CA2034156A1 - Unsaturated cyclohexylacetic acid derivatives, and crop-protection agents containing same - Google Patents
Unsaturated cyclohexylacetic acid derivatives, and crop-protection agents containing sameInfo
- Publication number
- CA2034156A1 CA2034156A1 CA002034156A CA2034156A CA2034156A1 CA 2034156 A1 CA2034156 A1 CA 2034156A1 CA 002034156 A CA002034156 A CA 002034156A CA 2034156 A CA2034156 A CA 2034156A CA 2034156 A1 CA2034156 A1 CA 2034156A1
- Authority
- CA
- Canada
- Prior art keywords
- phenyl
- pyridyl
- methyl
- single bond
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
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- 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
Abstract
O.Z. 0050/41358 ABSTRACT OF THE DISCLOSURE: Unsaturated cyclohexylacetic acid derivatives of the formula I
I
where U is =NOCH3, =CHOCH3, =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 O, and oxygen, sulfur or a single bond when n is not O, and the plant-compatible acid addition products and base addition products thereof, and fungicides and insecticides containing these compounds.
I
where U is =NOCH3, =CHOCH3, =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 O, and oxygen, sulfur or a single bond when n is not O, and the plant-compatible acid addition products and base addition products thereof, and fungicides and insecticides containing these compounds.
Description
2~3~6 0.2. 0050/41358 Unsaturated cyclohexylacetic acid deri~atives, and crop-protection aqents containinq same The present invention relates to cyclohexylacetic acid derivatives having a fungicidal and in~ecticidal action, to fungicides and insecticides containing these compounds, and to a method of combating fungi.
We ha~e found that unsaturated cyclohexylacetic acid derivatives of the formula I
A-X-(CH2)n`S ~ I
H 3CO 2C u where U i8 =NOCH3, =CHOCH3, =CH2, =CH-CH3, =CX-CH2-CH3, =N-NH-C~3 or =CH-S-CH3, n is fxom 0 to 10, A i~ hydrogen or substituted or unsubstituted alkyl, cyeloalkyl, aryl or hetaryl, and X is a single bond in the case where n = O, and oxygen, sul~ur or a ~ingle bond in the ca~3e where n i~ not 0, and the plant--compatible acid-additiLon products and ~ase-addition products thereof have a high fungitoxie and inseetieidal action and very goocl plant compatibility.
Examples of acids for acid-addition products are mineral acids, sg. hydrochlorie acid, hydrobromic acid, phosphoric aeid, sulfurie aeid or nitrie acid, or car-boxylie acid~, ~uch as formic ac.id, acetic aeid, oxalic acid, malonie acid, lactic acid, malic acid, succinic acid, tartarie aeid! citric acid or salicylic acid, p-toluenesulfonie acid, dodecylbenzenesulfonic acid, or proton-aeidie compounds in general, eg. saecharin.
Examples of bases for base-addition products are potassium hydroxide, potassium carbonate, sodium hydrox-ide, sodium carbonate and ammonium hydroxide.
The novel compounds of the fonmula I may be produced a~ mîxtures of stereoisomers ~E~Z isomers, diastereomer~ or enantiomers), which can ~e resol~ed into the indi~idual components in a conventional manner, for 2 ~
- 2 - O.Z. 005~/41358 example by cry~tallization or c:hromato~raphy. The indi-vidual i~omers and their mixtures can be us~d as fungi-cides or insecticides and ar~ included in the invention.
If U can occur in syn/anti-isomers, the invention 5relates to all the isomers, in particular the anti-isomers.
In particular, the invention relates to all the diastereomers, in paxticular those having a bis-equatorial arrangement at the two centers of chixality in 10the cyclohexane ring.
U is =NOCH3, =CHOCH3, =CH2, =C~-CH3, =CH-CHz-CH3~
=N-NH-CH3 or =CH-S-CH3, in particular =O, =NOCH3, =CH-OCH3 or =CH-CH3, preferably =NOCH3.
n i~ from 0 to 10, in particular from 0 to 5, 15prefe~ably 0, 1 r 2 or 3.
A is, for example, a saturated or unsaturated, straight-chain ox branched hydrocarbon radical having from 1 to 6, in particular from 1 to 4, carbon atoms or a C3-CB-cycloalkyl radical, or phenyl, thienyl, fu.ryl, 20pyrryl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrLmidyl, pyrazinyl, quinolyl, iso~uinolyl, indolyl, benzLmidazolyl, quin-azolyl, or quinoxslyl, tho cycloalkyl~, alkyls, aryls or hetaryls mentioned being unsubstituted or suhstituted by 25from 1 to 3 idontical or diferent substituents from the group comprising halogen, eg. fluorine, chlorine, bromine or iodine, Cl Ca-alkyl, Cl-Ca-alkylthio, Cl-Ca-alkyl-sulfinyl, ~yano, hydroxyl, nitro, Cl-C8-alkoximino, Cl-C~-alkoxy, phenyl, Cl-C4-haloalkyl, Cl-Ca-alkenyloximino, 30formyl, Cl-Cg-alkylcarbonyl or C1-CB-alkoxycarbonyl, or phenyl which is substituted by from 1 to 3 identical or different substituents from the group comprising halogen, eg. fluorine, chlorine/ bromin~ or iodine, Cl-C8-al~yl, C1-CB-alkylthio, Cl-C8-alkylsulfinyl, cyano, hydroxyl, 35nitro, Cl-C8-alkoximino, C1-CB-alXoxyt phenyl, Cl-Cs-halo-alkyl ~ cl-cB-alk~nyloxLmino ~ fo~myl or Cl-Cg-alkylcarbonyl-A i~ preferably a saturat~d or unsaturated, ~3i~5~
We ha~e found that unsaturated cyclohexylacetic acid derivatives of the formula I
A-X-(CH2)n`S ~ I
H 3CO 2C u where U i8 =NOCH3, =CHOCH3, =CH2, =CH-CH3, =CX-CH2-CH3, =N-NH-C~3 or =CH-S-CH3, n is fxom 0 to 10, A i~ hydrogen or substituted or unsubstituted alkyl, cyeloalkyl, aryl or hetaryl, and X is a single bond in the case where n = O, and oxygen, sul~ur or a ~ingle bond in the ca~3e where n i~ not 0, and the plant--compatible acid-additiLon products and ~ase-addition products thereof have a high fungitoxie and inseetieidal action and very goocl plant compatibility.
Examples of acids for acid-addition products are mineral acids, sg. hydrochlorie acid, hydrobromic acid, phosphoric aeid, sulfurie aeid or nitrie acid, or car-boxylie acid~, ~uch as formic ac.id, acetic aeid, oxalic acid, malonie acid, lactic acid, malic acid, succinic acid, tartarie aeid! citric acid or salicylic acid, p-toluenesulfonie acid, dodecylbenzenesulfonic acid, or proton-aeidie compounds in general, eg. saecharin.
Examples of bases for base-addition products are potassium hydroxide, potassium carbonate, sodium hydrox-ide, sodium carbonate and ammonium hydroxide.
The novel compounds of the fonmula I may be produced a~ mîxtures of stereoisomers ~E~Z isomers, diastereomer~ or enantiomers), which can ~e resol~ed into the indi~idual components in a conventional manner, for 2 ~
- 2 - O.Z. 005~/41358 example by cry~tallization or c:hromato~raphy. The indi-vidual i~omers and their mixtures can be us~d as fungi-cides or insecticides and ar~ included in the invention.
If U can occur in syn/anti-isomers, the invention 5relates to all the isomers, in particular the anti-isomers.
In particular, the invention relates to all the diastereomers, in paxticular those having a bis-equatorial arrangement at the two centers of chixality in 10the cyclohexane ring.
U is =NOCH3, =CHOCH3, =CH2, =C~-CH3, =CH-CHz-CH3~
=N-NH-CH3 or =CH-S-CH3, in particular =O, =NOCH3, =CH-OCH3 or =CH-CH3, preferably =NOCH3.
n i~ from 0 to 10, in particular from 0 to 5, 15prefe~ably 0, 1 r 2 or 3.
A is, for example, a saturated or unsaturated, straight-chain ox branched hydrocarbon radical having from 1 to 6, in particular from 1 to 4, carbon atoms or a C3-CB-cycloalkyl radical, or phenyl, thienyl, fu.ryl, 20pyrryl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrLmidyl, pyrazinyl, quinolyl, iso~uinolyl, indolyl, benzLmidazolyl, quin-azolyl, or quinoxslyl, tho cycloalkyl~, alkyls, aryls or hetaryls mentioned being unsubstituted or suhstituted by 25from 1 to 3 idontical or diferent substituents from the group comprising halogen, eg. fluorine, chlorine, bromine or iodine, Cl Ca-alkyl, Cl-Ca-alkylthio, Cl-Ca-alkyl-sulfinyl, ~yano, hydroxyl, nitro, Cl-C8-alkoximino, Cl-C~-alkoxy, phenyl, Cl-C4-haloalkyl, Cl-Ca-alkenyloximino, 30formyl, Cl-Cg-alkylcarbonyl or C1-CB-alkoxycarbonyl, or phenyl which is substituted by from 1 to 3 identical or different substituents from the group comprising halogen, eg. fluorine, chlorine/ bromin~ or iodine, Cl-C8-al~yl, C1-CB-alkylthio, Cl-C8-alkylsulfinyl, cyano, hydroxyl, 35nitro, Cl-C8-alkoximino, C1-CB-alXoxyt phenyl, Cl-Cs-halo-alkyl ~ cl-cB-alk~nyloxLmino ~ fo~myl or Cl-Cg-alkylcarbonyl-A i~ preferably a saturat~d or unsaturated, ~3i~5~
- 3 - O.Z. 0050/41358 straight-chain or branched hydrocarbQn radical having from 1 to 6, in particular from 1 to 4, carbon atoms or a C3-Cs-cycloalkyl radical, or phenyl, pyridyl or benz-Lmidazolyl.
