposes a very useful microbicidal spectrum against phytopathogenic fungi and bacteria. They can be used both in plant protection for controlling harmful microorganisms on cultivated plants and in storage protection for preserving perishable goods. The compounds of formula 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 different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms. The intermediates of formula II' also have a corresponding activity.
The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphe, Sclerotinia, Fusarium, Monilinia, Helminthosporiumj Basidiomycetes, e.g. Puccinia, Tilletia, Rhizoctoniaj 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 harmful fungi of the family of the Fungi imperfecti, e.g. against Cercospora, Piricularia and, in particular, against Botrytis. Botrytis spp. (B. Cinerea, B. allii) and the grey mould on vines, strawberries, apples, onions and other varieties of fruit and vegetables, are a source of significant economic damage. In addition, the compounds of formula I can be used successfully for protecting perishable goods of vegetable or animal origin. They combat mould fungi such as Penicillium, Aspergillus, Rhizopus, Fusarium, Helminthosporium, Nigrospora and Alternaria as 543 11 - 15 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 advantageous 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 I for controlling phytopathogenic microorganisms, especially harmful fungi, and for the preventive treatment of plants and storable goods of vegetable or animal origin to protect them from attack by such microorganisms.
The invention further embraces the preparation of aggrochemical compositions which comprises homogeneously mixing an active ingredient with one or more substances or groups of substances described herein. The invention furthermore relates to a method of treating plants or storable goods, which comprises applying to plants, parts of plants, the locus 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, - 16 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, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites).
In storage protection, the compounds of formulae I and II1 are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to 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. polymer substances. The methods of application, such as spraying, atomising, dusting, scattering or pouring, and the formulation of the composition, are chosen in accordance with the intended objectives and the prevailing circumstances. Suitable rates of application are in general in the range from 0.01 to at most 2 kg of active ingredient per 100 kg of substrate to be protected. However, they depend very materially on the nature (surface area, consistency, moisture content) of the substrate and its environmental influences.
Within the scope of this invention, storable goods will be understood as meaning natural substances of vegetable and/or animal origin and the products obtained therefrom by further processing, for example the plants listed below whose natural life cycle has been interrupted and the parts thereof (stalks, 4 311 17 ' leaves, tubers, seeds, fruit, grains) which are in freshlyharvested or further processed form (predried, moistened, crushed, ground, roasted). The following produce may be cited by way of example, without any restriction to the field of use within the 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, cherries, strawberries, rasherries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts); cucumber plants (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute,ramie); citrus fruit; vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), or maize, tobacco, nuts, coffee, sugar cane, tea, vines, chestnuts, hops, bananas, grass and hay.
Examples of natural products of animal origin are, in particular, dried meat and processed fish 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 attack by mould fungi and other harmful microorganisms. The formation of toxic and in some cases carcinogenic mould fungi (aflatoxins and ochratoxins) is inhibited, the goods are preserved from deterioration, and their quality is maintained over a prolonged period of time. The method of the invention is susceptible of application to all forms of dry and moist storable goods which are liable to attack by microorganisms such as yeast fungi, bacteria and, in particular, mould fungi. 4 3 1 1 - 18 A preferred method 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 formula I are normally applied in the form 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 formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers. Phospholipids are particularly useful adjuvants.
A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is foliar (leaf) application. The number of applications and the rate of application depend on the intensity of infestation by the corresponding pathogen (type of fungus). However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The compounds of formula I may also 1 3 1 I - 19 be applied to seeds (coating), by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation. In special cases, further types of application are also possible, e.g. selective treatment of the plant stems or buds.
The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are choseq in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.
The formulations, i.e. the compositions containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g, by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalates or dioctyl phthalate, aliphatic hydro5 4 3 1 1 - 20 carbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum kaolin, montmorillonite or attapulgite.
In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers arc porous types, for example pumice, broken brick, sepolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of preganulated materials of 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 compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts - 21 of higher fatty acids (^0-^22^ ’ e'S* t^e soc,i-unl or potassium salts of olcic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyl laurin salts.
More frequently,’ however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol' ether groups - 22 and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22~ alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp. Ringwood, Neii Jersey, 1979, and Sisely and Wood, Encyclopedia of 543 11 Surface Active Agents, Chemical Publishing Co., Inc.
New York, 1980.
The agrochemical compositionsusually contain 0.1 to 99%, preferably 0.1 to 95%, of 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 formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
Such agrochemical compositions also constitute an object of the present invention.
The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.
Preparatory Examples a) Starting materials Example a: Preparation of \-Z -Cti=CH-CN -CN (compound 24) 3-(2-Methylthiophenyl·) -4-cyanopyrrole A solution of 123 g (0.7 mole) of E/Z-3-(2-thiomethylphenyl)acrylonitrile and 192 g (0.98 mole) of tosylmethyl isocyanide in 800 ml of tetrahydrofuran is added slowly dropwise at -13° to +8°C to a solution of 158 g (1.4 moles) of potassium tert-butylate in 400 ml of tetrahydrofuran. 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 semisaturated sodium chloride solution, dried over sodium sulfate, decolorised with silica gel and activated carbon, filtered 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°-124°C. The mother liquor is worked up to give another 21 g of substance. Repeated recrystallisation from dichloromethane/petroleum ether yields an almost colourless product with a melting point of 128°-134°C.
Example b: Preparation of (compound 49) 3-(2-Chlorophenyl)-4-acetylpyrrole A solution of 60 g (0.33 mole) of E/Z-4-(2-chlorophenyl)-3buten-2-one and 75 g (0.38 mole) of tosylmethyl isocyanide in 400 ml of tetrahydrofuran is slowly added dropwise at -10° to +30°C to a solution of 48 g (0.43 mole) of potassium tert-butylate in 100 ml of tetrahydrofuran. The reaction mixture is stirred for 2¾ hours at 5°-10°C, 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 gel and fuller's earth, filtered and the filtrate is concentrated. The residue is digested in dichloromethane under reflux, cooled and filtered. Yield: 40 g of beige-coloured crystals with a melting point of 198°-2O1°C.
Example c: Preparation of Cl, V (compound 41) 3-(3-Chloropheny1)-4-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 efficient stirring, a solution of 5.5 g (0.03 mole) of 2-(3-chlorophenyl)-l-nitroethene and 5.9 g (0.03 mole) of tosylmethyl isocyanide in 20 ml of dimethylsulfoxide 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 subsided, 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 4 times with semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and the filtrate is concentrated. The residue is recrystallised from dichloromethane/petroleum ether to give yellow crystals with a melting point of 133°135°C.
Example d: Preparation of A —CH=CH-CN ·— · \ z •s* -CN (compound 10) 5431 1 3-(3-Methylphenyl)-4-cyanopyrrole 6.1 g of a 55% dispersion of sodium hydride in mineral oil are washed with petroleum ether and then 60 ml of dimethoxyethane and 10 ml of dimethylsulfoxide are added. With stirring, a solution of 14.3 g of 3-methylcinnamonitrile and 21.5 g of tosylmethyl isocyanide in 60 ml of dimethoxyethane and 10 ml of dimethylsulfoxide are added slowly dropwise at -25° to -20°C. The mixture is stirred for 1¾ hours in a thawing ice bathj then poured onto ice and extracted twice with ethyl acetate. The organic phase is washed with aqueous sodium chloride solution, dried over sodium sulfate, filtered and the filtrate is concentrated, to give 19 g of a viscous oil which, after recrystallisation from dichloromethane/ petroleum ether, yields crystalline 3-(3-methylphenyl)-4cyanopyrrole with a melting point of 1O9°-111°C.
Example e: Preparation of -► \ /’ il llCN (compound 1) 3-(3-Chlorophenyl)-4-cyanopyrrole a) 10.5 g of a 55% dispersion of sodium hydride in mineral oil are washed with petroleum ether and then 120 ml of tetrahydrofuran are added. A solution of 30.7 g of 3-chlorocinnamonitrile and 41 g of tosylmethyl isocyanide in 180 ml of tetrahydrofuran and 20 ml of dimethylsulfoxide is then added dropwise at-25° to -20°C, and the mixture is stirred for 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 sulfate and filtered.
The filtrate is concentrated and the residue is recrystallised from dichloromethane, affording crystalline 3-(3-chlorophenyl)-4-cyanopyrrole xri.th a melting point of 138°-130°C. 543 11 - 27 Example f; Preparation of ci \h=ch-cooch3 ci (compound 40)* zcooch3 —· II / 3-(3-Chlorophenyl)-4-methyloxvcarbonylpyrroJ.e With stirring, a solution of 136 g of methyl E/Z-3-(3-chlorophenyl)-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°-10°C from two drip funnels to 400 ml of tetrahydrofuran. The mixture is stirred for 1¾ hours at 0°-5°C and for % hour at 25°C, 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 under reflux and the mixture is left to stand overnight at -18°C and filtered, yielding 131 g of colourless product with a melting point of 187°-189°C.
Example g: Preparation of /\ , /X • · ·. A zcn 'V \il=CH-CN ·-{J « · (compound 63) With stirring, a solution of 128.8 g of 3-(2-pyridyl)-prop2-ene nitrile and 200 g of tosylmethyl isocyanide in 1500 ml of tetrahydrofuran and a solution of 140 g of potassium tert-butylate in 1500 ml of tetrahydrofurane are each added dropwise simultaneously from two drip funnels at -10° to 0°C to 200 ml of tetrahydrofuran. The mixture is stirred for 1 hour at 0°-5°C and for 1 hour at 25°C, then poured onto ice and extracted twice with ethyl acetate. The organic 543 11 - 28 phase is washed twice with aqueous sodium chloride solution, dried over sodium sulfate, stirred with silica gel and activated carbon, filtered and the filtrate is concentrated. The dark residue is crystallised from dichloromethane at -20°C, affording 75.5 g of brown crystals with a melting point of 148°-151°C.
All intermediates, also those listed in the table, can be prepared in corresponding manner. The compounds 8, 9, 11, 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. 543 i l - 29 Table of intermediates of the formula X ζ’Ίί l’rR z ·=· · · Com- R pound n R m.p- [°C] 1 3-Cl CN 138-140° 2 2,4-Cl2 CN 150-152° 3 4-C1 CN 153-155° 4 2-C1 CN 136-138° 5 4-F CN 137-138° 6 3-F CN 138-139° 7 3-Br CN 132-134° 8* 4-N(CH3)2 CN 180-182°9* 3-N(CH3)2 CN 144-146° 10 3-Ch3 CN 109-111° 11* 3-N02 CN 232-234’ 12 3-Cl?3 CN 87-89° 13* 3-006Η5 CN 124-126° 14* 3-0CH3 CN 125-128° 15* 3-0CHF2 CN 95-97° 16* 2-0CH3 CN 135-136° 17* 2-0CHF2 CN 105-107° 18*2-°c2h5 CN 134-135° 19* 2-0CH(CH V 3 2 CN 80-81° 20* 2-0CH2CH=CH2 CN 83-86° 21*2-°CH2C6H5 CN 91-93° 22* 2-OH CN 130-132° 23* 3-SCH3 CN 115-117° 543 1 1 Com- jound R n R 24 * 2-SCH3 ON 128-134° 25* 2-S0-CH3 ON 168-171° 26 * 2-S02-CH3 ON 150-152° 27 *2SC2H5 ON 121-123° 28 * 2-SO-C H ON 144-145° 29 * 2-S0,-C,H^ ON 141-143° 30* 2-s-cii(ch3)2 ON 121-123° 31 * 2-S0,-CH(CH^), CM 139-141° 32 * 2-S-C4H9-n ON 61-65° 33 * 2-SO-C.H -n ON 120-123° 34* 2-SO2C4Vn ON 151-152° 35* 2-C00C2H5 ON 130-132° 36* 3-C=C-C(0H)(CH3)z CN oil 37 * 3-0=0-11 CN 132-134° 38 * 2-0=0-0(OH)(CH3)2 CN 140-143° 39 * 2-C=C-H CN 109-115° 40* 3-C1 CO-OCH 187-189° 41 * 3-C1 cs o s 133-135° 42* 2-C1 no2 137-139° 43* 3-C1 p(o)(oc2h5)2 102-104° 44* 3-C1 p(o)(och3)2 120-122° 45* 2-C1 Ρ(θ)(002Η5)2 129-131° 46 * 2-01 p(0)(och3)2 146-148° 47*2,4-012 Ρ(0)(00,Ης), 89-90° 48* 3-01 C0-CH3 193-195° 49* 2-01 CO-CH3 198-201’ 50* 2,4-Cl2 CO-CH3 184-186° 51* H C0-CH3 156-158° 52* 3-CH3 C0-CH3 120-123° 4 311 Com- pound R n R m.p. [°c3 53* 4-Cl co-ch3 170-174° 54* 3,4-Cl2 co-ch3 162-164° 55* 4-0ClI3 co-ch3 179-182° 56*. 4-CH3 co-ch3 181-184° 57* 3-C1 so2-ch3 125-127° 58* 4-Cl SO -CH 154-156° 59* 2,4-Cl2 so2-c„3 174-177° 60· 3-M>2S02-CH3 133-135° 61* 2-C1, 4-N02 so2-ch3 197-200° 62* 2-C1s°2-ch3 178-180° 63*4C6K5 CN 249-254* 64* H CN 120-123° 65* H SOCH_ 2 3 Table of intermediates of the formula Com- pound R m.p. [°C] 66* 2-pyridyl 148-151° 67* 3-pyridyl 160-162° 68* 4-pyridyl 200-203° 69* 2-(5-chloropyridyl) 204-206° 70* 3-(2-chloropyridyl) 217-220° 71* 2 - ( 3 j 5 - d ichloropyddyi 176-179° 72* 2-thienyl 122-124° 73* 2-furyl 98-100° 74* 2-(N-methylpyrrole) 174-175° 75* 2-(6-methylthienyl) 108-110° 76* 2-(3-methylthienyl) 132-137° 4 3 1 1 β) Final products Example Hl: Preparation of (compound N-Fluorodichloromethylsulfenyl-S-(2-chlorophenyl)-4acetylpyrrole A solution of 6 ml (0.0575 mole) of fluorodichloromethylsulfenyl chloride in 20 ml of tetrahydrofuran is initially added dropwise at 3°-5°C to a solution of 11 g (0.05 mole) of 3-(2-chlorophenyl)-4-acetylpyrrole in 100 ml of tetrahydrofuran, followed by the dropwise addition of 8 ml (0.0575 mole) of triethylamine in 20 ml of tetrahydrofuran at 5°-8°C. The mixture 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 of 85°-87°C. A further crop of beige crystals (4.5 g) with a melting point of 84°-86°C is obtained after purification by chromatography over silica gel with dichloromethane/ petroleum ether (4:1) as eluant, concentration of the mother liquor and recrystallisation from diethyl ether/petroleum ether.
Example H2: Preparation of CH.
COCH, (compound 1.31) s-cci N-Trichloromethylsulfenyl-3-(3-methylphenyl)-4-acetylpyrrole 3.9 ml (0.036 mole) of trichloromethylmercaptan in 30 ml of tetrahydrofuran are initially added dropwise at 0°-5°C to a 4 311 solution of 6 g (0.03 mole) of 3-(3-methylphenyl)-4-acetylpyrrole in 100 ml of tetrahydrofuran, followed by the dropwise addition at 5°-8°C 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 purified by column chromatography over silica gel with dichloromethane/ petroleum ether (2:1) as eluant. Recrystallisation from petroleum ether yields 5 g of colourless crystals with a melting point of 58°-59°C.
Example H3: Preparation of (compound 1.15) N-Fluorodichloromethylsulfenyl-S-C2-ethoxyphenyl)-4-cyanopyrrole A solution of 4 ml (0.039 mole) of fluorodichloromethylsulfenyl chloride in 15 ml of ethyl acetate is initially added dropwise at 3°-7°C to a solution of 7.2 g (0.034 mole) of 3-(2-ethoxyphenyl)-4-cyanopyrrole in 100 ml of ethyl acetate, followed by the dropwise addition of 5.4 ml (0.039 mole) of triethylamine in 15 ml of ethyl acetate. The reaction mixture is stirred for 16 hours in a thawing ice bath and then filtered. The filtrate is concentrated and the residue is recrystallised from petroleum ether, affording 9.9 g of beige crystals with a melting point of 80°-83°C.
Example H4: Preparation of __ II 11 (compound 2.1) i S-CFC1, '2 - 34 N-Fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole 3.9 ml (0.037 mole) of fluorodichloromethylsulfenyl chloride in 10 ml of tetrahydrofuran are initially added dropwise at 0°-5°C to a solution of 5.2 g (0.33 mole) of 3-(2-furyl)-4cyanopyrrole in 100 ml of tetrahydrofuran, followed by the dropwise addition of 5.2 ml (0.037 mole) of triethylamine in 10 ml of tetrahydrofuran at 5°-8°C. The reaction 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. Recrystallisation from petroleum ether yields 7 g of yellowish crystals with a melting point of 74°-76°C.
Example H5: Preparation of I II —z II II V* .CN I ii (compound 2.3) Y x.—z II II .CN Ycci N-Trichloromethvlsulfenyl-3-(2-pyridyl)-4-cyanopyrrole A solution of 13.7 g of perchloromethylmercaptan in 20 ml of tetrahydrofuran is initially added dropwise at 0°-10°C to a solution of 16.9 g of 3-(2-pyridyl)-4-cyanopyrrole in 200 ml of tetrahydrofuran, followed by the dropwise addition of 17.4 ml of triethylamine in 20 ml of tetrahydrofuran. The mixture is stirred for 16 hours in a thawing ice bath and then concentrated. 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 semisaturated 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 of 30°C. The 4 3 1 i - 35 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 140°C.
Example H6: Preparation of Cl' • · I II ·. · ,Ζ \ Z \ /C00CH3 II II V* I H /\ Λ Λ ZC00Ctt3 Cl · II II • « (compound 1.34) γ i-CFCl„ N-riuorodichloromethylsulfenyl-S-C 3-chlorophenyl)-4-methoxycarbonylpyrrole A solution of 20.4 g of fluorodichloromethylsulfenyl chloride in 15 ml of tetrahydrofuran is initially added dropwise at 0°-5°C to a suspension of 23.6 g of 3-(3-chlorophenyl)-4methoxycarbonylpyrrole in 150 ml of tetrahydrofuran, followed by the dropwise addition of 12.2 g of triethylamine in 15 ml of tetrahydrofuran. The mixture is stirred for 16 hours in a thawing ice bath and then filtered. The filtrate is concentrated and the residue is crystallised from ethyl acetate/ petroleum ether, affording 28 g of colourless product with a melting point of 77°-79°C.
The following individual compounds of the formula I may be prepared in corresponding manner.
S4311 - 36 Table 1: Compounds of the formula V £r3 Com- R R- R, Tl.p.[°C] pound n 3 2 1.1 3-0CH3 CC12F CN oil 1.2 2-S-C2H5 CC12F CN 59-60° 1.3 2-S-C2H5 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 CC1 F CN 86-87° 1.7 2-SCH3 CC13 CN 125-127° 1.8 2-SC.H -n CC12F CN 44-46° 1.9 2-SC,Hn-n 4 9 CC13 CN 41-42° 1.10 2-0CH(CH3)2 CC12F CN 95-98° 1.11 2-0CH(CH3)2 cci3 CN 100-102° 1.12 2-benzyloxy CClgF CN 127-129° 1.13 2-benzyloxy CC13 CN 111-113° 1.14 2-Br CC12F CN 69-71° 1.15 2-0C2H5CC12F CN 80-83° 1.16 2-0C2h5 CC13 CN 107-110° 1.17 2-0CH2CH=CH2 Cd2F CN 66-68° 1.18 2-0CH2CH=CH2 CC13 CN 79-80° 1.19 3-C1 CG12F CN 87-89° 1.20 3-C1 CC13 CN 81-84° 1.21 2-C1 CC12F CN 59-61° 1.22 H cci2f co-ch3 43-45° 1.23 HCC13 co-ch3 86-88° 1.24 2-C1 CC12F co-ch3 86-88° 1.25 2-C1 CC13 co-ch3 104-109° - 37 Table 1; (continuation) Com- pound R nR3R2 m.p a°C] 1.26 4-CH3 CC12F C0-CH3 82-84° 1.27 4-0¾ CC13 C0-CH3 100-102° 1.28 3-C1 cci2f C0-CH3 63-6.4° 1.29 3-C1 CC13 CO-CH3 82-84° 1.30 3-CH3 cci2f C0-CH3 52 : 1.587X 1.31 3-CH3 CC13 C0-CH3 58-59° 1.32 4-och3 cci2f C0-CH3 52 tv : 1.5927 ης2: 1.6098 1.33 4-0CH3 CC13 C0-CH3 1.34 3-C1 CC12F C00CH3 77-79° 1.35 3-C1 CC13 COOCH3. 89-90° 1.36 3-C1 cci2f S07CHq oil 1.37 3-C1 CC13 SO^CH^ 104-107° 1.38 2,4-Cl2 CC12FS02CH3 106-108° 1.39 2,4-Cl2 cci3 S02CHq 111-113° 1.40 2-C1 cci2FS02CH3 86-88° 1.412-°C2H5 CC1?CHG17 CH 103° decompos . 1.42 2-C1CC13 CH 93-95° 1.43 2-0CH3 CC12F CH 39-42° 1.44 2-0CH3 cgi3 CH resin. 1.45 2-0C3H7-h cci2f CN 122-127° 1.46 2-0C3H7-n cci3 CN 1.47 2-0C4Hg-n CC12F CH 1.48 2-0C4Hg-n CC13 CH 1.492-SC3H7-ncc12f CH 1.502-SC3H7_n gci3 CH 1.51 2-CH cci2f CH 112-115° 1.52 j 2-CN CC13 CH resin 1.532,3-012 CC12F co-ch3 1.54 2,3-012 CC13 C0-CH3 C0-CH3 1.55 4-C1 cci2f - 38 Table I: (continuation) Com- R R, R, m.p. [°C] pound n 3 2 1.56 4-Cl CC13 CO-CH. J 1.57 2-SCH3 Cd2F C0-CH3 1.58 2-SCH3 cd3 CO-CH3 1.59 2-0CH3 Cd2F CO-CH3 1.60 2-OCH3 CC13 C0-CH3 1.61 2-CN CC12F CO-CH3 1.62 2-CN CC13 C0-CH3 1.63 4-N(CH3)2 CC12F co-ch3 1.64 4-N(CH3)2 CC13 CO-CH3 1.65 3-CF3 CC12F C0-CH3 1.66 3-CF3 Cd3 C0-CH3 1.67 2-Cl CC12F C00CH3 oil 1.68 2-Cl CC13 C00CH3 83-86° 1.69 4-Cl cci2f C00CH3 1.70 4-Cl CC13 C00CH3 1.71 3,4-Cl2 CC12F C00CH3 92-94° 1.72 3,4-Cl2 CC13 COOCHg 89-90° 1.73 4-CH3 CC12F C00CH3 1.74 4-C«3 CC13 COOCILj 1.75 4-OCH3 CC12F COOCH3 97-99° 1.76 4-OCH3 cci3 C00CH3 1.77 2-0CH3 CC12F C00CH3 1.78 2-0CH3 CC13 C00CH3 1.79 2-CN CC12F COOCH3 1.80 2-CN cci3 C00CH3 1.81 2-Cl CC12F conCch^ 1.82 2-Cl CC13 conCch^ 1.83 3-Cl CC12F conCch^ 1.84 3-Cl CC13 conCch^ 1.85 4-Cl CC1ZF con(ch3)2 4 3 11 - 39 Table 1; (continuation) Com- pound R nR3R2 m.p.[»c] 1.86 4-Cl CC13 CONCCH^ 1.87 4-CH3 CC12F CON(CH,)? 1.89 4-0Η3 cci3. C0N(CH3), 1.90 4-0CH3 CC12F con(ch3)9 1.91 4-0CH3 cci3 con (CH^ 1.92 2-0CH3 CC12F con(ch3)2 1.93 2-0CH3 cci3 CON (CH^ 1.94 2-0C2H5 CC12F CON(CHq), 1.95 2-0C2H5 ggi3 CONCCH,), 1.96 2-CN cci2f conCch^ 1.97 2-CN CC13 ΟΟΝζΟΗ^ 1.98 2-C1 CC13 SO,CH, 118-121° 1.99 4-Cl CC12F SO CH 1.100 4-Cl CC13 so2ch3 1.101 4-CH3 CC12F so2ch3 1.102 4-CH3 cci3 SO,CH, 1.103 4-och3 cci2f SO,CH, 1.104 4-0CH3 CC13 SO CH 1.105 3,4-Cl2 cci2f 1.106 3,4-Cl2 cci3 1.107 2-0CH3 cci2f S02ch, 1.108 2-0CH3 CC13 SO?CHq 1.109 2-SC.H -n 4 9 CC12F SO?CH, 1.110 2-SC.H -n 4 9 cci3 SO?CHq 1.111 2-CN CC12F SO CH, 1.112 2-CN CC13 J SO CH, 1.113 1.114 2-C1 2-C1 cci2f CC13S02N(CH3)2 S02K(CH3)2 103-105° 1.115 3-C1 cci2f s°2n(ch3)2 543 1 1 - 40 Table 1: (continuation) Com- R R, R, m.p.[°c] pound n 3 2 1.116 3-Cl CC13 so n(ch3)2 1.117 4-CH3 cci2f so,n(ch3)2 1.118 4-CH3 CC13 so2n(ch3)2 1.119 4-0CH3 cci2f so2n(ch3)2 1.120 4-OCH Cd3 so,n(ch3)2 1.121 4-C1 CC12F so n(ch3)2 1.122 4-C1 CC13 so2n(ch3)2 1.123 2-C1 CC12P -p(o) (OC9H3)9 oil 1.124 2-C1 CC13 -f(0)(0C2h5)2 oil 1.125 3-Cl cci2f -P(O) (OC9I1S), 1.126 3-Cl CC13 -P(0) (ΟΟ,Ης), 1.127 4-C1 cci2f -P(0)(0C9Hq), 1.128 4-C1 CC13 -p(o) (oc2h5)9 1.129 2-C1 -Cd2F -N02 · 85-87° 1.130 2-C1 -CC13 -N02 1.131 3-Cl -Cd2F -NO 1.132 3-Cl -Cd3 1.133 2-C1 -CC12F tCH3 1.134 2-C1 -CC13 -JCH3 1.135 2-C1 -CC12F T-3 1.136 2-C1 cci9-chci9 CN 123-125° 1.137 4-C6H5 CC13 CN 168-175° 1.138 4-C6H5 cfci2 CN 173-177° 1.139 H cci2f CN 96-98° 1.140 H cci3 CN 102-103° 1.141 H cfci2SO2CH3 1.142 3-Cl CC1„CHC1 2 2 COOCH3 S 4 3 1! - 41 Table 1; (continuation) Com- pound R nR3R2 m.p(’C] 1.143 2-Br cci3 CN 114-115 1.144 2~CH3 cci2f C0CH3 85-89° 1.145 2-CH3 Cd3 COCH3 94-99° 1.146 2,3-Cl2 CC12F CN 105-107° 1.147 HCC12F so N(CH ) 124-126° 1.148 HCCi2f CON(CH ) oil 1.149 H CC13 J 2 CON(CH ) 75-79° 1.150 2,3-Cl2 cci2f cooch3 56-61° 4 3 1 1 - 42 Table 2: Compounds of the formula Com- R.Ro R„ m.p. [OC] pound 1 2 3 2.1 2-furyl CN CC12F 74-76’ 2.2 2-pyridyl ON CC12F 92-100’deocmp, 2.3 2-pyridyl CN CC13 131-140°d2anp, 2.4 2-pyridyl cooch3 CC12F 2.5 2-pyridyl cooch3 CC13 2.6 2-pyridyl conCch^ CC12F 2.7 2-pyridyl conCch^ cci3 2.8 3-(2-chlaropy r i dy 1) CN cci2f 2.9 3-(2-ch]orapy r idy 1) CN CC13 142-144’ 2.10 3-(2-diloropyridyl) CO-CH3 cci2f 2.11 3-(2-chloropyridyl) CO-CH3 cci3 2.12 2-(6-chloropyridyl) CN cci2f 2.13 2-(6-chloropyridyl) CN cci3 2.14 2-(6-chl or opy r i dy 1) C00CH3 cci2f 2.15 2-(6-cKLoropyridyl) C00CH3 cci3 2.16 2-thienyl CN CC1 F 72-77’ 2.17 2-thienyl CN CClj 85-89’ 2.18 2-thienyl conCch^ cci2f 2.19 2-thienyl CONiCH^ CC13 2.20 2-pyridyl CN CC1,-CHC19 103-106’ 2.21 3-pyridyl CN cci2f 123-126 ’cfecomp. 2.22 3-pyridyl CN CC13 decanp. from 156’ 2.23 ^-pyridyl CN CC12F decamp, fran 145° 2.24 4-pyridyl CNCC13 decomp. firm 154° 543 1 1 Formula Lion Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) FI Emulsifiable concentrates a) b) c) a compound of the tables 25 7 ; 4o % 50 . 7= calcium dodecylbenzenesulfonate 5 7 ; 8 % 6 % castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 7 - tributylphcnol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4 % cyclohexanone - 15 % 20 % xylene mixture 65 ' 1 25 % 20 % Emulsions of any required concentration can be produced from such concentrates by dilution with water.
Solutions a) b). c) d) a compound of the tables 80 7, 10 % 5 7> 95 7a ethylene glycol monomethyl ether 20 7. - - - polyethylene glycol MS 400 - 70 % - - N-methyl-2-pyrrolidone - 20 % - - epoxidised coconut oil - - 1 % 5 7a ligroin (boiling range 160-190°) - - 94 7= - These solutions are suitable for application in the form of microcrops. 4 3 11 F3 Granulates a) b) a compound of the tables '5 % 10 7 kaolin 94 % - highly dispersed silicic acid 1 % - attapulgite - 90 % The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. F4 Dusts a) . b) a compound of the tables 2 7 5 % highly dispersed silicic acid 1 % 5 % talcum 97 % - kaolin - 90 7» Ready for use dusts are obtained by intimately mixing the carriers with the active ingredient.
Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight) F5 Wcttable powders a) b) c) a compound of the tables 25 % 50 % 75 % sodium lignosulfonate 5 7, 5 7, sodium laurylsulfate 3 7 - 5 7 sodium diisobutylnaphthalenesulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 7 highly dispersed silicic acid 5 7 10 % 10 % kaolin 62 % 27 7 4 311 - 45 The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
F6 Emulsifiable concentrate a compound of the tables 10 7. octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (36 moles of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
F7 Dusts a) b) a compound of the tables 5 % 8 % talcum 95 °k kaolin - 92 7.
Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
F8 Extruder granulate a compound of the tables lo % sodium lignosulfonate 2 % carhoxymethylcellulose 1 % kaolin 87 7.. 543 11 - 46 The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
F9 Coated granulate a compound of the tables 3 % polyethylene gylcoL MG 200 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with 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 7„ sodium- lignosulfonate 10 % carboxymethylcellulose 1 % Yo aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 32 Y„.
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Both the final products of the formula I and the intermediates of the formulae I and II' can be formulated in accordance with Examples Fl to F10. 4 311 - 47 Biological Examples Example BI: Action against 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 ingredient (0.06 %) . After 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 Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.006% based on the volume of the soil). After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The plants are then incubated for 48 hours at 95-100 % relative humidity and about 20°C and then stood in a greenhouse at about 22°C. Evaluation of rust pustule development is made 12 days after infection. Compounds of tables 1 and 2 are very effective against Puccinia fungi. 100 °L Puccinia attack is found on untreated and infected control plants. Among others, compounds 16, 1.24, 1.26, 1.38, 1.75 and 1.144 inhibit fungus attack to 0-5 %.
Example B2: Action against Cercospora arachidicola in groundnut plants Residual-protective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (concentration 0.006%) and infected 543 1 1 - 48 48 hours later with a conidia suspension of the fungus. The infected plants are incubated 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.
Compared with untreated and infected controls (number and size of the specks = 100%), Cercospora attack on the groundnut plants treated with compounds of Tables 1 and 2 is greatly reduced. For example, compounds 23, 1.11, 1.15, 1.17, 1.24, 1.26, 1.40, 1.75 and 1.44 inhibit speck development almost completely (8%) in the above tests. Compound 24 has this activity even when diluted to a concentration of 0.002%.
Example B3: Action against Ervsiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 %) prepared from the active ingredient formulated as a wettable powder. The treated plants are dusted with conidia of the fungus after 3-4 hours. The infected barley plants are then stood in a greenhouse at about 22°C. The fungus attack is evaluated after 10 days. h) Systemic action Barley plants about 8 on in height are treated with a spray mixture (0.006 %, based on the volume of the soil) preprared from the active ingredient formulated as wettable powder. Care is taken that the spray mixture does not come in contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a conidia suspension of the fungus. The infected barley plants are then stood in a greenhouse at about 22°C and 4 311 - 49 evaluation of fungus 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 inhibit attack almost completely (0-5%). The most active compounds are compounds 1.24 and 1.36.
Example B4: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.06%) prepared from a wettable 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°-24°C. 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, 1.24, 1.26, 1.28, 1.34, 1.36, 1.40, 1.52, 1.144, 2,3 and others inhibit attack to less than 10%. Venturia attack is 100% on untreated and infected controls. Compounds 1.24, 1.26, 1.40 and 2.3 are still fully effective (0%, attack) when diluted to a concentration of 0.006%.
Example B5: Residual protective action against Botrytis cinerea on beans Bean plants about 10 cm in height are sprayed with a spray mixture (0.02%) prepared from the active ingredient formulated as wettable powder. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100%, relative humidity and 21°C, and evaluation of the fungus attack is then made. The compounds of Tables 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, 4 311 - 50 1.19, ΐ.20, 1.34 and 2.1 are fully effective at a concentration of 0.027, (0 to 57. attack). Attack on untreated and infected plants is 1007,. The intermediates 16 and 24 are also equally effective.
Example B6: Action against Botrytis cinerea on apples Artificially 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 about 20°C.
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 fungus attack almost completely. The intermediates 16 and 24 are also equally effective.
Example B7: Action against Alternaria solani on tomato plants Tomato plants are sprayed, after 3 weeks' cultivation, with a spray mixture prepared from the active ingredient formulated as a wettable powder (0.06%). After 24 hours, the treated plants are infested with a conidia suspension of the fungus. Evaluation of the fungus attack is made after incubation of the infested plants for 8 days at 18° to 22°C and high humidity. Compounds of Tables 1 and 2 effect a strong reduction of Alternaria attack. For example, compounds 1.23, 1.24 and 1.26 inhibit attack completely (0.5%). ' 4 3 1 X - 51 Example B8: Action against 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 plants 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 24°C and 95°-100°C relative humidity. Compounds of the formula I effect good inhibition of Piricularia attack. For example, compounds 1.23, 1.24, 1.26, 1.75 and 1.144 inhibit attack to less than 10%.
Example B9: Grain preservative test a) Short-term test against mould fungi 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 of an aqueous suspension, emulsion or solution. The application of active ingredient is made so as to give a concentration of 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 for 2-3 weeks at about 20°C, a mixed population of mould fungi develops spontaneously on the maize samples treated only with water. There is no need to make an artificial infection. The effectiveness of the compounds of the formulae I and II' is evaluated by determining the extent of fungus development after 3 weeks. b) Long-term test against mould fungi on moist maize X The maize samples exhibiting no fungus attack after 3 weeks are incubated for a further two months. A visual assessment is made after each month, applying the same criteria as in test a) 4 311 - 52 T1 The test procedure is in principle the same ;is in ;i) and b), except that the text compound of the formula I or II' is used in concentrations of 2000, 600 and 200 ppm a.i. (based on the dry weight of the maize) over 6 months.
In all three tests a), bi) and bll), the formation 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 formula I of all Tables.
For example, compounds 16, 24, 1.14 and 1.15 in all three tests a), bl) and bll) inhibit mould fungus attack almost completely (0-57. attack) at a test concentration of 600 ppm a.i.
Treatment with compounds of the formulae I and II' in similar tests using, alternatively, cereals (oats), hay, carrot chips or broad beans instead of fodder maize, give similar results of long-term protection over several months.
Example BIO: Action against Tilletia caries Tilletia spores are suspended for 15 minutes in a spray mixture containing 600 ppm of active ingredient. The spore/ compound mixture is pipetted dropwise onto the surface of finely sieved, moistened soil in Petri dishes. These prepared dishes are then kept at high humidity (95-1007,) and 20°C. Spore formation is evaluated microscopically after about 10 days. The action of the test compounds is determined in accordance with the number and length of the sporocysts. Compounds of the formulae I and II1 are very effective against Tilletia caries fungi. For example, compounds 1, 4, 6, 7, 10, 24, 1.6, 1.14, 1.15, 1.17, 1.21, 1.24, 1.26, 1.28, 1.36, 1.40, 1.52 and 2.3 inhibit the formation of sporocysts completely.

Claims (26)

What is claimed is: R -.1 II
1.A compound of the general formula 1 'V I SR„ wherein R^ 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)1, wherein X, Y and Z are each independently selected from the group consisting of hydrogen, halogen, Cj-C^alkyl, C^-Cghaloalkyl, di(C^C^alkyl)amino, nitro, cyano, -COO(C^-C^alkyl), -CON(C^C^alkyl^ and the group -E-R^, where E is -0-, -S-, -S0or “SO^-, R^ is C^-C^alkyl which is unsubstituted or substituted by C^-C^alkoxy, Cg-C^alkenyl which is unsubstituted or substituted by halogen, Cg-Cgalkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CHg-tX.Y,Z(phenyl)]; U, V and W are each independently selected from the group consisting of hydrogen, halogen and C^-C^alkyl, R 2 is -COO(C 1 -C 6 alkyl) , -COiC^-C^alkyl), -CO-NiC^-Cgalkyl^, cyano, nitro, -SC^-iC^-Cgalkyl), -P(0)-(C^-Cgalkoxy)2, -SO-(C^-Cgalkyl) or -SOg-NiC^-Cgalkyl^! and Rg is Cj-Cghaloalkyl.
2. A compound of the formula I according to claim I, wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)], tX,Y,Z(biphenyl3-yl)], tX,Y,Z(biphenyl-2-yl)], IU,V,W(2-pyridyl)], [U,V,W(3 pyridyl)], [U,V,W(4-pyridyl)], [U,V,W(2-furyl)1, (U,V,W(3furyl)1, [U,V,W(2-thienyl)] or [U,V,W(3-thienyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, C^-Cgalkyl, C^-Cghaloalkyl, 5 4 311 - 54 dl(C^-G 3 a]kyl)aininu, nitro, cyano, -COO(Cj-Chalky1), -CON(Cj-Cyilkyl) , Cj-C^nlkoxy, C^-C^alkylLhlo, C^-Cyi Ikeny1oxy, C^-C^haloalkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, halogen or C^-C^alkyl; R 2 ΐ θ “COOCC^-C^alkyl), -CO-CC^-C^alkyl), -CO-N(C 1 -C 3 alkyl) 2> cyano, nitro, -S0 2 (C^-C 3 alkyl), -P(0)(C^-C 3 alkoxy) 2 or -SO 2 -N(C 1 -C 3 alkyl) 2 ; and R 3 is C^-C 3 haloalkyl.
3. A compound of the formula I according to claim 1, wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)], [X,Y,Z(biphenyl-4-yl)J, (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 hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, -N(CH 3 ) 2 , -N(C 2 H 3 ) 2> -COOCH 3 > -COOC 2 H 3 , -CONCCH^Y C^-C^alkoxy, C^-C^alkylthio, C^j-C^alkenyloxy, C^-C^haloalkenyloxy, phenoxy and benzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C^-C^alkyl; r 2 is -cooch 3 , -cooc 2 h 5> -coch 3 , -coc 2 h 5 , -con(ch 3 ) 2 , -C0N(C 2 H 3 ) 2 , cyano, nitro, -SO 2 GH 3> -δΟ,,Ο,,Η^, -P(0)(OCH 3 ) 2> -P(O)(0C 2 H 5 ) 2 , -SO-CH 3 , -SO 2 -N(CH 3 ) 2 or -SO 2 -N(C 2 H 5 ) 2 ; and R 3 is C^-C 2 haloalkyl.
4. A compound of the formula I according to claim 3, wherein R^ 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)I, wherein X, Y and Z are each independently selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, C^-C 3 alkoxy and C^-Cgalkylthio; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl or ethyl; R 2 is -C00CH 3> COCH 3 > N0 2 and CN; and R 3 is CFCl 2 or CCl 3<
5. 4 3 11 - 55 5. A compound of the formula I according to claim 2, wherein R^ is a fragment selected from the group consisting of [X,Y,Z(phenyl)] or [U,V,W(2-furyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl, N(CH 3 ) 2> -COOCH^, -CON(CH 3 ) 2> C^-C^alkoxy, C^-C^alkylthio, C^alkenyloxy, phenoxy and henzyloxy; U, V and W are each independently selected from the group consisting of hydrogen, chlorine, bromine and C^-C 2 alkyl; R 2 is -COOCH^, -COCH 3> -CON(CH 3 ) 2 > cyano, nitro, -SO 2 -CH 3 , -P(0)(OC 2 H 5 ) 2 or -SO 2 -N(CH 3 ) 2 ; and R g is CCl 3> CC1 2 F, CC1 2 H, CC1H 2> CF 3> CF 2 H, C 2 C1 5 orCCl 2 CHCl 2 .
6. A compound of the formula I according to claim 5, wherein R^ is the fragment tX,Y,Z(phenyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, chlorine, bromine, methyl, C^-C^alkoxy, C^-C^alkylthio and C 3 alkenyloxy; R 2 is -C0CH 3 or cyano; and R 3 is CCl 3 , GC1 3 F or CC1 2 CHC1 2 .
7. A compound of the formula I according to claim 3, selected from the group consisting of: N-fluorodichloromethylsul£enyl-3-(2-allyloxyphenyl)-4-cyanopyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-cyanopyrrole, N-fluorodichloromethylsulfenyl-3-phenyl-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(4-methylphenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-acetylpyrrole, N-fluorodichloromethylsulfenyl-3-(3-methylphenyl)-4-acetylpyrrole, J '1 J i i -56N-fluorodichloromethylsulfenyl-3-(3-chlorophenyl)-4-methoxycarbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-methoxycarbonylpyrrole, N-fluorodichloromethylsulfenyl-3-(2-chlorophenyl)-4-nitropyrrole, N-fluorodichloromethylsulfenyl-3-(2-furyl)-4-cyanopyrrole, N-trichloromethylsulfenyl-3-(2-pyridyl)-4-cyanopyrrole, N - fluorodichloromethylsulfenyl-3-(2,3-dichlorophenyl)-4cyanopyrrole,
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 R — t-ft 1 II II 2 (II) Y I H wherein R^ and Rg are as defined for formula I, at the pyrrole nitrogen with a reactive acid derivative of a sulfenic acid of the formula III r 3 -s-oh (III) wherein R 3 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. 5 4 3 1 t - 57
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-dimethylaminopyridine 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 microbicidal composition for controlling phytopathogenic microorganisms or for protecting living plants from attack by such microorganisms and/or for preserving perishable storable goods of vegetable or animal origin, which composition contains as active component at least one compound as defined in claim 1.
17. A composition according to claim 16, which contains as active component at least one compound as defined in any one of claims 2 to 6.
18. A composition according to claim 16, which comprises 0.1 to 99% of a compound of formula I, 99.9 to 1% of a solid or liquid adjuvant and 0 to 25% of a surfactant.
19. A composition according to claim 18, which comprises 0.1 to 95% of a compound of formula I, 99.8 to 5% of a solid or liquid adjuvant and 0.1 to 25% of a surfactant.
20. A method of controlling phytopathogenic microorganisms or of protecting cultivated plants from attack by said micro organisms,which method comprises applying to said plants, to parts of plants or to the locus thereof a microbicidally - 58 effective amount of a compound of the formula I as defined in claim 1.
21. A method of preserving or protecting storable goods of vegetable or animal origin from attack by harmful microorganisms, which method comprises treating said goods with a microbicidally effective amount of a compound of the formula 1 according to claim 1,
22. A method according to claim 21, wherein the storable goods are products of meat or fish processing.
23. A method according to claim 21, wherein the storable goods are harvested plants or parts of plants whose natural life cycle has been interrupted.
24. A pyrrole derivative of the formula II 1 (IV), V I H wherein R^ 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)] or [U,V,W(thienyl)], wherein X, Y and Z are each independently selected from the group consisting of hydrogen, C^-C^alky1, C|-C 3 haloalkyl, di(C 1 -C^alkyl)amino, nitro, cyano; -COOCC^-C^alkyl), -CONCC^-C^alky!^ and the group -E-R^, wherein E is -0-, -S-, -SO- or -S0 2 -, R^ is C^-C^alkyl which is unsubstituted or substituted by C^-C^alkoxy, C^-C^alkenyl which is unsubstituted or substituted by halogen, C^-C^alkynyl which is unsubstituted or substituted by halogen or hydroxy, or is [X,Y,Z(phenyl)] or -CH 2 -tX,Y,Z(phenyl)], and U, V and W are each independently selected from the group consisting of hydrogen, halogen and C^-C^alkyl; R 2 is -COOiCi-C^alkyl), -CO-iC^-C^alkyl), 5 4 311 - 59 -C0-N(C^-C A alkyl)2> nitro, -SC^-(C^-C^alkyl), -P(O)(C^-C^alkoxy)2> -SO-iG^-C^alkyl) or -SOg-NCC^-C^alkyl^, and, where R^ is a fragment (X,Y,Z(biphenyl)], [U ,V,W(pyridyl)], (U,V,W(furyl)] or [U,V,W(thienyl)], R2 is additionally cyano.
25. 3-(2-Methylthiophenyl)-4-eyanopyrrole according to claim 24.
26. 3-(2-Methoxyphenyl)-4-cyanopyrrole according to claim 24 -Ϊ1 <-x^· i r.oa.i, ?1ίι$·. '.M iijfi, 1 ?‘G?;’:TS ΓΟΚ THE ASPLICAJiS.
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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
CA1135705A (en) * 1978-07-20 1982-11-16 Jens-Uwe Bliesener N-arylsulfonylpyrroles, their preparation, and therapeutic agents containing these compounds
DE2843644A1 (en) * 1978-10-06 1980-04-24 Basf Ag 4-NITRO-2-TRICHLORMETHYLPHENYLSULFENAMIDE

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IL67498A0 (en) 1983-05-15
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ES8401938A1 (en) 1984-01-16
EP0096142A2 (en) 1983-12-21
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CA1197248A (en) 1985-11-26
EP0096142A3 (en) 1984-02-22
PT75998B (en) 1985-12-03
ES518339A0 (en) 1984-01-16
AU9162782A (en) 1983-06-23
AU560531B2 (en) 1987-04-09
EP0096142B1 (en) 1989-01-18
ZA829269B (en) 1983-10-26
JPS58116462A (en) 1983-07-11
IL67498A (en) 1986-08-31
PT75998A (en) 1983-01-01
DE3279368D1 (en) 1989-02-23
ATE40114T1 (en) 1989-02-15

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