CA2020416A1 - 3-anilinobenzoisothiazoles and fungicides containing these - Google Patents
3-anilinobenzoisothiazoles and fungicides containing theseInfo
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- CA2020416A1 CA2020416A1 CA002020416A CA2020416A CA2020416A1 CA 2020416 A1 CA2020416 A1 CA 2020416A1 CA 002020416 A CA002020416 A CA 002020416A CA 2020416 A CA2020416 A CA 2020416A CA 2020416 A1 CA2020416 A1 CA 2020416A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
O.Z. 0050/40923 ABSTRACT OF THE DISCLOSURE: 3-Anilinobenzoisothiazoles of the formula
Description
20~a~ 6 O.Z. 0050/~0923 3-Anilinobenzoisothiazoles and funqicides con~aining these The present invention relates to novel, valuable 3-anilinobenzoisothiazoles, a process for the preparation S thereof, fungicidal agents containing these compounds, and the use thereof as fungicides.
It has been disclosed (EP 244 705) that 2-anil-inobenzothiazoles, eg. 2-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino)-6-methoxybenzothiazole or 2-(2,6-dinitro-3-chloro-4-trifluoromethylanilino)-6-nitrobenzo-thiazole, have a good fungicidal action. HoweYer, the action is not always satisfactory at low application rates and use concentrations.
We have now found, surprisingly, that 3-anilino-benzoisothiazoles of the formula I
m~ H02 Rl N~R 2 where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, Cl-C4-alkyl,C3-C6-cycloalkyl,Cl-C4-haloalkyl,Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, or phenoxy or phenylthio each of which is unsubstituted or substi-tuted in the phenyl, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, Rl is hydrogen, halogen, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenyl-thio, benzyloxy or benzylthio each o f which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one anoth~r, hydrogen, NO2, halogen, CN, C1-Cs-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, So2NR3R6, Cl-C4-haloalkoxy, CoOR5 or CoNR5R6, 202041~
It has been disclosed (EP 244 705) that 2-anil-inobenzothiazoles, eg. 2-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino)-6-methoxybenzothiazole or 2-(2,6-dinitro-3-chloro-4-trifluoromethylanilino)-6-nitrobenzo-thiazole, have a good fungicidal action. HoweYer, the action is not always satisfactory at low application rates and use concentrations.
We have now found, surprisingly, that 3-anilino-benzoisothiazoles of the formula I
m~ H02 Rl N~R 2 where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, Cl-C4-alkyl,C3-C6-cycloalkyl,Cl-C4-haloalkyl,Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, or phenoxy or phenylthio each of which is unsubstituted or substi-tuted in the phenyl, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, Rl is hydrogen, halogen, Cl-C4-alkoxy, Cl-C4-haloalkyl, Cl-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenyl-thio, benzyloxy or benzylthio each o f which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one anoth~r, hydrogen, NO2, halogen, CN, C1-Cs-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, So2NR3R6, Cl-C4-haloalkoxy, CoOR5 or CoNR5R6, 202041~
- 2 - O.Z. OOS0/40923 R~ is hydrogen, CooR7, CoNR5R6, CHO, CQR7 or So~R7, R5 and R6 are, independently of one another, hydrogen or Cl-C4-alkyl, R7 is Cl-C~-alkyl, C~-C4-haloalkyl, benzyl, or aryl which is substituted or unsubstituted, and the salts thereof which are tolerated by plants have a very good fungicidal action while being excellently tolerated by plants.
The term alkyl, as such or as part of another substituent, such as haloalkyl, alkoxy, alkylthio and haloalkoxy, means, depending on the number of stated carbon atoms, the following straight-chain or branched groups: in particular C1-C4-alkyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl and n-hexyl. The prefix halo in the name of a substituent means, here and hereinafter, that this substituent can contain one or more halogen atoms. Halo represents F, Cl, Br or I. Thus haloalkyl is a mono- to perhalogenated alkyl such as CH2Cl, CHCl2, CCl3, CH2F, CHF2, CF3, CH2Br, CHBrCl, CF2Cl, C2Cl$, C2F5, CHF2, CF2-CHF2, CH2CH2Cl, CH2CH2Br, C3F7 or C4Fg.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclo-pentyl and cyclohexyl, it being possible for the rings to be substituted by one or two methyls, such as 1-methyl-cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclo-propyl, l-methylcyclopentyl or 1-me~hylcyclohexyl.
Examples of aryl which is substituted or unsub-stituted are phenyl, Cl-C4-alkylphenyl, 2-, 3- and 4-tolyl, halophenyl~ 4-bromophenyl, 4-chlorophenyl, 4-I-~fluorophenyl~ nitrophenyl, 2-nitrophenyl, 4-nitrophenyl, and 1- and 2-naphthyl.
Where phenoxy, phenylthio, benzyloxy or benzyl-thio is substituted the aromatic ring carries one to ~hree halogens, such as 2-Cl, 2-F, 3-Cl, 4-Cl, 4-Br, 2,3-Cl2, 2,4-Cl2, 2,5-Cl2, 2,6-C12, 3,5-C12, 2,4,6-C13or 3,4,5-Cl3, or one or two substituents such as nitro or methyl, 2-NO2, 4~NO2, 2-CH3, 4-CH3, 2,6-(CH3)2 or 3,5-(CH3)2.
202~
The term alkyl, as such or as part of another substituent, such as haloalkyl, alkoxy, alkylthio and haloalkoxy, means, depending on the number of stated carbon atoms, the following straight-chain or branched groups: in particular C1-C4-alkyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl and n-hexyl. The prefix halo in the name of a substituent means, here and hereinafter, that this substituent can contain one or more halogen atoms. Halo represents F, Cl, Br or I. Thus haloalkyl is a mono- to perhalogenated alkyl such as CH2Cl, CHCl2, CCl3, CH2F, CHF2, CF3, CH2Br, CHBrCl, CF2Cl, C2Cl$, C2F5, CHF2, CF2-CHF2, CH2CH2Cl, CH2CH2Br, C3F7 or C4Fg.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclo-pentyl and cyclohexyl, it being possible for the rings to be substituted by one or two methyls, such as 1-methyl-cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclo-propyl, l-methylcyclopentyl or 1-me~hylcyclohexyl.
Examples of aryl which is substituted or unsub-stituted are phenyl, Cl-C4-alkylphenyl, 2-, 3- and 4-tolyl, halophenyl~ 4-bromophenyl, 4-chlorophenyl, 4-I-~fluorophenyl~ nitrophenyl, 2-nitrophenyl, 4-nitrophenyl, and 1- and 2-naphthyl.
Where phenoxy, phenylthio, benzyloxy or benzyl-thio is substituted the aromatic ring carries one to ~hree halogens, such as 2-Cl, 2-F, 3-Cl, 4-Cl, 4-Br, 2,3-Cl2, 2,4-Cl2, 2,5-Cl2, 2,6-C12, 3,5-C12, 2,4,6-C13or 3,4,5-Cl3, or one or two substituents such as nitro or methyl, 2-NO2, 4~NO2, 2-CH3, 4-CH3, 2,6-(CH3)2 or 3,5-(CH3)2.
202~
- 3 - O.Z. 0050/40923 Examples of suitable cations for the salts are Na~, Li , K+, Mg2+, Fe3~, NH4~, singly or multiply al~ylated, hydroxyalkylated and/or arylated ammonium cations such as diisopropylammonium, tetramethylammonium, tetrabutyl-ammonium, trimethylbenzyla~monium, N,N-dimethylanilinium or trimethyl(2-hydroxyethyl)ammonium, where the alkyl has l to 4 carbon atoms and the aryl is phenyl or benzyl.
The compounds of the formula I as claimed in claim 1, in which R4 is hydrogen, are prepared, for example, by reacting a benzoisothiazole of the formula II
~S~
m ~ II
where X and m have the meanings specified in claim 1, with compounds of the formula III
Rl NO2 ~ R2 III
Y ~
where Rl, R2 and R3 ha~e the meanings specified in claim 1, with or without a solvent or diluent, in the presence or absence of an organic or inorganic base, at from -20 to 200C, where Y and Z are different from one another and are NHz or halogen.
In both cases, the reaction takes place with elimination of hydrogen halide. This is why it is advan-~tageous to use acid-binding agents or bases in both cases.
Bases and acid-binding agents which can be used are organic or inorganic compounds such as alkali metal and alkaline earth metal hydroxides (LiOH, NaOH, ROH, Ca(OH) 2 ) ~ oxides (Na2O, Li2O, CaO, MgO), hydrides (LiH, NaH, KH, CaH2), amides (LiNH2, NaNH2, RNH2), carbonates (Li2CO3, Na2CO3, CaC03), bicarbonates (NaHCO3), alkyls 2020~6 - 4 - O.z. 0050/40923 ~butylLi, CH3Li, cH3Mgcl)r C t -C5-alc oholates (NaOCH3, NaOC~H5~ KOC7H5, KO-tert-butyl, ~g(OCH3).), amines, especi-ally tertiary amines (eg. trimethylamine, triethylamine, diisopropylethylamine, N-methylpiperidine), pyridine, substituted pyridines (collidine, lutidines, 4-dLmethyl-aminopyridine), and bicyclic amines.
The reactions can be carried out in the presence of inert solvents or diluents.
Suitable examples are aliphatic and aromatic hydrocarbons such as toluene, xylenes, cyclohexane, petroleum ether; halohydrocarbons such as chlorobenzene, methylene chloride, chloroform; ethers such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran;
nitriles such as acetonitrile, propionitrile; N,N-di-alkylated amides such as dimethylformamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, tert-butyl methyl ketone, methyl ethyl ketone; alcohols such as methanol, ethanol, n- and iso-propanol, butanols, especially tert-butanol, and mixtures of such solvents.
The reaction temperature can be varied within wide limits. It is advantageously from -20C to 200C or the boiling point of the solvent or solvent mixture, depending on the nature of the substituents X, R1, RZ, R3, R5, R5 and R7 and the nu~ber m thereof.
It may also be advantageous in some cases to carry out the reac~ion under a protective gas and/or in anhydrous solvents. Suitable pro~ective gases are inert gases such as helium, argon and, preferably, nitrogen.
~-~ The starting compounds are known or can be easily prepared by known methods. The haloaromatic compounds (or the phenols which can easily be converted into these) and anilines which are used are known.
The following citations relate to 3-amino- and 3-halo-benzoisothiazoles: DE-A 3112164, DE 1915387, DE
2603864.
The compounds of the formula I as claimed in 202n4l6 - 5 - O.Z. 0050/40923 claim 1, with the proviso that R4 is different from hydrogen, are prepared, for example, by reacting a 3-anilinobenzoisothiazole of the formula I in which R4 is hydrogen, and X, m, R1, R2, R3, Rs, R and R7 have the S meanings specified in claLm 1, with an acylating or sulfonating agent of the formula IV
where R4 has the meaning specified in claim 1, apart from hydrogen, and L is a nucleophilically displaceable leaving group, in the presence or absence of a solvent or diluent and in the presence or absence of an organic or inorganic base at from -20C to 150C.
Suitable and preferred nucleophilically displace-able groups are halogens such as F, Cl, Br and I, sulfo-nates (methanesulfonate, benzenesulfonate etc.), alcohol-ates (ethylate, benzylate etc.) and carboxylates (acetate etc.).
~ he bases which can be used are the same com-pounds as for the preparation of compounds of the formula I (R4 = H) from compounds of the formulae II and III.
The reactions are generally carried out at from - 20C to 150C or at the boiling point of the solvent or solvent mixture.
One or more inert solvents or diluents can be present in the reaction. Suitable examples are aliphatic and aromatic hydrocarbons such as toluene, xylenes, cyclohexane, petroleum ether; halohydrocarbons such as '~chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachloroethylene; ethers such as dialkyl ethers (diethyl ether, diisGpropyl ether, tert-butyl methyl ether etc.~, anisole, dioxane, tetrahydrofuran;
nitriles such as acetonitrile, propionitrile; N,N-dialky-lated amides such as dimethylformamide; dimethyl sulf-oxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone, tert-butyl methyl ketone, and mixtures of 202~-~16 - 6 - O.Z. 0050/40923 such solvents.
The novel compounds are isolated by conventional methods. The resulting products can be purified by recrystalli~ation, extraction or chromatography. The 5following examples are intended to illustrate the prepar-ation:
A solution of 23.5 g (0.21 mol) of potassium tert-butylate in 250 ml of tert-butanol is added drop-10wise, at 0C to 5C, in the course of 1 hour to a vigor-ously stirred suspension of 19.5 g (0.1 mol) of 3-amino-5-nitrobenzoisothiazole and 32 g (0.105 mol) of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 300 ml of 1:1 tet.rahydrofuran/tert-butanol. After a further hour at 150C, the mixture is warmed to room temperature and acidified with glacial acetic acid, 500 ml of water are added, and the precipitate is filtered off with suction and washed with cold methanol; 36.1 g (78 %) of compound 1.46, yellow crystals, melting point 168-170C.
0.24 g (0.01 mol) of sodium hydride is added a little at a time to a solution of 3.4 g (0.01 mol) of 3-(2-nitro-4-trifluoromethylanilino~benzoisothiazole (compound 1.20) in 25 ml of tetrahydrofuran. After 2515 minutes, 2.0 g (0.02 mol) of acetic anhydride are added dropwise at room temperature. After 48 h at 20C, 150 ml of water are added, and the mixture is extracted 3 times with 100 ml of ether each tLme. The combined ether extracts are washed with saturated brine, dried " over MgSO~ and concentrated. The residue is chromato-graphed (silica gel, 19:1 cyclohexane/ethyl acetate).
1.3 g (34 %) of compound 2.4 are obtained as pale yellow crystals, melting point 108 to 111C, in addition to 1.4 g of starting material.
6.5 ml of a 40 % strength aqueous solution of tetrabutylammonium hydroxide (0.01 mol) are added 2 0 2 ~ 6 - 7 - O.Z. 0050/40923 dropwise to a still hot solution of 4.6 g (0.01 mol) of compound 1.46 (5-nitro-3-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino)benzoisothiazole) in 150 ml of ethanol.. After cooling, the precipitate is filtered off with suction and washed with ethanol and diisopropyl ether; 5.4 g (75 %) of compound 3.7, dark red crystals, melting point 143C.
2~2~416 8 O.Z. 0050/40g23 Table I
X ~ N R1 ~R2 1, H R ~
No. Xm R R2 R3 m.p. (C) 5 1.1 - Cl CF3 NO2 125 1.2 - Cl CN N02 1.3 - Cl COOC2Hs No2 1.4 - Cl CONH2 No2 1.5 _ F CF3 No2 10 1.6 - SCH3 CF3 NO2 1.8 ~ SC2H5 CF3 NO2 1.9 _ CF3 NO2 146-148 1.10 - H CN NO2 15 1.11 - H Cl N02 1.12 - Cl Cl NO2 1.13 - H 502CH3 No2 1.14 - H COOCH3 No2 1.15 _ H CH3 No2 20 1.16 - H NO2 CF3 152-158 1.17 - H NO2 Cl 1.18 - H NO2 CHMeEt 1 . 19 - Cl Cl Cl 1.20 - H CF3 H 130-133 25 1.21 - CF3 CF3 NO2 1.22 4-NO2 Cl CF3 NO2 1.23 4-NO2 F CF3 No2 1.24 4-No2 H CF3 No2 1.25 4-NO2 H NO2 CF3 30 1.26 4-N02 H NO2 Cl 1.27 4-NO2 Cl Cl No2 1.28 4-NO2 Cl CN No2 1.29 4-NO2 Cl COOC2H5 No2 1.30 4-Cl Cl CF3 NO2 173-178 35 1.31 4-Cl F CF3 No2 1.32 4-Cl H CF3 No2 1.33 4-CI H NO2 CF3 147-149 1.34 4-Cl H NO2 Cl 202~16 9 O.Z. 0050/40923 Table 1 (contd.) No. xm ~1 R2 R3 m.p. (C) 5 1.35 4-Cl Cl Cl NO2 1.36 4-Cl Cl CN NO2 1.37 4-CI Cl COOC2Hs No2 1.38 4-CF3 Cl CF3 NO2 1.39 4-CF3 F CF3 No2 10 1.40 4-CF3 H CF3 No2 1.41 4-CF3 H NO2 CF3 1.42 4-CF3 H NO2 Cl 1.43 4-CF3 Cl Cl No2 1.44 4-CF3 Cl CN No2 15 1.45 4-CF3 Cl COOC2Hs No2 1.46 5-NO2 Cl CF3 NO2 168-170 1.47 5-NO2 F CF3 No2 76- 84 1.48 5-NO2 Br CF3 NO2 1.49 5-NO2 CF3 C~3 NO2 2Q 1.50 5-No2 SCH3 CF3 NO2 1.51 5-NO2 OCH3 CF3 NO2 1.52 5-No2 SC2H5 CF3 NO2 1.53 5-NO2 OC2H5 CF3 NO2 1.54 5-NO2 OC4Hg-n CF3 NO2 25 1.55 5-NO2 OCF3 CF3 NO2 1.56 5-NO2 OCF2CHF2 CF3 NO2 1-57 5-NO2 oCH2C6H5 CF3 NO2 1.58 5-NO2 OC6H5 CF3 NO2 30 1.60 5-NO2 SC6H5 CF3 NO2 1.61 5-NO2 OC6H4-P-Cl CF3 No2 1.62 5-NO2 SC6H4-p-Cl CF3 No2 1.63 5-NO2 H CF3 No2 174-178 1.64 5-NO2 H H F
35 1.65 5-NO2 H Br No2 1.66 5-NO2 H Cl No2 1.67 5-NO2 H CN No? >220 1.68 5-NO2 H CONH2 No2 1.69 5-NO2 H CoN(cH3)2 No2 40 1.70 5-NO2 H COOH No2 1.71 5-NO2 H COOCH3 No2 145-155 1.72 5-NO2 Cl CN No2 1.73 5-No2 Cl COOC2H5 No2 179-185 2~20~ 6 O.Z. 0050/40923 Table 1 (contd.) No. Xm - R1 R2 R3 m.p. (C) 5 1.74 5-No2 Cl CONH2 No2 1.75 5-NO2 H 502CH3 No2 >220 1.76 5-NO2 H S2NH2 No2 1.77 5-No2 H 5O2N(CH3)2 NO2 1.78 5-No2 H CH3 No2 >220 1O 1.79 5-NO2 H C(CH3)3 No2 >220 1.80 5-NO2 H OCF3 No2 1.81 5-No2 H OCF2CHF2 No2 1.82 5-NO2 H NO2 CF3 192-194 1.83 5-NO2 H NO2 Cl 178-180 15 1.84 5-NO2 H NO2 CH3 1.85 5-NO2 H NO2 CHMeEt 84-9O
1.86 5-NO2 Cl Cl No2 >220 1.87 5-NO2 Cl Cl Cl 204-212 1.88 5-NO2 H CF3 H >220 20 1.89 5-CF3 Cl CF3 NO2 134-137 1.90 5-CF3 Cl CN No2 1.91 5-CF3 Cl COOC2Hs No2 1.92 5-CF3 Cl CONH2 No2 1.93 5-CF3 F CF3 No2 25 1.94 5-CF3 OCH3 CF3 NO2 1.95 5-CF3 H CF3 No2 125-129 1.96 5-CF3 H CN No2 1.97 5-CF3 H Cl No2 1.98 5-CF3 Cl Cl NQ2 3~ 1.99 5-CF3 H SO2CH3 No2 1.100 5-CF3 H COOCH3 No2 1.101 5-CF3 H CH3 No2 1.102 5-CF3 H NO2 CF3 118-119 1.103 5-CF3 H NO2 Cl 35 1.104 5-CF3 H NO2 CHMeEt 1.105 5-CF3 Cl Cl Cl 1.106 5-Cl Cl CF3 NO2 1.107 5-Cl Cl CN NO2 1.108 5-Cl Cl COOC2H5 No2 4~ 1.109 5-CI Cl CONH2 No2 1.110 5-Cl F CF3 No2 1.111 5-Cl OCH3 CF3 NO2 1.112 5-Cl H CF3 No2 2020~16 11 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) 5 1.113 5-CI H CN N02 1~114 5-CI H Cl NO2 1.115 5-CI Cl Cl NO2 1.116 5-CI H SO2CH3 No2 1.117 5-CI H COOCH3 No2 10 1.118 5-Cl H CH3 No2 1.119 5-Cl H NO2 CF3 1.120 5-CI H NO2 Cl 1.121 5-CI H NO2 CHMeEt 1.122 5-CI Cl C1 C~
15 1.123 6-N02 Cl CF3 NO2 1.124 6-NO2 Cl CN No2 1.125 6-NO2 Cl COOC2H5 No2 1.126 6-NO2 Cl CONH2 No2 1.127 6-N32 F CF3 No2 20 1.128 6-NO2 OCH3 CF3 NO2 1.129 6-NO2 H CF3 No2 1.130 6-NO2 H CN No2 1.131 6-NO2 H Cl No2 1.132 6-NO2 Cl Cl No2 25 1.133 6-NO2 H SO2CH3 No2 1.134 6-NO2 H COOCH3 No2 1.135 6-NO2 H CH3 No2 1.136 6-NO2 H NO2 CF3 1.137 6-NO2 H NO2 Cl 30 1.138 6-NO2 H NO2 CHMeEt 1.139 6-NO2 Cl Cl Cl 1.140 6-CF3 Cl CF3 NO2 1.141 6-CF3 Cl CN No2 1.142 6-CF3 Cl COQC2H5 No2 35 1.143 6-CF3 Cl CONH2 No2 1.144 6-CF3 F CF3 No2 1.145 6-CF3 OCH3 CF3 NO2 1.146 6-CF3 H CF3 No2 1.147 6-CF3 H CN No2 40 1.148 6-CF3 H Cl No2 1.149 6-CF3 Cl Cl No2 1.150 6-CF3 H SO2CH3 No2 1.151 6-CF3 H COOCH3 No2 ~2~416 12 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) 5 1.152 6-CF3 H CH3 No2 1.153 6-CF3 H N02 CF3 1.154 6-CF3 H N02 Cl 1.155 6-CF3 H NO2 CHMeEt 1.156 6-CF3 Cl Cl Cl 10 1.157 6-CI Cl CF3 N02 169-172 1.158 6-CI Cl CN NO2 1.159 6-Cl Cl COOC2Hs No2 1.160 6-CI Cl C0NH2 No2 1.161 6-CI F CF3 No2 15 1.162 6-CI OCH3 CF3 NO2 1.163 6-CI H CF3 No2 1.164 6-CI H CN NO2 1.165 6-CI