5The novel compounds can b~ prepared, for example, by the following processe~:
Methyl ~-cyclohexen-l-yl-~-oxoacetate 1 (G. Neef et al., THL 1977 (32), 2825-8~ is reacted with a thiol 2, if ne~essary with base catalysis, to give a thioether 3 10(Y. Yankar et al., J. Chem. Research 1989, 178-179) (~cheme 1).
Scheme 1 ~lJ IA--X--( CH 2 ) n-SH A--X--( CH 2 ) n`SJ~J
O~CO 2CH 3 H 3C0 2C O
A and n are as above.
15Substituted methyl ~-oxoacetates 3 are converted into the aCtiVQ ingred~entq 4 by reaction with CH3-0-NH3Cl or H2N-NH-CH3 (scheme 2).
Scheme 2 A-X- ( CH 2 ) n`sJ~lA-X- ( CH 2 ) n~s--P
3Co2c o H3C02C ~ u U is =NOCH3 or -N-NHCH3, and A and n are as abovs .
The methyl ~-octoacetates 3 can be used toprepare the compounds 5 by a Wittig reaction with (C6Hs)3P+-CH3X-, ( C6H5 ) 3P -CH2-CH3$ ~ ( C6HS ) 3P -CH2-CH2-CH3X (X - halogen3 or ( ~6H5 ) 3P -CH2-0-cH3cl t ( C6~s ) 2P ( =0 )-CH2-O-CH3 or by Peterson olefin formation u~ing ~CH3)3Si-CHz-O-CH3 tscheme 3~.
Scheme 3 A-X- ( CH 2 ~ n`S~ A--X--( CH 2 ) n`sJ~l ~3~1~S
5The novel compounds can b~ prepared, for example, by the following processe~:
Methyl ~-cyclohexen-l-yl-~-oxoacetate 1 (G. Neef et al., THL 1977 (32), 2825-8~ is reacted with a thiol 2, if ne~essary with base catalysis, to give a thioether 3 10(Y. Yankar et al., J. Chem. Research 1989, 178-179) (~cheme 1).
Scheme 1 ~lJ IA--X--( CH 2 ) n-SH A--X--( CH 2 ) n`SJ~J
O~CO 2CH 3 H 3C0 2C O
A and n are as above.
15Substituted methyl ~-oxoacetates 3 are converted into the aCtiVQ ingred~entq 4 by reaction with CH3-0-NH3Cl or H2N-NH-CH3 (scheme 2).
Scheme 2 A-X- ( CH 2 ) n`sJ~lA-X- ( CH 2 ) n~s--P
3Co2c o H3C02C ~ u U is =NOCH3 or -N-NHCH3, and A and n are as abovs .
The methyl ~-octoacetates 3 can be used toprepare the compounds 5 by a Wittig reaction with (C6Hs)3P+-CH3X-, ( C6H5 ) 3P -CH2-CH3$ ~ ( C6HS ) 3P -CH2-CH2-CH3X (X - halogen3 or ( ~6H5 ) 3P -CH2-0-cH3cl t ( C6~s ) 2P ( =0 )-CH2-O-CH3 or by Peterson olefin formation u~ing ~CH3)3Si-CHz-O-CH3 tscheme 3~.
Scheme 3 A-X- ( CH 2 ~ n`S~ A--X--( CH 2 ) n`sJ~l ~3~1~S
- 4 - O.Z. 0050/41358 U is =CH2, -C~-CH3, -CH-C~2-CH3 or =CHOCH3, and A and n are a~ above.
The thioenol ethers 7 can be obtained rom the enol ethers 6 by reaction with methyl mercaptan (EP
5178 826, scheme 4~.
Scheme 4 A-X- ( CH 2 ) n`S~~ A--X--( CH 2 ) n`S~
H 3C0 2C~CHOCH 3 H 3C0 2C~CHSCH 3 6 . 7 A and n are as above.
Th~ Examples below illustrate the preparation of novel compounds.
Methyl ~-(2-benzylthioc:yclohexyl)--oxoacetate (Compound No. 1.15) 2 g (12 mmol) of methyl ~-cyclohexlenyl-~-oxo-acetate, 1.5 g (12 mmol) of benzyl mercaptan and 1 g (10 mmol) o triethylamine in 10 ml of methylene chloride are stirred at room temperature (20C~ for 15 hour~.
After the ~tirring period, water is added to the batch, and the aqueous phase i~ extracted with methylene chloride. The organic pha~e i9 extracted with water, dried over MgSO~ and evaporated.
Chromatographic purification of the crude product gi~es 2.3 g (66 ~) of the title compound as a pale yellow oil.
IR (cm1): 2933, 1727, 1277, 1069.
Methyl ~-(2-benzylthiocyclohexyl)-~-axoacetate O-methyl oxime (Compound No. 2.15) 2.3 g (7.9 mmol) of methyl ~-(2-benzylthiocyclo-he~yl)-~-oxoacetate (E~ample 1) and 0.~6 g (8 mmol) of methoxyamine hydrochloride in 15 ml of methanol are stirred at room temperature for 15 hours.
~3~
_ 5 _ o.Z. 0050/41358 Water is added to the reaction mixture~ and the aqueou~ phase is extracted with ether. The organic phase is washed with water, dried over MgSO4 and evaporated.
Chromatographic purification of the crude product gives S 1 g (40 %) of the title compound as a pale yellow oil.
IR (cm~l): 2935, 1726,1151, 1042.
2~3'~
89082~
6 o.Z~ 0050/41358 Table I
A-X-~CH2)n`S~
No. A-X-(CH2)n mp. IR: v~cm~1) 5 1. 1 H
1. 2 methyl 1. 3 ethyl 1. 4 isopropyl 1. 5 butyl 10 1. 6 sec.-butyl 1. 7 t-butyl 1. 8 isobutyl 1. 9 pentyl 1.10 pivaloyl 15 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 20 1.16 phenylethyl 1.17 phenylpropyl 1.18 phenylpentyl I .1 9 1 -naphthy l 1.20 2-naphthyl 25 1.21 2-bromophenyl 1.22 3-bromophenyl 1.23 4-bromophenyl 1.24 2-chlorophenyl 1.25 3-chlorophenyl 30 1.26 4-chlorophenyl 1.27 2-fluorophenyl 1.28 3-fluorophenyl 1.29 4-fluorophenyl 1.30 2-methylphenyl 35 1.31 3-methylphenyl 1.32 4-methylphenyl 1.33 2-ethyl-phenyl 1.34 3-ethyl-phenyl 1.35 4-ethyl-phenyl 7 O.Z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~1) 5 1.36 2-iso-propyl-phenyl 1.37 3-iso-propyl-phenyl 1.38 4-iso-propyl-phenyl 1.39 2-tert.-butyl-phenyl 1.40 3-tert.-butyl-phenyl 10 1.41 4-tert.-butyl-phenyl 1.42 4-butyl-phenyl 1.43 4-hexyl-phenyl 1.44 4-nonyl-phenyl 1.45 4-decyl-phenyl 15 1.46 2-methoxy-phenyl 1.47 3-methoxy-phenyl 1.48 4-methoxy-phenyl 1.49 2-trifluoromethyl-phenyl 1.50 3-trifluoromethyl-phenyl 20 1.51 4-trifluoromethyl-phenyl 1.52 2-formylphenyl 1.53 3-formylphenyl 1.54 4-formylphenyl 1.55 2-allyl-O-N=CH-phenyl 25 1.S6 3-allyl-O-N=CH-phenyl 1.57 4-alIyl-O-N-CH-phenyl 1.58 2-nitro-phenyl 1.59 3-nitro-phenyl 1.60 2,4-dichlorophenyl 30 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 35 1.66 2,3,4-trichlorophenyl 1.67 2,4,5-trichlorophenyl 1.68 2,4,6-trichlorophenyl 1. 69 2,3,4,6-tetrachlorophenyl 1. 70 2,3,4,5,6-pentachlorophenyl 40 1. 71 2,3,4,5-tetrafluorophenyl 1. 72 2,3,5,6-tetrafluorophenyl 1. 73 2,3,4,5,6-penta~luorophenyl 2~
8 O.Z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 1. 74 2-chloro, 4-fluorophenyl 1. 75 3-chloro, 4-fluorophenyl 1. 76 2-chloro, 6-methyl-phenyl 1. 77 4-chloro, 2-methyl-phenyl 1. 78 2,4-dichloro, 5-methyl-phenyl 10 l. 79 4-chloro, 2,5-dimethyl-phenyl 1. 80 4-bromo, 2-methyl-phenyl 1. 81 3,5-bistrifluoromethyl-phenyl 1. 82 2,3-dimethyl-phenyl 1. 83 2,4-dimethyl-phenyl 15 1. 84 2,5-dimethyl-phenyl 1. 85 2,6-dimethyl-phenyl 1. 86 3,4-dimethyl-phenyl 1. 87 3,5-dimethyl-phenyl 1. 88 2,4,5-trilnethyl-phenyl 20 1. 89 2,6-diethyl-phenyl 1. 90 2,4-di-tert.-butyl-phenyl 1. 91 2,5-dimethoxy-phenyl 1. 92 3,4-dimethoxy-phenyl 1. 93 2-methyl, 4-terlt.-butyl-phenyl 25 1. 94 2-methoxycarbonyl-phenyl 1. 95 2-ethoxycarbonyl-phenyl 1. 96 2-propoxycarbonyl-phenyl 1. 97 2-butoxycarbonyl-phenyl 1. 98 2-cyano-phenyl 30 1. 99 3-cyano-phenyl 1.100 4-cyano-phenyl 1.101 1-naphthylmethyl 1.102 2-naphthylmethyl 1.103 2-bromobenzyl 35 1.104 3-bromobenzyl 1.105 4-bromobenzyl 1.106 2-chlorobenzyl 1.107 3-chlorobenzyl 1.108 4-chlorobenzyl 40 1.109 2-fluorobenzyl 1.110 3-fluorobenzyl 1.111 4-fluorobenzyl 1.112 2-methylbenzyl 2~3~ ~ ~5 9 o.z. 0050/41358 Table 1 (contd.) No. A-X-lC~l2)n mp. IR: v(cm~1) 5 1.113 3-methylbenzyl 1.114 4-methylbenzyl 1.115 2-methoxybenyzl 1.116 3-~ethoxybenzyl 1.117 4-methoxybenzyl 10 1.118 4-ethoxybenzyl 1.119 4-butyloxybenzyl 1.120 4-benzyloxybenzyl 1.121 2-trifluoromethyl-benzyl 1.122 3-trifluoromethyl-benzyl lS 1.123 4-trifluoromethyl-benzyl 1.124 2-formylbenzyl 1.125 3-formylbenzyl 1.126 4-formylbenzyl 1.127 2-allyl-O-N=CH-benzyl 2~ 1.128 3-allyl--O-N=CH-benzyl 1.129 4-allyl--O-N=CH-benzyl 1.130 2-nitrobenzyl 1.131 3-nitrobenzyl 1.132 2,4-dichlorobenzyl 25 1.133 2,6-dichlorobenzyl 1.134 3,4-dichlorobenzyl 1.135 2,3-dichlorobenzyl 1.136 3,5-dichlorobenzyl 1.137 2,3-dimethylbenzyl 3~ 1.138 2,4-dimethylbenzyl 1.139 2,5-di~ethylbenzyl 1.140 2,6-dimethylbenzyl 1.141 3,4-dimethylbenzyl 1.142 3,5-dimethylbenzyl 35 1.143 4-chloro-2-methylbenzyl t.144 2-methoxycarbonyl-benzyl 1.145 2-ethoxycarbonyl-benzyl 1.146 2-butoxycarbonyl-benzyl 1.147 2-cyano-benzyl 40 1.148 3-cyano-benzyl 1.149 4-cyano-benzyl 1.150 2-pyridyl 1.151 3-pyridyl 2 ~ 1 5 ~
o.z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 1.152 4-pyridyl 1.153 6-methyt-2-pyridyl 1.154 6-ethyl-2-pyridyl 1.155 6-n-propyl-2-pyridyl 1.156 6-n-butyl-2-pyridyl 10 1.157 6-tert.-butyl-2-pyridyl 1.158 6-n-hexyl-2-pyridyl 1.159 6-phenyl-2-pyridyl 1.160 6-benzyl-2-pyridyl 1.161 6-trifluoromethyl-2-pyridyl 15 1.162 6-methoxy-2-pyridyl 1.163 6-chloro-2-pyridyl 1.164 3,6-dimethyl-2-pyridyl 1.165 4,6-dimethyl-2-pyridyl 1.166 5,6-dimethyl-2-pyridyl 20 1.167 4-phenyl-6-methyl-2-pyridyl 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-dimethyl-2-pyridyl 25 1.172 3-cyano-6-~ethyl-2-pyridyl 1.173 3-cyano-6-phenyl-2-pyridyl 1.174 3-methyloxycarbonyl-2-pyridyl 1.175 3-methyloxycarbonyl-6-iso-propyl-2-pyridyl 1.176 5-trifluoromethyl-2-pyridyl 30 1.177 2-quinolyl 1.178 3-methyl-2-quinolyl 1.179 4-phenyl-2-quinolyl 1.180 8-chloro-2-quinolyl 1.181 4-methyl-8-methoxy-2-quinolyt 35 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 40 1.187 4-trifluoromethyl-2-pyrimidinyl 1.188 4,6-dimethyl-5-chloro-2-pyrimidinyl 1.189 3,5-dimethyl-4-pyrimidinyl 1.190 2-pyrazinyl 2~t3~
ll o.Z~ 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. 1~: v(cm~1) 5 1 . 191 2-thienyl 1.192 3-thienyl 1.193 3-methyl-2-quinoxalinyl 1.194 3-phenyl-5-isoxazolyl 1.195 2-benzoxazolyl 10 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-methyl-2-benzothiazolyl 15 1.201 6-methoxy-2-benzothiazolyl 203l~ L~6 12 O.Z. 0050/41358 Table 2 A-X--(CH2)n`S~
No. A-X-(CH2)n mp. IR: v(cm~1) 5 2. 1 H
2. 2 methyl 2. 3 ethyl 2. 4 isopropyl 2. 5 butyl 10 2. 6 sec.-butyl 2. 7 t-butyl 2. 8 isobutyl 2. 9 pentyl 2.10 pivaloyl 15 2.11 hexyl 2.12 octyl 2.13 decyl 2.14 phenyl oi1 2935,1738,1722,1152,1043 2.15 benzyl oil 2935,1726,1151,1042 20 2.16 phenylethyl 2.17 phenylpropyl 2~18 phenylpentyl 2.19 I-naphthyl 2.20 2-naphthyl 25 2.21 2-bromophenyl 2.22 3-bromophenyl 2.23 4-bromophenyl 2.24 2-chlorophenyl 2.25 3-chlorophenyl 30 2.26 4-chlorophenyl 2.27 2-fluorophenyl 2.28 3-fluorophenyl 2.29 4-~luorophenyl 2.30 2-methylphenyl 35 2.31 3-methylphenyl 2.32 4-methylphenyl 2.33 2-ethyl-phenyl 2.34 3-ethyl-phenyl 2.35 4-ethyl-phenyl . .
.
2~3~
~90828 13 o.Z. 0050/~1358 Table 2 (contd.) No. A-%-lCH2)n mp. IR: v(cm~l) 5 2.36 2-iso-propyl-phenyl 2.37 3-iso-propyl-phenyl 2.38 4-iso-propyl-phenyl 2.39 2-tert.-butyl-phenyl 2.40 3-tert.-butyl-phenyl 10 2.41 4-tert.-butyl-phenyl 2.42 4-butyl-phenyl 2.43 4-hexyl-phenyl 2.44 4-nonyl-pheny1 2.45 4-decyl-phenyl 15 2.46 2-methoxy-phenyl 2.47 3-methoxy-phenyl 2.48 4-methoxy-phenyl 2.49 2-trifluoromethyl-phenyl 2.50 3-trifluoromethyl-phenyl 20 2.51 4-trifluoromethyl-phenyl 2.52 2-formylpheryl 2.53 3-formylphenyl 2.54 4-formylphenyl 2.55 2-alIyl-O-N=C~phenyl 25 2.56 3-alIyl-O-N=CH-phenyl 2.57 4-alIyl-O-N-CH-phenyl 2.58 2-nitro-phenyl 2.59 3-nitro-phenyl 2.60 2,4-dichlorophenyl 30 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 35 2.66 2,3,4-trichlorophenyl 2.67 2,4,5-trichlorophenyl 2.68 2,4,6-trichlorophenyl 2. 69 2,3,4,6-tetrachlorophenyl 2. 70 2,3,4,5,6-pentachlorophenyl 40 2. 71 2,3,4,5-tetrafluorophenyl 2. 72 2,3,5,6-tetrafluorophenyl 2. 73 2,3,4,5,6-pentafluorophenyl 2. 74 2-chloro, 4-fluorophenyl "` 2~3~
14 O.z. 0050/41358 Table 2 tcontd.) No. A-X-~C~2)n mp. IR: v(cm~l) 5 2. 75 3-chloro, 4-fluorophenyl 2. 76 2-chloro, 6-methyl-phenyl 2. 77 4-chloro, 2-methyl-phenyl 2. 78 2,4-dichloro, 5-methyl-phenyl 2. 79 4-chloro, 2,5-dimethyl-phenyl 10 2. 80 4-bromo, 2-methyl-phenyl 2. 81 3,5-bistrifluoromethyl-phenyl 2. 82 2,3-dimethyl-phenyl 2. 83 2,4-dimethyl-phenyl 2. 84 2,5-dimethyl-phenyl 15 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 20 2. 90 2,4-di-tert.-butyl-phenyl 2. 91 2,5-dimethoxy-phenyl 2. 92 3,4-dimethoxy-phenyl 2. 93 2-methyl, 4-tert.-butyl-phenyl 2. 94 2-methoxycarbonyl-phenyl 25 2. 95 2-ethoxycarbonyl-phenyl 2. 96 2-propoxycarbonyl-phenyl 2. 97 2-butoxycarbonyl-phenyl 2. 98 2-cyano-phenyl 2. 99 3-cyano-phenyl 30 2.100 4-cyano-phenyl 2. 101 I-naphthylmethyl 2.102 2-naphthylmethyl 2.103 2-bromobenzyl 2.104 3-bromobenzyl 35 2.105 4-bromobenzyl 2.106 2-chlorobenzyl 2.107 3-chlorobenzyl 2.108 4-chlorobenzyl 2.109 2-fluorobenzyl 40 2.110 3-fluorobenzyl 2.111 4-fluorobenzyl 2.112 2-methylbenzyl 2.113 3-methylbenzyl .
~3~
O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.114 4-methylbenzyl 2.115 2-methoxybenyzl 2.116 3-methoxybenzyl 2. 117 4-methoxybenzyl 2.118 4-ethoxybenzyl 10 2.119 4-butyloxybenzyl 2.120 4-benzyloxybenzyl 2.121 2-trifluoromethyl-benzyl 2.122 3-trifluoromethyl-benzyl 2.123 4-trifluoromethyl-benzyl 15 2.124 2-formylbenzyl 2.125 3-formylbenzyl 2.126 4-formylbenzyl 2.12 7 2-allyl-O-N=CH-benzyl 2.128 3-allyl-O-N=CH-benzyl 20 2.129 4-allyl-O-N=CH-benzyl 2.130 2-nitrobenzyl 2.131 3-nitrobenzyl 2.132 2,4-dichlorobenzyl 2.133 2,6-dichlorobenzyl 25 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 30 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 35 2.144 2-methoxycarbonyl-benzyl 2.145 2-ethoxycarbonyl-benzyl 2.146 2-butoxycarbonyl-benzyl 2.147 2-cyano-benzyl 2.148 3-cyano-benzyl 40 2.149 4-cyano-benzyl 2~150 2-pyridyl 2.151 3-pyridyl 2.152 4-pyridyl 2~3'~15~
16 O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.153 6-methyl-2-pyridyl 2.154 6-ethyl-2-pyridyl 2.155 6-n-propyl-2-pyridyl 2.156 6-n-butyl-2-pyridyl 2.157 6-tert.-buty1-2 pyridyl 10 2.158 6-n-hexyl-2-pyridyl 2.159 6-phenyl-2-pyridyl 2.160 6-benzyl-2-pyridyl 2.161 6-trifluoromethyl-2-pyridyl 2.162 6-metho~y-2-pyridyl 15 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-phenyl-6-methyl-2-pyridyl 20 2.168 ~,4-dichloro-6-methyl-2-pyridyl 2.169 3,4,5-trichloro-6-methyl-2-pyridyl 2.170 4-trifluoromethyl-6-methyl-2-pyridyl 2.171 3-acetyl-4,6-dimethyl 2-pyridyl 2.172 3-cyano-6-methyl-2-pyridyl 25 2.173 3-cyano-6-phenyl-2-pyridyl 2.174 3-methyloxycarbonyl-2-pyridyl 2.175 3-methyloxycarbonyl-6-iso-propyl-2-pyridyl 2.176 5-trifluoromethyl-2-pyridyl 2.177 2-quinolyl 30 2.178 3-methyl-2-quin~lyl 2.179 4-phenyl-2-quinolyl 2.180 8-chloro-2-quinolyl 2.181 4-methyl-8-methoxy-2-quinolyl 2.182 4-quinolyl 35 2.183 2,6-dimethyl-4-quinolyl 2.184 8-quinolyl 2.185 5,7-dichloro-8-quinolyl 2.186 2-pyrimidinyl 2.187 4-trifluoromethyl-2-pyrimidinyl 40 2.188 4,6-dimethyl-5-chloro-2-pyrimidinyl 2.189 3,5-dimethyl-4-pyrimidinyl 2.190 2-pyra7inyl 2. 191 2-thienyl ~03~
17 O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.192 3-thienyl 2.193 3-methyl-2-quinoxalinyl 2.194 3-phenyl-5-isoxazolyl 2.195 2-benzoxazolyl 2.196 2-benzthiazolyl 10 2.197 4-chloro-2-benzothiazolyl 2.198 5-chloro-2-benzothiazolyl 2~199 6-chloro-2-benzothiazolyl 2.200 6-methyl-2-benzothiazolyl 2.201 6-methoxy-2-benzothiazolyl 203~
18 o.Z. 0050/41358 Table 3 f~
A--X--(CH2)n`$~
H3C02C-l~CHOCH3 No. A-X-(CH2)n mp. IR: v~cm~1) 5 3. I n-butyl 3. 2 phenyl 3. 3 2-methoxyphenyl 3. 4 3-methoxyphenyl 3. 5 4-methoxyphenyl 10 3. 6 2-chlorophenyl 3. 7 3-chlorophenyl 3. 8 4-chlorophenyl 3. 9 2-methylphenyl 3.10 3-methylphenyl 15 3.11 4-methylphenyl 3.12 2,3-dimethylphenyl 3.13 2,4-dimethylphenyl 3.14 2,5-dimethylphenyl 3.15 2,6-dimethylphenyl 20 3.16 3,4-dimethylphçnyl 3.17 3,5 dimethylphenyl 3.18 4-chloro-2-methylphenyl 3.19 4-methoxycarbonylphenyl 3.20 4-ethoxycarbonylphenyl 25 3.21 4-butoxycarbonylphenyl 3.22 2-alIyl-0-N=CH-phenyl 3.23 3-alIyl-0-N=CH-phenyl 3.24 4-allyl-0-N=CH-phenyl 3.25 2-pyridyl 30 3.26 6-methyl-2-pyridyl 3.27 6-chloro-2-pyridyl 3.28 4-chloro-2-benzothiazolyl 3.29 5-chloro-2-benzothiazolyl 3.30 6-chloro-2-benzothiazolyl 35 3.31 2-methoxybenzyl 3.32 3-methoxybenzyl 3.33 4-methoxybenzyl 3.34 2-chlorobenzene 3.35 3-chlorobenzene 2~3~
19 0.7. 0050~41358 Table 3 (contd.) No. A-x-lc~i2)n mp. IR: v(cm~1) 5 3.36 4-chlorobenzyl 3.37 2-methylbenzyl 3.38 3-methylbenzyl 3.39 4-methylbenzyl 3.40 2,3-dimethylbenzyl 10 3.41 2,4-dimethylbenzyl 3.42 2,5-dimethylbenzyl 3~43 2,6-dimethylbenzyl 3.44 3,4-dimethylbenzyl 3.45 3,5-dimethyIbenzyl 15 3.46 4-chloro-2-methylbenzyl 3.47 4-methoxycarbonylb~nzyl 3.48 4-ethoxycarbonylbenzyl 3.49 4-butoxycarbonylbenzyl 3.50 2-allyl-O-N=CH-phenyl 20 3.51 3-allyl-O-N=CH-phenyl 3.52 4-allyl-O-N=CH-phenyl 2~3~S
O.Z. 0050J41358 Table 4 A-X-(CH2)n`S ~
No. A-X-(CH2)n mp. IR: v(cm~1) 5 4. 1 n-butyl 4. 2 phenyl 4. 3 2-methoxyphenyl 4. 4 3-methoxyphenyl 4. 5 4-methoxyphenyl 10 4. 6 2-chlorophenyl 4. 7 3-chlorophenyl 4. 8 4-chlorophenyl 4. 9 2-methylphenyl 4.10 3-methylphenyl 15 4.11 4-methylphenyl 4.12 2,3-dimethylphenyl 4.13 2,4-dimethylphenyl 4.14 2,5-dimethylphenyl 4.15 2,6-dimethylphenyl 2~ 4.16 3,4-dimethylphenyl 4.17 3,5-dimethylphenyl 4.18 4-chloro-2-methylphenyl 4.19 4-methoxycarbonylphenyl 4.20 4-ethoxycarbonylphenyl 25 4.21 4-butoxycarbonylphenyl 4.22 2-alIyl-O-N=CH-phenyl 4.23 3-allyl-O-N=CH-phenyl 4.24 4-allyl-O-N=CH-phenyl 4.25 2-pyridyl 30 4.26 6-methyl-2-pyridyl 4.27 6-chloro-2-pyridyl 4.28 4-chloro-2-benzothiazolyl 4.29 5-chloro-2-benzothiazolyl 4.30 6-chloro-2-benzothiazolyl 35 4.31 2-methoxybenzyl 4.32 3-methoxybenzyl 4.33 4-methoxybenzyl 4.34 2-chlorobenzene 4.35 3-chlorobenzene ~3~
21 O.Z. 0050/41358 Table 4 (contd.) No. A-X-¦CH2)n mp. IR: v(cm~1) 5 4.36 4-chlorobenzyl 4.37 ~-methylbenzyl 4.38 3-methylbenzyl 4.39 4-methylbenzyl 4.40 2,3-dimethylbenzyl 10 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 15 4.46 4-chloro-2-methylbenzyl 4.47 4-methoxycarbonylbenzyl 4.48 4-ethoxycarbonylbenzyl 4.49 4-butoxycarbonylbenzyl 4.50 2-allyl-O-N=CH-phenyl 20 4.51 3-allyl-O-N=CH-phenyl 4.52 4-alIyl-O-N=CH-phenyl ~031~5~
89~828 22 O.Z. 0050/41358 Table 5 f~ .
A-x-(cH2)n`s~
H3CO2C~U
No. A-X-(CH2)n U mp. I~: Y/cm 1) 5 5. 1 2-methylphenyl CH2 5. 2 3-methoxyphenyl CH2 5. 3 4-chlorophenyl CH2 5. 4 2-allyl-O-N=CH-phenyl CH2 5. 5 3-methoxycarbonylphenyl CH2 10 5. 6 6-chloro-2-pyridyl CH2 5. 7 6-chloro-2-benzothiazolyl CH2 5. 8 2-methylbenzyl CH2 5. 9 3-methoxybenzyl CH2 5.10 4-chlorobenzyl CH2 15 5.11 2-alIyl-O-N=CH-benzyl CH2 5.12 3-methoxycarbonyl-benzyl CH2 5.13 2-methylphenyl CH-CH2-CH3 5.14 3-methoxyphenyl CH-CH2-CH3 5.15 4-chlorophenyl CH-CH2-CHl3 20 5.16 2-allyl-O-N=CH-phenyl CH-CH2-CHl3 5.17 3-methoxycarbonylphenyl CH-CH2-CHl3 5.18 6-chloro-2-pyridyl CH-CH2-C~ll3 5.19 6-chloro-2-benzothiazolyl CH-CH2-CH3 5.20 2-methylbenzyl cH-cH2-c~l3 z5 5.21 3-methoxybenzyl CH-CH2-C~l3 5.22 4-chlorobenzyl CH-CH2-CH3 5.23 2-allyl-O-N=CH-benzyl CH-CH2-CH3 5.24 3-methoxycarbonyl-benzyl CH-CH2-CH3 5.25 2-methylphenyl N-NH-CH3 30 5~26 3-methoxyph~nyl N-NH-CH3 5.27 4-chlorophenyl N-NH-CH3 5.28 2-allyl-O-N=CH-phenyl N-NH-CH3 5.29 3-methoxycarbonylphenyl N-NH-CH3 5.30 6-chloro-2-pyridyl N-NH-CH3 35 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-allyl-O-N=CH-benzyl N-NH-CH3 2 ~ 3 ~ 6 23 O.Z. 0050/41358 Table 5 (contd.) No. A-X-(CH2)n U mp. IR: v/cm~1) 5 5.36 3-methoxycarbonyl-benzyl N-NH-CH3 5.37 2-methylphenyl CH-S-CH3 5.38 3-methoxyphenyl CH-S-CH3 5.39 4-chlorophenyl CH-S-CH3 5.40 2-allyl-0-N=CH-phenyl CH-S-CH3 10 5.41 3-methoxycarbonylphenyl CH-S-CH3 5.42 6-chloro-2-pyridyl CH-S-CH3 5.43 6-chloro-2-benzothiazolyl CH-S-CH3 5.44 2-methylbenzyl CH-S-CH3 5.45 3-methoxybenzyl CH-S-CH3 15 5.46 4-chlorobenzyl CH-S-CH3 5.47 2-allyl-0-N=CH-benzyl CH-S-CH3 5.48 3-methoxycarbonyl-benzyl CH-S-CH3 2 ~
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 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula neçator in vines, Puccinia species in cereals, 20 Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea (gray mold) in strawberries and grapes, t:ercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in ~heat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 30 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 35 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 40 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 ~3~t~
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., 5 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-lO ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants 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 15 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.
Exarnples 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--pyrrolidone, which is suitable for application in the 30 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 I mole of oleic acid-N-monoethanolamide, 5 parts by 35 weight of the calcium salt of dodecy1benzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and I mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is obtained.
40 III. An aqueous dispersion of 20 parts hy weight of compound no. 2.15, 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.
2n3~
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 ~10 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor 5 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 diisobutylnaphthalene--sulfonic 10 acid, 10 parts by weight of the sodium salt of a lignin-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.
15 Vl . An intimate mixture of 3 parts by weight of compound no. 2.15 and 97 parts by weight of particulate kaolin. The dust contains 3wt70 of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 2.15, 920 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.
Vlll. A stable aqueous dispersion of 40 parts by weight of compound no.
25 2.15, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts o-f 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, 30 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.
35 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 fertili ers. Admixture with other fun-gicides frequently results in a greater fungicidal action spectrum.
4~
2 8 3 '~
27 O.Z. 0050J41358 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.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, 10 zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfides, 15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N -propylenebisdithiocarbamate, zinc N,N -propylenebisdithioccarbamate and N,N -polypropylenebis(thiocarbamyl) disulfide;
20 nitro derivatives, such as dinitro(l-methylheptyl)-phenyl crotonate, 2-sec-but~yl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbollate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 3~ 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio~4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 35 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, 4~
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothia~ole, l,4-dichloro-2,5-dimethoxyben7ene, 2~3~
28 O.Z. 0050/41358 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethyl~uran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, 15 piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyImorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-~3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, 20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-one, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1~1-1,2,4-triazol-1-yl)-butan-2-ol, a-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, 30 bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis~(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as 3~ dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2 -methoxyacetyl)-alanate, 40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, ~ ~3 3 '~
29 O.Z. 0050/41358 N-(3,5-dichlorophenyl)-1,2-dimethylcyclcpropane-1,2-dicarboximide, 2--cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide, l-[2-(2~4-dich!orophenyl)-pentyl]-lH-l~2~4-triazole~
2,4-difluoro--(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, 5 N-(3-chloro-2,6-dinitro-4 trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and l-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
use Example lO 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 22C in a high-humidity (90 - 95%) chamber. During 15 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~o 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 22C and a relative humidity of 65 to 70%. The 20 extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredient 2.15, applied as a 0.025wt% spray liquor, has a good fungicidal action (100%).
3~
The thioenol ethers 7 can be obtained rom the enol ethers 6 by reaction with methyl mercaptan (EP
5178 826, scheme 4~.
Scheme 4 A-X- ( CH 2 ) n`S~~ A--X--( CH 2 ) n`S~
H 3C0 2C~CHOCH 3 H 3C0 2C~CHSCH 3 6 . 7 A and n are as above.
Th~ Examples below illustrate the preparation of novel compounds.
Methyl ~-(2-benzylthioc:yclohexyl)--oxoacetate (Compound No. 1.15) 2 g (12 mmol) of methyl ~-cyclohexlenyl-~-oxo-acetate, 1.5 g (12 mmol) of benzyl mercaptan and 1 g (10 mmol) o triethylamine in 10 ml of methylene chloride are stirred at room temperature (20C~ for 15 hour~.
After the ~tirring period, water is added to the batch, and the aqueous phase i~ extracted with methylene chloride. The organic pha~e i9 extracted with water, dried over MgSO~ and evaporated.
Chromatographic purification of the crude product gi~es 2.3 g (66 ~) of the title compound as a pale yellow oil.
IR (cm1): 2933, 1727, 1277, 1069.
Methyl ~-(2-benzylthiocyclohexyl)-~-axoacetate O-methyl oxime (Compound No. 2.15) 2.3 g (7.9 mmol) of methyl ~-(2-benzylthiocyclo-he~yl)-~-oxoacetate (E~ample 1) and 0.~6 g (8 mmol) of methoxyamine hydrochloride in 15 ml of methanol are stirred at room temperature for 15 hours.
~3~
_ 5 _ o.Z. 0050/41358 Water is added to the reaction mixture~ and the aqueou~ phase is extracted with ether. The organic phase is washed with water, dried over MgSO4 and evaporated.
Chromatographic purification of the crude product gives S 1 g (40 %) of the title compound as a pale yellow oil.
IR (cm~l): 2935, 1726,1151, 1042.
2~3'~
89082~
6 o.Z~ 0050/41358 Table I
A-X-~CH2)n`S~
No. A-X-(CH2)n mp. IR: v~cm~1) 5 1. 1 H
1. 2 methyl 1. 3 ethyl 1. 4 isopropyl 1. 5 butyl 10 1. 6 sec.-butyl 1. 7 t-butyl 1. 8 isobutyl 1. 9 pentyl 1.10 pivaloyl 15 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 20 1.16 phenylethyl 1.17 phenylpropyl 1.18 phenylpentyl I .1 9 1 -naphthy l 1.20 2-naphthyl 25 1.21 2-bromophenyl 1.22 3-bromophenyl 1.23 4-bromophenyl 1.24 2-chlorophenyl 1.25 3-chlorophenyl 30 1.26 4-chlorophenyl 1.27 2-fluorophenyl 1.28 3-fluorophenyl 1.29 4-fluorophenyl 1.30 2-methylphenyl 35 1.31 3-methylphenyl 1.32 4-methylphenyl 1.33 2-ethyl-phenyl 1.34 3-ethyl-phenyl 1.35 4-ethyl-phenyl 7 O.Z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~1) 5 1.36 2-iso-propyl-phenyl 1.37 3-iso-propyl-phenyl 1.38 4-iso-propyl-phenyl 1.39 2-tert.-butyl-phenyl 1.40 3-tert.-butyl-phenyl 10 1.41 4-tert.-butyl-phenyl 1.42 4-butyl-phenyl 1.43 4-hexyl-phenyl 1.44 4-nonyl-phenyl 1.45 4-decyl-phenyl 15 1.46 2-methoxy-phenyl 1.47 3-methoxy-phenyl 1.48 4-methoxy-phenyl 1.49 2-trifluoromethyl-phenyl 1.50 3-trifluoromethyl-phenyl 20 1.51 4-trifluoromethyl-phenyl 1.52 2-formylphenyl 1.53 3-formylphenyl 1.54 4-formylphenyl 1.55 2-allyl-O-N=CH-phenyl 25 1.S6 3-allyl-O-N=CH-phenyl 1.57 4-alIyl-O-N-CH-phenyl 1.58 2-nitro-phenyl 1.59 3-nitro-phenyl 1.60 2,4-dichlorophenyl 30 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 35 1.66 2,3,4-trichlorophenyl 1.67 2,4,5-trichlorophenyl 1.68 2,4,6-trichlorophenyl 1. 69 2,3,4,6-tetrachlorophenyl 1. 70 2,3,4,5,6-pentachlorophenyl 40 1. 71 2,3,4,5-tetrafluorophenyl 1. 72 2,3,5,6-tetrafluorophenyl 1. 73 2,3,4,5,6-penta~luorophenyl 2~
8 O.Z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 1. 74 2-chloro, 4-fluorophenyl 1. 75 3-chloro, 4-fluorophenyl 1. 76 2-chloro, 6-methyl-phenyl 1. 77 4-chloro, 2-methyl-phenyl 1. 78 2,4-dichloro, 5-methyl-phenyl 10 l. 79 4-chloro, 2,5-dimethyl-phenyl 1. 80 4-bromo, 2-methyl-phenyl 1. 81 3,5-bistrifluoromethyl-phenyl 1. 82 2,3-dimethyl-phenyl 1. 83 2,4-dimethyl-phenyl 15 1. 84 2,5-dimethyl-phenyl 1. 85 2,6-dimethyl-phenyl 1. 86 3,4-dimethyl-phenyl 1. 87 3,5-dimethyl-phenyl 1. 88 2,4,5-trilnethyl-phenyl 20 1. 89 2,6-diethyl-phenyl 1. 90 2,4-di-tert.-butyl-phenyl 1. 91 2,5-dimethoxy-phenyl 1. 92 3,4-dimethoxy-phenyl 1. 93 2-methyl, 4-terlt.-butyl-phenyl 25 1. 94 2-methoxycarbonyl-phenyl 1. 95 2-ethoxycarbonyl-phenyl 1. 96 2-propoxycarbonyl-phenyl 1. 97 2-butoxycarbonyl-phenyl 1. 98 2-cyano-phenyl 30 1. 99 3-cyano-phenyl 1.100 4-cyano-phenyl 1.101 1-naphthylmethyl 1.102 2-naphthylmethyl 1.103 2-bromobenzyl 35 1.104 3-bromobenzyl 1.105 4-bromobenzyl 1.106 2-chlorobenzyl 1.107 3-chlorobenzyl 1.108 4-chlorobenzyl 40 1.109 2-fluorobenzyl 1.110 3-fluorobenzyl 1.111 4-fluorobenzyl 1.112 2-methylbenzyl 2~3~ ~ ~5 9 o.z. 0050/41358 Table 1 (contd.) No. A-X-lC~l2)n mp. IR: v(cm~1) 5 1.113 3-methylbenzyl 1.114 4-methylbenzyl 1.115 2-methoxybenyzl 1.116 3-~ethoxybenzyl 1.117 4-methoxybenzyl 10 1.118 4-ethoxybenzyl 1.119 4-butyloxybenzyl 1.120 4-benzyloxybenzyl 1.121 2-trifluoromethyl-benzyl 1.122 3-trifluoromethyl-benzyl lS 1.123 4-trifluoromethyl-benzyl 1.124 2-formylbenzyl 1.125 3-formylbenzyl 1.126 4-formylbenzyl 1.127 2-allyl-O-N=CH-benzyl 2~ 1.128 3-allyl--O-N=CH-benzyl 1.129 4-allyl--O-N=CH-benzyl 1.130 2-nitrobenzyl 1.131 3-nitrobenzyl 1.132 2,4-dichlorobenzyl 25 1.133 2,6-dichlorobenzyl 1.134 3,4-dichlorobenzyl 1.135 2,3-dichlorobenzyl 1.136 3,5-dichlorobenzyl 1.137 2,3-dimethylbenzyl 3~ 1.138 2,4-dimethylbenzyl 1.139 2,5-di~ethylbenzyl 1.140 2,6-dimethylbenzyl 1.141 3,4-dimethylbenzyl 1.142 3,5-dimethylbenzyl 35 1.143 4-chloro-2-methylbenzyl t.144 2-methoxycarbonyl-benzyl 1.145 2-ethoxycarbonyl-benzyl 1.146 2-butoxycarbonyl-benzyl 1.147 2-cyano-benzyl 40 1.148 3-cyano-benzyl 1.149 4-cyano-benzyl 1.150 2-pyridyl 1.151 3-pyridyl 2 ~ 1 5 ~
o.z. 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 1.152 4-pyridyl 1.153 6-methyt-2-pyridyl 1.154 6-ethyl-2-pyridyl 1.155 6-n-propyl-2-pyridyl 1.156 6-n-butyl-2-pyridyl 10 1.157 6-tert.-butyl-2-pyridyl 1.158 6-n-hexyl-2-pyridyl 1.159 6-phenyl-2-pyridyl 1.160 6-benzyl-2-pyridyl 1.161 6-trifluoromethyl-2-pyridyl 15 1.162 6-methoxy-2-pyridyl 1.163 6-chloro-2-pyridyl 1.164 3,6-dimethyl-2-pyridyl 1.165 4,6-dimethyl-2-pyridyl 1.166 5,6-dimethyl-2-pyridyl 20 1.167 4-phenyl-6-methyl-2-pyridyl 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-dimethyl-2-pyridyl 25 1.172 3-cyano-6-~ethyl-2-pyridyl 1.173 3-cyano-6-phenyl-2-pyridyl 1.174 3-methyloxycarbonyl-2-pyridyl 1.175 3-methyloxycarbonyl-6-iso-propyl-2-pyridyl 1.176 5-trifluoromethyl-2-pyridyl 30 1.177 2-quinolyl 1.178 3-methyl-2-quinolyl 1.179 4-phenyl-2-quinolyl 1.180 8-chloro-2-quinolyl 1.181 4-methyl-8-methoxy-2-quinolyt 35 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 40 1.187 4-trifluoromethyl-2-pyrimidinyl 1.188 4,6-dimethyl-5-chloro-2-pyrimidinyl 1.189 3,5-dimethyl-4-pyrimidinyl 1.190 2-pyrazinyl 2~t3~
ll o.Z~ 0050/41358 Table I (contd.) No. A-X-(CH2)n mp. 1~: v(cm~1) 5 1 . 191 2-thienyl 1.192 3-thienyl 1.193 3-methyl-2-quinoxalinyl 1.194 3-phenyl-5-isoxazolyl 1.195 2-benzoxazolyl 10 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-methyl-2-benzothiazolyl 15 1.201 6-methoxy-2-benzothiazolyl 203l~ L~6 12 O.Z. 0050/41358 Table 2 A-X--(CH2)n`S~
No. A-X-(CH2)n mp. IR: v(cm~1) 5 2. 1 H
2. 2 methyl 2. 3 ethyl 2. 4 isopropyl 2. 5 butyl 10 2. 6 sec.-butyl 2. 7 t-butyl 2. 8 isobutyl 2. 9 pentyl 2.10 pivaloyl 15 2.11 hexyl 2.12 octyl 2.13 decyl 2.14 phenyl oi1 2935,1738,1722,1152,1043 2.15 benzyl oil 2935,1726,1151,1042 20 2.16 phenylethyl 2.17 phenylpropyl 2~18 phenylpentyl 2.19 I-naphthyl 2.20 2-naphthyl 25 2.21 2-bromophenyl 2.22 3-bromophenyl 2.23 4-bromophenyl 2.24 2-chlorophenyl 2.25 3-chlorophenyl 30 2.26 4-chlorophenyl 2.27 2-fluorophenyl 2.28 3-fluorophenyl 2.29 4-~luorophenyl 2.30 2-methylphenyl 35 2.31 3-methylphenyl 2.32 4-methylphenyl 2.33 2-ethyl-phenyl 2.34 3-ethyl-phenyl 2.35 4-ethyl-phenyl . .
.
2~3~
~90828 13 o.Z. 0050/~1358 Table 2 (contd.) No. A-%-lCH2)n mp. IR: v(cm~l) 5 2.36 2-iso-propyl-phenyl 2.37 3-iso-propyl-phenyl 2.38 4-iso-propyl-phenyl 2.39 2-tert.-butyl-phenyl 2.40 3-tert.-butyl-phenyl 10 2.41 4-tert.-butyl-phenyl 2.42 4-butyl-phenyl 2.43 4-hexyl-phenyl 2.44 4-nonyl-pheny1 2.45 4-decyl-phenyl 15 2.46 2-methoxy-phenyl 2.47 3-methoxy-phenyl 2.48 4-methoxy-phenyl 2.49 2-trifluoromethyl-phenyl 2.50 3-trifluoromethyl-phenyl 20 2.51 4-trifluoromethyl-phenyl 2.52 2-formylpheryl 2.53 3-formylphenyl 2.54 4-formylphenyl 2.55 2-alIyl-O-N=C~phenyl 25 2.56 3-alIyl-O-N=CH-phenyl 2.57 4-alIyl-O-N-CH-phenyl 2.58 2-nitro-phenyl 2.59 3-nitro-phenyl 2.60 2,4-dichlorophenyl 30 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 35 2.66 2,3,4-trichlorophenyl 2.67 2,4,5-trichlorophenyl 2.68 2,4,6-trichlorophenyl 2. 69 2,3,4,6-tetrachlorophenyl 2. 70 2,3,4,5,6-pentachlorophenyl 40 2. 71 2,3,4,5-tetrafluorophenyl 2. 72 2,3,5,6-tetrafluorophenyl 2. 73 2,3,4,5,6-pentafluorophenyl 2. 74 2-chloro, 4-fluorophenyl "` 2~3~
14 O.z. 0050/41358 Table 2 tcontd.) No. A-X-~C~2)n mp. IR: v(cm~l) 5 2. 75 3-chloro, 4-fluorophenyl 2. 76 2-chloro, 6-methyl-phenyl 2. 77 4-chloro, 2-methyl-phenyl 2. 78 2,4-dichloro, 5-methyl-phenyl 2. 79 4-chloro, 2,5-dimethyl-phenyl 10 2. 80 4-bromo, 2-methyl-phenyl 2. 81 3,5-bistrifluoromethyl-phenyl 2. 82 2,3-dimethyl-phenyl 2. 83 2,4-dimethyl-phenyl 2. 84 2,5-dimethyl-phenyl 15 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 20 2. 90 2,4-di-tert.-butyl-phenyl 2. 91 2,5-dimethoxy-phenyl 2. 92 3,4-dimethoxy-phenyl 2. 93 2-methyl, 4-tert.-butyl-phenyl 2. 94 2-methoxycarbonyl-phenyl 25 2. 95 2-ethoxycarbonyl-phenyl 2. 96 2-propoxycarbonyl-phenyl 2. 97 2-butoxycarbonyl-phenyl 2. 98 2-cyano-phenyl 2. 99 3-cyano-phenyl 30 2.100 4-cyano-phenyl 2. 101 I-naphthylmethyl 2.102 2-naphthylmethyl 2.103 2-bromobenzyl 2.104 3-bromobenzyl 35 2.105 4-bromobenzyl 2.106 2-chlorobenzyl 2.107 3-chlorobenzyl 2.108 4-chlorobenzyl 2.109 2-fluorobenzyl 40 2.110 3-fluorobenzyl 2.111 4-fluorobenzyl 2.112 2-methylbenzyl 2.113 3-methylbenzyl .
~3~
O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.114 4-methylbenzyl 2.115 2-methoxybenyzl 2.116 3-methoxybenzyl 2. 117 4-methoxybenzyl 2.118 4-ethoxybenzyl 10 2.119 4-butyloxybenzyl 2.120 4-benzyloxybenzyl 2.121 2-trifluoromethyl-benzyl 2.122 3-trifluoromethyl-benzyl 2.123 4-trifluoromethyl-benzyl 15 2.124 2-formylbenzyl 2.125 3-formylbenzyl 2.126 4-formylbenzyl 2.12 7 2-allyl-O-N=CH-benzyl 2.128 3-allyl-O-N=CH-benzyl 20 2.129 4-allyl-O-N=CH-benzyl 2.130 2-nitrobenzyl 2.131 3-nitrobenzyl 2.132 2,4-dichlorobenzyl 2.133 2,6-dichlorobenzyl 25 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 30 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 35 2.144 2-methoxycarbonyl-benzyl 2.145 2-ethoxycarbonyl-benzyl 2.146 2-butoxycarbonyl-benzyl 2.147 2-cyano-benzyl 2.148 3-cyano-benzyl 40 2.149 4-cyano-benzyl 2~150 2-pyridyl 2.151 3-pyridyl 2.152 4-pyridyl 2~3'~15~
16 O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.153 6-methyl-2-pyridyl 2.154 6-ethyl-2-pyridyl 2.155 6-n-propyl-2-pyridyl 2.156 6-n-butyl-2-pyridyl 2.157 6-tert.-buty1-2 pyridyl 10 2.158 6-n-hexyl-2-pyridyl 2.159 6-phenyl-2-pyridyl 2.160 6-benzyl-2-pyridyl 2.161 6-trifluoromethyl-2-pyridyl 2.162 6-metho~y-2-pyridyl 15 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-phenyl-6-methyl-2-pyridyl 20 2.168 ~,4-dichloro-6-methyl-2-pyridyl 2.169 3,4,5-trichloro-6-methyl-2-pyridyl 2.170 4-trifluoromethyl-6-methyl-2-pyridyl 2.171 3-acetyl-4,6-dimethyl 2-pyridyl 2.172 3-cyano-6-methyl-2-pyridyl 25 2.173 3-cyano-6-phenyl-2-pyridyl 2.174 3-methyloxycarbonyl-2-pyridyl 2.175 3-methyloxycarbonyl-6-iso-propyl-2-pyridyl 2.176 5-trifluoromethyl-2-pyridyl 2.177 2-quinolyl 30 2.178 3-methyl-2-quin~lyl 2.179 4-phenyl-2-quinolyl 2.180 8-chloro-2-quinolyl 2.181 4-methyl-8-methoxy-2-quinolyl 2.182 4-quinolyl 35 2.183 2,6-dimethyl-4-quinolyl 2.184 8-quinolyl 2.185 5,7-dichloro-8-quinolyl 2.186 2-pyrimidinyl 2.187 4-trifluoromethyl-2-pyrimidinyl 40 2.188 4,6-dimethyl-5-chloro-2-pyrimidinyl 2.189 3,5-dimethyl-4-pyrimidinyl 2.190 2-pyra7inyl 2. 191 2-thienyl ~03~
17 O.Z. 0050/41358 Table 2 (contd.) No. A-X-(CH2)n mp. IR: v(cm~l) 5 2.192 3-thienyl 2.193 3-methyl-2-quinoxalinyl 2.194 3-phenyl-5-isoxazolyl 2.195 2-benzoxazolyl 2.196 2-benzthiazolyl 10 2.197 4-chloro-2-benzothiazolyl 2.198 5-chloro-2-benzothiazolyl 2~199 6-chloro-2-benzothiazolyl 2.200 6-methyl-2-benzothiazolyl 2.201 6-methoxy-2-benzothiazolyl 203~
18 o.Z. 0050/41358 Table 3 f~
A--X--(CH2)n`$~
H3C02C-l~CHOCH3 No. A-X-(CH2)n mp. IR: v~cm~1) 5 3. I n-butyl 3. 2 phenyl 3. 3 2-methoxyphenyl 3. 4 3-methoxyphenyl 3. 5 4-methoxyphenyl 10 3. 6 2-chlorophenyl 3. 7 3-chlorophenyl 3. 8 4-chlorophenyl 3. 9 2-methylphenyl 3.10 3-methylphenyl 15 3.11 4-methylphenyl 3.12 2,3-dimethylphenyl 3.13 2,4-dimethylphenyl 3.14 2,5-dimethylphenyl 3.15 2,6-dimethylphenyl 20 3.16 3,4-dimethylphçnyl 3.17 3,5 dimethylphenyl 3.18 4-chloro-2-methylphenyl 3.19 4-methoxycarbonylphenyl 3.20 4-ethoxycarbonylphenyl 25 3.21 4-butoxycarbonylphenyl 3.22 2-alIyl-0-N=CH-phenyl 3.23 3-alIyl-0-N=CH-phenyl 3.24 4-allyl-0-N=CH-phenyl 3.25 2-pyridyl 30 3.26 6-methyl-2-pyridyl 3.27 6-chloro-2-pyridyl 3.28 4-chloro-2-benzothiazolyl 3.29 5-chloro-2-benzothiazolyl 3.30 6-chloro-2-benzothiazolyl 35 3.31 2-methoxybenzyl 3.32 3-methoxybenzyl 3.33 4-methoxybenzyl 3.34 2-chlorobenzene 3.35 3-chlorobenzene 2~3~
19 0.7. 0050~41358 Table 3 (contd.) No. A-x-lc~i2)n mp. IR: v(cm~1) 5 3.36 4-chlorobenzyl 3.37 2-methylbenzyl 3.38 3-methylbenzyl 3.39 4-methylbenzyl 3.40 2,3-dimethylbenzyl 10 3.41 2,4-dimethylbenzyl 3.42 2,5-dimethylbenzyl 3~43 2,6-dimethylbenzyl 3.44 3,4-dimethylbenzyl 3.45 3,5-dimethyIbenzyl 15 3.46 4-chloro-2-methylbenzyl 3.47 4-methoxycarbonylb~nzyl 3.48 4-ethoxycarbonylbenzyl 3.49 4-butoxycarbonylbenzyl 3.50 2-allyl-O-N=CH-phenyl 20 3.51 3-allyl-O-N=CH-phenyl 3.52 4-allyl-O-N=CH-phenyl 2~3~S
O.Z. 0050J41358 Table 4 A-X-(CH2)n`S ~
No. A-X-(CH2)n mp. IR: v(cm~1) 5 4. 1 n-butyl 4. 2 phenyl 4. 3 2-methoxyphenyl 4. 4 3-methoxyphenyl 4. 5 4-methoxyphenyl 10 4. 6 2-chlorophenyl 4. 7 3-chlorophenyl 4. 8 4-chlorophenyl 4. 9 2-methylphenyl 4.10 3-methylphenyl 15 4.11 4-methylphenyl 4.12 2,3-dimethylphenyl 4.13 2,4-dimethylphenyl 4.14 2,5-dimethylphenyl 4.15 2,6-dimethylphenyl 2~ 4.16 3,4-dimethylphenyl 4.17 3,5-dimethylphenyl 4.18 4-chloro-2-methylphenyl 4.19 4-methoxycarbonylphenyl 4.20 4-ethoxycarbonylphenyl 25 4.21 4-butoxycarbonylphenyl 4.22 2-alIyl-O-N=CH-phenyl 4.23 3-allyl-O-N=CH-phenyl 4.24 4-allyl-O-N=CH-phenyl 4.25 2-pyridyl 30 4.26 6-methyl-2-pyridyl 4.27 6-chloro-2-pyridyl 4.28 4-chloro-2-benzothiazolyl 4.29 5-chloro-2-benzothiazolyl 4.30 6-chloro-2-benzothiazolyl 35 4.31 2-methoxybenzyl 4.32 3-methoxybenzyl 4.33 4-methoxybenzyl 4.34 2-chlorobenzene 4.35 3-chlorobenzene ~3~
21 O.Z. 0050/41358 Table 4 (contd.) No. A-X-¦CH2)n mp. IR: v(cm~1) 5 4.36 4-chlorobenzyl 4.37 ~-methylbenzyl 4.38 3-methylbenzyl 4.39 4-methylbenzyl 4.40 2,3-dimethylbenzyl 10 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 15 4.46 4-chloro-2-methylbenzyl 4.47 4-methoxycarbonylbenzyl 4.48 4-ethoxycarbonylbenzyl 4.49 4-butoxycarbonylbenzyl 4.50 2-allyl-O-N=CH-phenyl 20 4.51 3-allyl-O-N=CH-phenyl 4.52 4-alIyl-O-N=CH-phenyl ~031~5~
89~828 22 O.Z. 0050/41358 Table 5 f~ .
A-x-(cH2)n`s~
H3CO2C~U
No. A-X-(CH2)n U mp. I~: Y/cm 1) 5 5. 1 2-methylphenyl CH2 5. 2 3-methoxyphenyl CH2 5. 3 4-chlorophenyl CH2 5. 4 2-allyl-O-N=CH-phenyl CH2 5. 5 3-methoxycarbonylphenyl CH2 10 5. 6 6-chloro-2-pyridyl CH2 5. 7 6-chloro-2-benzothiazolyl CH2 5. 8 2-methylbenzyl CH2 5. 9 3-methoxybenzyl CH2 5.10 4-chlorobenzyl CH2 15 5.11 2-alIyl-O-N=CH-benzyl CH2 5.12 3-methoxycarbonyl-benzyl CH2 5.13 2-methylphenyl CH-CH2-CH3 5.14 3-methoxyphenyl CH-CH2-CH3 5.15 4-chlorophenyl CH-CH2-CHl3 20 5.16 2-allyl-O-N=CH-phenyl CH-CH2-CHl3 5.17 3-methoxycarbonylphenyl CH-CH2-CHl3 5.18 6-chloro-2-pyridyl CH-CH2-C~ll3 5.19 6-chloro-2-benzothiazolyl CH-CH2-CH3 5.20 2-methylbenzyl cH-cH2-c~l3 z5 5.21 3-methoxybenzyl CH-CH2-C~l3 5.22 4-chlorobenzyl CH-CH2-CH3 5.23 2-allyl-O-N=CH-benzyl CH-CH2-CH3 5.24 3-methoxycarbonyl-benzyl CH-CH2-CH3 5.25 2-methylphenyl N-NH-CH3 30 5~26 3-methoxyph~nyl N-NH-CH3 5.27 4-chlorophenyl N-NH-CH3 5.28 2-allyl-O-N=CH-phenyl N-NH-CH3 5.29 3-methoxycarbonylphenyl N-NH-CH3 5.30 6-chloro-2-pyridyl N-NH-CH3 35 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-allyl-O-N=CH-benzyl N-NH-CH3 2 ~ 3 ~ 6 23 O.Z. 0050/41358 Table 5 (contd.) No. A-X-(CH2)n U mp. IR: v/cm~1) 5 5.36 3-methoxycarbonyl-benzyl N-NH-CH3 5.37 2-methylphenyl CH-S-CH3 5.38 3-methoxyphenyl CH-S-CH3 5.39 4-chlorophenyl CH-S-CH3 5.40 2-allyl-0-N=CH-phenyl CH-S-CH3 10 5.41 3-methoxycarbonylphenyl CH-S-CH3 5.42 6-chloro-2-pyridyl CH-S-CH3 5.43 6-chloro-2-benzothiazolyl CH-S-CH3 5.44 2-methylbenzyl CH-S-CH3 5.45 3-methoxybenzyl CH-S-CH3 15 5.46 4-chlorobenzyl CH-S-CH3 5.47 2-allyl-0-N=CH-benzyl CH-S-CH3 5.48 3-methoxycarbonyl-benzyl CH-S-CH3 2 ~
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 10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
15 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula neçator in vines, Puccinia species in cereals, 20 Rhizoctonia solani in cotton, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, 25 Botrytis cinerea (gray mold) in strawberries and grapes, t:ercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in ~heat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, 30 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 35 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 40 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 ~3~t~
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., 5 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-lO ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants 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 15 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.
Exarnples 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--pyrrolidone, which is suitable for application in the 30 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 I mole of oleic acid-N-monoethanolamide, 5 parts by 35 weight of the calcium salt of dodecy1benzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and I mole of castor oil. By finely dispersing the mixture in water, an aqueous dispersion is obtained.
40 III. An aqueous dispersion of 20 parts hy weight of compound no. 2.15, 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.
2n3~
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 ~10 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor 5 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 diisobutylnaphthalene--sulfonic 10 acid, 10 parts by weight of the sodium salt of a lignin-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.
15 Vl . An intimate mixture of 3 parts by weight of compound no. 2.15 and 97 parts by weight of particulate kaolin. The dust contains 3wt70 of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 2.15, 920 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.
Vlll. A stable aqueous dispersion of 40 parts by weight of compound no.
25 2.15, 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts o-f 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, 30 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.
35 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 fertili ers. Admixture with other fun-gicides frequently results in a greater fungicidal action spectrum.
4~
2 8 3 '~
27 O.Z. 0050J41358 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.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, 10 zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfides, 15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate, ammonia complex of zinc N,N -propylenebisdithiocarbamate, zinc N,N -propylenebisdithioccarbamate and N,N -polypropylenebis(thiocarbamyl) disulfide;
20 nitro derivatives, such as dinitro(l-methylheptyl)-phenyl crotonate, 2-sec-but~yl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbollate and diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as 2-heptadecylimidazol-2-yl acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 3~ 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio~4,5-b]quinoxaline, methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 35 2-(fur-2-yl)-benzimidazole, 2-(thiazol-4-yl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, 4~
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothia~ole, l,4-dichloro-2,5-dimethoxyben7ene, 2~3~
28 O.Z. 0050/41358 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine l-oxide, 8-hydroxyquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne, 5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, 10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-diethyl~uran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethylacetal, 15 piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide), 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyImorpholine and its salts, 2,6-dimethyl-N-cyclododecylmorpholine and its salts, N-~3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, 20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4--triazole, 25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-one, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1~1-1,2,4-triazol-1-yl)-butan-2-ol, a-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine, 30 bis-(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis~(3-ethoxycarbonyl-2-thioureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as 3~ dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene, DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, methyl DL-N-(2,6-dimethylphenyl)-N-(2 -methoxyacetyl)-alanate, 40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin, ~ ~3 3 '~
29 O.Z. 0050/41358 N-(3,5-dichlorophenyl)-1,2-dimethylcyclcpropane-1,2-dicarboximide, 2--cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide, l-[2-(2~4-dich!orophenyl)-pentyl]-lH-l~2~4-triazole~
2,4-difluoro--(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, 5 N-(3-chloro-2,6-dinitro-4 trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and l-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
use Example lO 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 22C in a high-humidity (90 - 95%) chamber. During 15 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~o 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 22C and a relative humidity of 65 to 70%. The 20 extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredient 2.15, applied as a 0.025wt% spray liquor, has a good fungicidal action (100%).
3~
Claims (5)
1. Unsaturated cyclohexylacetic acid derivatives of the formula I
I
where U is =NOCH3, =CHOCH3, =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.
I
where U is =NOCH3, =CHOCH3, =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 =NOCH3, n is 1, 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
I
where U is =NOCH3, =CHOCH3, =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.
US,CA,AU,NZ,TW,KR,IL
31 O.Z. 0050/41358
I
where U is =NOCH3, =CHOCH3, =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.
US,CA,AU,NZ,TW,KR,IL
31 O.Z. 0050/41358
4. An insecticide containing an inert carrier and an insecticidally effective amount of a compound of the formula I
I
where U is =NOCH3, =CHOCH3, =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.
I
where U is =NOCH3, =CHOCH3, =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.
5. A process for combating fungi, wherein the fungi or the plants, seed, materials or the soil to be protected agalnst fungus attack are treated with a fungicidally effective amount of a compound of the formula I
I
where U is =NOCH3, =CHOCH3, =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.
I
where U is =NOCH3, =CHOCH3, =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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4001618.8 | 1990-01-20 | ||
| DE4001618A DE4001618A1 (en) | 1990-01-20 | 1990-01-20 | UNSATURED CYCLOHEXYL ACETIC DERIVATIVES AND PLANT PROTECTION PRODUCTS CONTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2034156A1 true CA2034156A1 (en) | 1991-07-21 |
Family
ID=6398465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002034156A Abandoned CA2034156A1 (en) | 1990-01-20 | 1991-01-15 | Unsaturated cyclohexylacetic acid derivatives, and crop-protection agents containing same |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0438726B1 (en) |
| JP (1) | JPH054961A (en) |
| KR (1) | KR910014346A (en) |
| AT (1) | ATE102922T1 (en) |
| AU (1) | AU629088B2 (en) |
| CA (1) | CA2034156A1 (en) |
| CS (1) | CS11391A2 (en) |
| DE (2) | DE4001618A1 (en) |
| DK (1) | DK0438726T3 (en) |
| ES (1) | ES2062278T3 (en) |
| HU (1) | HU208310B (en) |
| IL (1) | IL96896A (en) |
| NZ (1) | NZ236824A (en) |
| ZA (1) | ZA91371B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4131311A1 (en) * | 1991-09-20 | 1993-04-01 | Basf Ag | DIHYDROPYRENE DERIVATIVES AND ITS PLANT PROTECTION AGENTS |
| AU3093897A (en) * | 1996-06-12 | 1998-01-07 | Novartis Ag | Pesticides |
| ATE212617T1 (en) * | 1996-06-25 | 2002-02-15 | PESTICIDES | |
| WO2013008593A1 (en) | 2011-07-08 | 2013-01-17 | 三洋化成工業株式会社 | Polyurethane resin for moisture-permeable water-proof materials, and polyurethane resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299969A (en) * | 1980-08-08 | 1981-11-10 | Smithkline Corporation | Method for preparing lower alkyl β-(S-benzylmercapto)-β,β-pentamethylenepropionates |
| DE68905765T3 (en) * | 1988-11-21 | 1998-03-26 | Zeneca Ltd | Fungicides. |
| DE3843439A1 (en) * | 1988-12-23 | 1990-06-28 | Basf Ag | SULFURIZED OXIMETERS AND FUNGICIDES CONTAINING THEM |
-
1990
- 1990-01-20 DE DE4001618A patent/DE4001618A1/en not_active Withdrawn
- 1990-12-18 EP EP90124481A patent/EP0438726B1/en not_active Expired - Lifetime
- 1990-12-18 DE DE90124481T patent/DE59005018D1/en not_active Expired - Lifetime
- 1990-12-18 ES ES90124481T patent/ES2062278T3/en not_active Expired - Lifetime
- 1990-12-18 AT AT90124481T patent/ATE102922T1/en not_active IP Right Cessation
- 1990-12-18 DK DK90124481.4T patent/DK0438726T3/en active
-
1991
- 1991-01-07 IL IL9689691A patent/IL96896A/en not_active IP Right Cessation
- 1991-01-15 CA CA002034156A patent/CA2034156A1/en not_active Abandoned
- 1991-01-16 JP JP3003260A patent/JPH054961A/en not_active Withdrawn
- 1991-01-17 KR KR1019910000691A patent/KR910014346A/en not_active Application Discontinuation
- 1991-01-18 HU HU91176A patent/HU208310B/en not_active IP Right Cessation
- 1991-01-18 AU AU69476/91A patent/AU629088B2/en not_active Ceased
- 1991-01-18 CS CS91113A patent/CS11391A2/en unknown
- 1991-01-18 NZ NZ236824A patent/NZ236824A/en unknown
- 1991-01-18 ZA ZA91371A patent/ZA91371B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2062278T3 (en) | 1994-12-16 |
| HU910176D0 (en) | 1991-08-28 |
| HUT56817A (en) | 1991-10-28 |
| ZA91371B (en) | 1992-09-30 |
| DK0438726T3 (en) | 1994-04-05 |
| AU6947691A (en) | 1991-07-25 |
| IL96896A (en) | 1994-10-21 |
| ATE102922T1 (en) | 1994-04-15 |
| DE4001618A1 (en) | 1991-07-25 |
| NZ236824A (en) | 1992-05-26 |
| JPH054961A (en) | 1993-01-14 |
| AU629088B2 (en) | 1992-09-24 |
| DE59005018D1 (en) | 1994-04-21 |
| CS11391A2 (en) | 1991-09-15 |
| EP0438726A1 (en) | 1991-07-31 |
| IL96896A0 (en) | 1992-03-29 |
| HU208310B (en) | 1993-09-28 |
| KR910014346A (en) | 1991-08-31 |
| EP0438726B1 (en) | 1994-03-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |