IL96896A - Cyclohexylacetic acid derivatives and their use as fungicides and insecticides - Google Patents

Cyclohexylacetic acid derivatives and their use as fungicides and insecticides

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IL96896A
IL96896A IL9689691A IL9689691A IL96896A IL 96896 A IL96896 A IL 96896A IL 9689691 A IL9689691 A IL 9689691A IL 9689691 A IL9689691 A IL 9689691A IL 96896 A IL96896 A IL 96896A
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phenyl
single bond
pyridyl
chloro
methyl
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IL9689691A
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Basf Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/61—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a ring other than a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/53—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing 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
    • 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
    • A01N37/36—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pyridine Compounds (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Quinoline Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Unsaturated cyclohexylacetic acid derivatives of the formula I <IMAGE> in which U is =NOCH3, =CHOCH3, =CH2, =CH-CH3, =CH-CH2-CH3, =N-NH-CH3 or =CH-S-CH3, n denotes the numbers 0 to 10, A denotes hydrogen or the optionally substituted radicals alkyl, cycloalkyl, aryl or hetaryl, and, if n = 0, X is a single bond or oxygen or sulphur, and the phytophysiologically acceptable acid addition products and base addition products thereof, and the fungicides and insecticides containing these compounds.

Description

96896/2 Ira ¾nn>v>m _vv>i.Np>opm p>.< nsmn p\» nmn HP nn in o>p-ini Jii>noa > oipD Unsaturated cyclohexylacetic acid derivatives and their use as fungicides and insecticides BASF AKTIENGESELLSCHAFT C: 82474/8 - 1 - 96896/2 The present invention relates to acyclohexylacetic acid derivatives having a fungicidal and insecticidal action, to fungicides and insecticides containing these compounds, and to a method of combating fungi.
Fungicidal ortho-substituted phenyl-B-methoxy acrylates and analogues are described in US-A 4,822,908, EP-A 178 826 (corresponding to IL 76851), EP-A 254 426 and 299 694.
We have found that unsaturated cyclohexylacetic acid derivatives of the formula I where U is =0, =N0CH3, =CH0CH3, =<¾, =CH-CH3, =CH-CH2-CH3, =N-NH-CH3 or =CH-S-CH3 , n is from 0 to 10, A is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl or hetaryl, and X is a single bond in the case where n = 0 , and oxygen, sulfur or a single bond in the case where n is not 0 , and the plant-compatible acid-addition products and base- addition products thereof have a high fungitoxic and insecticidal action and very good plant compatibility.
Examples of acids for acid-addition products are mineral acids, eg. hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid or nitric acid, or car- boxylic acids, such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, succinic acid, tartaric acid, citric acid or salicylic acid, p- toluenesulfonic acid, dodecylbenzenesulfonic acid, or proton-acidic compounds in general, eg. saccharin.
Examples of bases for base-addition products are potassium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate and ammonium hydroxide.
The novel compounds of the formula I may be produced as mixtures of stereoisomers (E/Z isomers, diastereomers or enantiomers ) , which can be resolved into the individual components in a conventional manner, for - 2 - 96896/2 example by crystallization or chromatography. The individual isomers and their mixtures can be used as fungicides or insecticides and are included in the invention.
If U can occur in syn/anti-isomers , the invention relates to all the isomers, in particular the anti-isomers .
In particular, the invention relates to all the diastereomers , in particular those having a bis-equatorial arrangement at the two centers of chirality in the cyclohexane ring.
U is =0, =N0CH3, =CH0CH3, =(¾, =CH-CH3, =CH-CH2-CH3, =N0CH3, =CH-0CH3 or =CH-CH3, preferably =N0CH3. n is from 0 to 10, in particular from 0 to 5, preferably 0, 1, 2 or 3.
A is, for example, a saturated or unsaturated, straight-chain or branched hydrocarbon radical having from 1 to 6, in particular from 1 to 4, carbon atoms or a C3-Ce-cycloalkyl radical, or phenyl, thienyl, furyl, pyrryl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, indolyl, benzimidazolyl, quin-azolyl, or quinoxalyl, the cycloalkyls, alkyls, aryls or hetaryls mentioned being unsubstituted or substituted by from 1 to 3 identical or different substituents from the group comprising halogen, eg. fluorine, chlorine, bromine or iodine, Ci-Ce-alkyl, Cx-Cg-alkyl-sulfinyl, cyano, hydroxyl, nitro, C^Ca-alkoximino, Cx-Ca-alkoxy, phenyl, Ci-Ct-haloalk l, Ci-Ca-alkenyloximino, formyl, Cx-C8-alkylcarbonyl or Ci-Ca-alkoxycarbonyl , or phenyl which is substituted by from 1 to 3 identical or different substituents from the group comprising halogen, eg. fluorine, chlorine, bromine or iodine, Ci-Ca-alkyl, Cx-C8-alkylthio, C^-Ce-alkylsulfinyl, cyano, hydroxyl, nitro, Ci-Ca-alkoximino, Ci-Cg-alkoxy, phenyl, Cx-C^halo-alkyl, .
A is preferably a saturated or unsaturated, - 3 - O.Z. 0050/41358 straight-chain or branched hydrocarbon radical having from 1 to 6, in particular from 1 to 4, carbon atoms or a C3-C6-cycloalkyl radical, or phenyl, pyridyl or benz-imidazolyl .
The novel compounds can be prepared, for example, by the following processes: Methyl o-cyclohexen-l-yl-o-oxoacetate 1 (G. Neef et al., THL 1977 (32), 2825-8) is reacted with a thiol 2, if necessary with base catalysis, to give a thioether 3 (Y. Vankar et al., J. Chera. Research 1989, 178-179) (scheme 1) .
Scheme 1 A and n are as above.