H Cl N02 1.166 6-CI Cl Cl N02 20 1.167 6-CI H SO2CH3 No2 1.168 6-CI H COOCH3 No2 1.169 6-CI H CH3 No2 1.170 6-Cl H NO2 CF3 146-147 1.171 6-Cl H NO2 Cl 25 1.172 6-CI H NO2 CHMeEt 1.173 ~-CI Cl Cl Cl 1.174 7-No2 Cl CF3 NO2 1.175 7-No2 F CF3 No2 1.176 7-NO2 H CF3 No2 30 1.177 7-NO2 H N02 CF3 1.178 7-NO2 H NO2 Cl 1.17g 7-No2 Cl Cl No2 1.180 7-No2 Cl CN No2 1.181 7-No2 Cl C00C2H5 No2 35 l.lB2 7-Cl Cl CF3 NO2 1.183 7-CI F CF3 ~2 1.184 7-CI H CF3 No2 1.185 7-Cl H NO2 CF3 1.186 7-Cl H N02 Cl 40 1.187 7-CI Cl Cl NO2 1.188 7-Cl Cl CN - N02 1.189 7-CI Cl C0OC2H5 No2 1.190 7-CF3 Cl CF3 NO2 202~16 13 O.Z. 0050/40923 Table 1 (contd.) No. Xm R1 R2 R3 m.p. (C) 5 1.191 7-CF3 F CF3 No2 1.192 7-CF3 H CF3 No2 1.193 7-CF3 H NO2 CF3 1.194 7-CF3 H NO2 C1-1.195 7-CF3 Cl Cl No2 lO 1.196 7-CF3 Cl CN No2 1.197 7-CF3 Cl COOC2Hs No2 1.198 4-OCH3 Cl CF3 NO2 1.199 4-OCH3 H NO2 CF3 1.200 5-OCH3 Cl CF3 NO2 15 1.201 S-OCH3 H NO2 CF3 1.202 6-OCH3 Cl CF3 NO2 1.203 6-OCH3 H NO2 CF3 1.204 7-OCH3 Cl CF3 NO2 1.205 7-OCH3 H NO2 CF3 20 1.206 4-Br Cl CF3 NO2 1.207 4-Br H NO2 CF3 1.208 5-Br Cl CF3 NO2 1.209 5-Br H NO2 CF3 1.210 6-Br Cl CF3 NO2 25 1.211 6-Br H NO2 CF3 1.212 7-Br Cl CF3 NO2 1.213 7-Br ~ NO2 CF3 1.214 4-F Cl CF3 NO2 1.215 4-F H NO2 CF3 30 1.216 5-F Cl CF3 NO2 1.217 5-F H NO2 CF3 1.218 6-F Cl CF3 NO2 1.219 6-F H NO2 CF3 1.220 7-F Cl CF3 NO2 35 1.221 7-F H NO2 CF3 1.222 4-cyclo-C3Hs Cl CF3 NO2 1.223 4-cyclo-C3Hs H NO2 CF3 1.224 5-cyclo-C3~5 Cl CF3 NO2 1.225 5-cyclo-C3Hs H NO2 CF3 40 1.226 6-cyclo-C3Hs Cl CF3 NO2 1.227 6-cyclo-C3Hs H NO2 CF3 1.228 7-cyclo-C3Hs Cl CF3 NO2 1.229 7-cyclo-C3Hs H NO2 CF3 2~204~ 6 14 O.Z. 0050/40923 Table 1 (contd. ) NO. Xm R1 R2 R3 m-P- (C) 5 1.230 5-OCF2CHF2 C1 CF3 NO2 1.231 5-OCF2CHF2 H NO2 CF3 1.232 6-CF2CHF2 Cl CF3 NO2 1.233 6-CF2CHF2 H NO2 CF3 1.234 5-OPh C1 CF3 NO2 10 1.235 5-OPh H NO2 CF3 1.236 5-SPh Cl CF3 NO2 1.237 5-SPh H NO2 CF3 1.238 4-CH3 Cl CF3 NO2 1.239 4-CH3 H NO2 CF3 15 1.240 5-CH3 Cl CF3 NO2 1.241 5-CH3 H NO2 CF3 1.242 6-CH3 Cl CF3 NO2 1.243 6-CH3 H NO2 CF3 1.244 7-CH3 C1 CF3 NO2 20 1.245 7-CH3 H NO2 CF3 1.246 5-OCF3 Cl CF3 NO2 1.247 5-OCF3 H NO2 CF3 1.248 6-OCF3 Cl CF3 NO2 1.249 6-OCF3 H NO2 CF3 25 1.250 4-CN Cl CF3 NO2 1.251 4-CN H NO2 CF3 1.252 5-CN Cl CF3 NO2 1.253 5-CN H NO2 CF3 1.254 6-CN Cl CF3 NO2 30 1.255 6-CN H NO2 CF3 1.256 7-CN Cl CF3 NO2 1.257 7-CN H NO2 CF3 1.258 6-C(CH3)3 C1 CF3 NO2 1.259 6-C(CH3)3 H NO2 CF3 35 1.260 4-SO2CH3 C1 CF3 NO2 1.261 4-SO2CH3 H NO2 CF3 1.262 5-SO2CH3 Cl CF3 NO2 1.263 5-SO2CH3 H NO2 CF3 1.264 6-S02CH3 Cl CF3 NO2 40 1.265 6-SO2CH3 H NO2 CF3 1.266 7-SO2CH3 Cl CF3 NO2 1.267 7-SO2CH3 H NO2 CF3 1.268 6-SCH3 Cl CF3 NO2 ~02~6 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) S 1.269 6-SCH3 H NO2 CF3 1.270 4,5-C12 Cl CF3 NO2 1.271 4,5-C12 F CF3 No2 1.272 4,5-C12 H CF3 No2 1.273 4,5-C12 H NO2 CF3 10 1.274 4,5-C12 H NO2 Cl 1.275 4,5-C12 Cl Cl No2 1.276 4,5-C12 Cl CN No2 1.277 4,5-Ct2 Cl COOC2Hs No2 1.278 4-CI, 5-CF3 Cl CF3 NO2 15 1.279 4-CI, S-CF3 F CF3 No2 1.280 4-CI, 5-CF3 H CF3 No2 1.281 4-CI, 5-CF3 H NO2 CF3 1.282 4-Cl, 5-CF3 H N02 Cl 1.283 4-Cl, 5-CF3 Cl Cl ~2 20 1.284 4-CI, 5-CF3 Cl CN No2 1.285 4-Ct, 5-CF3 Cl COOC2Hs No2 1.286 7-CI, 5-CF3 Cl CF3 N02 1.287 7-CI, 5-CF3 F CF3 No2 1.288 7-CI, 5-CF3 H CF3 No2 25 1.289 7-Cl, 5-CF3 H NO2 CF3 1.290 7-Cl, 5-CF3 H NO2 Cl 1.291 7-Cl, 5-CF3 Cl Cl No2 1.292 7-CI, 5-CF3 Cl CN No2 1.293 7-Cl, 5-CF3 Cl COOC2H5 No2 30 1.294 s,6-C12 Cl CF3 NO2 1.295 5,6-C12 F CF3 No2 1.296 s,6-C12 H CF3 No2 1.297 5,6 C12 H ~2 CF3 1.298 s,6-C12 H NO2 Cl 35 1.299 s,6-C12 Cl Cl No2 1.300 5,6-C12 Cl CN No2 1.301 5,Ç-C12 Cl COOC2H5 No2 1.302 5,7-(N02)2 Cl CF3 NO2 1.303 5,7-(NO~)2 F CF3 No2 40 1.204 5,7-(N02)2 H CF3 No2 i.305 5,7-(N~2)2 H N02 CF3 1.306 5,7-~N02)2 H NO2 Cl 1.307 5,7-(N02)2 Cl Cl No2 890376 2 0 2 ~ ~ ~ 6 16 O.Z. OOS0/40923 Table l (contd.) No . Xm Rl R2 R3 m.p. (C) 5 1.308 5,7-(N02)2 Cl CN No2 1.309 5,7-(N02)2 Cl COOC2H5 No2 1.310 5-NO2, 7-CI Cl CF3 NO2 1.311 5-No2, 7-CI F CF3 No2 1.312 5-NO2, 7-CI H CF3 No2 10 1.313 5-N02, 7-CI H NO2 CF3 1.314 5-NO2, 7-Cl H NO2 Cl 1.315 5-NO2, 7-CI Cl Cl No2 1.316 5-N02, 7-CI Cl CN No2 1.317 5-No2, 7-CI Cl COOC2Hs No2 15 1.318 4-CI, 5-NO2 Cl CF3 NO2 1.319 4-CI, 5-NO2 F CF3 No2 1.320 4-CI, 5-NO2 H CF3 No2 1.321 4-CI, 5-NO2 H NO2 CF3 1.322 4-CI, 5-NO2 H NO2 Cl 20 1.323 4-CI, 5-NO2 Cl Cl No2 1.324 4-CI, 5-NO2 Cl CN No2 1.325 4-CI, 5-NO2 Cl COOC2Hs No2 1.326 4-CI, 7-NO2 Cl ~F3 NO2 1.327 4-CI, 7-NO2 F CF3 No2 25 1.228 4-CI, 7-NO2 H CF3 No2 1.329 4-CI, 7-NO2 H N02 CF3 1.330 4-CI, 7-NO2 H NO2 Cl 1.331 4-CI, 7-NO2 Cl Cl No2 1.332 4-CI, 7-NO2 Cl CN No2 30 1.333 4-CI, 7-N02 Cl COOC2H5 N2 1.334 6-CI, 5,7-(No232 Cl CF3 NO2 1.335 6-CI, 5,7-(N02)2 F CF3 No2 1.336 6-CI, 5,7-(N02)2 H CF3 No2 1.337 6-CI, 5,7-(NO2)2 H N02 CF3 35 1.338 6-Cl, 5,7-(NO2)2 H NO2 Cl 1.339 6-CI, 5,7-(N02)2 Cl Cl No2 1.340 6-CI, 5~7-(N02)2 Cl CN No2 1.341 6-CI, 5,7-1NO2)2 Cl COOC2H5 No2 1.342 6-F, 5,7-(N02)2 Cl CF3 NO2 40 1.343 6-F, 5,7-(N02)2 H NO2 CF3 1.344 6-Br, 5,7-(NO2)2 Cl CF3 NO2 1.345 6-Br, 5,7-(N02)2 H N02 CF3 1.346 6-CN, 5,7-(N02)2 Cl CF3 NO2 17 O.Z. 0050/40923 Table I (contd.) No. Xm R1 R2 R3 m.p. (C) 5 1.347 6-CN, 5,7-(N02)2 H NO2 CF3 1.348 6-OCH3, 5,7-(N02)2 Cl CF3 NO2 1.349 6-OCH3, 5,7-(NO2)2 Cl No2 CF3 1.350 6-SC2Hs, 5,7-(N02)2 Cl CF3 NO2 1.351 6-SC2Hs, 5,7-(N02)2 H No2 CF3 10 1.352 6-OPh, 5,7-(NO2)2 Cl CF3 NO2 1.353 6-OPh, 5,7-(N02)2 H NO2 CF3 1.354 6-SPh, 5,7-(N02)2 Cl CF3 NO2 1.355 6-SPh, 5,7-(N02)2 H NO2 CF3 1.356 4-0CH3, 5-N02 Cl CF3 NO2 15 1.357 4-OCH3, 5-NO2 H NO2 CF3 1.358 4-CN, 5-NO2 Cl CF3 NO2 1.359 4-CN, 5-N02 H N02 CF3 1.360 4-0CH3, 7-N02 Cl CF3 N02 1.361 4-0CH3, 7-NO2 H N02 CF3 20 1.362 4-CN, 7-NO2 Cl CF3 NO2 1.363 4-CN, 7-NO2 H NO2 CF3 1.364 4-OCH3, 5-Ct Cl CF3 NO2 1.365 4-OCH3, 5-Cl H NO2 CF3 1.366 5-No2, 6-Cl Cl CF3 NO2 25 1.367 5-NO2, 6-CI H NO2 CF3 1.368 5-NO2, 6-CF3 Cl CF3 N03 1.369 5-NO2, 6-CF3 H NO2 CF3 1.370 5-NO2, 4-CF3 Cl CF3 NO2 1.371 5-NO2, 4-CF3 H NO2 CF3 30 1.372 5,7-(CF3)2 Cl CF3 NO2 1.373 5,7-tCF3)2 H NO2 CF3 1.374 5-CI, 7-CF3 Cl CF3 N02 1.375 5-Cl, 7-CF3 H NO2 CF3 1.376 s,7-C12 Cl CF3 NO2 35 1.377 s,7-C12 H NO2 CF3 1.378 5,7-Br2 Cl CF3 NO2 1.379 5,7-Br2 H NO2 CF3 1.380 5-CN, 7-CI Cl CF3 NO2 1.381 5-CN, 7-Cl H NO2 CF3 40 1.382 5-CN, 4-Cl Cl CF3 NO2 1.383 5-CN, 4-CI H NO2 CF3 20~0~ 6 18 O.Z. 0050/40923 Table 2 ~S~
X ~ N02 R
~ R2 I, No. Xm Rl R2 R3 R4 m.p. (C) 5 2.1 - Cl CF3 N02 S02phenyl 2.2 - H N02 CF3 S02Ph 2.3 - H CF3 H 502Ph 2.4 _ H CF3 H COCH3 108-111 2.5 _ H CF3 H COOCH3 10 2.6 5-Cl Cl CF3 N02 502Ph 2.7 S-Cl H N02 CF3 502Ph 2.8 5-N02, 7-Cl Cl CF3 N02 S02Ph 2.9 5-No2, 7-Cl Cl CF3 N02 CONH2 2.10 5-N02, 7-CI H N2 CF3 COOCH2Ph 15 2.11 5-N02, 7-Cl H N02 CF3 502Ph 2.12 5-N02, 7-Cl H CF3 H S02Ph 2.13 5-N02 H CF3 H COCH2CI
2.14 5-N02 H CF3 H S02Ph 2.15 5-No2 H CF3 H COCHC12 20 2.16 5-N02 Cl CF3 N02 502Ph 2.17 5-N02 Cl CF3 N02 COCH3 2.18 5-N02 Cl CF3 N02 COCHC12 2.19 5-No2 Cl CF3 N02 COPh 2. 20 5-N02 Cl CF3 N02 COOCH3 25 2.21 5-N02 Cl CF3 N02 CONH2 2.22 5-N02 Cl CF3 N02 CHO