Substituted methyl a-oxoacetates 3 are converted into the active ingredients 4 by reaction with CH3-0-NH3Cl or H2N-NH-CH3 (scheme 2).
Scheme 2 U is =N0CH3 or =N-NHCH3, and A and n are as above.
The methyl a-octoacetates 3 can be used to prepare the compounds 5 by a Wittig reaction with (C6H3)3P+-CH3X~, (CeHsJaP^CHz-CHsX", (C6H5) 3P+-CH2-CH2-CH3X" (X = halogen) or (C6H3)3P+-CH2-0-CH3cr, (C6H5)2P(=0)-CH2-0-CH3 or by Peterson olefin formation using (CH3)3Si-CH2-0-CH3 (scheme 3).
Scheme 3 - 4 - O.Z. 0050/41358 U is =CH2/ =CH-CH3, =CH-CHZ-CH3 or =CHOCH3, and A and n are as above.
The thioenol ethers 7 can be obtained from the enol ethers 6 by reaction with methyl mercaptan (EP 178 826; scheme 4) .
Scheme 4 6 .7 A and n are as above.
The Examples below illustrate the preparation of novel compounds.
EXAMPLE 1 Methyl a-( 2-benzylthiocyclohexyl) -a-oxoacetate (Compound No . 1.15) 2 g (12 mmol) of methyl a-cyclohexenyl-a-oxo-acetate, 1.5 g (12 mmol) of benzyl mercaptan and 1 g (10 mmol) of triethylamine in 10 ml of methylene chloride are stirred at room temperature (20°C) for 15 hours.
After the stirring period, water is added to the batch, and the aqueous phase is extracted with methylene chloride. The organic phase is extracted with water, dried over MgS04 and evaporated.
Chromatographic purification of the crude product gives 2.3 g (66 %) of the title compound as a pale yellow oil.
IR (cm"1): 2933, 1727, 1277, 1069.
EXAMPLE 2 Methyl a-( 2-benzylthiocyclohexyl)-a-oxoacetate O-methyl oxime (Compound No. 2.15) 2.3 g (7.9 mmol) of methyl a-( 2-benzylthiocyclohexyl) -a-oxoacetate (Example 1) and 0.66 g (8 mmol) of methoxyamine hydrochloride in 15 ml of methanol are stirred at room temperature for 15 hours. 5 - O.Z. 0050/41358 Water is added to the reaction mixture, and the aqueous phase is extracted with ether. The organic phase is washed with water, dried over MgS04 and evaporated. Chromatographic purification of the crude product gives 1 g (40 %) of the title compound as a pale yellow oil. IR (cm"1): 2935, 1726,1151, 1042. 890828 6 O.Z. 0050/41358 Table 1 No. A-X-(CH2)n mp. IR: v(cm-1) 1. 1 H 1. 2 methyl 1. 3 ethyl 1. 4 isopropyl 1. 5 butyl 1. 6 sec. -butyl 1. 7 t-butyl 1. 8 isobutyl 1. 9 pentyl 1. 10 pivaloyl 1. 11 hexyl 1. 12 octyl 1. 13 decyl 1. 14 phenyl oil 2935, 1729, 1276, 1069 1. 15 benzyl oil 2933, 1727, 1277, 1069 1. 16 phenylethyl 1. 17 phenylpropyl 1. 18 phenylpentyl 1. 19 1-naphthyl 1. 20 2-naphthyl 1. 21 2-bromophen l 1. 22 3-bromophenyl 1. 23 4-bromophenyl 1. 24 2-chlorophenyl 1. 25 3-chlorophenyl 1. 26 4-chlorophenyl 1. 27 2-fluorophenyl 1. 28 3-fluorophenyl 1. 29 4-fluorophenyl 1. 30 2-methylphenyl 1. 31 3-methylphenyl 1. 32 4-methy I henyl 1. 33 2-ethyl-phenyl 1.34 3-ethyl-phenyl 1. ,35 4-ethyl-phenyl 890828 7 O.Z. 0050/41358 Table 1 (contd.) NO. A-X-(CH2)n «"p. 1 .36 2-i so-propy 1 -phen 1 1 .37 3- i so-prop 1-pheny1 1 .38 4-i so-prop 1-pheny 1 1 .39 2-tert . -buty1-pheny I 1 .40 3-tert . -buty 1-pheny I 1 .41 4-tert . -buty I-phen I 1 .42 4-butyl-pheny 1 .43 4-hexyl-phenyl 1 .44 4-nonyl-phenyl 1 .45 4-decy 1-pheny1 1 .46 2-methoxy-phenyl 1 .47 3-methoxy-phenyl 1 .48 4-methoxy-pheny 1 1 .49 2-tri uoromethy1-pheny1 1 .50 3-trifluoromethyl-phenyl 1 .51 4-trif uoromethy 1-pheny1 1 .52 2-formylphenyl 1 .53 3- ormylphenyl 1 .54 4-formy phenyl 1 .55 2-a yl-0-N=CH-pheny1 1 .56 3-allyl-0-N=CH-phenyl 1 .57 4-a11y 1 -O-N-CH-pheny1 1 .58 2-nitro-pheny 1 .59 3-nitro-pheny I 1.60 2, 4-dichlorophenyl 1 .61 2, 5-dichlorophenyl 1 .62 2, 6-dichlorophenyl 1 .63 3, 4-dichlorophenyl 1 .64 2, 3-dichlorophenyl 1 .65 3, 5-dichlorophenyl 1 .66 2, 3, 4-trichlorophenyl 1.67 2, 4, 5-trichlorophenyl 1 .68 2, 4, 6-trichlorophenyl 1 . 69 2, 3, 4, 6-tetrachloropheny 1 1 . 70 2, 3, 4, 5, 6-pentachlorophenyl 1 . 71 2, 3, 4, 5-tetrafluorophenyl 1 . 72 2, 3, 5, 6-tetrafluorophenyl 1 . 73 2, 3, , 5, 6-pentafluorophenyl 890828 8 O.Z. 0050/41358 Table 1 (contd.) NO • A-X-(CH2)n mp. I 1. 74 2-chloro, b- fluorophenyl 1. 75 3-chloro, 4-f luorophenyl 1. 76 2-chloro, 6-methyl -phenyl 1. 77 4-chloro, 2-methyl-phenyl 1. 78 2, 4-dichloro, 5-methyl -phenyl 1. 79 4-chloro, 2, 5-dimethyl-phenyl 1. 80 4-bromo, 2-methyl-phenyl 1. 81 3, 5-bistrif uoromethyl-phenyl 1. 82 2, 3-dimethyl-phenyl 1. 83 2, 4-dimethy -phenyl 1. 84 2, 5-dimethy -phenyl 1. 85 2, 6-dimethyl-phenyl 1. 86 3, 4-d i meth 1 -pheny 1 1. 87 3, 5-dimethyl-phenyl 1. 88 2, 4, 5-trimethyl-phenyl 1. 89 2,6-diethyl-phenyl 1. 90 2, -d i -tert . -buty 1 -phen 1 1. 91 2, 5-dimethoxy-phenyl 1. 92 3, 4-dimethoxy-phenyl 1. 93 2-methy I, 4-tert. -but l -pheny I 1. 94 2-metnoxycarbon 1 -pheny 1 1. 95 2-ethoxycarbonyl-phenyl 1. 96 2-propoxycarbonyl-phenyl 1. 97 2-butox c arbon 1 -pheny 1 1. 98 2-cyano-phenyl 1. 99 3-cyano-phenyl 1. 100 4-cyano-phenyl 1. 101 1-naphthylmethyl 1. 102 2-naphthylmethyl 1. 103 2-bromobenzyl 1. 104 3-bromobenzyl 1. 105 4-bromobenzyl 1. 106 2-chlorobenzyl 1. 107 3-chlorobenzyl 1. 108 4-chlorobenzyl 1. 109 2-f luorobenzyl 1. 110 3-fluorobenzyl 1. 111 4-f luorobenz l 1. 112 2-methy 1 benzyl 890828 Ο.Ζ. 0050/41358 Table 1 (contd.) No. A-X-(CH2)n mP- IR: v(cm-1) 1 .113 3-meth benzy 1 .114 4-methylbenzyl 1 .115 2-^methoxybenyzl 1 .116 3-methoxy benzy 1 .117 4-methoxybenzyl 1 .118 4-ethoxy benz l 1 .119 4-butyloxybenzyl 1 .120 4-benzyloxybenzyl 1 .121 2-tri f luoromethyl-benzyl 1 .122 3-trif luoromethyl-benzy I 1 .123 4-tr i f uoromethy -benzy 1 1 .124 2-formylbenzyl 1 .125 3-formylbenzyl 1 .126 4-formylbenzyl 1 .127 2-a ly -0-N=CH-benz 1 1 .128 3-a ly 1 -0-N=CH-benzy 1 1 .129 4-allyl -0-N=CH-benzy 1 1 .130 2-nitrobenzyl 1 .131 3-nitrobenzyl 1 .132 2,4-dichlorobenzyl 1 .133 2, 6-dichlorobenzyl 1 .134 3, 4-dichlorobenzy 1 .135 2, 3-dichlorobenzyl 1 .136 3, 5-dichlorobenzyl 1 .137 2, 3-dimethylbenzyl 1 .138 2, 4-dimethylbenzy 1 .139 2, 5-dimethylbenzyl 1 .140 2,6-dimethylbenzy 1 .141 3, 4-dimethylbenzyl 1 .142 3, 5-dimethylbenzyl 1 .143 4-chloro-2-methylbenzyl 1 .144 2-methoxycarbony -benzy 1 .145 2-ethoxycarbonyl-benzy 1 .146 2-butoxy c arbony 1 -benzy 1 1 .147 2-cyano-benzyl 1 .148 3-cyano-benzy 1 .149 4-cyano-benzy 1 .150 2-pyridyl 1 .151 3-pyridyl 890828 10 O.Z. 0050/41358 Table 1 (contd.) No. A-X-(CH2)n πφ· IR! v(cm_1) 1.152 4-pyridyl 1.153 6-methy1-2-pyridy1 1.154 6-ethyl-2-pyridyl 1.155 6-n-propyl-2-pyridyl 1.156 6-n-butyl-2-pyridyl 1.157 6-tert.-butyl-2-pyridyl 1.158 6-n-hexyl-2-pyridyl 1.159 6-phenyl-2-pyrid l 1.160 6-benzyl-2-pyridyl 1.161 6-tri fluoromethy -2-pyridyl 1.162 6-methoxy-2-p ri dy1 1.163 6-chloro-2-pyridyl 1.164 3, 6-dimethyl-2-pyridyl 1.165 4, 6-dimethyl-2-pyridyl 1.166 5, 6-d imethyl-2-pyridyl 1.167 4-pheny 1-6-methy 1-2-pyridy1 1.168 3, 4-dichloro-6-methyl-2-pyridyl 1.169 3, 4, 5-trichloro-6-methyl-2-pyridyl 1.170 4-trifluoromethyl-6-methyl-2-pyridyl 1.171 3-acetyl-4, 6-dimethy -2-pyr idyl 1.172 3rcyano-6-meth 1-2-pyridyI 1.173 3-cyano-6-phenyl-2-pyridyl 1.174 3-methyloxycarbony 1-2-pyridyl 1.175 3-methy1oxycarbony 1-6-i so-propy I-2-pyridy1 1.176 5-tri f1uorometh 1 -2-pyri dy1 177 2-quinolyl 1.178 3-meth 1-2-quino1y 1 1.179 4-pheny -2-quinolyl 1.180 8-chloro-2-quinolyl 1.181 4-methy1-8-methoxy-2-quino1y1 1.182 4-quinolyl 1.183 2, 6-dimethyl-4-quinolyl 1.184 8-quinolyl 1.185 5, 7-dichloro-8-quinolyl 1.186 2-pyrimidinyl 1.187 4-trifluoromethyl-2-pyrimidinyl 1.188 4, 6-dimethyl-5-chloro-2-pyrimidiny 1 1.189 3, 5-dimethyl-4-pyrimidinyl 1.190 2-pyraziny 90 2 11 O.Z. 0050/41358 Table 1 (contd.) NO A-X-(CH2)n mp. 1. 191 2-thienyl 1. 192 3-thienyl 1. 193 3-methyl-2-quinoxal inyl 1. 194 3-phenyl-5-isoxazolyl 1. 195 2-benzoxazolyl 1. 196 2-benzthiazolyl 1. 197 4-chloro-2-benzothiazolyl 1. 198 5-chloro-2-benzothiazolyl 1. 199 6-chloro-2-benzothiazolyl 1. 200 6-methy -2-benzoth i azo y I 1. 201 6-methoxy-2-benzothiazolyl 890828 12 O.Z. 0050/41358 Table 2 No A-X-(CH2)n mp. IR: v(cm-1) 2. 1 H 2. 2 methyl 2. 3 ethyl 2. 4 isopropyl 2. 5 butyl 2. 6 sec .-butyl 2. 7 t-butyl 2. 8 isobutyl 2. 9 pentyl 2. 10 pivaloyl 2. 11 hexyl 2. 12 octyl 2. 13 decyl 2. 14 phenyl oil 2935,1738,1722,1152,1043 2. 15 benzyl oil 2935, 1726,1151, 1042 2. 16 phenylethyl 2. 17 phenyl ropyl 2. 18 phenylpentyl 2. 19 1-naphthyl 2. 20 2-naphthyl 2. 21 2-bromophenyl 2. 22 3-bromophenyl 2. 23 4-bromophenyl 2. 24 2-chlorophenyl 2. 25 3-chlorophenyl 2. 26 4-chlorophenyl 2. 27 2-f luorophenyl 2. 28 3-f luorophenyl 2. 29 4-f luorophenyl 2. 30 2-methyl phenyl 2. 31 3-methyl phenyl 2. 32 4-methyl phenyl 2. 33 2-ethyl-phenyl 2. 34 3-ethyl-phenyl 2. 35 4-ethyl-phenyl 890828 13 O.Z. 0050/41358 Table 2 (contd. ) NO. A-x-(CH2)n mp- 2.36 2- iso-propy -phenyl 2.37 3- i so-propy l-pheny 1 2.38 4- i so-propy 1 -pheny I 2.39 2-tert. -butyl -phenyl 2.40 3-tert . -but 1 -pheny 1 2.41 4-tert . -buty 1 -phen 1 2.42 4-butyl -phenyl 2.43 4-hexy -phenyl 2.44 4-nony l-pheny I 2.45 4-decyl -phen l 2.46 2-methoxy-phenyl 2.47 3-methoxy-phenyl 2.48 4-methoxy-pheny I 2.49 2-tr i f uorometh 1 -pheny 1 2.50 3-tr i I uoromethy 1 -pheny 1 2.51 4-trif luorometh l-pheny 2.52 2-formyl phenyl 2.53 3- formy phenyl 2.54 4-formylpheny 1 2.55 2-a 1 ly -0-N=CH-pheny 1 2.56 3-al ly l-0-N=CH-pheny 1 2.57 4-allyl-0-N-CH-phenyl 2.58 2-nitro-phenyl 2.59 3-nitro-phenyl 2.60 2, 4-dichlorophenyl 2.61 2, 5-dichlorophenyl 2.62 2,6-dichlorophenyl 2.63 3, 4-dichlorophenyl 2.64 2, 3-dichlorophenyl 2.65 3, 5-dichlorophenyl 2.66 2, 3, -trichlorophenyl 2.67 2, 4, 5-trichloropheny 2.68 2, 4, 6-trichlorophenyl 2. 69 2, 3, 4, 6-tetrachlorophenyl 2. 70 2, 3, 4, 5, 6-pentachloropheny I 2. 71 2, 3, 4, 5-tetra luorophenyl 2. 72 2, 3, 5, 6-tetraf luorophenyl 2. 73 2, 3, 4, 5, 6-pentaf luorophenyl 2. 74 2-chloro, 4-fluorophenyl 890828 14 O.Z. 0050/41358 Table 2 (contd.) No • A-X-(CH2)n mP- 1 2. 75 3-chloro, 4-fluorophenyl 2. 76 2-chloro, 6-methyl-phenyl 2. 77 4-chloro, 2-meth l-phen l 2. 78 2, 4-dichloro, 5-methyl-phenyl 2. 79 4-chloro, 2, 5-dimethyl-phenyl 2. 80 4-bromo, 2-methyl -phenyl 2. 81 3, 5-bistrifluoromethyl-pheny I 2. 82 2, 3-dimethyl-phenyl 2. 83 2, 4-dimethyl-phenyl 2. 84 2, 5-dimethyl-phenyl 2. 85 2, 6-dimethyl-phenyl 2. 86 3, 4-dimethyl-phenyl 2. 87 3, 5-dimethyl-phenyl 2. 88 2, 4, 5-trimethyl-phenyl 2. 89 2,6-diethyl-phenyl 2. 90 2, 4-di -tert . -buty 1-pheny 2. 91 2, 5-dimethoxy-phenyl 2. 92 3, 4-dimethoxy-phenyl 2. 93 2-methyl, 4-tert. -butyl-phenyl 2. 94 2-methoxycarbony1-pheny1 2. 95 2-ethoxycarbonyl-phenyl 2. 96 2-propoxycarbon I-phenyl 2. 97 2-butoxycarbony1-pheny1 2. 98 2-cyano-phenyl 2. 99 3-cyano-pheny 2. 100 4-cyano-phenyl 2. 101 1-naphth Imeth l 2. 102 2-naphthyImethyl 2. 103 2-bromobenz l 2. 104 3-bromobenz l 2. 105 4-bromobenzyl 2. 106 2-chlorobenzyl 2. 107 3-chlorobenzyl 2. 108 4-ch orobenzyl 2. 109 2-fluorobenzyl 2. 110 3-fluorobenzyl 2. 111 4- luorobenzyl 2. 112 2-methy benzyl 2. 11.3 3-methylbenzy 1 15 Ο.Ζ. 0050>41358 Table 2 (contd.) NO A-X-(CH2)n "Φ· IR: v(cm-1) 2. 114 4-methylbenz 1 2. 115 2-methoxybenyzl 2. 116 3-methox benzyl 2. 117 4-methoxybenz l 2. 118 4-ethoxybenzyl 2. 119 4-butyloxybenzyl 2. 120 4-benzyloxybenzyl 2. 121 2-trif luoromethyl-benzyl 2. 122 3-trif luoromethyl-benzy 2. 123 4-trif luoromethyl-benzy 1 2. 124 2-formylbenzyl 2. 125 3-formyl benzyl 2. 126 4-formylbenzyl 2. 127 2-allyl-0-N=CH-benzyl 2. 128 3-allyl-0-N=CH-benzyl 2. 129 4-a 11 y 1 -0-N=CH-benzy I 2. 130 2-nitrobenzyl 2. 131 3-nitrobenzyl 2. 132 2, 4-dichlorobenzyl 2. 133 2, 6-dichlorobenz l 2. 134 3, 4-dichlorobenzyl 2. 135 2, 3-dichlorobenzyl 2. 136 3, 5-dichlorobenzyl 2. 137 2, 3-dimethylbenzyl 2. 138 2, 4-dimethylbenzyl 2. 139 2, 5-dimethylbenzyl 2. 140 2,6-dimethylbenzyl 2. 141 3, 4-dimethylbenzyl 2. 142 3, 5-dimethylbenzyl 2. 143 4-chloro-2-methylbenzyl 2. 144 2-methoxycarbonyl-benz l 2. 145 2-ethoxycarbonyl-benzyl 2. 146 2-butoxy c arbony I -benzy 1 2. 147 2-cyano-benzyl 2. 148 3-cyano-benzyl 2. 149 4-cyano-benzyl 2. 150 2-pyridyl 2. 151 3-pyridyl 2. 152 4-pyridyl 890828 16 O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n πφ· IR: v(cm_1) 2.153 6-methy1-2-pyri dyI 2.154 6-ethyl -2-pyridyl 2.155 6-n-propyl-2-pyridy 1 2.156 6-ii-butyl-2-pyridyl 2.157 6-tert.-butyl-2-pyrid 1 2.158 6-n-hexyl-2-pyridyl 2.159 6-phen l-2-p ridyl 2.160 6-benz 1-2-pyri dy1 2.161 6-trifluoromethyl-2-pyridyl 2.162 6-methoxy-2-pyrid l 2.163 6-chloro-2-pyridyl 2.164 3,6-dimethyl-2-pyridyl 2.165 4, 6-dimethyl-2-pyridyl 2.166 5, 6-dimethyl-2-pyridyl 2.167 4-pheny -6-methy1-2-pyridy1 2.168 3, 4-dichloro-6-methy 1-2-pyrid I 2.169 3, 4, 5-trichloro-6-methyl-2-pyridyl 2.170 4-tri f1 uoromethy 1-6-methy I-2-pyri dy1 .171 3-acety 1-4, 6-dimethy1-2-pyri dy 2.172 3-cyano-6-methy1-2-pyridy1 .173 3-cyano-6-pheny 1-2-pyri dy 1 .174 3-methy1ox carbony1-2-pyridy1 2.175 3-methy 1oxycarbony I-6-i so-propy 1-2-pyridy I .176 5-tri f1 uorometh 1-2-p ridyl .177 2-quinolyl .178 3-methy1-2-qu i noly 1 .179 4-pheny 1-2-qui nol 1 .180 8-chloro-2-quinolyl .181 4-methyl-8-methoxy-2-quinolyl .182 4-quinolyl .183 2, 6-dimethyl-4-quinolyl .184 8-quinoly 1 .185 5, 7-dichloro-8-quinolyl .186 2-pyrimidinyl .187 4-tr ifIuoromethy1-2-pyrimidinyl .188 4,6-dimethyl-5-chloro-2-pyrimidinyl .189 3, 5-dimethyl-4-pyrimidinyl .190 2-pyrazinyl .191 2-thienyl 890828 17 O.Z. 0050/41358 Table 2 (contd.) NO A-X-(CH2)n mP- 2. 192 3-t ienyl 2. 193 3-methy -2-qu i noxa1 i ny 1 2. 194 3-phenyl-5-isoxazolyl 2. 195 2-benzoxazoly I 2. 196 2-benzthiazolyl 2. 197 4-chloro-2-benzothiazolyl 2. 198 5-chloro-2-benzothiazol l 2. 199 6-ch Ioro-2-benzoth i azoly1 2. 200 6-methyl-2-benzothiazolyl 2. 201 6-methoxy-2-benzothiazolyl 890828 18 O.Z. 0050/41358 3 (CH2)n mp. IR l l hoxyphenyl hoxyphen l hoxyphenyl lorophenyl lorophenyl lorophenyl hylphen l hylphenyl hylphenyl imethylphenyl imeth lphenyl imethylphenyl imethylphenyl imethylphenyl imethylphenyl loro-2-methylphen l hoxycarbony1pheny oxycarbonylphenyl oxycarbonylphenyl lyl-0-N=CH-phenyl yI-0-N=CH-phen 1 lyl-0-N=CH-phenyl idyl hyl-2-pyridyl loro-2-pyridyl loro-2-benzothiazolyl loro-2-benzothiazolyl loro-2-benzothiazolyl hoxybenzyl hoxybenz l hoxybenzyl lorobenzene lorobenzene 890828 19 O . Z . 0050/41358 Table 3 (contd. ) NO >. A-x-(CH2)n mp. 3. 36 4-chlorobenz 1 3. 37 2-methy Ibenzy 1 3. 38 3-methyIbenzy 3. 39 4-methylbenzyl 3. 40 2, 3-dimethylbenzyl 3. 41 2, 4-dimethylbenzyl 3. 42 2, 5-dimethylbenz l 3. 43 2, 6-dimethylbenzyl 3. 44 3, 4-dimethylbenzyl 3. 45 3, 5-dimethylbenzyl 3. 46 4-ch 1oro-2-methy 1benzy I 3. 47 4-methoxycarbonyIbenzy 1 3. 48 4-ethoxycarbonyIbenz 1 3. 49 4-butoxycarbony Ibenzy 1 3. 50 2-al 1y 1 -0-N=CH-pheny 1 3. 51 3-allyl-0-N=CH-phenyl 3. 52 4-al yl-0-N=CH-phenyl 890828 20 O.Z. 0050/41358 Table 4 No. A-X-(CH2)n mp. IR: v(cm-l) 4. 1 n-butyl 4. 2 phenyl 4. 3 2-methoxyphenyl 4. 4 3-methoxy henyl 4. 5 4-methoxyphenyl 4. 6 2-chlorophenyl 4. 7 3-chlorophenyl 4. 8 4-chlorophenyl 4. 9 2-methylphenyl 4.10 3-methylphenyl 4.11 4-methyl phenyl 4.12 2, 3-d imethy phenyl 4.13 2, 4-dimethylphenyl 4.14 2, 5-dimethylphenyl 4.15 2,6-dimethylphenyl 4.16 3, 4-dimethylphenyl 4.17 3, 5-dimethylphenyl 4.18 4-ch1oro-2-methy1 pheny 1 4.19 4-methoxycarbony1pheny1 4.20 4-ethoxycarbonyl henyl 4.21 4-butoxycarbon 1pheny 1 4.22 2-a1 ly 1-0-N=CH-pheny1 4.23 3-al ly1 -0-N=CH-pheny I 4.24 4-allyl-0-N=CH-phenyl 4.25 2-pyridyl 4.26 6-methy1-2-pyridy1 4.27 6-chloro-2-pyridyl 4.28 4-chloro-2-benzothiazolyl 4.29 5-chloro-2-benzothiazolyl 4.30 6-chloro-2-benzothiazolyl 4.31 2-methoxybenzyl 4.32 3-methoxybenzyl 4.33 4-methoxybenzyl 4.34 2-chlorobenzene 4.35 3-chlorobenzene 890828 21 O.Z. 0050/41358 Table 4 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 4.36 4-ch orobenzyl 4.37 2-methylbenzyl 4.38 3-methy Ibenzy 4.39 4-methy Ibenzy I 4.40 2, 3-dimethy benzyl 4.41 2, 4-dimethylbenzyl 4.42 2, 5-dimethylbenzyl 4.43 2, 6-dimethylbenzyl 4.44 3, 4-dimethylbenzyl 4.45 3, 5-dimethylbenzyl 4.46 4-chloro-2-methyIbenzyI 4.47 4-methoxycarbony Ibenzy 4.48 4-ethoxycarbonyIbenzy 4.49 4-butoxycarbony Ibenzy 1 4.50 2-a11y 1-0-N=CH-phenyI 4.51 3-a1 ly -0-N=CH-pheny1 4.52 4-a lyl-0-N=CH-phenyI 890828 22 O.Z. 0050/41358 Table 5 NO. A-X-(CH2)n U mp. IR: v/cm ) 5. 1 2-methyl henyl CH2 5. 2 3-methoxy henyl CH2 5. 3 4-chlorophenyl CH2 5. 4 2-allyl-0-N=CH-phenyl CH2 5. 5 3-methoxycarbony1pheny I CH2 5. 6 6-chloro-2-pyridyl CH2 5. 7 6-ch1oro-2-benzothiazo1y1 CH2 5. 8 2-meth l enz l CH2 5. 9 3-methoxybenzyl CH2 5.10 4-chlorobenzy 1 CH2 5.11 2-allyl-0-N=CH-benzyl CH2 5.12 3-methoxycarbony1-benzyl CH2 5.13 2-methy phenyl CH-CH2-CH3 5.14 3-methoxyphen l r. CH-CH2-CH3 5.15 4-chlorophenyl CH-CH2-CH3 5.16 2-allyl-0-N=CH-phenyl CH-CH2-CH3 5.17 3-methoxycarbony1pheny1 CH-CH2-CH3 5.18 6-chloro-2-pyridyl CH-CH2-CH3 5.19 6-chloro-2-benzothiazolyl CH-CH2-CH3 5.20 2-methylbenzyl CH-CH2-CH3 5.21 3-methoxybenz l CH-CH2-CH3 5.22 4-chlorobenzy CH-CH2-CH3 5.23 2-a1 ly -0-N=CH-benzy 1 CH-CH2-CH3 5.24 3-methoxycarbony 1-benzyI CH-CH2-CH3 5.25 2-methylphenyl N-NH-CH3 5.26 3-methoxyphen l N-NH-CH3 5.27 4-chlorophenyl N-NH-CH3 5.28 2-allyl-0-N=CH-phenyl N-NH-CH3 5.29 3-methoxycarbony 1 phen 1 N-NH-CH3 5.30 6-chloro-2-pyridyl N-NH-CH3 5.31 6-chloro-2-benzothiazolyl N-NH-CH3 5.32 2-methylbenzyl N-NH-CH3 5.33 3-methoxybenzyl N-NH-CH3 5.34 4-chlorobenzyl N-NH-CH3 5.35 2-al lyl-0-N=CH-benzy1 N-NH-CH3 890828 23 O . Z . 0050/41358 Table 5 (contd.) NO. A-X-(CH2)n U 5.36 3-methoxycarbony 1-benzy I N-NH-CH3 5.37 2-methy 1 phenyl CH-S-CH3 5.38 3-methoxyphenyl CH-S-CH3 5.39 4-chlorophenyl CH-S-CH3 5.40 2-a 1 ly 1 -0-N=CH-pheny 1 CH-S-CH3 5. 41 3-methoxycarbony 1phenyl CH-S-CH3 5.42 6-chloro-2-pyridyl CH-S-CH3 5.43 6-ch Ioro-2-benzothi azolyI CH-S-CH3 5.44 2-methy benzyl CH-S-CH3 5.45 3-methoxybenzyl CH-S-CH3 5. 46 4-chlorobenzyl CH-S-CH3 5.47 2-allyl-0-N=CH-benzyl CH-S-CH3 5.48 3-methoxycarbony 1-benzyl CH-S-CH3 24 O.Z. 0050/41358 In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water 25 O . Z . 0050/41358 is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), Ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide) , and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyl-ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from 0. 1 to 95, and preferably from 0. 5 to 90, wt% of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials (timber), e.g., against Paecilomyces variotii. When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0. 01 to 20, g per kg of seed are generally required.
The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. A solution of 90 parts by weight of compound no. 2. 15 and 10 parts by weight of N-methyl-o-pyrrol idone, which is suitable for application in the form of very fine drops.
II. A mixture of 20 parts by weight of compound no. 2 . 15, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecy Ibenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is obtained.
III. An aqueous dispersion of 20 parts by weight of compound no. 2. 1 5, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely dispersing it therein, an aqueous dispersion is obtained. 26 O.Z. 0050/41358 IV. An aqueous dispersion of 20 parts by weight of compound no. 2.15, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely dispersing it therein, an aqueous dispersion is obtained.
V. A hammer-milled mixture of 80 parts by weight of compound no. 2.15, 3 parts by weight of the sodium salt of di isobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a 1 ignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in water, a spray liquor is obtained.
VI. An intimate mixture of 3 parts by weight of compound no. 2.15 and 97 parts by weight of particulate kaolin. The dust contains 3wt% of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 2.15, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.
VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 2.15, 10 parts of the sodium salt of a phenol sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.
IX. A stable oily dispersion of 20 parts by weight of compound no. 2.15, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.
In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in a greater fungicidal action spectrum. 27 O.Z. 0050/41358 The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
Examples of fungicides which may be combined with the novel compounds are: sulfur, dithiocarbamates and their derivatives, such as ferric dimethy Idithiocarbamate, zinc dimethy Idithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethy1enebi sdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethy Ithiuram disulfides, ammonia complex of zinc N, N' -ethy enebisdithiocarbamate, ammonia complex of zinc N, N'-propy1enebisdithiocarbamate, zinc N, N' -propylenebisdithioccarbamate and N, N'-pol prop lenebi s (thiocarbam I ) disul ide; nitro derivatives, such as di n i tro ( 1-methy1 ept 1 )-phen I crotonate, 2-sec-butyl-4, 6-dinitrophenyl 3, 3-dimethy lacrylate, 2-sec-butyl-4, 6-dinitrophenyl isopropylcarbonate and diisopropyl 5-nitroisophthalate ; heterocyclic substances, such as 2-heptadecy 1 imidazol-2-yl acetate, 2, -dichloro-6-(o-chloroanil ino)-s-triazine, 0, O-diethyl phthal imidophosphonothioate, 5-amino-l-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-l, 2, 4-triazole, 2.3-dicyano-l, -dithioanthraquinone, 2-thio-l, 3-dithio[4, 5-b]quinoxal ine, methyl l-(butylcarbam l )-2-benzimidazolecarbamate, 2-methoxycarbonyl aminobenz imidazole, 2-(fur-2-yl )-benzimidazole, 2-(thiazol-4-yl )benzimidazole, N-(l, 1,2, 2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichlorometh lthiophthalimide, N-dichlorofluoromethylthio-N', '-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-l, 2, 3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1. -dichloro-2, 5-dimethoxybenzene, 28 O.Z. 0050/41358 4- (2-ch1oropheny 1 hydrazono) -3-methy1 -5-i soxazolone, 2-th iopyridine 1-oxide, 8-hydroxyquinol ine and its copper salt, 2, 3-dihydro-5-carboxani 1 ido-6-methyl-l, 4-oxathiyne, 2, 3-dihydro-5-carboxani I ido-6-meth 1-1, 4-oxathiyne 4, 4-dioxide, 2-methy 1-5, 6-di hydro-4H-pyran-3-carboxan i 1 i de, 2-methylfuran-3-carboxani I ide, 2.5-dimethylfuran-3-carboxani 1 ide, 2, , 5-trimethy lfuran-3-carboxani 1 ide, 2, 5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyc Iohexy 1 -N-methoxy-2, 5-di ethy 1 furan-3-carboxami de, 2-methy lbenzani 1 ide, 2- iodobenzani I ide, N-formy -N-morphol ine-2, 2, 2-trichloroethylacetal, piperazine-l,4-diylbis-(l-(2, 2, 2-trichloroethyl)-formamide), l-(3, 4-dichloroanilino)-l-formylamino-2, 2, 2-trichloroethane, 2.6-dimethyl-N-tridecylmorphol ine and its salts, 2, 6-dimethyl-N-cyclododecylmorpholine and its salts, N- [3- (p-tert . -buty 1pheny1 ) -2-methy Ipropy I ]-c i s-2, 6-dimethy Imorpho I ine, N- [3- (p-tert. -butyl phenyl) -2-methyIpropy ] -pi peri dine, l-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-dioxolan-2-ylethyl]-lH-l, 2,4--triazole, l-[2-(2,4-dichlorophenyl)-4-n-propyl-l,3-dioxolan-2-ylethyl]-lH-l, 2, 4--triazole, N-(n-propyl)-N-(2, 4, 6-trichlorophenoxyethyl )-N'-imidazolyl-urea, l-(4-chlorophenoxy)-3, 3-dimethyl-l-(lH-l, 2, 4-triazol-l-y 1 )-butan-2-one, l-(4-chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)-butan-2-ol, ct-(2-chlorophenyl )-ot-(4-chlorophenyl )-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis-(p-chlorophenyl)-3-pyridinemethanol, 1, 2-bis-(3-ethoxycarbonyl-2-thioureido) -benzene, 1 , 2-bi s- (3-methoxycarbony 1 -2-th ioureido) -benzene, and various fungicides, such as dodecy Iguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene, DL-methy1 -N- (2, 6-dimethy 1pheny1 ) -N-fur-2-y1 al anate, methyl DL-N-( 2, 6-dimethylphenyl)-N- (2' -methoxyacetyl )-alanate, N- (2, 6-dimethy lpheny I )-N-chloroacetyl-DL-2-aminobutyrolactone, methy 1 OL-N- (2, 6-d imethy 1pheny1 ) -N- (pheny 1 acety1 ) -a anate, 5-methyl-5-vinyl-3-(3, 5-dichlorophenyl)-2, 4-dioxo-l, 3-oxazol idine, 3-[3, 5-dichlorophenyl]-5-methyl-5-methoxymethyl-l,3-oxazolidine-2,4-dione, 3-(3, 5-dichlorophenyl)-l-isopropylcarbamylhydantoin, 29 O.Z. 0050/41358 N-(3, 5-dichlorophenyl)-l, 2-dimethy lcyclopropane-1, 2-dicarboximide, 2-cyano- [N- (ethy1 ami nocarbony I ) -2-methox imino] -acetamide, l-[2-(2, 4-dichlorophenyl)-pentyl]-lH-l, 2, 4-triazole, 2, -difluoro- -(lH-l, 2, 4-triazol-l- lmethy I )-benzhydry 1 alcohol, N-(3-chloro-2, 6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethy 1-3-chloro-2-aminopyridine, and l-( (bis- (4-fluorophenyl ) -methyls i lyl ) -methyl )-lH-l, 2, 4-triazole.
Use Example Action on brown rust of wheat Leaves of pot-grown wheat seedlings of the "Kanzler" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20 to 22°C in a high-humidity (90 - 95%) chamber. During this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20 to 22°C and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredient 2A5^ applied as a 0.025wt% spray liquor, has a good fungicidal action (100%).

Claims (5)

- 30 - 96896/2 CLAIMS:
1. Unsaturated cyclohexylacetic acid derivatives of the formula I where U is =0, =N0CH3, =CH0CH3. =CH2, =CH-CH3, =CH-CH2-CH3, =N-NH-CH3 or =CH-S-CH3 , n is from 0 to 10, A is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl or hetaryl, and X is a single bond when n is 0, and oxygen, sulfur or a single bond when n is not 0, and the plant-compatible acid addition products and base addition products thereof.
2. A compound of the formula I as set forth in claim 1, where U is =N0CH3, n is i, A is phenyl, and X is a single bond.
3. A fungicide containing an inert carrier and a fungicidally effective amount of a compound of the formula I where U is =0, =N0CH3, =CH0CH3, =CH2. =CH-CH3, =CH-CH2-CH3 , =N-NH-CH3 or =CH-S-CH3, n is from 0 to 10, A is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl or hetaryl, and X is a single bond when n is 0, and oxygen, sulfur or a single bond when n is not 0, or a plant-compatible acid addition product or base addition product thereof. - 31 - 96896/2
4. An insecticide containing an inert carrier and an insecticidally effective amount of a compound of the formula I ^ where U is =0, =N0CH3, =CH0CH3, =CH2, =CH-CH3, =CH-CH2-CH3. =N- H-CH3 or =CH-S-CH3 , n is from 0 to 10, A is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl or hetaryl, and X is a single bond when n is 0, and oxygen, sulfur or a single bond when n is not 0, or a plant-compatible acid addition product or base addition product thereof.
5. A process for combating fungi, wherein the fungi or the plants, seed, materials or the soil to be protected against fungus attack are treated with a fungicidally effective amount of a compound of the formula I where U is =0, =N0CH3, =CH0CH3, =CH2, =CH-CH3, =CH-CH2-CH3, =N-NH-CH3 or =CH-S-CH3, n is from 0 to 10, A is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl or hetaryl, and X is a single bond when n is 0, and oxygen, sulfur or a single bond when n is not 0, or a plant-compatible acid addition product or base addition product thereof. For thi A^wplicants PARTNERS
IL9689691A 1990-01-20 1991-01-07 Cyclohexylacetic acid derivatives and their use as fungicides and insecticides IL96896A (en)

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