2.23 5,7-C12 Cl CF3 N02 502Ph 2.24 5,7-C12 H N02 CF3 S02Ph 2.25 5,7-C12 H N02 CF3 COOCH3 30 2.26 5,7-C12 H N02 CF3 COCH2Cl 2.27 4-CI Cl CF3 N02 S02Ph 2.28 4-CI H N02 CF3 S02Ph 2.29 6-N02 Cl CF3 N02 502Ph 2.30 6-N02 H N02 CF3 S02Ph 2 0 ~
The compounds of the formula I as claimed in claim 1, in which R4 is hydrogen, are prepared, for example, by reacting a benzoisothiazole of the formula II
~S~
m ~ II
where X and m have the meanings specified in claim 1, with compounds of the formula III
Rl NO2 ~ R2 III
Y ~
where Rl, R2 and R3 ha~e the meanings specified in claim 1, with or without a solvent or diluent, in the presence or absence of an organic or inorganic base, at from -20 to 200C, where Y and Z are different from one another and are NHz or halogen.
In both cases, the reaction takes place with elimination of hydrogen halide. This is why it is advan-~tageous to use acid-binding agents or bases in both cases.
Bases and acid-binding agents which can be used are organic or inorganic compounds such as alkali metal and alkaline earth metal hydroxides (LiOH, NaOH, ROH, Ca(OH) 2 ) ~ oxides (Na2O, Li2O, CaO, MgO), hydrides (LiH, NaH, KH, CaH2), amides (LiNH2, NaNH2, RNH2), carbonates (Li2CO3, Na2CO3, CaC03), bicarbonates (NaHCO3), alkyls 2020~6 - 4 - O.z. 0050/40923 ~butylLi, CH3Li, cH3Mgcl)r C t -C5-alc oholates (NaOCH3, NaOC~H5~ KOC7H5, KO-tert-butyl, ~g(OCH3).), amines, especi-ally tertiary amines (eg. trimethylamine, triethylamine, diisopropylethylamine, N-methylpiperidine), pyridine, substituted pyridines (collidine, lutidines, 4-dLmethyl-aminopyridine), and bicyclic amines.
The reactions can be carried out in the presence of inert solvents or diluents.
Suitable examples are aliphatic and aromatic hydrocarbons such as toluene, xylenes, cyclohexane, petroleum ether; halohydrocarbons such as chlorobenzene, methylene chloride, chloroform; ethers such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether etc.), anisole, dioxane, tetrahydrofuran;
nitriles such as acetonitrile, propionitrile; N,N-di-alkylated amides such as dimethylformamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, tert-butyl methyl ketone, methyl ethyl ketone; alcohols such as methanol, ethanol, n- and iso-propanol, butanols, especially tert-butanol, and mixtures of such solvents.
The reaction temperature can be varied within wide limits. It is advantageously from -20C to 200C or the boiling point of the solvent or solvent mixture, depending on the nature of the substituents X, R1, RZ, R3, R5, R5 and R7 and the nu~ber m thereof.
It may also be advantageous in some cases to carry out the reac~ion under a protective gas and/or in anhydrous solvents. Suitable pro~ective gases are inert gases such as helium, argon and, preferably, nitrogen.
~-~ The starting compounds are known or can be easily prepared by known methods. The haloaromatic compounds (or the phenols which can easily be converted into these) and anilines which are used are known.
The following citations relate to 3-amino- and 3-halo-benzoisothiazoles: DE-A 3112164, DE 1915387, DE
2603864.
The compounds of the formula I as claimed in 202n4l6 - 5 - O.Z. 0050/40923 claim 1, with the proviso that R4 is different from hydrogen, are prepared, for example, by reacting a 3-anilinobenzoisothiazole of the formula I in which R4 is hydrogen, and X, m, R1, R2, R3, Rs, R and R7 have the S meanings specified in claLm 1, with an acylating or sulfonating agent of the formula IV
where R4 has the meaning specified in claim 1, apart from hydrogen, and L is a nucleophilically displaceable leaving group, in the presence or absence of a solvent or diluent and in the presence or absence of an organic or inorganic base at from -20C to 150C.
Suitable and preferred nucleophilically displace-able groups are halogens such as F, Cl, Br and I, sulfo-nates (methanesulfonate, benzenesulfonate etc.), alcohol-ates (ethylate, benzylate etc.) and carboxylates (acetate etc.).
~ he bases which can be used are the same com-pounds as for the preparation of compounds of the formula I (R4 = H) from compounds of the formulae II and III.
The reactions are generally carried out at from - 20C to 150C or at the boiling point of the solvent or solvent mixture.
One or more inert solvents or diluents can be present in the reaction. Suitable examples are aliphatic and aromatic hydrocarbons such as toluene, xylenes, cyclohexane, petroleum ether; halohydrocarbons such as '~chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachloroethylene; ethers such as dialkyl ethers (diethyl ether, diisGpropyl ether, tert-butyl methyl ether etc.~, anisole, dioxane, tetrahydrofuran;
nitriles such as acetonitrile, propionitrile; N,N-dialky-lated amides such as dimethylformamide; dimethyl sulf-oxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone, tert-butyl methyl ketone, and mixtures of 202~-~16 - 6 - O.Z. 0050/40923 such solvents.
The novel compounds are isolated by conventional methods. The resulting products can be purified by recrystalli~ation, extraction or chromatography. The 5following examples are intended to illustrate the prepar-ation:
A solution of 23.5 g (0.21 mol) of potassium tert-butylate in 250 ml of tert-butanol is added drop-10wise, at 0C to 5C, in the course of 1 hour to a vigor-ously stirred suspension of 19.5 g (0.1 mol) of 3-amino-5-nitrobenzoisothiazole and 32 g (0.105 mol) of 2,4-dichloro-3,5-dinitrobenzotrifluoride in 300 ml of 1:1 tet.rahydrofuran/tert-butanol. After a further hour at 150C, the mixture is warmed to room temperature and acidified with glacial acetic acid, 500 ml of water are added, and the precipitate is filtered off with suction and washed with cold methanol; 36.1 g (78 %) of compound 1.46, yellow crystals, melting point 168-170C.
0.24 g (0.01 mol) of sodium hydride is added a little at a time to a solution of 3.4 g (0.01 mol) of 3-(2-nitro-4-trifluoromethylanilino~benzoisothiazole (compound 1.20) in 25 ml of tetrahydrofuran. After 2515 minutes, 2.0 g (0.02 mol) of acetic anhydride are added dropwise at room temperature. After 48 h at 20C, 150 ml of water are added, and the mixture is extracted 3 times with 100 ml of ether each tLme. The combined ether extracts are washed with saturated brine, dried " over MgSO~ and concentrated. The residue is chromato-graphed (silica gel, 19:1 cyclohexane/ethyl acetate).
1.3 g (34 %) of compound 2.4 are obtained as pale yellow crystals, melting point 108 to 111C, in addition to 1.4 g of starting material.
6.5 ml of a 40 % strength aqueous solution of tetrabutylammonium hydroxide (0.01 mol) are added 2 0 2 ~ 6 - 7 - O.Z. 0050/40923 dropwise to a still hot solution of 4.6 g (0.01 mol) of compound 1.46 (5-nitro-3-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino)benzoisothiazole) in 150 ml of ethanol.. After cooling, the precipitate is filtered off with suction and washed with ethanol and diisopropyl ether; 5.4 g (75 %) of compound 3.7, dark red crystals, melting point 143C.
2~2~416 8 O.Z. 0050/40g23 Table I
X ~ N R1 ~R2 1, H R ~
No. Xm R R2 R3 m.p. (C) 5 1.1 - Cl CF3 NO2 125 1.2 - Cl CN N02 1.3 - Cl COOC2Hs No2 1.4 - Cl CONH2 No2 1.5 _ F CF3 No2 10 1.6 - SCH3 CF3 NO2 1.8 ~ SC2H5 CF3 NO2 1.9 _ CF3 NO2 146-148 1.10 - H CN NO2 15 1.11 - H Cl N02 1.12 - Cl Cl NO2 1.13 - H 502CH3 No2 1.14 - H COOCH3 No2 1.15 _ H CH3 No2 20 1.16 - H NO2 CF3 152-158 1.17 - H NO2 Cl 1.18 - H NO2 CHMeEt 1 . 19 - Cl Cl Cl 1.20 - H CF3 H 130-133 25 1.21 - CF3 CF3 NO2 1.22 4-NO2 Cl CF3 NO2 1.23 4-NO2 F CF3 No2 1.24 4-No2 H CF3 No2 1.25 4-NO2 H NO2 CF3 30 1.26 4-N02 H NO2 Cl 1.27 4-NO2 Cl Cl No2 1.28 4-NO2 Cl CN No2 1.29 4-NO2 Cl COOC2H5 No2 1.30 4-Cl Cl CF3 NO2 173-178 35 1.31 4-Cl F CF3 No2 1.32 4-Cl H CF3 No2 1.33 4-CI H NO2 CF3 147-149 1.34 4-Cl H NO2 Cl 202~16 9 O.Z. 0050/40923 Table 1 (contd.) No. xm ~1 R2 R3 m.p. (C) 5 1.35 4-Cl Cl Cl NO2 1.36 4-Cl Cl CN NO2 1.37 4-CI Cl COOC2Hs No2 1.38 4-CF3 Cl CF3 NO2 1.39 4-CF3 F CF3 No2 10 1.40 4-CF3 H CF3 No2 1.41 4-CF3 H NO2 CF3 1.42 4-CF3 H NO2 Cl 1.43 4-CF3 Cl Cl No2 1.44 4-CF3 Cl CN No2 15 1.45 4-CF3 Cl COOC2Hs No2 1.46 5-NO2 Cl CF3 NO2 168-170 1.47 5-NO2 F CF3 No2 76- 84 1.48 5-NO2 Br CF3 NO2 1.49 5-NO2 CF3 C~3 NO2 2Q 1.50 5-No2 SCH3 CF3 NO2 1.51 5-NO2 OCH3 CF3 NO2 1.52 5-No2 SC2H5 CF3 NO2 1.53 5-NO2 OC2H5 CF3 NO2 1.54 5-NO2 OC4Hg-n CF3 NO2 25 1.55 5-NO2 OCF3 CF3 NO2 1.56 5-NO2 OCF2CHF2 CF3 NO2 1-57 5-NO2 oCH2C6H5 CF3 NO2 1.58 5-NO2 OC6H5 CF3 NO2 30 1.60 5-NO2 SC6H5 CF3 NO2 1.61 5-NO2 OC6H4-P-Cl CF3 No2 1.62 5-NO2 SC6H4-p-Cl CF3 No2 1.63 5-NO2 H CF3 No2 174-178 1.64 5-NO2 H H F
35 1.65 5-NO2 H Br No2 1.66 5-NO2 H Cl No2 1.67 5-NO2 H CN No? >220 1.68 5-NO2 H CONH2 No2 1.69 5-NO2 H CoN(cH3)2 No2 40 1.70 5-NO2 H COOH No2 1.71 5-NO2 H COOCH3 No2 145-155 1.72 5-NO2 Cl CN No2 1.73 5-No2 Cl COOC2H5 No2 179-185 2~20~ 6 O.Z. 0050/40923 Table 1 (contd.) No. Xm - R1 R2 R3 m.p. (C) 5 1.74 5-No2 Cl CONH2 No2 1.75 5-NO2 H 502CH3 No2 >220 1.76 5-NO2 H S2NH2 No2 1.77 5-No2 H 5O2N(CH3)2 NO2 1.78 5-No2 H CH3 No2 >220 1O 1.79 5-NO2 H C(CH3)3 No2 >220 1.80 5-NO2 H OCF3 No2 1.81 5-No2 H OCF2CHF2 No2 1.82 5-NO2 H NO2 CF3 192-194 1.83 5-NO2 H NO2 Cl 178-180 15 1.84 5-NO2 H NO2 CH3 1.85 5-NO2 H NO2 CHMeEt 84-9O
1.86 5-NO2 Cl Cl No2 >220 1.87 5-NO2 Cl Cl Cl 204-212 1.88 5-NO2 H CF3 H >220 20 1.89 5-CF3 Cl CF3 NO2 134-137 1.90 5-CF3 Cl CN No2 1.91 5-CF3 Cl COOC2Hs No2 1.92 5-CF3 Cl CONH2 No2 1.93 5-CF3 F CF3 No2 25 1.94 5-CF3 OCH3 CF3 NO2 1.95 5-CF3 H CF3 No2 125-129 1.96 5-CF3 H CN No2 1.97 5-CF3 H Cl No2 1.98 5-CF3 Cl Cl NQ2 3~ 1.99 5-CF3 H SO2CH3 No2 1.100 5-CF3 H COOCH3 No2 1.101 5-CF3 H CH3 No2 1.102 5-CF3 H NO2 CF3 118-119 1.103 5-CF3 H NO2 Cl 35 1.104 5-CF3 H NO2 CHMeEt 1.105 5-CF3 Cl Cl Cl 1.106 5-Cl Cl CF3 NO2 1.107 5-Cl Cl CN NO2 1.108 5-Cl Cl COOC2H5 No2 4~ 1.109 5-CI Cl CONH2 No2 1.110 5-Cl F CF3 No2 1.111 5-Cl OCH3 CF3 NO2 1.112 5-Cl H CF3 No2 2020~16 11 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) 5 1.113 5-CI H CN N02 1~114 5-CI H Cl NO2 1.115 5-CI Cl Cl NO2 1.116 5-CI H SO2CH3 No2 1.117 5-CI H COOCH3 No2 10 1.118 5-Cl H CH3 No2 1.119 5-Cl H NO2 CF3 1.120 5-CI H NO2 Cl 1.121 5-CI H NO2 CHMeEt 1.122 5-CI Cl C1 C~
15 1.123 6-N02 Cl CF3 NO2 1.124 6-NO2 Cl CN No2 1.125 6-NO2 Cl COOC2H5 No2 1.126 6-NO2 Cl CONH2 No2 1.127 6-N32 F CF3 No2 20 1.128 6-NO2 OCH3 CF3 NO2 1.129 6-NO2 H CF3 No2 1.130 6-NO2 H CN No2 1.131 6-NO2 H Cl No2 1.132 6-NO2 Cl Cl No2 25 1.133 6-NO2 H SO2CH3 No2 1.134 6-NO2 H COOCH3 No2 1.135 6-NO2 H CH3 No2 1.136 6-NO2 H NO2 CF3 1.137 6-NO2 H NO2 Cl 30 1.138 6-NO2 H NO2 CHMeEt 1.139 6-NO2 Cl Cl Cl 1.140 6-CF3 Cl CF3 NO2 1.141 6-CF3 Cl CN No2 1.142 6-CF3 Cl COQC2H5 No2 35 1.143 6-CF3 Cl CONH2 No2 1.144 6-CF3 F CF3 No2 1.145 6-CF3 OCH3 CF3 NO2 1.146 6-CF3 H CF3 No2 1.147 6-CF3 H CN No2 40 1.148 6-CF3 H Cl No2 1.149 6-CF3 Cl Cl No2 1.150 6-CF3 H SO2CH3 No2 1.151 6-CF3 H COOCH3 No2 ~2~416 12 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) 5 1.152 6-CF3 H CH3 No2 1.153 6-CF3 H N02 CF3 1.154 6-CF3 H N02 Cl 1.155 6-CF3 H NO2 CHMeEt 1.156 6-CF3 Cl Cl Cl 10 1.157 6-CI Cl CF3 N02 169-172 1.158 6-CI Cl CN NO2 1.159 6-Cl Cl COOC2Hs No2 1.160 6-CI Cl C0NH2 No2 1.161 6-CI F CF3 No2 15 1.162 6-CI OCH3 CF3 NO2 1.163 6-CI H CF3 No2 1.164 6-CI H CN NO2 1.165 6-CI H Cl N02 1.166 6-CI Cl Cl N02 20 1.167 6-CI H SO2CH3 No2 1.168 6-CI H COOCH3 No2 1.169 6-CI H CH3 No2 1.170 6-Cl H NO2 CF3 146-147 1.171 6-Cl H NO2 Cl 25 1.172 6-CI H NO2 CHMeEt 1.173 ~-CI Cl Cl Cl 1.174 7-No2 Cl CF3 NO2 1.175 7-No2 F CF3 No2 1.176 7-NO2 H CF3 No2 30 1.177 7-NO2 H N02 CF3 1.178 7-NO2 H NO2 Cl 1.17g 7-No2 Cl Cl No2 1.180 7-No2 Cl CN No2 1.181 7-No2 Cl C00C2H5 No2 35 l.lB2 7-Cl Cl CF3 NO2 1.183 7-CI F CF3 ~2 1.184 7-CI H CF3 No2 1.185 7-Cl H NO2 CF3 1.186 7-Cl H N02 Cl 40 1.187 7-CI Cl Cl NO2 1.188 7-Cl Cl CN - N02 1.189 7-CI Cl C0OC2H5 No2 1.190 7-CF3 Cl CF3 NO2 202~16 13 O.Z. 0050/40923 Table 1 (contd.) No. Xm R1 R2 R3 m.p. (C) 5 1.191 7-CF3 F CF3 No2 1.192 7-CF3 H CF3 No2 1.193 7-CF3 H NO2 CF3 1.194 7-CF3 H NO2 C1-1.195 7-CF3 Cl Cl No2 lO 1.196 7-CF3 Cl CN No2 1.197 7-CF3 Cl COOC2Hs No2 1.198 4-OCH3 Cl CF3 NO2 1.199 4-OCH3 H NO2 CF3 1.200 5-OCH3 Cl CF3 NO2 15 1.201 S-OCH3 H NO2 CF3 1.202 6-OCH3 Cl CF3 NO2 1.203 6-OCH3 H NO2 CF3 1.204 7-OCH3 Cl CF3 NO2 1.205 7-OCH3 H NO2 CF3 20 1.206 4-Br Cl CF3 NO2 1.207 4-Br H NO2 CF3 1.208 5-Br Cl CF3 NO2 1.209 5-Br H NO2 CF3 1.210 6-Br Cl CF3 NO2 25 1.211 6-Br H NO2 CF3 1.212 7-Br Cl CF3 NO2 1.213 7-Br ~ NO2 CF3 1.214 4-F Cl CF3 NO2 1.215 4-F H NO2 CF3 30 1.216 5-F Cl CF3 NO2 1.217 5-F H NO2 CF3 1.218 6-F Cl CF3 NO2 1.219 6-F H NO2 CF3 1.220 7-F Cl CF3 NO2 35 1.221 7-F H NO2 CF3 1.222 4-cyclo-C3Hs Cl CF3 NO2 1.223 4-cyclo-C3Hs H NO2 CF3 1.224 5-cyclo-C3~5 Cl CF3 NO2 1.225 5-cyclo-C3Hs H NO2 CF3 40 1.226 6-cyclo-C3Hs Cl CF3 NO2 1.227 6-cyclo-C3Hs H NO2 CF3 1.228 7-cyclo-C3Hs Cl CF3 NO2 1.229 7-cyclo-C3Hs H NO2 CF3 2~204~ 6 14 O.Z. 0050/40923 Table 1 (contd. ) NO. Xm R1 R2 R3 m-P- (C) 5 1.230 5-OCF2CHF2 C1 CF3 NO2 1.231 5-OCF2CHF2 H NO2 CF3 1.232 6-CF2CHF2 Cl CF3 NO2 1.233 6-CF2CHF2 H NO2 CF3 1.234 5-OPh C1 CF3 NO2 10 1.235 5-OPh H NO2 CF3 1.236 5-SPh Cl CF3 NO2 1.237 5-SPh H NO2 CF3 1.238 4-CH3 Cl CF3 NO2 1.239 4-CH3 H NO2 CF3 15 1.240 5-CH3 Cl CF3 NO2 1.241 5-CH3 H NO2 CF3 1.242 6-CH3 Cl CF3 NO2 1.243 6-CH3 H NO2 CF3 1.244 7-CH3 C1 CF3 NO2 20 1.245 7-CH3 H NO2 CF3 1.246 5-OCF3 Cl CF3 NO2 1.247 5-OCF3 H NO2 CF3 1.248 6-OCF3 Cl CF3 NO2 1.249 6-OCF3 H NO2 CF3 25 1.250 4-CN Cl CF3 NO2 1.251 4-CN H NO2 CF3 1.252 5-CN Cl CF3 NO2 1.253 5-CN H NO2 CF3 1.254 6-CN Cl CF3 NO2 30 1.255 6-CN H NO2 CF3 1.256 7-CN Cl CF3 NO2 1.257 7-CN H NO2 CF3 1.258 6-C(CH3)3 C1 CF3 NO2 1.259 6-C(CH3)3 H NO2 CF3 35 1.260 4-SO2CH3 C1 CF3 NO2 1.261 4-SO2CH3 H NO2 CF3 1.262 5-SO2CH3 Cl CF3 NO2 1.263 5-SO2CH3 H NO2 CF3 1.264 6-S02CH3 Cl CF3 NO2 40 1.265 6-SO2CH3 H NO2 CF3 1.266 7-SO2CH3 Cl CF3 NO2 1.267 7-SO2CH3 H NO2 CF3 1.268 6-SCH3 Cl CF3 NO2 ~02~6 O.Z. 0050/40923 Table 1 (contd.) No. Xm Rl R2 R3 m.p. (C) S 1.269 6-SCH3 H NO2 CF3 1.270 4,5-C12 Cl CF3 NO2 1.271 4,5-C12 F CF3 No2 1.272 4,5-C12 H CF3 No2 1.273 4,5-C12 H NO2 CF3 10 1.274 4,5-C12 H NO2 Cl 1.275 4,5-C12 Cl Cl No2 1.276 4,5-C12 Cl CN No2 1.277 4,5-Ct2 Cl COOC2Hs No2 1.278 4-CI, 5-CF3 Cl CF3 NO2 15 1.279 4-CI, S-CF3 F CF3 No2 1.280 4-CI, 5-CF3 H CF3 No2 1.281 4-CI, 5-CF3 H NO2 CF3 1.282 4-Cl, 5-CF3 H N02 Cl 1.283 4-Cl, 5-CF3 Cl Cl ~2 20 1.284 4-CI, 5-CF3 Cl CN No2 1.285 4-Ct, 5-CF3 Cl COOC2Hs No2 1.286 7-CI, 5-CF3 Cl CF3 N02 1.287 7-CI, 5-CF3 F CF3 No2 1.288 7-CI, 5-CF3 H CF3 No2 25 1.289 7-Cl, 5-CF3 H NO2 CF3 1.290 7-Cl, 5-CF3 H NO2 Cl 1.291 7-Cl, 5-CF3 Cl Cl No2 1.292 7-CI, 5-CF3 Cl CN No2 1.293 7-Cl, 5-CF3 Cl COOC2H5 No2 30 1.294 s,6-C12 Cl CF3 NO2 1.295 5,6-C12 F CF3 No2 1.296 s,6-C12 H CF3 No2 1.297 5,6 C12 H ~2 CF3 1.298 s,6-C12 H NO2 Cl 35 1.299 s,6-C12 Cl Cl No2 1.300 5,6-C12 Cl CN No2 1.301 5,Ç-C12 Cl COOC2H5 No2 1.302 5,7-(N02)2 Cl CF3 NO2 1.303 5,7-(NO~)2 F CF3 No2 40 1.204 5,7-(N02)2 H CF3 No2 i.305 5,7-(N~2)2 H N02 CF3 1.306 5,7-~N02)2 H NO2 Cl 1.307 5,7-(N02)2 Cl Cl No2 890376 2 0 2 ~ ~ ~ 6 16 O.Z. OOS0/40923 Table l (contd.) No . Xm Rl R2 R3 m.p. (C) 5 1.308 5,7-(N02)2 Cl CN No2 1.309 5,7-(N02)2 Cl COOC2H5 No2 1.310 5-NO2, 7-CI Cl CF3 NO2 1.311 5-No2, 7-CI F CF3 No2 1.312 5-NO2, 7-CI H CF3 No2 10 1.313 5-N02, 7-CI H NO2 CF3 1.314 5-NO2, 7-Cl H NO2 Cl 1.315 5-NO2, 7-CI Cl Cl No2 1.316 5-N02, 7-CI Cl CN No2 1.317 5-No2, 7-CI Cl COOC2Hs No2 15 1.318 4-CI, 5-NO2 Cl CF3 NO2 1.319 4-CI, 5-NO2 F CF3 No2 1.320 4-CI, 5-NO2 H CF3 No2 1.321 4-CI, 5-NO2 H NO2 CF3 1.322 4-CI, 5-NO2 H NO2 Cl 20 1.323 4-CI, 5-NO2 Cl Cl No2 1.324 4-CI, 5-NO2 Cl CN No2 1.325 4-CI, 5-NO2 Cl COOC2Hs No2 1.326 4-CI, 7-NO2 Cl ~F3 NO2 1.327 4-CI, 7-NO2 F CF3 No2 25 1.228 4-CI, 7-NO2 H CF3 No2 1.329 4-CI, 7-NO2 H N02 CF3 1.330 4-CI, 7-NO2 H NO2 Cl 1.331 4-CI, 7-NO2 Cl Cl No2 1.332 4-CI, 7-NO2 Cl CN No2 30 1.333 4-CI, 7-N02 Cl COOC2H5 N2 1.334 6-CI, 5,7-(No232 Cl CF3 NO2 1.335 6-CI, 5,7-(N02)2 F CF3 No2 1.336 6-CI, 5,7-(N02)2 H CF3 No2 1.337 6-CI, 5,7-(NO2)2 H N02 CF3 35 1.338 6-Cl, 5,7-(NO2)2 H NO2 Cl 1.339 6-CI, 5,7-(N02)2 Cl Cl No2 1.340 6-CI, 5~7-(N02)2 Cl CN No2 1.341 6-CI, 5,7-1NO2)2 Cl COOC2H5 No2 1.342 6-F, 5,7-(N02)2 Cl CF3 NO2 40 1.343 6-F, 5,7-(N02)2 H NO2 CF3 1.344 6-Br, 5,7-(NO2)2 Cl CF3 NO2 1.345 6-Br, 5,7-(N02)2 H N02 CF3 1.346 6-CN, 5,7-(N02)2 Cl CF3 NO2 17 O.Z. 0050/40923 Table I (contd.) No. Xm R1 R2 R3 m.p. (C) 5 1.347 6-CN, 5,7-(N02)2 H NO2 CF3 1.348 6-OCH3, 5,7-(N02)2 Cl CF3 NO2 1.349 6-OCH3, 5,7-(NO2)2 Cl No2 CF3 1.350 6-SC2Hs, 5,7-(N02)2 Cl CF3 NO2 1.351 6-SC2Hs, 5,7-(N02)2 H No2 CF3 10 1.352 6-OPh, 5,7-(NO2)2 Cl CF3 NO2 1.353 6-OPh, 5,7-(N02)2 H NO2 CF3 1.354 6-SPh, 5,7-(N02)2 Cl CF3 NO2 1.355 6-SPh, 5,7-(N02)2 H NO2 CF3 1.356 4-0CH3, 5-N02 Cl CF3 NO2 15 1.357 4-OCH3, 5-NO2 H NO2 CF3 1.358 4-CN, 5-NO2 Cl CF3 NO2 1.359 4-CN, 5-N02 H N02 CF3 1.360 4-0CH3, 7-N02 Cl CF3 N02 1.361 4-0CH3, 7-NO2 H N02 CF3 20 1.362 4-CN, 7-NO2 Cl CF3 NO2 1.363 4-CN, 7-NO2 H NO2 CF3 1.364 4-OCH3, 5-Ct Cl CF3 NO2 1.365 4-OCH3, 5-Cl H NO2 CF3 1.366 5-No2, 6-Cl Cl CF3 NO2 25 1.367 5-NO2, 6-CI H NO2 CF3 1.368 5-NO2, 6-CF3 Cl CF3 N03 1.369 5-NO2, 6-CF3 H NO2 CF3 1.370 5-NO2, 4-CF3 Cl CF3 NO2 1.371 5-NO2, 4-CF3 H NO2 CF3 30 1.372 5,7-(CF3)2 Cl CF3 NO2 1.373 5,7-tCF3)2 H NO2 CF3 1.374 5-CI, 7-CF3 Cl CF3 N02 1.375 5-Cl, 7-CF3 H NO2 CF3 1.376 s,7-C12 Cl CF3 NO2 35 1.377 s,7-C12 H NO2 CF3 1.378 5,7-Br2 Cl CF3 NO2 1.379 5,7-Br2 H NO2 CF3 1.380 5-CN, 7-CI Cl CF3 NO2 1.381 5-CN, 7-Cl H NO2 CF3 40 1.382 5-CN, 4-Cl Cl CF3 NO2 1.383 5-CN, 4-CI H NO2 CF3 20~0~ 6 18 O.Z. 0050/40923 Table 2 ~S~
X ~ N02 R
~ R2 I, No. Xm Rl R2 R3 R4 m.p. (C) 5 2.1 - Cl CF3 N02 S02phenyl 2.2 - H N02 CF3 S02Ph 2.3 - H CF3 H 502Ph 2.4 _ H CF3 H COCH3 108-111 2.5 _ H CF3 H COOCH3 10 2.6 5-Cl Cl CF3 N02 502Ph 2.7 S-Cl H N02 CF3 502Ph 2.8 5-N02, 7-Cl Cl CF3 N02 S02Ph 2.9 5-No2, 7-Cl Cl CF3 N02 CONH2 2.10 5-N02, 7-CI H N2 CF3 COOCH2Ph 15 2.11 5-N02, 7-Cl H N02 CF3 502Ph 2.12 5-N02, 7-Cl H CF3 H S02Ph 2.13 5-N02 H CF3 H COCH2CI
2.14 5-N02 H CF3 H S02Ph 2.15 5-No2 H CF3 H COCHC12 20 2.16 5-N02 Cl CF3 N02 502Ph 2.17 5-N02 Cl CF3 N02 COCH3 2.18 5-N02 Cl CF3 N02 COCHC12 2.19 5-No2 Cl CF3 N02 COPh 2. 20 5-N02 Cl CF3 N02 COOCH3 25 2.21 5-N02 Cl CF3 N02 CONH2 2.22 5-N02 Cl CF3 N02 CHO
2.23 5,7-C12 Cl CF3 N02 502Ph 2.24 5,7-C12 H N02 CF3 S02Ph 2.25 5,7-C12 H N02 CF3 COOCH3 30 2.26 5,7-C12 H N02 CF3 COCH2Cl 2.27 4-CI Cl CF3 N02 S02Ph 2.28 4-CI H N02 CF3 S02Ph 2.29 6-N02 Cl CF3 N02 502Ph 2.30 6-N02 H N02 CF3 S02Ph 2 0 ~
19 O.Z. 0050/40923 Table 2 (contd.) No. X~ Rl R2 R3 R4 m.p. (C) 5 2.31 6-CF3 Cl CF3 NO2 SO2Ph 2.32 6-CF3 H NO2 CF3 SO2Ph 2.33 5-CF3 Cl CF3 NO2 COCH2CI
2.34 5-CF3 Cl CF3 NO2 ~ SO2Ph 2.35 5-CF3 Cl CF3 NO2 COOCH3 lO 2.36 5-CF3 Cl CF3 NO2 CONH2 2.37 5-CF3 Cl CF3 NO2 COPh 2.38 5-CF3 H CF3 H SO2Ph 2.39 5-CF3 H NO2 CF3 SO2Ph 2.40 5-CF3 H ~2 CF3 COOCH3 15 2.41 5-CF3 H NO2 CF3 CONH2 2.42 5-CF3 H NO2 CF3 COPh 2.43 5-CF3 H NO2 CF3 COCHC 12 2.44 4-OCH3 Cl CF3 N~2 SO2Ph 2.45 7-NO2 Cl CF3 NO2 SO2Ph 20 2.46 7-NO2 H NO2 CF3 SO2Ph ~32~4~6 O.Z. 0050/40923 Table 3 X ~ NO2 R1 N ~ R2 R3 M~
No. X~ Rl R2 R3 ~ M~ m.p.
(C~
3.1 _ Cl CF3 NO2 K~
3.2 - Cl CF3 NO2 N(C4H9)4~ 165 3.3 - H No2 CF3 N(C4~9)4 3.4 - H CF3 H N(C4Hg)4~
10 3.5 S-NO2 Cl CF3 NO2 K~185-190 3.6 5-NO2 Cl CF3 NO2 N(CH3)3CH2c6H5~
3.7 5-N02 Cl CF3 N02 N(C4H9)4~ 143 3.8 5-NO2 H CF3 H N(~4Hg)4~
3.9 5-NO2 H CF3 No2 N(C4H9)4~ 159 15 3.10 5-NO2 H NO2 CF3N(C4H9)4~
3.11 5-N02 Cl COOC2H5 No2 N(Ç4H9) ~ 159-161 3.12 5-NO2 H COOCH3 No2 N~C4H9)4~ 93 3.13 5-NO2 H SO2CH3 No2 N(C4H9)4~ 142-145 3.14 5-No2 Cl Cl Cl N(C4H9)4~ 105-110 20 3.15 5-Cl Cl CF3 NO2 K~
3.16 S-Cl Cl CF3 N02 N(C4H9)4 3.17 5-CI H NO2 CF3 N(C4H9)4 3.18 5-CF3 Cl CF3 N02 K~
3.19 5-CF3 Cl CF3 NO2 N(CH3)4 25 3.20 5-CF3 Cl CF3 NO2N(C~Hg)4 3.21 5-CF3 Cl CF3 NO2 NH2~i-C3H7)2 3.22 5-CF3 Cl ~F3 NO2 (CH3)3NCH2CH2OH~
3.23 5-CF3 H N02 CF3 K~
3.24 5-CF3 H NO2 CF3 N(C4H9)4 30 3.25 5-CF3 H N02 CF3 NH2(i-C3H7)2 3.26 5-Br Cl CF3 N02 N(C4H9)4 3.27 5-Br H NO2 CF3 N(C4H9~4 3.28 s,7-Cl2 Cl CF3 NO2 K~
3.29 5 7-C12 Cl CF3 NO2 N(C4Hg) 2V~01.~5 21 O.Z. 0050/40923 Table 3 (contd.) No. Xm Rl R2 R3 M+ m. p .
( o C ) 3.30 5,7-C12 H NO2 CF3 K~
3.31 5,7-C12 H NO2 CF3 N(C4H9)4 3.32 5-NO2, 7-Cl Cl CF3 NO2 N(C4H9)4 3.33 5-NO2, 7-CI H NO2 CF3 N(C4H9)4 3.34 4-CI Cl CF3 NO2 N(C4H9)4 3.35 4-Cl H NO2 CF3 N(C4H9)4 3.36 6-NO2 Cl CF3 NO2 N(C4H9)4 3.37 6-NO2 H NO2 CF3 N(C4H9)4 3.38 6-CF3 Cl CF3 NO2 N(C4H9)4~
3.39 6-CF3 H N02 CF3 N(C4Hg)43 3.40 4-OCH3 Cl CF3 NO2 N(C4H9)4 3.41 7-CF3 Cl CF3 NO2 N(C4H9)4 3.42 7-NO2 Cl CF3 NO2 N(C4H9)4 3.43 7-NO2 H NO2 CF3 N(C4Hg)4 3.44 7-CI Cl CF3 NO2 N(C4H9)4 3.45 7-Cl H NO2 CF3 N(C4H9)4 3.46 7-CI H CH3 No2 N(C4H9)4 3.47 6-CI Cl CF3 NO2 N(C4H9)4 3.48 6-CI H NO2 CF3 N(C4H9)4 3.49 6-CI Cl CF3 NO2 K~
Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. So~e of them have a systemic action and can be used as foliar and soil fun~icides.
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 noYel compounds are particularly useful for controlling the following plant diseases:
~0~41~
2.34 5-CF3 Cl CF3 NO2 ~ SO2Ph 2.35 5-CF3 Cl CF3 NO2 COOCH3 lO 2.36 5-CF3 Cl CF3 NO2 CONH2 2.37 5-CF3 Cl CF3 NO2 COPh 2.38 5-CF3 H CF3 H SO2Ph 2.39 5-CF3 H NO2 CF3 SO2Ph 2.40 5-CF3 H ~2 CF3 COOCH3 15 2.41 5-CF3 H NO2 CF3 CONH2 2.42 5-CF3 H NO2 CF3 COPh 2.43 5-CF3 H NO2 CF3 COCHC 12 2.44 4-OCH3 Cl CF3 N~2 SO2Ph 2.45 7-NO2 Cl CF3 NO2 SO2Ph 20 2.46 7-NO2 H NO2 CF3 SO2Ph ~32~4~6 O.Z. 0050/40923 Table 3 X ~ NO2 R1 N ~ R2 R3 M~
No. X~ Rl R2 R3 ~ M~ m.p.
(C~
3.1 _ Cl CF3 NO2 K~
3.2 - Cl CF3 NO2 N(C4H9)4~ 165 3.3 - H No2 CF3 N(C4~9)4 3.4 - H CF3 H N(C4Hg)4~
10 3.5 S-NO2 Cl CF3 NO2 K~185-190 3.6 5-NO2 Cl CF3 NO2 N(CH3)3CH2c6H5~
3.7 5-N02 Cl CF3 N02 N(C4H9)4~ 143 3.8 5-NO2 H CF3 H N(~4Hg)4~
3.9 5-NO2 H CF3 No2 N(C4H9)4~ 159 15 3.10 5-NO2 H NO2 CF3N(C4H9)4~
3.11 5-N02 Cl COOC2H5 No2 N(Ç4H9) ~ 159-161 3.12 5-NO2 H COOCH3 No2 N~C4H9)4~ 93 3.13 5-NO2 H SO2CH3 No2 N(C4H9)4~ 142-145 3.14 5-No2 Cl Cl Cl N(C4H9)4~ 105-110 20 3.15 5-Cl Cl CF3 NO2 K~
3.16 S-Cl Cl CF3 N02 N(C4H9)4 3.17 5-CI H NO2 CF3 N(C4H9)4 3.18 5-CF3 Cl CF3 N02 K~
3.19 5-CF3 Cl CF3 NO2 N(CH3)4 25 3.20 5-CF3 Cl CF3 NO2N(C~Hg)4 3.21 5-CF3 Cl CF3 NO2 NH2~i-C3H7)2 3.22 5-CF3 Cl ~F3 NO2 (CH3)3NCH2CH2OH~
3.23 5-CF3 H N02 CF3 K~
3.24 5-CF3 H NO2 CF3 N(C4H9)4 30 3.25 5-CF3 H N02 CF3 NH2(i-C3H7)2 3.26 5-Br Cl CF3 N02 N(C4H9)4 3.27 5-Br H NO2 CF3 N(C4H9~4 3.28 s,7-Cl2 Cl CF3 NO2 K~
3.29 5 7-C12 Cl CF3 NO2 N(C4Hg) 2V~01.~5 21 O.Z. 0050/40923 Table 3 (contd.) No. Xm Rl R2 R3 M+ m. p .
( o C ) 3.30 5,7-C12 H NO2 CF3 K~
3.31 5,7-C12 H NO2 CF3 N(C4H9)4 3.32 5-NO2, 7-Cl Cl CF3 NO2 N(C4H9)4 3.33 5-NO2, 7-CI H NO2 CF3 N(C4H9)4 3.34 4-CI Cl CF3 NO2 N(C4H9)4 3.35 4-Cl H NO2 CF3 N(C4H9)4 3.36 6-NO2 Cl CF3 NO2 N(C4H9)4 3.37 6-NO2 H NO2 CF3 N(C4H9)4 3.38 6-CF3 Cl CF3 NO2 N(C4H9)4~
3.39 6-CF3 H N02 CF3 N(C4Hg)43 3.40 4-OCH3 Cl CF3 NO2 N(C4H9)4 3.41 7-CF3 Cl CF3 NO2 N(C4H9)4 3.42 7-NO2 Cl CF3 NO2 N(C4H9)4 3.43 7-NO2 H NO2 CF3 N(C4Hg)4 3.44 7-CI Cl CF3 NO2 N(C4H9)4 3.45 7-Cl H NO2 CF3 N(C4H9)4 3.46 7-CI H CH3 No2 N(C4H9)4 3.47 6-CI Cl CF3 NO2 N(C4H9)4 3.48 6-CI H NO2 CF3 N(C4H9)4 3.49 6-CI Cl CF3 NO2 K~
Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. So~e of them have a systemic action and can be used as foliar and soil fun~icides.
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 noYel compounds are particularly useful for controlling the following plant diseases:
~0~41~
22 O.Z. OOS0/40923 Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, 5 Puccinia species in cereals, Rhizoctonia species in cotton and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, 10 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, 15 Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in various plants, Plasmopara viticola in grapes, Alternaria species in vegetables and fruit.
20 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. Either the fungi themselves, or the objects to be protected against fungal attack are treated with a fungicidally effective 25 amount of the active ingredient.
The novel substances can be converted into conYentional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are 3Q 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 is used as solvent, it is also possible to employ other organic solvents 35 as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene~, chlorinated aromatics (e.g., chlorobenz-enes), paraffins (e.g., crude oil fractions), alcohols te.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals 40 (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., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
202~16 23 O.Z. 0050/40923 The fungicidal agents 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 protect-5 ing materials (wood), for example against Paecilomyces variotii.
When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, 9 per kg of seed are usually employed.
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.
1. 90 parts by weight of ccmpound no. l.1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable 20 for application in the form of very fine drops.
II. 20 parts by weight of compound no. 1.16 is dissolved in a mixture consisting of 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-25 monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 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 uniformly distributing it therein, an aqueous dispersion is obtained.
30 III. 20 parts by weight of compound no. 1.33 is dissolved in a mixture consisting of 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 distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 1.46 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 40 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
~02~4~6 24 O.Z. 0050/40923 V. 80 parts by weight of compound no. 1.82 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic 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, 5 and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 1.1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
10 by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1.16 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and ~
8 parts by weight of paraffin oil which has been sprayed onto the surface 15 of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 1.33 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-20 formaldehyde condensate, 2 parts of silica gel and 48 parts of water togive a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts by weight of compound no. 1.46 is intimately mixed with 25 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. A stable oily dispersion is obtained.
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 fun-35 gicides frequently results in an increase in the fungicidal spectrum.
Use examples For comparison purposes, 2-(2,6-dinitro-3-chloro-4-trifluoromethyl-40 anilino)-6-methoxybenzthiazole ~A) and 2-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino~-6-nitrobenzthiazole (B) disclosed in EP 244,705 were used.
2(~2~416 O.Z. 0050/40923 Use Example 1 Action on Botrytis cinerea in pimientos 5 Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5 well developed leaves were sprayed to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier.
After the sprayed-on layer had dried, the plants were sprayed with a conidial suspension of the fungus 8Otrytis cinerea and kept in a high-10 humidity chamber at 22 to 24C. After 5 days, the disease had spread onthe untreated control plants to such an extent that the necroses covered the major portion of the leaves. The leaf attack was assessed.
The results show that active ingredient 1.46, applied as a 0.05wt% spray, 15 has a better fungicidal action ~97%) than prior art active ingredients A
(3~%) and B (2~%).
Use Example 2 20 Action on Plasmopara viticola Leaves of potted vines of the MUller~Thurgau variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, ths plants were set up, 25 after the sprayed-on layer had dried, for 8 days in the gr~enhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viti-cola. rhe plants were first placed for 48 hours in a water vapor-saturated chamber at 24C and then in a greenhouse for 5 days at from 20 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were 30 then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1.1, 1.16, 1.33, 1.46 and 1.82, applied as 0.05wt# spray liquors, have a better fungicidal action l100#) 35 than prior art comparative agents A (65%) and B (65%).
Use Example 3 Action on Phytophthora infestans Leaves of potted tomatoes of the "Gro~e Fleischtomate" variety were sprayed with aqueous liquors consisting (dry basis) of 8~% of active ingredient and 20% of ~mulsifier. After 24 hours, the leaves were inf~cted with a zoospore suspension of the fungus Phytophthora infestans. The ~0.~416 26 O.z. 0050/40923 plants were set up in a water vapor-saturated chamber at 16 to 18C. After 6 days the disease had spread to such an extent on the untreated but infected control plants that the fungicidal action of the compounds was able to be assessed.
The results show that active ingredients 1.16, 1.33, 1.46 and 1.82, applied as 0.025wt% spray liquors, have a better fungicidal action (97%) than prior art comparative agents A (20%) and B (50%~.
20 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. Either the fungi themselves, or the objects to be protected against fungal attack are treated with a fungicidally effective 25 amount of the active ingredient.
The novel substances can be converted into conYentional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are 3Q 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 is used as solvent, it is also possible to employ other organic solvents 35 as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene~, chlorinated aromatics (e.g., chlorobenz-enes), paraffins (e.g., crude oil fractions), alcohols te.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals 40 (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., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
202~16 23 O.Z. 0050/40923 The fungicidal agents 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 protect-5 ing materials (wood), for example against Paecilomyces variotii.
When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, 9 per kg of seed are usually employed.
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.
1. 90 parts by weight of ccmpound no. l.1 is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable 20 for application in the form of very fine drops.
II. 20 parts by weight of compound no. 1.16 is dissolved in a mixture consisting of 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-25 monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 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 uniformly distributing it therein, an aqueous dispersion is obtained.
30 III. 20 parts by weight of compound no. 1.33 is dissolved in a mixture consisting of 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 distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 1.46 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 40 of castor oil. By pouring the solution into water and uniformly distribut-ing it therein, an aqueous dispersion is obtained.
~02~4~6 24 O.Z. 0050/40923 V. 80 parts by weight of compound no. 1.82 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic 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, 5 and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 1.1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
10 by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1.16 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and ~
8 parts by weight of paraffin oil which has been sprayed onto the surface 15 of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 1.33 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-20 formaldehyde condensate, 2 parts of silica gel and 48 parts of water togive a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts by weight of compound no. 1.46 is intimately mixed with 25 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. A stable oily dispersion is obtained.
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 fun-35 gicides frequently results in an increase in the fungicidal spectrum.
Use examples For comparison purposes, 2-(2,6-dinitro-3-chloro-4-trifluoromethyl-40 anilino)-6-methoxybenzthiazole ~A) and 2-(2,6-dinitro-3-chloro-4-tri-fluoromethylanilino~-6-nitrobenzthiazole (B) disclosed in EP 244,705 were used.
2(~2~416 O.Z. 0050/40923 Use Example 1 Action on Botrytis cinerea in pimientos 5 Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5 well developed leaves were sprayed to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier.
After the sprayed-on layer had dried, the plants were sprayed with a conidial suspension of the fungus 8Otrytis cinerea and kept in a high-10 humidity chamber at 22 to 24C. After 5 days, the disease had spread onthe untreated control plants to such an extent that the necroses covered the major portion of the leaves. The leaf attack was assessed.
The results show that active ingredient 1.46, applied as a 0.05wt% spray, 15 has a better fungicidal action ~97%) than prior art active ingredients A
(3~%) and B (2~%).
Use Example 2 20 Action on Plasmopara viticola Leaves of potted vines of the MUller~Thurgau variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, ths plants were set up, 25 after the sprayed-on layer had dried, for 8 days in the gr~enhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viti-cola. rhe plants were first placed for 48 hours in a water vapor-saturated chamber at 24C and then in a greenhouse for 5 days at from 20 to 30C. To accelerate and intensify the sporangiophore discharge, the plants were 30 then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1.1, 1.16, 1.33, 1.46 and 1.82, applied as 0.05wt# spray liquors, have a better fungicidal action l100#) 35 than prior art comparative agents A (65%) and B (65%).
Use Example 3 Action on Phytophthora infestans Leaves of potted tomatoes of the "Gro~e Fleischtomate" variety were sprayed with aqueous liquors consisting (dry basis) of 8~% of active ingredient and 20% of ~mulsifier. After 24 hours, the leaves were inf~cted with a zoospore suspension of the fungus Phytophthora infestans. The ~0.~416 26 O.z. 0050/40923 plants were set up in a water vapor-saturated chamber at 16 to 18C. After 6 days the disease had spread to such an extent on the untreated but infected control plants that the fungicidal action of the compounds was able to be assessed.
The results show that active ingredients 1.16, 1.33, 1.46 and 1.82, applied as 0.025wt% spray liquors, have a better fungicidal action (97%) than prior art comparative agents A (20%) and B (50%~.
Claims (6)
1. 3-Anilinobenzoisothiazoles of the formula I
I, where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, and plant-tolerated salts thereof.
I, where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, and plant-tolerated salts thereof.
2. A fungicidal agent containing a solid or liquid carrier and a fungi-cidally effective amount of a compound of the formula I
I, 28 O.Z. 0050/40923 where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, or a plant-tolerated salt thereof.
I, 28 O.Z. 0050/40923 where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, or a plant-tolerated salt thereof.
3. A process for combating fungi, wherein a fungicidally effective amount of a compound of the formula I
I, where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, 29 O.Z. 0050/40923 m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, or a plant-tolerated salt thereof, is allowed to act on the fungi, or the plants, seed, materials or soil threatened by fungus attack.
I, where X is hydrogen, NO2, CN, halogen, SO2-C1-C4-alkyl, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, or phenoxy or phenylthio, each of which is unsubstituted or substituted, 29 O.Z. 0050/40923 m is an integer from 1 to 4, with the individual radicals being identical or different when m is greater than 1, R1 is hydrogen, halogen, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkoxy, or phenoxy, phenylthio, benzyl-oxy or benzylthio, each of which is unsubstituted or substituted in the phenyl, R2 and R3 are, independently of one another, hydrogen, NO2, halogen, CN, C1-C6-alkyl, SO2-C1-C4-alkyl, C1-C6-haloalkyl, SO2NR5R6, C1-C4-haloalkoxy, COOR5 or CONR5R6, R4 is hydrogen, COOR7, CONR5R6, CHO, COR7 or SO2R7, R5 and R6 are, independently of one another, hydrogen or C1-C4-alkyl, R7 is C1-C4-alkyl, C1-C4-haloalkyl, benzyl, or aryl which is unsubstituted or substituted, or a plant-tolerated salt thereof, is allowed to act on the fungi, or the plants, seed, materials or soil threatened by fungus attack.
4. A compound of the formula I as set forth in claim 1, where Xm is
5-NO2, R1 is Cl, R2 is CF3, R3 is NO2 and R4 is hydrogen.
5. A compound of the formula I as set forth in claim 1, where Xm is hydrogen, R1 is Cl, R2 is CF3, R3 is NO2 and R4 is hydrogen.
5. A compound of the formula I as set forth in claim 1, where Xm is hydrogen, R1 is Cl, R2 is CF3, R3 is NO2 and R4 is hydrogen.
6. A compound of the formula I as set forth in claim 1, where Xm is hydrogen, R1 is hydrogen, R2 is NO2, R3 is CF3 and R4 is hydrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3922088.5 | 1989-07-05 | ||
| DE3922088A DE3922088A1 (en) | 1989-07-05 | 1989-07-05 | 3-ANILINO-BENZISOTHIAZOLE AND FUNGICIDES CONTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2020416A1 true CA2020416A1 (en) | 1991-01-06 |
Family
ID=6384349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002020416A Abandoned CA2020416A1 (en) | 1989-07-05 | 1990-07-04 | 3-anilinobenzoisothiazoles and fungicides containing these |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0406700B1 (en) |
| JP (1) | JPH03128304A (en) |
| AT (1) | ATE104288T1 (en) |
| CA (1) | CA2020416A1 (en) |
| DE (2) | DE3922088A1 (en) |
| DK (1) | DK0406700T3 (en) |
| ES (1) | ES2063204T3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4029771A1 (en) * | 1990-09-20 | 1992-03-26 | Basf Ag | N-HETEROARYL-2-NITROANILINE |
| JPH07500116A (en) * | 1992-03-26 | 1995-01-05 | ダウエランコ | N-heterocyclic nitroanilines as fungicides |
| EP1871743A4 (en) * | 2005-04-11 | 2009-12-30 | Univ Murdoch | Antiparasitic compounds |
| DE602007003332D1 (en) * | 2006-03-31 | 2009-12-31 | Basf Se | 3-AMINO-1,2-BENZISOTHIAZOL COMPOUNDS FOR COMBATING ANIMAL PEST |
| BR112020000085A2 (en) * | 2017-07-03 | 2020-07-07 | Bayer Cropscience Aktiengesellschaft | new isothiazole-based bicycles, processes for their preparation and use as herbicides and / or plant growth regulators. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133418A3 (en) * | 1983-08-09 | 1985-04-03 | Ciba-Geigy Ag | Use of 3-acylamino-benzisothiazoles in pest control |
| DE3343091A1 (en) * | 1983-11-29 | 1985-06-05 | Bayer Ag, 5090 Leverkusen | USE OF 3-AMINO-1,2-BENZISOTHIAZOLES AS MICROBICIDES TO PROTECT TECHNICAL MATERIALS |
| DE3544436A1 (en) * | 1984-12-18 | 1986-06-19 | Ciba-Geigy Ag, Basel | Novel dioxides |
| DE3614595A1 (en) * | 1986-04-30 | 1987-11-05 | Hoechst Ag | BENZOXAZOLYL AND BENTHIAZOLYLANILINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A FUNGICIDE AGENT |
-
1989
- 1989-07-05 DE DE3922088A patent/DE3922088A1/en not_active Withdrawn
-
1990
- 1990-06-28 EP EP90112326A patent/EP0406700B1/en not_active Expired - Lifetime
- 1990-06-28 DE DE59005325T patent/DE59005325D1/en not_active Expired - Lifetime
- 1990-06-28 DK DK90112326.5T patent/DK0406700T3/en active
- 1990-06-28 ES ES90112326T patent/ES2063204T3/en not_active Expired - Lifetime
- 1990-06-28 AT AT90112326T patent/ATE104288T1/en not_active IP Right Cessation
- 1990-06-29 JP JP2170402A patent/JPH03128304A/en active Pending
- 1990-07-04 CA CA002020416A patent/CA2020416A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ATE104288T1 (en) | 1994-04-15 |
| DE3922088A1 (en) | 1991-01-17 |
| EP0406700A1 (en) | 1991-01-09 |
| EP0406700B1 (en) | 1994-04-13 |
| JPH03128304A (en) | 1991-05-31 |
| DK0406700T3 (en) | 1994-05-16 |
| DE59005325D1 (en) | 1994-05-19 |
| ES2063204T3 (en) | 1995-01-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |